Exploiting magnetic properties of Fe doping in zirconia. From first-principles simulations to the experimental growth and characterization of thin films

NASA Astrophysics Data System (ADS)

Sangalli, Davide; Cianci, Elena; Lamperti, Alessio; Ciprian, Roberta; Albertini, Franca; Casoli, Francesca; Lupo, Pierpaolo; Nasi, Lucia; Campanini, Marco; Debernardi, Alberto

2013-05-01

In this study we explore, both from theoretical and experimental side, the effect of Fe doping in ZrO2 (ZrO2:Fe). By means of first principles simulation, we study the magnetization density and the magnetic interaction between Fe atoms. We also consider how this is affected by the presence of oxygen vacancies and compare our findings with models based on impurity band [J.M.D. Coey, M. Venkatesan, C.B. Fitzgerald, Nat. Mater. 4, 173 (2005)] and carrier mediated magnetic interaction [T. Dietl, H. Ohno, F. Matsukura, J. Cibert, D. Ferrand, Science 287, 1019 (2000)]. Experimentally, thin films (≈20 nm) of ZrO2:Fe at high doping concentration are grown by atomic layer deposition. We provide experimental evidence that Fe is uniformly distributed in the ZrO2 by transmission electron microscopy and energy dispersive X-ray mapping, while X-ray diffraction evidences the presence of the fluorite crystal structure. Alternating gradient force magnetometer measurements show magnetic signal at room temperature, however, with low magnetic moment per atom. Results from experimental measures and theoretical simulations are compared.

Preparation of magnetron sputtered ZrO2 films on Si for gate dielectric application

NASA Astrophysics Data System (ADS)

Kondaiah, P.; Mohan Rao, G.; Uthanna, S.

2012-11-01

Zirconium oxide (ZrO2) thin films were deposited on to p - Si and quartz substrates by sputtering of zirconium target at an oxygen partial pressure of 4x10-2 Pa and sputter pressure of 0.4 Pa by using DC reactive magnetron sputtering technique. The effect of annealing temperature on structural, optical, electrical and dielectric properties of the ZrO2 films was systematically studied. The as-deposited films were mixed phases of monoclinic and orthorhombic ZrO2. As the annealing temperature increased to 1073 K, the films were transformed in to single phase orthorhombic ZrO2. Fourier transform infrared studies conform the presence of interfacial layer between Si and ZrO2. The optical band gap and refractive index of the as-deposited films were 5.82 eV and 1.81. As the annealing temperature increased to 1073 K the optical band gap and refractive index increased to 5.92 eV and 2.10 respectively. The structural changes were influenced the capacitance-voltage and current-voltage characteristics of Al/ZrO2/p-Si capacitors. The dielectric constant was increased from 11.6 to 24.5 and the leakage current was decreased from 1.65×10-7 to 3.30×10-9 A/ cm2 for the as-deposited and annealed at 1073 K respectively.

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.

Surface Modification of Solution-Processed ZrO2 Films through Double Coating for Pentacene Thin-Film Transistors

NASA Astrophysics Data System (ADS)

Kwon, Jin-Hyuk; Bae, Jin-Hyuk; Lee, Hyeonju; Park, Jaehoon

2018-03-01

We report the modification of surface properties of solution-processed zirconium oxide (ZrO2) dielectric films achieved by using double-coating process. It is proven that the surface properties of the ZrO2 film are modified through the double-coating process; the surface roughness decreases and the surface energy increases. The present surface modification of the ZrO2 film contributes to an increase in grain size of the pentacene film, thereby increasing the field-effect mobility and decreasing the threshold voltage of the pentacene thin-film transistors (TFTs) having the ZrO2 gate dielectric. Herein, the molecular orientation of pentacene film is also studied based on the results of contact angle and X-ray diffraction measurements. Pentacene molecules on the double-coated ZrO2 film are found to be more tilted than those on the single-coated ZrO2 film, which is attributed to the surface modification of the ZrO2 film. However, no significant differences are observed in insulating properties between the single-and the double-coated ZrO2 dielectric films. Consequently, the characteristic improvements of the pentacene TFTs with the double-coated ZrO2 gate dielectric film can be understood through the increase in pentacene grain size and the reduction in grain boundary density.

Structural Studies of dielectric HDPE+ZrO2 polymer nanocomposites: filler concentration dependences

NASA Astrophysics Data System (ADS)

Nabiyev, A. A.; Islamov, A. Kh; Maharramov, A. M.; Nuriyev, M. A.; Ismayilova, R. S.; Doroshkevic, A. S.; Pawlukojc, A.; Turchenko, V. A.; Olejniczak, A.; Rulev, M. İ.; Almasan, V.; Kuklin, A. I.

2018-03-01

Structural properties of HDPE+ZrO2 polymer nanocomposites thin films of 80-100μm thicknesses were investigated using SANS, XRD, Laser Raman and FTIR spectroscopy. The mass fraction of the filler was 1, 3, 10, and 20%. Results of XRD analysis showed that ZrO2 powder was crystallized both in monoclinic and in cubic phase under normal conditions. The percentages of monoclinic and cubic phase were found to be 99.8% and 0.2%, respectively. It was found that ZrO2 nanoparticles did not affect the main crystal and chemical structure of HDPE, but the degree of crystallinity of the polymer decreases with increasing concentration of zirconium oxide. SANS experiments showed that at ambient conditions ZrO2 nanoparticles mainly distributed like mono-particles in the polymer matrix at all concentrations of filler.The structure of HDPE+ZrO2 does not changes up to 132°C at 1-3% of filler, excepting changing of the polymer structure at temperatures upper 82°C. At high concentrations of filler 10-20% the aggregation of ZrO2 nanoparticles occurs, forming domains of 2.5μm. The results of Raman and FTIR spectroscopy did not show additional specific chemical bonds between the filler and the polymer matrix. New peaks formation was not observed. These results suggest that core-shell structure does not exist in the polymer nanocomposite system.

A simple method for the sonochemical synthesis of PVA/ZrO2-vitamin B1 nanocomposites: Morphology, mechanical, thermal and wettability investigations.

PubMed

Mallakpour, Shadpour; Shafiee, Elaheh

2018-01-01

Poly(vinyl alcohol) (PVA) based nanocomposites (NCs) filled by various weight percent of modified ZrO 2 nanoparticles (NPs) with vitamin B 1 (VB 1 ) up to 7wt% were fabricated via ultrasonication method then was cast to thin films. The ultrasonication was applied for the preparation and modification process asan easy, safe and fast method. Ultrasonic was responsible for great homogeneities of NPs into PVA matrix, which could not be achieved by mechanical or magnetically stirring. The creation of polymer NCs and changes in the structural properties were examined by X-ray diffraction. FT-IR spectroscopy indicated the possible interactions of the ZrO 2 -VB 1 NPs with the PVA backbones and also, existence of absorption bands related to PVA and ZrO 2 NPs in the NC structures. The distribution of nano-fillers and uniform morphology of the NCs showed that the ZrO 2 -VB 1 NPs were homogeneously dispersed in the polymer matrix in the nanosized scale. UV-Vis analysis shown that the the optical absorption were improved by evolution of ZrO 2 -VB 1 NPs content. The tensile strength of PVA film was increased significantly with increasing the ZrO 2 -VB 1 NPs content. Thermal gravimetric analysis confirmed that NCs displayed higher thermal stability than the pristine PVA. Also, water contact angle analysis indicated that the hydrophilicity of NC films was enhanced with increasing the concentration of ZrO 2 NPs. Copyright © 2017 Elsevier B.V. All rights reserved.

Miscibility of amorphous ZrO2-Al2O3 binary alloy

NASA Astrophysics Data System (ADS)

Zhao, C.; Richard, O.; Bender, H.; Caymax, M.; De Gendt, S.; Heyns, M.; Young, E.; Roebben, G.; Van Der Biest, O.; Haukka, S.

2002-04-01

Miscibility is a key factor for maintaining the homogeneity of the amorphous structure in a ZrO2-Al2O3 binary alloy high-k dielectric layer. In the present work, a ZrO2/Al2O3 laminate thin layer has been prepared by atomic layer chemical vapor deposition on a Si (100) wafer. This layer, with artificially induced inhomogeneity (lamination), enables one to study the change in homogeneity of the amorphous phase in the ZrO2/Al2O3 system during annealing. High temperature grazing incidence x-ray diffraction (HT-XRD) was used to investigate the change in intensity of the constructive interference peak of the x-ray beams which are reflected from the interfaces of ZrO2/Al2O3 laminae. The HT-XRD spectra show that the intensity of the peak decreases with an increase in the anneal temperature, and at 800 °C, the peak disappears. The same samples were annealed by a rapid thermal process (RTP) at temperatures between 700 and 1000 °C for 60 s. Room temperature XRD of the RTP annealed samples shows a similar decrease in peak intensity. Transmission electronic microscope images confirm that the laminate structure is destroyed by RTP anneals and, just below the crystallization onset temperature, a homogeneous amorphous ZrAlxOy phase forms. The results demonstrate that the two artificially separated phases, ZrO2 and Al2O3 laminae, tend to mix into a homogeneous amorphous phase before crystallization. This observation indicates that the thermal stability of ZrO2-Al2O3 amorphous phase is suitable for high-k applications.

Process-Parameter-Dependent Optical and Structural Properties of ZrO2MgO Mixed-Composite Films Evaporated from the solid Solution

NASA Technical Reports Server (NTRS)

Sahoo, N. K.; Shapiro, A. P.

1998-01-01

The process-parameter-dependent optical and structural properties of ZrO2MgO mixed-composite material have been investigated. Optical properties were derived from spectrophotometric measurements. By use of atomic force microscopy, x-ray diffraction analysis, and energy-dispersive x-ray (EDX) analysis, the surface morphology, grain size distributions, crystallographic phases, and process-dependent material composition of films have been investigated. EDX analysis made evident the correlation between the oxygen enrichment in the films prepared at a high level of oxygen pressure and the very low refractive index. Since oxygen pressure can be dynamically varied during a deposition process, coatings constructed of suitable mixed-composite thin films can benefit from continuous modulation of the index of refraction. A step modulation approach is used to develop various multilayer-equivalent thin-film devices.

Effect of annealing temperature on optical and electrical properties of ZrO2-SnO2 based nanocomposite thin films

NASA Astrophysics Data System (ADS)

Anitha, V. S.; Lekshmy, S. Sujatha; Berlin, I. John; Joy, K.

2014-01-01

Transparent nanocomposite ZrO2-SnO2 thin films were prepared by sol-gel dip-coating technique. Films were annealed at 500°C, 800°C and 1200°C respectively. X-ray diffraction(XRD) spectra showed a mixture of three phases: tetragonal ZrO2 and SnO2 and orthorhombic ZrSnO4. The grain size of all the three phases' increased with annealing temperature. An average transmittance greater than 85%(in UV-Visible region) is observed for all the films. The band gap for the films decreased from 4.79 eV to 4.62 eV with increase in annealing temperature from 500 to 1200 °C. The electrical resistivity increased with increase in annealing temperature. Such composite ZrO2-SnO2 films can be used in many applications and in optoelectronic devices.

Electrical characteristics of SiO2/ZrO2 hybrid tunnel barrier for charge trap flash memory

NASA Astrophysics Data System (ADS)

Choi, Jaeho; Bae, Juhyun; Ahn, Jaeyoung; Hwang, Kihyun; Chung, Ilsub

2017-08-01

In this paper, we investigate the electrical characteristics of SiO2/ZrO2 hybrid tunnel oxide in metal-Al2O3-SiO2-Si3N4-SiO2-silicon (MAONOS) structure in an effort to improve program and erase speed as well as retention characteristics. Inserting ZrO2 into the conventional MAONOS structure increased the programmed V th variation to 6.8 V, and increased the erased V th variation to -3.7 V at 17 MV/cm. The results can be understood in terms of reducing the Fowler-Nordheim (F/N) tunneling barrier due to high-k ZrO2 in the tunneling oxide. In addition, Zr diffusion in SiO2 caused the formation of Zr x Si1- x O2 at the interface region, which reduced the energy band gap of SiO2. The retention property of the hybrid tunnel oxide varied depending on the thickness of SiO2. For thin SiO2 less than 30 Å, the retention properties of the tunneling oxides were poor compared with those of the SiO2 only tunneling oxides. However, the hybrid tunneling oxides with SiO2 thickness thicker than 40 Å yielded improved retention behavior compared with those of the SiO2-only tunneling oxides. The detailed analysis in charge density of ZrO2 was carried out by ISPP test. The obtained charge density was quite small compared to that of the total charge density, which indicates that the inserted ZrO2 layer serves as a tunneling material rather than charge storage dielectric.

Effect of ZrO2 film thickness on the photoelectric properties of mixed-cation perovskite solar cells

NASA Astrophysics Data System (ADS)

Li, Yanyan; Zhao, Li; Wei, Shoubin; Xiao, Meng; Dong, Binghai; Wan, Li; Wang, Shimin

2018-05-01

In this work, perovskite solar cells (PSCs) were fabricated in the ambient air, with a scaffold layer composed of TiO2/ZrO2 double layer as the mesoscopic layer and carbon as the counter electrode. The effect of ZrO2 thin film thickness on the photovoltaic performances of PSCs was also studied in detail. Results showed that the photoelectric properties of as-prepared PSCs largely depend on the thin film thickness due to a series of factors, including surface roughness, charge transport resistance, and electron-hole recombination rate. The power conversion efficiency of PSCs increased from 8.37% to 11.33% by varying the thin film thickness from 75 nm to 305 nm, and the optimal power conversion efficiency was realized up to the 11.33% with a thin film thickness of 167 nm. This research demonstrates a promising route for the high-efficiency and low-cost photovoltaic technology.

Study of thin film production of ceramic ZrO2 on silicon wafer using second harmonic Nd-Yag laser with pulsed laser deposition technique

NASA Astrophysics Data System (ADS)

Suliyanti, Maria M.; Hidayah, Affi Nur; Kurniawan, K. H.

2012-06-01

Study about thin film production using technique pulsed laser deposition have been done. The Pulsed Laser Deposition (PLD) method has been used for growing thin film of ZrO2 on silicon wafer substrate (111 single crystal, thickness 400μm and diameter 7.5 cm). The target made from Zirconia oxide powder mixing with PVA and press using pressure 100kgN. The laser beam was focused by a lens (f = 100mm) through a quartz window onto the sample surface and the substrate was placed in parallel line with target. The distance between the target and the substrate is about 1 cm. The early results of this synthesis using 75 mJ Nd-YAG second harmonic laser pulse (532 nm Nd-YAG) and low pressure chamber surrounding gas 5 Torr. The irradiation of laser take around 6000 shoots or 10 minutes using frequencies laser 10 Hz. The micro thickness of film can be produced on silicon wafer using this technique. The results of ZrO2 thin film on substrate about 26.92%.

Dielectric Properties of BST/(Y 2O 3) x(ZrO 2) 1-x/BST Trilayer Films

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

Sahoo, Santosh K.; Misra, D.

2011-01-31

Thin films of Ba1-xSrxTiO3 (BST) are being actively investigated for applications in dynamic random access memories (DRAM) because of their properties such as high dielectric constant, low leakage current, and high dielectric breakdown strength. Various approaches have been used to improve the dielectric properties of BST thin films such as doping, graded compositions, and multilayer structures. We have found that inserting a ZrO2 layer in between two BST layers results in a significant reduction in dielectric constant as well as dielectric loss. In this work the effect of Y2O3 doped ZrO2 on the dielectric properties of BST/ZrO2/BST trilayer structure ismore » studied. The structure Ba0.8Sr0.2TiO3/(Y2O3)x(ZrO2)1-x/Ba0.8Sr0.2TiO3 is deposited by a sol-gel process on platinized Si substrate. The composition (x) of the middle layer is varied while keeping the total thickness of the trilayer film constant. The dielectric constant of the multilayer film decreases with the increase of Y2O3 amount in the film whereas there is a slight variation in dielectric loss. In Y2O3 doped multilayer thin films, the dielectric loss is lower in comparison to other films and also there is good frequency stability in the loss in the measured frequency range and hence very suitable for microwave device applications.« less

Local epitaxial growth of ZrO2 on Ge (100) substrates by atomic layer epitaxy

NASA Astrophysics Data System (ADS)

Kim, Hyoungsub; Chui, Chi On; Saraswat, Krishna C.; McIntyre, Paul C.

2003-09-01

High-k dielectric deposition processes for gate dielectric preparation on Si surfaces usually result in the unavoidable and uncontrolled formation of a thin interfacial oxide layer. Atomic layer deposition of ˜55-Å ZrO2 film on a Ge (100) substrate using ZrCl4 and H2O at 300 °C was found to produce local epitaxial growth [(001) Ge//(001) ZrO2 and [100] Ge//[100] ZrO2] without a distinct interfacial layer, unlike the situation observed when ZrO2 is deposited using the same method on Si. Relatively large lattice mismatch (˜10%) between ZrO2 and Ge produced a high areal density of interfacial misfit dislocations. Large hysteresis (>200 mV) and high frequency dispersion were observed in capacitance-voltage measurements due to the high density of interface states. However, a low leakage current density, comparable to values obtained on Si substrates, was observed with the same capacitance density regardless of the high defect density.

Atomic layer deposited high-k dielectric on graphene by functionalization through atmospheric plasma treatment

NASA Astrophysics Data System (ADS)

Shin, Jeong Woo; Kang, Myung Hoon; Oh, Seongkook; Yang, Byung Chan; Seong, Kwonil; Ahn, Hyo-Sok; Lee, Tae Hoon; An, Jihwan

2018-05-01

Atomic layer-deposited (ALD) dielectric films on graphene usually show noncontinuous and rough morphology owing to the inert surface of graphene. Here, we demonstrate the deposition of thin and uniform ALD ZrO2 films with no seed layer on chemical vapor-deposited graphene functionalized by atmospheric oxygen plasma treatment. Transmission electron microscopy showed that the ALD ZrO2 films were highly crystalline, despite a low ALD temperature of 150 °C. The ALD ZrO2 film served as an effective passivation layer for graphene, which was shown by negative shifts in the Dirac voltage and the enhanced air stability of graphene field-effect transistors after ALD of ZrO2. The ALD ZrO2 film on the functionalized graphene may find use in flexible graphene electronics and biosensors owing to its low process temperature and its capacity to improve device performance and stability.

Atomic layer deposited high-k dielectric on graphene by functionalization through atmospheric plasma treatment.

PubMed

Shin, Jeong Woo; Kang, Myung Hoon; Oh, Seongkook; Yang, Byung Chan; Seong, Kwonil; Ahn, Hyo-Sok; Lee, Tae Hoon; An, Jihwan

2018-05-11

Atomic layer-deposited (ALD) dielectric films on graphene usually show noncontinuous and rough morphology owing to the inert surface of graphene. Here, we demonstrate the deposition of thin and uniform ALD ZrO 2 films with no seed layer on chemical vapor-deposited graphene functionalized by atmospheric oxygen plasma treatment. Transmission electron microscopy showed that the ALD ZrO 2 films were highly crystalline, despite a low ALD temperature of 150 °C. The ALD ZrO 2 film served as an effective passivation layer for graphene, which was shown by negative shifts in the Dirac voltage and the enhanced air stability of graphene field-effect transistors after ALD of ZrO 2 . The ALD ZrO 2 film on the functionalized graphene may find use in flexible graphene electronics and biosensors owing to its low process temperature and its capacity to improve device performance and stability.

Determination and analysis of non-linear index profiles in electron-beam-deposited MgOAl2O3ZrO2 ternary composite thin-film optical coatings

NASA Astrophysics Data System (ADS)

Sahoo, N. K.; Thakur, S.; Senthilkumar, M.; Das, N. C.

2005-02-01

Thickness-dependent index non-linearity in thin films has been a thought provoking as well as intriguing topic in the field of optical coatings. The characterization and analysis of such inhomogeneous index profiles pose several degrees of challenges to thin-film researchers depending upon the availability of relevant experimental and process-monitoring-related information. In the present work, a variety of novel experimental non-linear index profiles have been observed in thin films of MgOAl2O3ZrO2 ternary composites in solid solution under various electron-beam deposition parameters. Analysis and derivation of these non-linear spectral index profiles have been carried out by an inverse-synthesis approach using a real-time optical monitoring signal and post-deposition transmittance and reflection spectra. Most of the non-linear index functions are observed to fit polynomial equations of order seven or eight very well. In this paper, the application of such a non-linear index function has also been demonstrated in designing electric-field-optimized high-damage-threshold multilayer coatings such as normal- and oblique-incidence edge filters and a broadband beam splitter for p-polarized light. Such designs can also advantageously maintain the microstructural stability of the multilayer structure due to the low stress factor of the non-linear ternary composite layers.

Atomic and electronic structures of an extremely fragile liquid.

PubMed

Kohara, Shinji; Akola, Jaakko; Patrikeev, Leonid; Ropo, Matti; Ohara, Koji; Itou, Masayoshi; Fujiwara, Akihiko; Yahiro, Jumpei; Okada, Junpei T; Ishikawa, Takehiko; Mizuno, Akitoshi; Masuno, Atsunobu; Watanabe, Yasuhiro; Usuki, Takeshi

2014-12-18

The structure of high-temperature liquids is an important topic for understanding the fragility of liquids. Here we report the structure of a high-temperature non-glass-forming oxide liquid, ZrO2, at an atomistic and electronic level. The Bhatia-Thornton number-number structure factor of ZrO2 does not show a first sharp diffraction peak. The atomic structure comprises ZrO5, ZrO6 and ZrO7 polyhedra with a significant contribution of edge sharing of oxygen in addition to corner sharing. The variety of large oxygen coordination and polyhedral connections with short Zr-O bond lifetimes, induced by the relatively large ionic radius of zirconium, disturbs the evolution of intermediate-range ordering, which leads to a reduced electronic band gap and increased delocalization in the ionic Zr-O bonding. The details of the chemical bonding explain the extremely low viscosity of the liquid and the absence of a first sharp diffraction peak, and indicate that liquid ZrO2 is an extremely fragile liquid.

Evolution of zirconyl-stearate Langmuir monolayers and the synthesized ZrO2 thin films with pH

NASA Astrophysics Data System (ADS)

Choudhary, Raveena; Sharma, Rajni; Brar, Loveleen K.

2018-04-01

ZrO2 thin films have a wide range of applications ranging from photonics, antireflection coatings, and resistive oxygen gas sensors, as a gate dielectric and in high temperature fuel cells. We have used the deposition of zirconyl stearate monolayers followed by their oxidation as a method for the synthesis of zirconium oxide thin films. The zirconyl stearate films have been studied and deposited for first time to the best of our knowledge. The Langmuir monolayers are studied using pressure-Area (π-A) isotherms and oscillatory barrier method. The morphology of the films for limited number of layers was studied with FE-SEM to determine the effect of pH on the final ZrO2 film. The 200 layer deposition films show pure monoclinic phase. The films have a band gap ˜6.0eV with a strong PL emission peak is at 490 nm and a weak peak is at 423 nm. So the films formed by this deposition method are suitable for luminescent applications

The Performance Improvement of N2 Plasma Treatment on ZrO2 Gate Dielectric Thin-Film Transistors with Atmospheric Pressure Plasma-Enhanced Chemical Vapor Deposition IGZO Channel.

PubMed

Wu, Chien-Hung; Huang, Bo-Wen; Chang, Kow-Ming; Wang, Shui-Jinn; Lin, Jian-Hong; Hsu, Jui-Mei

2016-06-01

The aim of this paper is to illustrate the N2 plasma treatment for high-κ ZrO2 gate dielectric stack (30 nm) with indium-gallium-zinc-oxide (IGZO) thin-film transistors (TFTs). Experimental results reveal that a suitable incorporation of nitrogen atoms could enhance the device performance by eliminating the oxygen vacancies and provide an amorphous surface with better surface roughness. With N2 plasma treated ZrO2 gate, IGZO channel is fabricated by atmospheric pressure plasma-enhanced chemical vapor deposition (AP-PECVD) technique. The best performance of the AP-PECVD IGZO TFTs are obtained with 20 W-90 sec N2 plasma treatment with field-effect mobility (μ(FET)) of 22.5 cm2/V-s, subthreshold swing (SS) of 155 mV/dec, and on/off current ratio (I(on)/I(off)) of 1.49 x 10(7).

Interface investigation of solution processed high- κ ZrO2/Si MOS structure by DLTS

NASA Astrophysics Data System (ADS)

Kumar, Arvind; Mondal, Sandip; Rao, Ksr Koteswara

The interfacial region is dominating due to the continuous downscaling and integration of high- k oxides in CMOS applications. The accurate characterization of high- k oxides/semiconductor interface has the significant importance towards its usage in memory and thin film devices. The interface traps at the high - k /semiconductor interface can be quantified by deep level transient spectroscopy (DLTS) with better accuracy in contrast to capacitance-voltage (CV) and conductance technique. We report the fabrication of high- k ZrO2 films on p-Si substrate by a simple and inexpensive sol-gel spin-coating technique. Further, the ZrO2/Si interface is characterized through DLTS. The flat-band voltage (VFB) and the density of slow interface states (oxide trapped charges) extracted from CV characteristics are 0.37 V and 2x10- 11 C/cm2, respectively. The activation energy, interface state density and capture cross-section quantified by DLTS are EV + 0.42 eV, 3.4x1011 eV- 1 cm- 2 and 5.8x10- 18 cm2, respectively. The high quality ZrO2 films own high dielectric constant 15 with low leakage current density might be an appropriate insulating layer in future electronic application. The low value of interface state density and capture cross-section are the indication of high quality interface and the defect present at the interface may not affect the device performance to a great extent. The DLTS study provides a broad understanding about the traps present at the interface of spin-coated ZrO2/Si.

TEM study on the initial oxidation of Zircaloy-4 thin foil specimens heated in a low vacuum air condition at 280-300 °C

NASA Astrophysics Data System (ADS)

Wang, Zhen; Zhou, Bang-xin; Zhu, Wei; Wen, Bang; Yao, Mei-yi; Li, Qiang; Wu, Lu; Zhang, Jin-long; Fang, Zhong-qiang

2017-04-01

As one of the important structural materials in nuclear industry, the corrosion resistance of zirconium alloy limits their in-pile application. Therefore, it is necessary to investigate the corrosion mechanism of zirconium alloys. The zirconium-oxygen reaction at the O/M interface is one of the factors that affect the oxidation process. There are few reports in this regard. Ideally, the reaction process at the O/M interface has certain relevance with the initiation oxidation of zirconium, which provided a new way to investigate the reaction process by observing the initiation oxidation behaviours. To investigate the oxidation behaviours of zirconium alloy at the initial stage, in this paper, zircaloy-4 TEM thin foil specimens in 3 mm diameter were studied by TEM observation after heating in air condition with a vacuum of 3 Pa at 280 °C, 290 °C and 300 °C for 30 min exposures. The results show that, ZrO2 begin to nucleate at a size of 3-5 nm at a high Zr/O ratio of 10.4 and oxide layer formed while Zr/O was 4.6. As a result of stress caused by the P.B ratio of Zr, slip bands formed and a bcc structure sub-oxide b-ZrOx (a = 0.51 nm) grew up along with the slip bands was observed. At both sides of b-ZrOx, two hcp structure sub-oxides having the same a-axis lattice parameter and different c-axis lattice parameter were detected.

Fabrication of dense and porous Li2ZrO3 nanofibers with electrospinning method

NASA Astrophysics Data System (ADS)

Yuan, Kangkang; Jin, Xiaotong; Xu, Chonghe; Wang, Xinqiang; Zhang, Guanghui; Zhu, Luyi; Xu, Dong

2018-06-01

Lithium zirconate (Li2ZrO3) has been extensively studied as CO2 capture material, electrolyte material and coating material. Most of the previous studies were focused on the powder structure, while seldom taking a consideration of fiber structure. In the present work, dense and porous Li2ZrO3 nanofibers with surface area of 16 m2 g-1 were prepared by electrospinning method. IR spectral results showed that lithium carbonate was the intermediate for the formation of Li2ZrO3. The phase transformation of Li2ZrO3 underwent the pathway of amorphous precursor fibers, tetragonal zirconia and Li2CO3, tetragonal Li2ZrO3, and monoclinic Li2ZrO3. XRD and XPS results further suggested that Li2O diffusion from the fiber body to surface occurred for Li2ZrO3 nanofibers when heat-treated above 900 °C, and the tetragonal Li2ZrO3 with high surface area could be obtained at 800 °C. Bamboo structure appeared both for the dense and porous nanofibers heat-treated at 1000 °C. The high surface area and high thermal stability of tetragonal phase of Li2ZrO3 make it a promising candidate in CO2 absorption, electrolyte and coating material.

Prototyping of Dental Structures Using Laser Milling

NASA Astrophysics Data System (ADS)

Andreev, A. O.; Kosenko, M. S.; Petrovskiy, V. N.; Mironov, V. D.

2016-02-01

The results of experimental studies of the effect of an ytterbium fiber laser radiation parameters on processing efficiency and quality of ZrO2 ceramics widely used in stomatology are presented. Laser operating conditions with optimum characteristics for obtaining high quality final surfaces and rapid material removal of dental structures are determined. The ability of forming thin-walled ceramic structures by laser milling technology (a minimum wall thickness of 50 μm) is demonstrated. The examples of three-dimensional dental structures created in computer 3D-models of human teeth using laser milling are shown.

Fabrication of solution-processed InSnZnO/ZrO2 thin film transistors.

PubMed

Hwang, Soo Min; Lee, Seung Muk; Choi, Jun Hyuk; Lim, Jun Hyung; Joo, Jinho

2013-11-01

We fabricated InSnZnO (ITZO) thin-film transistors (TFTs) with a high-permittivity (K) ZrO2 gate insulator using a solution process and explored the microstructure and electrical properties. ZrO2 and ITZO (In:Sn:Zn = 2:1:1) precursor solutions were deposited using consecutive spin-coating and drying steps on highly doped p-type Si substrate, followed by annealing at 700 degrees C in ambient air. The ITZO/ZrO2 TFT device showed n-channel depletion mode characteristics, and it possessed a high saturation mobility of approximately 9.8 cm2/V x s, a small subthreshold voltage swing of approximately 2.3 V/decade, and a negative V(TH) of approximately 1.5 V, but a relatively low on/off current ratio of approximately 10(-3). These results were thought to be due to the use of the high-kappa crystallized ZrO2 dielectric (kappa approximately 21.8) as the gate insulator, which could permit low-voltage operation of the solution-processed ITZO TFT devices for applications to high-throughput, low-cost, flexible and transparent electronics.

The affects of doping Eu 3+ on structures and morphology of ZrO 2 nanocrystals

NASA Astrophysics Data System (ADS)

Yu, Lixin; Liu, Hai; Nogami, Masayuki

2010-07-01

The ZrO 2 and ZrO 2:Eu 3+ nanocrystals (NCs) were prepared by a hydrothermal method. The samples were sintered at different temperatures (500, 800 and 1100 °C). The results indicate that the Eu 3+ ions affect not only the structures of hosts (ZrO 2), but also the morphology of hosts. The shape of ZrO 2:Eu 3+ NCs heated at 1100 °C is the one-dimensional nanorod, while is the zero-dimensional nanoparticle for pure ZrO 2 samples sintered at the same temperature. The excitation and emission spectra of ZrO 2:Eu 3+ NCs were studied. In excitation spectra, the charge transfer band of Eu 3+ in ZrO 2 NCs heated at 1100 °C evidently blue-shifts in comparison with the NCs calcined at 500 and 800 °C. The relative intensity of 5D-7F transitions of Eu 3+ ions and color chromaticity for nanorods are increased in comparison with the nanoparticles.

Heterophase-structured nanocrystals as superior supports for Ru-based catalysts in selective hydrogenation of benzene

PubMed Central

Peng, Zhikun; Liu, Xu; Li, Shuaihui; Li, Zhongjun; Li, Baojun; Liu, Zhongyi; Liu, Shouchang

2017-01-01

ZrO2 heterophase structure nanocrystals (HSNCs) were synthesized with tunable ratios of monoclinic ZrO2 (m-ZrO2) to tetragonal ZrO2 (t-ZrO2). The phase mole ratio of m-ZrO2 versus t-ZrO2 in ZrO2 HSNCs was tuned from 40% to 100%. The concentration of the surface hydroxyl groups on m-ZrO2 is higher than that on t-ZrO2. ZrO2 HSNCs have different surface hydroxyl groups on two crystalline phases. This creates more intimate synergistic effects than their single-phase counterparts. The ZrO2 HSNCs were used as effective supports to fabricate heterophase-structured Ru/ZrO2 catalysts for benzene-selective hydrogenation. The excellent catalytic performance including high activity and selectivity is attributed to the heterogeneous strong/weak hydrophilic interface and water layer formed at the m-ZrO2/t-ZrO2 catalyst junction. PMID:28057914

Atomic and electronic structures of an extremely fragile liquid

PubMed Central

Kohara, Shinji; Akola, Jaakko; Patrikeev, Leonid; Ropo, Matti; Ohara, Koji; Itou, Masayoshi; Fujiwara, Akihiko; Yahiro, Jumpei; Okada, Junpei T.; Ishikawa, Takehiko; Mizuno, Akitoshi; Masuno, Atsunobu; Watanabe, Yasuhiro; Usuki, Takeshi

2014-01-01

The structure of high-temperature liquids is an important topic for understanding the fragility of liquids. Here we report the structure of a high-temperature non-glass-forming oxide liquid, ZrO2, at an atomistic and electronic level. The Bhatia–Thornton number–number structure factor of ZrO2 does not show a first sharp diffraction peak. The atomic structure comprises ZrO5, ZrO6 and ZrO7 polyhedra with a significant contribution of edge sharing of oxygen in addition to corner sharing. The variety of large oxygen coordination and polyhedral connections with short Zr–O bond lifetimes, induced by the relatively large ionic radius of zirconium, disturbs the evolution of intermediate-range ordering, which leads to a reduced electronic band gap and increased delocalization in the ionic Zr–O bonding. The details of the chemical bonding explain the extremely low viscosity of the liquid and the absence of a first sharp diffraction peak, and indicate that liquid ZrO2 is an extremely fragile liquid. PMID:25520236

Surface Crystallization of a MgO/Y2O3/SiO2/Al2O3/ZrO2 Glass: Growth of an Oriented β-Y2Si2O7 Layer and Epitaxial ZrO2

PubMed Central

Wisniewski, Wolfgang; Seidel, Sabrina; Patzig, Christian; Rüssel, Christian

2017-01-01

The crystallization behavior of a glass with the composition 54.7 SiO2·10.9 Al2O3·15.0 MgO·3.4 ZrO2·16.0 Y2O3 is studied using X-ray diffraction (XRD), scanning electron microscopy (SEM) including electron backscatter diffraction (EBSD) and (scanning) transmission electron microscopy [(S)TEM] including energy-dispersive X-ray spectrometry (EDXS). This glass shows the sole surface crystallization of four different yttrium silicates of the composition Y2Si2O7 (YS). The almost simultaneous but independent nucleation of α-, β-, δ-, and ε-YS at the surface is followed by growth into the bulk, where ε-YS quickly dominates a first crystallized layer. An accumulation of Mg at the growth front probably triggers a secondary nucleation of β-YS, which forms a thin compact layer before fragmenting into a highly oriented layer of fine grained crystals occupying the remaining bulk. The residual glass between the YS growth structures allows the crystallization of indialite, yttrium stabilized ZrO2 (Y-ZrO2) and very probably μ-cordierite during cooling. Hence, this glass basically shows the inverted order of crystallization observed in other magnesium yttrium alumosilicate glasses containing less Y2O3. An epitaxial relationship between Y-ZrO2 and ε-YS is proven and multiple twinning relationships occur in the YS phases. PMID:28281661

Fabrication and magnetic properties of Fe and Co co-doped ZrO2

NASA Astrophysics Data System (ADS)

Okabayashi, J.; Kono, S.; Yamada, Y.; Nomura, K.

2011-12-01

We investigate the effects of Fe and Co co-doping on the magnetic and electronic properties of ZrO2 ceramics prepared by a sol-gel method, and study their dependence on the annealing temperature. Dilute Fe and Co co-doping into ZrO2 exhibits ferromagnetic behavior at room temperature for annealing temperatures above 900 °C, accompanying the phase transition from tetragonal to monoclinic structure in ZrO2. The electronic structures are studied by x-ray absorption spectroscopy and Mössbauer spectroscopy, which suggest that the Fe3+ and Co2+/Co3+ mixing states are dominant in Fe and Co co-doped ZrO2.

Study the structural and optical behaviour of polyaniline/ZrO2 nanocomposites

NASA Astrophysics Data System (ADS)

Sidhu, Gaganpreet Kaur; Kumar, Naresh; Kumar, Rajesh

2018-05-01

In nanoscience, hybrid material based on polymer and nanoparticles are of great interest because of much improved properties of components. Polymers are of enormous interest because of their various properties like flexibility, low weight and easy processing. Here, we studied the influence of ZrO2 nanoparticles on the structural and optical properties of Polyaniline (PANI). ZrO2 mixed with PANI, improve its structural and optical properties. XRD studies reveal that ZrO2 nanoparticles exist in the tetragonal phase in ZrO2/PANI nanocomposites. UV-Vis spectroscopic studies have been carried out to understand the presence of various energy levels and their involvement in absorbance of light. In PANI nanocomposites, aniline monomer attach with ZrO2 nanoparticles through p-p stacking interaction, Vander waal force and hydrogen bonding interaction.

Raman Spectrum of Er-Y-codoped ZrO2 and Fluorescence Properties of Er3+

NASA Astrophysics Data System (ADS)

He, Jun; Luo, Meng-fei; Jin, Ling-yun; He, Mai; Fang, Ping; Xie, Yun-long

2007-02-01

Er-Y-codoped ZrO2 mixed oxides with monoclinic, tetragonal and cubic structures were prepared by a sol-gel method. The crystal structure of ZrO2 matrix and the effect of the ZrO2 phases on the fluorescence properties of Er3+ were studied using Raman spectroscopy. The results indicated that the fluorescence properties of Er3+ depend on its local ZrO2 crystal structures. As ZrO2 matrix transferred from monoclinic to tetragonal and cubic phase, the Raman and fluorescence bands of Er3+ decreased in intensities and tended to form a single peak. With 632.8 nm excitation, the bands between 640 and 680 nm were attributed to the fluorescence of Er3+ in the ZrO2 environment. However, only the fluorescence was observed and no Raman spectra were seen under 514.5 nm excitation, while only Raman spectra were observed under 325 nm excitation. UV Raman spectroscopy was found to be more sensitive in the surface region while the information provided by XRD mainly came from the bulk. The phase with lower symmetry forms more easily on the surface than in the bulk.

Improving Corrosion Resistance of 316L Austenitic Stainless Steel Using ZrO2 Sol-Gel Coating in Nitric Acid Solution

NASA Astrophysics Data System (ADS)

Kazazi, Mahdi; Haghighi, Milad; Yarali, Davood; Zaynolabedini, Masoomeh H.

2018-03-01

In this study, thin-film coating of zirconium oxide (ZrO2) was prepared by sol-gel method and subsequent heat treatment process. The sol was prepared by controlled hydrolysis of zirconium tetrapropoxide using acetic acid and ethanol/acetylacetone mixture as catalyst and chelating agent, respectively, and finally deposited onto the 316L austenitic stainless steel (316L SS) using dip coating method in order to improve its corrosion resistance in nitric acid medium. The composition, structure, and morphology of the coated surface were investigated by x-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and atomic force microscopy (AFM). The obtained results from XRD and FTIR state the formation of tetragonal and monoclinic ZrO2 phase. Also, the obtained results from surface morphology investigation by SEM and AFM indicate the formation of smooth, homogeneous and uniform coatings on the steel substrate. Then, the corrosion behavior of stainless steel was investigated in a 1 and 10 M nitric acid solutions using electrochemical impedance spectroscopy and linear polarization test. The obtained results from these tests for ZrO2-coated specimens indicated a considerable improvement in the corrosion resistance of 316L stainless steel by an increase in corrosion potential and transpassive potential, and a decrease in passive current density and corrosion current density. The decrease in passive current density in both the concentration of solutions was two orders of magnitude from bare to coated specimens.

Conduction mechanism of leakage current due to the traps in ZrO2 thin film

NASA Astrophysics Data System (ADS)

Seo, Yohan; Lee, Sangyouk; An, Ilsin; Song, Chulgi; Jeong, Heejun

2009-11-01

In this work, a metal-oxide-semiconductor capacitor with zirconium oxide (ZrO2) gate dielectric was fabricated by an atomic layer deposition (ALD) technique and the leakage current characteristics under negative bias were studied. From the result of current-voltage curves there are two possible conduction mechanisms to explain the leakage current in the ZrO2 thin film. The dominant mechanism is the space charge limited conduction in the high-electric field region (1.5-5.0 MV cm-1) while the trap-assisted tunneling due to the existence of traps is prevailed in the low-electric field region (0.8-1.5 MV cm-1). Conduction caused by the trap-assisted tunneling is found from the experimental results of a weak temperature dependence of current, and the trap barrier height is obtained. The space charge limited conduction is evidenced, for different temperatures, by Child's law dependence of current density versus voltage. Child's law dependence can be explained by considering a single discrete trapping level and we can obtain the activation energy of 0.22 eV.

Fabrication of SiO2@ZrO2@Y2O3:Eu3+ core-multi-shell structured phosphor.

PubMed

Gao, Xuan; He, Diping; Jiao, Huan; Chen, Juan; Meng, Xin

2011-08-01

ZrO2 interface was designed to block the reaction between SiO2 and Y2O3 in SiO2@Y2O3:Eu coreshell structure phosphor. SiO2@ZrO2@Y2O3:Eu core-multi-shell phosphors were successfully synthesized by combing an LBL method with a Sol-gel process. Based on electron microscopy, X-ray diffraction, and spectroscopy experiments, compelling evidence for the formation of the Y2O3:Eu outer shell on ZrO2 were presented. The presence of ZrO2 layer on SiO2 core can block the reaction of SiO2 core and Y2O3 shell effectively. By this kind of structure, the reaction temperature of the SiO2 core and Y2O3 shell in the SiO2@Y2O3:Eu core-shell structure phosphor can be increased about 200-300 degrees C and the luminescent intensity of this structure phosphor can be improved obviously. Under the excitation of ultraviolet (254 nm), the Eu3+ ion mainly shows its characteristic red (611 nm, 5D0-7F2) emissions in the core-multi-shell particles from Y2O3:Eu3+ shells. The emission intensity of Eu3+ ions can be tuned by the annealing temperatures, the number of coating times, and the thickness of ZrO2 interface, respectively.

Intermixing and thermal oxidation of ZrO2 thin films grown on a-Si, SiN, and SiO2 by metallic and oxidic mode magnetron sputtering

NASA Astrophysics Data System (ADS)

Coloma Ribera, R.; van de Kruijs, R. W. E.; Sturm, J. M.; Yakshin, A. E.; Bijkerk, F.

2017-03-01

The initial growth of DC sputtered ZrO2 on top of a-Si, SiN, and SiO2 layers has been studied by in vacuo high-sensitivity low energy ion scattering for two gas deposition conditions with different oxygen contents (high-O and low-O conditions). This unique surface sensitive technique allowed the determination of surface composition and thicknesses required to close the ZrO2 layer on all three substrates for both conditions. The ZrO2 layer closes similarly on all substrates due to more favorable enthalpies of formation for ZrO2 and ZrSiO4, resulting in passivation of the Si from the substrate. However, this layer closes at about half of the thickness (˜1.7 nm) for low-O conditions due to less oxidative conditions and less energetic particles arriving at the sample, which leads to less intermixing via silicate formation. In contrast, for high-O conditions, there is more ZrSiO4 and/or SiOx formation, giving more intermixing (˜3.4 nm). In vacuo X-ray photoelectron spectroscopy (XPS) measurements revealed similar stoichiometric ZrO2 layers deposited by both conditions and a higher interaction of the ZrO2 layer with the underlying a-Si for high-O conditions. In addition, oxygen diffusion through low-O ZrO2 films on a-Si has been investigated by ex situ angular-resolved XPS of samples annealed in atmospheric oxygen. For temperatures below 400 °C, no additional oxidation of the underlying a-Si was observed. This, together with the amorphous nature and smoothness of these samples, makes ZrO2 a good candidate as an oxidation protective layer on top of a-Si.

Effect of SiO 2-ZrO 2 supports prepared by a grafting method on hydrogen production by steam reforming of liquefied natural gas over Ni/SiO 2-ZrO 2 catalysts

NASA Astrophysics Data System (ADS)

Seo, Jeong Gil; Youn, Min Hye; Song, In Kyu

SiO 2-ZrO 2 supports with various zirconium contents are prepared by grafting a zirconium precursor onto the surface of commercial Carbosil silica. Ni(20 wt.%)/SiO 2-ZrO 2 catalysts are then prepared by an impregnation method, and are applied to hydrogen production by steam reforming of liquefied natural gas (LNG). The effect of SiO 2-ZrO 2 supports on the performance of the Ni(20 wt.%)/SiO 2-ZrO 2 catalysts is investigated. SiO 2-ZrO 2 prepared by a grafting method serves as an efficient support for the nickel catalyst in the steam reforming of LNG. Zirconia enhances the resistance of silica to steam significantly and increases the interaction between nickel and the support, and furthermore, prevents the growth of nickel oxide species during the calcination process through the formation of a ZrO 2-SiO 2 composite structure. The crystalline structures and catalytic activities of the Ni(20 wt.%)/SiO 2-ZrO 2 catalysts are strongly influenced by the amount of zirconium grafted. The conversion of LNG and the yield of hydrogen show volcano-shaped curves with respect to zirconium content. Among the catalysts tested, the Ni(20 wt.%)/SiO 2-ZrO 2 (Zr/Si = 0.54) sample shows the best catalytic performance in terms of both LNG conversion and hydrogen yield. The well-developed and pure tetragonal phase of ZrO 2-SiO 2 (Zr/Si = 0.54) appears to play an important role in the adsorption of steam and subsequent spillover of steam from the support to the active nickel. The small particle size of the metallic nickel in the Ni(20 wt.%)/SiO 2-ZrO 2 (Zr/Si = 0.54) catalyst is also responsible for its high performance.

Compositional Dependence of Optical and Structural Properties of Nanogranular Mixed ZrO2/ZnO/SnO2 Thin Film

NASA Astrophysics Data System (ADS)

Salari, S.; Ghodsi, F. E.

2018-06-01

A study on the optical properties and photoluminescence (PL) spectra of ternary oxide nanogranular thin films comprising Zr, Zn, and Sn revealed that the change in component ratio could direct the roadmap to improve characteristics of the films. Grazing angle X-ray diffraction analysis showed that incorporation of Sn atoms into the tetragonal structure of Zn/Zr thin film resulted in an amorphous structure. The band gap of film was tunable by precisely controlling the concentration of components. The widening of band gap could correlate to the quantum confinement effect. PL spectra of the composite thin films under excitation at 365 nm showed a sharp red emission with relatively Gaussian line shape, which was intensified in the optimum percentage ratio of 50/30/20. This nearly red emission is attributed to the radiative emission of electrons captured at low-energy traps located near the valence band. An optimum red emission is strongly desirable for use in white LEDs. The comparative study on FTIR spectra of unary, binary, and ternary thin films confirmed successful composition of three different metal oxides in ternary thin films. Detailed investigation on FTIR spectra of ternary compounds revealed that the quenching in PL emission at higher percentage of Sn was originally due to the hydroxyl group.

Optical and structural characterization of Ge clusters embedded in ZrO2

NASA Astrophysics Data System (ADS)

Agocs, E.; Zolnai, Z.; Rossall, A. K.; van den Berg, J. A.; Fodor, B.; Lehninger, D.; Khomenkova, L.; Ponomaryov, S.; Gudymenko, O.; Yukhymchuk, V.; Kalas, B.; Heitmann, J.; Petrik, P.

2017-11-01

The change of optical and structural properties of Ge nanoclusters in ZrO2 matrix have been investigated by spectroscopic ellipsometry versus annealing temperatures. Radio-frequency top-down magnetron sputtering approach was used to produce the samples of different types, i.e. single-layers of pure Ge, pure ZrO2 and Ge-rich-ZrO2 as well as multi-layers stacked of 40 periods of 5-nm-Ge-rich-ZrO2 layers alternated by 5-nm-ZrO2 ones. Germanium nanoclusters in ZrO2 host were formed by rapid-thermal annealing at 600-800 °C during 30 s in nitrogen atmosphere. Reference optical properties for pure ZrO2 and pure Ge have been extracted using single-layer samples. As-deposited multi-layer structures can be perfectly modeled using the effective medium theory. However, annealed multi-layers demonstrated a significant diffusion of elements that was confirmed by medium energy ion scattering measurements. This fact prevents fitting of such annealed structure either by homogeneous or by periodic multi-layer models.

Structural, electronic, elastic and thermodynamic properties of Li2ZrO3: A comprehensive study using DFT formalism

NASA Astrophysics Data System (ADS)

Chattaraj, D.

2017-12-01

Lithium zirconate is considered to be potential tritium breeder material for fusion reactors. Here I report a comprehensive study on structural, electronic, elastic, and thermodynamic properties of Li2ZrO3 using plane wave based density functional theory. While the electron-ion interaction term has been described by projected-augmented wave method, the exchange-correlation energy was taken care of through generalized gradient approximation scheme. The optimized lattice and internal parameters of Li2ZrO3 unit cell agree well within ±1-2% from the experimental values. From the electronic structure analysis it is seen that the Fermi energy has significant contribution from the 2s, 2p and 4d orbitals of Li, O and Zr atoms, respectively. Elastic property calculation of Li2ZrO3 showed mechanical stability and anisotropy at ambient pressure. The formation energy (ΔfH) of Li2ZrO3 at 0 K, after zero point energy correction, has been estimated to be -1550 kJ/mol. The temperature dependent thermodynamic functions of Li2ZrO3 have also been calculated from the Debye-Grüneisen quasi-harmonic approximation and reported here.

Low-temperature remote plasma enhanced atomic layer deposition of ZrO2/zircone nanolaminate film for efficient encapsulation of flexible organic light-emitting diodes.

PubMed

Chen, Zheng; Wang, Haoran; Wang, Xiao; Chen, Ping; Liu, Yunfei; Zhao, Hongyu; Zhao, Yi; Duan, Yu

2017-01-06

Encapsulation is essential to protect the air-sensitive components of organic light-emitting diodes (OLEDs) such as active layers and cathode electrodes. In this study, hybrid zirconium inorganic/organic nanolaminates were fabricated using remote plasma enhanced atomic layer deposition (PEALD) and molecular layer deposition at a low temperature. The nanolaminate serves as a thin-film encapsulation layer for OLEDs. The reaction mechanism of PEALD process was investigated using an in-situ quartz crystal microbalance (QCM) and in-situ quadrupole mass spectrometer (QMS). The bonds present in the films were determined by Fourier transform infrared spectroscopy. The primary reaction byproducts in PEALD, such as CO, CO 2 , NO, H 2 O, as well as the related fragments during the O 2 plasma process were characterized using the QMS, indicating a combustion-like reaction process. The self-limiting nature and growth mechanisms of the ZrO 2 during the complex surface chemical reaction of the ligand and O 2 plasma were monitored using the QCM. The remote PEALD ZrO 2 /zircone nanolaminate structure prolonged the transmission path of water vapor and smooth surface morphology. Consequently, the water barrier properties were significantly improved (reaching 3.078 × 10 -5  g/m 2 /day). This study also shows that flexible OLEDs can be successfully encapsulated to achieve a significantly longer lifetime.

Low-temperature remote plasma enhanced atomic layer deposition of ZrO2/zircone nanolaminate film for efficient encapsulation of flexible organic light-emitting diodes

NASA Astrophysics Data System (ADS)

Chen, Zheng; Wang, Haoran; Wang, Xiao; Chen, Ping; Liu, Yunfei; Zhao, Hongyu; Zhao, Yi; Duan, Yu

2017-01-01

Encapsulation is essential to protect the air-sensitive components of organic light-emitting diodes (OLEDs) such as active layers and cathode electrodes. In this study, hybrid zirconium inorganic/organic nanolaminates were fabricated using remote plasma enhanced atomic layer deposition (PEALD) and molecular layer deposition at a low temperature. The nanolaminate serves as a thin-film encapsulation layer for OLEDs. The reaction mechanism of PEALD process was investigated using an in-situ quartz crystal microbalance (QCM) and in-situ quadrupole mass spectrometer (QMS). The bonds present in the films were determined by Fourier transform infrared spectroscopy. The primary reaction byproducts in PEALD, such as CO, CO2, NO, H2O, as well as the related fragments during the O2 plasma process were characterized using the QMS, indicating a combustion-like reaction process. The self-limiting nature and growth mechanisms of the ZrO2 during the complex surface chemical reaction of the ligand and O2 plasma were monitored using the QCM. The remote PEALD ZrO2/zircone nanolaminate structure prolonged the transmission path of water vapor and smooth surface morphology. Consequently, the water barrier properties were significantly improved (reaching 3.078 × 10-5 g/m2/day). This study also shows that flexible OLEDs can be successfully encapsulated to achieve a significantly longer lifetime.

Large Energy Storage Density and High Thermal Stability in a Highly Textured (111)-Oriented Pb0.8Ba0.2ZrO3 Relaxor Thin Film with the Coexistence of Antiferroelectric and Ferroelectric Phases.

PubMed

Peng, Biaolin; Zhang, Qi; Li, Xing; Sun, Tieyu; Fan, Huiqing; Ke, Shanming; Ye, Mao; Wang, Yu; Lu, Wei; Niu, Hanben; Zeng, Xierong; Huang, Haitao

2015-06-24

A highly textured (111)-oriented Pb0.8Ba0.2ZrO3 (PBZ) relaxor thin film with the coexistence of antiferroelectric (AFE) and ferroelectric (FE) phases was prepared on a Pt/TiOx/SiO2/Si(100) substrate by using a sol-gel method. A large recoverable energy storage density of 40.18 J/cm(3) along with an efficiency of 64.1% was achieved at room temperature. Over a wide temperature range of 250 K (from room temperature to 523 K), the variation of the energy density is within 5%, indicating a high thermal stability. The high energy storage performance was endowed by a large dielectric breakdown strength, great relaxor dispersion, highly textured orientation, and the coexistence of FE and AFE phases. The PBZ thin film is believed to be an attractive material for applications in energy storage systems over a wide temperature range.

A mixed solution-processed gate dielectric for zinc-tin oxide thin-film transistor and its MIS capacitance

NASA Astrophysics Data System (ADS)

Kim, Hunho; Kwack, Young-Jin; Yun, Eui-Jung; Choi, Woon-Seop

2016-09-01

Solution-processed gate dielectrics were fabricated with the combined ZrO2 and Al2O3 (ZAO) in the form of mixed and stacked types for oxide thin film transistors (TFTs). ZAO thin films prepared with double coatings for solid gate dielectrics were characterized by analytical tools. For the first time, the capacitance of the oxide semiconductor was extracted from the capacitance-voltage properties of the zinc-tin oxide (ZTO) TFTs with the combined ZAO dielectrics by using the proposed metal-insulator-semiconductor (MIS) structure model. The capacitance evolution of the semiconductor from the TFT model structure described well the threshold voltage shift observed in the ZTO TFT with the ZAO (1:2) gate dielectric. The electrical properties of the ZTO TFT with a ZAO (1:2) gate dielectric showed low voltage driving with a field effect mobility of 37.01 cm2/Vs, a threshold voltage of 2.00 V, an on-to-off current ratio of 1.46 × 105, and a subthreshold slope of 0.10 V/dec.

A mixed solution-processed gate dielectric for zinc-tin oxide thin-film transistor and its MIS capacitance

PubMed Central

Kim, Hunho; Kwack, Young-Jin; Yun, Eui-Jung; Choi, Woon-Seop

2016-01-01

Solution-processed gate dielectrics were fabricated with the combined ZrO2 and Al2O3 (ZAO) in the form of mixed and stacked types for oxide thin film transistors (TFTs). ZAO thin films prepared with double coatings for solid gate dielectrics were characterized by analytical tools. For the first time, the capacitance of the oxide semiconductor was extracted from the capacitance-voltage properties of the zinc-tin oxide (ZTO) TFTs with the combined ZAO dielectrics by using the proposed metal-insulator-semiconductor (MIS) structure model. The capacitance evolution of the semiconductor from the TFT model structure described well the threshold voltage shift observed in the ZTO TFT with the ZAO (1:2) gate dielectric. The electrical properties of the ZTO TFT with a ZAO (1:2) gate dielectric showed low voltage driving with a field effect mobility of 37.01 cm2/Vs, a threshold voltage of 2.00 V, an on-to-off current ratio of 1.46 × 105, and a subthreshold slope of 0.10 V/dec. PMID:27641430

Oxidant effect of La(NO3)3·6H2O solution on the crystalline characteristics of nanocrystalline ZrO2 films grown by atomic layer deposition

NASA Astrophysics Data System (ADS)

Oh, Nam Khen; Kim, Jin-Tae; Kang, Goru; An, Jong-Ki; Nam, Minwoo; Kim, So Yeon; Park, In-Sung; Yun, Ju-Young

2017-02-01

Nanocrystalline ZrO2 films were synthesized by atomic layer deposition method using CpZr[N(CH3)2]3 (Cp = C5H5) as the metal precursor and La(NO3)3·6H2O solution as the oxygen source. La element in the deposited ZrO2 films could not be detected as its content was below the resolution limit of the X-ray photoelectron spectroscopy. The alternative introduction of La(NO3)3·6H2O solution to conventionally used H2O as the oxidant effectively altered the crystalline structure, grain size, and surface roughness of the grown ZrO2 films. Specifically, the crystalline structure of the ZrO2 film changed from a mixture of tetragonal and monoclinic phases to monoclinic phase. The average grain size also increased, and the resulting film surface became rougher. The average grain sizes of the ZrO2 films prepared from La(NO3)3·6H2O solution at concentrations of 10, 20, 30, and 40% were 280, 256, 208, and 200 nm, respectively, whereas that prepared using H2O oxidant was 142 nm. However, the concentration of La(NO3)3·6H2O solution minimally influenced the crystalline characteristics of the nanocrystalline ZrO2 films i.e., the crystalline structure, grain size, and surface roughness except for crystallite size.

Sequentially evaporated thin Y-Ba-Co-O superconducting films on microwave substrates

NASA Technical Reports Server (NTRS)

Valco, G. J.; Rohrer, N. J.; Warner, J. D.; Bhasin, K. B.

1989-01-01

The development of high T sub c superconducting thin films on various microwave substrates is of major interest in space electronic systems. Thin films of YBa2Cu3O(7-Delta) were formed on SrTiO3, MgO, ZrO2 coated Al2O3, and LaAlO3 substrates by multi-layer sequential evaporation and subsequent annealing in oxygen. The technique allows controlled deposition of Cu, BaF2 and Y layers, as well as the ZrO buffer layers, to achieve reproducibility for microwave circuit fabrication. The three layer structure of Cu/BaF2/Y is repeated a minimum of four times. The films were annealed in an ambient of oxygen bubbled through water at temperatures between 850 C and 900 C followed by slow cooling (-2 C/minute) to 450 C, a low temperature anneal, and slow cooling to room temperature. Annealing times ranged from 15 minutes to 5 hrs. at high temperature and 0 to 6 hr. at 450 C. Silver contacts for four probe electrical measurements were formed by evaporation followed with an anneal at 500 C. The films were characterized by resistance-temperature measurements, energy dispersive X-ray spectroscopy, X-ray diffraction, and scanning electron microscopy. Critical transition temperatures ranged from 30 K to 87 K as a function of the substrate, composition of the film, thicknesses of the layers, and annealing conditions. Microwave ring resonator circuits were also patterned on these MgO and LaAlO3 substrates.

Spinodal decomposition in amorphous metal-silicate thin films: Phase diagram analysis and interface effects on kinetics

NASA Astrophysics Data System (ADS)

Kim, H.; McIntyre, P. C.

2002-11-01

Among several metal silicate candidates for high permittivity gate dielectric applications, the mixing thermodynamics of the ZrO2-SiO2 system were analyzed, based on previously published experimental phase diagrams. The driving force for spinodal decomposition was investigated in an amorphous silicate that was treated as a supercooled liquid solution. A subregular model was used for the excess free energy of mixing of the liquid, and measured invariant points were adopted for the calculations. The resulting simulated ZrO2-SiO2 phase diagram matched the experimental results reasonably well and indicated that a driving force exists for amorphous Zr-silicate compositions between approx40 mol % and approx90 mol % SiO2 to decompose into a ZrO2-rich phase (approx20 mol % SiO2) and SiO2-rich phase (>98 mol % SiO2) through diffusional phase separation at a temperature of 900 degC. These predictions are consistent with recent experimental reports of phase separation in amorphous Zr-silicate thin films. Other metal-silicate systems were also investigated and composition ranges for phase separation in amorphous Hf, La, and Y silicates were identified from the published bulk phase diagrams. The kinetics of one-dimensional spinodal decomposition normal to the plane of the film were simulated for an initially homogeneous Zr-silicate dielectric layer. We examined the effects that local stresses and the capillary driving force for component segregation to the interface have on the rate of spinodal decomposition in amorphous metal-silicate thin films.

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.

FAST TRACK COMMUNICATION: Deposition temperature effect on electrical properties and interface of high-k ZrO2 capacitor

NASA Astrophysics Data System (ADS)

Kim, Joo-Hyung; Ignatova, Velislava A.; Heitmann, Johannes; Oberbeck, Lars

2008-09-01

The electrical characteristics, i.e. leakage current and capacitance, of ZrO2 based metal-insulator-metal structures, grown at 225, 250 and 275 °C by atomic layer deposition, were studied. The lowest leakage current was obtained at 250 °C deposition temperature, while the highest dielectric constant (k ~ 43) was measured for the samples grown at 275 °C, most probably due to the formation of tetragonal/cubic phases in the ZrO2 layer. We have shown that the main leakage current of these ZrO2 capacitors is governed by the Poole-Frenkel conduction mechanism. It was observed by x-ray photoelectron spectroscopy depth profiling that at 275 °C deposition temperature the oxygen content at and beyond the ZrO2/TiN interface is higher than at lower deposition temperatures, most probably due to oxygen inter-diffusion towards the electrode layer, forming a mixed TiN-TiOxNy interface layer. At and above 275 °C the ZrO2 layer changes its structure and becomes crystalline as proven by XRD analysis.

Novel approach to the fabrication of an artificial small bone using a combination of sponge replica and electrospinning methods

NASA Astrophysics Data System (ADS)

Kim, Yang-Hee; Lee, Byong-Taek

2011-06-01

In this study, a novel artificial small bone consisting of ZrO2-biphasic calcium phosphate/polymethylmethacrylate-polycaprolactone-hydroxyapatite (ZrO2-BCP/PMMA-PCL-HAp) was fabricated using a combination of sponge replica and electrospinning methods. To mimic the cancellous bone, the ZrO2/BCP scaffold was composed of three layers, ZrO2, ZrO2/BCP and BCP, fabricated by the sponge replica method. The PMMA-PCL fibers loaded with HAp powder were wrapped around the ZrO2/BCP scaffold using the electrospinning process. To imitate the Haversian canal region of the bone, HAp-loaded PMMA-PCL fibers were wrapped around a steel wire of 0.3 mm diameter. As a result, the bundles of fiber wrapped around the wires imitated the osteon structure of the cortical bone. Finally, the ZrO2/BCP scaffold was surrounded by HAp-loaded PMMA-PCL composite bundles. After removal of the steel wires, the ZrO2/BCP scaffold and bundles of HAp-loaded PMMA-PCL formed an interconnected structure resembling the human bone. Its diameter, compressive strength and porosity were approximately 12 mm, 5 MPa and 70%, respectively, and the viability of MG-63 osteoblast-like cells was determined to be over 90% by the MTT (3-(4, 5-dimethylthiazol-2-yl)-2, 5-diphenyltetrazolium bromide) assay. This artificial bone shows excellent cytocompatibility and is a promising bone regeneration material.

Novel approach to the fabrication of an artificial small bone using a combination of sponge replica and electrospinning methods

PubMed Central

Kim, Yang-Hee; Lee, Byong-Taek

2011-01-01

In this study, a novel artificial small bone consisting of ZrO2-biphasic calcium phosphate/polymethylmethacrylate-polycaprolactone-hydroxyapatite (ZrO2-BCP/PMMA-PCL-HAp) was fabricated using a combination of sponge replica and electrospinning methods. To mimic the cancellous bone, the ZrO2/BCP scaffold was composed of three layers, ZrO2, ZrO2/BCP and BCP, fabricated by the sponge replica method. The PMMA-PCL fibers loaded with HAp powder were wrapped around the ZrO2/BCP scaffold using the electrospinning process. To imitate the Haversian canal region of the bone, HAp-loaded PMMA-PCL fibers were wrapped around a steel wire of 0.3 mm diameter. As a result, the bundles of fiber wrapped around the wires imitated the osteon structure of the cortical bone. Finally, the ZrO2/BCP scaffold was surrounded by HAp-loaded PMMA-PCL composite bundles. After removal of the steel wires, the ZrO2/BCP scaffold and bundles of HAp-loaded PMMA-PCL formed an interconnected structure resembling the human bone. Its diameter, compressive strength and porosity were approximately 12 mm, 5 MPa and 70%, respectively, and the viability of MG-63 osteoblast-like cells was determined to be over 90% by the MTT (3-(4, 5-dimethylthiazol-2-yl)-2, 5-diphenyltetrazolium bromide) assay. This artificial bone shows excellent cytocompatibility and is a promising bone regeneration material. PMID:27877406

Creep Resistance of ZrO2 Ceramic Improved by the Addition of a Small Amount of Er2O3

NASA Technical Reports Server (NTRS)

Martinez-Fernandez, Julian; Sayir, Ali; Farmer, Serene C.

2003-01-01

Zirconia (ZrO2) has great technological importance in structural, electrical, and chemical applications. It is the crucial component for state-of-the art thermal barrier coatings and an enabling component as a solid electrolyte for solid-oxide fuel cell systems. Pure ZrO2 is of limited use for industrial applications because of the phase transformations that occur. Upon the addition of stabilizers, cubic (c-ZrO2) and tetragonal (t-ZrO2) forms can be preserved. It is the stabilized and partially stabilized forms of zirconia that function as thermal barrier coatings, solid electrolytes, and oxygen sensors and that have numerous applications in the electrochemical industry. The cubic form of ZrO2 is typically stabilized through Y2O3 additions. However, Y2O3-stabilized zirconia is susceptible to deformation at high temperatures (greater than 900 C) because of the large number of slip systems and the high oxygen diffusion rates, which result in high creep rates at high temperatures. Successful use of ZrO2 at high temperatures requires that new dopant additives be found that will retain or enhance the desirable properties of cubic ZrO2 and yet produce a material with lower creep rates. At the NASA Glenn Research Center, erbium oxide (Er2O3) was identified as a promising dopant for improving the creep resistance of. ZrO2. The selection of Er2O3 was based on the strong interactions of point defects and dislocations. Single crystals of 5 mol% Er2O3- doped ZrO2 rods (4 mm in diameter) and monofilaments (200 to 300 mm in diameter and 30 cm long) were grown using the laser-heated float zone technique, and their creep behavior was measured as a function of temperature. The addition of 5 mol% Er2O3 to single-crystal ZrO2 improved its creep resistance at high temperatures by 2 to 3 orders of magnitude over state-of-the-art Y2O3-doped crystals. Detailed microstructural characterization of ZrO2-Er2O3 single crystals has identified new mechanisms for improving the creep resistance of this class of materials. Adding Er2O3 to ZrO2 results in microstructure of stable and metastable tetragonal precipitates that with thermal treatment evolve to a tweed structure of nanosize tetragonal lamellae. The superior high-temperature creep resistance of Er2O3-doped ZrO2 is attributed to nanoscale precipitation hardening. Doping with Er2O3 will significantly increase the upper-use temperature limit of ZrO2. Potential applications include using Er2O3-doped ZrO2 as a high-temperature fiber for structural applications and adding Er2O3 to reduce the sintering rates of ZrO2 thermal barrier coatings. This work was conducted at Dpto. de F sica de la Materia Condensada, Universidad de Sevilla, Spain, and at NASA Glenn.

A comparative study of fibrinogen adsorption onto metal oxide thin films

NASA Astrophysics Data System (ADS)

Silva-Bermudez, P.; Muhl, S.; Rodil, S. E.

2013-10-01

One of the first events occurring upon foreign material-biological medium contact is the adsorption of proteins, which evolution greatly determines the cells response to the material. Protein-surface interactions are a complex phenomenon driven by the physicochemical properties of the surface, protein(s) and liquid medium involve in the interaction. In this article the adsorption of fibrinogen (Fbg) onto Ta2O5, Nb2O5, TiO2 and ZrO2 thin films is reported. The adsorption kinetics and characteristics of the adsorbed fibrinogen layer were studied in situ using dynamic and spectroscopic ellipsometry. The films wettability, surface energy (γLW/AB) and roughness were characterized aiming to elucidate their correlations with Fbg adsorption. The adsorption rate changed accordingly to the film; the fastest adsorption rate and highest Fbg surface mass concentration (Γ) was observed on ZrO2. The hydrophobic/hydrophilic character of the oxide highly influenced Fbg adsorption. On Ta2O5, Nb2O5 and TiO2, which were either hydrophilic or in the breaking-point between hydrophilicity and hydrophobicity, Γ was correlated to the polar component of γLW/AB and roughness of the surface. On ZrO2, clearly hydrophobic, Γ increased significantly off the correlation observed for the other films. The results indicated different adsorption dynamics and orientations of the Fbg molecules dependent on the surface hydrophobic/hydrophilic character.

Low-temperature remote plasma enhanced atomic layer deposition of ZrO2/zircone nanolaminate film for efficient encapsulation of flexible organic light-emitting diodes

PubMed Central

Chen, Zheng; Wang, Haoran; Wang, Xiao; Chen, Ping; Liu, Yunfei; Zhao, Hongyu; Zhao, Yi; Duan, Yu

2017-01-01

Encapsulation is essential to protect the air-sensitive components of organic light-emitting diodes (OLEDs) such as active layers and cathode electrodes. In this study, hybrid zirconium inorganic/organic nanolaminates were fabricated using remote plasma enhanced atomic layer deposition (PEALD) and molecular layer deposition at a low temperature. The nanolaminate serves as a thin-film encapsulation layer for OLEDs. The reaction mechanism of PEALD process was investigated using an in-situ quartz crystal microbalance (QCM) and in-situ quadrupole mass spectrometer (QMS). The bonds present in the films were determined by Fourier transform infrared spectroscopy. The primary reaction byproducts in PEALD, such as CO, CO2, NO, H2O, as well as the related fragments during the O2 plasma process were characterized using the QMS, indicating a combustion-like reaction process. The self-limiting nature and growth mechanisms of the ZrO2 during the complex surface chemical reaction of the ligand and O2 plasma were monitored using the QCM. The remote PEALD ZrO2/zircone nanolaminate structure prolonged the transmission path of water vapor and smooth surface morphology. Consequently, the water barrier properties were significantly improved (reaching 3.078 × 10−5 g/m2/day). This study also shows that flexible OLEDs can be successfully encapsulated to achieve a significantly longer lifetime. PMID:28059160

Electrodeposition and characterization of Ni-Mo-ZrO2 composite coatings

NASA Astrophysics Data System (ADS)

Laszczyńska, A.; Winiarski, J.; Szczygieł, B.; Szczygieł, I.

2016-04-01

Ni-Mo-ZrO2 composite coatings were produced by electrodeposition technique from citrate electrolytes containing dispersed ZrO2 nanopowder. The influence of deposition parameters i.e. concentration of molybdate and ZrO2 nanoparticles in the electrolyte, bath pH and deposition current density on the composition and surface morphology of the coating has been investigated. The structure, microhardness and corrosion properties of Ni-Mo-ZrO2 composites with different molybdenum and ZrO2 content have been also examined. It was found that ZrO2 content in the deposit is increased by rising the nanoparticles concentration in the plating solution up to 20 g dm-3. An increase in molybdate concentration in the electrolyte affects negatively the amount of codeposited ZrO2 nanoparticles. The correlation between the deposition current efficiency and ZrO2 content in the composite coating has been also observed. A decrease in deposition current efficiency leads to deposition of Ni-Mo-ZrO2 composite with low nanoparticles content. This may be explained by formation of higher amounts of gas bubbles on the cathode surface, which prevent the adsorption of ZrO2 nanoparticles on the growing deposit. The XRD analysis revealed that all the studied Ni-Mo-ZrO2 coatings were composed of a single, nanocrystalline phase with FCC structure. It was found that the incorporation of ZrO2 nanoparticles into Ni-Mo alloy matrix affects positively the microhardness and also slightly improves the corrosion properties of Ni-Mo alloy coating.

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.

Effect of UV lamp irradiation during oxidation of Zr/Pt/Si structure on electrical properties of Pt/ZrO 2/Pt/Si structure

NASA Astrophysics Data System (ADS)

Bae, Joon Woo; Lim, Jae-Won; Mimura, Kouji; Uchikoshi, Masahito; Miyazaki, Takamichi; Isshiki, Minoru

2010-03-01

Metal-insulator-metal (MIM) capacitors were fabricated using ZrO 2 films and the effects of structural and native defects of the ZrO 2 films on the electrical and dielectric properties were investigated. For preparing ZrO 2 films, Zr films were deposited on Pt/Si substrates by ion beam deposition (IBD) system with/without substrate bias voltages and oxidized at 200 °C for 60 min under 0.1 MPa O 2 atmosphere with/without UV light irradiation ( λ = 193 nm, Deep UV lamp). The ZrO 2(˜12 nm) films on Pt(˜100 nm)/Si were characterized by X-ray diffraction pattern (XRD), field emission scanning electron microscopy (FE-SEM) and high-resolution transmission electron microscopy (HRTEM), capacitance-voltage ( C- V) and current-voltage ( I- V) measurements were carried out on MIM structures. ZrO 2 films, fabricated by oxidizing the Zr film deposited with substrate bias voltage under UV light irradiation, show the highest capacitance (784 pF) and the lowest leakage current density. The active oxygen species formed by UV irradiation are considered to play an important role in the reduction of the leakage current density, because they can reduce the density of oxygen vacancies.

Zirconia-hydroxyapatite composite material with micro porous structure.

PubMed

Matsumoto, Takuya Junior; An, Sang-Hyun; Ishimoto, Takuya; Nakano, Takayoshi; Matsumoto, Takuya; Imazato, Satoshi

2011-11-01

Titanium plates and apatite blocks are commonly used for restoring large osseous defects in dental and orthopedic surgery. However, several cases of allergies against titanium have been recently reported. Also, sintered apatite block does not possess sufficient mechanical strength. In this study, we attempted to fabricate a composite material that has mechanical properties similar to biocortical bone and high bioaffinity by compounding hydroxyapatite (HAp) with the base material zirconia (ZrO(2)), which possesses high mechanical properties and low toxicity toward living organisms. After mixing the raw material powders at several different ZrO(2)/HAp mixing ratios, the material was compressed in a metal mold (8 mm in diameter) at 5 MPa. Subsequently, it was sintered for 5 h at 1500°C to obtain the ZrO(2)/HAp composite. The mechanical property and biocompatibility of materials were investigated. Furthermore, osteoconductivity of materials was investigated by animal studies. A composite material with a minute porous structure was successfully created using ZrO(2)/HAp powders, having different particle sizes, as the starting material. The material also showed high protein adsorption and a favorable cellular affinity. When the mixing ratio was ZrO(2)/HAp=70/30, the strength was equal to cortical bone. Furthermore, in vivo experiments confirmed its high osteoconductivity. The composite material had strength similar to biocortical bones with high cell and tissue affinities by compounding ZrO(2) and HAp. The ZrO(2)/HAp composite material having micro porous structure would be a promising bone restorative material. Copyright © 2011 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Popcorn balls-like ZnFe2O4-ZrO2 microsphere for photocatalytic degradation of 2,4-dinitrophenol

NASA Astrophysics Data System (ADS)

Chen, Xi; Liu, Yutang; Xia, Xinnian; Wang, Longlu

2017-06-01

In this paper, novel popcorn balls-like ZnFe2O4-ZrO2 composite microspheres were successfully fabricated by a simple hydrothermal method. The morphology, structure and optical property of the microspheres were characterized. The microspheres were used as the photocatalysts to degrade 2,4-dinitrophenol, and exhibited superior photocatalytic performance. Under simulated solar visible light irradiation, the degradation rate of ZnFe2O4-ZrO2 photocatalyst (mass ratio of ZnFe2O4/ZrO2 = 2:1) was almost 7.4 and 2.4 times higher than those of pure ZnFe2O4 and ZrO2. The enhancement could attribute to stronger light absorption, lower carrier recombination and multi-porous structure of the microspheres. Moreover, the popcorn balls-like photocatalysts can be easily separated, because of the magnetism of the samples. After five times runs, the photocatalyst still showed 90% of its photocatalytic degradation efficiency. This work demonstrated a good prospect for removing organic pollutants in water.

Comparing the Thermodynamic Behaviour of Al(1)+ZrO2(s) to Al(1)+Al2O3(s)

NASA Technical Reports Server (NTRS)

Copland, Evan

2004-01-01

In an effort to better determine the thermodynamic properties of Al(g) and Al2O(g). the vapor in equilibrium with Al(l)+ZrO2(s) was compared to the vapor in equilibrium with Al(l)+Al2O3(s) over temperature range 1197-to-1509K. The comparison was made directly by Knudsen effusion-cell mass spectrometry with an instrument configured for a multiple effusion-cell vapor source (multi-cell KEMS). Second law enthalpies of vaporization of Al(g) and Al2O(g) together with activity measurements show that Al(l)+ZrO2(s) is thermodynamically equivalent to Al(l)+Al2O3(s), indicating Al(l) remained pure and Al2O3(s) was present in the ZrO2-cell. Subsequent observation of the Al(l)/ZrO2 and vapor/ZrO2 interfaces revealed a thin Al2O3-layer had formed, separating the ZrO2-cell from Al(l) and Al(g)+Al2O(g), effectively transforming it into an Al2O3 effusion-cell. This behavior agrees with recent observations made for Beta-NiAl(Pt) alloys measured in ZrO2 effusion-cell.

DFT-based ab initio MD simulation of the ionic conduction in doped ZrO₂ systems under epitaxial strain.

PubMed

Oka, M; Kamisaka, H; Fukumura, T; Hasegawa, T

2015-11-21

The oxygen ionic conduction in ZrO2 systems under tensile epitaxial strain was investigated by performing ab initio molecular dynamics (MD) calculations based on density functional theory (DFT) to elucidate the essential factors in the colossal ionic conductivity observed in the yttria stabilized ZrO2 (YSZ)/SrTiO3 heterostructure. Three factors were evaluated: lattice strain, oxygen vacancies, and dopants. Phonon calculations based on density functional perturbation theory (DFPT) were used to obtain the most stable structure for nondoped ZrO2 under 7% tensile strain along the a- and b-axes. This structure has the space group Pbcn, which is entirely different from that of cubic ZrO2, suggesting that previous ab initio MD calculations assuming cubic ZrO2 may have overestimated the ionic conductivity due to relaxation from the initial structure to the stable structure (Pbcn). Our MD calculations revealed that the ionic conductivity is enhanced only when tensile strain and oxygen vacancies are incorporated, although the presently obtained diffusion constant is far below the range for the colossal ionic conduction experimentally observed. The enhanced ionic conductivity is due to the combined effects of oxygen sublattice formation induced by strain and deformation of this sublattice by oxygen vacancies.

ZrO2/MoS2 heterojunction photocatalysts for efficient photocatalytic degradation of methyl orange

NASA Astrophysics Data System (ADS)

Prabhakar Vattikuti, Surya Veerendra; Byon, Chan; Reddy, Chandragiri Venkata

2016-10-01

We report a simple solution-chemistry approach for the synthesis of ZrO2/MoS2 hybrid photocatalysts, which contain MoS2 as a cocatalyst. The material is usually obtained by a wet chemical method using ZrO(NO3)2 or (NH4)6Mo7O24·4H2O and C8H6S as precursors. The structural features of obtained materials were characterized by X-ray diffraction (XRD), highresolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), thermal analysis (TG-DTA), N2 adsorption-desorption, and photoluminescence (PL). The influence on the photocatalytic activity of the MoS2 cocatalyst concentration with ZrO2 nanoparticles was studied. The MZr-2 hybrid sample had the highest photocatalytic activity for the degradation of methyl orange (MO), which was 8.45 times higher than that of pristine ZrO2 ascribed to high specific surface area and absorbance efficiency. Recycling experiments revealed that the reusability of the MZr-2 hybrid was due to the low photocorrosive effect and good catalytic stability. PL spectra confirmed the electronic interaction between ZrO2 and MoS2. The photoinduced electrons could be easily transferred from CB of ZrO2 to the MoS2 cocatalyst, which facilitate effective charge separation and enhanced the photocatalytic degradation in the UV region. A photocatalytic mechanism is proposed. It is believed that the ZrO2/MoS2 hybrid structure has promise as a photocatalyst with low cost and high efficiency for photoreactions.

(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.

Role of oxygen vacancies on the structure and density of states of iron-doped zirconia

NASA Astrophysics Data System (ADS)

Sangalli, Davide; Lamperti, Alessio; Cianci, Elena; Ciprian, Roberta; Perego, Michele; Debernardi, Alberto

2013-02-01

In this paper, we study the effect of iron doping in zirconia using both theoretical and experimental approaches. Combining density functional theory (DFT) simulations with the experimental characterization of thin films, we show that iron is in the Fe3+ oxidation state and, accordingly, the films are rich in oxygen vacancies (VO••). VO•• favor the formation of the tetragonal phase in doped zirconia (ZrO2:Fe) and affect the density of states at the Fermi level as well as the local magnetization of Fe atoms. We also show that the Fe(2p) and Fe(3p) energy levels can be used as a marker for the presence of vacancies in the doped system. In particular, the computed position of the Fe(3p) peak is strongly sensitive to the VO•• to Fe atoms ratio. A comparison of the theoretical and experimental Fe(3p) peak positions suggests that in our films this ratio is close to 0.5. Besides the interest in the material by itself, ZrO2:Fe constitutes a test case for the application of DFT on transition metals embedded in oxides. In ZrO2:Fe, the inclusion of the Hubbard U correction significantly changes the electronic properties of the system. However, the inclusion of this correction, at least for the value U=3.3 eV chosen in the present work, worsen the agreement with the measured photoemission valence band spectra.

High thermal stability of La 2O 3 and CeO 2-stabilized tetragonal ZrO 2

DOE PAGES

Wang, Shichao; Xie, Hong; Lin, Yuyuan; ...

2016-02-15

Catalyst support materials of tetragonal ZrO 2, stabilized by either La 2O 3 (La 2O 3-ZrO 2) or CeO 2 (CeO 2-ZrO 2), were synthesized under hydrothermal conditions at 200 °C with NH 4OH or tetramethylammonium hydroxide as the mineralizer. From In Situ synchrotron powder X-ray diffraction and small-angle X-ray scattering measurements, the calcined La 2O 3-ZrO 2 and CeO 2-ZrO 2 supports were nonporous nanocrystallites that exhibited rectangular shapes with thermal stability up to 1000 °C in air. These supports had an average size of ~10 nm and a surface area of 59-97 m 2/g. The catalysts Pt/La 2Omore » 3-ZrO 2 and Pt/CeO 2-ZrO 2 were prepared by using atomic layer deposition with varying Pt loadings from 6.3-12.4 wt %. Mono-dispersed Pt nanoparticles of ~3 nm were obtained for these catalysts. As a result, the incorporation of La 2O 3 and CeO 2 into the t-ZrO 2 structure did not affect the nature of the active sites for the Pt/ZrO 2 catalysts for the water-gas-shift (WGS) reaction.« less

Ultra-thin solid oxide fuel cells: Materials and devices

NASA Astrophysics Data System (ADS)

Kerman, Kian

Solid oxide fuel cells are electrochemical energy conversion devices utilizing solid electrolytes transporting O2- that typically operate in the 800 -- 1000 °C temperature range due to the large activation barrier for ionic transport. Reducing electrolyte thickness or increasing ionic conductivity can enable lower temperature operation for both stationary and portable applications. This thesis is focused on the fabrication of free standing ultrathin (<100 nm) oxide membranes of prototypical O 2- conducting electrolytes, namely Y2O3-doped ZrO2 and Gd2O3-doped CeO2. Fabrication of such membranes requires an understanding of thin plate mechanics coupled with controllable thin film deposition processes. Integration of free standing membranes into proof-of-concept fuel cell devices necessitates ideal electrode assemblies as well as creative processing schemes to experimentally test devices in a high temperature dual environment chamber. We present a simple elastic model to determine stable buckling configurations for free standing oxide membranes. This guides the experimental methodology for Y 2O3-doped ZrO2 film processing, which enables tunable internal stress in the films. Using these criteria, we fabricate robust Y2O3-doped ZrO2 membranes on Si and composite polymeric substrates by semiconductor and micro-machining processes, respectively. Fuel cell devices integrating these membranes with metallic electrodes are demonstrated to operate in the 300 -- 500 °C range, exhibiting record performance at such temperatures. A model combining physical transport of electronic carriers in an insulating film and electrochemical aspects of transport is developed to determine the limits of performance enhancement expected via electrolyte thickness reduction. Free standing oxide heterostructures, i.e. electrolyte membrane and oxide electrodes, are demonstrated. Lastly, using Y2O3-doped ZrO2 and Gd2O 3-doped CeO2, novel electrolyte fabrication schemes are explored to develop oxide alloys and nanoscale compositionally graded membranes that are thermomechanically robust and provide added interfacial functionality. The work in this thesis advances experimental state-of-the-art with respect to solid oxide fuel cell operation temperature, provides fundamental boundaries expected for ultrathin electrolytes, develops the ability to integrate highly dissimilar material (such as oxide-polymer) heterostructures, and introduces nanoscale compositionally graded electrolyte membranes that can lead to monolithic materials having multiple functionalities.

Low temperature solution processed high-κ ZrO2 gate dielectrics for nanoelectonics

NASA Astrophysics Data System (ADS)

Kumar, Arvind; Mondal, Sandip; Rao, K. S. R. Koteswara

2016-05-01

The high-κ gate dielectrics, specifically amorphous films offer salient features such as exceptional mechanical flexibility, smooth surfaces and better uniformity associated with low leakage current density. In this work, ∼35 nm thick amorphous ZrO2 films were deposited on silicon substrate at low temperature (300 °C, 1 h) from facile spin-coating method and characterized by various analytical techniques. The X-ray diffraction and X-ray photoelectron spectroscopy reveal the formation of amorphous phase ZrO2, while ellipsometry analysis together with the Atomic Force Microscope suggest the formation of dense film with surface roughness of 1.5 Å, respectively. The fabricated films were integrated in metal-oxide-semiconductor (MOS) structures to check the electrical capabilities. The oxide capacitance (Cox), flat band capacitance (CFB), flat band voltage (VFB), dielectric constant (κ) and oxide trapped charges (Qot) extracted from high frequency (1 MHz) C-V curve are 186 pF, 104 pF, 0.37 V, 15 and 2 × 10-11 C, respectively. The small flat band voltage 0.37 V, narrow hysteresis and very little frequency dispersion between 10 kHz-1 MHz suggest an excellent a-ZrO2/Si interface with very less trapped charges in the oxide. The films exhibit a low leakage current density 4.7 × 10-9 A/cm2 at 1 V. In addition, the charge transport mechanism across the MOSC is analyzed and found to have a strong bias dependence. The space charge limited conduction mechanism is dominant in the high electric field region (1.3-5 V) due to the presence of traps, while the trap-supported tunneling is prevailed in the intermediate region (0.35-1.3 V). Low temperature solution processed ZrO2 thin films obtained are of high quality and find their importance as a potential dielectric layer on Si and polymer based flexible electronics.

Ag nanoparticle effects on the thermoluminescent properties of monoclinic ZrO2 exposed to ultraviolet and gamma radiation

NASA Astrophysics Data System (ADS)

Villa-Sanchéz, G.; Mendoza-Anaya, D.; Gutiérrez-Wing, C.; Pérez-Hernández, R.; González-Martínez, P. R.; Ángeles-Chavez, C.

2007-07-01

The goal of this work was to analyse ZrO2 in the pure state and when doped with Ag nanoparticles, by electron microscopy, x-ray diffraction and thermoluminescence methods. According to the results obtained, Ag nanoparticles did not modify the morphology or the crystalline structure of the ZrO2. The thermoluminescent (TL) response of pure ZrO2 showed two peaks, one at 334 K and the other at 417 K, when it was exposed to ultraviolet (UV) radiation, and at 342 and 397 K when gamma radiation was used. For ZrO2 impregnated with Ag nanoparticles a diminished TL intensity due to nanoparticle shielding was observed, but the glow curve shape was similar. However, when Ag nanoparticles were added during the ZrO2 synthesis, a shift of the TL peaks towards higher temperature values with reference to pure ZrO2 was observed. A linear dependence of the integrated TL signal as a function of the irradiation dose was observed in all analysed samples. It was possible to determine some kinetic parameters, such as activation energy, kinetic order and frequency factor, using the sequential quadratic programming glow curve deconvolution; it was found that these values are highly dependent on the type of radiation used. Ag nanoparticles present in ZrO2 also modified the kinetic parameters, mainly when they were added during the synthesis of ZrO2. Our results reinforce the possibilities of using pure and doped ZrO2 as an appropriate dosimetric material in radiation physics.

Effect of O 2 gas partial pressure on structures and dielectric characteristics of rf sputtered ZrO 2 thin films

NASA Astrophysics Data System (ADS)

Ma, C. Y.; Lapostolle, F.; Briois, P.; Zhang, Q. Y.

2007-08-01

Amorphous and polycrystalline zirconium oxide thin films have been deposited by reactive rf magnetron sputtering in a mixed argon/oxygen or pure oxygen atmosphere with no intentional heating of the substrate. The films were characterized by high-resolution transmission electron microscopy (HR-TEM), atomic force microscopy (AFM), spectroscopic ellipsometry (SE), and capacitance versus voltage ( C- V) measurements to investigate the variation of structure, surface morphology, thickness of SiO 2-like interfacial layer as well as dielectric characteristics with different oxygen partial pressures. The films deposited at low oxygen partial pressures (less than 15%) are amorphous and dense with a smooth surface. In contrast, the films prepared at an oxygen partial pressure higher than 73% are crystallized with the microstructure changing from the mixture of monoclinic and tetragonal phases to a single monoclinic structure. The film structural transition is believed to be consequences of decrease in the oxygen vacancy concentration in the film and of increase of the energetically neutral particles in the plasma due to an increased oxygen partial pressure. SE measurements showed that significant interfacial SiO 2 growth has taken place above approximately 51%. The best C- V results in terms of relative dielectric constant values are obtained for thin films prepared at an oxygen partial pressure of 15%.

Nanocomposites of polyimide and mixed oxide nanoparticles for high performance nanohybrid gate dielectrics in flexible thin film transistors

NASA Astrophysics Data System (ADS)

Kim, Ju Hyun; Hwang, Byeong-Ung; Kim, Do-Il; Kim, Jin Soo; Seol, Young Gug; Kim, Tae Woong; Lee, Nae-Eung

2017-05-01

Organic gate dielectrics in thin film transistors (TFTs) for flexible display have advantages of high flexibility yet have the disadvantage of low dielectric constant (low- k). To supplement low- k characteristics of organic gate dielectrics, an organic/inorganic nanocomposite insulator loaded with high- k inorganic oxide nanoparticles (NPs) has been investigated but high loading of high- k NPs in polymer matrix is essential. Herein, compositing of over-coated polyimide (PI) on self-assembled (SA) layer of mixed HfO2 and ZrO2 NPs as inorganic fillers was used to make dielectric constant higher and leakage characteristics lower. A flexible TFT with lower the threshold voltage and high current on/off ratio could be fabricated by using the hybrid gate dielectric structure of the nanocomposite with SA layer of mixed NPs on ultrathin atomic-layer deposited Al2O3. [Figure not available: see fulltext.

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.

Synthesis, integration, and characterization of metal oxide films as alternative gate dielectric materials

NASA Astrophysics Data System (ADS)

Lin, You-Sheng

ZrO2 and HfO2 were investigated in this study to replace SiO2 as the potential gate dielectric materials in metal-oxide-semiconductor field effect transistors. ZrO2 and HfO2 films were deposited on p-type Si (100) wafers by an atomic layer chemical vapor deposition (ALCVD) process using zirconium (IV) t-butoxide and hafnium (IV) t-butoxide as the metal precursors, respectively. Oxygen was used alternatively with these metal alkoxide precursors into the reactor with purging and evacuation in between. The as-deposited ZrO2 and HfO2 films were stoichiometric and uniform based on X-ray photoemission spectroscopy and ellipsometry measurements. X-ray diffraction analysis indicated that the deposited films were amorphous, however, the high-resolution transmission electron microscopy showed an interfacial layer formation on the silicon substrate. Time-of-flight secondary ion mass spectrometry and medium energy ion scattering analysis showed significant intermixing between metal oxides and Si, indicating the formation of metal silicates, which were confirmed by their chemical etching resistance in HF solutions. The thermal stability of ZrO2 and HfO2 thin films on silicon was examined by monitoring their decomposition temperatures in ultra-high vacuum, using in-situ synchrotron radiation ultra-violet photoemission spectroscopy. The as-deposited ZrO2 and HfO2 thin films were thermally stable up to 880°C and 950°C in vacuum, respectively. The highest achieveable dielectric constants of as-deposited ZrO 2 and HfO2 were 21 and 24, respectively, which were slightly lower than the reported dielectric constants of bulk ZrO2 and HfO 2. These slight reductions in dielectric constants were attributed to the formation of the interfacial metal silicate layers. Very small hysteresis and interface state density were observed for both metal oxide films. Their leakage currents were a few orders of magnitude lower than that of SiO 2 at the same equivalent oxide thickness. NMOSFETs were also fabricated with the as-deposited metal oxide films, and reasonable ID-V D and IG-VG results were obtained. The electron mobilities were high from devices built using a plasma etching process to pattern the metal oxide films. However, they can be degraded if an HF wet etching process was used due to the large contact resistences. Upon oxygen annealing, the formation of SiOx at the interface improved the thermal stability of the as-deposited metal oxide films, however, lower overall dielectric constant and higher leakage current were observed. Upon ammonia annealing, the formation of SiOxNy improved not only the thermal stability but also reduced the leakage current. However, the overall dielectric constant of the film was still reduced due to the formation of the additional interfacial layer.

Physics and applications of electrochromic devices

NASA Astrophysics Data System (ADS)

Pawlicka, Agnieszka; Avellaneda, Cesar O.

2003-07-01

Solid state electrochromic devices (ECD) are of considerable technological and commercial interest because of their controllable transmission, absorption and/or reflectance. For instance, a major application of these devices is in smart windows that can regulate the solar gains of buildings and also in glare attenuation in automobile rear view mirrors. Other applications include solar cells, small and large area flat panel displays, satellite temperature control, food monitoring, and document authentication. A typical electrochromic device has a five-layer structure: GS/TC/EC/IC/IS/TC/GS, where GS is a glass substrate, TC is a transparent conductor, generally ITO (indium tin oxide) or FTO (fluorine tin oxide), EC is an electrochromic coating, IC is an ion conductor (solid or liquid electrolyte) and IS is an ion storage coating. Generally, the EC and IS layers are deposited separately on the TC coatings and then jointed with the IC and sealed. The EC and IS are thin films that can be deposited by sputtering, CVD, sol-gel precursors, etc. There are different kinds of organic, inorganic and organic-inorganic films that can be used to make electrochromic devices. Thin electrochromic films can be: WO3, Nb2O5, Nb2O5:Li+ or Nb2O5-TiO2 coatings, ions storage films: CeO2-TiO2, CeO2-ZrO2 or CeO2-TiO2-ZrO2 and electrolytes like Organically Modified Electrolytes (Ormolytes) or polymeric films also based on natural polymers like starch or cellulose. These last are very interesting due to their high ionic conductivity, high transparency and good mechanical properties. This paper describes construction and properties of different thin oxide and polymeric films and also shows the optical response of an all sol-gel electrochromic device with WO3/Ormolyte/CeO2-TiO2 configuration.

Structural identification of Zn xZr yO z catalysts for Cascade aldolization and self-deoxygenation reactions

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

Baylon, Rebecca A. L.; Sun, Junming; Kovarik, Libor

Complementary characterizations, such as nitrogen sorption, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), visible Raman, scanning transmission electron microscopy (STEM) coupled with elemental mapping, NH3/CO2 temperature programmed desorption (NH3/CO2-TPD), infrared spectroscopic analysis of adsorbed pyridine (Py-IR), and CO2-IR, have been employed to identify the structure and surface chemistry (i.e., acid-base) of mixed Zn xZr yO z oxide catalysts of varied ratios of Zn/Zr. Atomically dispersed Zn2+ species are present in the framework within a thin surface shell (1.5-2.0 nm) of ZrO2 particles when the Zn/Zr ratio is smaller than 1/10; when the ratio is above this, both atomically dispersed Zn2+more » and ZnO clusters coexist in mixed Zn xZr yO z oxide catalysts. The presence of ZnO clusters shows no significant side effect but only a slight increase of selectivity to CO2, caused by steam reforming. The incorporation of atomic Zn2+ into the ZrO2 framework was found to not only passivate strong Lewis acid sites (i.e., Zr-O-Zr) on ZrO2, but to also generate new Lewis acid-base site pairs with enhanced Lewis basicity on the bridged O (i.e., ). In the mixed ketone (i.e., acetone and methyl ethyl ketone (MEK)) reactions, while the passivation of strong acid sites can be correlated to the inhibition of side reactions, such as ketone decomposition and coking, the new Lewis acid-base pairs introduced enhance the cascade aldolization and self-deoxygenation reactions involved in olefin (C3=-C6=) production. More importantly, the surface acid-base properties change with varying Zn/Zr ratios, which in turn affect the cross- and self-condensation reactivity and subsequent distribution of olefins.« less

Structural Identification of Zn xZr yO z Catalysts for Cascade Aldolization and Self-Deoxygenation Reactions

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

Baylon, Rebecca A. L.; Sun, Junming; Kovarik, Libor

Here, complementary characterizations, such as nitrogen sorption, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), visible Raman, scanning transmission electron microscopy (STEM) coupled with elemental mapping, NH 3/CO 2 temperature programmed desorption (NH 3/CO 2-TPD), infrared spectroscopic analysis of adsorbed pyridine (Py-IR), and CO 2-IR, have been employed to identify the structure and surface chemistry (i.e., acid-base) of mixed Zn xZr yO z oxide catalysts of varied ratios of Zn/Zr. Atomically dispersed Zn 2+ species are present in the framework within a thin surface shell (1.5-2.0 nm) of ZrO 2 particles when the Zn/Zr ratio is smaller than 1/10; when the ratio is above this, both atomically dispersed Zn 2+ and ZnO clusters coexist in mixed Zn xZr yO z oxide catalysts. The presence of ZnO clusters shows no significant side effect but only a slight increase of selectivity to CO 2, caused by steam reforming. The incorporation of atomic Zn 2+ into the ZrO 2 framework was found to not only passivate strong Lewis acid sites (i.e., Zr-O-Zr) on ZrO 2, but to also generate new Lewis acid-base site pairs with enhanced Lewis basicity on the bridged O (i.e., Zr—omore » $$\\curvearrowleft\\atop{e\\atop—}$$Zn). In the mixed ketone (i.e., acetone and methyl ethyl ketone (MEK)) reactions, while the passivation of strong acid sites can be correlated to the inhibition of side reactions, such as ketone decomposition and coking, the new Lewis acid-base pairs introduced enhance the cascade aldolization and self-deoxygenation reactions involved in olefin (C 3 =-C 6 =) production. More importantly, the surface acid-base properties change with varying Zn/Zr ratios, which in turn affect the cross- and self-condensation reactivity and subsequent distribution of olefins.« less

Structural Identification of Zn xZr yO z Catalysts for Cascade Aldolization and Self-Deoxygenation Reactions

DOE PAGES

Baylon, Rebecca A. L.; Sun, Junming; Kovarik, Libor; ...

2018-04-22

Here, complementary characterizations, such as nitrogen sorption, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), visible Raman, scanning transmission electron microscopy (STEM) coupled with elemental mapping, NH 3/CO 2 temperature programmed desorption (NH 3/CO 2-TPD), infrared spectroscopic analysis of adsorbed pyridine (Py-IR), and CO 2-IR, have been employed to identify the structure and surface chemistry (i.e., acid-base) of mixed Zn xZr yO z oxide catalysts of varied ratios of Zn/Zr. Atomically dispersed Zn 2+ species are present in the framework within a thin surface shell (1.5-2.0 nm) of ZrO 2 particles when the Zn/Zr ratio is smaller than 1/10; when the ratio is above this, both atomically dispersed Zn 2+ and ZnO clusters coexist in mixed Zn xZr yO z oxide catalysts. The presence of ZnO clusters shows no significant side effect but only a slight increase of selectivity to CO 2, caused by steam reforming. The incorporation of atomic Zn 2+ into the ZrO 2 framework was found to not only passivate strong Lewis acid sites (i.e., Zr-O-Zr) on ZrO 2, but to also generate new Lewis acid-base site pairs with enhanced Lewis basicity on the bridged O (i.e., Zr—omore » $$\\curvearrowleft\\atop{e\\atop—}$$Zn). In the mixed ketone (i.e., acetone and methyl ethyl ketone (MEK)) reactions, while the passivation of strong acid sites can be correlated to the inhibition of side reactions, such as ketone decomposition and coking, the new Lewis acid-base pairs introduced enhance the cascade aldolization and self-deoxygenation reactions involved in olefin (C 3 =-C 6 =) production. More importantly, the surface acid-base properties change with varying Zn/Zr ratios, which in turn affect the cross- and self-condensation reactivity and subsequent distribution of olefins.« less

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.

Antiferroelectricity in lanthanum doped zirconia without metallic capping layers and post-deposition/-metallization anneals

NASA Astrophysics Data System (ADS)

Wang, Zheng; Gaskell, Anthony Arthur; Dopita, Milan; Kriegner, Dominik; Tasneem, Nujhat; Mack, Jerry; Mukherjee, Niloy; Karim, Zia; Khan, Asif Islam

2018-05-01

We report the effects of lanthanum doping/alloying on antiferroelectric (AFE) properties of ZrO2. Starting with pure ZrO2, an increase in La doping leads to the narrowing of the AFE double hysteresis loops and an increase in the critical voltage/electric field for AFE → ferroelectric transition. At higher La contents, the polarization-voltage characteristics of doped/alloyed ZrO2 resemble that of a non-linear dielectric without any discernible AFE-type hysteresis. X-ray diffraction based analysis indicates that the increased La content while preserving the non-polar, parent AFE, tetragonal P42/nmc phase leads to a decrease in tetragonality and the (nano-)crystallite size and an increase in the unit cell volume. Furthermore, antiferroelectric behavior is obtained in the as-deposited thin films without requiring any capping metallic layers and post-deposition/-metallization anneals due to which our specific atomic layer deposition system configuration crystallizes and stabilizes the AFE tetragonal phase during growth.

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

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.

High Performance Crystalline Organic Transistors and Circuit

DTIC Science & Technology

2011-08-02

pentacene -based OFETs, low voltage operation is possible. 3 Figure 1: Device structure for a low voltage pentacene OFET using a ZrO2 gate...first SiO Z OPentacene Au Pentacene ZrO2 AuPd SiO2 4 film. Bilayer dielectrics exhibit lower defect-related leakage effects, as pinholes or...other defects in one layer may be isolated by the other layer. 350 Å of pentacene was thermally evaporated on the ZrO2 dielectric at a rate of 0.1 Å

Descriptions of crack growth behaviors in glass-ZrO2 bilayers under thermal residual stresses.

PubMed

Belli, Renan; Wendler, Michael; Zorzin, José I; Petschelt, Anselm; Tanaka, Carina B; Meira, Josete; Lohbauer, Ulrich

2016-09-01

This study was intended to separate residual stresses arising from the mismatch in coefficients of thermal expansion between glass and zirconia (ZrO2) from those stresses arising solely from the cooling process. Slow crack growth experimentes were undertaken to demonstrate how cracks grow in different residual stress fields. Aluminosilicate glass discs were sintered onto ZrO2 to form glass-ZrO2 bilayers. Glass discs were allowed to bond to the ZrO2 substrate during sintering or prevented from bonding by means of coating the ZrO2 with a thin boron nitrade coating. Residual stress gradients on "bonded" and "unbonded" bilayers were assessed using birefringence measurements. Unbonded glass discs were further tested under biaxial flexure in dynamic fatigue conditions in order to evaluate the effect of residual stress on the slow crack growth behavior. When fast-ccoling was induced, residual tensile stresses on the glass increased significantly on the side toward the ZrO2 substrate. By allowing the bond between glass and ZrO2, those tensile stresses observed in unbonded specimens are overwhelmed by the contraction mismatch stresses between the ZrO2 substrate and the glassy overlayer. Specimens containing residual tensile stresses on the bending surface showed a time-dependent strength increase in relation to stress-free annealed samples in the dynamic biaxial bending test, with this effect being dependent on the magnitude of the residual tensile stress. The phenomenon observed is explained here on the basis of the water toughening effect, in which water diffuses into the glass promoting local swelling. An additional residual tensile stress at the crack tip adds an applied-stress-independent (Kres) term to the total tip stress intensity factor (Ktip), increasing the stress-enhanced diffusion and the shielding of the crack tip through swelling of the crack faces. Residual stresses in the glass influence the crack growth behavior of veneered-ZrO2 bilayered dental prostheses. The role of water in crack growth might be of higher complexity when residual stresses are present in the glass layer. Copyright © 2016 The Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

The new insight into the structure-activity relation of Pd/CeO2-ZrO2-Nd2O3 catalysts by Raman, in situ DRIFTS and XRD Rietveld analysis.

PubMed

Yang, X; Yang, L; Lin, J; Zhou, R

2016-01-28

Pd/CeO2-ZrO2-Nd2O3 (CZN) catalysts with different CeO2/ZrO2 molar ratios were synthesized and have been characterized by multiple techniques, e.g. XRD in combination with Rietveld refinement, UV-Raman, XPS and in situ DRIFTS. The XRD pattern of CZN with CeO2/ZrO2 molar ratios ≥1/2 can be indexed satisfactorily to the fluorite structure with a space group Fm3̄m, while the XRD patterns of CZ12 only display diffraction peaks of the tetragonal phase (S.G. P42/nmc). Nd addition can effectively stabilize the cubic structure of the CZN support and increase the enrichment of defect sites on the surface, which may be related to the better catalytic activity of Pd/CZN12 catalysts compared with Pd/CZ12. The presence of moderate ZrO2 can increase the concentration of O* active species, leading to accelerate the formation of nitrate species and thus enhance the catalytic activity of NOx and HC elimination. The Pd-dispersion decreases with the increasing Zr content, leading to the decreased CO catalytic activity, especially for the aged catalysts. The change regularity of the OSC value is almost the same with the in situ dynamic operational window, demonstrating that the in situ dynamic operational window is basically affected by the OSC value.

Laser Direct Writing Process for Making Electrodes and High-k Sol-Gel ZrO2 for Boosting Performances of MoS2 Transistors.

PubMed

Kwon, Hyuk-Jun; Jang, Jaewon; Grigoropoulos, Costas P

2016-04-13

A series of two-dimensional (2D) transition metal dichalcogenides (TMDCs), including molybdenum disulfide (MoS2), can be attractive materials for photonic and electronic applications due to their exceptional properties. Among these unique properties, high mobility of 2D TMDCs enables realization of high-performance nanoelectronics based on a thin film transistor (TFT) platform. In this contribution, we report highly enhanced field effect mobility (μ(eff) = 50.1 cm(2)/(V s), ∼2.5 times) of MoS2 TFTs through the sol-gel processed high-k ZrO2 (∼22.0) insulator, compared to those of typical MoS2/SiO2/Si structures (μ(eff) = 19.4 cm(2)/(V s)) because a high-k dielectric layer can suppress Coulomb electron scattering and reduce interface trap concentration. Additionally, in order to avoid costly conventional mask based photolithography and define the patterns, we employ a simple laser direct writing (LDW) process. This process allows precise and flexible control with reasonable resolution (up to ∼10 nm), depending on the system, and enables fabrication of arbitrarily patterned devices. Taking advantage of continuing developments in laser technology offers a substantial cost decrease, and LDW may emerge as a promising technology.

Characterization of ZrO2 buffer layers for sequentially evaporated Y-Ba-CuO on Si and Al2O3 substrates

NASA Technical Reports Server (NTRS)

Valco, George J.; Rohrer, Norman J.; Pouch, John J.; Warner, Joseph D.; Bhasin, Kul B.

1988-01-01

Thin film high temperature superconductors have the potential to change the microwave technology for space communications systems. For such applications it is desirable that the films be formed on substrates such as Al2O3 which have good microwave properties. The use of ZrO2 buffer layers between Y-Ba-Cu-O and the substrate has been investigated. These superconducting films have been formed by multilayer sequential electron beam evaporation of Cu, BaF2 and Y with subsequent annealing. The three layer sequence of Y/BaF2/Cu is repeated four times for a total of twelve layers. Such a multilayer film, approximately 1 micron thick, deposited directly on SrTiO3 and annealed at 900 C for 45 min produces a film with a superconducting onset of 93 K and critical temperature of 85 K. Auger electron spectroscopy in conjunction with argon ion sputtering was used to obtain the distribution of each element as a function of depth for an unannealed film, the annealed film on SrTiO3 and annealed films on ZrO2 buffer layers. The individual layers were apparent. After annealing, the bulk of the film on SrTiO3 is observed to be fairly uniform while films on the substrates with buffer layers are less uniform. The Y-Ba-Cu-O/ZrO2 interface is broad with a long Ba tail into the ZrO2, suggesting interaction between the film and the buffer layer. The underlying ZrO2/Si interface is sharper. The detailed Auger results are presented and compared with samples annealed at different temperatures and durations.

A comparison study of the Born effective charges and dielectric properties of the cubic, tetragonal, monoclinic, ortho-I, ortho-II and ortho-III phases of zirconia

NASA Astrophysics Data System (ADS)

Zhang, Yan; Chen, Hua-Xin; Duan, Li; Fan, Ji-Bin; Ni, Lei; Ji, Vincent

2018-07-01

Using density-functional perturbation theory, we systematically investigate the Born effective charges and dielectric properties of cubic, tetragonal, monoclinic, ortho-I (Pbca), ortho-II (Pnma) and ortho-III (Pca21) phases of ZrO2. The magnitudes of the Born effective charges of the Zr and oxygen atoms are greater than their nominal ionic valences (+4 for Zr and -2 for oxygen), indicating a strong dynamic charge transfer from Zr atoms to O atoms and a mixed covalent-ionic bonding in six phases of ZrO2. For all six phases of ZrO2, the electronic contributions εij∞ to the static dielectric constant are rather small (range from 5 to 6.5) and neither strongly anisotropic nor strongly dependent on the structural phase, while the ionic contributions εijion to the static dielectric constant are large and not only anisotropic but also dependent on the structural phase. The average dielectric constant εbar0 of the six ZrO2 phases decreases in the sequence of tetragonal, cubic, ortho-II (Pnma), ortho-I (Pbca), ortho-III (Pca21) and monoclinic. So among six phases of ZrO2, the tetragonal and cubic phases are two suitable phases to replace SiO2 as the gate dielectric material in modern integrated-circuit technology. Furthermore, for the tetragonal ZrO2 the best orientation is [100].

Preparation, chromatographic evaluation and application of adenosine 5'-monophosphate modified ZrO2/SiO2 stationary phase in hydrophilic interaction chromatography.

PubMed

Wang, Qing; Luo, Zhi-Yuan; Ye, Mao; Wang, Yu-Zhuo; Xu, Li; Shi, Zhi-Guo; Xu, Lanying

2015-02-27

The zirconia-coated silica (ZrO2/SiO2) material was obtained by coupling layer-by-layer (LbL) self-assembly method and sol-gel technology, to take dual advantages of the suitable porous structure of SiO2 and basic resistance of ZrO2. Adenosine 5'-monophosphate (5'-AMP) was then self-assembled onto ZrO2/SiO2 via Lewis acid-base interaction, generating 5'-AMP-ZrO2/SiO2. The chromatographic properties of 5'-AMP-ZrO2/SiO2 were systemically studied by evaluating the effect of acetonitrile content, pH and buffer concentration in the mobile phase. The results demonstrated that the 5'-AMP-ZrO2/SiO2 possessed hydrophilic interaction chromatographic (HILIC) property comprising hydrophilic, hydrogen-bonding, electrostatic and ion-exchange interactions. For basic analytes, the column efficiency of ZrO2/SiO2 and 5'-AMP-ZrO2/SiO2 was superior to the bare ZrO2, and different selectivity was obtained after the introduction of 5'-AMP. For acidic analytes, good resolution was obtained on 5'-AMP-ZrO2/SiO2 while the analysis failed on the bare ZrO2 column owing to strong adsorption. Hence, the proposed 5'-AMP-ZrO2/SiO2 had great potential in analyzing acidic compounds in HILIC mode. It was an extended application of ZrO2 based SP. Copyright © 2015 Elsevier B.V. All rights reserved.

Oxygen Migration and Local Structural Changes with Schottky Defects in Pure Zirconium Oxide Crystals

NASA Astrophysics Data System (ADS)

Terada, Yayoi; Mohri, Tetsuo

2018-05-01

By employing the Buckingham potential, we performed classical molecular-dynamics computer simulations at constant pressure and temperature for a pure ZrO2 crystal without any vacancies and for a pure ZrO2 crystal containing zirconium vacancies and oxygen vacancies. We examined the positions of atoms and vacancies in the steady state, and we investigated the migration behavior of atoms and the local structure of vacancies of the pure ZrO2 crystal. We found that Schottky defects (aggregates consisting of one zirconium vacancy with an effective charge of -4 and two oxygen vacancies each with an effective charge of +2 to maintain charge neutrality) are the main defects formed in the steady state in cubic ZrO2, and that oxygen migration occurs through a mechanism involving vacancies on the oxygen sublattice near such defects. We also found that several oxygen atoms near each defect are displaced far from the sublattice site and induce oxygen migration.

SPS-RS technique for solid-phase “in situ” synthesis of biocompatible ZrO2 porous ceramics

NASA Astrophysics Data System (ADS)

Shichalin, O. O.; Medkov, M. A.; Grishchenko, D. N.; Mayorov, V. Yu; Fedorets, A. N.; Belov, A. A.; Golub, A. V.; Gridasova, E. A.; Papynov, E. K.

2018-02-01

The prospective method of spark plasma sintering-reaction synthesis (SPS-RS) for fabrication of ceramics based on ZrO2 and biocompatible with living tissue is presented. Nanostructured ceramics has high mechanical strength (more than 400 MPa) and controlled porosity depending on specified sintering conditions. Biocompatible phases Ca10(PO4)6(OH)2 are formed “in situ” during SPS sintering of ZrO2 powder due to chemical interaction of phosphate precursors preliminary introduced into the mixture. The effective method to improve (to develop) porous structure of bioceramics obtained by SPS or SPS-RS techniques using poreforming agent (carbon black) is proposed. Suggested original SPS-RS “in situ” technique provides fabrication of new ZrO2 ceramics containing biocompatible phosphate components and possessing unique structural and mechanical characteristics. Such ceramics is indispensable for bone-ceramic implants that are able to activate processes of osteogenesis during bone tissue recovery.

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.

Hierarchical Na-doped cubic ZrO2 synthesis by a simple hydrothermal route and its application in biodiesel production

NASA Astrophysics Data System (ADS)

Lara-García, Hugo A.; Romero-Ibarra, Issis C.; Pfeiffer, Heriberto

2014-10-01

Hierarchical growth of cubic ZrO2 phase was successfully synthesized via a simple hydrothermal process in the presence of different surfactants (cationic, non-ionic and anionic) and sodium hydroxide. The structural and microstructural characterizations of different ZrO2 powders were performed using various techniques, such as X-ray diffraction, transmission electron microscopy, N2 adsorption-desorption, scanning electron microscopy and infrared. Results indicated that sodium addition stabilized the cubic ZrO2 phase by a Na-doping process, independently of the surfactant used. In contrast, microstructural characteristics varied as a function of the surfactant and sodium presence. In addition, water vapor (H2O) and carbon dioxide (CO2) sorption properties were evaluated on ZrO2 samples. Results evidenced that sample surface reactivity changed as a function of the sodium content. Finally, this surface reactivity was evaluated on the biodiesel transesterification reaction using the different synthesized samples, obtaining yields of 93%.

Ion-enhanced chemical etching of ZrO2 in a chlorine discharge

NASA Astrophysics Data System (ADS)

Sha, Lin; Cho, Byeong-Ok; Chang, Jane P.

2002-09-01

Chlorine plasma is found to chemically etch ZrO2 thin films in an electron cyclotron resonance reactor, and the etch rate scaled linearly with the square root of ion energy at high ion energies with a threshold energy between 12-20 eV. The etching rate decreased monotonically with increasing chamber pressures, which corresponds to reduced electron temperatures. Optical emission spectroscopy and quadrupole mass spectrometry were used to identify the reaction etching products. No Zr, O, or ZrCl were detected as etching products, but highly chlorinated zirconium compounds (ZrCl2, ZrCl3, and ZrCl4) and ClO were found to be the dominant etching products. ZrCl3 was the dominant etching products at low ion energies, while ZrCl4 became dominant at higher ion energies. This is consistent with greater momentum transfer and enhanced surface chlorination, as determined by x-ray photoelectron spectroscopy, at increased ion energies. Several ion-enhanced chemical reactions are proposed to contribute to the ZrO2 etching. copyright 2002 American Vacuum Society.

Potential of SiO2/ZrO2 matrix doped with CoFe2O4 magnetic nanoparticles in achieving integrated magneto-optical isolators

NASA Astrophysics Data System (ADS)

Zamani, Mehdi; Hocini, Abdesselam

2017-05-01

We have investigated the potential of the SiO2/ZrO2 matrix doped with CoFe2O4 magnetic nanoparticles in order to overcome the problem of integration of the magneto-optical isolators (MOIs). In this way, we have performed a theoretical study for the case of designing perfect and adjustable MOIs based on magnetophotonic crystals (MPCs) containing SiO2/ZrO2 matrix doped with CoFe2O4 magnetic nanoparticles as a magnetic medium. Despite the existence the attenuation coefficient for SiO2/ZrO2 matrix at wavelength 1550 nm that leads to a non-perfect transmittance, we could introduce an MPC structure having no reflectance; therefore, an ideal MOI for eliminating unwanted back-reflection could be achieved.

Thin-film-based optical fiber Fabry-Perot interferometer used for humidity sensing.

PubMed

Peng, Jiankun; Qu, Yapeng; Wang, Weijia; Sun, Tengpeng; Yang, Minghong

2018-04-20

A thin-film-based optical fiber Fabry-Perot interferometer that consists of ZrO 2 and SiO 2 porous thin films is designed and fabricated by electron beam physical vapor deposition. Since the SiO 2 porous thin film has the capability of water adsorption, the proposed Fabry-Perot interferometer is appropriate to detect humidity. Experimental results show that the prepared sensor has a humidity detection range from 0.06% RH to 70% RH. A cycling test shows that the humidity sensor has a responding or recover time of 4 s and good repeatability among different humidity environments. Especially, the proposed humidity sensor is insensitive to temperature variation and suitable for the detection of low relative humidity.

Electronic structural studies on the improved thermal stability of Li(Ni0.8Co0.15Al0.05)O2 by ZrO2 coating for lithium ion batteries

DOE PAGES

Kim, Ji-Young; Kim, Sang Hoon; Kim, Dong Hyun; ...

2017-03-21

The electronic structures of bare and ZrO 2-coated Li(Ni 0.8Co 0.15Al 0.05)O 2 electrode systems were investigated using a combination of time-resolved X-ray diffraction and soft X-ray absorption spectroscopy (XAS) techniques. The ZrO 2 coating on the surface of Li(Ni 0.8Co 0.15Al 0.05)O 2 was effective in elevating the onset temperature of the dissociation of charged Li 0.33(Ni 0.8Co 0.15Al 0.05)O 2, which will enhance the safety of Li-ion cells. Lastly, soft XAS spectra of the Ni LII,III-edge in the partial electron yield mode were obtained, which showed that the enhanced electrochemical properties and thermal stability of the cathode materialsmore » by ZrO 2 coating can be attributed to the suppression of unwanted Ni oxidation state changes at the surface.« less

Gadolinium-doped hollow CeO2-ZrO2 nanoplatform as multifunctional MRI/CT dual-modal imaging agent and drug delivery vehicle.

PubMed

Wei, Zuwu; Wu, Ming; Li, Zuanfang; Lin, Zhan; Zeng, Jinhua; Sun, Haiyan; Liu, Xiaolong; Liu, Jingfeng; Li, Buhong; Zeng, Yongyi

2018-11-01

Developing multifunctional nanoparticle-based theranostic platform for cancer diagnosis and treatment is highly desirable, however, most of the present theranostic platforms are fabricated via complicated structure/composition design and time-consuming synthesis procedures. Herein, the multifunctional Gd/CeO 2 -ZrO 2 /DOX-PEG nanoplatform with single nano-structure was fabricated through a facile route, which possessed MR/CT dual-model imaging and chemotherapy ability. The nanoplatform not only exhibited well-defined shapes, tunable compositions and narrow size distributions, but also presented a well anti-cancer effect and MR/CT imaging ability. Therefore, the Gd/CeO 2 -ZrO 2 /DOX-PEG nanoplatform could be applied for chemotherapy as well as dual-model MR/CT imaging.

Promotional effect of Al2O3 on WO3/CeO2-ZrO2 monolithic catalyst for selective catalytic reduction of nitrogen oxides with ammonia after hydrothermal aging treatment

NASA Astrophysics Data System (ADS)

Xu, Haidi; Liu, Shuang; Wang, Yun; Lin, Qingjin; Lin, Chenlu; Lan, Li; Wang, Qin; Chen, Yaoqiang

2018-01-01

Hydrothermal stability of catalysts for selective catalytic reduction of NOx with NH3 (NH3-SCR) has always been recognized as a challenge in development of candidate catalysts for applications in diesel engine emissions. In this study, Al2O3 was introduced into CeO2-ZrO2 to improve the NH3-SCR activity of WO3/CeO2-ZrO2 after hydrothermal aging (HA) treatment at 800 °C for 12 h. The activity results indicated that the NH3-SCR activity of WO3/CeO2-ZrO2-HA was obviously improved in the whole reaction temperature range after doping Al2O3 into CeO2-ZrO2, for example, the average and maximum NOx conversion were separately increased by ca. 20% and 25% after HA treatment. XRD, Raman, TEM and EDX results revealed that the introduction of Al2O3 inhibited the sintering and agglomeration of CeO2-ZrO2 and WO3 and the formation of Ce2(WO4)3 after HA treatment. Accordingly, WO3/CeO2-ZrO2-Al2O3-HA showed remarkably improved structural stability and reducibility, increased surface acidity, and facilitated the reactivity between adsorbed NH3 and nitrate species, which together contributed to its better catalytic performance after hydrothermal aging treatment.

Exceptional arsenic (III,V) removal performance of highly porous, nanostructured ZrO2 spheres for fixed bed reactors and the full-scale system modeling.

PubMed

Cui, Hang; Su, Yu; Li, Qi; Gao, Shian; Shang, Jian Ku

2013-10-15

Highly porous, nanostructured zirconium oxide spheres were fabricated from ZrO2 nanoparticles with the assistance of agar powder to form spheres with size at millimeter level followed with a heat treatment at 450 °C to remove agar network, which provided a simple, low-cost, and safe process for the synthesis of ZrO2 spheres. These ZrO2 spheres had a dual-pore structure, in which interconnected macropores were beneficial for liquid transport and the mesopores could largely increase their surface area (about 98 m(2)/g) for effective contact with arsenic species in water. These ZrO2 spheres demonstrated an even better arsenic removal performance on both As(III) and As(V) than ZrO2 nanoparticles, and could be readily applied to commonly used fixed-bed adsorption reactors in the industry. A short bed adsorbent test was conducted to validate the calculated external mass transport coefficient and the pore diffusion coefficient. The performance of full-scale fixed bed systems with these ZrO2 spheres as the adsorber was estimated by the validated pore surface diffusion modeling. With the empty bed contact time (EBCT) at 10 min and the initial arsenic concentration at 30 ppb, the number of bed volumes that could be treated by these dry ZrO2 spheres reached ~255,000 BVs and ~271,000 BVs for As(III) and As(V), respectively, until the maximum contaminant level of 10 ppb was reached. These ZrO2 spheres are non-toxic, highly stable, and resistant to acid and alkali, have a high arsenic adsorption capacity, and could be easily adapted for various arsenic removal apparatus. Thus, these ZrO2 spheres may have a promising potential for their application in water treatment practice. Copyright © 2013 Elsevier Ltd. All rights reserved.

The Role of the Substrate on Photophysical Properties of Highly Ordered 15R-SiC Thin Films

NASA Astrophysics Data System (ADS)

Mourya, Satyendra; Jaiswal, Jyoti; Malik, Gaurav; Kumar, Brijesh; Chandra, Ramesh

2018-06-01

We report on the structural optimization and photophysical properties of in situ RF-sputtered single crystalline 15R-SiC thin films deposited on various substrates (ZrO2, MgO, SiC, and Si). The role of the substrates on the structural, electronic, and photodynamic behavior of the grown films have been demonstrated using x-ray diffraction, photoluminescence (PL) and time-resolved photoluminescence spectroscopy. The appropriate bonding order and the presence of native oxide on the surface of the grown samples are confirmed by x-ray photoelectron spectroscopy measurement. A deep-blue PL emission has been observed corresponding to the Si-centered defects occurring in the native oxide. Deconvolution of the PL spectra manifested two decay mechanisms corresponding to the radiative recombination. The PL intensity and carrier lifetime were found to be substrate- dependent which may be ascribed to the variation in the trap-density of the films grown on different substrates.

Structural and dielectric properties of CTAB modified ZrO2 nanoparticles

NASA Astrophysics Data System (ADS)

Sidhu, Gaganpreet Kaur; Tripathi, S. K.; Kumar, Rajesh

2016-05-01

Zirconia (ZrO2) has been considered as one of the most investigated materials among various metal oxides due its outstanding dielectric properties and ionic conduction properties, which is mainly due to its high oxygen ion conduction. ZrO2 nanoparticles were synthesized using surfactant (CTAB) to study the variation of its dielectric behavior at room temperature. Surfactants form a unique class of chemical compounds, because of their remarkable ability to influence the properties of surfaces and interfaces of nanostructures. The dielectric properties of prepared nanoparticles were studied using LCR meter.

Thermally activated charge transport in modified tetragonal zirconia thin films prepared by sol-gel method

NASA Astrophysics Data System (ADS)

Aboulkacem, Khiali; Abdelkader, Ammari; Bediaf, Benrabah; Amar, Bouaza; Abdelmalek, Kharoubi; Hadj, Benhebal

2018-04-01

Films of Sn-doped ZrO2 were prepared using the sol-gel based dip-coating technique. The X-ray diffraction patterns showed a tetragonal structure with a preferential orientation along the (111) plane. The average grain size of the samples varies from 9.53 to 12.64 nm. Thermal analysis revealed endothermic peaks in the range 84-90 °C and exothermic peaks appearing in the range 489-531 °C. Fourier transform infrared (FTIR) spectra depicted bands located at 612 and 736 cm-1, which are attributed to stretching mode and asymmetric vibrations of Zr-O and O-Zr-O bonds respectively. All films exhibited high transmittance in the visible range above 60% and the optical band gap (E g) decreases from 4.085 to 4.061 eV. The impedance measurements show that the equivalent circuit of the samples is an R p C p where C p is the capacitance of the layer and R p its resistance. The electrical conductivity was found to follows an Arrhenius law with two activation energies.

X ray photoelectron spectroscopy (XPS) analysis of Photosensitive ZrO2 array

NASA Astrophysics Data System (ADS)

Li, Y.; Zhao, G.; Zhu, R.; Kou, Z.

2018-03-01

Based on organic zirconium source as the starting material, by adding chemical modifiers which are made up with photosensitive ZrO2 sol. A uniformed ZrO2 array dot was fabricated with a mean diameter of around 800 nm. By using UV-vis spectra and X-ray photoelectron spectroscopy analysis method, studies the photosensitive ZrO2 gel film of photochemical reaction process and the photosensitive mechanism, to determine the zirconium atom centered chelate structure, reaction formed by metal chelate Zr atom for the center, and to establish the molecular model of the chelate. And studied the ultraviolet light in the process of the variation of the XPS spectra, Zr3d5/2 to 184.9 eV corresponding to the binding energy of the as the combination of state peak gradually reduce; By combining with the status of Zr-O peak gradually increase; The strength of the peak is gradually decline. This suggests that in the process of ultraviolet light photo chemical reaction happened. This study is of great significance to the micro fabrication of ZrO2 array not only to the memory devices but also to the optical devices.

X-Ray Absorption Spectroscopy Studies of the Atomic Structure of Zirconium-Doped Lithium Silicate Glasses and Glass-Ceramics, Zirconium-Doped Lithium Borate Glasses, and Vitreous Rare-Earth Phosphates

NASA Astrophysics Data System (ADS)

Yoo, Changhyeon

In the first part of this work, the atomic-scale structure around rare-earth (RE = Pr, Nd, Eu, Dy, and Er) cations (RE3+) in rare-earth sodium ultraphosphate (REUP) glasses were investigated using RE LIII -edge (RE = Nd, Er, Dy, and Eu) and K-edge (RE = Pr and Dy) Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy. (RE2O 3)x(Na2O)y(P2O5) 1-x-y glasses in the compositional range 0 ≤ x ≤ 0.14 and 0.3 ≤ x + y ≤ 0.4 were studied. For the nearest oxygen shell, the RE-oxygen (RE-O) coordination number decreases from 10.8 to 6.5 with increasing RE content for Pr-, Nd-, Dy-, and Er-doped sodium ultraphosphate glasses. For Eu-doped samples, the Eu-O coordination number was between 7.5 and 8.8. Also, the RE-O mean distance ranges were between 2.43-2.45 A, 2.40-2.43 A, 2.36-2.38 A, 2.30-2.35 A, and 2.28-2.30 A for Pr-, Nd-, Eu-, Dy-, and Er-doped samples, respectively. In the second part, a series of Zr-doped (3-10 mol%) lithium silicate (ZRLS) glass-ceramics and their parent glasses and a series of Zr-doped (2-6 mol% ZrO2) lithium borate (ZRLB) glasses were investigated using Zr K-edge EXAFS and X-ray Absorption Near Edge Structure (XANES) spectroscopy. Immediate coordination environments of all ZRLS glasses are remarkably similar for different compositions. For the nearest oxygen shell, the Zr-O coordination number ranges were between 6.1 and 6.3 for nucleated and crystallized samples, respectively. Also, the Zr-O mean distance remains similar around 2.10 A. For these glasses, the composition dependence of structural parameters was small. Small changes in the coordination environment were observed for ZRLS glass-ceramics after thermal treatments. In contrast, Zr coordination environment in ZRLB glasses appear to depend appreciably on the Zr concentration. For the nearest oxygen shell, the Zr-O coordination number increased from 6.1 to 6.8 and the Zr-O distance decreased from 2.18 A to 2.14 A with decreasing ZrO2 content.

Influence of in situ and ex situ ZrO2 addition on the properties of MgB2

NASA Astrophysics Data System (ADS)

Chen, S. K.; Glowacki, B. A.; MacManus-Driscoll, J. L.; Vickers, M. E.; Majoros, M.

2004-02-01

The effect of ZrO2 addition on the properties of MgB2 has been studied using in situ and ex situ processes. The in situ process was performed by introducing ZrO2 from the milling tools into MgB2 throughout the planetary ball milling, whereas the ex situ process was accomplished by mixing ZrO2 from the milling tools with MgB2 by hand grinding in a mortar. A detectable amount of ZrO2 was present in MgB2 after 4 h of milling during the in situ process and its content increased with milling time as expected. The 400 h milled powder was partially amorphized and showed the formation of a minority ZrB2 phase. For milling up to 100 h, diamagnetism of MgB2 was significantly reduced while Tc remained unchanged. Superconductivity was totally destroyed after 148 h of milling. The loss of superconductivity is attributed to the effect of disordering induced by mechanical milling. As a result of in situ ZrO2 addition, the initial Tc and crystal structure of MgB2 could not be restored upon annealing. With increasing milling time, the expansion of lattice parameters in both the a-axis and c-axis may be due to possible substitution of Mg or B by Zr. The result from the magnetic measurement shows that Jc of MgB2 is deteriorated by in situ ZrO2 addition. On the other hand, ex situ ZrO2 addition with annealing did not degrade the Tc of MgB2.

Physicochemical properties of precursors of Al2O3-ZrO2 oxide ceramics prepared by electrochemical method

NASA Astrophysics Data System (ADS)

Petrova, E. V.; Dresvyannikov, A. F.; Ahmadi Daryakenari, M.; Khairullina, A. I.

2016-05-01

Scanning electron microscopy, X-ray, and thermal analysis are used to examine the structure and properties of dispersive systems based on aluminum and zirconium oxides prepared electrochemically. The effect the conditions of synthesis have on the structure and morphology of Al2O3-ZrO2 particles is studied. It is shown that the effect of an electric field on the reaction medium allows us to adjust the physicochemical properties and morphology.

Effects of Different Surfactants on Structural, Tribological and Electrical Properties of Pulsed Electro-Codeposited Cu-ZrO2 Composite Coatings

NASA Astrophysics Data System (ADS)

Maharana, H. S.; Basu, A.

2018-03-01

Cu-ZrO2 composite coating was synthesized by pulse electrodeposition from an acidic sulfate electrolyte dispersed with nano-sized ZrO2 particles. Effects of different surfactants in different amounts on the codeposition and distribution of ZrO2 particles in the copper matrix, surface-mechanical (hardness and wear) and electrical (conductivity) properties of developed composite coatings have been thoroughly investigated. Sodium dodecyl sulfate (SDS), poly acrylic acid (PAA) and glucose have been added in the electrolyte in different concentrations as anionic, polymeric and nonionic surfactants. Obtained experimental results confirmed that addition of SDS up to 1 g/L improves the amount of codeposited ZrO2 particles in the copper matrix and surface-mechanical properties of the nanocomposite coatings. But, in case of PAA- and glucose-assisted coatings, highest amount of ZrO2 codeposition was observed in 0.5 g/L PAA and 20 g/L glucose-assisted coatings, which in turn affected the mechanical properties. Surface-mechanical properties were found to be affected by coating matrix morphology and crystallographic orientation along with embedded ZrO2 particle content. Electrical conductivity of all the deposits not only depends upon the codeposition of ZrO2 particles in the matrix but also on the microstructure and crystallographic orientation.

Trade-off between Zr Passivation and Sn Doping on Hematite Nanorod Photoanodes for Efficient Solar Water Oxidation: Effects of a ZrO2 Underlayer and FTO Deformation.

PubMed

Subramanian, Arunprabaharan; Annamalai, Alagappan; Lee, Hyun Hwi; Choi, Sun Hee; Ryu, Jungho; Park, Jung Hee; Jang, Jum Suk

2016-08-03

Herein we report the influence of a ZrO2 underlayer on the PEC (photoelectrochemical) behavior of hematite nanorod photoanodes for efficient solar water splitting. Particular attention was given to the cathodic shift in onset potential and photocurrent enhancement. Akaganite (β-FeOOH) nanorods were grown on ZrO2-coated FTO (fluorine-doped tin oxide) substrates. Sintering at 800 °C transformed akaganite to the hematite (α-Fe2O3) phase and induced Sn diffusion into the crystal structure of hematite nanorods from the FTO substrates and surface migration, shallow doping of Zr atoms from the ZrO2 underlayer. The ZrO2 underlayer-treated photoanode showed better water oxidation performance compared to the pristine (α-Fe2O3) photoanode. A cathodic shift in the onset potential and photocurrent enhancement was achieved by surface passivation and shallow doping of Zr from the ZrO2 underlayer, along with Sn doping from the FTO substrate to the crystal lattice of hematite nanorods. The Zr based hematite nanorod photoanode achieved 1 mA/cm(2) at 1.23 VRHE with a low turn-on voltage of 0.80 VRHE. Sn doping and Zr passivation, as well as shallow doping, were confirmed by XPS, Iph, and M-S plot analyses. Electrochemical impedance spectroscopy revealed that the presence of a ZrO2 underlayer decreased the deformation of FTO substrate, improved electron transfer at the hematite/FTO interface and increased charge-transfer resistance at the electrolyte/hematite interface. This is the first systematic investigation of the effects of Zr passivation, shallow doping, and Sn doping on hematite nanorod photoanodes through application of a ZrO2 underlayer on the FTO substrate.

Microwave Synthesis, Characterization, and Photoluminescence Properties of Nanocrystalline Zirconia

PubMed Central

Singh, A. K.; Nakate, Umesh T.

2014-01-01

We report synthesis of ZrO2 nanoparticles (NPs) using microwave assisted chemical method at 80°C temperature. Synthesized ZrO2 NPs were calcinated at 400°C under air atmosphere and characterized using FTIR, XRD, SEM, TEM, BET, and EDS for their formation, structure, morphology, size, and elemental composition. XRD results revealed the formation of mixed phase monoclinic and tetragonal ZrO2 phases having crystallite size of the order 8.8 nm from most intense XRD peak as obtained using Scherrer formula. Electron microscope analysis shows that the NPs were less than 10 nm and highly uniform in size having spherical morphology. BET surface area of ZrO2 NPs was found to be 65.85 m2/g with corresponding particle size of 16 nm. The band gap of synthesized NPs was found to be 2.49 eV and PL spectra of ZrO2 synthesized NPs showed strong peak at 414 nm, which corresponds to near band edge emission (UV emission) and a relatively weak peak at 475 and 562 nm. PMID:24578628

Multi-layer thin-film electrolytes for metal supported solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Haydn, Markus; Ortner, Kai; Franco, Thomas; Uhlenbruck, Sven; Menzler, Norbert H.; Stöver, Detlev; Bräuer, Günter; Venskutonis, Andreas; Sigl, Lorenz S.; Buchkremer, Hans-Peter; Vaßen, Robert

2014-06-01

A key to the development of metal-supported solid oxide fuel cells (MSCs) is the manufacturing of gas-tight thin-film electrolytes, which separate the cathode from the anode. This paper focuses the electrolyte manufacturing on the basis of 8YSZ (8 mol.-% Y2O3 stabilized ZrO2). The electrolyte layers are applied by a physical vapor deposition (PVD) gas flow sputtering (GFS) process. The gas-tightness of the electrolyte is significantly improved when sequential oxidic and metallic thin-film multi-layers are deposited, which interrupt the columnar grain structure of single-layer electrolytes. Such electrolytes with two or eight oxide/metal layers and a total thickness of about 4 μm obtain leakage rates of less than 3 × 10-4 hPa dm3 s-1 cm-2 (Δp: 100 hPa) at room temperature and therefore fulfill the gas tightness requirements. They are also highly tolerant with respect to surface flaws and particulate impurities which can be present on the graded anode underground. MSC cell tests with double-layer and multilayer electrolytes feature high power densities more than 1.4 W cm-2 at 850 °C and underline the high potential of MSC cells.

Effect of ZrO2 on the sintering behavior, strength and high-frequency dielectric properties of electrical ceramic porcelain insulator

NASA Astrophysics Data System (ADS)

Singh Mehta, Niraj; Sahu, Praveen Kumar; Ershad, Md; Saxena, Vipul; Pyare, Ram; Ranjan Majhi, Manas

2018-01-01

In the present study, the effect of ZrO2 on the sintering, strength and dielectric behavior of electrical ceramic porcelain insulator with substituting alumina content by zirconia (in weight percentage from 0% to 30%) is investigated. The different composition of samples containing different zirconia (ZrO2) contents of 0, 10, 20, and 30 wt% are prepared using the uniaxial pressure technique applying 160 MPa pressure. Further, the prepared samples are also analyzed for sintering temperatures (1350 °C), and effects are observed on mechanical and electric properties of porcelain insulator. Different characterizations such as Dilatometer, x-ray diffraction, scanning electron microscopy and differential thermal analysis/thermo gravimetric analysis were used to evaluate the thermal, phase detection, micro structural and weight loss changes by increasing concentration of ZrO2 on base porcelain composition. At 1350 °C, for the composition having 20 wt% ZrO2 with 10 wt% alumina, the maximum density was observed 2.81 g cm-3 with a porosity of 2.23%. The highest tensile strength of 41 ± 3 MPa is observed for the same sample composition. The minimum value of thermal expansion coefficient is found to be in the range of 10-6 for the sample with 30 wt% ZrO2 content sintered at 1350 °C compared to other prepared samples. Similarly, the highest dielectric value (5.1-4.4) having dielectric loss (0.08-0.12) is achieved for the sample with 30 wt% ZrO2 content sintered at 1350 °C in the frequency range of 4-20 GHz at room temperature. According to the mechanical properties, the composition having 20 wt% ZrO2 on base ceramic porcelain composition has enormous potential to serve as a high strength refractory material. For dielectric properties, the composition having 30 wt% ZrO2 is more suitable for the electrical application.

Growth of an Ultrathin Zirconia Film on Pt3Zr Examined by High-Resolution X-ray Photoelectron Spectroscopy, Temperature-Programmed Desorption, Scanning Tunneling Microscopy, and Density Functional Theory.

PubMed

Li, Hao; Choi, Joong-Il Jake; Mayr-Schmölzer, Wernfried; Weilach, Christian; Rameshan, Christoph; Mittendorfer, Florian; Redinger, Josef; Schmid, Michael; Rupprechter, Günther

2015-02-05

Ultrathin (∼3 Å) zirconium oxide films were grown on a single-crystalline Pt 3 Zr(0001) substrate by oxidation in 1 × 10 -7 mbar of O 2 at 673 K, followed by annealing at temperatures up to 1023 K. The ZrO 2 films are intended to serve as model supports for reforming catalysts and fuel cell anodes. The atomic and electronic structure and composition of the ZrO 2 films were determined by synchrotron-based high-resolution X-ray photoelectron spectroscopy (HR-XPS) (including depth profiling), low-energy electron diffraction (LEED), scanning tunneling microscopy (STM), and density functional theory (DFT) calculations. Oxidation mainly leads to ultrathin trilayer (O-Zr-O) films on the alloy; only a small area fraction (10-15%) is covered by ZrO 2 clusters (thickness ∼0.5-10 nm). The amount of clusters decreases with increasing annealing temperature. Temperature-programmed desorption (TPD) of CO was utilized to confirm complete coverage of the Pt 3 Zr substrate by ZrO 2 , that is, formation of a closed oxide overlayer. Experiments and DFT calculations show that the core level shifts of Zr in the trilayer ZrO 2 films are between those of metallic Zr and thick (bulklike) ZrO 2 . Therefore, the assignment of such XPS core level shifts to substoichiometric ZrO x is not necessarily correct, because these XPS signals may equally well arise from ultrathin ZrO 2 films or metal/ZrO 2 interfaces. Furthermore, our results indicate that the common approach of calculating core level shifts by DFT including final-state effects should be taken with care for thicker insulating films, clusters, and bulk insulators.

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.

The glass-like thermal conductivity in ZrO2-Dy3TaO7 ceramic for promising thermal barrier coating application

NASA Astrophysics Data System (ADS)

Wu, Peng; Hu, Ming Yu; Chong, Xiao Yu; Feng, Jing

2018-03-01

Using the solid-state reaction method, the (ZrO2)x-(Dy3TaO7)1-x (x = 0, 0.02, 0.04, 0.06, 0.08, and 0.1) ceramics are synthesized in this work. The identification of the crystal structures indicates that the (ZrO2)x-(Dy3TaO7)1-x ceramics belong to the orthorhombic system, and the space group is C2221 in spite of the value of x increasing to 0.1. The thermal conductivities of the (ZrO2)x-(Dy3TaO7)1-x ceramics range from 1.3 W/(m K) to 1.8 W/(m K), and this value is much lower than that of 7-8 YSZ (yttria-stabilized zirconia). Besides, the (ZrO2)x-(Dy3TaO7)1-x ceramics possess the glass-like thermal conductivity caused by intrinsic oxygen vacancies existing in the lattice of Dy3TaO7. Moreover, the results of thermal expansion rates demonstrate that the (ZrO2)x-(Dy3TaO7)1-x ceramics possess excellent high temperature phase stability, and the thermal expansion coefficients [(9.7-11) × 10-6 K-1] are comparable to that of 7-8 YSZ.

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.

Morphology evaluation of ZrO2 dip coating on mild steel and its corrosion performance in NaOH solution

NASA Astrophysics Data System (ADS)

Anwar, M. A.; Kurniawan, T.; Asmara, Y. P.; Harun, W. S. W.; Oumar, A. N.; Nandyanto, A. B. D.

2017-10-01

In this work, the morphology of ZrO2 thin film from dip coating process on mild steel has been investigated. Mild steel was dip-coated on solution made of zirconium butoxide as a precursor, ethanol as solvent, acetylacetone as chelating agent and water for hydrolysis. Number of dipping was adjusted at 3, 5 and 7 times. The dipped sample then annealed at 350°C for two hours by adjusting the heating rate at 1°C/min respectively. The optical microscope showed that micro-cracks were observed on the surface of the coating with its concentration reduced as dipping sequence increased. The XRD result showed that annealing process can produce polycrystalline tetragonal-ZrO2. Meanwhile, SEM image showed that the thicknesses of the ZrO2 coatings were in between 400-600 nm. The corrosion resistance of uncoated and coated substrates was studied by polarization test through potentio-dynamic polarization curve at 1mV/s immersed in with 3.5% NaCl. The coating efficiency was improved as the number of layer dip coated increased, which showed improvement in corrosion protection.

Exceptional capability of nanosized CeO(2) materials to "dissolve" lanthanide oxides established by time-gated excitation and emission spectroscopy.

PubMed

Tiseanu, Carmen; Parvulescu, Vasile; Avram, Daniel; Cojocaru, Bogdan; Sanchez-Dominguez, Margarita

2014-05-28

The atomic scale homogeneity of Ce and Zr oxygen bonds represents the main reason for enhanced total oxygen storage capability of CeO2-ZrO2 (Ce/Zr = 1) as compared to that of CeO2. Here, we demonstrate that the addition of 10% Eu(3+) by wet impregnation on preformed nanosized CeO2-ZrO2 (Ce/Zr = 1) followed by calcination induces a remarkable homogeneity of 10% Eu(3+)-CeO2-ZrO2 solid solution. By use of time-resolved emission and excitation spectroscopies, the improvement of the nanoscale chemical and structural homogeneity of 10% Eu(3+)-CeO2-ZrO2 calcined at 1000 as compared to sample calcined at 750 °C is demonstrated. Based on the comparison of luminescence properties of 10% Eu(3+) impregnated on preformed nanosized CeO2-ZrO2 and CeO2, we also show that the presence of zirconium does not only preserve the ability of cerium oxide to "dissolve" lanthanide oxide, but also determines an important stabilization of defects (oxygen vacancies) generated upon Eu(3+) doping.

A room temperature process for the fabrication of amorphous indium gallium zinc oxide thin-film transistors with co-sputtered Zr x Si1- x O2 Gate dielectric and improved electrical and hysteresis performance

NASA Astrophysics Data System (ADS)

Hung, Chien-Hsiung; Wang, Shui-Jinn; Liu, Pang-Yi; Wu, Chien-Hung; Wu, Nai-Sheng; Yan, Hao-Ping; Lin, Tseng-Hsing

2017-04-01

The use of co-sputtered zirconium silicon oxide (Zr x Si1- x O2) gate dielectrics to improve the gate controllability of amorphous indium gallium zinc oxide (α-IGZO) thin-film transistors (TFTs) through a room-temperature fabrication process is proposed and demonstrated. With the sputtering power of the SiO2 target in the range of 0-150 W and with that of the ZrO2 target kept at 100 W, a dielectric constant ranging from approximately 28.1 to 7.8 is obtained. The poly-structure formation immunity of the Zr x Si1- x O2 dielectrics, reduction of the interface trap density suppression, and gate leakage current are examined. Our experimental results reveal that the Zr0.85Si0.15O2 gate dielectric can lead to significantly improved TFT subthreshold swing performance (103 mV/dec) and field effect mobility (33.76 cm2 V-1 s-1).

Labeling of HeLa cells using ZrO2:Yb3+-Er3+ nanoparticles with upconversion emission

NASA Astrophysics Data System (ADS)

Ceja-Fdez, Andrea; López-Luke, Tzarara; Oliva, Jorge; Vivero-Escoto, Juan; Gonzalez-Yebra, Ana Lilia; Rojas, Ruben A. Rodriguez; Martínez-Pérez, Andrea; de la Rosa, Elder

2015-04-01

This work reports the synthesis, structural characterization, and optical properties of ZrO2:Yb3+-Er3+ (2-1 mol%) nanocrystals. The nanoparticles were coated with 3-aminopropyl triethoxysilane (APTES) and further modified with biomolecules, such as Biotin-Anti-rabbit (mouse IgG) and rabbit antibody-AntiKi-67, through a conjugation method. The conjugation was successfully confirmed by Fourier transform infrared, zeta potential, and dynamic light scattering. The internalization of the conjugated nanoparticles in human cervical cancer (HeLa) cells was followed by two-photon confocal microscopy. The ZrO2:Yb3+-Er3+ nanocrystals exhibited strong red emission under 970-nm excitation. Moreover, the luminescence change due to the addition of APTES molecules and biomolecules on the nanocrystals was also studied. These results demonstrate that ZrO2:Yb3+-Er3+ nanocrystals can be successfully functionalized with biomolecules to develop platforms for biolabeling and bioimaging.

Influence of miscut Y2O3-stabilized ZrO2 substrates on the azimuthal domain structure and ferroelectric properties of epitaxial La-substituted Bi4Ti3O12 films

NASA Astrophysics Data System (ADS)

Lee, Sung Kyun; Hesse, Dietrich; Gösele, Ulrich; Lee, Ho Nyung

2006-09-01

We have investigated the influence of both miscut angle and miscut direction of Y2O3-stabilized ZrO2 (YSZ) (100) single crystal substrates on the azimuthal domain structure of SrRuO3 electrode layers as well as of La-substituted Bi4Ti3O12 (BLT) ferroelectric thin films, both grown on these substrates by pulsed laser deposition. X-ray diffraction ϕ scan and pole figure characterizations revealed that the YSZ[011] miscut direction is more effective to uniformly reduce the number of azimuthal domain variants in the films than the YSZ[001] miscut direction. The BLT films on YSZ(100) substrates with miscut angle of 5° and [011] miscut direction involve only half the number of azimuthal domains, compared to the BLT films on exactly cut YSZ(100) substrates. Atomic force microscopy and plan-view transmission electron microscopy also confirmed that almost all BLT grains on these miscut YSZ(100) substrates are arranged along only two (out of four) specific azimuthal directions. The BLT films on YSZ(100) substrates with 5° miscut towards YSZ[011] showed an about 1.3 times higher remanent polarization (Pr=12.5μC /cm2) than the BLT films on exactly cut YSZ(100) substrates (Pr=9.5μC/cm2), due most probably to a lower areal density of azimuthal domain boundaries. It thus appears that reducing the structural domains can be an effective way to further enhance the ferroelectric properties of multiply twinned, epitaxial ferroelectric films.

Flexible Mixed-Potential-Type (MPT) NO2 Sensor Based on An Ultra-Thin Ceramic Film

PubMed Central

You, Rui; Jing, Gaoshan; Yu, Hongyan; Cui, Tianhong

2017-01-01

A novel flexible mixed-potential-type (MPT) sensor was designed and fabricated for NO2 detection from 0 to 500 ppm at 200 °C. An ultra-thin Y2O3-doped ZrO2 (YSZ) ceramic film 20 µm thick was sandwiched between a heating electrode and reference/sensing electrodes. The heating electrode was fabricated by a conventional lift-off process, while the porous reference and the sensing electrodes were fabricated by a two-step patterning method using shadow masks. The sensor’s sensitivity is achieved as 58.4 mV/decade at the working temperature of 200 °C, as well as a detection limit of 26.7 ppm and small response time of less than 10 s at 200 ppm. Additionally, the flexible MPT sensor demonstrates superior mechanical stability after bending over 50 times due to the mechanical stability of the YSZ ceramic film. This simply structured, but highly reliable flexible MPT NO2 sensor may lead to wide application in the automobile industry for vehicle emission systems to reduce NO2 emissions and improve fuel efficiency. PMID:28758933

Low-temperature CO oxidation over Cu/Pt co-doped ZrO2 nanoparticles synthesized by solution combustion.

PubMed

Singhania, Amit; Gupta, Shipra Mital

2017-01-01

Zirconia (ZrO 2 ) nanoparticles co-doped with Cu and Pt were applied as catalysts for carbon monoxide (CO) oxidation. These materials were prepared through solution combustion in order to obtain highly active and stable catalytic nanomaterials. This method allows Pt 2+ and Cu 2+ ions to dissolve into the ZrO 2 lattice and thus creates oxygen vacancies due to lattice distortion and charge imbalance. High-resolution transmission electron microscopy (HRTEM) results showed Cu/Pt co-doped ZrO 2 nanoparticles with a size of ca. 10 nm. X-ray diffraction (XRD) and Raman spectra confirmed cubic structure and larger oxygen vacancies. The nanoparticles showed excellent activity for CO oxidation. The temperature T 50 (the temperature at which 50% of CO are converted) was lowered by 175 °C in comparison to bare ZrO 2 . Further, they exhibited very high stability for CO reaction (time-on-stream ≈ 70 h). This is due to combined effect of smaller particle size, large oxygen vacancies, high specific surface area and better thermal stability of the Cu/Pt co-doped ZrO 2 nanoparticles. The apparent activation energy for CO oxidation is found to be 45.6 kJ·mol -1 . The CO conversion decreases with increase in gas hourly space velocity (GHSV) and initial CO concentration.

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.

Microstructural Improvement of Hydroxyapatite-ZrO2 Composite Ceramics via Thermal Precipitation Techniques.

NASA Astrophysics Data System (ADS)

Sangmala, A.; Limsuwan, P.; Kaewwiset, W.; Naemchanthara, K.

2017-09-01

Hydroxyapatite-ZrO2 composite ceramic were synthesized using a thermal precipitation techniques. The chemical precursors were prepared from di-ammonium hydrogen orthophosphate, calcium oxide (CaO) derived from chicken eggshell, zirconium dioxide (ZrO2) and distilled water. The mixture were heated at the various temperatures from 100 to 700 °C in the furnace with an incremental temperature of 100 °C. The ZrO2 contents in the composite ceramic were varied from 0 to 15 percent weight of CaO. The prepared composites were then annealed at 300, 600 and 700 °C for 4 h in air. The crystal structure, function group and morphology of all samples were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), field emission scanning electron microscopy (FESEM) and universal testing machine (UTM), respectively. The results indicated that the undoped-ZrO2 samples hydroxyapatite phase with a hexagonal structure. However, the hydroxyapatite was transformed to the tri-calcium phosphate after thermal treatment at 700 °C. For the doped-ZrO2 samples, the hydroxyapatite and ZrO2 phases were found. Moreover, the result showed that the compressive strength of hydroxyapatite-ZrO2 composite ceramic increased with increasing the ZrO2 content.

ZrO2 nanoparticles labeled via a native protein corona: detection by fluorescence microscopy and Raman microspectroscopy in rat lungs.

PubMed

Silge, Anja; Bräutigam, Katharina; Bocklitz, Thomas; Rösch, Petra; Vennemann, Antje; Schmitz, Inge; Popp, Jürgen; Wiemann, Martin

2015-08-07

ZrO2 nanoparticles are frequently used in composite materials such as dental fillers from where they may be released and inhaled upon polishing and grinding. Since the overall distribution of ZrO2 NP inside the lung parenchyma can hardly be observed by routine histology, here a labeling with a fluorphore was used secondary to the adsorption of serum proteins. Particles were then intratracheally instilled into rat lungs. After 3 h fluorescent structures consisted of agglomerates scattered throughout the lung parenchyma, which were mainly concentrated in alveolar macrophages after 3 d. A detection method based on Raman microspectroscopy was established to investigate the chemical composition of those fluorescent structures in detail. Raman measurements were arranged such that no spectral interference with the protein-bound fluorescence label was evident. Applying chemometrical methods, Raman signals of the ZrO2 nanomaterial were co-localized with the fluorescence label, indicating the stability of the nanomaterial-protein-dye complex inside the rat lung. The combination of Raman microspectroscopy and adsorptive fluorescence labeling may, therefore, become a useful tool for studying the localization of protein-coated nanomaterials in cells and tissues.

Density functional analysis of fluorite-structured (Ce, Zr)O 2/CeO 2 interfaces [Density functional analysis of fluorite-structured (Ce, Zr)O 2/CeO 2 interfaces: Implications for catalysis and energy applications

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

Weck, Philippe F.; Juan, Pierre -Alexandre; Dingreville, Remi

The structures and properties of Ce 1–xZr xO 2 (x = 0–1) solid solutions, selected Ce 1–xZr xO 2 surfaces, and Ce 1–xZr xO 2/CeO 2 interfaces were computed within the framework of density functional theory corrected for strong electron correlation (DFT+ U). The calculated Debye temperature increases steadily with Zr content in (Ce, Zr)O 2 phases, indicating a significant rise in microhardness from CeO 2 to ZrO 2, without appreciable loss in ductility as the interfacial stoichiometry changes. Surface energy calculations for the low-index CeO 2(111) and (110) surfaces show limited sensitivity to strong 4f-electron correlation. The fracture energymore » of Ce 1–xZr xO 2(111)/CeO 2(111) increases markedly with Zr content, with a significant decrease in energy for thicker Ce 1–xZr xO 2 films. These findings suggest the crucial role of Zr acting as a binder at the Ce 1–xZr xO 2/CeO 2 interfaces, due to the more covalent character of Zr–O bonds compared to Ce–O. Finally, the impact of surface relaxation upon interface cracking was assessed and found to reach a maximum for Ce 0.25Zr 0.75O 2/CeO 2 interfaces.« less

Density functional analysis of fluorite-structured (Ce, Zr)O 2/CeO 2 interfaces [Density functional analysis of fluorite-structured (Ce, Zr)O 2/CeO 2 interfaces: Implications for catalysis and energy applications

DOE PAGES

Weck, Philippe F.; Juan, Pierre -Alexandre; Dingreville, Remi; ...

2017-06-21

The structures and properties of Ce 1–xZr xO 2 (x = 0–1) solid solutions, selected Ce 1–xZr xO 2 surfaces, and Ce 1–xZr xO 2/CeO 2 interfaces were computed within the framework of density functional theory corrected for strong electron correlation (DFT+ U). The calculated Debye temperature increases steadily with Zr content in (Ce, Zr)O 2 phases, indicating a significant rise in microhardness from CeO 2 to ZrO 2, without appreciable loss in ductility as the interfacial stoichiometry changes. Surface energy calculations for the low-index CeO 2(111) and (110) surfaces show limited sensitivity to strong 4f-electron correlation. The fracture energymore » of Ce 1–xZr xO 2(111)/CeO 2(111) increases markedly with Zr content, with a significant decrease in energy for thicker Ce 1–xZr xO 2 films. These findings suggest the crucial role of Zr acting as a binder at the Ce 1–xZr xO 2/CeO 2 interfaces, due to the more covalent character of Zr–O bonds compared to Ce–O. Finally, the impact of surface relaxation upon interface cracking was assessed and found to reach a maximum for Ce 0.25Zr 0.75O 2/CeO 2 interfaces.« less

Effect of Er3+ concentration on the luminescence properties of Al2O3-ZrO2 powder

NASA Astrophysics Data System (ADS)

Clabel H., J. L.; Rivera, V. A. G.; Nogueira, I. C.; Leite, E. R.; Siu Li, M.; Marega, E.

2016-12-01

This manuscript reports on the effects of the luminescence properties of Er3+ on Al2O3-ZrO2 powder synthesized by the conventional solid-state method. The best conditions found for the calcinations were 1500 °C and 4 h. The structural dependence of the luminescence on Er3+:Al2O3-ZrO2 is associated with phase transformations of the Al2O3-ZrO2 host and presence of the OH group. Green and red emissions at room temperature from the 2H11/2, 4S3/2 → 4I15/2 and 4F9/2 → 4I15/2 levels of Er3+ ions were observed under 482 nm pumping. The green-to-red emission intensity ratios and CIE chromaticity coordinates were determined from emission spectra for the evaluation of light emitted as a function of the Er3+ concentration. The Er3+ luminescence quenching due to group OH and variation in the Er3+ concentration plays an important role in the definition of the luminescent response.

Electronic Structure, Phonon Dynamical Properties, and CO 2 Capture Capability of Na 2 - x M x Zr O 3 ( M = Li ,K): Density-Functional Calculations and Experimental Validations

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

Duan, Yuhua; Lekse, Jonathan; Wang, Xianfeng

2015-04-22

The electronic structural and phonon properties of Na 2-αM αZrO 3 (M ¼ Li,K, α = ¼ 0.0,0.5,1.0,1.5,2.0) are investigated by first-principles density-functional theory and phonon dynamics. The thermodynamic properties of CO 2 absorption and desorption in these materials are also analyzed. With increasing doping level α, the binding energies of Na 2-αLi αZrO 3 are increased while the binding energies of Na 2-α K αZrO 3 are decreased to destabilize the structures. The calculated band structures and density of states also show that, at the same doping level, the doping sites play a significant role in the electronic properties.more » The phonon dispersion results show that few soft modes are found in several doped configurations, which indicates that these structures are less stable than other configurations with different doping levels. From the calculated relationships among the chemical-potential change, the CO 2 pressure, and the temperature of the CO 2 capture reactions by Na 2-αM αZrO 3, and from thermogravimetric-analysis experimental measurements, the Li- and K-doped mixtures Na 2-αM αZrO 3 have lower turnover temperatures (T t) and higher CO 2 capture capacities, compared to pure Na 2ZrO 3. The Li-doped systems have a larger T t decrease than the K-doped systems. When increasing the Li-doping level α, the T t of the corresponding mixture Na 2-αLi αZrO 3 decreases further to a low-temperature range. However, in the case of K-doped systems Na 2-αK αZrO 3, although doping K into Na 2ZrO 3 initially shifts its T t to lower temperatures, further increases of the K-doping level α causes T t to increase. Therefore, doping Li into Na 2ZrO 3 has a larger influence on its CO 2 capture performance than the K-doped Na 2ZrO 3. Compared with pure solidsM 2ZrO 3, after doping with other elements, these doped systems’ CO 2 capture performances are improved.« less

ZrO2 Layer Thickness Dependent Electrical and Dielectric Properties of BST/ZrO2/BST Multilayer Thin Films

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

Sahoo, S. K.; Misra, D.; Agrawal, D. C.

2011-01-01

Recently, high K materials play an important role in microelectronic devices such as capacitors, memory devices, and microwave devices. Now a days ferroelectric barium strontium titanate [Ba{sub x}Sr{sub 1-x}TiO{sub 3}, (BST)] thin film is being actively investigated for applications in dynamic random access memories (DRAM), field effect transistor (FET), and tunable devices because of its properties such as high dielectric constant, low leakage current, low dielectric loss, and high dielectric breakdown strength. Several approaches have been used to optimize the dielectric and electrical properties of BST thin films such as doping, graded compositions, and multilayer structures. We have found thatmore » inserting a ZrO{sub 2} layer in between two BST layers results in a significant reduction in dielectric constant, loss tangent, and leakage current in the multilayer thin films. Also it is shown that the properties of multilayer structure are found to depend strongly on the sublayer thicknesses. In this work the effect of ZrO{sub 2} layer thickness on the dielectric, ferroelectric as well as electrical properties of BST/ZrO{sub 2}/BST multilayer structure is studied. The multilayer Ba{sub 0.8}Sr{sub 0.2}TiO{sub 3}/ZrO{sub 2}/Ba{sub 0.8}Sr{sub 0.2}TiO{sub 3} film is deposited by a sol-gel process on the platinized Si substrate. The thickness of the middle ZrO{sub 2} layer is varied while keeping the top and bottom BST layer thickness as fixed. It is observed that the dielectric constant, dielectric loss tangent, and leakage current of the multilayer films reduce with the increase of ZrO{sub 2} layer thickness and hence suitable for memory device applications. The ferroelectric properties of the multilayer film also decrease with the ZrO{sub 2} layer thickness.« less

Oral intake of zirconia nanoparticle alters neuronal development and behaviour of Drosophila melanogaster

NASA Astrophysics Data System (ADS)

Mishra, Monalisa; Sabat, Debabrat; Ekka, Basanti; Sahu, Swetapadma; P, Unnikannan; Dash, Priyabrat

2017-08-01

Zirconia nanoparticles (ZrO2 NPs) have been extensively used in teeth and bone implants and thus get a chance to interact with the physiological system. The current study investigated the oral administration of various concentrations of ZrO2 NPs synthesized by the hydrothermal method (0.25 to 5.0 mg L-1) on Drosophila physiology and behaviour. The size of the currently studied nanoparticle varies from 10 to 12 nm. ZrO2 NPs accumulated within the gut in a concentration-dependent manner and generate reactive oxygen species (ROS) only at 2.5 and 5.0 mg L-1 concentrations. ROS was detected by nitroblue tetrazolium (NBT) assay and 2',7'-dichlorofluorescein http://www.ncbi.nlm.nih.gov/pubmed/20370560 (H2DCF) staining. The ROS toxicity alters the larval gut structure as revealed by DAPI staining. The NP stress of larvae affects the Drosophila development by distressing pupa count and varying the phenotypic changes in sensory organs (eye, thorax bristle, wings). Besides phenotypic changes, flawed climbing behaviour against gravity was seen in ZrO2 NP-treated flies. All together, for the first time, we have reported that a ROS-mediated ZrO2 NP toxicity alters neuronal development and functioning using Drosophila as a model organism. [Figure not available: see fulltext.

Processing of La(1.8)Sr(0.2)CuO4 and YBa2Cu3O7 superconducting thin films by dual-ion-beam sputtering

NASA Astrophysics Data System (ADS)

Madakson, P.; Cuomo, J. J.; Yee, D. S.; Roy, R. A.; Scilla, G.

1988-03-01

High-quality La(1.8)Sr(0.2)CuO4 and YBa2Cu3O7 superconducting thin films, with zero resistance at 88 K, have been made by dual-ion-beam sputtering of metal and oxide targets at elevated temperatures. The films are about 1.0 micron thick and are single phase after annealing. The substrates investigated are Nd-YAP, MgO, SrF2, Si, CaF2, ZrO2-(9 pct)Y2O3, BaF2, Al2O3, and SrTiO3. Characterization of the films was carried out using Rutherford backscattering spectroscopy, resistivity measurements, TEM, X-ray diffraction, and SIMS. Substrate/film interaction was observed in every case. This generally involves diffusion of the substrate into the film, which is accompanied by, for example, the replacement of Ba by Sr in the YBa2Cu2O7 structure, in the case of SrTiO3 substrate. The best substrates were those that did not significantly diffuse into the film and which did not react chemically with the film.

CO Oxidation and Subsequent CO 2 Chemisorption on Alkaline Zirconates: Li 2 ZrO 3 and Na 2 ZrO 3

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

Alcántar-Vázquez, Brenda; Duan, Yuhua; Pfeiffer, Heriberto

Here, two different alkaline zirconates (Li 2ZrO 3 and Na 2ZrO 3) were studied as possible bifunctional catalytic-captor materials for CO oxidation and the subsequent CO 2 chemisorption process. Initially, CO oxidation reactions were analyzed in a catalytic reactor coupled to a gas chromatograph, using Li 2ZrO 3 and Na 2ZrO 3, under different O 2 partial flows. We found results clearly showed that Na 2ZrO 3 possesses much better catalytic properties than Li 2ZrO 3. After the CO-O 2 oxidation catalytic analysis, CO2 chemisorption process was analyzed by thermogravimetric analysis, only for the Na 2ZrO 3 ceramic. The resultsmore » confirmed that Na 2ZrO 3 is able to work as a bifunctional material (CO oxidation and subsequent CO 2 chemisorption), although the kinetic CO 2 capture process was not the best one under the physicochemical condition used in this case. For Na 2ZrO 3, the best CO conversions were found between 445 and 580 °C (100%), while Li 2ZrO 3 only showed a 35% of efficiency between 460 and 503 °C. However, in the Na 2ZrO 3 case, at temperatures higher than 580 °C its catalytic activity gradually decreases as a result of CO 2 capture process. Finally, all these experiments were compared and supported with theoretical thermodynamic data.« less

CO Oxidation and Subsequent CO 2 Chemisorption on Alkaline Zirconates: Li 2 ZrO 3 and Na 2 ZrO 3

DOE PAGES

Alcántar-Vázquez, Brenda; Duan, Yuhua; Pfeiffer, Heriberto

2016-08-26

Here, two different alkaline zirconates (Li 2ZrO 3 and Na 2ZrO 3) were studied as possible bifunctional catalytic-captor materials for CO oxidation and the subsequent CO 2 chemisorption process. Initially, CO oxidation reactions were analyzed in a catalytic reactor coupled to a gas chromatograph, using Li 2ZrO 3 and Na 2ZrO 3, under different O 2 partial flows. We found results clearly showed that Na 2ZrO 3 possesses much better catalytic properties than Li 2ZrO 3. After the CO-O 2 oxidation catalytic analysis, CO2 chemisorption process was analyzed by thermogravimetric analysis, only for the Na 2ZrO 3 ceramic. The resultsmore » confirmed that Na 2ZrO 3 is able to work as a bifunctional material (CO oxidation and subsequent CO 2 chemisorption), although the kinetic CO 2 capture process was not the best one under the physicochemical condition used in this case. For Na 2ZrO 3, the best CO conversions were found between 445 and 580 °C (100%), while Li 2ZrO 3 only showed a 35% of efficiency between 460 and 503 °C. However, in the Na 2ZrO 3 case, at temperatures higher than 580 °C its catalytic activity gradually decreases as a result of CO 2 capture process. Finally, all these experiments were compared and supported with theoretical thermodynamic data.« less

Defects versus grain size effects on the ferromagnetism of ZrO2 nanocrystals clarified by positron annihilation

NASA Astrophysics Data System (ADS)

Wang, D. D.; Qi, N.; Jiang, M.; Chen, Z. Q.

2013-01-01

Undoped ZrO2 nanocrystals were annealed in open air from 100 °C to 1300 °C. X-ray diffraction and transmission electron microscope were used to study the structure change and grain growth. Both the methods reveal that the ZrO2 grain size has very slight increase after annealing up to 900 °C. Positron annihilation measurements reveal a high concentration of vacancy defects which most probably exist in the grain boundary region. Thermal annealing above 500 °C causes recovery of these defects, and after annealing at 1200 °C, most of them are removed. Room temperature ferromagnetism is observed for the sample annealed at 100 °C and 500 °C. The magnetization becomes very weak after the nanocrystals are annealed at 700 °C, and it almost disappears at 1000 °C. It is clear that the intrinsic ferromagnetism in our ZrO2 nanocrystals is mostly related with the interfacial defects instead of grain size effects.

ZrO2:Sm3+ nanophosphor: synthesis, Rietveld refinement, optical and thermoluminescent properties

NASA Astrophysics Data System (ADS)

Ponkumar, S.; Janaki, K.; Prakashbabu, D.; Ramalingam, H. B.; Munirathnam, K.; Sreekanth, T. V. M.; Dhoble, S. J.

2018-02-01

We have synthesized undoped and Sm3+ ions doped ZrO2 nanophosphors by solution combustion method. These nanophosphors crystallized in cubic structure. Rietveld refinement of the samples was performed to estimate lattice parameters. Spherical particles with the sizes of 10-25 nm were observed by transmission electron microscopy. Photoluminescence and thermoluminescence (TL) properties of samples were investigated. Under 400 nm excitation, the nanophosphors have intense red emission at 600 nm. The color coordinates (0.67, 0.33) were located in the red region of CIE diagram. TL properties of nanophosphors were studied by exposing the samples to γ-rays. 5 mol% Sm3+ doped ZrO2 nanophosphor has shown maximum TL intensity after γ-irradiation. To test suitability of the nanophosphors for practical application in dosimetry, the 5 mol% Sm3+ doped ZrO2 sample was irradiated by 14 MeV electron beam in various electron fluence ranging from 100 to 900 Gy and their TL response was recorded.

Improved electrical properties of atomic layer deposited tin disulfide at low temperatures using ZrO2 layer

NASA Astrophysics Data System (ADS)

Lee, Juhyun; Lee, Jeongsu; Ham, Giyul; Shin, Seokyoon; Park, Joohyun; Choi, Hyeongsu; Lee, Seungjin; Kim, Juyoung; Sul, Onejae; Lee, Seungbeck; Jeon, Hyeongtag

2017-02-01

We report the effect of zirconium oxide (ZrO2) layers on the electrical characteristics of multilayered tin disulfide (SnS2) formed by atomic layer deposition (ALD) at low temperatures. SnS2 is a two-dimensional (2D) layered material which exhibits a promising electrical characteristics as a channel material for field-effect transistors (FETs) because of its high mobility, good on/off ratio and low temperature processability. In order to apply these 2D materials to large-scale and flexible electronics, it is essential to develop processes that are compatible with current electronic device manufacturing technology which should be conducted at low temperatures. Here, we deposited a crystalline SnS2 at 150 °C using ALD, and we then annealed at 300 °C. X-ray diffraction (XRD) and Raman spectroscopy measurements before and after the annealing showed that SnS2 had a hexagonal (001) peak at 14.9° and A1g mode at 313 cm-1. The annealed SnS2 exhibited clearly a layered structure confirmed by the high resolution transmission electron microscope (HRTEM) images. Back-gate FETs with SnS2 channel sandwiched by top and bottom ZrO2 on p++Si/SiO2 substrate were suggested to improve electrical characteristics. We used a bottom ZrO2 layer to increase adhesion between the channel and the substrate and a top ZrO2 layer to improve contact property, passivate surface, and protect from process-induced damages to the channel. ZTZ (ZrO2/SnS2/ZrO2) FETs showed improved electrical characteristics with an on/off ratio of from 0.39×103 to 6.39×103 and a mobility of from 0.0076 cm2/Vs to 0.06 cm2/Vs.

Fabrication of ceramic substrate-reinforced and free forms

NASA Technical Reports Server (NTRS)

Quentmeyer, R. J.; Mcdonald, G.; Hendricks, R. C.

1985-01-01

Components fabricated of, or coated with, ceramics have lower parasitic cooling requirements. Techniques are discussed for fabricating thin-shell ceramic components and ceramic coatings for applications in rocket or jet engine environments. Thin ceramic shells with complex geometric forms involving convolutions and reentrant surfaces were fabricated by mandrel removal. Mandrel removal was combined with electroplating or plasma spraying and isostatic pressing to form a metal support for the ceramic. Rocket engine thrust chambers coated with 0.08 mm (3 mil) of ZrO2-8Y2O3 had no failures and a tenfold increase in engine life. Some measured mechanical properties of the plasma-sprayed ceramic are presented.

Selection by current compliance of negative and positive bipolar resistive switching behaviour in ZrO2-x /ZrO2 bilayer memory

NASA Astrophysics Data System (ADS)

Huang, Ruomeng; Yan, Xingzhao; Morgan, Katrina A.; Charlton, Martin D. B.; (Kees de Groot, C. H.

2017-05-01

We report here a ZrO2-x /ZrO2-based bilayer resistive switching memory with unique properties that enables the selection of the switching mode by applying different electroforming current compliances. Two opposite polarity modes, positive bipolar and negative bipolar, correspond to the switching in the ZrO2 and ZrO2-x layer, respectively. The ZrO2 layer is proved to be responsible for the negative bipolar mode which is also observed in a ZrO2 single layer device. The oxygen deficient ZrO2-x layer plays the dominant role in the positive bipolar mode, which is exclusive to the bilayer memory. A systematic investigation of the ZrO2-x composition in the bilayer memory suggests that ZrO1.8 layer demonstrates optimum switching performance with low switching voltage, narrow switching voltage distribution and good cycling endurance. An excess of oxygen vacancies, beyond this composition, leads to a deterioration of switching properties. The formation and dissolution of the oxygen vacancy filament model has been proposed to explain both polarity switching behaviours and the improved properties in the bilayer positive bipolar mode are attributed to the confined oxygen vacancy filament size within the ZrO2-x layer.

Formation and reduction behaviors of zirconium oxide compounds in LiCl-Li2O melt at 923 K

NASA Astrophysics Data System (ADS)

Sakamura, Yoshiharu; Iizuka, Masatoshi; Kitawaki, Shinichi; Nakayoshi, Akira; Kofuji, Hirohide

2015-11-01

The reduction behaviors of ZrO2, Li2ZrO3 and (U,Pu,Zr)O2 in a LiCl-Li2O salt bath at 923 K were investigated. This study was conducted as part of a feasibility study on the pyrochemical treatment of damaged fuel debris generated by severe accidents at light water reactors. It was demonstrated in electrolytic reduction tests that the uranium in synthetic corium specimens of (U,Pu,Zr)O2 with various ZrO2 contents could be reduced to the metallic form and that part of the zirconium was converted to Li2ZrO3. Zirconium metal and Li2ZrO3 were obtained by the reduction of ZrO2. The reduction of Li2ZrO3 did not proceed even in LiCl containing no Li2O. Moreover, the stable chemical forms of the ZrO2-Li2O complex oxide were investigated as a function of the Li2O concentration in LiCl. ZrO2 was converted to Li2ZrO3 at a Li2O concentration of 0.018 wt%. As the Li2O concentration was increased, Li2ZrO3 was converted to Li6Zr2O7 and then to Li8ZrO6. It is suggested that the removal of Li2ZrO3 from the reduction product is a key point in the pyrochemical treatment of corium.

Facile biological synthetic strategy to morphologically aligned CeO2/ZrO2 core nanoparticles using Justicia adhatoda extract and ionic liquid: Enhancement of its bio-medical properties.

PubMed

Pandiyan, Nithya; Murugesan, Balaji; Sonamuthu, Jegatheeswaran; Samayanan, Selvam; Mahalingam, Sundrarajan

2018-01-01

In this study, a typical green synthesis route has approached for CeO 2 /ZrO 2 core metal oxide nanoparticles using ionic liquid mediated Justicia adhatoda extract. This synthesis method is carried out at simple room temperature condition to obtain the core metal oxide nanoparticles. XRD, SEM and TEM studies employed to study the crystalline and surface morphological properties under nucleation, growth, and aggregation processes. CeO 2 /ZrO 2 core metal oxides display agglomerated nano stick-like structure with 20-45nm size. GC-MS spectroscopy confirms the presence of vasicinone and N,N-Dimethylglycine present in the plant extract, which are capable of converting the corresponding metal ion precursor to CeO 2 /ZrO 2 core metal oxide nanoparticles. In FTIR, the corresponding stretching for Ce-O and Zr-O bands indicated at 498 and 416cm -1 and Raman spectroscopy also supports typical stretching frequencies at 463 and 160cm -1 . Band gap energy of the CeO 2 /ZrO 2 core metal oxide is 3.37eV calculated from UV- DRS spectroscopy. The anti-bacterial studies performed against a set of bacterial strains the result showed that core metal oxide nanoparticles more susceptible to gram-positive (G+) bacteria than gram-negative (G-) bacteria. A unique feature of the antioxidant behaviors core metal oxides reduces the concentration of DPPH radical up to 89%. The CeO 2 /ZrO 2 core metal oxide nanoparticles control the S. marcescent bio-film formation and restrict the quorum sensing. The toxicology behavior of CeO 2 /ZrO 2 core metal oxide NPs is found due to the high oxygen site vacancies, ROS formation, smallest particle size and higher surface area. This type of green synthesis route may efficient and the core metal oxide nanoparticles will possess a good bio-medical agent in future. Copyright © 2017 Elsevier B.V. All rights reserved.

Y-doped Li 8ZrO 6: A Li-Ion Battery Cathode Material with High Capacity

DOE PAGES

Huang, Shuping; Wilson, Benjamin E.; Wang, Bo; ...

2015-08-11

We study—experimentally and theoretically—the energetics, structural changes, and charge flows during the charging and discharging processes for a new high-capacity cathode material, Li 8ZrO 6 (LZO), which we study both pure and yttrium-doped. We quantum mechanically calculated the stable delithiated configurations, the delithiation energy, the charge flow during delithiation, and the stability of the delithiated materials. We find that Li atoms are easier to extract from tetrahedral sites than octahedral ones. We calculate a large average voltage of 4.04 eV vs Li/Li + for delithiation of the first Li atom in a primitive cell, which is confirmed by galvanostatic charge/dischargemore » cycling data. Energy calculations indicate that topotactic delithiation is kinetically favored over decomposition into Li, ZrO 2, and O 2 during the charging process, although the thermodynamic energy of the topotactic reaction is less favorable. When one or two lithium atoms are extracted from a primitive cell of LZO, its volume and structure change little, whereas extraction of the third lithium greatly distorts the layered structure. The Li 6ZrO 6 and Li 5ZrO 6 delithiation products can be thermodynamically metastable to release of O 2. Experimentally, materials with sufficiently small particle size for efficient delithiation and relithiation were achieved within an yttrium-doped LZO/carbon composite cathode that exhibited an initial discharge capacity of at least 200 mAh/g over the first 10 cycles, with 142 mAh/g maintained after 60 cycles. Computations predict that during the charging process, the oxygen ion near the Li vacancy is oxidized for both pure LZO and yttrium-doped LZO, which leads to a small-polaron hole.« less

Y-doped Li 8ZrO 6: A Li-Ion Battery Cathode Material with High Capacity

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

Huang, Shuping; Wilson, Benjamin E.; Wang, Bo

We study—experimentally and theoretically—the energetics, structural changes, and charge flows during the charging and discharging processes for a new high-capacity cathode material, Li 8ZrO 6 (LZO), which we study both pure and yttrium-doped. We quantum mechanically calculated the stable delithiated configurations, the delithiation energy, the charge flow during delithiation, and the stability of the delithiated materials. We find that Li atoms are easier to extract from tetrahedral sites than octahedral ones. We calculate a large average voltage of 4.04 eV vs Li/Li + for delithiation of the first Li atom in a primitive cell, which is confirmed by galvanostatic charge/dischargemore » cycling data. Energy calculations indicate that topotactic delithiation is kinetically favored over decomposition into Li, ZrO 2, and O 2 during the charging process, although the thermodynamic energy of the topotactic reaction is less favorable. When one or two lithium atoms are extracted from a primitive cell of LZO, its volume and structure change little, whereas extraction of the third lithium greatly distorts the layered structure. The Li 6ZrO 6 and Li 5ZrO 6 delithiation products can be thermodynamically metastable to release of O 2. Experimentally, materials with sufficiently small particle size for efficient delithiation and relithiation were achieved within an yttrium-doped LZO/carbon composite cathode that exhibited an initial discharge capacity of at least 200 mAh/g over the first 10 cycles, with 142 mAh/g maintained after 60 cycles. Computations predict that during the charging process, the oxygen ion near the Li vacancy is oxidized for both pure LZO and yttrium-doped LZO, which leads to a small-polaron hole.« less

Porous Ceramic Composite ZrO2(MgO)-MgO for Osteoimplantology

NASA Astrophysics Data System (ADS)

Buyakov, A. S.; Kulkov, S. N.

2017-02-01

Pore and crystalline structure, biocompatibility of ceramic composite ZrO2(MgO)-MgO were studied. The main mechanical characteristics were determined and it has been shown that compression strength directly depends on microstresses obtained from X-ray data. In-vitro studies of mesenchymal stromal stem cells (MMSC), cultivated on material surface are shown that cell proliferation and differentiation of MMSC goes throw osteogenic type.

From Zirconium Nanograins to Zirconia Nanoneedles

PubMed Central

Zalnezhad, E.; Hamouda, A. M. S.; Jaworski, J.; Do Kim, Young

2016-01-01

Combinations of three simple techniques were utilized to gradually form zirconia nanoneedles from zirconium nanograins. First, a physical vapor deposition magnetron sputtering technique was used to deposit pure zirconium nanograins on top of a substrate. Second, an anodic oxidation was applied to fabricate zirconia nanotubular arrays. Finally, heat treatment was used at different annealing temperatures in order to change the structure and morphology from nanotubes to nanowires and subsequently to nanoneedles in the presence of argon gas. The size of the pure zirconium nanograins was estimated to be approximately 200–300 nm. ZrO2 nanotubular arrays with diameters of 70–120 nm were obtained. Both tetragonal and monoclinic ZrO2 were observed after annealing at 450 °C and 650 °C. Only a few tetragonal peaks appeared at 850 °C, while monoclinic ZrO2 was obtained at 900 °C and 950 °C. In assessing the biocompatibility of the ZrO2 surface, the human cell line MDA-MB-231 was found to attach and proliferate well on surfaces annealed at 850 °C and 450 °C; however, the amorphous ZrO2 surface, which was not heat treated, did not permit extensive cell growth, presumably due to remaining fluoride. PMID:27623486

The preparation and characterization of optical thin films produced by ion-assisted deposition

NASA Astrophysics Data System (ADS)

Martin, P. J.; Netterfield, R. P.; Sainty, W. G.; Pacey, C. G.

1984-06-01

Ion-based deposition techniques have been successfully used to deposit compound films suitable for photothermal applications, as well as dielectric films with stable and reproducible optical properties. Thus, thin films of TiN, a-Si:H, and PbS have been obtained by ion-assisted deposition for photothermal solar-selective elements and similarly prepared dielectric layers of ZrO2, SiO2, and Al2O3 have been used as protective coatings on Ag and Al mirrors. It is shown that the technique of ion-assisted deposition affords control over the film density, microstructure, adhesion, composition, and optical properties. Details of the process and film properties are discussed.

Fatigue and retention in ferroelectric Y-Ba-Cu-O/Pb-Zr-Ti-O/Y-Ba-Cu-O heterostructures

NASA Astrophysics Data System (ADS)

Ramesh, R.; Chan, W. K.; Wilkens, B.; Gilchrist, H.; Sands, T.; Tarascon, J. M.; Keramidas, V. G.; Fork, D. K.; Lee, J.; Safari, A.

1992-09-01

Fatigue and retention characteristics of ferroelectric lead zirconate titanate thin films grown with Y-Ba-Cu-O(YBCO) thin-film top and bottom electrodes are found to be far superior to those obtained with conventional Pt top electrodes. The heterostructures reported here have been grown in situ by pulsed laser deposition on yttria-stabilized ZrO2 buffer [100] Si and on [001] LaAlO3. Both the a- and c-axis orientations of the YBCO lattice have been used as electrodes. They were prepared using suitable changes in growth conditions.

High Performance Crystalline Organic Transistors and Circuit

DTIC Science & Technology

2009-10-14

this material into pentacene -based OFETs, low voltage operation is possible. 3 Figure 1: Device structure for a low voltage pentacene OFET...issues with the first SiO Z OPentacene Au Pentacene ZrO2 AuPd SiO2 4 film. Bilayer dielectrics exhibit lower defect-related leakage...effects, as pinholes or other defects in one layer may be isolated by the other layer. 350 Å of pentacene was thermally evaporated on the ZrO2 dielectric

Lead zirconate titanate (PZT)-based thin film capacitors for embedded passive applications

NASA Astrophysics Data System (ADS)

Kim, Taeyun

Investigations on the key processing parameters and properties relationship for lead zirconate titanate (PZT, 52/48) based thin film capacitors for embedded passive capacitor application were performed using electroless Ni coated Cu foils as substrates. Undoped and Ca-doped PZT (52/48) thin film capacitors were prepared on electroless Ni coated Cu foil by chemical solution deposition. For PZT (52/48) thin film capacitors on electroless Ni coated Cu foil, voltage independent (zero tunability) capacitance behavior was observed. Dielectric constant reduced to more than half of the identical capacitor processed on Pt/SiO2/Si. Dielectric properties of the capacitors were mostly dependent on the crystallization temperature. Capacitance densities of almost 350 nF/cm2 and 0.02˜0.03 of loss tangent were routinely measured for capacitors crystallized at 575˜600°C. Leakage current showed dependence on film thickness and crystallization temperature. From a two-capacitor model, the existence of a low permittivity interface layer (permittivity ˜30) was suggested. For Ca-doped PZT (52/48) thin film capacitors prepared on Pt, typical ferroelectric and dielectric properties were measured up to 5 mol% Ca doping. When Ca-doped PZT (52/48) thin film capacitors were prepared on electroless Ni coated Cu foil, phase stability was influenced by Ca doping and phosphorous content. Dielectric properties showed dependence on the crystallization temperature and phosphorous content. Capacitance density of ˜400 nF/cm2 was achieved, which is an improvement by more than 30% compared to undoped composition. Ca doping also reduced the temperature coefficient of capacitance (TCC) less than 10%, all of them were consistent in satisfying the requirements of embedded passive capacitor. Leakage current density was not affected significantly by doping. To tailor the dielectric and reliability properties, ZrO2 was selected as buffer layer between PZT and electroless Ni. Only RF magnetron sputtering process could yield stable ZrO2 layers on electroless Ni coated Cu foil. Other processes resulted in secondary phase formation, which supports the reaction between PZT capacitor and electroless Ni might be dominated by phosphorous component. (Abstract shortened by UMI.)

Laser Damage in Thin Film Optical Coatings

DTIC Science & Technology

1992-07-01

10) using E- beam evaporation and laser tests performed to determine the effect of conditioning laser spot size and coating design on improvement in...1.06 pm) consisting of a 15 layer 3 quarter-wave design (HFO2/SiO 2 and ZrO2/SiO 2) were fabricated by E- beam evaporation. Sol-gel processing was used to... designers select laser damage resistant coatings for optical elements to be employed in military systems using lasers or encountering lasers used as

Good Biocompatibility and Sintering Properties of Zirconia Nanoparticles Synthesized via Vapor-phase Hydrolysis

PubMed Central

Wang, Jigang; Yin, Wenyan; He, Xiao; Wang, Qiang; Guo, Ming; Chen, Shaowei

2016-01-01

ZrO2 nanoparticles were synthesized by a vapor-phase hydrolysis process, and characterized in terms of crystalline structures, hardness and microstructures by X-ray diffraction, Vickers hardness test method, and atomic force microscopy (AFM) measurements. Moreover, in vitro cytotoxicity evaluation and hemolysis assay showed that the nanoparticles possessed good biocompatibility. Hardness investigations and AFM measurements indicated that both the sintering temperature and compression force played an important role in determining the physical behaviors (hardness, roughness and density) of flakes of the ZrO2 nanoparticles. When ZrO2 nanoparticles synthesized at 500 °C were pressed into flakes under 6 MPa and sintered at 1400 °C, the resulting flakes exhibited an optimal combination of hardness (534.58 gf·mm−2), roughness (0.07 μm) and density (4.41 g·cm−3). As the Vickers hardness value of human bones is of 315~535 gf·mm−2 and the density of adult femuris about 1.3~1.7 g·cm−3, the experimental results showed that the ZrO2 flakes were comparable to human bones with a higher density. As a result, the synthesized ZrO2 NPs may be useful for biomedical applications, especially for bone repair and replacement in future. PMID:27725744

Improved Epitaxy and Surface Morphology in YBa2Cu3Oy Thin Films Grown on Double Buffered Si Wafers

NASA Astrophysics Data System (ADS)

Gao, J.; Kang, L.; Wong, H. Y.; Cheung, Y. L.; Yang, J.

Highly epitaxial thin films of YBCO have been obtained on silicon wafers using a Eu2CuO4/YSZ (yttrium-stabilized ZrO2) double buffer. Our results showed that application of such a double buffer can significantly enhance the epitaxy of grown YBCO. It also leads to an excellent surface morphology. The average surface roughness was found less than 5 nm in a large range. The results of X-ray small angle reflection and positron spectroscpy demonstrate a very clear and flat interface between YBCO and buffer layers. The Eu2CuO4/YSZ double buffer could be promising for coating high-TC superconducting films on various reactive substrates.

Fabrication of ceramic substrate-reinforced and free forms by mandrel plasma spraying metal-ceramic composites

NASA Technical Reports Server (NTRS)

Quentmeyer, R. J.; Mcdonald, G.; Hendricks, R. C.

1985-01-01

Components fabricated of, or coated with, ceramics have lower parasitic cooling requirements. Techniques are discussed for fabricating thin-shell ceramic components and ceramic coatings for applications in rocket or jet engine environments. Thin ceramic shells with complex geometric forms involving convolutions and reentrant surfaces were fabricated by mandrel removal. Mandrel removal was combined with electroplating or plasma spraying and isostatic pressing to form a metal support for the ceramic. Rocket engine thrust chambers coated with 0.08 mm (3 mil) of ZrO2-8Y2O3 had no failures and a tenfold increase in engine life. Some measured mechanical properties of the plasma-sprayed ceramic are presented.

Strengthening and Strength Uniformity of Structural Ceramics

DTIC Science & Technology

1984-04-01

Center. Thousand Oaks, California 91360 APPENDIX III Alumina and M230,/ZrO2 (I to 10 vo1%) composite powders 1. Introductioni were mixed and conslidated...distribution for the A1O 3 . Different mixing the flocced slurries with deionized water, followed by magnifications were used for bimodal microstructures...2 with HCi, size of the A120 (A) and ZRO: (Z), mean size ratio of the two mixing together with ultrasonic treatment, and again floccing at phases

Interfacial interactions between Skeletonema costatum extracellular organic matter and metal oxides: Implications for ceramic membrane filtration.

PubMed

Zaouri, Noor; Gutierrez, Leonardo; Dramas, Laure; Garces, Daniel; Croue, Jean-Philippe

2017-06-01

In the current study, the interfacial interactions between the high molecular weight (HMW) compounds of Skeletonema costatum (SKC) extracellular organic matter (EOM) and ZrO 2 or Al 2 O 3 , were investigated by atomic force microscopy (AFM). HMW SKC-EOM was rigorously characterized and described as a hydrophilic organic compound mainly comprised of polysaccharide-like structures. Lipids and proteins were also observed, although in lower abundance. HMW SKC-EOM displayed attractive forces during approaching (i.e., leading to jump-to-contact events) and adhesion forces during retracting regime to both metal oxides at all solution conditions tested, where electrostatics and hydrogen bonding were suggested as dominant interacting mechanisms. However, the magnitude of these forces was significantly higher on ZrO 2 surfaces, irrespective of cation type (Na + or Ca 2+ ) or concentration. Interestingly, while HMW SKC-EOM interacting forces to Al 2 O 3 were practically insensitive to solution chemistry, the interactions between ZrO 2 and HMW SKC-EOM increased with increasing cation concentration in solution. The structure, and lower charge, hydrophilicity, and density of hydroxyl groups on ZrO 2 surface would play a key role on favoring zirconia associations with HMW SKC-EOM. The current results contribute to advance our fundamental understanding of Algogenic Organic Matter (AOM) interfacial interactions with metal oxides (i.e., AOM membrane fouling), and would highly assist in the proper selection of membrane material during episodic algal blooms. Copyright © 2017 Elsevier Ltd. All rights reserved.

Zirconia based dental ceramics: structure, mechanical properties, biocompatibility and applications.

PubMed

Gautam, Chandkiram; Joyner, Jarin; Gautam, Amarendra; Rao, Jitendra; Vajtai, Robert

2016-12-06

Zirconia (ZrO 2 ) based dental ceramics have been considered to be advantageous materials with adequate mechanical properties for the manufacturing of medical devices. Due to its very high compression strength of 2000 MPa, ZrO 2 can resist differing mechanical environments. During the crack propagation on the application of stress on the surface of ZrO 2 , a crystalline modification diminishes the propagation of cracks. In addition, zirconia's biocompatibility has been studied in vivo, leading to the observation of no adverse response upon the insertion of ZrO 2 samples into the bone or muscle. In vitro experimentation has exhibited the absence of mutations and good viability of cells cultured on this material leading to the use of ZrO 2 in the manufacturing of hip head prostheses. The mechanical properties of zirconia fixed partial dentures (FPDs) have proven to be superior to other ceramic/composite restorations and hence leading to their significant applications in implant supported rehabilitations. Recent developments were focused on the synthesis of zirconia based dental materials. More recently, zirconia has been introduced in prosthetic dentistry for the fabrication of crowns and fixed partial dentures in combination with computer aided design/computer aided manufacturing (CAD/CAM) techniques. This systematic review covers the results of past as well as recent scientific studies on the properties of zirconia based ceramics such as their specific compositions, microstructures, mechanical strength, biocompatibility and other applications in dentistry.

ZrO2-Nanoparticle-Modified Graphite Felt: Bifunctional Effects on Vanadium Flow Batteries.

PubMed

Zhou, Haipeng; Shen, Yi; Xi, Jingyu; Qiu, Xinping; Chen, Liquan

2016-06-22

To improve the electrochemical performance of graphite felt (GF) electrodes in vanadium flow batteries (VFBs), we synthesize a series of ZrO2-modified GF (ZrO2/GF) electrodes with varying ZrO2 contents via a facile immersion-precipitation approach. It is found that the uniform immobilization of ZrO2 nanoparticles on the GF not only significantly promotes the accessibility of vanadium electrolyte, but also provides more active sites for the redox reactions, thereby resulting in better electrochemical activity and reversibility toward the VO(2+)/VO2(+) and V(2+)/V(3+) redox reactions as compared with those of GF. In particular, The ZrO2/GF composite with 0.3 wt % ZrO2 displays the best electrochemical performance with voltage and energy efficiencies of 71.9% and 67.4%, respectively, which are much higher than those of 57.3% and 53.8% as obtained from the GF electrode at 200 mA cm(-2). The cycle life tests demonstrate that the ZrO2/GF electrodes exhibit outstanding stability. The ZrO2/GF-based VFB battery shows negligible activity decay after 200 cycles.

Templated electrochemical deposition of zirconia thin films on "recordable CDs.".

PubMed

Yu, Hua-Zhong; Rowe, Aaron W; Waugh, Damien M

2002-11-15

In this paper, we describe a practical method of using gold films constructed from recordable compact disks (CD-Rs) as simple, inexpensive, and micropatterned conductive substrates for the fabrication of inorganic material microstructures. Extending from their application for the fabrication of self-assembled monolayers (SAMs) reported recently, bare and SAM-modified CD-R gold substrates have been used for template-directed electrodeposition of zirconia (ZrO2) thin films (i.e., the controlled formation of zirconia thin films on the different areas of the prefabricated, micrometer mountain-valley CD-R gold substrate surfaces). The present results demonstrate that the variation of the functional groups of the selected SAMs combined with electrodynamic control can be very successful to "customize" the formation and microstructure of functional inorganic thin films, which hold promise for modern technological applications.

Direct nanopatterning of 100 nm metal oxide periodic structures by Deep-UV immersion lithography.

PubMed

Stehlin, Fabrice; Bourgin, Yannick; Spangenberg, Arnaud; Jourlin, Yves; Parriaux, Olivier; Reynaud, Stéphanie; Wieder, Fernand; Soppera, Olivier

2012-11-15

Deep-UV lithography using high-efficiency phase mask has been developed to print 100 nm period grating on sol-gel based thin layer. High efficiency phase mask has been designed to produce a high-contrast interferogram (periodic fringes) under water immersion conditions for 244 nm laser. The demonstration has been applied to a new developed immersion-compatible sol-gel layer. A sol-gel photoresist prepared from zirconium alkoxides caped with methacrylic acids was developed to achieve 50 nm resolution in a single step exposure. The nanostructures can be thermally annealed into ZrO(2). Such route considerably simplifies the process for elaborating nanopatterned surfaces of transition metal oxides, and opens new routes for integrating materials of interest for applications in the field of photocatalysis, photovoltaic, optics, photonics or microelectronics.

Facile Synthesis and Characterization of ZrO₂ Nanoparticles via Modified Co-Precipitation Method.

PubMed

Ramachandran, M; Subadevi, R; Liu, Wei-Ren; Sivakumar, M

2018-01-01

The crystalline Zirconium oxide (ZrO2) nano particles were synthesized using optimized content of Zirconium nitrate (Zr(NO3)2·3H2O) with varying KOH concentration (0.5, 1 and 1.5 M) by co-precipitation method. The thermal history of the precursor was carefully analyzed through Thermogravimetric (TG/DTA) measurement. The as prepared samples were characterized to ensure structural, functional, morphological, compositional, chemical composition and band gap by X-ray diffractometer (XRD), Fourier transform infrared spectroscopy (FTIR), Laser Raman, scanning electron microscopy (SEM), High resolution Transverse Electron Microscopy (HR-TEM), X-ray photo electron spectroscopy (XPS), EDX, Photo luminescence spectroscopy (PL). The monoclinic structure with space group P21/c has been confirmed from XRD (JCPDS 89-9066). The Zr-O stretching vibration and Zr-O2-Zr bending vibrations were confirmed through FTIR analysis. The well dispersed particles with spherical morphology were confirmed through SEM and TEM analysis. The oxidation states of Zr, O and C were confirmed through XPS analysis. The oxygen vacancies and band gap of the particles were investigated through PL analysis.

Mass-Mobility Characterization of Flame-made ZrO2 Aerosols: Primary Particle Diameter & Extent of Aggregation

PubMed Central

Eggersdorfer, M.L.; Gröhn, A.J.; Sorensen, C.M.; McMurry, P.H.; Pratsinis, S.E.

2013-01-01

Gas-borne nanoparticles undergoing coagulation and sintering form irregular or fractal-like structures affecting their transport, light scattering, effective surface area and density. Here, zirconia (ZrO2) nanoparticles are generated by scalable spray combustion, and their mobility diameter and mass are obtained nearly in-situ by differential mobility analyzer (DMA) and aerosol particle mass (APM) measurements. Using these data, the density of ZrO2 and a power law between mobility and primary particle diameters, the structure of fractal-like particles is determined (mass-mobility exponent, prefactor and average number and surface area mean diameter of primary particles, dva). The dva determined by DMA-APM measurements and this power law is in good agreement with the dva obtained by ex-situ nitrogen adsorption and microscopic analysis. Using this combination of measurements and above power law, the effect of flame spray process parameters (e.g. precursor solution and oxygen flow rate as well as zirconium concentration) on fractal-like particle structure characteristics is investigated in detail. This reveals that predominantly agglomerates (physically-bonded particles) and aggregates (chemically- or sinter-bonded particles) of nanoparticles are formed at low and high particle concentrations, respectively. PMID:22959835

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.

Ultrasonic Welding of Thin Alumina and Aluminum Using Inserts

NASA Astrophysics Data System (ADS)

Ishikuro, Tomoaki; Matsuoka, Shin-Ichi

This paper describes an experimental study of ultrasonic welding of thin ceramics and metals using inserts. Ultrasonic welding has enable the joining of various thick ceramics, such as Al2O3 and ZrO2, to aluminum at room temperature quickly and easily as compared to other welding methods. However, for thin ceramics, which are brittle, welding is difficult to perform without causing damage. In this study, aluminum anodized oxide with different anodizing time was used as thin alumina ceramic. Vapor deposition of aluminum alloys was used to create an effective binder layer for welding at a low pressure and within a short duration in order to prevent damage to the anodic oxide film formed with a short anodizing time. For example, ultrasonic welding of thin Al2O3/Al was accomplished under the following conditions: ultrasonic horn tip amplitude of 30µm, welding pressure of 5MPa, and required duration of 0.1s. However, since the vapor deposition film tends to exfoliate as observed in the anodic oxide film formed with a long anodizing time, welding was difficult.

Development of quantitative laser ionization mass spectrometry (LIMS). Final report, 1 Aug 87-1 Jan 90

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

Odom, R.W.

1991-06-04

The objective of the research was to develop quantitative microanalysis methods for dielectric thin films using the laser ionization mass spectrometry (LIMS) technique. The research involved preparation of thin (5,000 A) films of SiO2, Al2O3, MgF2, TiO2, Cr2O3, Ta2O5, Si3N4, and ZrO2, and doping these films with ion implant impurities of 11B, 40Ca, 56Fe, 68Zn, 81Br, and 121Sb. Laser ionization mass spectrometry (LIMS), secondary ion mass spectrometry (SIMS) and Rutherford backscattering spectrometry (RBS) were performed on these films. The research demonstrated quantitative LIMS analysis down to detection levels of 10-100 ppm, and led to the development of (1) a compoundmore » thin film standards product line for the performing organization, (2) routine LIMS analytical methods, and (3) the manufacture of high speed preamplifiers for time-of-flight mass spectrometry (TOF-MS) techniques.« less

A scaling law for distinct electrocaloric cooling performance in low-dimensional organic, relaxor and anti-ferroelectrics.

PubMed

Shi, Yuping; Huang, Limin; Soh, Ai Kah; Weng, George J; Liu, Shuangyi; Redfern, Simon A T

2017-09-11

Electrocaloric (EC) materials show promise in eco-friendly solid-state refrigeration and integrable on-chip thermal management. While direct measurement of EC thin-films still remains challenging, a generic theoretical framework for quantifying the cooling properties of rich EC materials including normal-, relaxor-, organic- and anti-ferroelectrics is imperative for exploiting new flexible and room-temperature cooling alternatives. Here, we present a versatile theory that combines Master equation with Maxwell relations and analytically relates the macroscopic cooling responses in EC materials with the intrinsic diffuseness of phase transitions and correlation characteristics. Under increased electric fields, both EC entropy and adiabatic temperature changes increase quadratically initially, followed by further linear growth and eventual gradual saturation. The upper bound of entropy change (∆S max ) is limited by distinct correlation volumes (V cr ) and transition diffuseness. The linearity between V cr and the transition diffuseness is emphasized, while ∆S max  = 300 kJ/(K.m 3 ) is obtained for Pb 0.8 Ba 0.2 ZrO 3 . The ∆S max in antiferroelectric Pb 0.95 Zr 0.05 TiO 3 , Pb 0.8 Ba 0.2 ZrO 3 and polymeric ferroelectrics scales proportionally with V cr -2.2 , owing to the one-dimensional structural constraint on lattice-scale depolarization dynamics; whereas ∆S max in relaxor and normal ferroelectrics scales as ∆S max ~ V cr -0.37 , which tallies with a dipolar interaction exponent of 2/3 in EC materials and the well-proven fractional dimensionality of 2.5 for ferroelectric domain walls.

Adsorption of Anionic, Cationic and Nonionic Surfactants on Carbonate Rock in Presence of ZrO 2 Nanoparticles

NASA Astrophysics Data System (ADS)

Esmaeilzadeh, Pouriya; Bahramian, Alireza; Fakhroueian, Zahra

The adsorption of surfactants at the solid-water interface is important for the control of wetting, lubrication, detergency and in mineral flotation.We have studied the adsorptions of different types of surfactants, cationic (Dodecyl trimethylammonium bromide, DTAB), anionic (sodium dodecyl sulfate, SDS) and non-anionic (lauryl alcohol-7 mole ethoxylate, LA7) on carbonate rock in presence of zirconium oxide spherical nanoparticles (17-19 nm). ZrO2 nanoparticles with tetrahedral structure have significant effect on adsorption of surfactants on the carbonate rock. We have used the measured conductivities to determine the rate of adsorption of surfactants at rock-water interfaces. The conductivity of DTAB in aqueous solutions containing calcite powder decreases more than the other surfactants in contact with ZrO2 nanoparticles. We have also investigated the adsorption of surfactants at the air-water interface. The presence of nanoparticles, as demonstrated by our experiments, enhances the surface activity and surface adsorption of the surfactants through electrostatic forces or formation of nanostructures. Dynamic light structuring data shows similar aggregation number of nanoparticles in presence of nanoparticles.

Synthesis of Zr2WP2O12/ZrO2 Composites with Adjustable Thermal Expansion.

PubMed

Zhang, Zhiping; Sun, Weikang; Liu, Hongfei; Xie, Guanhua; Chen, Xiaobing; Zeng, Xianghua

2017-01-01

Zr 2 WP 2 O 12 /ZrO 2 composites were fabricated by solid state reaction with the goal of tailoring the thermal expansion coefficient. XRD, SEM and TMA were used to investigate the composition, microstructure, and thermal expansion behavior of Zr 2 WP 2 O 12 /ZrO 2 composites with different mass ratio. Relative densities of all the resulting Zr 2 WP 2 O 12 /ZrO 2 samples were also tested by Archimedes' methods. The obtained Zr 2 WP 2 O 12 /ZrO 2 composites were comprised of orthorhombic Zr 2 WP 2 O 12 and monoclinic ZrO 2 . As the increase of the Zr 2 WP 2 O 12 , the relative densities of Zr 2 WP 2 O 12 /ZrO 2 ceramic composites increased gradually. The coefficient of thermal expansion of the Zr 2 WP 2 O 12 /ZrO 2 composites can be tailored from 4.1 × 10 -6 K -1 to -3.3 × 10 -6 K -1 by changing the content of Zr 2 WP 2 O 12 . The 2:1 Zr 2 WP 2 O 12 /ZrO 2 specimen shows close to zero thermal expansion from 25 to 700°C with an average linear thermal expansion coefficient of -0.09 × 10 -6 K -1 . These adjustable and near zero expansion ceramic composites will have great potential application in many fields.

Protein Adsorption to Titanium and Zirconia Using a Quartz Crystal Microbalance Method

PubMed Central

Kusakawa, You

2017-01-01

Protein adsorption onto titanium (Ti) or zirconia (ZrO2) was evaluated using a 27 MHz quartz crystal microbalance (QCM). As proteins, fibronectin (Fn), a cell adhesive protein, and albumin (Alb), a cell adhesion-inhibiting protein, were evaluated. The Ti and ZrO2 sensors for QCM were characterized by atomic force microscopy and electron probe microanalysis observation, measurement of contact angle against water, and surface roughness. The amounts of Fn and Alb adsorbed onto the Ti and ZrO2 sensors and apparent reaction rate were obtained using QCM measurements. Ti sensor showed greater adsorption of Fn and Alb than the ZrO2 sensor. In addition, amount of Fn adsorbed onto the Ti or ZrO2 sensors was higher than that of Alb. The surface roughness and hydrophilicity of Ti or ZrO2 may influence the adsorption of Fn or Alb. With regard to the adsorption rate, Alb adsorbed more rapidly than Fn onto Ti. Comparing Ti and ZrO2, Alb adsorption rate to Ti was faster than that to ZrO2. Fn adsorption will be effective for cell activities, but Alb adsorption will not. QCM method could simulate in vivo Fn and Alb adsorption to Ti or ZrO2. PMID:28246591

Resistive and Capacitive Memory Effects in Oxide Insulator/ Oxide Conductor Hetero-Structures

NASA Astrophysics Data System (ADS)

Meyer, Rene; Miao, Maosheng; Wu, Jian; Chevallier, Christophe

2013-03-01

We report resistive and capacitive memory effects observed in oxide insulator/ oxide conductor hetero-structures. Electronic transport properties of Pt/ZrO2/PCMO/Pt structures with ZrO2 thicknesses ranging from 20A to 40A are studied before and after applying short voltage pulses of positive and negative polarity for set and reset operation. As processed devices display a non-linear IV characteristic which we attribute to trap assisted tunneling through the ZrO2 tunnel oxide. Current scaling with electrode area and tunnel oxide thickness confirms uniform conduction. The set/reset operation cause an up/down shift of the IV characteristic indicating that the conduction mechanism of both states is still dominated by tunneling. A change in the resistance is associated with a capacitance change of the device. An exponential relation between program voltages and set times is found. A model based on electric field mediated non-linear transport of oxygen ions across the ZrO2/PCMO interface is proposed. The change in the tunnel current is explained by ionic charge transfer between tunnel oxide and conductive metal oxide changing both tunnel barrier height and PCMO conductivity. DFT techniques are employed to explain the conductivity change in the PCMO interfacial layer observed through capacitance measurements.

Spray‐Dried Sodium Zirconate: A Rapid Absorption Powder for CO2 Capture with Enhanced Cyclic Stability

PubMed Central

Bamiduro, Faith; Ji, Guozhao; Brown, Andy P.; Dupont, Valerie A.

2017-01-01

Abstract Improved powders for capturing CO2 at high temperatures are required for H2 production using sorption‐enhanced steam reforming. Here, we examine the relationship between particle structure and carbonation rate for two types of Na2ZrO3 powders. Hollow spray‐dried microgranules with a wall thickness of 100–300 nm corresponding to the dimensions of the primary acetate‐derived particles gave about 75 wt % theoretical CO2 conversion after a process‐relevant 5 min exposure to 15 vol % CO2. A conventional powder prepared by solid‐state reaction carbonated more slowly, achieving only 50 % conversion owing to a greater proportion of the reaction requiring bulk diffusion through the densely agglomerated particles. The hollow granular structure of the spray‐dried powder was retained postcarbonation but chemical segregation resulted in islands of an amorphous Na‐rich phase (Na2CO3) within a crystalline ZrO2 particle matrix. Despite this phase separation, the reverse reaction to re‐form Na2ZrO3 could be achieved by heating each powder to 900 °C in N2 (no dwell time). This resulted in a very stable multicycle performance in 40 cycle tests using thermogravimetric analysis for both powders. Kinetic analysis of thermogravimetric data showed the carbonation process fits an Avrami–Erofeyev 2 D nucleation and nuclei growth model, consistent with microstructural evidence of a surface‐driven transformation. Thus, we demonstrate that spray drying is a viable processing route to enhance the carbon capture performance of Na2ZrO3 powder. PMID:28371521

Improved Tribological Performance of Amorphous Carbon (a-C) Coating by ZrO2 Nanoparticles

PubMed Central

Tang, Jinzhu; Ding, Qi; Zhang, Songwei; Wu, Guizhi; Hu, Litian

2016-01-01

Nanomaterials, such as Graphene, h-BN nanoparticles and MoS2 nanotubes, have shown their ability in improving the tribological performance of amorphous carbon (a-C) coatings. In the current study, the effectiveness of ZrO2 nanoparticles (ZrO2-NPs) in lubricating the self-mated nonhydrogenated a-C contacts was investigated in boundary lubrication regime. The results showed that 13% less friction and 50% less wear compared to the base oil were achieved by employing ZrO2-NPs in the base oil in self-mated a-C contacts. Via analyzing the ZrO2-NPs and the worn a-C surface after tests, it was found that the improved lubrication by ZrO2-NPs was based on “polishing effects”, which is a new phenomenon observed between a-C and nanoparticles. Under the “polishing effect”, micro-plateaus with extremely smooth surface and uniform height were produced on the analyzed a-C surface. The resulting topography of the a-C coating is suitable for ZrO2-NPs to act as nano-bearings between rubbing surfaces. Especially, the ZrO2-NPs exhibited excellent mechanical and chemical stability, even under the severe service condition, suggesting that the combination of nonhydrogenated a-C coating with ZrO2-NPs is an effective, long lasting and environment-friendly lubrication solution. PMID:28773916

Tailoring properties of lossy-mode resonance optical fiber sensors with atomic layer deposition technique

NASA Astrophysics Data System (ADS)

Kosiel, Kamil; Koba, Marcin; Masiewicz, Marcin; Śmietana, Mateusz

2018-06-01

The paper shows application of atomic layer deposition (ALD) technique as a tool for tailoring sensorial properties of lossy-mode-resonance (LMR)-based optical fiber sensors. Hafnium dioxide (HfO2), zirconium dioxide (ZrO2), and tantalum oxide (TaxOy), as high-refractive-index dielectrics that are particularly convenient for LMR-sensor fabrication, were deposited by low-temperature (100 °C) ALD ensuring safe conditions for thermally vulnerable fibers. Applicability of HfO2 and ZrO2 overlays, deposited with ALD-related atomic level thickness accuracy for fabrication of LMR-sensors with controlled sensorial properties was presented. Additionally, for the first time according to our best knowledge, the double-layer overlay composed of two different materials - silicon nitride (SixNy) and TaxOy - is presented for the LMR fiber sensors. The thin films of such overlay were deposited by two different techniques - PECVD (the SixNy) and ALD (the TaxOy). Such approach ensures fast overlay fabrication and at the same time facility for resonant wavelength tuning, yielding devices with satisfactory sensorial properties.

Effect of annealing temperature on microstructural evolution and electrical properties of sol-gel processed ZrO2/Si films

NASA Astrophysics Data System (ADS)

Hwang, Soo Min; Lee, Seung Muk; Park, Kyung; Lee, Myung Soo; Joo, Jinho; Lim, Jun Hyung; Kim, Hyoungsub; Yoon, Jae Jin; Kim, Young Dong

2011-01-01

High-permittivity (k) ZrO2/Si(100) films were fabricated by a sol-gel technique and the microstructural evolution with the annealing temperature (Ta) was correlated with the variation of their electrical performance. With increasing Ta, the ZrO2 films crystallized into a tetragonal (t) phase which was maintained until 700 °C at nanoscale thicknesses. Although the formation of the t-ZrO2 phase obviously enhanced the k value of the ZrO2 dielectric layer, the maximum capacitance in accumulation was decreased by the growth of a low-k interfacial layer (IL) between ZrO2 and Si with increasing Ta. On the other hand, the gate leakage current was remarkably depressed with increasing Ta probably due to the combined effects of the increased IL thickness, optical band gap of ZrO2, and density of ZrO2 and decreased remnant organic components.

Modeling of methanol decomposition on Pt/CeO2/ZrO2 catalyst in a packed bed microreactor

NASA Astrophysics Data System (ADS)

Pohar, Andrej; Belavič, Darko; Dolanc, Gregor; Hočevar, Stanko

2014-06-01

Methanol decomposition on Pt/CeO2/ZrO2 catalyst is studied inside a packed bed microreactor in the temperature range of 300-380 °C. The microreactor is fabricated using low-temperature co-fired ceramic (LTCC) technology, which is well suited for the production of relatively complex three-dimensional structures. It is packed with 2 wt% Pt-CeO2 catalyst, which is deposited onto ZrO2 spherical particles. A 1D mathematical model, which incorporates diffusion, convection and mass transfer through the boundary layer to the catalyst particles, as well as a 3D computational fluid dynamics model, are developed to describe the methanol decomposition process inside the packed bed. The microreactor exhibits reliable operation and no catalyst deactivation was observed during three months of experimentation. A comparison between the 1D mathematical model and the 3D model, considering the full 3D geometry of the microreactor is made and the differences between the models are identified and evaluated.

Chitosan /Zeolite Y/Nano ZrO2 nanocomposite as an adsorbent for the removal of nitrate from the aqueous solution.

PubMed

Teimouri, Abbas; Nasab, Shima Ghanavati; Vahdatpoor, Niaz; Habibollahi, Saeed; Salavati, Hossein; Chermahini, Alireza Najafi

2016-12-01

In the present study, a series of chitosan/Zeolite Y/Nano Zirconium oxide (CTS/ZY/Nano ZrO 2 ) nanocomposites were made by controlling the molar ratio of chitosan (CTS) to Zeolite Y/Nano Zirconium oxide in order to remove nitrate (NO 3 - ) ions in the aqueous solution. The nanocomposite adsorbents were characterized by XRD, FTIR, BET, SEM and TEM. The influence of different molar ratios of CTS to ZY/Nano ZrO 2 , the initial pH value of the nitrate solution, contact time, temperature, the initial concentration of nitrate and adsorbent dose was studied. The adsorption isotherms and kinetics were also analyzed. It was attempted to describe the sorption processes by the Langmuir equation and the theoretical adsorption capacity (Q 0 ) was found to be 23.58mg nitrate per g of the adsorbent. The optimal conditions for nitrate removal were found to be: molar ratio of CTS/ZY/Nano ZrO 2 : 5:1; pH: 3; 0.02g of adsorbent and temperature: 35°C, for 60min. The adsorption capacities of CTS, ZY, Nano ZrO 2 , CTS/Nano ZrO 2 , CTS/ZY and CTS/ZY/Nano ZrO 2 nanocomposites for nitrate removal were compared, showing that the adsorption ability of CTS/ZY/Nano ZrO 2 nanocomposite was higher than the average values of those of CTS (1.95mg/g for nitrate removal), ZY, Nano ZrO 2 , CTS/Nano ZrO 2, and CTS/ZY. Copyright © 2016. Published by Elsevier B.V.

Improved WO3 photocatalytic efficiency using ZrO2 and Ru for the degradation of carbofuran and ampicillin.

PubMed

Gar Alalm, Mohamed; Ookawara, Shinichi; Fukushi, Daisuke; Sato, Akira; Tawfik, Ahmed

2016-01-25

The photocatalytic degradation of carbofuran (pesticide) and ampicillin (pharmaceutical) using synthesized WO3/ZrO2 nanoparticles under simulated solar light was investigated. Transmission electron microscopy (TEM), X-ray diffraction (XRD), and Raman spectra analyses were used to characterize the prepared catalysts. The optimum ratio of WO3 to ZrO2 was determined to be 1:1 for the degradation of both contaminants. The degradation of carbofuran and ampicillin by WO3/ZrO2 after 240 min of irradiation was 100% and 96%, respectively. Ruthenium (Ru) was employed as an additive to WO3/ZrO2 to enhance the photocatalytic degradation rate. Ru/WO3/ZrO2 exhibited faster degradation rates than WO3/ZrO2. Furthermore, 100% and 97% degradation of carbofuran and ampicillin, respectively, was achieved using Ru/WO3/ZrO2 after 180 min of irradiation. The durability of the catalyst was investigated by reusing the same suspended catalyst, which achieved 92% of its initial efficiency. The photocatalytic degradation of ampicillin and carbofuran followed pseudo-first order kinetics according to the Langmuir-Hinshelwood model. Copyright © 2015 Elsevier B.V. All rights reserved.

Ultraviolet-assisted direct patterning and low-temperature formation of flexible ZrO2 resistive switching arrays on PET/ITO substrates

NASA Astrophysics Data System (ADS)

Li, Lingwei; Chen, Yuanqing; Yin, Xiaoru; Song, Yang; Li, Na; Niu, Jinfen; Wu, Huimin; Qu, Wenwen

2017-12-01

We demonstrate a low-cost and facile photochemical solution method to prepare the ZrO2 resistive switching arrays as memristive units on flexible PET/ITO substrates. ZrO2 solution sensitive to UV light of 337 nm was synthesized using zirconium n-butyl alcohol as the precursor, and benzoylacetone as the complexing agent. After the dip-coated ZrO2 gel films were irradiated through a mask under the UV lamp (with wavelength of 325-365 nm) at room temperature and rinsed in ethanol, the ZrO2 gel arrays were obtained on PET/ITO substrates. Subsequently, the ZrO2 gel arrays were irradiated by deep UV light of 254 and 185 nm at 150 °C, resulting in the amorphous ZrO2 memristive micro-arrays. The ZrO2 units on flexible PET/ITO substrates exhibited excellent memristive properties. A high ratio of 104 of on-state and off-state resistance was obtained. The resistive switching behavior of the flexible device remained stable after being bent for 103 times. The device showed stable flexibility up to a minimum bending diameter of 1.25 cm.

Synthesis of zirconia (ZrO2) nanowires via chemical vapor deposition

NASA Astrophysics Data System (ADS)

Baek, M. K.; Park, S. J.; Choi, D. J.

2017-02-01

Monoclinic zirconia nanowires were synthesized by chemical vapor deposition using ZrCl4 powder as a starting material at 1200 °C and 760 Torr. Graphite was employed as a substrate, and an Au thin film was pre-deposited on the graphite as a catalyst. The zirconia nanostructure morphology was observed through scanning electron microscopy and transmission electron microscopy. Based on X-ray diffraction, selected area electron diffraction, and Raman spectroscopy data, the resulting crystal structure was found to be single crystalline monoclinic zirconia. The homogeneous distributions of Zr, O and Au were studied by scanning transmission electron microscopy with energy dispersive X-ray spectroscopy mapping, and there was no metal droplet at the nanowire tips despite the use of an Au metal catalyst. This result is apart from that of conventional metal catalyzed nanowires.

High-yield sol-gel synthesis of well-dispersed, colorless ZrO(2) nanocrystals.

PubMed

Mizuno, Mikihisa; Sasaki, Yuichi; Lee, Sungkil; Katakura, Hitoshi

2006-08-15

A 93% high-yield synthesis of well-dispersed, colorless zirconium dioxide (ZrO(2)) nanocrystals is reported. In this synthesis, hydrolysis and condensation reactions of zirconium(IV) tert-butoxide in the presence of oleic acid (100 degrees C) formed ZrO(2) precursors. The ZrO(2) precursors were made of -Zr-O-Zr- networks surrounded by oleic acid molecules. Annealing (280 degrees C) the precursors dispersed in dioctyl ether caused crystallization of the -Zr-O-Zr- networks, thereby generating 4 nm ZrO(2) nanocrystals stabilized with oleic acid. The particles were highly crystalline and tetragonal phase. A dense ZrO(2) nanocrystal dispersion in toluene (280 mg/mL) showed a transmittance of about 90% (3 mm optical path length) in the whole visible region.

A high performance transparent resistive switching memory made from ZrO2/AlON bilayer structure

NASA Astrophysics Data System (ADS)

Tsai, Tsung-Ling; Chang, Hsiang-Yu; Lou, Jesse Jen-Chung; Tseng, Tseung-Yuen

2016-04-01

In this study, the switching properties of an indium tin oxide (ITO)/zirconium oxide (ZrO2)/ITO single layer device and those of a device with an aluminum oxynitride (AlON) layer were investigated. The devices with highly transparent characteristics were fabricated. Compared with the ITO/ZrO2/ITO single layer device, the ITO/ZrO2/AlON/ITO bilayer device exhibited a larger ON/OFF ratio, higher endurance performance, and superior retention properties by using a simple two-step forming process. These substantial improvements in the resistive switching properties were attributed to the minimized influence of oxygen migration through the ITO top electrode (TE), which can be realized by forming an asymmetrical conductive filament with the weakest part at the ZrO2/AlON interface. Therefore, in the ITO/ZrO2/AlON/ITO bilayer device, the regions where conductive filament formation and rupture occur can be effectively moved from the TE interface to the interior of the device.

Ceramic Spheres From Cation Exchange Beads

NASA Technical Reports Server (NTRS)

Dynys, F. W.

2003-01-01

Porous ZrO2 and hollow TiO2 spheres were synthesized from a strong acid cation exchange resin. Spherical cation exchange beads, polystyrene based polymer, were used as a morphological-directing template. Aqueous ion exchange reaction was used to chemically bind (ZrO)(2+) ions to the polystyrene structure. The pyrolysis of the polystyrene at 600 C produces porous ZrO2 spheres with a surface area of 24 sq m/g with a mean sphere size of 42 microns. Hollow TiO2 spheres were synthesized by using the beads as a micro-reactor. A direct surface reaction - between titanium isopropoxide and the resin beads forms a hydrous TiO2 shell around the polystyrene core. The pyrolysis of the polystyrene core at 600 C produces hollow anatase spheres with a surface area of 42 sq m/g with a mean sphere size of 38 microns. The formation of ceramic spheres was studied by XRD, SEM and B.E.T. nitrogen adsorption measurements.

Analysis of protein phosphorylation by monolithic extraction columns based on poly(divinylbenzene) containing embedded titanium dioxide and zirconium dioxide nano-powders.

PubMed

Rainer, Matthias; Sonderegger, Harald; Bakry, Rania; Huck, Christian W; Morandell, Sandra; Huber, Lukas A; Gjerde, Douglas T; Bonn, Günther K

2008-11-01

The potential of an organic monolith with incorporated titanium dioxide (TiO(2)) and zirconium dioxide (ZrO(2)) nanoparticles was evaluated for the selective enrichment of phosphorylated peptides from tryptic digests. A pipette tip was fitted with a monolith based on divinylbenzene (DVB) of highly porous structure, which allows sample to pass through the monolithic bed. The enrichment of phosphopeptides was enhanced by increasing the pipetting cycles during the sample preparation and a higher recovery could be achieved with adequate buffer systems. A complete automated process was developed for enrichment of phosphopeptides leading to high reproducibility and resulting in a robust method designed to minimize analytical variance while providing high sensitivity at high sample throughput. The effect of particle size on the selectivity of phosphopeptides was investigated by comparative studies with nano- and microscale TiO(2) and ZrO(2) powders. Eleven phosphopeptides from alpha-casein digest could be recovered by an optimized mixture of microscale TiO(2)/ZrO(2) particles, whereas nine additional phosphopeptides could be retained by the same mixture of nano-structured material. When compared to conventional immobilized metal-ion affinity chromatography and commercial phosphorylation-enrichment kits, higher selectivity was observed in case of self fabricated tips. About 20 phosphopeptides could be retained from alpha-casein and five from beta-casein digests by using TiO(2) and ZrO(2) based extraction tips. Further selectivity for phosphopeptides was demonstrated by enriching a digest of in vitro phosphorylated extracellular signal regulated kinase 1 (ERK1). Two phosphorylated peptides of ERK1 could be identified by MALDI-MS/MS measurements and a following MASCOT database search.

Laser ablated high T(sub c) superconducting thin YBa2Cu3O(7-x) films on substrates suitable for microwave applications

NASA Astrophysics Data System (ADS)

Warner, J. D.; Meola, J. E.; Jenkins, K. A.; Bhasin, K. B.

1990-04-01

The development of high temperature superconducting YBa2Cu3O(7-x) thin films on substrates suitable for microwave applications is of great interest for evaluating their applications for space radar, communication, and sensor systems. Thin films of YBa2Cu3O(7-x) were formed on SrTiO3, ZrO2, MgO, and LaAlO3 substrates by laser ablation. The wavelength used was 248 nm from a KrF excimer laser. During deposition the films were heated to 600 C in a flowing oxygen environment, and required no post annealing. The low substrate temperature during deposition with no post annealing gave films which were smooth, which had their c-axis aligned to the substrates, and which had grains ranging from 0.2 to 0.5 microns in size. The films being c-axis aligned gave excellent surface resistance at 35 GHz which was lower than that of copper at 77 K. At present, LaAlO3 substrates with a dielectric constant of 22, appears suitable as a substrate for microwave and electronic applications. The films were characterized by resistance-temperature measurements, scanning electron microscopy, and x ray diffraction. The highest critical transition temperatures (T sub c) are above 89 K for films on SrTiO3 and LaAlO3, above 88 K for ZrO2, and above 86 K for MgO. The critical current density (J sub c) of the films on SrTiO3 is above 2 x 10(exp 6) amperes/sq cm at 77 K. The T(sub c) and J(sub c) are reported as a function of laser power, composition of the substrate, and temperature of the substrate during deposition.

Impact of the oxygen defects and the hydrogen concentration on the surface of tetragonal and monoclinic ZrO2 on the reduction rates of stearic acid on Ni/ZrO2

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

Foraita, Sebastian D.; Fulton, John L.; Chase, Zizwe A.

2015-02-02

The effect of the physicochemical properties of ZrO2 phases on the activity of Ni/ZrO2 catalysts for hydrodeoxygenation of stearic acid are described. A synergistic interaction between Ni and ZrO2 support was found. The effect is greatest for the monoclinic phase of ZrO2.

Density functional theory calculations of the water interactions with ZrO2 nanoparticles Y2O3 doped

NASA Astrophysics Data System (ADS)

Subhoni, Mekhrdod; Kholmurodov, Kholmirzo; Doroshkevich, Aleksandr; Asgerov, Elmar; Yamamoto, Tomoyuki; Lyubchyk, Andrei; Almasan, Valer; Madadzada, Afag

2018-03-01

Development of a new electricity generation techniques is one of the most relevant tasks, especially nowadays under conditions of extreme growth in energy consumption. The exothermic heterogeneous electrochemical energy conversion to the electric energy through interaction of the ZrO2 based nanopowder system with atmospheric moisture is one of the ways of electric energy obtaining. The questions of conversion into the electric form of the energy of water molecules adsorption in 3 mol% Y2O3 doped ZrO2 nanopowder systems were investigated using the density functional theory calculations. The density functional theory calculations has been realized as in the Kohn-Sham formulation, where the exchange-correlation potential is approximated by a functional of the electronic density. The electronic density, total energy and band structure calculations are carried out using the all-electron, full potential, linear augmented plane wave method of the electronic density and related approximations, i.e. the local density, the generalized gradient and their hybrid approximations.

Effects of milling media on the fabrication of melt-derived bioactive glass powder for biomaterial application

NASA Astrophysics Data System (ADS)

Ibrahim, Nurul Farhana; Mohamad, Hasmaliza; Noor, Siti Noor Fazliah Mohd

2016-12-01

The present work aims to study the effects of using different milling media on bioactive glass produced through melt-derived method for biomaterial application. The bioactive glass powder based on SiO2-CaO-Na2O-P2O5 system was fabricated using two different types of milling media which are tungsten carbide (WC) and zirconia (ZrO2) balls. However, in this work, no P2O5 was added in the new composition. XRF analysis indicated that tungsten trioxide (WO3) was observed in glass powder milled using WC balls whereas ZrO2 was observed in glass powder milled using ZrO2 balls. Amorphous structure was detected with no crystalline peak observed through XRD analysis for both glass powders. FTIR analysis confirmed the formation of silica network with the existence of functional groups Si-O-Si (bend), Si-O-Si (tetrahedral) and Si-O-Si (stretch) for both glass powders. The results revealed that there was no significant effect of milling media on amorphous silica network glass structure which shows that WC and zirconia can be used as milling media for bioactive glass fabrication without any contamination. Therefore, the fabricated BG can be tested safely for bioactivity assessment in biological fluids environment.

Thermoluminescence (TL) of europium-doped ZrO2 obtained by sol-gel method

NASA Astrophysics Data System (ADS)

Rivera, T.; Furetta, C.; Azorín, J.; Barrera, M.; Soto, A. M.

This article reports the preparation and characterization of europium-doped zirconium oxide (ZrO2:Eu3+) formed by homogeneous precipitation from propoxyde of zirconium [Zr(OC3H7)4]. The alkoxide sol gel process is an efficient method to prepare the zirconium oxide matrix by the hydrolysis of alkoxide precursors followed by condensation to yield a polymeric oxo-bridged ZrO2 network. All compounds were characterized by thermal analysis and the X-ray diffractometry method. The thermoluminescence (TL) emission properties of ZrO2:Eu3+ under beta radiation effects are studied. The europium-doped sintered zirconia powder presents a TL glow curve with two peaks (Tmax) centered at around 204 and around 292 °C, respectively. TL response of ZrO2:Eu3+ as a function of beta-absorbed dose was linear from 2 Gy up to 90 Gy. The europium ion (Eu3+)-doped ZrO2 was found to be more sensitive to beta radiation than undoped ZrO2 obtained by the same method and presented a little fading of the TL signal compared with undoped zirconium oxide.

Developing porous ceramics on the base of zirconia oxide with thin and permeable pores by crystallization of organic additive method

NASA Astrophysics Data System (ADS)

Kamyshnaya, K. S.; Khabas, T. A.

2016-11-01

In this paper porous ceramics on the base of ZrO2 nanopowders and micropowders has been developed by freeze-casting method. A zirconia/carbamide slurry was frozen in mold and dehydrated in CaCl2 at room temperature. This simple process enabled the formation of porous ceramics with highly aligned pores as a replica of the carbamide crystals. The samples showed higher porosity of 47.9%. In addition, these materials could be used as membrane for air cleaning.

Effect of the ZrCl4 concentration in the (NaCl-KCl)eqiv-UO2Cl2-ZrCl4 melt and the electrolysis current density on the quantitative composition of UO2-ZrO2 cathode deposits. Calculation and experiment

NASA Astrophysics Data System (ADS)

Krotov, V. E.; Filatov, E. C.

2014-08-01

A method is proposed for calculating the ZrO2 content in the (NaCl-KCl)eqiv-UO2Cl2-ZrCl4 melt. Based on the known composition of a UO2-ZrO2 cathode deposit, the content is calculated at current densities of 0.08-0.63 A/cm2 and ZrCl4 concentrations of 0-12.3 wt %. The calculated and experimental ZrO2 contents in UO2-ZrO2 cathode deposits are in qualitative and adequate quantitative agreement.

Evaluation of zirconia, thoria and zirconium diboride for advanced resistojet use

NASA Technical Reports Server (NTRS)

Page, R. J.; Short, R. A.; Halbach, C. R.

1972-01-01

A literature survey was conducted to collect material properties data on all advanced high temperature materials. Three of these, Y2O3-stabilized ZrO2, ThO2, and ZrB2 with additives of C and SiC were selected for further study. Stabilized ZrO2 and ThO2 were found to have higher temperature oxidation resistance than any metal and great potential for use in advanced biowaste resistojets. ZrO2 has a lower electrical resistivity and sublimation and a higher creep endurance strength. ZrO2 and ThO2 tubular heat exchangers, electrically heated indirectly, were evaluated in short tests to about 1900 K in flowing CO2. ZrO2 was subjected to N2, H2, H2O and vacuum as well. X-ray diffraction and fluorescence analyses were made. The metal-to-ceramic seal technology for ZrO2 and ThO2 was developed using chemical vapor deposition of tantalum for metallizing and 82 Au - 18 Ni filler braze.

Thermodynamic Assessment of the Y2o3-yb2o3-zro2 System

NASA Technical Reports Server (NTRS)

Jacobson, Nathan S.; Liu, Zi-Kui; Kaufman, Larry; Zhang, Fan

2002-01-01

Yttria-zirconia (Y2O3-ZrO2) is the most widely used of the rare earth oxide-zirconia systems. There are numerous experimental studies of the phase boundaries in this system. In this paper, we assess these data and derive parameters for the solution models in this system. There is current interest in other rare earth oxide-zirconia systems as well as systems with several rare earth oxides and zirconia, which may offer improved properties over the Y2O3-ZrO2 system. For this reason, we also assess the ytterbia-zirconia (Yb2O3-ZrO2) and Y2O3-Yb2O3-ZrO2 system.

In Situ FT-IR Spectroscopic Study of CO2 and CO Adsorption on Y2O3, ZrO2, and Yttria-Stabilized ZrO2

PubMed Central

2013-01-01

In situ FT-IR spectroscopy was exploited to study the adsorption of CO2 and CO on commercially available yttria-stabilized ZrO2 (8 mol % Y, YSZ-8), Y2O3, and ZrO2. All three oxides were pretreated at high temperatures (1173 K) in air, which leads to effective dehydroxylation of pure ZrO2. Both Y2O3 and YSZ-8 show a much higher reactivity toward CO and CO2 adsorption than ZrO2 because of more facile rehydroxylation of Y-containing phases. Several different carbonate species have been observed following CO2 adsorption on Y2O3 and YSZ-8, which are much more strongly bound on the former, due to formation of higher-coordinated polydentate carbonate species upon annealing. As the crucial factor governing the formation of carbonates, the presence of reactive (basic) surface hydroxyl groups on Y-centers was identified. Therefore, chemisorption of CO2 most likely includes insertion of the CO2 molecule into a reactive surface hydroxyl group and the subsequent formation of a bicarbonate species. Formate formation following CO adsorption has been observed on all three oxides but is less pronounced on ZrO2 due to effective dehydroxylation of the surface during high-temperature treatment. The latter generally causes suppression of the surface reactivity of ZrO2 samples regarding reactions involving CO or CO2 as reaction intermediates. PMID:24009780

Doped ZrO2 for future lead free piezoelectric devices

NASA Astrophysics Data System (ADS)

Starschich, S.; Böttger, U.

2018-01-01

The ferroelectric and piezoelectric properties of doped ZrO2 prepared by chemical solution deposition (CSD) are investigated. Doping with different elements such as Mg, In, La, and Y leads to a stabilization of the constricted hysteresis. As shown in a previous work, for the constricted hysteresis of ZrO2, the piezoelectric response is significantly larger compared to ZrO2 with a normal hysteresis. The Mg doped ZrO2 shows a strong temperature and cycle stability. For the piezoelectric properties, a magnesium concentration of 7% shows the largest piezoelectric response with a piezoelectric coefficient of >10 pm/V, as well as the best cycle stability. Due to thicker films, which can be realized by the CSD technique, the shown doped ZrO2 films are a promising candidate for energy related applications such as piezoelectric energy harvesting as well as for microelectromechanical systems.

Defect-related electroluminescence from metal-oxide-semiconductor devices with ZrO2 films on silicon

NASA Astrophysics Data System (ADS)

Lv, Chunyan; Zhu, Chen; Wang, Canxing; Li, Dongsheng; Ma, Xiangyang; Yang, Deren

2016-11-01

Defect-related electroluminescence (EL) from ZrO2 films annealed under different atmosphere has been realized by means of electrical pumping scheme of metal-oxide-semiconductor (MOS) devices. At the same injection current, the acquired EL from the MOS device with the vacuum-annealed ZrO2 film is much stronger than that from the counterpart with the oxygen-annealed ZrO2 film. This is because the vacuum-annealed ZrO2 film contains more oxygen vacancies and Zr3+ ions. Analysis on the current-voltage characteristic of the ZrO2-based MOS devices indicates the P-F conduction mechanism dominates the electron transportation at the EL-enabling voltages under forward bias. It is tentatively proposed that the recombination of the electrons trapped in multiple oxygen-vacancy-related states with the holes in the defect level pertaining to Zr3+ ions brings about the EL emissions.

Variable microstructural response of baddeleyite to shock metamorphism in young basaltic shergottite NWA 5298 and improved U-Pb dating of Solar System events

NASA Astrophysics Data System (ADS)

Darling, James R.; Moser, Desmond E.; Barker, Ivan R.; Tait, Kim T.; Chamberlain, Kevin R.; Schmitt, Axel K.; Hyde, Brendt C.

2016-06-01

The accurate dating of igneous and impact events is vital for the understanding of Solar System evolution, but has been hampered by limited knowledge of how shock metamorphism affects mineral and whole-rock isotopic systems used for geochronology. Baddeleyite (monoclinic ZrO2) is a refractory mineral chronometer of great potential to date these processes due to its widespread occurrence in achondrites and robust U-Pb isotopic systematics, but there is little understanding of shock-effects on this phase. Here we present new nano-structural measurements of baddeleyite grains in a thin-section of the highly-shocked basaltic shergottite Northwest Africa (NWA) 5298, using high-resolution electron backscattered diffraction (EBSD) and scanning transmission electron microscopy (STEM) techniques, to investigate shock-effects and their linkage with U-Pb isotopic disturbance that has previously been documented by in-situ U-Pb isotopic analyses. The shock-altered state of originally igneous baddeleyite grains is highly variable across the thin-section and often within single grains. Analyzed grains range from those that preserve primary (magmatic) twinning and trace-element zonation (baddeleyite shock Group 1), to quasi-amorphous ZrO2 (Group 2) and to recrystallized micro-granular domains of baddeleyite (Group 3). These groups correlate closely with measured U-Pb isotope compositions. Primary igneous features in Group 1 baddeleyites (n = 5) are retained in high shock impedance grain environments, and an average of these grains yields a revised late-Amazonian magmatic crystallization age of 175 ± 30 Ma for this shergottite. The youngest U-Pb dates occur from Group 3 recrystallized nano- to micro-granular baddeleyite grains, indicating that it is post-shock heating and new mineral growth that drives much of the isotopic disturbance, rather than just shock deformation and phase transitions. Our data demonstrate that a systematic multi-stage microstructural evolution in baddeleyite results from a single cycle of shock-loading, heating and cooling during transit to space, and that this leads to variable disturbance of the U-Pb isotope system. Furthermore, by linking in-situ U-Pb isotopic measurements with detailed micro- to nano-structural analyses, it is possible to resolve the timing of both endogenic crustal processes and impact events in highly-shocked planetary materials using baddeleyite. This opens up new opportunities to refine the timing of major events across the Solar System.

Composite materials based on high-modulus compounds for additive technology

NASA Astrophysics Data System (ADS)

Grigoriev, M.; Kotelnikov, N.; Buyakova, S.; Kulkov, S.

2016-07-01

The effect of adding nanocrystalline ZrO2 and submicron TiC to ultrafine Al2O3 on mechanical properties and the microstructure of the composites developed by hot pressing was investigated. It was shown that by means of hot pressing in argon atmosphere at the sintering temperature of 1500 °C one can obtain the composites of Al2O3-ZrO2-TiC with a fine structure and minimal porosity. It was shown that in the material a multi-scale hierarchical structure is formed, which possesses high physical and mechanical properties: the hardness and fracture toughness was 22 GPa and 5.2 MPa*m1/2, respectively. It has been shown that mechanical properties of the composite are better than those of commercial composites based on aluminum oxide (Al2O3, ZTA, Al2O3-TiC) and are comparable to those of silicon nitride.

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.

Fabrication and Characterization of Nanoporous Niobia, and Nanotubular Tantala, Titania and Zirconia via Anodization

PubMed Central

Minagar, Sepideh; Berndt, Christopher C.; Wen, Cuie

2015-01-01

Valve metals such as titanium (Ti), zirconium (Zr), niobium (Nb) and tantalum (Ta) that confer a stable oxide layer on their surfaces are commonly used as implant materials or alloying elements for titanium-based implants, due to their exceptional high corrosion resistance and excellent biocompatibility. The aim of this study was to investigate the bioactivity of the nanostructures of tantala (Ta2O5), niobia (Nb2O5), zirconia (ZrO2) and titania (TiO2) in accordance to their roughness and wettability. Therefore, four kinds of metal oxide nanoporous and nanotubular Ta2O5, Nb2O5, ZrO2 and TiO2 were fabricated via anodization. The nanosize distribution, morphology and the physical and chemical properties of the nanolayers and their surface energies and bioactivities were investigated using SEM-EDS, X-ray diffraction (XRD) analysis and 3D profilometer. It was found that the nanoporous Ta2O5 exhibited an irregular porous structure, high roughness and high surface energy as compared to bare tantalum metal; and exhibited the most superior bioactivity after annealing among the four kinds of nanoporous structures. The nanoporous Nb2O5 showed a uniform porous structure and low roughness, but no bioactivity before annealing. Overall, the nanoporous and nanotubular layers of Ta2O5, Nb2O5, ZrO2 and TiO2 demonstrated promising potential for enhanced bioactivity to improve their biomedical application alone or to improve the usage in other biocompatible metal implants. PMID:25837724

Multifunctional phosphate-based inorganic-organic hybrid nanoparticles.

PubMed

Heck, Joachim G; Napp, Joanna; Simonato, Sara; Möllmer, Jens; Lange, Marcus; Reichardt, Holger M; Staudt, Reiner; Alves, Frauke; Feldmann, Claus

2015-06-17

Phosphate-based inorganic-organic hybrid nanoparticles (IOH-NPs) with the general composition [M](2+)[Rfunction(O)PO3](2-) (M = ZrO, Mg2O; R = functional organic group) show multipurpose and multifunctional properties. If [Rfunction(O)PO3](2-) is a fluorescent dye anion ([RdyeOPO3](2-)), the IOH-NPs show blue, green, red, and near-infrared fluorescence. This is shown for [ZrO](2+)[PUP](2-), [ZrO](2+)[MFP](2-), [ZrO](2+)[RRP](2-), and [ZrO](2+)[DUT](2-) (PUP = phenylumbelliferon phosphate, MFP = methylfluorescein phosphate, RRP = resorufin phosphate, DUT = Dyomics-647 uridine triphosphate). With pharmaceutical agents as functional anions ([RdrugOPO3](2-)), drug transport and release of anti-inflammatory ([ZrO](2+)[BMP](2-)) and antitumor agents ([ZrO](2+)[FdUMP](2-)) with an up to 80% load of active drug is possible (BMP = betamethason phosphate, FdUMP = 5'-fluoro-2'-deoxyuridine 5'-monophosphate). A combination of fluorescent dye and drug anions is possible as well and shown for [ZrO](2+)[BMP](2-)0.996[DUT](2-)0.004. Merging of functional anions, in general, results in [ZrO](2+)([RdrugOPO3]1-x[RdyeOPO3]x)(2-) nanoparticles and is highly relevant for theranostics. Amine-based functional anions in [MgO](2+)[RaminePO3](2-) IOH-NPs, finally, show CO2 sorption (up to 180 mg g(-1)) and can be used for CO2/N2 separation (selectivity up to α = 23). This includes aminomethyl phosphonate [AMP](2-), 1-aminoethyl phosphonate [1AEP](2-), 2-aminoethyl phosphonate [2AEP](2-), aminopropyl phosphonate [APP](2-), and aminobutyl phosphonate [ABP](2-). All [M](2+)[Rfunction(O)PO3](2-) IOH-NPs are prepared via noncomplex synthesis in water, which facilitates practical handling and which is optimal for biomedical application. In sum, all IOH-NPs have very similar chemical compositions but can address a variety of different functions, including fluorescence, drug delivery, and CO2 sorption.

Drying-induced atomic structural rearrangements in sodium-based calcium-alumino-silicate-hydrate gel and the mitigating effects of ZrO 2 nanoparticles

DOE PAGES

Yang, Kengran; Özçelik, V. Ongun; Garg, Nishant; ...

2018-01-01

Drying-induced nanoscopic alterations to the local atomic structure of silicate-activated slag and the mitigated effects of nano-ZrO2 are elucidated using in situ X-ray pair distribution function analysis.

Drying-induced atomic structural rearrangements in sodium-based calcium-alumino-silicate-hydrate gel and the mitigating effects of ZrO 2 nanoparticles

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

Yang, Kengran; Özçelik, V. Ongun; Garg, Nishant

Drying-induced nanoscopic alterations to the local atomic structure of silicate-activated slag and the mitigated effects of nano-ZrO2 are elucidated using in situ X-ray pair distribution function analysis.

Tribological improvements of carbon-carbon composites by infiltration of atomic layer deposited lubricious nanostructured ceramic oxides

NASA Astrophysics Data System (ADS)

Mohseni, Hamidreza

A number of investigators have reported enhancement in oxidation and wear resistant of carbon-carbon composites (CCC) in the presence of protective coating layers. However, application of a surface and subsurface coating system that can preserve its oxidation and wear resistance along with maintaining lubricity at high temperature remains unsolved. To this end, thermodynamically stable protective oxides (ZnO/Al2O3/ZrO2) have been deposited by atomic layer deposition (ALD) to infiltrate porous CCC and graphite foams in order to improve the thermal stability and wear resistance in low and high speed sliding contacts. Characterization of microstructural evolution was achieved by using energy dispersive x-ray spectroscopy (EDS) mapping in scanning electron microscope (SEM) coupled with focused ion beam (FIB), x-ray tomography, high resolution transmission electron microscopy (HRTEM), scanning transmission electron microscopy (STEM) and X-ray diffraction (XRD). Evaluation of the tribological properties of CCC coated with abovementioned ALD thin films were performed by employing low speed pure sliding tribometer and a high speed/frequency reciprocating rig to simulate the fretting wear behavior at ambient temperature and elevated temperatures of 400°C. It was determined with x-ray tomography imaging and EDS mapping that ALD ZnO/Al2O3/ZrO2 nanolaminates and baseline ZrO2 coatings exhibited excellent conformality and pore-filling capabilities down to ˜100 microm and 1.5 mm in the porous CCC and graphite foam, respectively, which were dependent on the exposure time of the ALD precursors. XRD and HRTEM determined the crystalline phases of {0002} textured ZnO (wurtzite), amorphous Al2O3, and {101}-tetragonal ZrO2. Significant improvements up to ˜65% in the sliding and fretting wear factors were determined for the nanolaminates in comparison to the uncoated CCC. A tribochemical sliding-induced mechanically mixed layer (MML) was found to be responsible for these improvements. HRTEM confirmed the presence of a high density of ZnO shear-induced basal stacking faults inside the wear tracks responsible for intrafilm shear velocity accommodation that mitigated friction and wear.

Sintering, thermal stability and mechanical properties of ZrO2-WC composites obtained by pulsed electric current sintering

NASA Astrophysics Data System (ADS)

Huang, Shuigen; Vanmeensel, Kim; van der Biest, Omer; Vleugels, Jozef

2011-03-01

ZrO2-WC composites exhibit comparable mechanical properties as traditional WC-Co materials, which provides an opportunity to partially replace WC-Co for some applications. In this study, 2 mol.% Y2O3 stabilized ZrO2 composites with 40 vol.% WC were consolidated in the 1150°C-1850°C range under a pressure of 60 MPa by pulsed electric current sintering (PECS). The densification behavior, microstructure and phase constitution of the composites were investigated to clarify the role of the sintering temperature on the grain growth, mechanical properties and thermal stability of ZrO2 and WC components. Analysis results indicated that the composites sintered at 1350°C and 1450°C exhibited the highest tetragonal ZrO2 phase transformability, maximum toughness, and hardness and an optimal flexural strength. Chemical reaction of ZrO2 and C, originating from the graphite die, was detected in the composite PECS for 20 min at 1850°C in vacuum.

Photocatalytic activity of nanostructured ZnO-ZrO2 binary oxide using fluorometric method

NASA Astrophysics Data System (ADS)

Ibrahim, M. M.

2015-06-01

Evaluation of the photocatalytic activity of ZnO-ZrO2 nanomaterials using fluorescence based technique has rarely been reported. In the present work, ZnO-ZrO2 mixed oxides coupled with various ZnO dosages (0, 10, 30, 50, 70 wt%) were prepared by impregnation method. These nanomaterials were characterized by studying their structural, surface and optical properties. The photocatalytic activity in term of quantitative determination of the active oxidative species (radOH) produced on the surface of binary oxide was evaluated using fluorescent probe method. The interaction between ZnO and ZrO2 was affected on the photocatalytic efficiency of mixture. The results show that, the addition of ZnO to ZrO2 decreased the electron-hole recombination and increased the rate of radOH radicals formation. 50 wt% ZnO-ZrO2 photocatalyst exhibited much higher photocatalytic activity. The profound effect of binary oxide catalyst was generally considered due to the high surface area, small particle size, high monoclinic phase of ZrO2 content, low band gap and the presence of surface OH groups.

Influence of finish line in the distribution of stress trough an all ceramic implant-supported crown.

PubMed Central

SANNINO, G.; GLORIA, F.; OTTRIA, L.; BARLATTANI, A.

2010-01-01

SUMMARY Porpose. The aim of this study was to evaluate, by finite element analysis (FEA), the influence of finish line on stress distribution and resistance to the loads of a ZrO2 crown and porcelain in implant-supported. Material and methods. The object of this analysis consisted of a fxture, an abutment, a passing screw, a layer of cement, a framework crown, a feldspatic porcelain veneering. The abutment’s marginal design was used in 3 different types of preparation: feather edge, slight chamfer and 50°, each of them was of 1 mm depth over the entire circumference. The ZrO2Y-TZP coping was 0.6 mm thick. Two material matching for the abutment and the framework was used for the simulations: ZrO2 framework and ZrO2 abutment, ZrO2 framework and T abutment. A 600 N axial force distributed over the entire surface of the crown was applied. The numerical simulations with finite elements were used to verify the different distribution of equivalent von Mises stress for three different geometries of abutment and framework. Results Slight chamfer on the matching ZrO2 - ZrO2 is the geometry with minimum equivalent stress of von Mises. Even for T abutment and ZrO2 framework slight chamfer is the best configuration to minimize the localized stress. Geometry that has the highest average stress is one with abutment at 50°, we see a downward trend for all three configurations using only zirconium for both components. Conclusions Finite element analysis. performed for the manifacturing of implant-supported crown, gives exact geometric guide lines about the choice of chamfer preparation, while the analysis of other marginal geometries suggests a possible improved behavior of the mating between ZrO2 abutment and ZrO2 coping. for three different geometries of the abutment and the coping. PMID:23285359

New evidence for Cu-decorated binary-oxides mediating bacterial inactivation/mineralization in aerobic media.

PubMed

Rtimi, S; Pulgarin, C; Bensimon, M; Kiwi, J

2016-08-01

Binary oxide semiconductors TiO2-ZrO2 and Cu-decorated TiO2-ZrO2 (TiO2-ZrO2-Cu) uniform films were sputtered on polyester (PES). These films were irradiated under low intensity solar simulated light and led to bacterial inactivation in aerobic and anaerobic media as evaluated by CFU-plate counting. But bacterial mineralization was only induced by TiO2-ZrO2-Cu in aerobic media. The highly oxidative radicals generated on the films surface under light were identified by the use of appropriate scavengers. The hole generated on the TiO2-ZrO2 films is shown to be the main specie leading to bacterial inactivation. TiO2-ZrO2 and Cu-decorated TiO2-ZrO2 films release Zr and Ti <1ppb and Cu 4.6ppb/cm(2) as determined by inductively coupled plasma mass spectrometry (ICP-MS) This level is far below the citotoxicity permitted level allowed for mammalian cells suggesting that bacterial disinfection proceeds through an oligodynamic effect. By Fourier transform attenuated infrared spectroscopy (ATR-FTIR) the systematic shift of the predominating νs(CH2) vibrational-rotational peak making up most of the bacterial cell-wall content in C was monitored. Based on this evidence a mechanism suggested leading to CH bond stretching followed by cell lysis and cell death. Bacterial inactivation cycling was observed on TiO2-ZrO2-Cu showing the stability of these films leading to bacterial inactivation. Copyright © 2016 Elsevier B.V. All rights reserved.

Unctuous ZrO2 nanoparticles with improved functional attributes as lubricant additives

NASA Astrophysics Data System (ADS)

Espina Casado, Jorge; Fernández González, Alfonso; José del Reguero Huerga, Ángel; Rodríguez-Solla, Humberto; Díaz-García, Marta Elena; Badía-Laíño, Rosana

2017-12-01

One of the main drawbacks in the application of metal-oxide nanoparticles as lubricant additives is their poor stability in organic media, despite the good anti-wear, friction-reducing and high-load capacity properties described for these materials. In this work, we present a novel procedure to chemically cap the surface of ZrO2 nanoparticles (ZrO2NPs) with long hydrocarbon chains in order to obtain stable dispersions of ZrO2NPs in non-aqueous media without disrupting their attributes as lubricant additives. C-8, C-10 and C-16 saturated flexible chains were attached to the ZrO2NP surface and their physical and chemical characterization was performed by transmission electron microscopy, thermogravimetric analysis, attenuated total reflectance Fourier transform infrared spectroscopy, x-ray photoelectron spectroscopy and solid-state nuclear magnetic resonance. The dispersion stability of the modified ZrO2NPs in non-aqueous media was studied using static multiple light scattering. Tribological tests demonstrated that dispersions of the long-chain capped ZrO2NPs in base lubricating oils exhibited low friction coefficients and improved the anti-wear properties of the base oil when compared with the raw lubricating oil.

Study of Pt-Rh/CeO2-ZrO2-MxOy (M = Y, La)/Al2O3 three-way catalysts

NASA Astrophysics Data System (ADS)

Jiaxiu, Guo; Zhonghua, Shi; Dongdong, Wu; Huaqiang, Yin; Maochu, Gong; Yaoqiang, Chen

2013-05-01

CeO2-ZrO2-MxOy (M = Y; La) mixed oxides, prepared by co-precipitation method and characterized by Brunauer-Emmett-Teller (BET), X-ray diffraction (XRD), Raman spectra (RM) and oxygen pulse reaction, were comparatively investigated to elucidate the combinational effects of Y and/or La oxide promoters on the catalytic activity and anti-aging performance of monolithic cordierite honeycomb catalysts with low Pt and Rh content. The catalytic activities, water-gas shift (WGS) and steam reforming reaction (SR) were studied under a simulated gas mixture. The catalysts were also characterized by H2-temperature-programmed reduction (H2-TPR) and O2-temperature-programmed desorption (O2-TPD). The results showed that the prepared CeO2-ZrO2-MxOy oxides have a face-centered cubic fluorite structure and are nanosize. La3+ ions can significantly improve thermal stability and efficiently retard CeO2-ZrO2 crystal sintering and growth. Doped CeO2-ZrO2 with Y3+ and La3+ has 105 and 60 m2/g surface area and 460 and 390 μmol/g OSC before and after aging. The T50 of fresh Pt-Rh/CZYL/LA is 170 °C for CO, 222 °C for C3H8 and 189 °C for NO, and shift to 205, 262 and 228 °C after hydrothermal aging, which are better than those of Pt-Rh/CZY/LA or Pt-Rh/CZL/LA. WGS and SR are relate to the OSC of oxygen storage materials and absorbed oxygen species on the catalyst surface and affect the three-way catalytic activities of catalysts. The reductive property of noble metals and the dissociatively adsorbed O2 on the surface of catalysts are closely related to the catalytic activities.

Doping effects of Yb 3+ on the crystal structures, nanoparticle properties and electrical behaviors of ZrO 2 derived from a facile urea-based hydrothermal route

NASA Astrophysics Data System (ADS)

Zhang, Ya-Wen; Sun, Xiao; Xu, Gang; Yan, Chun-Hua

2004-06-01

Weakly-agglomerated nanocrystalline (ZrO 2) 1- x(Yb 2O 3) x ( x=0.02-0.2) powders with high surface area (109-151 m 2 g -1) were synthesized by a two-step hydrothermal process in the presence of urea: a stock solution of metal nitrates and urea was heated at 80 °C for 24 h and then at 180 °C for 48 h. For x=0.04-0.2, the as-derived powders were an assembly of uniform nanoparticles with well-defined edges in the size between 6.1-8.4 nm. Before and after calcination at 800 °C, the lattice parameters, microstrain and surface area of the (ZrO 2) 1- x(Yb 2O 3) x samples tended to increase with Yb 3+ concentration; while, the average crystallite size decreased correspondingly. In the Arrhenius plots over the measurement temperature range of 400-800 °C, the bulk ionic conductivity of the compacts sintered at 1400 °C for 24 h showed a maximum value at the composition of x=0.08 in cubic structure, with an activation energy of 0.89 eV. At 800 °C, σb=0.049 S cm -1 for x=0.08.

Defect-Rich Dopant-Free ZrO2 Nanostructures with Superior Dilute Ferromagnetic Semiconductor Properties.

PubMed

Rahman, Md Anisur; Rout, S; Thomas, Joseph P; McGillivray, Donald; Leung, Kam Tong

2016-09-14

Control of the spin degree of freedom of an electron has brought about a new era in spin-based applications, particularly spin-based electronics, with the potential to outperform the traditional charge-based semiconductor technology for data storage and information processing. However, the realization of functional spin-based devices for information processing remains elusive due to several fundamental challenges such as the low Curie temperature of group III-V and II-VI semiconductors (<200 K), and the low spin-injection efficiencies of existing III-V, II-VI, and transparent conductive oxide semiconductors in a multilayer device structure, which are caused by precipitation and migration of dopants from the host layer to the adjacent layers. Here, we use catalyst-assisted pulsed laser deposition to grow, for the first time, oxygen vacancy defect-rich, dopant-free ZrO2 nanostructures with high TC (700 K) and high magnetization (5.9 emu/g). The observed magnetization is significantly greater than both doped and defect-rich transparent conductive oxide nanomaterials reported to date. We also provide the first experimental evidence that it is the amounts and types of oxygen vacancy defects in, and not the phase of ZrO2 that control the ferromagnetic order in undoped ZrO2 nanostructures. To explain the origin of ferromagnetism in these ZrO2 nanostructures, we hypothesize a new defect-induced bound polaron model, which is generally applicable to other defect-rich, dopant-free transparent conductive oxide nanostructures. These results provide new insights into magnetic ordering in undoped dilute ferromagnetic semiconductor oxides and contribute to the design of exotic magnetic and novel multifunctional materials.

Development of sputtered techniques for thrust chambers

NASA Technical Reports Server (NTRS)

Mullaly, J. R.; Hecht, R. J.; Schmid, T. E.; Torrey, C. T.

1975-01-01

Techniques and materials were developed and evaluated for the fabrication and coating of advanced, long life, regeneratively cooled thrust chambers. Materials were analyzed as fillers for sputter application of OFHC copper as a closeout layer to channeled inner structures; of the materials evaluated, aluminum was found to provide the highest bond strength and to be the most desirable for chamber fabrication. The structures and properties were investigated of thick sputtered OFHC copper, 0.15 Zr-Cu, Al2O3,-Cu, and SiC-Cu. Layered structures of OFHC copper and 0.15 Zr-Cu were investigated as means of improving chamber inner wall fatigue life. The evaluation of sputtered Ti-5Al-2.5Sn, NASA IIb-11, aluminum and Al2O3-Al alloys as high strength chamber outer jackets was performed. Techniques for refurbishing degraded thrust chambers with OFHC copper and coating thrust chambers with protective ZrO2 and graded ZrO2-copper thermal barrier coatings were developed.

Development of Oxide Dispersion Strengthened MCrAlY Coatings

NASA Astrophysics Data System (ADS)

Bobzin, K.; Schläfer, T.; Richardt, K.; Brühl, M.

2008-12-01

MCrAlY materials are widely used as bond coats for thermal barrier coatings on turbine blades. The aim of this work is to improve mechanical properties and wear resistance of thermal sprayed NiCoCrAlY-coatings by strengthening the coating with hard phase particles. In order to retain the effect of the dispersion reinforcement at high temperatures, the use of temperature-stable oxide hard phases such as ZrO2-Y2O3 is necessary. To realize this new material structure, the high-energy ball-milling process is applied and analyzed. The mixture ratio between NiCoCrAlY and ZrO2-Y2O3 was varied between 5 and 10 wt.% ZrO2-Y2O3. The influences of the milling time of the high-energy ball-milling process on the distribution of the hard phases in the metal matrix were analyzed. After spraying with a HVOF system the mechanical properties of the coatings are measured and compared with conventional NiCoCrAlY coatings.

Efficient removal of arsenite through photocatalytic oxidation and adsorption by ZrO2-Fe3O4 magnetic nanoparticles

NASA Astrophysics Data System (ADS)

Sun, Tianyi; Zhao, Zhiwei; Liang, Zhijie; Liu, Jie; Shi, Wenxin; Cui, Fuyi

2017-09-01

Bifunctional ZrO2-Fe3O4 magnetic nanoparticles were synthesized and characterized, to remove As(III) through photocatalyic oxidation and adsorption. With a saturation magnetization of 27.39 emu/g, ZrO2-Fe3O4 nanoparticles with size of 10-30 nm could be easily separated from solutions with a simple magnetic process. Under UV light, As(III) could be completely oxidized to less toxic As(V) by ZrO2-Fe3O4 nanoparticles within 40 min in the photocatalytic reaction. Simultaneously, As(V) could be adsorbed onto the surface of nanoparticles with high efficiency. The adsorption of As(V) was well fitted by the pseudo-second-order model and the Freundlich isotherm model, respectively, and the maximum adsorption capacities of the nanoparticles was 133.48 mg/g at pH 7.0. As(III) could be effectively removed by ZrO2-Fe3O4 nanoparticles at initial pH range from 4 to 8. Among all the common coexisting ions investigated, except for chloride and sulfate, carbonate, silicate and phosphate decreased the As(III) removal by competing with arsenic species for adsorption sites. The synthesized magnetic ZrO2-Fe3O4 combined the photocatalytic oxidation property of ZrO2 and the high adsorption capacity of both ZrO2 and Fe3O4, which make it have significant potential applications in the As(III)-contaminated water treatment.

Zirconia/Hydroxyapatite Composites Synthesized Via Sol-Gel: Influence of Hydroxyapatite Content and Heating on Their Biological Properties

PubMed Central

Bollino, Flavia; Armenia, Emilia; Tranquillo, Elisabetta

2017-01-01

Zirconia (ZrO2) and zirconia-based glasses and ceramics are materials proposed for use in the dental and orthopedic fields. In this work, ZrO2 glass was modified by adding different amounts of bioactive and biocompatible hydroxyapatite (HAp). ZrO2/HAp composites were synthesized via the sol-gel method and heated to different temperatures to induce modifications of their chemical structure, as ascertained by Fourier transform infrared spectroscopy (FTIR) analysis. The aim was to investigate the effect of both HAp content and heating on the biological performances of ZrO2. The materials’ bioactivity was studied by soaking samples in a simulated body fluid (SBF). FTIR and scanning electron microscopy (SEM)) analyses carried out after exposure to SBF showed that all materials are bioactive, i.e., they are able to form a hydroxyapatite layer on their surface. Moreover, the samples were soaked in a solution containing bovine serum albumin (BSA). FTIR analysis proved that the synthesized materials are able to adsorb the blood protein, the first step of cell adhesion. WST-8 ([2-(2-methoxy-4-nitrophenyl)-3-(4-nitrophenyl)-5-(2,4-disulfophenyl)-2H-tetrazolium, monosodium salt]) assay showed that no cytotoxicity effects were induced by the materials’ extract. However, the results proved that bioactivity increases with both the HAp content and the temperature used for the thermal treatment, whereas biocompatibility increases with heating but is not affected by the HAp content. PMID:28773116

Free-standing coating patterns fabricated by ultraviolet contact lithography using photosensitive sol-gel coatings

NASA Astrophysics Data System (ADS)

Xiang, Youlai; Du, Ai; Li, Xiaoguang; Sun, Wei; Wu, Shuai; Li, Tiemin; Liu, Mingfang; Zhou, Bin

2017-07-01

Photosensitive ZrO2-SiO2 hybrid sol-gel coatings containing large contents of chelating rings were prepared by using the zirconium n-butoxide (TBOZ) and methyltriethoxysilane (MTES) as hybrid precursors, and benzoylacetone (BZAC) as chelating agent. The change of ultraviolet (UV) absorption spectra, chemical composition, and optical properties of ZrO2-SiO2 hybrid sol-gel coatings were analyzed before and after UV exposure and calcination. The refractive index of the ZrO2-SiO2 hybrid gel coatings decreased from 1.673 to 1.561 with the increase of the molar content of MTES in precursors. The sol-gel coating patterns with the periods of 20.24 μm, 10.11 μm and 3.99 μm on the PAMS substrates were firstly obtained by using the photosensitive ZrO2-SiO2 hybrid sol-gel films as fundamental materials through a process of UV contact lithography with photo masks and etching with ethanol. Finally, the free-standing gel coating patterns supported by copper grids, with the period of 12.70 μm and line width of 4.93 μm, and the period of 14.20 μm and line width of 3.82 μm, were obtained by removing the PAMS thermal degradation sacrifice layer after being calcined at 330 °C. Micrometer-periodic free-standing gel coating patterns with different structure have potential applications in the laser physical experiments.

MgO-Al2O3-ZrO2 Amorphous Ternary Composite: A Dense and Stable Optical Coating

NASA Technical Reports Server (NTRS)

Shaoo, Naba K.; Shapiro, Alan P.

1998-01-01

The process-parameter-dependent optical and structural properties of MgO-Al2O3-ZrO2 ternary mixed-composite material were investigated. Optical properties were derived from spectrophotometric measurements. The surface morphology, grain size distributions, crystallographic phases, and process- dependent material composition of films were investigated through the use of atomic force microscopy, x-ray diffraction analysis, and energy-dispersive x-ray analysis. Energy-dispersive x-ray analysis made evident the correlation between the optical constants and the process-dependent compositions in the films. It is possible to achieve environmentally stable amorphous films with high packing density under certain optimized process conditions.

Atomic layer deposition of ZrO2 on W for metal-insulator-metal capacitor application

NASA Astrophysics Data System (ADS)

Lee, Sang-Yun; Kim, Hyoungsub; McIntyre, Paul C.; Saraswat, Krishna C.; Byun, Jeong-Soo

2003-04-01

A metal-insulator-metal (MIM) capacitor using ZrO2 on tungsten (W) metal bottom electrode was demonstrated and characterized in this letter. Both ZrO2 and W metal were synthesized by an atomic layer deposition (ALD) method. High-quality 110˜115 Å ZrO2 films were grown uniformly on ALD W using ZrCl4 and H2O precursors at 300 °C, and polycrystalline ZrO2 in the ALD regime could be obtained. A 13˜14-Å-thick interfacial layer between ZrO2 and W was observed after fabrication, and it was identified as WOx through angle-resolved x-ray photoelectron spectroscopy analysis with wet chemical etching. The apparent equivalent oxide thickness was 20˜21 Å. An effective dielectric constant of 22˜25 including an interfacial WOx layer was obtained by measuring capacitance and thickness of MIM capacitors with Pt top electrodes. High capacitance per area (16˜17 fF/μm2) and low leakage current (10-7 A/cm2 at ±1 V) were achieved.

Structural and optical characteristics of in-situ sputtered highly oriented 15R-SiC thin films on different substrates

NASA Astrophysics Data System (ADS)

Mourya, Satyendra; Jaiswal, Jyoti; Malik, Gaurav; Kumar, Brijesh; Chandra, Ramesh

2018-01-01

In this work, we have reported the in-situ fabrication of nanocrystalline rhombohedral silicon carbide (15R-SiC) thin films by RF-magnetron sputtering at 800 °C substrate temperature. The structural and optical properties were investigated for the films grown on four different substrates (ZrO2, MgO, SiC, and Si). The contact angle measurement was performed on all the substrates to investigate the role of interfacial surface energy in nucleation and growth of the films. The XRD measurement revealed the growth of (1 0 10) orientation for all the samples and demonstrated better crystallinity on Si substrate, which was further corroborated by the TEM results. The Raman spectroscopy confirmed the growth of rhombohedral phase with 15R polytype. Surface characteristics of the films have been investigated by energy dispersive x-ray spectroscopy, FTIR, and atomic force microscope (AFM) to account for chemical composition, bonding, and root mean square surface roughness (δrms). The optical dispersion behavior of 15R-SiC thin films was examined by variable angle spectroscopic ellipsometry in the wide spectral range (246-1688 nm), including the surface characteristics in the optical model. The non-linear optical parameters (χ3 and n2) of the samples have been calculated by the Tichy and Ticha relation using a single effective oscillator model of Wemple and Didomenico. Additionally, our optical results provided an alternative way to measure the ratio of carrier concentration to the effective mass (N/m*). These investigated optical parameters allow one to design and fabricate optoelectronic, photonic, and telecommunication devices for deployment in extreme environment.

Formation of metallic clusters in oxide insulators by means of ion beam mixing

NASA Astrophysics Data System (ADS)

Talut, G.; Potzger, K.; Mücklich, A.; Zhou, Shengqiang

2008-04-01

The intermixing and near-interface cluster formation of Pt and FePt thin films deposited on different oxide surfaces by means of Pt+ ion irradiation and subsequent annealing was investigated. Irradiated as well as postannealed samples were investigated using high resolution transmission electron microscopy. In MgO and Y :ZrO2 covered with Pt, crystalline clusters with mean sizes of 2 and 3.5nm were found after the Pt+ irradiations with 8×1015 and 2×1016cm-2 and subsequent annealing, respectively. In MgO samples covered with FePt, clusters with mean sizes of 1 and 2nm were found after the Pt+ irradiations with 8×1015 and 2×1016cm-2 and subsequent annealing, respectively. In Y :ZrO2 samples covered with FePt, clusters up to 5nm in size were found after the Pt+ irradiation with 2×1016cm-2 and subsequent annealing. In LaAlO3 the irradiation was accompanied by a full amorphization of the host matrix and appearance of embedded clusters of different sizes. The determination of the lattice constant and thus the kind of the clusters in samples covered by FePt was hindered due to strong deviation of the electron beam by the ferromagnetic FePt.

Afterglow dosimetry performance of beta particle irradiated lithium zirconate.

PubMed

Hernández-Pérez, T C; Bernal, R; Cruz-Vázquez, C; Brown, F; Mendoza-Córdova, A; Salas-Juárez, Ch J; Avilés-Monreal, R

2018-08-01

In this work, we report for the very first time on the thermoluminescence (TL) and afterglow (AG) properties of Li 2 ZrO 3 . The ternary oxide Li 2 ZrO 3 was synthesized by solid state reaction of a mixture of Li 2 CO 3 and ZrO 2 subjected to thermal annealing at 400°C for 2h and 1000°C during 24h in air. The characteristic glow curves of beta particle irradiated samples exhibit an intense TL emission located around 150°C. From the shape of the TL curve, a 0.4 form factor was determined, suggesting that first order kinetics processes are involved. The afterglow decay curves were recorded after exposure to beta particle irradiation in the dose range from 0.5 up to 2kGy. The AG integrated in the time interval from 510 to 600s after radiation exposure shows a linear dependence as a function of the irradiation dose from 0.5 up to 256Gy. A method is proposed to compute the lower detection limit and the AG sensitivity and applied to the studied phosphors. Structural and morphological characterization were carried out by X-ray diffraction and Scanning Electron Microscopy, respectively. From the results presented, it is concluded that the AG response of the synthesized Li 2 ZrO 3 presents features suitable to develop radiation detectors and dosimeters. Copyright © 2017 Elsevier Ltd. All rights reserved.

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.

Excellent selector performance in engineered Ag/ZrO2:Ag/Pt structure for high-density bipolar RRAM applications

NASA Astrophysics Data System (ADS)

Wang, Chao; Song, Bing; Zeng, Zhongming

2017-12-01

A high-performance selector with bidirectional threshold switching (TS) characteristics of Ag/ZrO2/Pt structure was prepared by incorporating metallic Ag into the ZrO2 matrix. The bidirectional TS device exhibited excellent switching uniformity, forming-free behavior, ultra-low off current of <1 nA and adjustable selectivity (from 102 to 107). The experiment results confirmed that metallic Ag clusters were penetrated into the ZrO2 matrix during the annealing process, which would function as an effective active source responsible for the bidirectional TS. The volatile behavior could be explained by the self-dissolution of unstable filaments caused by minimization of the interfacial energy and thermal effect. Furthermore, a bipolar-type one selector-one resistor (1S-1R) memory device was successfully fabricated and exhibited significant suppression of the undesired sneak current, indicating the great potential as selector in a cross-point array.

Interfacial control of oxygen vacancy doping and electrical conduction in thin film oxide heterostructures

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

Veal, Boyd W.; Kim, Seong Keun; Zapol, Peter

2016-06-10

Oxygen vacancies in proximity to surfaces and heterointerfaces in oxide thin film heterostructures have major effects on properties, resulting, for example, in emergent conduction behaviour, large changes in metal-insulator transition temperatures or enhanced catalytic activity. Here we report the discovery of a means of reversibly controlling the oxygen vacancy concentration and distribution in oxide heterostructures consisting of electronically conducting In2O3 films grown on ionically conducting Y2O3-stabilized ZrO2 substrates. Oxygen ion redistribution across the heterointerface is induced using an applied electric field oriented in the plane of the interface, resulting in controlled oxygen vacancy (and hence electron) doping of the filmmore » and possible orders-of-magnitude enhancement of the film's electrical conduction. The reversible modified behaviour is dependent on interface properties and is attained without cation doping or changes in the gas environment.« less

Interfacial control of oxygen vacancy doping and electrical conduction in thin film oxide heterostructures

DOE PAGES

Veal, Boyd W.; Kim, Seong Keun; Zapol, Peter; ...

2016-06-10

Oxygen vacancies in proximity to surfaces and heterointerfaces in oxide thin film heterostructures have major effects on properties, resulting, for example, in emergent conduction behavior, large changes in metal-insulator transition temperatures, or enhanced catalytic activity. Here in this paper, we report the discovery of a means of reversibly controlling the oxygen vacancy concentration and distribution in oxide heterostructures consisting of electronically conducting In 2O 3 films grown on ionically conducting Y 2O 3-stabilized ZrO 2 substrates. Oxygen ion redistribution across the heterointerface is induced using an applied electric field oriented in the plane of the interface, resulting in controlled oxygenmore » vacancy (and hence electron) doping of the film and possible orders-of-magnitude enhancement of the film's electrical conduction. The reversible modified behavior is dependent on interface properties and is attained without cation doping or changes in the gas environment.« less

First-principles modeling of hafnia-based nanotubes.

PubMed

Evarestov, Robert A; Bandura, Andrei V; Porsev, Vitaly V; Kovalenko, Alexey V

2017-09-15

Hybrid density functional theory calculations were performed for the first time on structure, stability, phonon frequencies, and thermodynamic functions of hafnia-based single-wall nanotubes. The nanotubes were rolled up from the thin free layers of cubic and tetragonal phases of HfO 2 . It was shown that the most stable HfO 2 single-wall nanotubes can be obtained from hexagonal (111) layer of the cubic phase. Phonon frequencies have been calculated for different HfO 2 nanolayers and nanotubes to prove the local stability and to find the thermal contributions to their thermodynamic functions. The role of phonons in stability of nanotubes seems to be negligible for the internal energy and noticeable for the Helmholtz free energy. Zone folding approach has been applied to estimate the connection between phonon modes of the layer and nanotubes and to approximate the nanotube thermodynamic properties. It is found that the zone-folding approximation is sufficiently accurate for heat capacity, but less accurate for entropy. The comparison has been done between the properties of TiO 2 , ZrO 2 , and HfO 2 . © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

Deconvolution Method on OSL Curves from ZrO2 Irradiated by Beta and UV Radiations

NASA Astrophysics Data System (ADS)

Rivera, T.; Kitis, G.; Azorín, J.; Furetta, C.

This paper reports the optically stimulated luminescent (OSL) response of ZrO2 to beta and ultraviolet radiations in order to investigate the potential use of this material as a radiation dosimeter. The experimentally obtained OSL decay curves were analyzed using the computerized curve de-convolution (CCD) method. It was found that the OSL curve structure, for the short (practical) illumination time used, consists of three first order components. The individual OSL dose response behavior of each component was found. The values of the time at the OSL peak maximum and the decay constant of each component were also estimated.

Enhancing low-temperature activity and durability of Pd-based diesel oxidation catalysts using ZrO 2 supports

DOE PAGES

Kim, Mi -Young; Kyriakidou, Eleni A.; Choi, Jae -Soon; ...

2016-01-18

In this study, we investigated the impact of ZrO 2 on the performance of palladium-based oxidation catalysts with respect to low-temperature activity, hydrothermal stability, and sulfur tolerance. Pd supported on ZrO 2 and SiO 2 were synthesized for a comparative study. Additionally, in an attempt to maximize the ZrO 2 surface area and improve sulfur tolerance, a Pd support with ZrO 2-dispersed onto SiO 2 was studied. The physicochemical properties of the catalysts were examined using ICP, N 2 sorption, XRD, SEM, TEM, and NH 3-, CO 2-, and NO x-TPD. The activity of the Pd catalysts were measured frommore » 60 to 600 °C in a flow of 4000 ppm CO, 500 ppm NO, 1000 ppm C 3H 6, 4% O 2, 5% H 2O, and Ar balance. The Pd catalysts were evaluated in fresh, sulfated, and hydrothermally aged states. Overall, the ZrO 2-containing catalysts showed considerably higher CO and C 3H 6 oxidation activity than Pd/SiO 2 under the reaction conditions studied.« less

Epitaxial growth of YBa2Cu3O7 - delta films on oxidized silicon with yttria- and zirconia-based buffer layers

NASA Astrophysics Data System (ADS)

Pechen, E. V.; Schoenberger, R.; Brunner, B.; Ritzinger, S.; Renk, K. F.; Sidorov, M. V.; Oktyabrsky, S. R.

1993-09-01

A study of epitaxial growth of YBa2Cu3O7-δ films on oxidized Si with yttria- and zirconia-based buffer layers is reported. Using substrates with either SiO2 free or naturally oxidized (100) surfaces of Si it was found that a thin SiO2 layer on top of the Si favors high-quality superconducting film formation. Compared to yttria-stabilized ZrO2 (YSZ) single layers, YSZY2O3 double and YSZ/Y2O3YSZ triple layers allows the deposition of thin YBa2Cu3O7-δ films with improved properties including reduced aging effects. In epitaxial YBa2Cu3O7-δ films grown on the double buffer layers a critical temperature Tc(R=0)=89.5 K and critical current densities of 3.5×106 A/cm2 at 77 K and 1×107 A/cm2 at 66 K were reached.

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.

Structural and electrical properties of atomic layer deposited Al-doped ZrO2 films and of the interface with TaN electrode

NASA Astrophysics Data System (ADS)

Spiga, S.; Rao, R.; Lamagna, L.; Wiemer, C.; Congedo, G.; Lamperti, A.; Molle, A.; Fanciulli, M.; Palma, F.; Irrera, F.

2012-07-01

Al-doped ZrO2 (Al-ZrO2) films deposited by atomic layer deposition onto silicon substrates and the interface with the TaN metal gate are investigated. In particular, structural properties of as-grown and annealed films in the 6-26 nm thickness range, as well as leakage and capacitive behavior of metal-oxide-semiconductor stacks are characterized. As-deposited Al-ZrO2 films in the mentioned thickness range are amorphous and crystallize in the ZrO2 cubic phase after thermal treatment at 900 °C. Correspondingly, the dielectric constant (k) value increases from 20 ± 1 to 27 ± 2. The Al-ZrO2 layers exhibit uniform composition through the film thickness and are thermally stable on Si, whereas chemical reactions take place at the TaN/Al-ZrO2 interface. A transient capacitance technique is adopted for monitoring charge trapping and flat band instability at short and long time scales. The role of traps nearby the TaN/Al-ZrO2 interface is discussed and compared with other metal/high-k oxide films. Further, analytical modeling of the flat band voltage shift with a power-law dependence on time allows extracting features of bulk traps close to the silicon/oxide interface, which exhibit energy levels in the 1.4-1.9 eV range above the valence band of the Al-ZrO2.

In Situ X-ray Diffraction Studies on the Mechanism of Capacity Retention Improvement by Coating at the Surface of Li CoO2

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

Chung,K.; Yoon, W.; McBreen, J.

2007-01-01

Synchrotron based in situ X-ray diffraction technique has been used to study the mechanism of capacity fading of LiCoO2 cycled to a higher voltage above the normal 4.2 V limit and to investigate the mechanism of capacity retention improvement by ZrO2 surface coating on LiCoO2. It was found that the capacity fading of LiCoO2 cycled at higher voltage limit is closely related to the increased polarization rather than the bulk crystal structure damage. The capacity of uncoated LiCoO2 sample dropped to less than 70 mAh g-1 when charged to 4.8 V after high voltage cycling. However, when the voltage limitmore » was further increased to 8.35 V, the capacity was partially restored and the corresponding structural changes were recovered to the similar level as seen in fresh sample. This indicates that the integrity of the bulk crystal structure of LiCoO2 was not seriously damaged during cycling to 4.8 V. The increased polarization seems to be responsible for the fading capacity and the uncompleted phase transformation of LiCoO2. The polarization-induced capacity fading can be significantly improved by ZrO2 surface coating. It was proposed that the effect of ZrO2-coating layer on the capacity retention during high voltage cycling is through the formation of protection layer on the surface of LiCoO2 particles, which can reduce the decomposition of the electrolyte at higher voltages.« less

Zetameter for microelectrophoresis studies of the oxide/water interface at temperatures up to 200 °C

NASA Astrophysics Data System (ADS)

Zhou, X. Y.; Wei, X. J.; Fedkin, M. V.; Strass, K. H.; Lvov, S. N.

2003-04-01

The zeta potential (ZP) is an important and measurable parameter related to the electrical double layer structure at a solid-aqueous solution interface. A high temperature zetameter based on the microelectrophoresis technique was developed to determine the zeta potential and the isoelectric point (IEP) of the metal oxide/water interfaces at temperatures up to 200 °C and pressures up to 50 bar. Design of the microelectrophoresis cell, the main unit of the zetameter, utilized a flow-through concept and the cell internals were made from corrosion resistant materials in order to minimize materials degradation and solution contamination. Two sapphire windows were installed to the microelectrophoresis cell to enable observation of the particle movement under an imposed electrical field. A ZrO2 powder was used to test the zetameter. The ZP for the ZrO2/water system was measured over wide ranges of temperature and pH. The IEP of the ZrO2/water system was found equal to 6.05 at room temperature, 5.00 at 120 °C, and 4.67 at 200 °C. Thus, at room temperature, the IEP obtained was within the confidence interval of the averaged literature data. In addition, it was found that the IEP of ZrO2 was sensitive to temperature and the difference between the IEP and 0.5pKw remained constant (1.00±0.2) with temperatures up to 200 °C.

High resistance ratio of bipolar resistive switching in a multiferroic/high-K Bi(Fe0.95Cr0.05)O3/ZrO2/Pt heterostructure

NASA Astrophysics Data System (ADS)

Dong, B. W.; Miao, Jun; Han, J. Z.; Shao, F.; Yuan, J.; Meng, K. K.; Wu, Y.; Xu, X. G.; Jiang, Y.

2018-03-01

An novel heterostructure composed of multiferroic Bi(Fe0.95Cr0.05)O3 (BFCO) and high-K ZrO2 (ZO) layers is investigated. Ferroelectric and electrical properties of the BFZO/ZO heterostructure have been investigated. A pronounced bipolar ferroelectric resistive switching characteristic was achieved in the heterostructure at room temperature. Interestingly, the BFCO/ZO structures exhibit a reproducible resistive switching with a high On/Off resistance ratio ∼2×103 and long retention time. The relationship between polarization and band structure at the interface of BFCO/ZO bilayer under the positive and negative sweepings has been discussed. As a result, the BFCO/ZO multiferroic/high-K heterostructure with high On/Off resistance ratio and long retention characterizes, exhibits a potential in future nonvolatile memory application.

Response to antiseptic agents of periodontal pathogens in in vitro biofilms on titanium and zirconium surfaces.

PubMed

Sánchez, M C; Fernández, E; Llama-Palacios, A; Figuero, E; Herrera, D; Sanz, M

2017-04-01

The aim of this study was to develop in vitro biofilms on SLA titanium (Ti-SLA) and zirconium oxide (ZrO 2 ) surfaces and to evaluate the effect of antiseptic agents on the number of putative periodontal pathogenic species. An in vitro biofilm model was developed on sterile discs of Ti-SLA and ZrO 2 . Three antiseptic agents [chlorhexidine and cetyl-pyridinium-chloride (CHX/CPC), essential oils (EEOOs) and cetyl-peridinium-chloride (CPC)] were applied to 72-h biofilms, immersing discs during 1min in the antiseptic solution, either with or without mechanical disruption. Viable bacteria [colony forming units (CFU/mL)] were measured by quantitative polymerase chain reaction (qPCR) combined with propidium monoazide. A generalized lineal model was constructed to determine the effect of the agents on the viable bacterial counts of Aggregatibacter actinomycetemcomitans, Porphyromonas gingivalis and Fusobacterium nucleatum on each surface. The exposure to each antiseptic solution resulted in a statistically significant reductions in the number of viable target species included in the in vitro multi-species biofilm, on both Ti-SLA and ZrO 2 (p<0.001) which was of up to 2 orders for A. actinomycetemcomitans, for P. gingivalis 2 orders on Ti-SLA and up to 3 orders on ZrO 2, and, for F. nucleatum up to 4 orders. No significant differences were found in counts of the tested bacteria between in vitro biofilms formed on both Ti-SLA and ZrO 2 , after topically exposure to the antimicrobial agents whether the application was purely chemical or combined with mechanical disruption. A. actinomycetemcomitans, P. gingivalis and F. nucleatum responded similarly to their exposure to antiseptics when grown in multispecies biofilms on titanium and zirconium surfaces, in spite of the described structural differences between these bacterial communities. Copyright © 2017 The Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Energy efficient engine high pressure turbine ceramic shroud support technology report

NASA Technical Reports Server (NTRS)

Nelson, W. A.; Carlson, R. G.

1982-01-01

This work represents the development and fabrication of ceramic HPT (high pressure turbine) shrouds for the Energy Efficient Engine (E3). Details are presented covering the work performed on the ceramic shroud development task of the NASA/GE Energy Efficient Engine (E3) component development program. The task consists of four phases which led to the selection of a ZrO2-BY2O3 ceramic shroud material system, the development of an automated plasma spray process to produce acceptable shroud structures, the fabrication of select shroud systems for evaluation in laboratory, component, and CF6-50 engine testing, and finally, the successful fabrication of ZrO2-8Y2O3/superpeg, engine quality shrouds for the E3 engine.

Thermodynamic Database for the NdO(1.5)-YO(1.5)-YbO(1.5)-ScO(1.5)-ZrO2 System

NASA Technical Reports Server (NTRS)

Jacobson, Nathan S.; Copland, Evan H.; Kaufman, Larry

2001-01-01

A database for YO(1.5)-NdO(1.5)-YbO(1.5)-ScO(1.5)-ZrO2 for ThermoCalc (ThermoCalc AB, Stockholm, Sweden) has been developed. The basis of this work is the YO(1.5)-ZrO2 assessment by Y. Du, Z. Jin, and P. Huang, 'Thermodynamic Assessment of the ZrO2-YO(1.5) System'. Experimentally only the YO(1.5)-ZrO2 system has been well-studied. All other systems are only approximately known. The major simplification in this work is the treatment of each single cation unit as a component. The pure liquid oxides are taken as reference states and two term lattice stability descriptions are used for each of the components. The limited experimental phase diagrams are reproduced.

Effect of La2O3 addition on interface chemistry between 4YSZ top layer and Ni based alloy bond coat in thermal barrier coating by EB PVD.

PubMed

Park, Chan-Young; Yang, Young-Hwan; Kim, Seong-Won; Lee, Sung-Min; Kim, Hyung-Tae; Jang, Byung-Koog; Lim, Dae-Soon; Oh, Yoon-Suk

2014-11-01

The effect of a 5 mol% La2O3 addition on the forming behavior and compositional variation at interface between a 4 mol% Yttria (Y2O3) stabilized ZrO2 (4YSZ) top coat and bond coat (NiCrAlY) as a thermal barrier coating (TBC) has been investigated. Top coats were deposited by electron beam physical vapor deposition (EB PVD) onto a super alloy (Ni-Cr-Co-Al) substrate without pre-oxidation of the bond coat. Top coats are found to consist of dense columnar grains with a thin interdiffusion layer between metallic bond coats. In the as-received 4YSZ coating, a thin interdiffusion zone at the interface between the top and bond coats was found to consist of a Ni-Zr intermetallic compound with a reduced quantity of Y, Al or O elements. On the other hand, in the case of an interdiffusion area of 5 mol% La2O3-added 4YSZ coating, it was found that the complicated composition and structure with La-added YSZ and Ni-Al rich compounds separately. The thermal conductivity of 5 mol% La2O3-added 4YSZ coating (- 1.6 W/m x k at 1100 degrees C) was lower than a 4YSZ coating (- 3.2 W/m x k at 1100 degrees C) alone.

Investigation of holmium-doped zirconium oxide ceramic phosphor as an ultraviolet wavelength-discriminating laser beam viewer

NASA Astrophysics Data System (ADS)

Yamanoi, Kohei; Hori, Tatsuhiro; Minami, Yuki; Empizo, Melvin John F.; Luong, Mui Viet; Shiro, Atsushi; Watanabe, Jun; Iwano, Keisuke; Iwasa, Yuki; Cadatal-Raduban, Marilou; Gabayno, Jacque Lynn; Shimizu, Toshihiko; Sarukura, Nobuhiko; Norimatsu, Takayoshi

2018-01-01

We report the fluorescence spectra of ZrO2 and trivalent Ho-doped ZrO2 ceramics under ultraviolet (UV) excitation at 213, 266, and 355 nm wavelengths. The Ho3+-doped ZrO2 ceramics exhibited varying fluorescence color tones depending on the excitation wavelength used. The different color tones match the fluorescence spectrum characteristics at each excitation wavelength. Our results demonstrate that Ho3+-doped ZrO2 ceramics can discriminate between UV light, specifically the third, fourth, and fifth harmonics of a Nd:YAG laser. It can potentially be used for developing UV laser beam viewers to aid laser alignment.

Sintering and Creep Behavior of Plasma-Sprayed Zirconia and Hafnia Based Thermal Barrier Coatings

NASA Technical Reports Server (NTRS)

Zhu, Dongming; Miller, Robert A.

1998-01-01

The sintering and creep of plasma-sprayed ceramic thermal barrier coatings under high temperature conditions are complex phenomena. Changes in thermomechanical and thermophysical properties and in the stress response of these coating systems as a result of the sintering and creep processes are detrimental to coating thermal fatigue resistance and performance. In this paper, the sintering characteristics of ZrO2-8wt%y2O3, ZrO2-25wt%CeO2-2.5wt%Y2O3, ZrO2-6w%NiO- 9wt%Y2O3, ZrO2-6wt%Sc2O3-2wt%y2O3 and HfO2-27wt%y2O3 coating materials were investigated using dilatometry. It was found that the HfO2-Y2O3 and baseline ZrO2-Y2O3 exhibited the best sintering resistance, while the NiO-doped ZrO2-Y2O3 showed the highest shrinkage strain rates during the tests. Higher shrinkage strain rates of the coating materials were also observed when the specimens were tested in Ar+5%H2 as compared to in air. This phenomenon was attributed to an enhanced metal cation interstitial diffusion mechanism under the reducing conditions. It is proposed that increased chemical stability of coating materials will improve the material sintering resistance.

Mesoporous ZrO2 fibers with enhanced surface area and the application as recyclable absorbent

NASA Astrophysics Data System (ADS)

Yu, Zhichao; Liu, Benxue; Zhou, Haifeng; Feng, Cong; Wang, Xinqiang; Yuan, Kangkang; Gan, Xinzhu; Zhu, Luyi; Zhang, Guanghui; Xu, Dong

2017-03-01

Highly crystalline mesoporous zirconia fibers with high surface area have been prepared by the use of electrospinning combined with precursors method. The obtained precursor fibers were treated in water steam and directly in air at different temperature respectively. Compared with the direct calcination in air, the water steam cannot only promote the crystallization of ZrO2 but also effectively remove off the organics and prevent the pore structure collapse. Moreover, through adding hydrochloric acid to modify the solution pH value, the obtained t-ZrO2 fibers treated in water steam at 300 °C have high surface area and large pore volume of 232.70 m2 g-1 and 0.36 cm3 g-1. The formation mechanism of the mesostucture was studied and the schematic was represented. Compared with the previous reports of mesoporous ZrO2 fibers, the as-synthesized materials exhibited the high crystallinity, large surface area and the long-range order mesostructure.The adsorption of Congo red indicates that the samples have a high adsorption capacity of 103.46 mg g-1 and long-periodic repeated availability.

Rocket thrust chamber thermal barrier coatings

NASA Technical Reports Server (NTRS)

Batakis, A. P.; Vogan, J. W.

1985-01-01

A research program was conducted to generate data and develop analytical techniques to predict the performance and reliability of ceramic thermal barrier coatings in high heat flux environments. A finite element model was used to analyze the thermomechanical behavior of coating systems in rocket thrust chambers. Candidate coating systems (using a copper substrate, NiCrAlY bond coat and ZrO2.8Y2O3 ceramic overcoat) were selected for detailed study based on photomicrographic evaluations of experimental test specimens. The effects of plasma spray application parameters on the material properties of these coatings were measured and the effects on coating performance evaluated using the finite element model. Coating design curves which define acceptable operating envelopes for seleted coating systems were constructed based on temperature and strain limitations. Spray gun power levels was found to have the most significant effect on coating structure. Three coating systems were selected for study using different power levels. Thermal conductivity, strain tolerance, density, and residual stress were measured for these coatings. Analyses indicated that extremely thin coatings ( 0.02 mm) are required to accommodate the high heat flux of a rocket thrust chamber and ensure structural integrity.

Strain-induced phase and oxygen-vacancy stability in ionic interfaces from first-principles calculations

DOE PAGES

Aidhy, Dilpuneet S.; Liu, Bin; Zhang, Yanwen; ...

2014-12-03

Understanding interfacial chemistry is becoming crucial in materials design for heterointerfaces. Using density functional theory, we elucidate the effect of strained interfaces on phase and oxygen-vacancy stability for CeO2 | ZrO2, ThO2 | ZrO2 and CeO2 | ThO2 interfaces. The calculations show that ZrO2 transforms from cubic fluorite to the orthorhombic columbite under tensile strain providing evidence of a previous experimental speculation of an unrecognized ZrO2 phase. We also show that oxygen vacancies could be preferably stabilized on either side of the interface by manipulating strain. We predict that they are stable in tensile-strain, and unstable in compressivestrained materials.

New ZrO2/Al2O3 Nanocomposite Fabricated from Hybrid Nanoparticles Prepared by CO2 Laser Co-Vaporization

PubMed Central

Bartolomé, José F.; Smirnov, Anton; Kurland, Heinz-Dieter; Grabow, Janet; Müller, Frank A.

2016-01-01

Alumina toughened zirconia (ATZ) and zirconia toughened alumina (ZTA) are currently the materials of choice to meet the need for tough, strong, and bioinert ceramics for medical devices. However, the mechanical properties of ZrO2/Al2O3 dispersion ceramics could be considerably increased by reducing the corresponding grain sizes and by improving the homogeneity of the phase dispersion. Here, we prepare nanoparticles with an intraparticular phase distribution of Zr(1−x)AlxO(2−x/2) and (γ-, δ-)Al2O3 by the simultaneous gas phase condensation of laser co-vaporized zirconia and alumina raw powders. During subsequent spark plasma sintering the zirconia defect structures and transition alumina phases transform to a homogeneously distributed dispersion of tetragonal ZrO2 (52.4 vol%) and α-Al2O3 (47.6 vol%). Ceramics sintered by spark plasma sintering are completely dense with average grain sizes in the range around 250 nm. Outstanding mechanical properties (flexural strength σf = 1500 MPa, fracture toughness KIc = 6.8 MPa m1/2) together with a high resistance against low temperature degradation make these materials promising candidates for next generation bioceramics in total hip replacements and for dental implants. PMID:26846310

New ZrO2/Al2O3 Nanocomposite Fabricated from Hybrid Nanoparticles Prepared by CO2 Laser Co-Vaporization

NASA Astrophysics Data System (ADS)

Bartolomé, José F.; Smirnov, Anton; Kurland, Heinz-Dieter; Grabow, Janet; Müller, Frank A.

2016-02-01

Alumina toughened zirconia (ATZ) and zirconia toughened alumina (ZTA) are currently the materials of choice to meet the need for tough, strong, and bioinert ceramics for medical devices. However, the mechanical properties of ZrO2/Al2O3 dispersion ceramics could be considerably increased by reducing the corresponding grain sizes and by improving the homogeneity of the phase dispersion. Here, we prepare nanoparticles with an intraparticular phase distribution of Zr(1-x)AlxO(2-x/2) and (γ-, δ-)Al2O3 by the simultaneous gas phase condensation of laser co-vaporized zirconia and alumina raw powders. During subsequent spark plasma sintering the zirconia defect structures and transition alumina phases transform to a homogeneously distributed dispersion of tetragonal ZrO2 (52.4 vol%) and α-Al2O3 (47.6 vol%). Ceramics sintered by spark plasma sintering are completely dense with average grain sizes in the range around 250 nm. Outstanding mechanical properties (flexural strength σf = 1500 MPa, fracture toughness KIc = 6.8 MPa m1/2) together with a high resistance against low temperature degradation make these materials promising candidates for next generation bioceramics in total hip replacements and for dental implants.

Calculation of Phase Equilibria in the Y2O3-Yb2O3-ZrO2 System

NASA Technical Reports Server (NTRS)

Jacobson, Nathan S.; Liu, Zi-Kui; Kaufman, Larry; Zhang, Fan

2001-01-01

Rare earth oxide stabilized zirconias find a wide range of applications. An understanding of phase equilibria is essential to all applications. In this study, the available phase boundary data and thermodynamic data is collected and assessed. Calphad-type databases are developed to completely describe the Y2O3-ZrO2, Yb2O3-ZrO2, and Y2O3-Yb2O3 systems. The oxide units are treated as components and regular and subregular solution models are used. The resultant calculated phase diagrams show good agreement with the experimental data. Then the binaries are combined to form the database for the Y2O3-Yb2O3-ZrO2 psuedo-ternary.

Drying-induced atomic structural rearrangements in sodium-based calcium-alumino-silicate-hydrate gel and the mitigating effects of ZrO2 nanoparticles

NASA Astrophysics Data System (ADS)

Yang, Kengran; Özçelik, V. Ongun; Garg, Nishant; Gong, Kai; White, Claire E.

Conventional drying of colloidal materials and gels (including cement) can lead to detrimental effects due to the buildup of internal stresses as water evaporates from the nano/microscopic pores. However, the underlying nanoscopic alterations in these gel materials that are, in part, responsible for macroscopically-measured strain values, especially at low relative humidity, remain a topic of open debate in the literature. In this study, sodium-based calcium-alumino-silicate-hydrate (C-(N)-A-S-H) gel, the major binding phase of silicate-activated blast furnace slag (one type of low-CO$_2$ cement), is investigated from a drying perspective, since it is known to suffer extensively from drying-induced microcracking. By employing in situ synchrotron X-ray total scattering measurements and pair distribution function (PDF) analysis we show that the significant contributing factor to the strain development in this material at extremely low relative humidity (0%) is the local atomic structural rearrangement of the C-(N)-A-S-H gel, including collapse of interlayer spacing and slight disintegration of the gel. Moreover, analysis of the medium range (1.0 - 2.2 nm) ordering in the PDF data reveals that the PDF-derived strain values are in much closer agreement (same order of magnitude) with the macroscopically measured strain data, compared to previous results based on reciprocal space X-ray diffraction data. From a mitigation standpoint, we show that small amounts of ZrO$_2$ nanoparticles are able to actively reinforce the structure of silicate-activated slag during drying, preventing atomic level strains from developing. Mechanistically, these nanoparticles induce growth of a silica-rich gel during drying, which, via density functional theory calculations, we show is attributed to the high surface reactivity of tetragonal ZrO$_2$.

Doping Li and K into Na2ZrO3 Sorbent to Improve Its CO2 Capture Capability

NASA Astrophysics Data System (ADS)

Duan, Yuhua

Carbon dioxide is one of the major combustion products which once released into the air can contribute to global climate change. Solid sorbents have been reported in several previous studies to be promising candidates for CO2 sorbent applications due to their high CO2 absorption capacities at moderate working temperatures. However, at a given CO2 pressure, the turnover temperature (Tt) of an individual solid capture CO2 reaction is fixed and may be outside the operating temperature range (ΔTo) for a particularly capture technology. In order to shift such Tt for a solid into the range of ΔTo, its corresponding thermodynamic property must be changed by changing its structure by reacting (mixing) with other materials or doping with other elements. As an example, by combining thermodynamic database searching with ab initio thermodynamics calculations, in this work, we explored the Li- and K-doping effects on the Tt shifts of Na2ZrO3 at different doping levels. The obtained results showed that compared to pure Na2ZrO3, the Li- and K-doped mixtures Na2-αMαZrO3 (M =Li, K) have lower Tt and higher CO2 capture capacities.

Active three-way catalysis of rhodium particles with a low oxidation state maintained under an oxidative atmosphere on a La-containing ZrO2 support.

PubMed

Kawabata, Hisaya; Koda, Yuki; Sumida, Hirosuke; Shigetsu, Masahiko; Takami, Akihide; Inumaru, Kei

2013-05-11

Rhodium on a La-containing ZrO2 support effectively eliminated NOx from a synthetic auto exhaust gas under fluctuating oxygen conditions. Rhodium particles maintained a low oxidation state on the ZrO2-La2O3 mixed oxide even after treatment with 5% O2 at 773 K, highlighting the significant effect of the La addition.

The Effect of ZrO2 Nanoparticles on the Microstructure and Properties of Sintered WC–Bronze-Based Diamond Composites

PubMed Central

Sun, Youhong; Wu, Haidong; Li, Meng; Meng, Qingnan; Gao, Ke; Lü, Xiaoshu; Liu, Baochang

2016-01-01

Metal matrix-impregnated diamond composites are widely used in diamond tool manufacturing. In order to satisfy the increasing engineering requirements, researchers have paid more and more attention to enhancing conventional metal matrices by applying novel methods. In this work, ZrO2 nanoparticles were introduced into the WC–bronze matrix with and without diamond grits via hot pressing to improve the performance of conventional diamond composites. The effects of ZrO2 nanoparticles on the microstructure, density, hardness, bending strength, and wear resistance of diamond composites were investigated. The results indicated that the hardness and relative density increased, while the bending strength decreased when the content of ZrO2 nanoparticles increased. The grinding ratio of diamond composites increased significantly by 60% as a result of nano-ZrO2 addition. The enhancement mechanism was discussed. Diamond composites showed the best overall properties with the addition of 1 wt % ZrO2 nanoparticles, thus paving the way for further applications. PMID:28773469

Morphological Evolution and Weak Interface Development within CVD-Zirconia Coating Deposited on Hi-Nicalon Fiber

NASA Technical Reports Server (NTRS)

Li, Hao; Lee, Jinil; Libera, Matthew R.; Lee, Woo Y.; Kebbede, Anteneh; Lance, Michael J.; Wang, Hongyu; Morscher, Gregory N.; Gray, Hugh R. (Technical Monitor)

2002-01-01

The phase contents and morphology of a ZrO2 fiber coating deposited at 1050 C on Hi-Nicalon(Tm) by chemical vapor deposition were examined as a function of deposition time from 5 to 120 min. The morphological evolution in the ZrO2 coating was correlated to the development of delamination within the ZrO2 coating. The delamination appears to occur as a result of: (1) continuous formation of tetragonal ZrO2 nuclei on the deposition surface; (2) martensitic transformation of the tetragonal phase to a monoclinic phase upon reaching a critical grain size; and (3) development of significant compressive hoop stresses due to the volume dilation associated with the transformation. Our observations suggest that it will be of critical importance to further understand and eventually control the nucleation and grain growth behavior of CVD ZrO2 and its phase transformation behavior for its potential applications for composites.

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.

TiO2, SiO2 and ZrO2 Nanoparticles Synergistically Provoke Cellular Oxidative Damage in Freshwater Microalgae

PubMed Central

Liu, Yinghan; Ye, Nan; Fang, Hao; Wang, Degao

2018-01-01

Metal-based nanoparticles (NPs) are the most widely used engineered nanomaterials. The individual toxicities of metal-based NPs have been plentifully studied. However, the mixture toxicity of multiple NP systems (n ≥ 3) remains much less understood. Herein, the toxicity of titanium dioxide (TiO2) nanoparticles (NPs), silicon dioxide (SiO2) NPs and zirconium dioxide (ZrO2) NPs to unicellular freshwater algae Scenedesmus obliquus was investigated individually and in binary and ternary combination. Results show that the ternary combination systems of TiO2, SiO2 and ZrO2 NPs at a mixture concentration of 1 mg/L significantly enhanced mitochondrial membrane potential and intracellular reactive oxygen species level in the algae. Moreover, the ternary NP systems remarkably increased the activity of the antioxidant defense enzymes superoxide dismutase and catalase, together with an increase in lipid peroxidation products and small molecule metabolites. Furthermore, the observation of superficial structures of S. obliquus revealed obvious oxidative damage induced by the ternary mixtures. Taken together, the ternary NP systems exerted more severe oxidative stress in the algae than the individual and the binary NP systems. Thus, our findings highlight the importance of the assessment of the synergistic toxicity of multi-nanomaterial systems. PMID:29419775

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

Electronic structure and electron energy-loss spectroscopy of ZrO2 zirconia

NASA Astrophysics Data System (ADS)

Dash, L. K.; Vast, Nathalie; Baranek, Philippe; Cheynet, Marie-Claude; Reining, Lucia

2004-12-01

The atomic and electronic structures of zirconia are calculated within density functional theory, and their evolution is analyzed as the crystal-field symmetry changes from tetrahedral [cubic (c-ZrO2) and tetragonal (t-ZrO2) phases] to octahedral (hypothetical rutile ZrO2 ), to a mixing of these symmetries (monoclinic phase, m-ZrO2 ). We find that the theoretical bulk modulus in c-ZrO2 is 30% larger than the experimental value, showing that the introduction of yttria in zirconia has a significant effect. Electronic structure fingerprints which characterize each phase from their electronic spectra are identified. We have carried out electron energy-loss spectroscopy experiments at low momentum transfer and compared these results to the theoretical spectra calculated within the random phase approximation. We show a dependence of the valence and 4p ( N2,3 edge) plasmons on the crystal structure, the dependence of the latter being brought into the spectra by local-field effects. Last, we attribute low energy excitations observed in EELS of m-ZrO2 to defect states 2eV above the top of the intrinsic valence band, and the EELS fundamental band gap value is reconciled with the 5.2 or 5.8eV gaps determined by vacuum ultraviolet spectroscopy.

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.

Microstructure-property relationships of chemically vapor deposited zirconia fiber coating for environmentally durable silicon carbide/silicon carbide composites

NASA Astrophysics Data System (ADS)

Li, Hao

In SiC/SiC ceramic matrix composites, toughness is obtained by adding a fiber coating, which provides a weak interface for crack deflection and debonding between the fiber and the matrix. However, the most commonly used fiber coatings, carbon and boron nitride, are unstable in oxidative environments. In the present study, the feasibility of using a chemically vapor deposited zirconia (CVD-ZrO2) fiber coating as an oxidation-resistant interphase for SiC/SiC composites was investigated. A study of morphological evolution in the CVD-ZrO2 coating suggested that a size-controlled displacive phase transformation from tetragonal ZrO2 ( t-ZrO2) to monoclinic ZrO2 (m-ZrO 2) was the key mechanism responsible for the weak interface behavior exhibited by the ZrO2 coating. It appeared that a low oxygen partial pressure in the CVD reactor chamber was essential for the nucleation of t-ZrO2 and therefore was responsible for the delamination behavior. With this understanding of the weak interface mechanism, minicomposite specimens containing various ZrO2 fiber coating morphologies were fabricated and tested. A fractographic analysis showed that in-situ fiber strength and minicomposite failure loads were strongly dependent on the phase contents and microstructure of the ZrO2 coating. We determined that an optimum microstructure of the ZrO2 coating should contain a predelaminated interface surrounded by a dense outer layer. The outer layer was needed to protect the fiber from degradation during the subsequent SiC matrix infiltration procedure. A preliminary tensile stress-rupture study indicated that the ZrO2 coating exhibited promising performance in terms of providing the weak interface behavior and maintaining the thermal and oxidative stability at elevated temperatures.

Tribology of Ceramics

DTIC Science & Technology

1988-01-01

Surface crystallography must be studied as modified by friction. Toughening and embrittling phase transformations have been discovered and modify the...2) dispersed ceramic whiskers, (3) long fiber rein- forcement, (4) precipitation , and (5) ductile metal phase . Each of these results in a...structure. Metastable structures of certain ceramics (Kingery et al., 1976) such as ZrO 2 allow a martensitic transformation under stress, which confers

Ceramic composite separators coated with moisturized ZrO(2) nanoparticles for improving the electrochemical performance and thermal stability of lithium ion batteries.

PubMed

Kim, Ki Jae; Kwon, Hyuk Kwon; Park, Min-Sik; Yim, Taeeun; Yu, Ji-Sang; Kim, Young-Jun

2014-05-28

We introduce a ceramic composite separator prepared by coating moisturized ZrO2 nanoparticles with a poly(vinylidene fluoride-co-hexafluoropropylene) (PVdF-12wt%HFP) copolymer on a polyethylene separator. The effect of moisturized ZrO2 nanoparticles on the morphology and the microstructure of the polymeric coating layer is investigated. A large number of micropores formed around the embedded ZrO2 nanoparticles in the coating layer as a result of the phase inversion caused by the adsorbed moisture. The formation of micropores highly affects the ionic conductivity and electrolyte uptake of the ceramic composite separator and, by extension, the rate discharge properties of lithium ion batteries. In particular, thermal stability of the ceramic composite separators coated with the highly moisturized ZrO2 nanoparticles (a moisture content of 16 000 ppm) is dramatically improved without any degradation in electrochemical performance compared to the performance of pristine polyethylene separators.

Influence of deposition temperature on mechanical properties of plasma-sprayed hydroxyapatite coating on titanium alloy with ZrO2 intermediate layer

NASA Astrophysics Data System (ADS)

Chou, Bang-Yen; Chang, Edward

2003-06-01

Hydroxyapatite coatings were plasma sprayed on the Ti6A14V substrate with and without an intermediate ZrO2 layer; meanwhile the temperatures of substrates were varied at 90, 140, and 200 °C. The coatings were subjected to the standard adhesion test per ASTM C633-79. The purpose of the investigation was to study the effects of those processing variables on the bonding strength and failure behavior of the system. It is found that the bonding strengths of HA/ZrO2 and HA coatings generally decrease with increasing substrate temperature, except for the HA/ZrO2 coating deposited at 200 °C. The rationale of the results is attributed to the residual stress reported in the literature. Introducing ZrO2 bond coat is found to significantly promote the bonding strength of HA coating. The possible strengthening mechanism is the rougher surface of ZrO2 bond coat and the higher toughness of ZrO2, which provide the mechanical strengthening effects. The slightly denser HA in 200 °C deposited HA coating cannot explain the high bonding strength of the HA/ZrO2 coating, nor the mechanical strengthening effect of ZrO2 intermediate layer should apply. It is believed that a stronger diffusion bonding is formed at the interface of HA and ZrO2, which increases the bonding between them chemically. The bonding strengths of HA/ZrO2 and HA coatings are correlated with the area fraction of adhesive failure of the coatings. The correlation explains the findings in this study.

In situ NAP-XPS spectroscopy during methane dry reforming on ZrO2/Pt(1 1 1) inverse model catalyst

NASA Astrophysics Data System (ADS)

Rameshan, C.; Li, H.; Anic, K.; Roiaz, M.; Pramhaas, V.; Rameshan, R.; Blume, R.; Hävecker, M.; Knudsen, J.; Knop-Gericke, A.; Rupprechter, G.

2018-07-01

Due to the need of sustainable energy sources, methane dry reforming is a useful reaction for conversion of the greenhouse gases CH4 and CO2 to synthesis gas (CO  +  H2). Syngas is the basis for a wide range of commodity chemicals and can be utilized for fuel production via Fischer–Tropsch synthesis. The current study focuses on spectroscopic investigations of the surface and reaction properties of a ZrO2/Pt inverse model catalyst, i.e. ZrO2 particles (islands) grown on a Pt(1 1 1) single crystal, with emphasis on in situ near ambient pressure x-ray photoelectron spectroscopy (NAP-XPS) during MDR reaction. In comparison to technological systems, model catalysts facilitate characterization of the surface (oxidation) state, surface adsorbates, and the role of the metal-support interface. Using XPS and infrared reflection absorption spectroscopy we demonstrated that under reducing conditions (UHV or CH4) the ZrO2 particles transformed to an ultrathin ZrO2 film that started to cover (wet) the Pt surface in an SMSI-like fashion, paralleled by a decrease in surface/interface oxygen. In contrast, (more oxidizing) dry reforming conditions with a 1:1 ratio of CH4 and CO2 were stabilizing the ZrO2 particles on the model catalyst surface (or were even reversing the strong metal support interaction (SMSI) effect), as revealed by in situ XPS. Carbon deposits resulting from CH4 dissociation were easily removed by CO2 or by switching to dry reforming conditions (673–873 K). Thus, at these temperatures the active Pt surface remained free of carbon deposits, also preserving the ZrO2/Pt interface.

Probing the bulk ionic conductivity by thin film hetero-epitaxial engineering

NASA Astrophysics Data System (ADS)

Pergolesi, Daniele; Roddatis, Vladimir; Fabbri, Emiliana; Schneider, Christof W.; Lippert, Thomas; Traversa, Enrico; Kilner, John A.

2015-02-01

Highly textured thin films with small grain boundary regions can be used as model systems to directly measure the bulk conductivity of oxygen ion conducting oxides. Ionic conducting thin films and epitaxial heterostructures are also widely used to probe the effect of strain on the oxygen ion migration in oxide materials. For the purpose of these investigations a good lattice matching between the film and the substrate is required to promote the ordered film growth. Moreover, the substrate should be a good electrical insulator at high temperature to allow a reliable electrical characterization of the deposited film. Here we report the fabrication of an epitaxial heterostructure made with a double buffer layer of BaZrO3 and SrTiO3 grown on MgO substrates that fulfills both requirements. Based on such template platform, highly ordered (001) epitaxially oriented thin films of 15% Sm-doped CeO2 and 8 mol% Y2O3 stabilized ZrO2 are grown. Bulk conductivities as well as activation energies are measured for both materials, confirming the success of the approach. The reported insulating template platform promises potential application also for the electrical characterization of other novel electrolyte materials that still need a thorough understanding of their ionic conductivity.

Influence of sulfides on the tribological properties of composites produced by pulse electric current sintering

NASA Astrophysics Data System (ADS)

Kim, Seung Ho

2014-01-01

Self-lubricating Al2O3-15wt% ZrO2 composites with sulfides, such as molybdenum disulfide (MoS2) and tungsten disulfide (WS2) serving as solid lubricants, were fabricated by using the pulse electric current sintering (PECS) technique. The coefficient of friction (COF) of the Al2O3-15wt% ZrO2 composite without/with sulfides was in the range of 0.37-0.48 and 0.27-0.49, respectively. As the amount of sulfides increased, the COF and the wear rate decreased. The reduction in COF and wear rate of the sulfide-containing composite is caused by a reduction in shear stresses between the specimen and the tribological medium due to the formation of a lubricating film resulting from the lamellar structure of sulfides located on the worn surface.

Comparison of fracture strength and failure mode of different ceramic implant abutments.

PubMed

Elsayed, Adham; Wille, Sebastian; Al-Akhali, Majed; Kern, Matthias

2017-04-01

The whitish color of zirconia (ZrO 2 ) abutments offers favorable esthetics compared with the grayish color of titanium (Ti) abutments. Nonetheless, ZrO 2 has greater opacity, making it difficult to achieve natural tooth color. Therefore, lithium disilicate (LaT) abutments have been suggested to replace metal abutments. The purpose of this in vitro study was to evaluate the fracture strength and failure mode of single-tooth implant restorations using ZrO 2 and LaT abutments, and to compare them with titanium (Ti) abutments. Five different types of abutments, Ti; ZrO 2 with no metal base; ZrO 2 with a metal base (ZrT); LaT; and LaT combination abutment and crown (LcT) were assembled on 40 Ti implants and restored with LaT crowns. Specimens were subjected to quasistatic loading using a universal testing machine, until the implant-abutment connection failed. As bending of the metal would be considered a clinical failure, the values of force (N) at which the plastic deformation of the metal occurred were calculated, and the rate of deformation was analyzed. Statistical analysis was done using the Mann-Whitney U test (α=.05). Group ZrO 2 revealed the lowest resistance to failure with a mean of 202 ±33 N. Groups ZrT, LaT, and LaC withstood higher forces without fracture or debonding of the ceramic suprastructure, and failure was due to deformation of metal bases, with no statistically significant differences between these groups regarding the bending behavior. Within the limitations of this in vitro study, it was concluded that LaT abutments have the potential to withstand the physiological occlusal forces that occur in the anterior region and that ZrO 2 abutments combined with Ti inserts have much higher fracture strength than pure ZrO 2 abutments. Copyright © 2016 Editorial Council for the Journal of Prosthetic Dentistry. Published by Elsevier Inc. All rights reserved.

Evaluation of oxide-coated iridium-rhenium chambers

NASA Astrophysics Data System (ADS)

Reed, Brian D.

1994-03-01

Iridium-coated rhenium (Ir-Re) provides long life operation of radiation-cooled rockets at temperatures up to 2200 C. Ceramic oxide coatings could be used to increase Ir-Re rocket lifetimes and allow operation in highly oxidizing environments. Ceramic oxide coatings promise to serve as both thermal and diffusion barriers for the iridium layer. Seven ceramic oxide-coated Ir-Re, 22-N rocket chambers were tested with gaseous hydrogen/gaseous oxygen (GHz/G02) propellants. Five chambers had thick (over 10 mils), monolithic coatings of either hafnia (HfO2) or zirconia (ZrO2). Two chambers had coatings with thicknesses less than 5 mils. One of these chambers had a thin-walled coating of ZrO2 infiltrated with sol gel HfO2. The other chamber had a coating composed of an Ir-oxide composite. The purpose of this test program was to assess the ability of the oxide coatings to withstand the thermal shock of combustion initiation, adhere under repeated thermal cycling, and operate in aggressively oxidizing environments. All of the coatings survived the thermal shock of combustion and demonstrated operation at mixture ratios up to 11. Testing the Ir-oxide composite-coated chamber included over 29 min at mixture ratio 16. The thicker walled coatings provided the larger temperature drops across the oxide layer (up to 570 C), but were susceptible to macrocracking and eventual chipping at a stress concentrator. The cracks apparently resealed during firing, under compression of the oxide layer. The thinner walled coatings did not experience the macrocracking and chipping of the chambers that was seen with the thick, monolithic coatings. However, burn-throughs in the throat region did occur in both of the thin-walled chambers at mixture ratios well above stoichiometric. The burn-throughs were probably the result of oxygen diffusion through the oxide coating that allowed the underlying Ir and Re layers to be oxidized. The results of this test program indicated that the thin-walled oxide coatings are better suited for repeated thermal cycling than the thick-walled coating, while thicker coatings may be required for operation in aggressively oxidizing environments.

Evaluation of oxide-coated iridium-rhenium chambers

NASA Technical Reports Server (NTRS)

Reed, Brian D.

1994-01-01

Iridium-coated rhenium (Ir-Re) provides long life operation of radiation-cooled rockets at temperatures up to 2200 C. Ceramic oxide coatings could be used to increase Ir-Re rocket lifetimes and allow operation in highly oxidizing environments. Ceramic oxide coatings promise to serve as both thermal and diffusion barriers for the iridium layer. Seven ceramic oxide-coated Ir-Re, 22-N rocket chambers were tested with gaseous hydrogen/gaseous oxygen (GHz/G02) propellants. Five chambers had thick (over 10 mils), monolithic coatings of either hafnia (HfO2) or zirconia (ZrO2). Two chambers had coatings with thicknesses less than 5 mils. One of these chambers had a thin-walled coating of ZrO2 infiltrated with sol gel HfO2. The other chamber had a coating composed of an Ir-oxide composite. The purpose of this test program was to assess the ability of the oxide coatings to withstand the thermal shock of combustion initiation, adhere under repeated thermal cycling, and operate in aggressively oxidizing environments. All of the coatings survived the thermal shock of combustion and demonstrated operation at mixture ratios up to 11. Testing the Ir-oxide composite-coated chamber included over 29 min at mixture ratio 16. The thicker walled coatings provided the larger temperature drops across the oxide layer (up to 570 C), but were susceptible to macrocracking and eventual chipping at a stress concentrator. The cracks apparently resealed during firing, under compression of the oxide layer. The thinner walled coatings did not experience the macrocracking and chipping of the chambers that was seen with the thick, monolithic coatings. However, burn-throughs in the throat region did occur in both of the thin-walled chambers at mixture ratios well above stoichiometric. The burn-throughs were probably the result of oxygen diffusion through the oxide coating that allowed the underlying Ir and Re layers to be oxidized. The results of this test program indicated that the thin-walled oxide coatings are better suited for repeated thermal cycling than the thick-walled coating, while thicker coatings may be required for operation in aggressively oxidizing environments.

Formation of high heat resistant coatings by using gas tunnel type plasma spraying.

PubMed

Kobayashi, A; Ando, Y; Kurokawa, K

2012-06-01

Zirconia sprayed coatings are widely used as thermal barrier coatings (TBC) for high temperature protection of metallic structures. However, their use in diesel engine combustion chamber components has the long run durability problems, such as the spallation at the interface between the coating and substrate due to the interface oxidation. Although zirconia coatings have been used in many applications, the interface spallation problem is still waiting to be solved under the critical conditions such as high temperature and high corrosion environment. The gas tunnel type plasma spraying developed by the author can make high quality ceramic coatings such as Al2O3 and ZrO2 coating compared to other plasma spraying method. A high hardness ceramic coating such as Al2O3 coating by the gas tunnel type plasma spraying, were investigated in the previous study. The Vickers hardness of the zirconia (ZrO2) coating increased with decreasing spraying distance, and a higher Vickers hardness of about Hv = 1200 could be obtained at a shorter spraying distance of L = 30 mm. ZrO2 coating formed has a high hardness layer at the surface side, which shows the graded functionality of hardness. In this study, ZrO2 composite coatings (TBCs) with Al2O3 were deposited on SS304 substrates by gas tunnel type plasma spraying. The performance such as the mechanical properties, thermal behavior and high temperature oxidation resistance of the functionally graded TBCs was investigated and discussed. The resultant coating samples with different spraying powders and thickness are compared in their corrosion resistance with coating thickness as variables. Corrosion potential was measured and analyzed corresponding to the microstructure of the coatings. High Heat Resistant Coatings, Gas Tunnel Type Plasma Spraying, Hardness,

[Preliminary study on DNA damage of ZrO(2)/LaPO(4) diphase ceramics on human peripheral blood lymphocytes in vitro].

PubMed

Zhu, Hui-fang; Chen, Li-ping; Zhang, Xiu-li; Zhang, Bao-wei

2009-06-01

To detect the genotoxicity of dental machinable ZrO(2)/LaPO(4) diphase ceramics on human peripheral blood lymphocytes in vitro. The evaluation of DNA damage on human lymphocytes was performed by comet assay for three groups of ZrO(2)/LaPO(4) diphase ceramics with 30wt% of LaPO(4) (with 3wt% and 5wt% of Y(2)O(3)) and 40wt% of LaPO(4) (with 5wt% of Y(2)O(3)). The results were analyzed with SPSS16.0 software package for one-factor ANOVA and LSD. Three experimental groups with different concentration of LaPO(4) of ZrO(2)/LaPO(4) diphase ceramics, the negative control of IPS Empress II ceramics and the blank behaved little migration of the DNA strands respectively after six-day test, and there was no significant difference in all the groups except the positive control (P>0.05). The study indicates little effect of DNA damage of ZrO(2)/LaPO(4) diphase ceramics.

The effect of micro-structure on upconversion luminescence of Nd3+/Yb3+ co-doped La2O3-TiO2-ZrO2 glass-ceramics

NASA Astrophysics Data System (ADS)

Zhang, Minghui; Wen, Haiqin; Pan, Xiuhong; Yu, Jianding; Jiang, Meng; Yu, Huimei; Tang, Meibo; Gai, Lijun; Ai, Fei

2018-03-01

Nd3+/Yb3+ co-doped La2O3-TiO2-ZrO2 glasses have been prepared by aerodynamic levitation method. The glasses show high refractive index of 2.28 and Abbe number of 18.3. Glass-ceramics heated at 880 °C for 50 min perform the strongest upconversion luminescence. X-ray diffraction patterns of glass-ceramics with different depths indicate that rare earth ions restrain crystallization. Body crystallization mechanism mixed with surface crystallization is confirmed in the heat treatment. Surface crystals achieve priority to grow, resulting in important effects on upconversion luminescence. The results of atomic force microscope and scanning electron microscope indicate that crystal particles with uniform size distribute densely and homogenously on the surface and large amount of glass matrix exists in the glass ceramics heated at 880 °C for 50 min. Crystals in the glass-ceramics present dense structure and strong boundaries, which can reduce the mutual nonradiative relaxation rate among rare earth ions and then improve upconversion luminescence effectively. Based on micro-structural study, the mechanism that upconversion luminescence can be improved by heat treatment has been revealed. The results of micro-structural analysis agree well with the spectra.

Enhanced initial protein adsorption on engineered nanostructured cubic zirconia.

PubMed

Sabirianov, R F; Rubinstein, A; Namavar, F

2011-04-14

Motivated by experimentally-observed biocompatibility enhancement of nanoengineered cubic zirconia (ZrO(2)) coatings to mesenchymal stromal cells, we have carried out computational analysis of the initial immobilization of one known structural fragment of the adhesive protein (fibronectin) on the corresponding surface. We constructed an atomistic model of the ZrO(2) nano-hillock of 3-fold symmetry based on Atom Force Microscopy and Transmission Electron Microscopy images. First principle quantum mechanical calculations show a substantial variation of electrostatic potential at the hillock due to the presence of surface features such as edges and vertexes. Using an implemented Monte Carlo simulated annealing method, we found the orientation of the immobilized protein on the ZrO(2) surface and the contribution of the amino acid residues from the protein sequence to the adsorption energy. Accounting for the variation of the dielectric permittivity at the protein-implant interface, we used a model distance-dependent dielectric function to describe the inter-atom electrostatic interactions in the adsorption potential. We found that the initial immobilization of the rigid protein fragment on the nanostructured pyramidal ZrO(2) surface is achieved with a magnitude of adsorption energy larger than that of the protein on the smooth (atomically flat) surface. The strong attractive electrostatic interactions are a major contributing factor in the enhanced adsorption at the nanostructured surface. In the case of adsorption on the flat, uncharged surface this factor is negligible. We show that the best electrostatic and steric fit of the protein to the inorganic surface corresponds to a minimum of the adsorption energy determined by the non-covalent interactions.

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.

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.

Tensile Strength and Microstructure of Al2O3-ZrO2 Hypo-Eutectic Fibers Studied

NASA Technical Reports Server (NTRS)

Farmer, Serene C.; Sayir, Ali

2001-01-01

Oxide eutectics offer high-temperature strength retention and creep resistance in oxidizing environments. Al2O3-ZrO2 eutectic strengths have been studied since the 1970's. Directionally solidified oxide eutectics exhibit improved resistance to slow crack growth and excellent strength retention at high temperatures up to 1400 C. Materials studied typically contain Y2O3 to metastably retain the high-temperature cubic and tetragonal polymorphs at room temperature. Al2O3-ZrO2 is of fundamental interest for creep studies because it combines a creep-resistant material, Al2O3, with a very low creep resistance material, ZrO2. Results on mechanical properties and microstructures of these materials will be used to define compositions for creep testing in future work. Substantial variations from the eutectic alumina to zirconia ratio can be tolerated without a loss in room-temperature strength. The effect of increasing Y2O3 addition on the room-temperature tensile strength of an Al2O3-ZrO2 material containing excess Al2O3 was examined at the NASA Glenn Research Center, where the materials were grown using Glenn's world-class laser growth facilities.

Fabrication and Properties of Plasma-Sprayed Al2O3/ZrO2 Composite Coatings

NASA Astrophysics Data System (ADS)

Dejang, N.; Limpichaipanit, A.; Watcharapasorn, A.; Wirojanupatump, S.; Niranatlumpong, P.; Jiansirisomboon, S.

2011-12-01

Al2O3 /xZrO2 (where x = 0, 3, 13, and 20 wt.%) composite coatings were deposited onto mild steel substrates by atmospheric plasma spraying of mixed α-Al2O3 and nano-sized monoclinic-ZrO2 powders. Microstructural investigation showed that the coatings comprised well-separated Al2O3 and ZrO2 lamellae, pores, and partially molten particles. The coating comprised mainly of metastable γ-Al2O3 and tetragonal-ZrO2 with trace of original α-Al2O3 and monoclinic-ZrO2 phases. The effect of ZrO2 addition on the properties of coatings were investigated in terms of microhardness, fracture toughness, and wear behavior. It was found that ZrO2 improved the fracture toughness, reduced friction coefficient, and wear rate of the coatings.

Structural and chemical degradation mechanisms of pure YSZ and its components ZrO2 and Y2O3 in carbon-rich fuel gases.

PubMed

Köck, Eva-Maria; Kogler, Michaela; Götsch, Thomas; Klötzer, Bernhard; Penner, Simon

2016-05-25

Structural and chemical degradation mechanisms of metal-free yttria stabilized zirconia (YSZ-8, 8 mol% Y2O3 in ZrO2) in comparison to its pure oxidic components ZrO2 and Y2O3 have been studied in carbon-rich fuel gases with respect to coking/graphitization and (oxy)carbide formation. By combining operando electrochemical impedance spectroscopy (EIS), operando Fourier-transform infrared (FT-IR) spectroscopy and X-ray photoelectron spectroscopy (XPS), the removal and suppression of CH4- and CO-induced carbon deposits and of those generated in more realistic fuel gas mixtures (syngas, mixtures of CH4 or CO with CO2 and H2O) was examined under SOFC-relevant conditions up to 1273 K and ambient pressures. Surface-near carbidization is a major problem already on the "isolated" (i.e. Nickel-free) cermet components, leading to irreversible changes of the conduction properties. Graphitic carbon deposition takes place already on the "isolated" oxides under sufficiently fuel-rich conditions, most pronounced in the pure gases CH4 and CO, but also significantly in fuel gas mixtures containing H2O and CO2. For YSZ, a comparative quantification of the total amount of deposited carbon in all gases and mixtures is provided and thus yields favorable and detrimental experimental approaches to suppress the carbon formation. In addition, the effectivity and reversibility of removal of the coke/graphite layers was comparably studied in the pure oxidants O2, CO2 and H2O and their effective contribution upon addition to the pure fuel gases CO and CH4 verified.

A composite material with CeO2-ZrO2 nanocrystallines embedded in SiO2 matrices and its enhanced thermal stability and oxygen storage capacity

NASA Astrophysics Data System (ADS)

Yang, Runnong; Liu, Yumei; Yu, Lin; Zhao, Xiangyun; Yang, Xiaobo; Sun, Ming; Luo, Junyin; Fan, Qun; Xiao, Jianming; Zhao, Yuzhong

2018-06-01

A simple hydrothermal procedure is introduced, which leads to the successful synthesis of a new composite material with fine CeO2-ZrO2 nanocrystallites embedded in amorphous and porous SiO2 matrices. The composite material possesses an extraordinary high thermal stability. After being calcined at 1000 °C, it retains CeO2-ZrO2 nanocrystallites of the size around 5 nm, a BET-specific surface area of 165 m2/g, and an oxygen storage capacity of 468 μmol/g. No phase segregation for CeO2-ZrO2 nanocrystallites is detected and the SiO2 matrices remain not crystallized. The composite material shows a great potential as a support of three-way catalyst, as evidenced in catalytic tests with supported Pt.

Hydrothermal-precipitation preparation of CdS@(Er3+:Y3Al5O12/ZrO2) coated composite and sonocatalytic degradation of caffeine.

PubMed

Huang, Yingying; Wang, Guowei; Zhang, Hongbo; Li, Guanshu; Fang, Dawei; Wang, Jun; Song, Youtao

2017-07-01

Here, we reported a novel method to dispose caffeine by means of ultrasound irradiation combinated with CdS@(Er 3+ :Y 3 Al 5 O 12 /ZrO 2 ) coated composite as sonocatalyst. The CdS@(Er 3+ :Y 3 Al 5 O 12 /ZrO 2 ) was synthesized via hydrothermal-precipitation method and then characterized by X-ray diffractometer (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray analysis (EDX) and UV-vis diffuse reflectance spectra (DRS). After that, the sonocatalytic degradation of caffeine in aqueous solution was conducted adopting CdS@(Er 3+ :Y 3 Al 5 O 12 /ZrO 2 ) and CdS@ZrO 2 coated composites as sonocatalysts. In addition, some influencing factors such as CdS and ZrO 2 molar proportion, caffeine concentration, ultrasonic irradiation time, sonocatalyst dosage and addition of several inorganic oxidants on sonocatalytic degradation of caffeine were investigated by using UV-vis spectra and gas chromatograph. The experimental results showed that the presence of Er 3+ :Y 3 Al 5 O 12 could effectively improve the sonocatalytic degradation activity of CdS@ZrO 2 . To a certain extent some inorganic oxidants can also enhance sonocatalytic degradation of caffeine in the presence of CdS@(Er 3+ :Y 3 Al 5 O 12 /ZrO 2 ). The best sonocatalytic degradation ratio (94.00%) of caffeine could be obtained when the conditions of 5.00mg/L caffeine, 1.00g/L prepared CdS@(Er 3+ :Y 3 Al 5 O 12 /ZrO 2 ), 10.00mmol/LK 2 S 2 O 8 , 180min ultrasonic irradiation (40kHz frequency and 50W output power), 100mL total volume and 25-28°C temperature were adopted. It seems that the method of sonocatalytic degradation caused by CdS@(Er 3+ :Y 3 Al 5 O 12 /ZrO 2 ) displayspotentialadvantages in disposing caffeine. Copyright © 2017 Elsevier B.V. All rights reserved.

Phenol-photodegradation on ZrO2. Enhancement by semiconductors.

PubMed

Karunakaran, C; Dhanalakshmi, R; Gomathisankar, P

2012-06-15

On illumination with light of wavelength 365 nm phenol undergoes degradation on the surface of ZrO(2). The rate of degradation enhances linearly with the concentration of phenol and also the light intensity but decreases with increase of pH. The photonic efficiency of degradation is higher with illumination at 254 nm than with 365 nm. The diffuse reflectance spectral study suggests phenol-sensitized activation of ZrO(2) with 365 nm light. TiO(2), Fe(2)O(3), CuO, ZnO, ZnS, Nb(2)O(5) and CdO particles enhance the photodegradation on ZrO(2), indicating inter-particle charge-transfer. Determination of size of the particles under suspension, by light scattering technique, shows agglomeration of particles supporting the proposition of charge-transfer between particles. Copyright © 2012 Elsevier B.V. All rights reserved.

Preparation and Characterization of Zirconia-Coated Nanodiamonds as a Pt Catalyst Support for Methanol Electro-Oxidation

PubMed Central

Lu, Jing; Zang, Jianbing; Wang, Yanhui; Xu, Yongchao; Xu, Xipeng

2016-01-01

Zirconia-coated nanodiamond (ZrO2/ND) electrode material was successfully prepared by one-step isothermal hydrolyzing from ND-dispersed ZrOCl2·8H2O aqueous solution. High-resolution transmission electron microscopy reveals that a highly conformal and uniform ZrO2 shell was deposited on NDs by this simple method. The coating obtained at 90 °C without further calcination was mainly composed of monoclinic nanocrystalline ZrO2 rather than common amorphous Zr(OH)4 clusters. The ZrO2/NDs and pristine ND powder were decorated with platinum (Pt) nanoparticles by electrodeposition from 5 mM chloroplatinic acid solution. The electrochemical studies indicate that Pt/ZrO2/ND catalysts have higher electrocatalytic activity and better stability for methanol oxidation than Pt/ND catalysts in acid. PMID:28335361

Frequency dispersion analysis of thin dielectric MOS capacitor in a five-element model

NASA Astrophysics Data System (ADS)

Zhang, Xizhen; Zhang, Sujuan; Zhu, Huichao; Pan, Xiuyu; Cheng, Chuanhui; Yu, Tao; Li, Xiangping; Cheng, Yi; Xing, Guichao; Zhang, Daming; Luo, Xixian; Chen, Baojiu

2018-02-01

An Al/ZrO2/IL/n-Si (IL: interface layer) MOS capacitor has been fabricated by metal organic decomposition of ZrO2 and thermal deposition Al. We have measured parallel capacitance (C m) and parallel resistance (R m) versus bias voltage curves (C m, R m-V) at different AC signal frequency (f), and C m, R m-f curves at different bias voltage. The curves of C m, R m-f measurements show obvious frequency dispersion in the range of 100 kHz-2 MHz. The energy band profile shows that a large voltage is applied on the ZrO2 layer and IL at accumulation, which suggests possible dielectric polarization processes by some traps in ZrO2 and IL. C m, R m-f data are used for frequency dispersion analysis. To exclude external frequency dispersion, we have extracted the parameters of C (real MOS capacitance), R p (parallel resistance), C IL (IL capacitance), R IL (IL resistance) and R s (Si resistance) in a five-element model by using a three-frequency method. We have analyzed intrinsic frequency dispersion of C, R p, C IL, R IL and R s by studying the dielectric characteristics and Si surface layer characteristics. At accumulation, the dispersion of C and R p is attributed to dielectric polarization such as dipolar orientation and oxide traps. The serious dispersion of C IL and R IL are relative to other dielectric polarization, such as border traps and fixed oxide traps. The dispersion of R s is mainly attributed to contact capacitance (C c) and contact resistance (R c). At depletion and inversion, the frequency dispersion of C, R p, C IL, R IL, and R s are mainly attributed to the depletion layer capacitance (C D). The interface trap capacitance (C it) and interface trap resistance (R it) are not dominant for the dispersion of C, R p, C IL, R IL, and R s.

Derivative effect of laser cladding on interface stability of YSZ@Ni coating on GH4169 alloy: An experimental and theoretical study

NASA Astrophysics Data System (ADS)

Zheng, Haizhong; Li, Bingtian; Tan, Yong; Li, Guifa; Shu, Xiaoyong; Peng, Ping

2018-01-01

Yttria-stabilized zirconia YSZ@Ni core-shell nanoparticles were used to prepare a thermal barrier coating (TBC) on a GH4169 alloy by laser cladding. Microstructural analysis showed that the TBC was composed of two parts: a ceramic and a bonding layer. In places where the ZrO2/Al2O3 eutectic structure was present in the ceramic layer, the Ni atoms diffused into the bonding layer, as confirmed by energy-dispersive X-ray spectroscopy (EDS). The derivative effect of laser cladding results in the original YSZ@Ni core-shell nanoparticles being translated into the Al2O3 crystal, activating the YSZ. The mechanism of ceramic/metal interface cohesion was studied in depth via first-principles and molecular dynamics simulation. The results show that the trend in the diffusion coefficients of Ni, Fe, Al, and Ti is DNi > DFe > DTi > DAl in the melting or solidification process of the material. The enthalpy of formation for Al2O3 is less than that of TiO2, resulting in a thermally grown oxide (TGO) Al2O3 phase transformation. With regard to the electronic structure, the trend in Mulliken population is QO-Ni > QZr-O > QO-Al. Although the bonding is slightly weakened between ZrO2/Al2O3 (QZr-O = 0.158 < QO-Ni = 0.220) compared to that in ZrO2/Ni, TGO Al2O3 can improve the oxidation resistance of the metal matrix. Thus, by comparing the connective and diffusive processes, our findings lay the groundwork for detailed and comprehensive studies of the laser cladding process for the production of composite materials.

Effect of the CTAB concentration on the upconversion emission of ZrO 2:Er 3+ nanocrystals

NASA Astrophysics Data System (ADS)

López-Luke, T.; De la Rosa, E.; Sólis, D.; Salas, P.; Angeles-Chavez, C.; Montoya, A.; Díaz-Torres, L. A.; Bribiesca, S.

2006-10-01

Upconversion emission of ZrO 2:Er 3+ (0.2 mol%) nanophosphor were studied as function of surfactant concentration after excitation at 968 nm. The strong green emission was produced by the transition 2H 11/2 + 4S 3/2 → 4I 15/2 and was explained in terms of cooperative energy transfer between neighboring ions. The upconverted signal was enhanced but the fluorescence decay time was reduced as either the surfactant concentration increases or the annealing time reduces. Experimental results show that surfactant concentration controls the particle size and morphology while annealing time control the phase composition and crystallite size. The highest intensity was obtained for a sample composed of a mixture of tetragonal (33 wt.%) and monoclinic (67 wt.%) phase with crystallite size of 31 and 59 nm, respectively. This result suggests that tetragonal crystalline structure and small crystallite size are more favorable for the upconversion emission.

Electrical characteristics and step coverage of ZrO2 films deposited by atomic layer deposition for through-silicon via and metal-insulator-metal applications

NASA Astrophysics Data System (ADS)

Choi, Kyeong-Keun; Park, Chan-Gyung; Kim, Deok-kee

2016-01-01

The electrical characteristics and step coverage of ZrO2 films deposited by atomic layer deposition were investigated for through-silicon via (TSV) and metal-insulator-metal applications at temperatures below 300 °C. ZrO2 films were able to be conformally deposited on the scallops of 50-µm-diameter, 100-µm-deep TSV holes. The mean breakdown field of 30-nm-thick ZrO2 films on 30-nm-thick Ta(N) increased about 41% (from 2.7 to 3.8 MV/cm) upon H2 plasma treatment. With the plasma treatment, the breakdown field of the film increased and the temperature coefficient of capacitance decreased significantly, probably as a result of the decreased carbon concentration in the film.

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.

Afterglow based detection and dosimetry of beta particle irradiated ZrO2.

PubMed

Salas-Juárez, Ch J; Cruz-Vázquez, C; Avilés-Monreal, R; Bernal, R

2018-08-01

In this work, we report on the afterglow (AG) response characterization of commercially available ZrO 2 . Pellet shaped samples previously annealed in air at 1000°C during 24h were exposed to beta particle irradiation in the dose range from 0.5 up to 128Gy and their AG decay curves recorded during 600s after irradiation exposure. The characteristic glow curves of beta particle irradiated ZrO 2 show two maxima located around 80°C and 150°C. The first one rapidly vanishes at room temperature, giving rise to AG. The integrated AG signal increases as dose increases from 0.5 to 128Gy, with a linear dependence from 0.5 up to ca. 32Gy. Excellent reproducibility of the AG response was observed in 10 irradiation - AG readout cycles, showing that the studied ZrO 2 samples are reusable. The results here presented show that ZrO 2 is a promising material for use as a radiation dosimeter based on the AG phenomenon. Copyright © 2017 Elsevier Ltd. All rights reserved.

Influence of ZrO2 addition on the microstructure and discharge properties of Mg-Zr-O protective layers in alternating current plasma display panels

NASA Astrophysics Data System (ADS)

Guo, Bingang; Liu, Chunliang; Song, Zhongxiao; Liu, Liu; Fan, Yufeng; Xia, Xing; Fan, Duowang

2005-08-01

Mg-Zr-O protective layers for alternating current plasma display panels were deposited by e-beam evaporation. The effect of the ZrO2 addition on both the discharge properties [firing voltage Vf, minimum sustaining voltage Vs, and memory coefficient (MC)] and the microstructure of deposited Mg-Zr-O films were investigated. The results show that the film microstructure changes and the electron emission enhancement due to the ZrO2 addition are the main reasons for the improvements of the discharge properties of Mg-Zr-O films. A small amount of Zr solution in MgO under its solid solubility can effectively increase the outer-shell valence electron emission yield so as to decrease Vf and Vs compared with using a pure MgO protective layer. The ZrO2/(MgO +ZrO2) ratio has a great effect on the film surface conditions. Proper surface morphologies make a good contribution to obtain large MC in accordance with lower firing voltage.

Conductive atomic force microscopy study of the photoexcitation effect on resistive switching in ZrO2(Y) films with Au nanoparticles

NASA Astrophysics Data System (ADS)

Novikov, A. S.; Filatov, D. O.; Antonov, D. A.; Antonov, I. N.; Shenina, M. E.; Gorshkov, O. N.

2018-03-01

We report on the experimental observation of the effect of optical excitation on resistive switching in ultrathin ZrO2(Y) films with single-layered arrays of Au nanoparticles. The samples were prepared by depositing nanometer-thick Au films sandwiched between two ZrO2(Y) layers by magnetron sputtering followed by annealing. Resistive switching was studied by conductive atomic force microscopy by measuring cyclic current-voltage curves of a probe-to-sample contact. The contact area was illuminated by radiation of a semiconductor laser diode with the wavelength corresponding to the plasmon resonance in an Au nanoparticle array. The enhancement of the hysteresis in cyclic current-voltage curves due to bipolar resistive switching under illumination was observed. The effect was attributed to heating of Au nanoparticles due to plasmonic optical absorption and a plasmon resonance, which enhances internal photoemission of electrons from the Fermi level in Au nanoparticles into the conduction band of ZrO2(Y). Both factors promote resistive switching in a ZrO2(Y) matrix.

Critical size of crystalline ZrO(2) nanoparticles synthesized in near- and supercritical water and supercritical isopropyl alcohol.

PubMed

Becker, Jacob; Hald, Peter; Bremholm, Martin; Pedersen, Jan S; Chevallier, Jacques; Iversen, Steen B; Iversen, Bo B

2008-05-01

Nanocrystalline ZrO(2) samples with narrow size distributions and mean particle sizes below 10 nm have been synthesized in a continuous flow reactor in near and supercritical water as well as supercritical isopropyl alcohol using a wide range of temperatures, pressures, concentrations and precursors. The samples were comprehensively characterized by powder X-ray diffraction (PXRD), transmission electron microscopy (TEM), and small-angle X-ray scattering (SAXS), and the influence of the synthesis parameters on the particle size, particle size distribution, shape, aggregation and crystallinity was studied. On the basis of the choice of synthesis parameters either monoclinic or tetragonal zirconia phases can be obtained. The results suggest a critical particle size of 5-6 nm for nanocrystalline monoclinic ZrO(2) under the present conditions, which is smaller than estimates reported in the literature. Thus, very small monoclinic ZrO(2) particles can be obtained using a continuous flow reactor. This is an important result with respect to improvement of the catalytic properties of nanocrystalline ZrO(2).

DLTS Analysis and Interface Engineering of Solution Route Fabricated Zirconia Based MIS Devices Using Plasma Treatment

NASA Astrophysics Data System (ADS)

Kumar, Arvind; Mondal, Sandip; Koteswara Rao, K. S. R.

2018-02-01

In this work, we have fabricated low-temperature sol-gel spin-coated and oxygen (O2) plasma treated ZrO2 thin film-based metal-insulator-semiconductor devices. To understand the impact of plasma treatment on the Si/ZrO2 interface, deep level transient spectroscopy measurements were performed. It is reported that the interface state density ( D it) comes down to 7.1 × 1010 eV-1 cm-2 from 4 × 1011 eV-1 cm-2, after plasma treatment. The reduction in D it is around five times and can be attributed to the passivation of oxygen vacancies near the Si/ZrO2 interface, as they try to relocate near the interface. The energy level position ( E T) of interfacial traps is estimated to be 0.36 eV below the conduction band edge. The untreated ZrO2 film displayed poor leakage behavior due to the presence of several traps within the film and at the interface; O2 plasma treated films show improved leakage current density as they have been reduced from 5.4 × 10-8 A/cm2 to 1.98 × 10-9 A/cm2 for gate injection mode and 6.4 × 10-8 A/cm2 to 6.3 × 10-10 A/cm2 for substrate injection mode at 1 V. Hence, we suggest that plasma treatment might be useful in future device fabrication technology.

Wear Behavior of Plasma Spray Deposited and Post Heat-Treated Hydroxyapatite (HA)-Based Composite Coating on Titanium Alloy (Ti-6Al-4V) Substrate

NASA Astrophysics Data System (ADS)

Kumari, Renu; Majumdar, Jyotsna Dutta

2018-04-01

The present study concerns a detailed evaluation of wear resistance property of plasma spray deposited composite hydroxyapatite (HA)-based (HA-50 wt pct TiO2 and HA-10 wt pct ZrO2) bioactive coatings developed on Ti-6Al-4V substrate and studying the effect of heat treatment on it. Heat treatment of plasma spray deposited samples has been carried out at 650 °C for 2 hours (for HA-50 wt pct TiO2 coating) and at 750 °C for 2 hours (for HA-10 wt pct ZrO2 coating). There is significant deterioration in wear resistance for HA-50 wt pctTiO2 coating and a marginal deterioration in wear resistance for HA-10 wt pct ZrO2 coating in as-sprayed state (as compared to as-received Ti-6Al-4V) which is, however, improved after heat treatment. The coefficient of friction is marginally increased for both HA-50 wt pct TiO2 and HA-10 wt pct ZrO2 coatings in as-sprayed condition as compared to Ti-6Al-4V substrate. However, coefficient of friction is decreased for both HA-50 wt pct TiO2 and HA-10 wt pct ZrO2 coatings after heat-treated condition as compared to Ti-6Al-4V substrate. The maximum improvement in wear resistance property is, however, observed for HA-10 wt pct ZrO2 sample after heat treatment. The mechanism of wear has been investigated.

Effect of zirconia nanoparticles on the rheological properties of silica-based shear thickening fluid

NASA Astrophysics Data System (ADS)

Sun, Li; Zhu, Jie; Wei, Minghai; Zhang, Chunwei; Song, Yansheng; Qi, Peipei

2018-05-01

In this study, the rheological characteristic of shear thickening fluid (STF) with various mass ratios of zirconium dioxide (ZrO2) to silicon dioxide (SiO2) was investigated. The influence of the ZrO2 mass ratio on the sensitivity of nano-ZrO2/SiO2-STF to temperature was further discussed. Nano-ZrO2/SiO2-STF of different concentrations (9.0–20.0 wt%) were prepared via an ultrasonication and mechanical stirring technique. The presence of ZrO2 and their interaction with the SiO2 nanoparticles in the STF were analyzed using scanning electron microscope (SEM), Energy dispersive spectroscopy (EDS) and x-ray diffractometer (XRD). The rheological testing results showed that the ZrO2/SiO2-STF system produced a considerable shear thickening effect; when the nano-ZrO2 mass ratio was 12%, the critical shear rate of the system was relatively small and the peak value of apparent viscosity was relatively large. More importantly, as the nano-ZrO2 mass ratio increased, temperature exerted less influence on the viscosity of the ZrO2/SiO2-STF system diminished, but still had a significant influence on the shear thickening effect.

Develop Roll-to-Roll Manufacturing Process of ZrO 2 Nanocrystals/Acrylic Nanocomposites for High Refractive Index Applications

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

Joshi, Pooran C.; Compton, Brett G.; Li, Jianlin

2015-04-01

The purpose of this Cooperative Research and Development Agreement (CRADA) was to develop and evaluate ZrO 2/acrylic nanocomposite coatings for integrated optoelectronic applications. The formulations engineered to be compatible with roll-to-roll process were evaluated in terms of optical and dielectric properties. The uniform distribution of the ZrO 2 nanocrystals in the polymer matrix resulted in highly tunable refractive index and dielectric response suitable for advanced photonic and electronic device applications.

Irradiation behavior of LiAlO 2 and Li 2ZrO 3 ceramics in the ALICE 3 experiment

NASA Astrophysics Data System (ADS)

Rasneur, B.; Thevenot, G.; Bouilloux, Y.

1992-09-01

Within the framework of the investigation of ceramic breeders for the DEMO relevant solid blankets developed in Europe, the ALICE 3 experiment was foreseen to study the irradiation behavior of the ceramics. The irradiation was performed in the core of the OSIRIS reactor for 46 FPD (full power days) at 400°C and 600°C. The three ceramics in the configuration contemplated in the BIT and BOT concepts were tested, i.e. LiAlO 2 and Li 2ZrO 3 pellets, Li 4SiO 4 and Li 2ZrO 3 pebbles, respectively. In this paper are reported the results of the post-irradiation examination carried out at CEA on CEA Li 2ZrO 3 and LiAlO 2 specimens: dimensions, X-ray diffraction, ultimate bending strength, diametral compressive strength and residual tritium.

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

Mohapatra, Pratyasha; Shaw, Santosh; Mendivelso-Perez, Deyny

Removing organics from hybrid nanostructures is a crucial step in many bottom-up materials fabrication approaches. It is usually assumed that calcination is an effective solution to this problem, especially for thin films. This assumption has led to its application in thousands of papers. Here in this paper, we show that this general assumption is incorrect by using a relevant and highly controlled model system consisting of thin films of ligand-capped ZrO 2 nanocrystals. After calcination at 800 °C for 12 h, while Raman spectroscopy fails to detect the ligands after calcination, elastic backscattering spectrometry characterization demonstrates that ~18% of themore » original carbon atoms are still present in the film. By comparison plasma processing successfully removes the ligands. Our growth kinetic analysis shows that the calcined materials have significantly different interfacial properties than the plasma-processed counterparts. Calcination is not a reliable strategy for the production of single-phase all-inorganic materials from colloidal nanoparticles.« less

Metal Adatoms and Clusters on Ultrathin Zirconia Films

PubMed Central

2016-01-01

Nucleation and growth of transition metals on zirconia has been studied by scanning tunneling microscopy (STM) and density functional theory (DFT) calculations. Since STM requires electrical conductivity, ultrathin ZrO2 films grown by oxidation of Pt3Zr(0001) and Pd3Zr(0001) were used as model systems. DFT studies were performed for single metal adatoms on supported ZrO2 films as well as the (1̅11) surface of monoclinic ZrO2. STM shows decreasing cluster size, indicative of increasing metal–oxide interaction, in the sequence Ag < Pd ≈ Au < Ni ≈ Fe. Ag and Pd nucleate mostly at steps and domain boundaries of ZrO2/Pt3Zr(0001) and form three-dimensional clusters. Deposition of low coverages of Ni and Fe at room temperature leads to a high density of few-atom clusters on the oxide terraces. Weak bonding of Ag to the oxide is demonstrated by removing Ag clusters with the STM tip. DFT calculations for single adatoms show that the metal–oxide interaction strength increases in the sequence Ag < Au < Pd < Ni on monoclinic ZrO2, and Ag ≈ Au < Pd < Ni on the supported ultrathin ZrO2 film. With the exception of Au, metal nucleation and growth on ultrathin zirconia films follow the usual rules: More reactive (more electropositive) metals result in a higher cluster density and wet the surface more strongly than more noble metals. These bind mainly to the oxygen anions of the oxide. Au is an exception because it can bind strongly to the Zr cations. Au diffusion may be impeded by changing its charge state between −1 and +1. We discuss differences between the supported ultrathin zirconia films and the surfaces of bulk ZrO2, such as the possibility of charge transfer to the substrate of the films. Due to their large in-plane lattice constant and the variety of adsorption sites, ZrO2{111} surfaces are more reactive than many other oxygen-terminated oxide surfaces. PMID:27213024

Effective Enrichment and Mass Spectrometry Analysis of Phosphopeptides Using Mesoporous Metal Oxide Nanomaterials

PubMed Central

Nelson, Cory A.; Szczech, Jeannine R.; Dooley, Chad J.; Xu, Qingge; Lawrence, Matthew J.; Zhu, Haoyue; Jin, Song; Ge, Ying

2010-01-01

Mass spectrometry (MS)-based phosphoproteomics remains challenging due to the low abundance of phosphoproteins and substoichiometric phosphorylation. This demands better methods to effectively enrich phosphoproteins/peptides prior to MS analysis. We have previously communicated the first use of mesoporous zirconium oxide (ZrO2) nanomaterials for effective phosphopeptide enrichment. Here we present the full report including the synthesis, characterization, and application of mesoporous titanium dioxide (TiO2), ZrO2, and hafnium oxide (HfO2) in phosphopeptide enrichment and MS analysis. Mesoporous ZrO2 and HfO2 are demonstrated to be superior to TiO2 for phosphopeptide enrichment from a complex mixture with high specificity (>99%), which could almost be considered as “a purification”, mainly because of the extremely large active surface area of mesoporous nanomaterials. A single enrichment and Fourier transform MS analysis of phosphopeptides digested from a complex mixture containing 7% of α-casein identified 21 out of 22 phosphorylation sites for α-casein. Moreover, the mesoporous ZrO2 and HfO2 can be reused after a simple solution regeneration procedure with comparable enrichment performance to that of fresh materials. Mesoporous ZrO2 and HfO2 nanomaterials hold great promise for applications in MS-based phosphoproteomics. PMID:20704311

Optical coatings for improved contrast in longitudinal magneto-optic Kerr effect measurements

NASA Astrophysics Data System (ADS)

Cantwell, P. R.; Gibson, U. J.; Allwood, D. A.; Macleod, H. A. M.

2006-11-01

We have studied the increases in the longitudinal magneto-optic Kerr effect signal contrast that can be achieved by the application of optical overlayers on magnetic films. For simple coatings, a factor of ˜3 improvement in signal contrast is possible. Matching the optical impedance of the magnetic material improves the raw Kerr signal and also reduces the sample reflectivity, yielding a large Kerr angle. The contrast can be optimized by increasing the rotated Kerr reflectivity component while maintaining enough of the base reflectivity Fresnel component to produce a strong signal. Calculations and experimental results are presented for single layer ZrO2 dielectric coatings on Ni along with calculations for a three-layer Au -ZrO2-Ni structure. Incidence angle effects are also presented.

Synthesis of methyl esters from relevant palm products in near-critical methanol with modified-zirconia catalysts.

PubMed

Laosiripojana, N; Kiatkittipong, W; Sutthisripok, W; Assabumrungrat, S

2010-11-01

The transesterification and esterification of palm products i.e. crude palm oil (CPO), refined palm oil (RPO) and palm fatty acid distillate (PFAD) under near-critical methanol in the presence of synthesized SO(4)-ZrO(2), WO(3)-ZrO(2) and TiO(2)-ZrO(2) (with various sulfur- and tungsten loadings, Ti/Zr ratios, and calcination temperatures) were studied. Among them, the reaction of RPO with 20%WO(3)-ZrO(2) (calcined at 800 degrees C) enhanced the highest fatty acid methyl ester (FAME) yield with greatest stability after several reaction cycles; furthermore, it required shorter time, lower temperature and less amount of methanol compared to the reactions without catalyst. These benefits were related to the high acid-site density and tetragonal phase formation of synthesized WO(3)-ZrO(2). For further improvement, the addition of toluene as co-solvent considerably reduced the requirement of methanol to maximize FAME yield, while the addition of molecular sieve along with catalyst significantly increased FAME yield from PFAD and CPO due to the inhibition of hydrolysis reaction. Copyright 2010 Elsevier Ltd. All rights reserved.

COMPARISON OF SODIUM AND POTASSIUM CARBONATES AS LITHIUM ZIRCONATE MODIFIERS FOR HIGH-TEMPERATURE CARBON DIOXIDE CAPTURE FROM BIOMASS-DERIVED SYNTHESIS GAS

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

Olstad, J.L.; Phillips, S.D.

2009-01-01

The process of gasifi cation converts biomass into synthesis gas (syngas), which can be used to produce biofuels. Solid-phase sorbents were investigated for the removal of CO2 from a N2/CO2 gas stream using a CO2 concentration similar to that found in a biomass gasifi cation process. During the gasifying process, large amounts of carbon dioxide (CO2) are created along with the syngas. The produced CO2 must be removed before the syngas can be used for fuel synthesis and to avoid the possible formation of unwanted byproducts. A thermogravimetric analyzer was used to test the CO2 absorption rates of sorbents composedmore » of lithium zirconate (Li2ZrO3), as well as mixtures of Li2ZrO3 with potassium carbonate (K2CO3) and sodium carbonate (Na2CO3). The experimental results show that Li2ZrO3 has a low absorption rate, but sorbents containing combinations of Li2ZrO3 and the K2CO3 and Na2CO3 additives have high uptake rates. Using different proportions of K2CO3 and Na2CO3 produces varying uptake rates, so an optimization experiment was performed to obtain an improved sorbent. The CO2 absorption and regeneration stability of the solid-phase sorbents were also examined. A sorbent composed of Li2ZrO3 and 12.1 weight % Na2CO3 was shown to be stable, based on the consistent CO2 uptake rates. Sorbents prepared with Li2ZrO3, 17.6 weight % K2CO3 and 18.1 weight % Na2CO3 showed instability during regeneration cycles in air at 800 °C. Sorbent stability improved during regeneration cycles at 700 °C. Further testing of the Li2ZrO3 sorbent under actual syngas conditions, including higher pressure and composition, should be done. Once the optimum sorbent has been found, a suitable support will be needed to use the sorbent in an actual reactor.« less

The photoelectronic behaviors of MoO3-loaded ZrO2/carbon cluster nanocomposite materials

NASA Astrophysics Data System (ADS)

Matsui, H.; Ishiko, A.; Karuppuchamy, S.; Hassan, M. A.; Yoshihara, M.

2012-03-01

A novel nano-sized ZrO2/carbon cluster composite materials (Ic's) were successfully obtained by the calcination of ZrCl4/starch complexes I's under an argon atmosphere. Pt- and/or MoO3-loaded ZrO2/carbon clusters composite materials were also prepared by doping Pt and/or MoO3 particles on the surface of Ic's. The surface characterization of the composite materials was carried out using transmission electron microscopy (TEM). The TEM observation of the materials showed the presence of particles with the diameters of a few nanometers, possibly Pt particles, and of 50-100 nm, possibly MoO3 particles, in the matrix. Pt- and/or MoO3-loaded ZrO2/carbon cluster composite materials show the efficient photocatalytic activity under visible light irradiation.

The Effect of Microstructure on Mechanical Properties of Directionally Solidified Al2O3/ZrO2(Y2O3) Eutectic

NASA Technical Reports Server (NTRS)

Sayir, Ali; Farmer, Serene C.

1999-01-01

The eutectic architecture of a continuous reinforcing phase within a higher volume fraction phase or matrix can be described as a naturally occurring in-situ composite. Here we report the results of experiments aimed at identifying the sources of high temperature creep resistance and high levels of strength in a two phase Al2O3/ZrO2(Y2O3) system. The mechanical properties of two phase Al2O3/ZrO2(Y2O3) eutectic are superior to those of either constituent alone due to strong constraining effects provided by the coherent interfaces and microstructure. The AlO3/ZrO2(Y2O3) eutectic maintains a low energy interface resulting from directional solidification and can produce strong and stable reinforcing phase/matrix bonding. The phases comprising a eutectic are thermodynamically compatible at higher homologous temperatures than man-made composites and as such offer the potential for superior high temperature properties.

Thermal stability, optical and Photoluminescence properties of spherical Ce x Zr1‑x O2 (x = 0.05) crystalline blue-emitting nanophosphors synthesized by microwave method

NASA Astrophysics Data System (ADS)

Manjunatha, S.; Dharmaprakash, M. S.

2018-03-01

Nanocrystalline ZrO2 based material is an impressive candidate for the various functional applications owing to their ease of preparation and high thermal stability. This paper reports the synthesis, structural and optical characterization of thermally stable monodispersed CexZr1‑xO2 (x = 0.05) nanoparticles. This method is based on the fact that, microwave irradiation allows the formation of size controlled and single phase cubic ZrO2 nanoparticles containing Ce+4 as a dopant. The XRD and Rietveld analysis revealed the formation of the crystalline cubic fluorite phase. The formation of nanoparticles was confirmed by FTIR. The morphology of the nanophosphors was characterised by FESEM and TEM. The optical band gap was calculated from the UV–visible absorption spectra and was found to vary from 3.93 to 4.25 eV with calcination temperature. It shows the decrease in the optical band gap from the pristine ZrO2. The particle size was measured by using HRTEM, and the average particle size was found to be 22 nm. Under the 268 nm Ultra Violet irradiation excitation a blue emission at 443 nm was observed at room temperature. The possible luminescence mechanism of CexZr1‑xO2 nanophosphor under UV excitation is discussed.

Oxidation of U-20 at% Zr alloy in air at 423 1063 K

NASA Astrophysics Data System (ADS)

Matsui, Tsuneo; Yamada, Takanobu; Ikai, Yasushi; Naito, Keiji

1993-01-01

The oxidation behavior of U 0.80Zr 0.20 alloy (two-phase mixture of U and UZr 2 below 878 K and single solid solution above 1008 K) was studied by thermogravimetry in the temperature range from 423 to 1063 K in air. During oxidation in the low temperature region (423-503 K), the sample kept its initial shape (a rectangular rod) and the surface of the sample was covered by a black thin adherent UO2 + x oxide layer. On the other hand, by oxidation in the middle temperature region, the sample broke to several pieces of thin plates and blocks, and fine powder at 643-723 K and entirely to fine powder at 775-878 K, all of which were analyzed to be a mixture of U 3O 8 and ZrO 2. By oxidation in the high temperature region (1008-1063 K) the sample broke to very fine powder, which consisted of U 3O 8 and ZrO 2. Based on the sample shape, the oxide phase identified after oxidation and the slope value of the bilogarithmic plots of the weight gain against time, the oxidation kinetics was analyzed with a paralinear equation in the low temperature region below 503 K and a linear equation in the middle and high temperature regions above 643 K. Oxidation rates of U 0.80Zr 0.20 (two-phase mixture) in the low and middle temperature regions were smaller than those of uranium metal. A discontinuity in the plot of the linear oxidation rate constant versus reciprocal temperature was found to be present between 723 and 838 K, similarly to the case of uranium metal previously reported. The linear rate constants of single-phase solid solution in the high temperature region above 1008 K seemed to be a little smaller than those estimated by the extrapolation of the values in the middle temperature region.

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.

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

Modified tricalcium silicate cement formulations with added zirconium oxide.

PubMed

Li, Xin; Yoshihara, Kumiko; De Munck, Jan; Cokic, Stevan; Pongprueksa, Pong; Putzeys, Eveline; Pedano, Mariano; Chen, Zhi; Van Landuyt, Kirsten; Van Meerbeek, Bart

2017-04-01

This study aims to investigate the effect of modifying tricalcium silicate (TCS) cements on three key properties by adding ZrO 2 . TCS powders were prepared by adding ZrO 2 at six different concentrations. The powders were mixed with 1 M CaCl 2 solution at a 3:1 weight ratio. Biodentine (contains 5 wt.% ZrO 2 ) served as control. To evaluate the potential effect on mechanical properties, the mini-fracture toughness (mini-FT) was measured. Regarding bioactivity, Ca release was assessed using ICP-AES. The component distribution within the cement matrix was evaluated by Feg-SEM/EPMA. Cytotoxicity was assessed using an XTT assay. Adding ZrO 2 to TCS did not alter the mini-FT (p = 0.52), which remained in range of that of Biodentine (p = 0.31). Ca release from TSC cements was slightly lower than that from Biodentine at 1 day (p > 0.05). After 1 week, Ca release from TCS 30 and TCS 50 increased to a level that was significantly higher than that from Biodentine (p < 0.05). After 1 month, Ca release all decreased (p < 0.05), yet TCS 0 and TCS 50 released comparable amounts of Ca as at 1 day (p > 0.05). EPMA revealed a more even distribution of ZrO 2 within the TCS cements. Particles with an un-reacted core were surrounded by a hydration zone. The 24-, 48-, and 72-h extracts of TCS 50 were the least cytotoxic. ZrO 2 can be added to TCS without affecting the mini-FT; Ca release was reduced initially, to reach a prolonged release thereafter; adding ZrO 2 made TCS cements more biocompatible. TCS 50 is a promising cement formulation to serve as a biocompatible hydraulic calcium silicate cement.

Chemical vapor deposited monolayer MoS2 top-gate MOSFET with atomic-layer-deposited ZrO2 as gate dielectric

NASA Astrophysics Data System (ADS)

Hu, Yaoqiao; Jiang, Huaxing; Lau, Kei May; Li, Qiang

2018-04-01

For the first time, ZrO2 dielectric deposition on pristine monolayer MoS2 by atomic layer deposition (ALD) is demonstrated and ZrO2/MoS2 top-gate MOSFETs have been fabricated. ALD ZrO2 overcoat, like other high-k oxides such as HfO2 and Al2O3, was shown to enhance the MoS2 channel mobility. As a result, an on/off current ratio of over 107, a subthreshold slope of 276 mV dec-1, and a field-effect electron mobility of 12.1 cm2 V-1 s-1 have been achieved. The maximum drain current of the MOSFET with a top-gate length of 4 μm and a source/drain spacing of 9 μm is measured to be 1.4 μA μm-1 at V DS = 5 V. The gate leakage current is below 10-2 A cm-2 under a gate bias of 10 V. A high dielectric breakdown field of 4.9 MV cm-1 is obtained. Gate hysteresis and frequency-dependent capacitance-voltage measurements were also performed to characterize the ZrO2/MoS2 interface quality, which yielded an interface state density of ˜3 × 1012 cm-2 eV-1.

Enhancement of ethanol oxidation at Pt and PtRu nanoparticles dispersed over hybrid zirconia-rhodium supports

NASA Astrophysics Data System (ADS)

Rutkowska, Iwona A.; Koster, Margaretta D.; Blanchard, Gary J.; Kulesza, Pawel J.

2014-12-01

A catalytic material for electrooxidation of ethanol that utilizes PtRu nanoparticles dispersed over thin films of rhodium-free and rhodium-containing zirconia (ZrO2) supports is described here. The enhancement of electrocatalytic activity (particularly in the potential range as low as 0.25-0.5 V vs. RHE), that has been achieved by dispersing PtRu nanoparticles (loading, 100 μg cm-2) over the hybrid Rh-ZrO2 support composed of nanostructured zirconia and metallic rhodium particles, is clearly evident from comparison of the respective voltammetric and chronoamperometric current densities recorded at room temperature (22 °C) in 0.5 mol dm-3 H2SO4 containing 0.5 mol dm-3 ethanol. Porous ZrO2 nanostructures, that provide a large population of hydroxyl groups in acidic medium in the vicinity of PtRu sites, are expected to facilitate the ruthenium-induced removal of passivating CO adsorbates from platinum, as is apparent from the diagnostic experiments with a small organic molecule such as methanol. Although Rh itself does not show directly any activity toward ethanol oxidation, the metal is expected to facilitate C-C bond splitting in C2H5OH. It has also been found during parallel voltammetric and chronoamperometric measurements that the hybrid Rh-ZrO2 support increases activity of the platinum component itself toward ethanol oxidation in the low potential range.

Effect of Co addition on the performance and structure of V/ZrCe catalyst for simultaneous removal of NO and Hg0 in simulated flue gas

NASA Astrophysics Data System (ADS)

Zhao, Lingkui; Li, Caiting; Du, Xueyu; Zeng, Guangming; Gao, Lei; Zhai, Yunbo; Wang, Teng; Zhang, Junyi

2018-04-01

The effect of CoOx addition on the performance and structure of V2O5/ZrO2-CeO2 catalyst for simultaneous removal of NO and Hg0 in simulated flue gas was investigated by various methods including SEM, BET, XRD, XPS, H2-TPR and FT-IR. It was found that the introduction of CoOx not only greatly enhanced the redox properties of catalysts, but also increased the catalytic performance for simultaneous removal of NO and Hg0. The CoOx-modified V2O5/ZrO2-CeO2 catalyst displayed excellent catalytic activity for NO conversion (89.6%) and Hg0 oxidation (88.9%) at 250 °C under SCR atmosphere. The synergistic effect among vanadium, cobalt, and the ZrCe support could induce oxygen vacancies formation and promote oxygen mobility via charge transfer. Besides, CoOx could assist vanadium species in rapidly changing the valence by the redox cycle of V5+ + Co2+ ↔ V4+ + Co3+. All the above features contribute to the excellent catalytic performance through CoOx addition.

Ultrasound-assisted sol-gel synthesis of ZrO2.

PubMed

Guel, Marlene Lariza Andrade; Jiménez, Lourdes Díaz; Hernández, Dora Alicia Cortés

2017-03-01

Synthesis of tetragonal ZrO 2 by both conventional sol-gel and ultrasound-assisted sol-gel methods and using a non-ionic surfactant Tween-20, was performed. A porous microstructure composed of nanometric particles was observed. Tetragonal ZrO 2 was obtained using a low heat treatment temperature of powders, 500°C by both methods. A higher crystallinity and a shorter reaction time were observed when ultrasound was used in the sol-gel method due to the cavitation phenomenon. Copyright © 2016 Elsevier B.V. All rights reserved.

Elaboration of Alumina-Zirconia Composites: Role of the Zirconia Content on the Microstructure and Mechanical Properties

PubMed Central

Naglieri, Valentina; Palmero, Paola; Montanaro, Laura; Chevalier, Jérôme

2013-01-01

Alumina-zirconia (AZ) composites are attractive structural materials, which combine the high hardness and Young’s modulus of the alumina matrix with additional toughening effects, due to the zirconia dispersion. In this study, AZ composites containing different amounts of zirconia (in the range 5–20 vol %) were prepared by a wet chemical method, consisting on the surface coating of alumina powders by mixing them with zirconium salt aqueous solutions. After spray-drying, powders were calcined at 600 °C for 1 h. Green bodies were then prepared by two methods: uniaxial pressing of spray-dried granules and slip casting of slurries, obtained by re-dispersing the spray dried granulates. After pressureless sintering at 1500 °C for 1 h, the slip cast samples gave rise to fully dense materials, characterized by a quite homogeneous distribution of ZrO2 grains in the alumina matrix. The microstructure, phase composition, tetragonal to monoclinic transformation behavior and mechanical properties were investigated and are here discussed as a function of the ZrO2 content. The material containing 10 vol % ZrO2 presented a relevant hardness and exhibited the maximum value of KI0, mainly imputable to the t → m transformation at the crack tip. PMID:28809262

Mastering the interface for advanced all-solid-state lithium rechargeable batteries

PubMed Central

Li, Yutao; Zhou, Weidong; Chen, Xi; Lü, Xujie; Cui, Zhiming; Xin, Sen; Xue, Leigang; Jia, Quanxi; Goodenough, John B.

2016-01-01

A solid electrolyte with a high Li-ion conductivity and a small interfacial resistance against a Li metal anode is a key component in all-solid-state Li metal batteries, but there is no ceramic oxide electrolyte available for this application except the thin-film Li-P oxynitride electrolyte; ceramic electrolytes are either easily reduced by Li metal or penetrated by Li dendrites in a short time. Here, we introduce a solid electrolyte LiZr2(PO4)3 with rhombohedral structure at room temperature that has a bulk Li-ion conductivity σLi = 2 × 10−4 S⋅cm−1 at 25 °C, a high electrochemical stability up to 5.5 V versus Li+/Li, and a small interfacial resistance for Li+ transfer. It reacts with a metallic lithium anode to form a Li+-conducting passivation layer (solid-electrolyte interphase) containing Li3P and Li8ZrO6 that is wet by the lithium anode and also wets the LiZr2(PO4)3 electrolyte. An all-solid-state Li/LiFePO4 cell with a polymer catholyte shows good cyclability and a long cycle life. PMID:27821751

Reactions and products in the Cs-Zr-I-O system relevant to fission product chemistry — a review

NASA Astrophysics Data System (ADS)

Chen, T.-M.; Kauzlarich, S. M.; Corbett, J. D.

1988-02-01

Some results and problems associated with the known chemistry of cesium and iodine in the presence of Zr/ZrO 2 at 400-600°C and under anaerobic conditions are described and discussed. These aspects include (1) the recently synthesized cesium zirconates Cs 2ZrO 3 and Cs 4ZrO 4 and some of their thermal and hydrolytic properties (2) the demonstration that the supposedly stable CsI reacts with ZrO 2 at 400-700°C to form Cs 2ZrO 3 and ZrI 4 (as Cs 2ZrI 6) and its implications regarding cesium and iodine distributions (3) present knowledge of binary zirconium iodides, their contamination reactions, and the limited inhibition of the reduction of ZrI 4 by metal provided by static ZrO 2 films (4) newly discovered ternary and quaternary zirconium iodides that are obtained in the presence of many common impurity atoms and, when prsesent, CsI (e.g., Zr 6I 12C, CsZr 6I 14C, Zr 6I 14Fe), the ease with which some of those form at least as low as 450°C, and the complications these and related new phases provide.

Hydrodeoxygenation of p -Cresol over Pt/Al 2 O 3 Catalyst Promoted by ZrO 2 , CeO 2 , and CeO 2 –ZrO 2

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

Wang, Weiyan; Wu, Kui; Liu, Pengli

2016-07-20

ZrO 2-Al 2O 3 and CeO 2-Al 2O 3 were prepared by a co-precipitation method and selected as supports for Pt catalysts. The effects of CeO 2 and ZrO 2 on the surface area and Brønsted acidity of Pt/Al 2O 3 were studied. In the hydrodeoxygenation (HDO) of p-cresol, the addition of ZrO 2 promoted the direct deoxygenation activity on Pt/ZrOO 2-Al 2O 3 via Caromatic-O bond scission without benzene ring saturation. Pt/CeOO 2-Al 2O 3 exhibited higher deoxygenation extent than Pt/Al 2O 3 due to the fact that Brønsted acid sites on the catalyst surface favored the adsorption ofmore » p-cresol. With the advantages of CeO 2 and ZrO 2 taken into consideration, CeO 2-ZrOO 2-Al 2O 3 was prepared, leading to the highest HDO activity of Pt/CeO 2-ZrOO 2-Al 2O 3. The deoxygenation extent for Pt/CeO 2-ZrOO 2-Al 2O 3 was 48.4% and 14.5% higher than that for Pt/ZrO2O 2-Al 2O 3 and Pt/CeOO 2-Al 2O 3, respectively.« less

Laser-induced damage thresholds of bulk and coating optical materials at 1030  nm, 500  fs.

PubMed

Gallais, Laurent; Commandré, Mireille

2014-02-01

We report on extensive femtosecond laser damage threshold measurements of optical materials in both bulk and thin-film form. This study, which is based on published and new data, involved simple oxide and fluoride films, composite films made from a mixture of two dielectric materials, metallic films, and the surfaces of various bulk materials: oxides, fluorides, semiconductors, and ionic crystals. The samples were tested in comparable conditions at 1030 nm, 375 to 600 fs, under single-pulse irradiation. A large number of different samples prepared by different deposition techniques have been tested, involving classical materials used in the fabrication of optical thin film components (Ag, AlF3, Al2O3, HfO2, MgF2, Nb2O5, Pt, Sc2O3, SiO2, Ta2O5, Y2O3, and ZrO2) and their combination with codeposition processes. Their behaviors are compared with the surfaces of bulk materials (Al2O3, BaF2, CaF2, Ge, KBr, LiF, MgF2, NaCl, Quartz, Si, ZnS, ZnSe, and different silica glasses). Tabulated values of results are presented and discussed.

Thermodynamic Modeling of the YO(l.5)-ZrO2 System

NASA Technical Reports Server (NTRS)

Jacobson, Nathan S.; Liu, Zi-Kui; Kaufman, Larry; Zhang, Fan

2003-01-01

The YO1.5-ZrO2 system consists of five solid solutions, one liquid solution, and one intermediate compound. A thermodynamic description of this system is developed, which allows calculation of the phase diagram and thermodynamic properties. Two different solution models are used-a neutral species model with YO1.5 and ZrO2 as the components and a charged species model with Y(+3), Zr(+4), O(-2), and vacancies as components. For each model, regular and sub-regular solution parameters are derived fiom selected equilibrium phase and thermodynamic data.

Influence of growth temperature on properties of zirconium dioxide films grown by atomic layer deposition

NASA Astrophysics Data System (ADS)

Kukli, Kaupo; Ritala, Mikko; Aarik, Jaan; Uustare, Teet; Leskela, Markku

2002-08-01

ZrO2 films were grown by atomic layer deposition from ZrCl4 and H2O or a mixture of H2O and H2O2 on Si(100) substrates in the temperature range of 180-600 degC. The films were evaluated in the as-deposited state, in order to follow the effect of deposition temperature on the film quality. The rate of crystal growth increased and the content of residual impurities decreased with increasing temperature. The zirconium-to-oxygen atomic ratio, determined by ion-beam analysis, corresponded to the stoichiometric dioxide regardless of the growth temperature. The effective permittivity of ZrO2 in Al/ZrO2/Si capacitor structures increased from 13-15 in the films grown at 180 degC to 19 in the films grown at 300-600 degC, measured at 100 kHz. The permittivity was relatively high in the crystallized films, compared to the amorphous ones, but rather insensitive to the crystal structure. The permittivity was higher in the films grown using water. The leakage current density tended to be lower and the breakdown field higher in the films grown using hydrogen peroxide.

Characterization of core–shell MOF particles by depth profiling experiments using on-line single particle mass spectrometry

DOE PAGES

Cahill, J. F.; Fei, H.; Cohen, S. M.; ...

2015-01-05

Materials with core-shell structures have distinct properties that lend themselves to a variety of potential applications. Characterization of small particle core-shell materials presents a unique analytical challenge. Herein, single particles of solid-state materials with core-shell structures were measured using on-line aerosol time-of-flight mass spectrometry (ATOFMS). Laser 'depth profiling' experiments verified the core-shell nature of two known core-shell particle configurations (< 2 mu m diameter) that possessed inverted, complimentary core-shell compositions (ZrO2@SiO2 versus SiO2@ZrO2). The average peak area ratios of Si and Zr ions were calculated to definitively show their core-shell composition. These ratio curves acted as a calibrant for anmore » uncharacterized sample - a metal-organic framework (MOF) material surround by silica (UiO-66(Zr)@SiO2; UiO = University of Oslo). ATOFMS depth profiling was used to show that these particles did indeed exhibit a core-shell architecture. The results presented here show that ATOFMS can provide unique insights into core-shell solid-state materials with particle diameters between 0.2-3 mu m.« less

Compositional changes at the interface between thorium-doped uranium dioxide and zirconium due to high-temperature annealing

NASA Astrophysics Data System (ADS)

Youn, Young-Sang; Lee, Jeongmook; Kim, Jandee; Kim, Jong-Yun

2018-06-01

Compositional changes at the interface between thorium-doped uranium dioxide (U0.97Th0.03O2) and Zr before and after annealing at 1700 °C for 18 h were studied by X-ray photoelectron spectroscopy, X-ray diffraction, and Raman spectroscopy. At room temperature, the U0.97Th0.03O2 pellet consisted of hyperstoichiometric UO2+x with UO2 and ThO2, and the Zr sample contained Zr with ZrO2. After annealing, the former contained stoichiometric UO2 with ThO2 and the latter consisted of ZrO2 along with ZrO2·2H2O.

Local structure in solid solutions of stabilised zirconia with actinide dioxides (UO{sub 2}, NpO{sub 2})

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

Walter, Marcus, E-mail: marcus.walter@vkta.d; Somers, Joseph; Bouexiere, Daniel

2011-04-15

The local structure of (Zr,Lu,U)O{sub 2-x} and (Zr,Y,Np)O{sub 2-x} solid solutions has been investigated by extended X-ray absorption fine structure (EXAFS). Samples were prepared by mixing reactive (Zr,Lu)O{sub 2-x} and (Zr,Y)O{sub 2-x} precursor materials with the actinide oxide powders, respectively. Sintering at 1600 {sup o}C in Ar/H{sub 2} yields a fluorite structure with U(IV) and Np(IV). As typical for stabilised zirconia the metal-oxygen and metal-metal distances are characteristic for the different metal ions. The bond lengths increase with actinide concentration, whereas highest adaptation to the bulk stabilised zirconia structure was observed for U---O and Np---O bonds. The Zr---O bond showsmore » only a slight increase from 2.14 A at 6 mol% actinide to 2.18 A at infinite dilution in UO{sub 2} and NpO{sub 2}. The short interatomic distance between Zr and the surrounding oxygen and metal atoms indicate a low relaxation of Zr with respect to the bulk structure, i.e. a strong Pauling behaviour. -- Graphical abstract: Metal-oxygen bond distances in (Zr,Lu,U)O{sub 2-x} solid solutions with different oxygen vacancy concentrations (Lu/Zr=1 and Lu/Zr=0.5). Display Omitted Research Highlights: {yields} EXAFS indicates high U and Np adaption to the bulk structure of stabilised zirconia. {yields} Zr---O bond length is 2.18 A at infinite Zr dilution in UO{sub 2} and NpO{sub 2}. {yields} Low relaxation (strong Pauling behaviour) of Zr explains its low solubility in UO{sub 2}.« less

The effect of heat treatment on the performance of the Ni/(Zr-Sm oxide) catalysts for carbon dioxide methanation

NASA Astrophysics Data System (ADS)

Takano, Hiroyuki; Izumiya, Koichi; Kumagai, Naokazu; Hashimoto, Koji

2011-07-01

The active catalysts for methane formation from the gas mixture of CO 2 + 4H 2 with almost 100% methane selectivity were prepared by reduction of the oxide mixture of NiO and ZrO 2 prepared by calcination of aqueous ZrO 2 sol with Sm(NO 3) 3 and Ni(NO 3) 2. The 50 at%Ni-50 at%(Zr-Sm oxide) catalyst consisting of 50 at%Ni-50 at%(Zr + Sm) with Zr/Sm = 5 calcined at 650 or 800 °C showed the highest activity for methanation. The active catalysts were Ni supported on tetragonal ZrO 2, and the activity for methanation increased by an increase in inclusion of Sm 3+ ions substituting Zr 4+ ions in the tetragonal ZrO 2 lattice as a result of an increase in calcination temperature. However, the increase in calcination temperature decreased BET surface area, metal dispersion and hydrogen uptake due to grain growth. Thus, the optimum calcination temperature existed.

Phase equilibria, crystal structures, and dielectric anomaly in the BaZrO 3-CaZrO 3 system

NASA Astrophysics Data System (ADS)

Levin, Igor; Amos, Tammy G.; Bell, Steven M.; Farber, Leon; Vanderah, Terrell A.; Roth, Robert S.; Toby, Brian H.

2003-11-01

Phase equilibria in the (1- x)BaZrO 3- xCaZrO 3 system were analyzed using a combination of X-ray and neutron powder diffraction, and transmission electron microscopy. The proposed phase diagram features two extended two-phase fields containing mixtures of a Ba-rich cubic phase and a tetragonal, or orthorhombic Ca-rich phase, all having perovskite-related structures. The symmetry differences in the Ca-rich phases are caused by different tilting patterns of the [ZrO 6] octahedra. In specimens quenched from 1650°C, CaZrO 3 dissolves only a few percent of Ba, whereas the solubility of Ca in BaZrO 3 is approximately 30 at% . The BaZrO 3-CaZrO 3 system features at least two tilting phase transitions, Pm3 m→ I4/ mcm and I4/ mcm→ Pbnm. Rietveld refinements of the Ba 0.8Ca 0.2ZrO 3 structure using variable-temperature neutron powder diffraction data confirmed that the Pm3 m→ I4/ mcm transition corresponds to a rotation of octahedra about one of the cubic axes; successive octahedra along this axis rotate in opposite directions. In situ variable-temperature electron diffraction studies indicated that the transition temperature increases with increasing Ca-substitution on the A-sites, from approximately -120°C at 5 at% Ca to 225°C at 20 at% Ca. Dielectric measurements revealed that the permittivity increases monotonically from 36 for BaZrO 3 to 53 for Ba 0.9Ca 0.1ZrO 3, and then decreases to 50 for Ba 0.8Ca 0.2ZrO 3. This later specimen was the Ca-richest composition for which pellets could be quenched from the single-phase cubic field with presently available equipment. Strongly non-monotonic behavior was also observed for the temperature coefficient of resonant frequency; however, in this case, the maximum occurred at a lower Ca concentration, 0.05⩽ x⩽0.1. The non-linear behavior of the dielectric properties was attributed to two competing structural effects: a positive effect associated with substitution of relatively small Ca cations on the A-sites, resulting in stretched Ca-O bonds, and a negative effect, related to the distortion of the A-site environment (bond strain relaxation) upon octahedral tilting.

Nanocomposite coatings on biomedical grade stainless steel for improved corrosion resistance and biocompatibility.

PubMed

Nagarajan, Srinivasan; Mohana, Marimuthu; Sudhagar, Pitchaimuthu; Raman, Vedarajan; Nishimura, Toshiyasu; Kim, Sanghyo; Kang, Yong Soo; Rajendran, Nallaiyan

2012-10-24

The 316 L stainless steel is one of the most commonly available commercial implant materials with a few limitations in its ease of biocompatibility and long-standing performance. Hence, porous TiO(2)/ZrO(2) nanocomposite coated over 316 L stainless steels was studied for their enhanced performance in terms of its biocompatibility and corrosion resistance, following a sol-gel process via dip-coating technique. The surface composition and porosity texture was studied to be uniform on the substrate. Biocompatibility studies on the TiO(2)/ZrO(2) nanocomposite coatings were investigated by placing the coated substrate in a simulated body fluid (SBF). The immersion procedure resulted in the complete coverage of the TiO(2)/ZrO(2) nanocomposite (coated on the surface of 316 L stainless steel) with the growth of a one-dimensional (1D) rod-like carbonate-containing apatite. The TiO(2)/ZrO(2) nanocomposite coated specimens showed a higher corrosion resistance in the SBF solution with an enhanced biocompatibility, surpassing the performance of the pure oxide coatings. The cell viability of TiO(2)/ZrO(2) nanocomposite coated implant surface was examined under human dermal fibroblasts culture, and it was observed that the composite coating enhances the proliferation through effective cellular attachment compared to pristine 316 L SS surface.

Transformation toughened ceramics for the heavy duty diesel engine technology program

NASA Technical Reports Server (NTRS)

Musikant, S.; Feingold, E.; Rauch, H.; Samanta, S.

1984-01-01

The objective of this program is to develop an advanced high temperature oxide structural ceramic for application to the heavy duty diesel engine. The approach is to employ transformation toughening by additions of ZrO.5HfO.5O2 solid solution to the oxide ceramics, mullite (2Al2O3S2SiO2) and alumina (Al2O3). The study is planned for three phases, each 12 months in duration. This report covers Phase 1. During this period, processing techniques were developed to incorporate the ZrO.5HfO.5O2 solid solution in the matrices while retaining the necessary metastable tetragonal phase. Modulus of rupture and of elasticity, coefficient of thermal expansion, fracture toughness by indent technique and thermal diffusivity of representative specimens were measured. In Phase 2, the process will be improved to provide higher mechanical strength and to define the techniques for scale up to component size. In Phase 3, full scale component prototypes will be fabri-]cated.

Spectroscopic properties of Sm3+ and V4+ ions in Na2O-SiO2-ZrO2 glasses

NASA Astrophysics Data System (ADS)

Neeraja, K.; Rao, T. G. V. M.; Kumar, A. Rupesh; Uma Lakshmi, V.; Veeraiah, N.; Rami Reddy, M.

2013-12-01

Na2O-SiO2-ZrO2 glasses of Sm3+ ions with and without V2O5 are characterized by spectroscopic and optical properties. The XRD and EDS spectra of the glass samples reveal an amorphous nature with different compositions within the glass matrix. The Infrared and Raman spectral studies are carried out and the existence of conventional structural units are analyzed in the glass network. The ESR spectra of the glass samples have indicating that a considerable proportion of vanadium ion exists in V4+ state. The optical absorption spectra of these glasses are recorded at room temperature, from the measured intensities of various absorption bands the Judd-Ofelt parameters Ω2, Ω4 and Ω6 are calculated. The photo-luminescence spectra recorded with excited wavelength 400 nm, five emission bands are observed; in this the energy transfer probability takes place between Sm3+ and V4+ ions.

Zirconia ceramics for excess weapons plutonium waste

NASA Astrophysics Data System (ADS)

Gong, W. L.; Lutze, W.; Ewing, R. C.

2000-01-01

We synthesized a zirconia (ZrO 2)-based single-phase ceramic containing simulated excess weapons plutonium waste. ZrO 2 has large solubility for other metallic oxides. More than 20 binary systems A xO y-ZrO 2 have been reported in the literature, including PuO 2, rare-earth oxides, and oxides of metals contained in weapons plutonium wastes. We show that significant amounts of gadolinium (neutron absorber) and yttrium (additional stabilizer of the cubic modification) can be dissolved in ZrO 2, together with plutonium (simulated by Ce 4+, U 4+ or Th 4+) and impurities (e.g., Ca, Mg, Fe, Si). Sol-gel and powder methods were applied to make homogeneous, single-phase zirconia solid solutions. Pu waste impurities were completely dissolved in the solid solutions. In contrast to other phases, e.g., zirconolite and pyrochlore, zirconia is extremely radiation resistant and does not undergo amorphization. Baddeleyite (ZrO 2) is suggested as the natural analogue to study long-term radiation resistance and chemical durability of zirconia-based waste forms.

Bioactivity and cell proliferation in radiopaque gel-derived CaO-P2O5-SiO2-ZrO2 glass and glass-ceramic powders.

PubMed

Montazerian, Maziar; Yekta, Bijan Eftekhari; Marghussian, Vahak Kaspari; Bellani, Caroline Faria; Siqueira, Renato Luiz; Zanotto, Edgar Dutra

2015-10-01

In this study, 10 mol% ZrO2 was added to a 27CaO-5P2O5-68SiO2 (mol%) base composition synthesized via a simple sol-gel method. This composition is similar to that of a frequently investigated bioactive gel-glass. The effects of ZrO2 on the in vitro bioactivity and MG-63 cell proliferation of the glass and its derivative polycrystalline (glass-ceramic) powder were investigated. The samples were characterized using thermo-gravimetric and differential thermal analysis (TG/DTA), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and scanning electron microscopy (SEM) coupled to energy dispersive X-ray spectroscopy (EDS). Release of Si, Ca, P and Zr into simulated body fluid (SBF) was determined by inductively coupled plasma (ICP). Upon heat treatment at 1000 °C, the glass powder crystallized into an apatite-wollastonite-zirconia glass-ceramic powder. Hydroxycarbonate apatite (HCA) formation on the surface of the glass and glass-ceramic particles containing ZrO2 was confirmed by FTIR and SEM. Addition of ZrO2 to the base glass composition decreased the rate of HCA formation in vitro from one day to three days, and hence, ZrO2 could be employed to control the rate of apatite formation. However, the rate of HCA formation on the glass-ceramic powder containing ZrO2 crystal was equal to that in the base glassy powder. Tests with a cultured human osteoblast-like MG-63 cells revealed that the glass and glass-ceramic materials stimulated cell proliferation, indicating that they are biocompatible and are not cytotoxic in vitro. Moreover, zirconia clearly increased osteoblast proliferation over that of the Zr-free samples. This increase is likely associated with the lower solubility of these samples and, consequently, a smaller variation in the media pH. Despite the low solubility of these materials, bioactivity was maintained, indicating that these glassy and polycrystalline powders are potential candidates for bone graft substitutes and bone cements with the special feature of radiopacity. Copyright © 2015 Elsevier B.V. All rights reserved.

Facile synthesis of highly stable and well-dispersed mesoporous ZrO(2)/carbon composites with high performance in oxidative dehydrogenation of ethylbenzene.

PubMed

Li, Qiang; Xu, Jie; Wu, Zhangxiong; Feng, Dan; Yang, Jianping; Wei, Jing; Wu, Qingling; Tu, Bo; Cao, Yong; Zhao, Dongyuan

2010-09-28

Highly ordered mesoporous ZrO(2)/carbon (FDU-15) composites have been synthesized via a facile evaporation induced triconstituent co-assembly (EISA) approach by using Pluronic F127 as a template and zirconium oxychloride octahydrate and resol as Zr and carbon sources. The synthesized mesoporous composites exhibit a highly ordered two-dimensional (2-D) hexagonal mesostructure with relatively high specific surface areas (up to 947 m(2) g(-1)), pore sizes around 3.8 nm and high pore volumes (up to 0.71 cm(3) g(-1)). The results clearly show that the crystalline zirconia nanoparticles (ca. 1.9-3.9 nm) are well-dispersed in amorphous matrices of the ordered mesoporous carbon FDU-15 materials, which construct the nanocomposites. The ordered mesostructures of the obtained ZrO(2)/FDU-15 composites can be well-retained even at the high pyrolysis temperature (up to 900 degrees C), suggesting a high thermal stability. The zirconia content of the ZrO(2)/FDU-15 composites can be tunable in a wide range (up to 47%). Moreover, the resultant mesoporous ZrO(2)/FDU-15 composites exhibit high catalytic activity in oxidative dehydrogenation (ODH) of ethylbenzene (EB) to styrene (ST), with high ethylbenzene conversion (59.6%) and styrene selectivity (90.4%), which is mainly attributed to the synergistic catalytic effect between the oxygen-containing groups located on the carbon pore walls and weakly basic sites of the nanocrystalline ZrO(2). Furthermore, the high specific surface areas and opening pore channels are also responsible for their high catalytic activity. Therefore, it is a very promising catalyst material in styrene production on an industrial scale.

Conductive bridge random access memory characteristics of SiCN based transparent device due to indium diffusion

NASA Astrophysics Data System (ADS)

Kumar, Dayanand; Aluguri, Rakesh; Chand, Umesh; Tseng, Tseung-Yuen

2018-03-01

In this work, the transparent bipolar resistive switching characteristics of a SiCN-based ITO/SiCN/AZO structure due to In diffusion from ITO is studied. The SiCN based device is found to be 80% transparent in the visible wavelength region. This device, with AZO as both top and bottom electrodes, does not show any RRAM property due to deposition of the high quality O2-free SiCN film. Replacing the AZO top electrode with ITO in this device results in good resistive switching (RS) characteristics with a high on/off ratio and long retention. Replacing the SiCN film with ZrO2 also results in excellent RS characteristics due to the formation of an oxygen vacancies filament inside the ZrO2 film. A resistance ratio of on/off is found to be higher in the SiCN based device compared to that of the ZrO2 device. Diffusion of In from ITO into the SiCN film on application of high positive voltage during forming can be attributed to the occurrence of RS in the device, which is confirmed by the analyses of energy dispersive spectroscopy and secondary-ion mass spectrometry. This study shows a pathway for the fabrication of CBRAM based transparent devices for non-volatile memory application.

Mechanical properties and rapid low-temperature consolidation of nanocrystalline Cu-ZrO2 composites by pulsed current activated heating

NASA Astrophysics Data System (ADS)

Kang, Bo-Ram; Yoon, Jin-kook; Hong, Kyung-Tae; Shon, In-Jin

2015-07-01

Metal-ceramic compositr can be obtained with an optimum combination of low density, high oxidation resistance, and high hardness of the ceramic and toughness of the metal. Therefore, metal matrix composites are recognized as candidates for aerospace, automotive, biomaterials, and defense applications. Despite its many attractive properties, the low fracture toughness of ZrO2 limits its wide application. One of the most obvious tactics to improve the mechanical properties has been to fabricate a nanostructured material and composite material. Nano-powders of Cu and ZrO2 were synthesized from 2CuO and Zr powders by high-energy ball milling. Nanocrystalline 2Cu-ZrO2 composite was consolidated within 5 minutes from mechanically synthesized powders of ZrO2 and 2Cu at low temperature, by a pulsed current activated sintering method. The relative density of the composite was 98.5%. The fracture toughness of 2Cu-ZrO2 composite in this study is higher than that of monolithic ZrO2, without great decrease of hardness.

About properties of ZrO2 thermal protective coatings obtained from spherical powder mixtures

NASA Astrophysics Data System (ADS)

Berdnik, O. B.; Tsareva, I. N.; Tarasenko, Yu P.

2017-05-01

It is developed the technology of high-energy plasma spraying of the zirconium dioxide (ZrO2) thermal protective coating on the basis of ZrO2 tetragonal and cubic phases with the spheroidal grain shape and the columnar substructure, with the total porosity P = 4 %, the hardness HV = 12 GPa, the roughness parameter R a ˜ 6 μm, the thickness 0.3-3 mm. As a sublayer it is used the heat-resistant coating of “Ni-Co-Cr-Al-Y” system with an intermetallic phase composition and the layered microstructure of the grains.

Corrosion resistance of zirconium oxynitride coatings deposited via DC unbalanced magnetron sputtering and spray pyrolysis-nitriding

NASA Astrophysics Data System (ADS)

Cubillos, G. I.; Bethencourt, M.; Olaya, J. J.

2015-02-01

ZrOxNy/ZrO2 thin films were deposited on stainless steel using two different methods: ultrasonic spray pyrolysis-nitriding (SPY-N) and the DC unbalanced magnetron sputtering technique (UBMS). Using the first method, ZrO2 was initially deposited and subsequently nitrided in an anhydrous ammonia atmosphere at 1023 K at atmospheric pressure. For UBMS, the film was deposited in an atmosphere of air/argon with a Φair/ΦAr flow ratio of 3.0. Structural analysis was carried out through X-ray diffraction (XRD), and morphological analysis was done through scanning electron microscopy (SEM) and atomic force microscopy (AFM). Chemical analysis was carried out using X-ray photoelectron spectroscopy (XPS). ZrOxNy rhombohedral polycrystalline film was produced with spray pyrolysis-nitriding, whereas using the UBMS technique, the oxynitride films grew with cubic Zr2ON2 crystalline structures preferentially oriented along the (2 2 2) plane. Upon chemical analysis of the surface, the coatings exhibited spectral lines of Zr3d, O1s, and N1s, characteristic of zirconium oxynitride/zirconia. SEM analysis showed the homogeneity of the films, and AFM showed morphological differences according to the deposition technique of the coatings. Zirconium oxynitride films enhanced the stainless steel's resistance to corrosion using both techniques. The protective efficacy was evaluated using electrochemical techniques based on linear polarization (LP). The results indicated that the layers provide good resistance to corrosion when exposed to chloride-containing media.

Solar/UV-induced photocatalytic degradation of three commercial textile dyes.

PubMed

Neppolian, B; Choi, H C; Sakthivel, S; Arabindoo, Banumathi; Murugesan, V

2002-01-28

The photocatalytic degradation of three commercial textile dyes with different structure has been investigated using TiO(2) (Degussa P25) photocatalyst in aqueous solution under solar irradiation. Experiments were conducted to optimise various parameters viz. amount of catalyst, concentration of dye, pH and solar light intensity. Degradation of all the dyes were examined by using chemical oxygen demand (COD) method. The degradation efficiency of the three dyes is as follows: Reactive Yellow 17(RY17) > Reactive Red 2(RR2) > Reactive Blue 4 (RB4), respectively. The experimental results indicate that TiO(2) (Degussa P25) is the best catalyst in comparison with other commercial photocatalysts such as, TiO(2) (Merck), ZnO, ZrO(2), WO(3) and CdS. Though the UV irradiation can efficiently degrade the dyes, naturally abundant solar irradiation is also very effective in the mineralisation of dyes. The comparison between thin-film coating and aqueous slurry method reveals that slurry method is more efficient than coating but the problems of leaching and the requirement of separation can be avoided by using coating technique. These observations indicate that all the three dyes could be degraded completely at different time intervals. Hence, it may be a viable technique for the safe disposal of textile wastewater into the water streams.

ZrO2/bamboo leaves ash (BLA) Catalyst in Biodiesel Conversion of Rice Bran Oil

NASA Astrophysics Data System (ADS)

Fatimah, Is; Taushiyah, Ana; Badriatun Najah, Fitri; Azmi, Ulil

2018-04-01

Preparation, characterization and catalytic activity of ZrO2/bamboo leaves ash (BLA) catalyst for conversion of rice bran oil to biodiesel have been investigated. The catalyst was prepared by impregnation method of ZrOCl2 as ZrO2 precursor with BLA at a theoretical content of 20% wt. followed by calcination. The physicochemical properties of the catalyst material were characterized by x-ray diffraction (XRD), FTIR and surface acidity measurement. Activity test of materials in biodiesel conversion of rice bran oil was used by reflux method and microwave (MW) assisted method. Reaction variables studied in the investigation were the effect of catalyst weight and time of MW irradiation compared with the use reflux method. The results showed that ZrO2/BLA catalyst exhibited competitively effective and efficient processes for the production of biodiesel. The reflux method demonstrated an higher conversion (%) compared to MW method, however MW method showed the better reusable properties.

Surface Modifier-Free Organic-Inorganic Hybridization To Produce Optically Transparent and Highly Refractive Bulk Materials Composed of Epoxy Resins and ZrO2 Nanoparticles.

PubMed

Enomoto, Kazushi; Kikuchi, Moriya; Narumi, Atsushi; Kawaguchi, Seigou

2018-04-25

Surface modifier-free hybridization of ZrO 2 nanoparticles (NPs) with epoxy-based polymers is demonstrated for the first time to afford highly transparent and refractive bulk materials. This is achieved by a unique and versatile hybridization via the one-pot direct phase transfer of ZrO 2 NPs from water to epoxy monomers without any aggregation followed by curing with anhydride. Three types of representative epoxy monomers, bisphenol A diglycidyl ether (BADGE), 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexane carboxylate (CEL), and 1,3,5-tris(3-(oxiran-2-yl)propyl)-1,3,5-triazinane-2,4,6-trione (TEPIC), are used to produce transparent viscous dispersions. The resulting ZrO 2 NPs are thoroughly characterized using dynamic light scattering (DLS), transmission electron microscopy (TEM), Fourier transform infrared (FT-IR), and solid-state 13 C CP/MAS NMR measurements. The results from DLS and TEM analyses indicate nanodispersion of ZrO 2 into epoxy monomers as a continuous medium. A surface modification mechanism and the binding fashion during phase transfer are proposed based on the FT-IR and solid-state 13 C CP/MAS NMR measurements. Epoxy-based hybrid materials with high transparency and refractive index are successfully fabricated by heat curing or polymerizing a mixture of monomers containing epoxy-functionalized ZrO 2 NPs and methylhexahydrophthalic anhydride in the presence of a phosphoric catalyst. The TEM and small-angle X-ray scattering measurements of the hybrids show a nanodispersion of ZrO 2 in the epoxy networks. The refractive index at 594 nm ( n 594 ) increases up to 1.765 for BADGE-based hybrids, 1.667 for CEL-based hybrids, and 1.693 for TEPIC-based hybrids. Their refractive indices and Abbe's numbers are quantitatively described by the Lorentz-Lorenz effective medium expansion theory. Their transmissivity is also reasonably explained using Fresnel refraction, Rayleigh scattering, and the Lambert-Beer theories. This surface modifier-free hybridization provides a versatile, fascinating, and promising method for synthesizing a variety of epoxy-based hybrid materials.

Extremely fine structured cathode for solid oxide fuel cells using Sr-doped LaMnO3 and Y2O3-stabilized ZrO2 nano-composite powder synthesized by spray pyrolysis

NASA Astrophysics Data System (ADS)

Shimada, Hiroyuki; Yamaguchi, Toshiaki; Sumi, Hirofumi; Nomura, Katsuhiro; Yamaguchi, Yuki; Fujishiro, Yoshinobu

2017-02-01

A solid oxide fuel cell (SOFC) for high power density operation was developed with a microstructure-controlled cathode using a nano-composite powder of Sr-doped LaMnO3 (LSM) and Y2O3-stabilized ZrO2 (YSZ) synthesized by spray pyrolysis. The individual LSM-YSZ nano-composite particles, formed by crystalline and amorphous nano-size LSM and YSZ particles, showed spherical morphology with uniform particle size. The use of this powder for cathode material led to an extremely fine microstructure, in which all the LSM and YSZ grains (approximately 100-200 nm) were highly dispersed and formed their own network structures. This microstructure was due to the two phase electrode structure control using the powder, namely, nano-order level in each particle and micro-order level between particles. An anode-supported SOFC with the LSM-YSZ cathode using humidified H2 as fuel and ambient air as oxidant exhibited high power densities, such as 1.29 W cm-2 under a voltage of 0.75 V and a maximum power density of 2.65 W cm-2 at 800 °C. Also, the SOFC could be stably operated for 250 h with no degradation, even at a high temperature of 800 °C.

Kinetics of chlorination of zirconia in mixture with petroleum coke by chlorine gas

NASA Astrophysics Data System (ADS)

Jena, P. K.; Brocchi, E. A.; Reis, M. L. Dos

1999-06-01

Studies on the kinetics of carbothermic chlorination of zirconium dioxide in gaseous chlorine were carried out with petroleum coke fines in powder form. The amounts of ZrO2 chlorinated were found to be directly proportional to the time of chlorination in the temperature range studied (973 to 1273 K). The activation energy values for chlorination of ZrO2, in mixture with petroleum coke, was found to be 18.3 kJ/mole. The influence of particle size of petroleum coke on the chlorination of ZrO2 (-38 + 25 µm) was studied, and it was found that the rate of chlorination increased up to the size range of -75 to +53 µm, and the size finer than this produced negligible increase. The amount of petroleum coke in the mixture above 17.41 pct in excess of the stoichiometry resulted in very little increase in the rate. The effect of the partial pressure of chlorine ( pCl2) on the rate of chlorination was found to obey the following relationship, derived from the Langmuir adsorption isotherm: v = {k \\cdot K \\cdot pCl_2 }/{l + K \\cdot pCl_2 } where v is the amount of ZrO2 (g/min) reacted, k is the rate constant, and K is the equilibrium constant for adsorption of two chlorine atoms (obtained from the dissociation of a molecule of Cl2 at the carbon surface) on the surface of ZrO2. By plotting 1/ v vs 1/ pCl2, a straight-line relationship with an intercept in x-axis is obtained, further supporting the preceding equation. The dissociation of the adsorbed complex, Cl … ZrO2 … Cl to ZrCl2 and O2 is suggested to be the rate-controlling step. Subsequently, the less stable ZrCl2 combines with Cl2 to form ZrCl4 and the oxygen combines with C to form CO and CO2.

Characterisation of high temperature refractory ceramics for nuclear applications

NASA Astrophysics Data System (ADS)

Bottomley, P. D. W.; Wiss, Th; Janssen, A.; Cremer, B.; Thiele, H.; Manara, D.; Scheindlin, M.; Murray-Farthing, M.; Lajarge, P.; Menna, M.; Bouexière, D.; Rondinella, V. V.

2012-03-01

The ternary oxide ceramic system UO2-ZrO2-FeO is a refractory system that is of great relevance to the nuclear industry as it represents one of the main systems resulting from the interaction of the Zircaloy cladding, the UO2 fuel and the structural elements of a nuclear reactor. It is particularly the high temperature properties that require investigation; that is, when substantial overheating of the nuclear core occurs and interactions can lead to its degradation, melting and result in a severe nuclear accident. There has been much work on the UO2-ZrO2 system and also on the ternary system with FeO but there is still a need to examine 2 further aspects; firstly the effect of sub-oxidized systems, the UO2-Zr and FeO-Zr systems, and secondly the effect of Fe/Zr or Fe/U ratios on the melting point of the U-Zr-Fe oxide system. Samples of UO2-Zr and UO2-ZrO2-FeO were fabricated at ITU and then characterized by optical microscopy (OM) and X-ray diffraction to determine the ceramic's structure and verify the composition. Thereafter the samples are to be melted by laser flash heating and their liquidus and solidus temperatures determined by pyrometry. This programme is currently ongoing. The frozen samples, after testing, were then sectioned, polished and the molten zone micro-analytically examined by OM & SEM-EDS in order to determine its structure and composition and to compare with the existing phase diagrams. Examples of results from these systems will be given. Finally, a reacted Zr-FeO thermite mixture was examined, which had been used to generate high temperatures during tests of reactor melt-concrete interactions. The aim was to assess the reaction and estimate the heat generation from this novel technique. These results allow verification or improvement of the phase diagram and are of primary importance as input to models used to predict materials interactions in a severe nuclear accident.

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.

A new generation of zirconia supported metal oxide catalysts for converting low grade renewable feedstocks to biodiesel.

PubMed

Kim, Manhoe; DiMaggio, Craig; Salley, Steven O; Simon Ng, K Y

2012-08-01

A new class of zirconia supported mixed metal oxides (ZnO-TiO(2)-Nd(2)O(3)/ZrO(2) and ZnO-SiO(2)-Yb(2)O(3)/ZrO(2)) has demonstrated the ability to convert low quality, high free fatty acid (FFA) bio-oils into biodiesel. Pelletized catalysts of ZrO(2) supported metal oxides were prepared via a sol-gel process and tested in continuous flow packed bed reactors for up to 6 months. In a single pass, while operating at mild to moderate reaction conditions, 195 °C and 300 psi, these catalysts can perform simultaneous esterification and transesterification reactions on feedstock of 33% FFA and 67% soybean oil to achieve FAME yields higher than 90%. Catalytic activity of the ZrO(2) supported metal oxide catalysts was highly dependent on the metal oxide composition. These heterogeneous catalysts will enable biodiesel manufacturers to avoid problems inherent in homogeneous processes, such as separation and washing, corrosive conditions, and excessive methanol usage. Copyright © 2012 Elsevier Ltd. All rights reserved.

Properties and rapid low-temperature consolidation of nanocrystalline Fe-ZrO2 composite by pulsed current activated sintering

NASA Astrophysics Data System (ADS)

Kang, Hyun-Su; Ko, In-Yong; Yoon, Jin-Kook; Doh, Jung-Mann; Hong, Kyung-Tae; Shon, In-Jin

2011-02-01

Nanopowders of Fe and ZrO2 were synthesized from Fe2O3 and Zr by high-energy ball milling. The powder sizes of Fe and ZrO2 were 70 nm and 12 nm, respectively. Highly dense nanostructured 4/3Fe-ZrO2 composite was consolidated by a pulsed current activated sintering method within 1 minute from the mechanically synthesized powders (Fe-ZrO2) and horizontal milled Fe2O3+Zr powders under the 1 GPa pressure. The grain sizes of Fe and ZrO2 in the composite were calculated. The average hardness and fracture toughness values of nanostuctured 4/3Fe-ZrO2 composite were investigated.

[Microwave sintering of nanometer powder of alumina and zirconia-based dental ceramics].

PubMed

Chen, Yi-Fan; Lu, Dong-Mei; Wan, Qian-Bing; Jin, Yong; Zhu, Ju-Mu

2006-02-01

The objective of the present study was to investigate the feasibility and reliability of sintering alumina and zirconia-based all-ceramic materials through a recently introduced microwave heating technique. The variation of crystal phases, the growth of grain sizes and microstructural features of these materials were evaluated after sintering. Four different groups of powder (l00%Al2O3, 60%Al2O3+40%ZrO2, 40% Al2O3+60%ZrO2, 100% ZrO2) were respectively press-compacted to fabricate green disk samples, 5 specimen of each group were prepared. All the samples were surrounded by refractory materials for heat containment and processed at 1 600 degrees C in a domestic microwave oven (850 W, 2 450 MHz), 1 600 degrees C/5 min for heating rate, 10 min for holding time. After sintering, the phase composition and average grain size of these ceramics were examined using X-ray diffraction (XRD). Their microstructure characteristics were studied by scanning electron microscopy (SEM). All the specimens were successfully sintered with the application of microwave heating system in combination with a suitable thermal insulator. No phase change was found in alumina while monoclinic-zirconia was found to be transformed to tetragonal-zirconia. A little grain size growth of Al2O3 and ZrO2 has been observed with Al2O3 24.1 nm/before and 51.8 nm/after; ZrO2 25.3 nm/before and 29.7 nm/after. The SEM photos indicated that the microwave-sintered Al2O3-ZrO2 ceramics had a uniform crystal distribution and their crystal sizes could be maintained within the range of nanometers. It is expected that in the near future microwave heating system could be a promising substitute for conventional processing methods due to its unparalled advantages, including more rapid heating rate, shortened sintering time, superfine grain size, improved microstructure and much less expensive equipment.

Millimeter wave transmission studies of YBa2Cu3O7-delta thin films in the 26.5 to 40.0 GHz frequency range

NASA Technical Reports Server (NTRS)

Miranda, F. A.; Gordon, W. L.; Bhasin, K. B.; Heinen, V. O.; Warner, J. D.; Valco, G. J.

1989-01-01

Millimeter wave transmission measurements through YBa2Cu3O(7-delta) thin films on MgO, ZrO2 and LaAlO3 substrates, are reported. The films (approx. 1 micron) were deposited by sequential evaporation and laser ablation techniques. Transition temperatures T sub c, ranging from 89.7 K for the Laser Ablated film on LaAlO3 to approximately 72 K for the sequentially evaporated film on MgO, were obtained. The values of the real and imaginary parts of the complex conductivity, sigma 1 and sigma 2, are obtained from the transmission data, assuming a two fluid model. The BCS approach is used to calculate values for an effective energy gap from the obtained values of sigma sub 1. A range of gap values from 2 DELTA o/K sub B T sub c = 4.19 to 4.35 was obtained. The magnetic penetration depth is evaluated from the deduced values of sigma 2. These results are discussed together with the frequency dependence of the normalized transmission amplitude, P/P sub c, below and above T sub c.

Mesoporous silica templated zirconia nanoparticles

NASA Astrophysics Data System (ADS)

Ballem, Mohamed A.; Córdoba, José M.; Odén, Magnus

2011-07-01

Nanoparticles of zirconium oxide (ZrO2) were synthesized by infiltration of a zirconia precursor (ZrOCl2·8H2O) into a SBA-15 mesoporous silica mold using a wet-impregnation technique. X-ray diffractometry and high-resolution transmission electron microscopy show formation of stable ZrO2 nanoparticles inside the silica pores after a thermal treatment at 550 °C. Subsequent leaching out of the silica template by NaOH resulted in well-dispersed ZrO2 nanoparticles with an average diameter of 4 nm. The formed single crystal nanoparticles are faceted with 110 surfaces termination suggesting it to be the preferred growth orientation. A growth model of these nanoparticles is also suggested.

Hydroxyaptite nanorods patterned ZrO2 bilayer coating on zirconium for the application of percutaneous implants.

PubMed

Zhang, Lan; Han, Yong; Tan, Guoxin

2015-03-01

Percutaneous implant requires a tight bond between the underlying dermis of skin and implant surface to prevent epithelial down-growth and infection, while fibroblasts play a key role in the skin-implant integration. In this work, nanorod-shaped hydroxyaptite (HA) with a mean diameter of 70 nm and length of 400 nm was hydrothermally grown on micro-arc oxidized (MAOed) Ca- and P-doped ZrO2 to form a bilayer coating. The hydrothermal formation mechanism of HA nanorods was explored, and the adsorption of total protein on the coating from α-MEM medium containing 10% fetal bovine serum was examined. Employing L-929 cells, the behaviors of fibroblasts on the bilayer coating, including adhesion and proliferation were evaluated together the polished Zr and as-MAOed ZrO2. The obtained results show that the HA nanorods nucleated on ZrO2 and grew at the expense of the doped Ca and P ions during the hydrothermal treatment (HT). The HA nanorods patterned coating enhanced protein absorption, and significantly improved the adhesion and proliferation of fibroblasts compared to the as-MAOed ZrO2 and polished Zr. It suggests that the HA nanorods/ZrO2 coated zirconium has a potential application for percutaneous implants to enhance the attachment of skin. Copyright © 2015 Elsevier B.V. All rights reserved.

Amorphization of nanocrystalline monoclinic ZrO2 by swift heavy ion irradiation.

PubMed

Lu, Fengyuan; Wang, Jianwei; Lang, Maik; Toulemonde, Marcel; Namavar, Fereydoon; Trautmann, Christina; Zhang, Jiaming; Ewing, Rodney C; Lian, Jie

2012-09-21

Bulk ZrO(2) polymorphs generally have an extremely high amorphization tolerance upon low energy ion and swift heavy ion irradiation in which ballistic interaction and ionization radiation dominate the ion-solid interaction, respectively. However, under very high-energy irradiation by 1.33 GeV U-238, nanocrystalline (40-50 nm) monoclinic ZrO(2) can be amorphized. A computational simulation based on a thermal spike model reveals that the strong ionizing radiation from swift heavy ions with a very high electronic energy loss of 52.2 keV nm(-1) can induce transient zones with temperatures well above the ZrO(2) melting point. The extreme electronic energy loss, coupled with the high energy state of the nanostructured materials and a high thermal confinement due to the less effective heat transport within the transient hot zone, may eventually be responsible for the ionizing radiation-induced amorphization without transforming to the tetragonal polymorph. The amorphization of nanocrystalline zirconia was also confirmed by 1.69 GeV Au ion irradiation with the electronic energy loss of 40 keV nm(-1). These results suggest that highly radiation tolerant materials in bulk forms, such as ZrO(2), may be radiation sensitive with the reduced length scale down to the nano-metered regime upon irradiation above a threshold value of electronic energy loss.

The influence of adding modified zirconium oxide-titanium dioxide nano-particles on mechanical properties of orthodontic adhesive: an in vitro study.

PubMed

Felemban, Nayef H; Ebrahim, Mohamed I

2017-01-13

The purpose of this in-vitro study was to examine the effect of incorporating different concentrations of Zirconium oxide-Titanium dioxide (ZrO2-TiO2) nanoparticles, which can have antibacterial properties, on the mechanical properties of an orthodontic adhesive. ZrO2-TiO2 (Zirconium oxide, HWNANO, Hongwu International Group Ltd, China) -Titanium dioxide, Nanoshell, USA) nanopowder were incorporated into orthodontic adhesive (Transbond XT, 3 M Unitek, Monrovia, USA) with different concentrations (0.5% weight nonofiller and 1% weight nanofiller). The size of nanoparticle was 70-80 nm for ZrO2 and less than 50 nm for TiO2. For measuring the shear bond strength of the three groups of orthodontic adhesives [Transbond (control), Transbond mixed with 0.5% weight ZrO2-TiO2, and Transbond mixed with 1% weight ZrO2-TiO2], 30 freshly extracted human first premolars were used and bonded with stainless steel metal brackets (Dentaurum®, Discovery®, Deutschland), using the 3 orthodontic adhesives and 3 M Unitek; Transbond TM Plus Self-Etching Primer (10 samples in each group). The recorded values of compressive strength and tensile strength (measured separately on 10 samples of orthodontic adhesives (add the 3 D size of sample, light cured for 40 s on both sides) of each orthodontic adhesives), as well as the shear bond strength in Mega Pascal unit (MPa) were collected and exposed to one-way analysis of variance (ANOVA) and Tukey's post-hoc tests. orthodontic adhesive with 1% weight ZrO2-TiO2 showed the highest mean compressive (73.42 ± 1.55 MPa, p: 0.003, F: 12.74), tensile strength (8.65 ± 0.74 MPa, p: 0.001, F: 68.20), and shear bond strength (20.05 ± 0.2 MPa, p: 0.001, F: 0.17). Adding ZrO2-TiO2 nanoparticle to orthodontic adhesive increased compressive strength, tensile strength, and shear bond strength in vitro, but in vivo studies and randomized clinical trials are needed to validate the present findings.

Microstructural Evolution of Al2O3-ZrO2 (Y2O3) Composites and its Correlation with Toughness

NASA Astrophysics Data System (ADS)

Kim, Hee Seung; Seo, Mi Young; Kim, Ik Jin

2008-02-01

The microstructure of zirconia (ZrO2) toughened alumina (Al2O3) ceramics was carefully controlled so as to obtain dense and fine-grained ceramics, thereby improving the properties and reliability of the ceramics for capillary applications in semiconductor bonding technology. Al2O3-ZrO2(Y2O3) composite was produced via Ceramic Injection Molding (CIM) technology, followed by Sinter-HIP process. Room temperature strength, hardness, Young's modulus, thermal expansion coefficient and toughness were determined, as well as surface strengthening induced by the fine grained homogenous microstructure and the thermal treatment. The changes in alumina/zirconia grain size, sintering condition and HIP treatment were found to be correlated.

A study of Pd/SO4/ZrO2/Al2O3 catalysts in n-hexane isomerization

NASA Astrophysics Data System (ADS)

Dzhikiya, O. V.; Smolikov, M. D.; Kazantsev, K. V.; Yablokova, S. S.; Kireeva, T. V.; Paukshtis, E. A.; Gulyaeva, T. I.; Belyi, A. S.

2017-08-01

The effect of palladium concentration in a range from 0.02 to 1.6 wt.% on characteristics of n-hexane isomerization was studied. The (O2-Hchem) titration and O2 chemisorption study revealed that palladium in Pd/SO4/ZrO2/Al2O3 systems adsorbs hydrogen in a ratio H/Pds = 1.13-1.65 at./at. Investigation of the charge state of the metal by IR spectroscopy of adsorbed CO showed the presence of both the metallic (Pd0) and charged palladium species. Pd/SO4/ZrO2/Al2O3 catalysts with charged palladium atoms exhibit high activity and selectivity in n-hexane isomerization.

The Peculiarities of Structure Formation and Properties of Zirconia-Based Nanocomposites with Addition of Al2O3 and NiO

NASA Astrophysics Data System (ADS)

Danilenko, I.; Lasko, G.; Brykhanova, I.; Burkhovetski, V.; Ahkhozov, L.

2017-02-01

The present study is devoted to the problem of enhancing fracture toughness of ZrO2 ceramic materials through the formation of composite structure by addition of Al2O3 and NiO particles. In this paper, we analyzed the general and distinguished features of microstructure of both composite materials and its effect on fracture toughness of materials. In this paper, we used the XRD, SEM, and EDS methods for determination of granulometric, phase, and chemical composition of sintered materials. The peculiarities of dependence of fracture toughness values from dopant concentration and changing the Y3+ amount in zirconia grains allow us to assume that at least two mechanisms can affect the fracture toughness of ZrO2 ceramics. Crack bridging/deflection processes with the "transformation toughening" affect the K1C values depending on the dopant concentration. Crack deflection mechanism affects the K1C values when the dopant concentrations are low, and transformation toughening affects the K1C values when the dopant concentrations begin to have an impact on microstructure reorganization-redistribution of Y3+ ions and formation of Y3+-depleted grains with high ability to phase transformation.

Substitutional Cd and Cd-Oxygen Vacancy Complexes in ZrO2 and Ce-doped ZrO_2

NASA Astrophysics Data System (ADS)

Zacate, Matthew O.; Karapetrova, E.; Platzer, R.; Gardner, J. A.; Evenson, W. E.; Sommers, J. A.

1996-03-01

We are using Perturbed Angular Correlation Spectroscopy (PAC) to study oxygen vacancy (V_O) dynamics in tetragonal ZrO2 and Ce-doped ZrO_2. PAC requires a radioactive probe atom, Cd in this study, which sits substitutionally for a Zr ion. Cd is doubly-negatively charged relative to the lattice and attracts doubly-positively charged V_Os. Pure tetragonal zirconia exists only above 950 ^circC and in this temperature range, the V_Os are very mobile. Above 950 ^circC we observe V_Os rapidly hopping about the Cd allowing us to determine the VO concentration and the trapping energy. We have been Ce-doping to stabilize the tetragonal phase to lower temperature to determine the electric field gradient the Cd experiences due to a stationary V_O. As a consequence of the Ce-doping, we observe a local lattice distortion about the Cd which increases with Ce-doping.

Physicochemical properties of calcium silicate cements associated with microparticulate and nanoparticulate radiopacifiers.

PubMed

Bosso-Martelo, Roberta; Guerreiro-Tanomaru, Juliane M; Viapiana, Raqueli; Berbert, Fabio Luiz C; Duarte, Marco Antonio Hungaro; Tanomaru-Filho, Mário

2016-01-01

The objective of this paper was to evaluate the physicochemical properties of calcium silicate cements with different chemical compositions, associated with radiopacifying agents. Mineral trioxide aggregate (MTA) Angelus, calcium silicate cement with additives (CSC), and resinous calcium silicate cement (CSCR) were evaluated, with the addition of the following radiopacifiers: microparticles (micro) or nanoparticles (nano) of zirconium oxide (ZrO(2)), niobium oxide (Nb(2)O(5)), bismuth oxide (Bi(2)O(3)), or calcium tungstate (CaWO(4)). Setting time was evaluated using Gilmore needles. Solubility was determined after immersion in water. The pH and calcium ion release were analyzed after 3, 12, and 24 h and 7, 14, and 21 days. The data obtained were submitted to analysis of variance and Tukey's test, at a level of significance of 5 %. CSC + CaWO(4) and CSCR + ZrO(2) micro, Nb(2)O(5) and CaWO(4) presented results similar to MTA, with a shorter final setting time than the other associations. CSC and CSCR+ ZrO(2) micro presented a higher degree of flow. All the cements evaluated presented low solubility. The materials presented alkaline pH and released calcium ions. ZrO(2) micro radiopacifier may be considered a potential substitute for Bi(2)O(3) when associated with CSC or CSCR. The proposed materials, especially when associated with ZrO(2), are potential materials for use as alternatives to MTA.

Aluminium surface treatment with ceramic phases using diode laser

NASA Astrophysics Data System (ADS)

Labisz, K.; Tański, T.; Brytan, Z.; Pakieła, W.; Wiśniowski, M.

2016-07-01

Ceramic particles powder feeding into surface layer of engineering metal alloy is a well-known and widely used technique. New approach into the topic is to obtain finely distributed nano-sized particles involved in the aluminium matrix using the traditional laser technology. In this paper are presented results of microstructure investigation of cast aluminium-silicon-copper alloys surface layer after heat treatment and alloying with ceramic carbides of WC and ZrO2 using high-power diode laser. The surface layer was specially prepared for the reason of reducing the reflectivity, which is the main problem in the up-to-date metal matrix composites production. With scanning electron microscopy, it was possible to determine the deformation process and distribution of WC and ZrO2 ceramic powder phase. Structure of the surface after laser treatment changes, revealing three zones—remelting zone, heat-affected zone and transition zone placed over the Al substrate. The structural changes of ceramic powder, its distribution and morphology as well as microstructure of the matrix material influence on functional properties, especially wear resistance and hardness of the achieved layer, were investigated.

Room Temperature Magnetic Behavior In Nanocrystalline Ni-Doped Zro2 By Microwave-Assisted Polyol Synthesis

NASA Astrophysics Data System (ADS)

Parimita Rath, Pragyan; Parhi, Pankaj Kumar; Ranjan Panda, Sirish; Priyadarshini, Barsharani; Ranjan Sahoo, Tapas

2017-08-01

This article, deals with a microwave-assisted polyol method to demonstrate a low temperature route < 250°C, to prepare a high temperature cubic zirconia phase. Powder XRD pattern shows broad diffraction peaks suggesting nanometric size of the particles. Magnetic behavior of 1-5 at% Ni doped samples show a threshold for substitutional induced room temperature ferromagnetism up to 3 at% of Ni. TGA data reveals that Ni-doped ZrO2 polyol precursors decompose exothermically below 300°C. IR data confirms the reduction of Zr(OH)4 precipitates to ZrO2, in agreement with the conclusions drawn from the TGA analysis.

(ZrO 2) 0.85( REO 1.5) 0.15 ( RE=Sc, Y) solid solutions prepared via three Pechini-type gel routes: 1—gel formation and calcination behaviors

NASA Astrophysics Data System (ADS)

Zhang, Yawen; Li, Ang; Yan, Zhengguang; Xu, Gang; Liao, Chunsheng; Yan, Chunhua

2003-02-01

(ZrO2)0.85(REO1.5)0.15 (RE=Sc, Y) nanoparticles with pure cubic fluorite structure have been synthesized by three Pechini-type gel routes, viz. poly(vinyl alcohol) containing-process (route I), poly(ethylene glycol) and formic acid-containing process (route II), and in situ polymerizable complex method (route III). The coordination modes between metal ions and polymers in the gels are shown to be highly correlative with the synthesis route used. The gels prepared by route III have the strongest coordination throughout their network and therefore the best chemical homogeneity. The altered variety of polymer and cross-linking within the gels adopted by these three routes has made the as-synthesized samples show appreciable differences in thermal behavior, powder reactivity and nanoparticle properties.

Effect of anodization on the surface characteristics and electrochemical behaviour of zirconium in artificial saliva.

PubMed

Romonti, Daniela E; Gomez Sanchez, Andrea V; Milošev, Ingrid; Demetrescu, Ioana; Ceré, Silvia

2016-05-01

The paper is focused on elaboration of ZrO2 films on pure zirconium via anodizing in phosphoric acid with and without fluoride at constant potentials of 30 V and 60 V. The structure and composition of the films were investigated using scanning electronic microscopy, Raman spectroscopy and X-ray photoelectron spectroscopy. The composition of the oxides formed at both potentials can be identified as monoclinic ZrO2. In addition to Zr and O, the layers formed in phosphoric acid contain phosphorus originating from the phosphoric acid. When the phosphoric acid solution contains NaF, fluorine is also incorporated into the oxide layer. The oxides formed at a higher voltage have greater roughness than those formed at 30 V. Anodized samples exhibit smaller current densities during anodic polarization compared to the as-received zirconium covered with native oxide. Copyright © 2016 Elsevier B.V. All rights reserved.

Corrosion properties of zirconium-based ceramic coatings for micro-bearing and biomedical applications

NASA Astrophysics Data System (ADS)

Walkowicz, J.; Zavaleyev, V.; Dobruchowska, E.; Murzynski, D.; Donkov, N.; Zykova, A.; Safonov, V.; Yakovin, S.

2016-03-01

Ceramic oxide ZrO2 and oxynitride ZrON coatings are widely used as protective coatings against diffusion and corrosion. The enhancement of the coatings' mechanical properties, as well as their wear and corrosion resistance, is very important for their tribological performance. In this work, ZrO2 and ZrON coatings were deposited by magnetron sputtering on stainless steel (AISI 316) substrates. The adhesion, hardness and elastic properties were evaluated by standard methods. The surface structure of the deposited coatings was observed by electron scanning microscopy (SEM) and atomic force microscopy (AFM). The composition of the coatings was analyzed by X-ray photoelectron spectroscopy (XPS) and energy dispersive X-ray spectroscopy (EDS). The corrosion resistance properties were evaluated using the potentiodynamic method. The results show that the corrosion parameters are significantly increased in the cases of both oxynitride and oxide coatings in comparison with the stainless steel (AISI 316) substrates.

Synthesis and structural characterization of (C sub 5 Me sub 5 )Zr(R) sub 2 (L) sub n sup + complexes

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

Crowther, D.J.; Jordan, R.F.; Baenziger, N.C.

1990-09-01

The reaction of (C{sub 5}Me{sub 5})Zr(CH{sub 3}){sub 3} with ((C{sub 5}H{sub 4}Me){sub 2}Fe)(BPh{sub 4}) in THF yields ((C{sub 5}Me{sub 5})Zr(CH{sub 3}){sub 2}(THF){sub 2})(BPh{sub 4}) (1) via oxidative cleavage of a Zr-CH{sub 3} bond. X-ray diffraction reveals that the cation of 1 adopts a square-pyramidal/four-legged piano-stool structure with cis CH{sub 3} groups. The orientations of the THF ligands and the Zr-O bond distances suggest that Zr-O {pi}-bonding is important for at least one of the THF ligands. Data for 1: a = 14.551 (2) {angstrom}, b = 15.191 (4) {angstrom}, c = 17.852 (19) {angstrom}, {beta} = 92.26 (3){degree}, V =more » 3,943 (6) {angstrom}{sup 3}, Z = 4 in space group P2{sub 1}/c. Reaction of 1 with excess dmpe in THF solution yields ((C{sub 5}Me{sub 5})Zr(CH{sub 3}){sub 2}(dmpe)(THF))(BPh{sub 4}) (2), which also has been characterized by X-ray diffraction.« less

Investigation of Gate-Stacked In-Ga-Zn-O TFTs with Ga-Zn-O Source/Drain Electrodes by Atmospheric Pressure Plasma-Enhanced Chemical Vapor Deposition.

PubMed

Wu, Chien-Hung; Chang, Kow-Ming; Chen, Yi-Ming; Huang, Bo-Wen; Zhang, Yu-Xin; Wang, Shui-Jinn; Hsu, Jui-Mei

2018-03-01

Atmospheric pressure plasma-enhanced chemical vapor deposition (AP-PECVD) was employed for the fabrication of indium gallium zinc oxide thin-film transistors (IGZO TFTs) with high transparent gallium zinc oxide (GZO) source/drain electrodes. The influence of post-deposition annealing (PDA) temperature on GZO source/drain and device performance was studied. Device with a 300 °C annealing demonstrated excellent electrical characteristics with on/off current ratio of 2.13 × 108, saturation mobility of 10 cm2/V-s, and low subthreshold swing of 0.2 V/dec. The gate stacked LaAlO3/ZrO2 of AP-IGZO TFTs with highly transparent and conductive AP-GZO source/drain electrode show excellent gate control ability at a low operating voltage.

Adsorption Analysis of Lactoferrin to Titanium, Stainless Steel, Zirconia, and Polymethyl Methacrylate Using the Quartz Crystal Microbalance Method

PubMed Central

Yoshida, Eiji; Hayakawa, Tohru

2016-01-01

It is postulated that biofilm formation in the oral cavity causes some oral diseases. Lactoferrin is an antibacterial protein in saliva and an important defense factor against biofilm development. We analyzed the adsorbed amount of lactoferrin and the dissociation constant (K d) of lactoferrin to the surface of different dental materials using an equilibrium analysis technique in a 27 MHz quartz crystal microbalance (QCM) measurement. Four different materials, titanium (Ti), stainless steel (SUS), zirconia (ZrO2) and polymethyl methacrylate (PMMA), were evaluated. These materials were coated onto QCM sensors and the surfaces characterized by atomic force microscopic observation, measurements of surface roughness, contact angles of water, and zeta potential. QCM measurements revealed that Ti and SUS showed a greater amount of lactoferrin adsorption than ZrO2 and PMMA. Surface roughness and zeta potential influenced the lactoferrin adsorption. On the contrary, the K d value analysis indicated that the adsorbed lactoferrin bound less tightly to the Ti and SUS surfaces than to the ZrO2 and PMMA surfaces. The hydrophobic interaction between lactoferrin and ZrO2 and PMMA is presumed to participate in better binding of lactoferrin to ZrO2 and PMMA surfaces. It was revealed that lactoferrin adsorption behavior was influenced by the characteristics of the material surface. PMID:26998486

Effect of Zirconium Oxide and Zinc Oxide Nanoparticles on Physicochemical Properties and Antibiofilm Activity of a Calcium Silicate-Based Material

PubMed Central

Guerreiro-Tanomaru, Juliane Maria; Trindade-Junior, Adinael; Cesar Costa, Bernardo; da Silva, Guilherme Ferreira; Drullis Cifali, Leonardo; Basso Bernardi, Maria Inês

2014-01-01

The aim of the present study was to evaluate the antibiofilm activity against Enterococcus faecalis, compressive strength. and radiopacity of Portland cement (PC) added to zirconium oxide (ZrO2), as radiopacifier, with or without nanoparticulated zinc oxide (ZnO). The following experimental materials were evaluated: PC, PC + ZrO2, PC + ZrO2 + ZnO (5%), and PC + ZrO2 + ZnO (10%). Antibiofilm activity was analyzed by using direct contact test (DCT) on Enterococcus faecalis biofilm, for 5 h or 15 h. The analysis was conducted by using the number of colony-forming units (CFU/mL). The compressive strength was performed in a mechanical testing machine. For the radiopacity tests, the specimens were radiographed together with an aluminium stepwedge. The results were submitted to ANOVA and Tukey tests, with level of significance at 5%. The results showed that all materials presented similar antibiofilm activity (P > 0.05). The addition of nanoparticulated ZnO decreased the compressive strength of PC. All materials presented higher radiopacity than pure PC. It can be concluded that the addition of ZrO2 and ZnO does not interfere with the antibiofilm activity and provides radiopacity to Portland cement. However, the presence of ZnO (5% or 10%) significantly decreased the compressive strength of the materials. PMID:25431798

Stress analysis of ZrO2/SiO2 multilayers deposited on different substrates with different thickness periods

NASA Astrophysics Data System (ADS)

Shao, Shuying; Shao, Jianda; He, Hongbo; Fan, Zhengxiu

2005-08-01

The effects of repeating thickness periods on stress are studied in ZrO2/SiO2 multilayers deposited by electron-beam evaporation on BK7 glass and fused-silica substrates. The results show that the residual stress is compressive and decreases with an increase of the periods of repeating thickness in the ZrO2/SiO2 multilayers. At the same time, the residual stress in multilayers deposited on BK7 glass is less than that of samples deposited on fused silica. The variation of the microstructure examined by x-ray diffraction shows that microscopic deformation does not correspond to macroscopic stress, which may be due to variation of the interface stress.

Effect of high intensity ultrasound on the mesostructure of hydrated zirconia

NASA Astrophysics Data System (ADS)

Kopitsa, G. P.; Baranchikov, A. E.; Ivanova, O. S.; Yapryntsev, A. D.; Grigoriev, S. V.; Pranzas, P. Klaus; Ivanov, V. K.

2012-02-01

We report structural changes in amorphous hydrated zirconia caused by high intensity ultrasonic treatment studied by means of small-angle neutron scattering (SANS) and X-ray diffraction (XRD). It was established that sonication affects the mesostructure of ZrO2×xH2O gels (i.e. decreases their homogeneity, increases surface fractal dimension and the size of monomer particles). Ultrasound induced structural changes in hydrated zirconia governs its thermal behaviour, namely decreases the rate of tetragonal to monoclinic zirconia phase transition.

Calcination does not remove all carbon from colloidal nanocrystal assemblies

DOE PAGES

Mohapatra, Pratyasha; Shaw, Santosh; Mendivelso-Perez, Deyny; ...

2017-12-11

Removing organics from hybrid nanostructures is a crucial step in many bottom-up materials fabrication approaches. It is usually assumed that calcination is an effective solution to this problem, especially for thin films. This assumption has led to its application in thousands of papers. Here in this paper, we show that this general assumption is incorrect by using a relevant and highly controlled model system consisting of thin films of ligand-capped ZrO 2 nanocrystals. After calcination at 800 °C for 12 h, while Raman spectroscopy fails to detect the ligands after calcination, elastic backscattering spectrometry characterization demonstrates that ~18% of themore » original carbon atoms are still present in the film. By comparison plasma processing successfully removes the ligands. Our growth kinetic analysis shows that the calcined materials have significantly different interfacial properties than the plasma-processed counterparts. Calcination is not a reliable strategy for the production of single-phase all-inorganic materials from colloidal nanoparticles.« less

Electrochemical reduction of UO2 in LiCl-Li2O molten salt using porous and nonporous anode shrouds

NASA Astrophysics Data System (ADS)

Choi, Eun-Young; Won, Chan Yeon; Cha, Ju-Sun; Park, Wooshin; Im, Hun Suk; Hong, Sun-Seok; Hur, Jin-Mok

2014-01-01

Electrochemical reductions of uranium oxide in a molten LiCl-Li2O electrolyte were carried out using porous and nonporous anode shrouds. The study focused on the effect of the type of anode shroud on the current density by running experiments with six anode shrouds. Dense ceramics, MgO, and MgO (3 wt%) stabilized ZrO2 (ZrO2-MgO) were used as nonporous shrouds. STS 20, 100, and 300 meshes and ZrO2-MgO coated STS 40 mesh were used as porous shrouds. The current densities (0.34-0.40 A cm-2) of the electrolysis runs using the nonporous anode shrouds were much lower than those (0.76-0.79 A cm-2) of the runs using the porous shrouds. The ZrO2-MgO shroud (600-700 MPa at 25 °C) showed better bending strength than that of MgO (170 MPa at 25 °C). The high current densities achieved in the electrolysis runs using the porous anode shrouds were attributed to the transport of O2- ions through the pores in meshes of the shroud wall. ZrO2-MgO coating on STS mesh was chemically unstable in a molten LiCl-Li2O electrolyte containing Li metal. The electrochemical reduction runs using STS 20, 100, and 300 meshes showed similar current densities in spite of their different opening sizes. The STS mesh shrouds which were immersed in a LiCl-Li2O electrolyte were stable without any damage or corrosion.

Effect of phase transformation on optical and dielectric properties of zirconium oxide nanoparticles

NASA Astrophysics Data System (ADS)

Chintaparty, Rajababu; Palagiri, Bhavani; Reddy Nagireddy, Ramamanohar; subbha Reddy Imma Reddy, Venkata

2015-09-01

Zirconium oxide nanoparticle (ZrO2) is synthesized by the hydrothermal method at different calcination temperatures. The structural analysis is carried out by X-ray diffraction and Raman spectra. The sample prepared at 400 °C and 1100 °C showed the cubic and monoclinic phase, respectively, and the sample calcined at 600 °C and 800 °C showed the mixed phase with co-existence of cubic and monoclinic phases. Furthermore, the morphology and particle size of these samples were investigated by scanning electron microscope (SEM) and transmission electron microscope (TEM) analysis. The band gap estimated from UV-Vis spectra of ZrO2 (zirconia) nanocrystalline materials calcined at different temperatures from 400 °C to 1100 °C was in the range of 2.6-4.2 eV. The frequency dependence of dielectric constant and dielectric loss was investigated at room temperature. The low frequency region of dielectric constant is attributed to space charge effects.

Hot corrosion behavior of magnesia-stabilized ceramic material in a lithium molten salt

NASA Astrophysics Data System (ADS)

Cho, Soo-Haeng; Kim, Sung-Wook; Kim, Dae-Young; Lee, Jong-Hyeon; Hur, Jin-Mok

2017-07-01

The isothermal and cyclic corrosion behaviors of magnesia-stabilized zirconia in a LiCl-Li2O molten salt were investigated at 650 °C in an argon atmosphere. The weights of as-received and corroded specimens were measured and the microstructures, morphologies, and chemical compositions were analyzed by scanning electron microscopy, X-ray energy dispersive spectroscopy, and X-ray diffraction. For processes where Li is formed at the cathode during electrolysis, the corrosion rate was about five times higher than those of isothermal and thermal cycling processes. During isothermal tests, the corrosion product Li2ZrO3 was formed after 216 h. During thermal cycling, Li2ZrO3 was not detected until after the completion of 14 cycles. There was no evidence of cracks, pores, or spallation on the corroded surfaces, except when Li was formed. We demonstrate that magnesia-stabilized zirconia is beneficial for increasing the hot corrosion resistance of structural materials subjected to high temperature molten salts containing Li2O.

Role of ZrO 2 in Promoting the Activity and Selectivity of Co-Based Fischer–Tropsch Synthesis Catalysts

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

Johnson, Gregory R.; Bell, Alexis T.

2015-11-17

The effects of Zr promotion on the structure and performance of Co-based Fischer-Tropsch synthesis (FTS) catalysts were investigated. Inclusion of Zr in the catalysts was found to increase the FTS turnover frequency and the selectivity to C 5+ hydrocarbons and to decrease the selectivity to methane under most operating conditions. These improvements to the catalytic performance are a function of Zr loading up to an atomic ratio of Zr/Co = 1.0, above which the product selectivity is insensitive to higher concentrations of the promoter. Characterization of the Co nanoparticles by different methods demonstrated that the optimal Zr loading corresponds tomore » half monolayer coverage of the Co surface by the promoter. Measurements of the rate of FTS at different pressures and temperatures established that the kinetics data for both the Zr-promoted and unpromoted catalysts are described by a two-parameter Langmuir-Hinshelwood expression. The parameters used to fit this rate law to the experimental data indicate that the apparent rate coefficient and the CO adsorption constant for the Zr-promoted catalysts are higher than those for the unpromoted catalyst. Elemental mapping by means of STEM-EDS provided evidence that Zr is highly dispersed over the catalyst surface and has limited preference for association with the Co nanoparticles. In situ X-ray absorption spectroscopy confirmed the absence of mixing between the Zr and Co in the nanoparticles. Here, these results suggest that Zr exists as a partial layer of ZrO 2 on the surface of the Co metal nanoparticles. Accordingly, it is proposed that Zr promotion effects originate from sites of enhanced activity at the interface between Co and ZrO 2. The possibility that ZrO 2 acts as a Lewis acid to assist in CO dissociation as well as to increase the ratio of CO to H adsorbed on the catalyst surface is discussed.« less

Design and development of multilayer wideband antireflection coating and its annealing study

NASA Astrophysics Data System (ADS)

Jena, S.; Tokas, R. B.; Udupa, D. V.; Thakur, S.; Sahoo, N. K.

2018-04-01

Reflection loss occurs at the glass-air interface, limits performance of many optical devices such as eyeglass, camera lenses, and photovoltaic solar cells. Antireflection (AR) coating on the glass reduces the reflection loss and improves efficiency of such devices. In this paper, wideband AR coating in the visible region has been designed and developed using ZrO2-MgO/SiO2 multilayer. The thicknesses of individual thin layers are numerically optimized to get maximum transmission of the visible light. The optimized four thin layers have been deposited on BK7 glass substrate using electron beam evaporation technique. The measured transmission spectrum of the 4-layer AR coating is compared with that of simulated spectrum. The transmission of the single side AR coating increases by more than 3% as compared to that of bare glass substrate in the wavelength region of 470 nm - 810 nm. The wideband AR coating has been annealed at 200°C for 4 hours in ambient condition. The transmission of the AR coating decreases after the annealing, resulting degradation in its wideband AR characteristics.

Metastable Phase Evolution in Oxide Systems

NASA Astrophysics Data System (ADS)

Levi, Carlos G.

2005-03-01

Multi-component ceramics are often synthesized by routes that facilitate mixing at the molecular scale and subsequently generate a solid product at low homologous temperatures. Examples include chemical and physical vapor deposition, thermal spray, and pyrolytic decomposition of precursor solutions. In these processes the solid evolves rapidly from a highly energized state, typically in a temperature regime wherein long-range diffusion is largely constrained and the equilibrium configuration can be kinetically suppressed. The resulting product may exhibit various forms of metastability such as amorphization, nanocrystallinity, extended solid solubility and alternate crystalline forms. The approach allows access to novel combinations of structure and composition with unprecedented defect structures that, if reasonably durable, could have properties of potential technological interest. Understanding phase selection and evolution is facilitated by having a suitable reference framework depicting the thermodynamic hierarchy of the phases available to the system under the relevant processing conditions. When transformations are partitionless the phase menu and hierarchy can be readily derived from the relative position of the T0 curves/surfaces for the different pairs of phases. The result is a phase hierarchy map, which is an analog of the phase diagram for partitionless equilibrium. Such maps can then be used to assess the kinetic effects on the selection of metastable states and their subsequent evolution. This presentation will discuss the evolution of metastable phases in oxides, with emphasis on systems involving fluorite phases and their ordered or distorted derivatives. The concepts will be illustrated primarily with zirconia-based systems, notably those of interest in thermal barrier coatings, fuel cells and ferroelectrics (ZrO2-MO3/2, where M = Y, Sc, the lanthanides and combinations thereof, as well as ZrO2-YO3/2-TiO2, ZrO2-TiO2-PbO, etc.). Of particular interest are the durabilities of metastable phases in systems that operate at high temperature, their decomposition paths and the implications to their functionality.

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.

Upconversion luminescence in Er3+ doped and Er3+/Yb3+ codoped zirconia and hafnia nanocrystals excited at 980 nm

NASA Astrophysics Data System (ADS)

Gómez, Luis A.; Menezes, Leonardo de S.; de Araújo, Cid B.; Gonçalves, Rogeria R.; Ribeiro, Sidney J. L.; Messaddeq, Younes

2010-06-01

Frequency upconversion (UC) luminescence in nanocrystalline zirconia (ZrO2) and hafnia (HfO2) doped with Er3+ and Yb3+ was studied under continuous-wave excitation at 980 nm. Samples of ZrO2:Er3+, ZrO2:Er3+/Yb3+, and HfO2:Er3+/Yb3+ were prepared by the sol-gel technique and characterized using x-ray diffraction and electron microscopy. A study of the infrared-to-green and infrared-to-red UC processes was performed including the analysis of the spectral and the temporal behavior. The mechanisms contributing to the UC luminescence were identified as excited state absorption and energy transfer among rare-earth ions.

Effects of Post-Deposition Annealing on ZrO2/n-GaN MOS Capacitors with H2O and O3 as the Oxidizers

NASA Astrophysics Data System (ADS)

Zheng, Meijuan; Zhang, Guozhen; Wang, Xiao; Wan, Jiaxian; Wu, Hao; Liu, Chang

2017-04-01

GaN-based metal-oxide-semiconductor capacitors with ZrO2 as the dielectric layer have been prepared by atomic layer deposition. The accumulation and depletion regions can be clearly distinguished when the voltage was swept from -4 to 4 V. Post-annealing results suggested that the capacitance in accumulation region went up gradually as the annealing temperature increased from 300 to 500 °C. A minimum leakage current density of 3 × 10-9 A/cm2 at 1 V was obtained when O3 was used for the growth of ZrO2. Leakage analysis revealed that Schottky emission and Fowler-Nordheim tunneling were the main leakage mechanisms.

Synthesis of Transparent Aqueous ZrO2 Nanodispersion with a Controllable Crystalline Phase without Modification for a High-Refractive-Index Nanocomposite Film.

PubMed

Xia, Yi; Zhang, Cong; Wang, Jie-Xin; Wang, Dan; Zeng, Xiao-Fei; Chen, Jian-Feng

2018-05-30

The controllable synthesis of metal oxide nanoparticles is of fundamental and technological interest. In this article, highly transparent aqueous nanodispersion of ZrO 2 with controllable crystalline phase, high concentration, and long-term stability was facilely prepared without any modification via the reaction of inexpensive inorganic zirconium salt and sodium hydroxide in water under an acid surrounding, combined with hydrothermal treatment. The as-prepared transparent nanodispersion had an average particle size of 7 nm, a high stability of 18 months, and a high solid content of 35 wt %. ZrO 2 nanocrystals could be readily dispersed in many solvents with high polarity including ethanol, dimethyl sulfoxide, acetic acid, ethylene glycol, and N, N-dimethylformamide, forming stable transparent nanodispersions. Furthermore, highly transparent polyvinyl alcohol/ZrO 2 nanocomposite films with high refractive index were successfully prepared with a simple solution mixing route. The refractive index could be tuned from 1.528 to 1.754 (@ 589 nm) by changing the mass fraction (0-80 wt %) of ZrO 2 in transparent nanocomposite films.

A theoretical study of the stability of anionic defects in cubic ZrO 2 at extreme conditions

DOE PAGES

Samanta, Amit

2016-02-19

Using first principles density functional theory calculations, we present a study of the structure, mobility, and the thermodynamic stability of anionic defects in the high-temperature cubic phase of ZrO 2. Our results suggest that the local structure of an oxygen interstitial depends on the charge state and the cubic symmetry of the anionic sublattice is unstable at 0 K. In addition, the oxygen interstitials and the vacancies exhibit symmetry breaking transitions to low-energy structures with tetragonal distortion of the oxygen sublattice at 0 K. However, the vibrational entropy stabilizes the defect structures with cubic symmetry at 2600–2980 K. The formationmore » free energies of the anionic defects and Gibbs free energy changes associated with different defect reactions are calculated by including the vibrational free energy contributions and the effect of pressure on these defect structures. By analyzing the defect chemistry, we obtain the defect concentrations at finite temperature and pressure conditions using the zero temperature ab initio results as input and find that at low oxygen partial pressures, neutral oxygen vacancies are most dominant and at high oxygen partial pressures, doubly charged anionic defects are dominant. As a result, the relevance of the results to the thermal protective coating capabilities of zirconium-based ceramic composites is elucidated.« less

Membrane electrode assembly fabricated with the combination of Pt/C and hollow shell structured-Pt-SiO2@ZrO2 sphere for self-humidifying proton exchange membrane fuel cell

NASA Astrophysics Data System (ADS)

Ko, Y. D.; Yang, H. N.; Züttel, Andreas; Kim, S. D.; Kim, W. J.

2017-11-01

The Pt-supported hollow structured Pt-HZrO2 with the shell thickness of 27 nm is successfully synthesized. The water retention ability of Pt-HZrO2 is significantly enhanced compared with that of SiO2@ZrO2 due to the hydrophilic hollow structured HZrO2with high BET surface area. Pt-C and Pt-HZrO2 are combined with different weight fractions to prepare the double catalyst electrode (DCE). The membrane electrode assembly with the DCE is fabricated and applied to both anode and cathode or anode side only. The water flooding and thus rapid voltage drop is affected by the presence/or absence of the DCE at the cathode side. The cell test and visual experiment suggests that the Pt-HZrO2 layer adsorb the water molecules generated by the oxygen reduction reaction (ORR), preventing the water flooding. The power generation under RH 0% strongly suggests the back-diffusion of water molecules generated by the ORR. The flow rate to the cathode significantly affects the water flooding and cell performance. Higher flow rate to the cathode is advantageous to expel the water generated by the ORR, thus preventing water flooding and enhancing the cell performance. Therefore, the weight fraction of Pt-C to Pt-HZrO2 and the flow rate to the cathode should be well balanced.

Development of bone-like zirconium oxide nanoceramic modified chitosan based porous nanocomposites for biomedical application.

PubMed

Bhowmick, Arundhati; Pramanik, Nilkamal; Jana, Piyali; Mitra, Tapas; Gnanamani, Arumugam; Das, Manas; Kundu, Patit Paban

2017-02-01

Here, zirconium oxide nanoparticles (ZrO 2 NPs) were incorporated for the first time in organic-inorganic hybrid composites containing chitosan, poly(ethylene glycol) and nano-hydroxypatite (CS-PEG-HA) to develop bone-like nanocomposites for bone tissue engineering application. These nanocomposites were characterized by FT-IR, XRD, TEM combined with SAED. SEM images and porosity measurements revealed highly porous structure having pore size of less than 1μm to 10μm. Enhanced water absorption capacity and mechanical strengths were obtained compared to previously reported CS-PEG-HA composite after addition of 0.1-0.3wt% of ZrO 2 NPs into these nanocomposites. The mechanical strengths and porosities were similar to that of human spongy bone. Strong antimicrobial effects against gram-negative and gram-positive bacterial strains were also observed. Along with getting low alkalinity pH (7.4) values, similar to the pH of human plasma, hemocompatibility and cytocompatibility with osteoblastic MG-63 cells were also established for these nanocomposites. Addition of 15wt% HA-ZrO 2 (having 0.3wt% ZrO 2 NPs) into CS-PEG (55:30wt%) composite resulted in greatest mechanical strength, porosity, antimicrobial property and cytocompatibility along with suitable water absorption capacity and compatibility with human pH and blood. Thus, this nanocomposite could serve as a potential candidate to be used for bone tissue engineering. Copyright © 2016 Elsevier B.V. All rights reserved.

Plasma spraying of zirconia-reinforced hydroxyapatite composite coatings on titanium: part I: phase, microstructure and bonding strength.

PubMed

Chang, E; Chang, W J; Wang, B C; Yang, C Y

1997-04-01

Plasma-sprayed hydroxyapatite (HA) coatings applied to metal substrates can induce a direct chemical bond with bone and hence achieve biological fixation of the implant. However, the poor bonding strength between HA and substrate has been of concern to orthopaedists. In this study, two submicrometre ZrO2 powders stabilized with both 3 and 8 mol% Y2O3 (TZ3Y and TZ8Y, respectively) were incorporated in a plasma-sprayed HA coating on Ti-6Al-4V substrate to investigate the change in phase, microstructure and bonding strength. The results show that ZrO2 composite coatings contain more unmelted particles and greater porosity. During plasma spraying, ZrO2 reacts with the CaO in HA to form CaZrO3 and accelerates HA decomposition to alpha-TCP and Ca4P2O9. Nevertheless, bonding strength increases with increase of ZrO2 content in the range 0 to 10 wt% studied. The higher Y2O3-containing TZ8Y apparently exerts a greater strengthening effect than the lower Y2O3-containing TZ3Y.

Enhanced thermoelectric figure-of-merit in Bi-Sb-Te nanocomposites with homogenously dispersed oxide ceramic ZrO2 nanoparticles

NASA Astrophysics Data System (ADS)

Madavali, B.; Kim, H. S.; Lee, K. H.; Hong, S. J.

2017-06-01

In this research, p-type BiSbTe/ZrO2 nanocomposite powders were fabricated by high-energy ball milling. Different weight percentages of ZrO2 (2, 4, and 6 wt. %) nanoparticles were incorporated into the bulk (BiSbTe) matrix by consolidation of as-synthesized nanocomposites (NCs) powder by spark plasma sintering at 673 K. The phase and existence of ZrO2 nano-inclusions was confirmed by X-ray diffraction and transmission electron microscopy-selected area electron diffraction analysis. The Seebeck coefficient of the BiSbTe/ZrO2 NCs was significantly improved (˜36% for 4 wt. % added NCs) by a decrease in the carrier concentration and energy filtering effect, whereas the thermal conductivity was much reduced via strong scattering of carriers/phonons. The peak thermoelectric figure-of-merit (1.34 ± 0.06) was obtained for BiSbTe into which 2 wt. % ZrO2 was dispersed, which was approximately 20% greater than that of the undispersed sample. The hardness of the nanocomposites was significantly improved (˜27%) due to grain-boundary hardening and a dispersion strengthening mechanism.

Immunotoxicity evaluation of novel bioactive composites in male mice as promising orthopaedic implants

PubMed Central

El-Bassyouni, Gehan T.; Eshak, Mariam G.; Barakat, Ibrahim A.H.

2017-01-01

Objective In orthopaedics, novel bioactive composites are largely needed to improve the synthetic achievement of the implants. In this work, semiconducting metal oxides such as SiO2, TiO2, and ZrO2 particles (Ps) were used individually and in different ratios to obtain different biphasic composites. The immunotoxicity of these composites was tested to inspect the potential toxicity prior to their use in further medical applications. Materials and methods In vitro mineralisation ability was inspected by soaking the composites in simulated body fluid (SBF). Additionally, in vivo experiments were performed consuming male mice using ISSR-PCR, micronucleus (MN) test, comet assay, glutathione peroxidase activity, and determination of albumin, globulin, lymphocyte population, ALT, and AST levels. Several groups of adult male albino mice were treated with 100, 200, and 400 mg/kg body weight of SiO2, TiO2, and ZrO2-Ps in pure or mixed forms. Results Our findings revealed that treatment of mice with low and medium doses of SiO2, TiO2, and ZrO2-Ps in pure or mixed form revealed values relatively similar to the control group. However, using 400 mg/kg especially from TiO2-Ps in genuine form or mixed with SiO2 showed proliferation in the toxicity rates compared with the high dose of SiO2 and ZrO2-Ps. Conclusions The results suggest that TiO2 composite induced in vivo toxicity, oxidative DNA damage, bargain of the antioxidant enzymes, and variations in the levels of albumin, globulin, lymphocyte population, ALT, and AST in a dose-dependent manner. However, SiO2, and ZrO2 composites revealed a lower toxicity in mice compared with that of TiO2. PMID:28680331

Effect of zirconium oxide nanofiller and dibutyl phthalate plasticizer on ionic conductivity and optical properties of solid polymer electrolyte.

PubMed

Yasin, Siti Mariah Mohd; Ibrahim, Suriani; Johan, Mohd Rafie

2014-01-01

New solid polymer electrolytes (SPE) based on poly(ethylene oxide) (PEO) doped with lithium trifluoromethanesulfonate (LiCF3SO3), dibutyl phthalate (DBP) plasticizer, and zirconium oxide (ZrO2) nanoparticles were prepared by solution-casting technique. The conductivity was enhanced by addition of dibutyl phthalate (DBP) plasticizer and ZrO2 nanofiller with maximum conductivity (1.38 × 10(-4) Scm(-1)). The absorption edge and band gap values showed decreases upon addition of LiSO3CF3, DBP, and ZrO2 due to the formation of localized states in the SPE and the degree of disorder in the films increased.

Effect of Zirconium Oxide Nanofiller and Dibutyl Phthalate Plasticizer on Ionic Conductivity and Optical Properties of Solid Polymer Electrolyte

PubMed Central

Yasin, Siti Mariah Mohd; Ibrahim, Suriani

2014-01-01

New solid polymer electrolytes (SPE) based on poly(ethylene oxide) (PEO) doped with lithium trifluoromethanesulfonate (LiCF3SO3), dibutyl phthalate (DBP) plasticizer, and zirconium oxide (ZrO2) nanoparticles were prepared by solution-casting technique. The conductivity was enhanced by addition of dibutyl phthalate (DBP) plasticizer and ZrO2 nanofiller with maximum conductivity (1.38 × 10−4 Scm−1). The absorption edge and band gap values showed decreases upon addition of LiSO3CF3, DBP, and ZrO2 due to the formation of localized states in the SPE and the degree of disorder in the films increased. PMID:25133244

Mechanical Properties and Plasma Erosion Resistance of ZrO2p(3Y)/BN-SiO2 Ceramic Composites under Different Sintering Temperature

NASA Astrophysics Data System (ADS)

Zhou, Yu; Duan1, Xiaoming; Jia, Dechang; Yang, Zhihua; Meng, Qingchang; Yu, Yang; Yu, Daren; Ding, Yongjie

2011-10-01

ZrO2p(3Y)/BN-SiO2 ceramic composites were hot pressed under different sintering temperature. The ceramic composites were composed by BN, m-ZrO2, t-ZrO2 and SiO2. The relative density, bending strength, elastic modulus and fracture toughness increase with the sintering temperature increasing, the maximum value of which at the sintering temperature of 1800°C are 97.5%, 229.9MPa, 60.8GPa and 3.55MPam1/2, respectively. The erosion resistance ability of ZrO2p(3Y)/BN-SiO2 ceramic composites rise gradually with the sintering temperature increasing, and the erosion rate of the ceramic composite sintered at 1800°C is 8.03×10-3mm/h.

Ethanol dehydrogenation on copper catalysts with ytterbium stabilized tetragonal ZrO2 support

NASA Astrophysics Data System (ADS)

Chuklina, S. G.; Pylinina, A. I.; Podzorova, L. I.; Mikhailina, N. A.; Mikhalenko, I. I.

2016-12-01

The physicochemical and catalytic properties of Cu-containing crystalline zirconia, obtained via sol-gel synthesis in the presence of Yb3+ ions and polyvinylpyrrolidone, are studied. DTG/DSC, TEM, XRD and BET methods are used to analyze the crystallization, texture, phase uniformity, surface and porosity of ZrO2 nanopowders. It is shown that increasing the copper content (1, 3, and 5 wt % from ZrO2) raises the dehydrogenation activity in the temperature range of 100-400°C and lowers the activation energy of acetaldehyde formation. It is found that the activity of all Cu/ t-ZrO2 catalysts grows under the effects of the reaction medium, due to the migration and redispersion of copper.

Dimensional stability and electrochemical behaviour of ZrO2 incorporated electrospun PVdF-HFP based nanocomposite polymer membrane electrolyte for Li-ion capacitors

PubMed Central

Solarajan, Arun Kumar; Murugadoss, Vignesh; Angaiah, Subramania

2017-01-01

Different weight percentages of ZrO2 (0, 3, 5, 7 and 10 wt%) incorporated electrospun PVDF-HFP nanocomposite polymer membranes (esCPMs) were prepared by electrospinning technique. They were activated by soaking in 1 M LiPF6 containing 1:1 volume ratio of EC : DMC (ethylene carbonate:dimethyl carbonate) to get electrospun nanocomposite polymer membrane electrolytes (esCPMEs). The influence of ZrO2 on the physical, mechanical and electrochemical properties of esCPM was studied in detail. Finally, coin type Li-ion capacitor cell was assembled using LiCo0.2Mn1.8O4 as the cathode, Activated carbon as the anode and the esCPME containing 7 wt% of ZrO2 as the separator, which delivered a discharge capacitance of 182.5 Fg−1 at the current density of 1Ag−1 and retained 92% of its initial discharge capacitance even after 2,000 cycles. It revealed that the electrospun PVdF-HFP/ZrO2 based nanocomposite membrane electrolyte could be used as a good candidate for high performance Li-ion capacitors. PMID:28397783

Dimensional stability and electrochemical behaviour of ZrO2 incorporated electrospun PVdF-HFP based nanocomposite polymer membrane electrolyte for Li-ion capacitors.

PubMed

Solarajan, Arun Kumar; Murugadoss, Vignesh; Angaiah, Subramania

2017-04-11

Different weight percentages of ZrO 2 (0, 3, 5, 7 and 10 wt%) incorporated electrospun PVDF-HFP nanocomposite polymer membranes (esCPMs) were prepared by electrospinning technique. They were activated by soaking in 1 M LiPF 6 containing 1:1 volume ratio of EC : DMC (ethylene carbonate:dimethyl carbonate) to get electrospun nanocomposite polymer membrane electrolytes (esCPMEs). The influence of ZrO 2 on the physical, mechanical and electrochemical properties of esCPM was studied in detail. Finally, coin type Li-ion capacitor cell was assembled using LiCo 0.2 Mn 1.8 O 4 as the cathode, Activated carbon as the anode and the esCPME containing 7 wt% of ZrO 2 as the separator, which delivered a discharge capacitance of 182.5 Fg -1 at the current density of 1Ag -1 and retained 92% of its initial discharge capacitance even after 2,000 cycles. It revealed that the electrospun PVdF-HFP/ZrO 2 based nanocomposite membrane electrolyte could be used as a good candidate for high performance Li-ion capacitors.

A Simple Method for High-Performance, Solution-Processed, Amorphous ZrO2 Gate Insulator TFT with a High Concentration Precursor

PubMed Central

Cai, Wei; Zhu, Zhennan; Wei, Jinglin; Fang, Zhiqiang; Zheng, Zeke; Zhou, Shangxiong; Peng, Junbiao; Lu, Xubing

2017-01-01

Solution-processed high-k dielectric TFTs attract much attention since they cost relatively little and have a simple fabrication process. However, it is still a challenge to reduce the leakage of the current density of solution-processed dielectric TFTs. Here, a simple solution method is presented towards enhanced performance of ZrO2 films by intentionally increasing the concentration of precursor. The ZrO2 films not only exhibit a low leakage current density of 10−6 A/cm2 at 10 V and a breakdown field of 2.5 MV/cm, but also demonstrate a saturation mobility of 12.6 cm2·V−1·s−1 and a Ion/Ioff ratio of 106 in DC pulse sputtering IGZO-TFTs based on these films. Moreover, the underlying mechanism of influence of precursor concentration on film formation is presented. Higher concentration precursor results in a thicker film within same coating times with reduced ZrO2/IGZO interface defects and roughness. It shows the importance of thickness, roughness, and annealing temperature in solution-processed dielectric oxide TFT and provides an approach to precisely control solution-processed oxide films thickness. PMID:28825652

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.

Zirconium oxide ceramic foam: a promising supporting biomaterial for massive production of glial cell line-derived neurotrophic factor*

PubMed Central

Liu, Zhong-wei; Li, Wen-qiang; Wang, Jun-kui; Ma, Xian-cang; Liang, Chen; Liu, Peng; Chu, Zheng; Dang, Yong-hui

2014-01-01

This study investigated the potential application of a zirconium oxide (ZrO2) ceramic foam culturing system to the production of glial cell line-derived neurotrophic factor (GDNF). Three sets of ZrO2 ceramic foams with different pore densities of 10, 20, and 30 pores per linear inch (PPI) were prepared to support a 3D culturing system. After primary astrocytes were cultured in these systems, production yields of GDNF were evaluated. The biomaterial biocompatibility, cell proliferation and activation of cellular signaling pathways in GDNF synthesis and secretion in the culturing systems were also assessed and compared with a conventional culturing system. In this study, we found that the ZrO2 ceramic foam culturing system was biocompatible, using which the GDNF yields were elevated and sustained by stimulated cell proliferation and activation of signaling pathways in astrocytes cultured in the system. In conclusion, the ZrO2 ceramic foam is promising for the development of a GDNF mass production device for Parkinson’s disease treatment. PMID:25471830

Efficient Decarbonylation of Furfural to Furan Catalyzed by Zirconia-Supported Palladium Clusters with Low Atomicity.

PubMed

Ishida, Tamao; Kume, Kurumi; Kinjo, Kota; Honma, Tetsuo; Nakada, Kengo; Ohashi, Hironori; Yokoyama, Takushi; Hamasaki, Akiyuki; Murayama, Haruno; Izawa, Yusuke; Utsunomiya, Masaru; Tokunaga, Makoto

2016-12-20

Decarbonylation of furfural to furan was efficiently catalyzed by ZrO 2 -supported Pd clusters in the liquid phase under a N 2 atmosphere without additives. Although Pd/C and Pd/Al 2 O 3 have frequently been used for decarbonylation, Pd/ZrO 2 exhibited superior catalytic performance compared with these conventional catalysts. Transmission electron microscopy and X-ray absorption fine structure measurements revealed that the size of the Pd particles decreased with an increase in the specific surface area of ZrO 2 . ZrO 2 with a high surface area immobilized Pd as clusters consisting of several (three to five) Pd atoms, whereas Pd aggregated to form nanoparticles on other supports such as carbon and Al 2 O 3 despite their high surface areas. The catalytic activity of Pd/ZrO 2 was enhanced with a decrease in particle size, and the smallest Pd/ZrO 2 was the most active catalyst for decarbonylation. When CeO 2 was used as the support, a decrease in Pd particle size with an increase in surface area was also observed. Single Pd atoms were deposited on CeO 2 with a high surface area, with a strong interaction through the formation of a Pd-O-Ce bond, which led to a lower catalytic activity than that of Pd/ZrO 2 . This result suggests that zero-valent small Pd clusters consisting of more than one Pd atom are the active species for the decarbonylation reaction. Recycling tests proved that Pd/ZrO 2 maintained its catalytic activity until its sixth use. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Platinum catalytic effect on oxygen fugacity of CO 2H 2 gas mixtures measured with ZrO 2 oxygen sensor at 105 Pa from 1300 to 700°C

NASA Astrophysics Data System (ADS)

Miyamoto, M.; Mikouchi, T.

1996-08-01

The oxygen fugacity of CO 2H 2 gas mixtures were measured with a ZrO 2 oxygen sensor at high temperatures in a furnace. We confirmed that the oxygen fugacity values measured by the ZrO 2 cell are more reducing than those of the CO 2H 2 gas mixtures calculated by using JANAF data at temperatures below 1150°C as was previously reported by Huebner (1975). We successfully decreased the deviation of the measured oxygen-fugacity value from the calculated one down to temperature of 800°C by using a Pt catalyst. Our results suggest that the deviation is probably due to incomplete equilibration of the gases.

Thermal phase separation of ZrSiO4 thin films and frequency- dependent electrical characteristics of the Al/ZrSiO4/p-Si/Al MOS capacitors

NASA Astrophysics Data System (ADS)

Lok, R.; Kaya, S.; Yilmaz, E.

2018-05-01

In this work, the thermal phase separation and annealing optimization of ZrSiO4 thin films have been carried out. Following annealing optimization, the frequency-dependent electrical characteristics of the Al/ZrSiO4/p-Si/Al MOS capacitors were investigated in detail. The chemical evolution of the films under various annealing temperatures was determined by Fourier transform infrared spectroscopy (FTIR) measurements. The phase separation was determined by x-ray diffraction (XRD) measurements. The electrical parameters were determined via the capacitance–voltage (C–V), conductance–voltage (G/ω) and leakage-current–voltage (Ig–Vg ). The results demonstrate that zirconium silicate formations are present at 1000 °C annealing with the SiO2 interfacial layer. The film was in amorphous form after annealing at 250 °C. The tetragonal phases of ZrO2 were obtained after annealing at 500 °C. When the temperature approaches 750 °C, transitions from the tetragonal phase to the monoclinic phase were observed. The obtained XRD peaks after 1000 °C annealing matched the crystalline peaks of ZrSiO4. This means that the crystalline zirconium dioxide in the structure has been converted into a crystalline silicate phase. The interface states increased to 5.71 × 1010 and the number of border traps decreased to 7.18 × 1010 cm‑2 with the increasing temperature. These results indicate that an excellent ZrSiO4/Si interface has been fabricated. The order of the leakage current varied from 10‑9 Acm‑2 to 10‑6 Acm‑2. The MOS capacitor fabricated with the films annealed at 1000 °C shows better behavior in terms of its structural, chemical and electrical properties. Hence, detailed frequency-dependent electrical characteristics were performed for the ZrSiO4 thin film annealed at 1000 °C. Very slight capacitance variations were observed under the frequency variations. This shows that the density of frequency-dependent charges is very low at the ZrSiO4/Si interface. The barrier height of the device varies slightly from 0.776 eV to 0.827 eV under frequency dispersion. Briefly, it is concluded that the devices annealed at 1000 °C exhibit promising electrical characteristics.

Effects of Post-Deposition Annealing on ZrO2/n-GaN MOS Capacitors with H2O and O3 as the Oxidizers.

PubMed

Zheng, Meijuan; Zhang, Guozhen; Wang, Xiao; Wan, Jiaxian; Wu, Hao; Liu, Chang

2017-12-01

GaN-based metal-oxide-semiconductor capacitors with ZrO 2 as the dielectric layer have been prepared by atomic layer deposition. The accumulation and depletion regions can be clearly distinguished when the voltage was swept from -4 to 4 V. Post-annealing results suggested that the capacitance in accumulation region went up gradually as the annealing temperature increased from 300 to 500 °C. A minimum leakage current density of 3 × 10 -9  A/cm 2 at 1 V was obtained when O 3 was used for the growth of ZrO 2 . Leakage analysis revealed that Schottky emission and Fowler-Nordheim tunneling were the main leakage mechanisms.

Electron localization and magnetism in SrRuO3 with non-magnetic cation substitution

NASA Astrophysics Data System (ADS)

Tong, W.; Huang, F.-Q.; Chen, I.-W.

2011-03-01

The destruction of the ferromagnetism of alloyed SrRuO3 can be caused by electron localization at the substitution sites. Among all the non-magnetic cations that enter the B site, Zr4 + is the least disruptive to conductivity and ferromagnetism. This is because Zr4 + does not cause any charge disorder, and its empty d electron states which are poorly matched in energy with the Ru t2g4 states cause the least resonance scattering of Ru's d electrons. Conducting Sr(Ru, Zr)O3 may be used as an electrode for perovskite-based thin film devices, while its insulating counterpart provides unprecedented magnetoresistance, seldom seen in other non-manganite and non-cobaltite perovskites.

Sunlight activated anodic freestanding ZrO2 nanotube arrays for Cr(VI) photoreduction.

PubMed

Bashirom, Nurulhuda; Tan, Wai Kian; Go, Kawamura; Matsuda, Atsunori; Abdul Razak, Khairunisak; Lockman, Zainovia

2018-06-14

Visible-light-active freestanding zirconia (ZrO2) nanotube (FSZNT) arrays were fabricated by a facile electrochemical anodization method in fluoride containing ethylene glycol electrolyte added to it 1 vol.% of potassium carbonate (K2CO3) at 60 V for 1 h. Poor adhesion at metal|oxide interface was induced by K2CO3 leading to formation of the FSZNT flakes. The effect of crystal structures of FSZNTs e.g., amorphous, amorphous/tetragonal, and tetragonal/monoclinic was investigated towards the photocatalytic reduction of 10 ppm hexavalent chromium, Cr(VI) at pH 2 under sunlight. The results demonstrate the amorphous FSZNTs exhibited the highest Cr(VI) removal efficiency than the crystalline FSZNTs (95 % versus 33 % after 5 h). The high photocatalytic activity of the amorphous FSZNTs can be attributed to enhanced Cr(VI) adsorption, high visible light absorption, and better charge carriers separation. The low photocatalytic activity of the crystalline FSZNTs annealed at 500 °C was mainly attributed to poor Cr(VI) adsorption, low visible light absorption, and less photoactive monoclinic-ZrO2. © 2018 IOP Publishing Ltd.

Effects of SnO2, WO3, and ZrO2 addition on the magnetic and mechanical properties of NiCuZn ferrites

NASA Astrophysics Data System (ADS)

Wang, Sea-Fue; Yang, Hsiao-Ching; Hsu, Yung-Fu; Hsieh, Chung-Kai

2015-01-01

In this study, the effects of SnO2, WO3 and ZrO2 addition at levels up to 5 wt% on the magnetic and mechanical properties of Ni0.5Cu0.3Zn0.2Fe2O4 ceramics were investigated. Only Ni0.5Cu0.3Zn0.2Fe2O4 ceramic with a SnO2 addition of ≥3.5 wt% required a densification temperature of 1150 °C, while the others reached maximum densification at 1075 °C. All samples revealed a pure spinel phase and a uniform microstructure, except for the Ni0.5Cu0.3Zn0.2Fe2O4 ceramic with the WO3 addition, which showed an exaggerated grain growth accompanied with a small amount of needle-shaped Cu0.85Zn0.15WO4 second phase. The fracture mode in the pure Ni0.5Cu0.3Zn0.2Fe2O4 ceramic revealed a transgranular phase, as the CuO second phase increased the grain boundary strength; the Ni0.5Cu0.3Zn0.2Fe2O4 ceramics sintered with 5 wt% additives showed an intergranular phase. The Vickers hardness and the bending strength of the Ni0.5Cu0.3Zn0.2Fe2O4 ceramic were 733.6 and 62.0 MPa, respectively. The Vickers hardness of the ferrite with added SnO2 or ZrO2 showed only a slight improvement, while an apparent change (832.7) was observed with the addition of 5.0 wt% WO3. The bending strength of the ferrite was optimized at 75.7 MPa with 2.0 wt% SnO2 and at 90.5 MPa with 3.5 wt% ZrO2, while that of the ferrite sintered with WO3 added dropped gradually from 62.0 to 47.7 MPa as the amount of WO3 was increased from 0 to 5.0 wt% due to the non-uniform microstructure. The pure Ni0.5Cu0.3Zn0.2Fe2O4 ceramic sintered at 1075 °C had an initial permeability of 356.9 and a quality factor of 71.2. The addition of ZrO2 led to a significant increase in the initial permeability (588.4 at 5.0 wt% ZrO2), but a slight decline in the quality factor (56.6 at 5.0 wt% ZrO2).

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.

Zirconia nanocrystals as submicron level biological label

NASA Astrophysics Data System (ADS)

Smits, K.; Liepins, J.; Gavare, M.; Patmalnieks, A.; Gruduls, A.; Jankovica, D.

2012-08-01

Inorganic nanocrystals are of increasing interest for their usage in biology and pharmacology research. Our interest was to justify ZrO2 nanocrystal usage as submicron level biological label in baker's yeast Saccharomyces cerevisia culture. For the first time (to our knowledge) images with sub micro up-conversion luminescent particles in biologic media were made. A set of undoped as well as Er and Yb doped ZrO2 samples at different concentrations were prepared by sol-gel method. The up-conversion luminescence for free standing and for nanocrystals with baker's yeast cells was studied and the differences in up-conversion luminescence spectra were analyzed. In vivo toxic effects of ZrO2 nanocrystals were tested by co-cultivation with baker's yeast.

Low-temperature carbon monoxide oxidation over zirconia-supported CuO-CeO2 catalysts: Effect of zirconia support properties

NASA Astrophysics Data System (ADS)

Moretti, Elisa; Molina, Antonia Infantes; Sponchia, Gabriele; Talon, Aldo; Frattini, Romana; Rodriguez-Castellon, Enrique; Storaro, Loretta

2017-05-01

A study was conducted to investigate the effect of the preparation route of ZrO2 in CuO-CeO2/ZrO2 catalysts for the oxidation of carbon monoxide at low temperature (COX). Four ZrO2 supports were synthetized via either type sol-gel methodology or precipitation. The final Cu-Ce-Zr oxide catalysts were prepared by incipient wetness co-impregnation with copper and cerium solutions (with a loading of 6 wt% of CuO and 20 wt% of CeO2). The catalyst crystalline phases, texture and active species reducibility were determined by XRD, N2 physisorption at -196 °C and H2-TPR, respectively; meanwhile the surface composition and copper-cerium electronic states were studied by XPS. The catalytic activity was evaluated in the oxidation of CO to CO2, in the 40-215 °C temperature range. Catalytic results evidenced that the samples prepared by a sol-gel methodology showed, after the impregnation, a severe decrease of specific surface area and pore volume attributable to a wide degree of pore blockage caused by the presence of metal oxide particles and a collapse of the structure partially burying the active sites. A simple co-impregnation of a zirconia support, obtained through facile and fast precipitation, provided instead a catalyst with very good redox properties and high dispersion of the active phases, which completely oxidizes CO in the range 115-215 °C with T50 of 65 °C. This higher observed activity was ascribed to the formation of a larger fraction of highly dispersed and easily reducible Cu species and ceria nanocrystallites, mainly present as Ce(IV), with an average size of 5 nm.

A bench-scale study on the removal and recovery of phosphate by hydrous zirconia-coated magnetite nanoparticles

NASA Astrophysics Data System (ADS)

Wang, Zhe; Fang, Wenkan; Xing, Mingchao; Wu, Deyi

2017-02-01

Owing to the easy magnetic separation from water for reuse, magnetic nanoparticles have drawn great interest as adsorbents. Herein hydrous zirconia-coated magnetite nanoparticles (Fe3O4@ZrO2) were created by a facile method and a bench-scale study was undertaken to evaluate its effectiveness and mechanism to remove phosphate at low concentrations. Results indicated that phosphate removal by Fe3O4@ZrO2 was fast (95% of phosphate removal within 10 min) and nearly complete removal could be achieved at the adsorbent dosage >0.6 g/L. In tap water or wastewater where competitive anions coexist, regulation of pH was found to be quite effective to augment the performance of phosphate removal. In pH-lowered adsorption systems, phosphate removal followed a good pattern similarly to pure water, i.e., a continuous high efficiency removal followed by a rapid saturation. Adsorption-desorption-regeneration studies showed that Fe3O4@ZrO2 could be repeatedly used for phosphate removal and adsorbed phosphate could be stripped for recovery. The fractionation of adsorbed phosphorus suggested that NaOH-P fraction was dominant. We also found that the adsorption reaction of phosphate with Fe3O4@ZrO2 shifted the isoelectric point of Fe3O4@ZrO2 from 9.0 to 3.0. FTIR measurements further showed the direct coordination of phosphate onto zirconium by replacement of hydroxyl groups. The formation of the monodentate (ZrO)PO2(OH) complex was proposed.

Interaction Studies of Ceramic Vacuum Plasma Spraying for the Melting Crucible Materials

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

Jong Hwan Kim; Hyung Tae Kim; Yoon Myung Woo

2013-10-01

Candidate coating materials for re-usable metallic nuclear fuel crucibles, TaC, TiC, ZrC, ZrO2, and Y2O3, were plasmasprayed onto a niobium substrate. The microstructure of the plasma-sprayed coatings and thermal cycling behavior were characterized, and U-Zr melt interaction studies were carried out. The TaC and Y2O3 coating layers had a uniform thickness, and high density with only a few small closed pores showing good consolidation, while the ZrC, TiC, and ZrO2 coatings were not well consolidated with a considerable amount of porosity. Thermal cycling tests showed that the adhesion of the TiC, ZrC, and ZrO2 coating layers with niobium was relativelymore » weak compared to the TaC and Y2O3 coatings. The TaC and Y2O3 coatings had better cycling characteristics with no interconnected cracks. In the interaction studies, ZrC and ZrO2 coated rods showed significant degradations after exposure to U-10 wt.% Zr melt at 1600 degrees C for 15 min., but TaC, TiC, and Y2O3 coatings showed good compatibility with U-Zr melt.« less

Optimizing the Synthesis of Alumina Inserts Using Hot Isostatic Pressing (HIP)

NASA Astrophysics Data System (ADS)

Ariff, T. F.; Azhar, A. Z.; Sariff, M. N.; Rasid, S. N.; Zahari, S. Z.; Bahar, R.; Karim, M.; Nurul Amin, AKM

2018-01-01

Alumina or Aluminium Oxide (Al2O3) is well known for its high strength and hardness. Its low heat retention and low specific heat characteristics make it attractive to be used widely as a cutting tool for grinding, milling and turning processes. Various synthesis methods have been used for the purpose of enhancing the properties of the alumina inserts. However, the optimization process using Hot Isostatic Pressing (HIP) has not been performed. This research aims in finding the optimum parameters in synthesizing the alumina inserts (98Al2O3 1.6ZrO2 0.4MgO, 93Al2O3 6.4ZrO2 0.6MgO and 85Al2O3 14.5ZrO2 0.5MgO) using HIP at different temperatures (1200, 1250 and 1300°C) and sintering time (10, 30 and 60 minutes). Hardness, density, shrinkage and microstructure using SEM were analysed. The optimum sintering condition for the alumina insert was found in 98Al2O3 1.6ZrO2 0.4MgO sintered at 1300°C for 60 minutes for it exhibited the highest values of hardness (1917HV), density (3.95g/cm3), shrinkage (9.6%).

Microstructural Evolution of Nanocrystalline ZrO2 in a Fe Matrix During High-Temperature Exposure

NASA Astrophysics Data System (ADS)

Raghavendra, K. G.; Dasgupta, Arup; Athreya, C. N.; Jayasankar, K.; Saroja, S.; Subramanya Sarma, V.

2018-06-01

The current study examines the evolution of nanocrystallites of ZrO2 with time and temperature in a Fe-ZrO2 composite. The crystallite sizes were determined through X-ray peak broadening analysis by the Williamson-Hall method together with dark field transmission electron microscopy. The ZrO2 crystallites were found to be stable and retained their sizes at 973 K and 1073 K for hold durations up to 600 minutes. On the other hand, the crystallites were seen to grow at 1173 K and reached up to 200 nm for a hold time of 600 minutes. The Ostwald ripening model was adopted to understand crystallite growth while a dislocation-driven pipe diffusion was adopted for understanding the kinetics of grain growth. The activation energy of grain growth was calculated as 379 kJ mol-1. The modeled and experimentally calculated size evolutions with time and temperature were shown to be in good agreement with each other. A detailed discussion on the kinetics and activation energy of grain growth of ZrO2 crystallites in a Fe matrix is presented in this manuscript.

Theoretical study of the promotional effect of ZrO2 on In2O3 catalyzed methanol synthesis from CO2 hydrogenation

NASA Astrophysics Data System (ADS)

Zhang, Minhua; Dou, Maobin; Yu, Yingzhe

2018-03-01

Methanol synthesis from CO2 hydrogenation on the ZrO2 doped In2O3(110) surface (Zr-In2O3(110)) with oxygen vacancy has been studied using the density functional theory calculations. The calculated results show that the doped ZrO2 species prohibits the excessive formation of oxygen vacancies and dissociation of H2 on In2O3 surface slightly, but enhances the adsorption of CO2 on both perfect and defective Zr-In2O3(110) surface. Methanol is formed via the HCOO route. The hydrogenation of CO2 to HCOO is both energetically and kinetically facile. The HCOO hydrogenates to polydentate H2CO (p-H2CO) species with an activation barrier of 0.75 eV. H3CO is produced from the hydrogenation of monodentate H2CO (mono-H2CO), transformation from p-H2CO with 0.82 eV reaction energy, with no barrier whether there is hydroxyl group between the mono-H2CO and the neighboring hydride or not. Methanol is the product of H3CO protonation with 0.75 eV barrier. The dissociation and protonation of CO2 are both energetically and kinetically prohibited on Zr-In2O3(110) surface. The doped ZrO2 species can further enhance the adsorption of all the intermediates involved in CO2 hydrogenation to methanol, activate the adsorbed CO2 and H2CO, and stabilize the HCOO, H2CO and H3CO, especially prohibit the dissociation of H2CO or the reaction of H2CO with neighboring hydride to form HCOO and gas phase H2. All these effects make the ZrO2 supported In2O3 catalyst exhibit higher activity and selectivity on methanol synthesis from CO2 hydrogenation.

Mechanical Properties of Plasma-Sprayed ZrO2-8 wt% Y2O3 Thermal Barrier Coatings

NASA Technical Reports Server (NTRS)

Choi, Sung R.; Zhu, Dongming; Miller, Robert A.

2004-01-01

Mechanical behavior of free standing, plasma-sprayed ZrO2-8 wt% Y2O3 thermal barrier coatings, including strength, fracture toughness, fatigue, constitutive relation, elastic modulus, and directionality, has been determined under various loading-specimen configurations. This report presents and describes a summary of mechanical properties of the plasma-sprayed coating material to provide them as a design database.

Electrochemical Corrosion and In Vitro Bioactivity of SiO2:ZrO2-Coated 316L Stainless Steel in Simulated Body Fluid

NASA Astrophysics Data System (ADS)

Srinivasan, A.; Rajendran, N.

2015-08-01

The effect of Si:Zr ratio on the in vitro bioactivity and electrochemical corrosion behavior of SiO2:ZrO2-mixed oxide-coated 316L stainless steel (SS) was evaluated in simulated body fluid (SBF) solution for 72, 120, and 168 h. Growth of Hydroxyapatite (HAp) was accelerated when Si content in the coating was increased. The Zr content in the coating improved the corrosion resistance of 316L SS rather than accelerating the HAp growth. When the Si:Zr ratio was 50:50, the coating exhibited significant improvement in corrosion resistance as well as HAp growth. The mechanism of HAp growth was proposed based on the change in surface zeta potential values of the coatings. Potentiodynamic polarization studies revealed about 10 and 5 times reduction in corrosion current density ( i corr) values for SiO2:ZrO2 (50:50)-coated 316L SS after 168 h of immersion compared to SiO2, ZrO2, and Si:Zr (70:30) coatings in SBF solutions thus confirming the superior corrosion resistance. The equivalent circuit parameters derived from electrochemical impedance spectroscopy studies further confirmed significant improvement in charge transfer resistance value even after 168 h of exposure.

Morphological structure of Gluconacetobacter xylinus cellulose and cellulose-based organic-inorganic composite materials

NASA Astrophysics Data System (ADS)

Smyslov, R. Yu; Ezdakova, K. V.; Kopitsa, G. P.; Khripunov, A. K.; Bugrov, A. N.; Tkachenko, A. A.; Angelov, B.; Pipich, V.; Szekely, N. K.; Baranchikov, A. E.; Latysheva, E.; Chetverikov, Yu O.; Haramus, V.

2017-05-01

Scanning electron microscopy, ultra-small-angle neutron scattering (USANS), small-angle neutron and X-ray scattering (SANS and SAXS), as well as low-temperature nitrogen adsorption, were used in the studies of micro- and mesostructure of polymer matrix prepared from air-dry preliminarily disintegrated cellulose nano-gel film (synthesized by Gluconacetobacter xylinus) and the composites based on this bacterial cellulose. The composites included ZrO2 nanoparticles, Tb3+ in the form of low molecular weight salt and of metal-polymer complex with poly(vinylpyrrolydone)-poly(methacryloyl-o-aminobenzoic acid) copolymer. The combined analysis of the data obtained allowed revealing three levels of fractal organization in mesostructure of G. xylinus cellulose and its composites. It was shown that both the composition and an aggregation state of dopants have a significant impact on the structural characteristics of the organic-inorganic composites. The composites containing Tb3+ ions demonstrate efficient luminescence; its intensity is an order of magnitude higher in the case of the composites with the metal-polymer complex. It was found that there is the optimal content of ZrO2 nanoparticles in composites resulting in increased Tb3+ luminescence.

Effects of the accumulated annealing parameter on the corrosion characteristics of a Zr-0.5Nb-1.0Sn-0.5Fe-0.25Cr alloy

NASA Astrophysics Data System (ADS)

Baek, Jong Hyuk; Jeong, Yong Hwan; Kim, In Sup

2000-07-01

Corrosion behavior, hydrogen pickup, oxide microstructure, and precipitate characterization have been studied in order to investigate the effect of the accumulated annealing parameter on the corrosion characteristics in a Zr-Nb-Sn-Fe-Cr alloy. An autoclave corrosion test was carried out in 400°C steam for 300 days on the Zr-0.5Nb-1.0Sn-0.5Fe-0.25Cr alloy, which had been given 18 different accumulated annealing parameters. The corrosion rate increased with increasing the accumulated annealing parameter. To investigate the crystal structure of oxide layer, the corroded specimens were prepared to have an equal oxide thickness (˜1.6 μm) by controlling exposure time. The relative fraction of tetragonal ZrO 2 also decreased gradually with increasing accumulated annealing parameter. From the hydrogen analysis of the corroded samples for 300 days, it was observed that, with increasing the size of precipitates, the hydrogen pickup was enhanced. It was revealed from transmission electron microscope (TEM) observation of the oxide that the larger precipitates still remained to be oxidized in the oxide layer and had undergone a reduction of Fe/Cr ratio from 2.1 to 1.5. The oxidation of the precipitates in the oxide gave rise to a volume expansion at the precipitate-oxide interface. This volume change could lead to the transformation in the oxide phase from tetragonal ZrO 2 to monoclinic ZrO 2 and in oxide structure from columnar grain to equiaxed grain. The precipitate in a Zr-0.5Nb-1.0Sn-0.5Fe-0.25Cr alloy is composed of Nb, Fe, and Cr and the Nb content in the precipitate increase with increasing accumulated annealing parameter. Thus, it can be thought that Nb within precipitates plays a key role in the microstructural change of oxide.

Theoretical study of methanol synthesis from CO2 and CO hydrogenation on the surface of ZrO2 supported In2O3 catalyst

NASA Astrophysics Data System (ADS)

Dou, Maobin; Zhang, Minhua; Chen, Yifei; Yu, Yingzhe

2018-06-01

The interactions between ZrO2 support and In2O3 catalyst play pivotal role in the catalytic conversion of CO2 to methanol. Herein, a density functional theory study has been conducted to research the mechanism of methanol synthesis from CO2 and CO hydrogenation on the defective ZrO2 supported In2O3(110) surface (D surface). The calculations reveal that methanol is produced mainly via the HCOO reaction pathway from CO2 hydrogenation on D surface, and the hydrogenation of HCOO to form H2COO species with an activation barrier of 1.21 eV plays the rate determining step for the HCOO reaction pathway. The direct dissociation of CO2 to CO on D surface is kinetically and energetically prohibited. Methanol synthesis from CO hydrogenation on D surface is much facile comparing with the elementary steps involved in CO2 hydrogenation. The rate determining step of CO hydrogenation to methanol is the formation of H3CO species on the vacancy site with a barrier of 0.51 eV. ZrO2 support has significant effect on the suppressing of the dissociation of CO2 and stabilization of H2COO species on the surface of In2O3 catalyst.

The Effect of Platinum-coatings on Hydrogen- and Water-absorption and Desorption Characteristics of Lithium Zirconate

NASA Astrophysics Data System (ADS)

Tsuchiya, B.; Bandow, S.; Nagata, S.; Saito, K.; Tokunaga, K.; Morita, K.

Hydrogen (H)- and water (H2O)-storage and desorption characteristics of 25 nm thick Pt films onLi2ZrO3composite materials, exposed to normal air at room temperature, have been investigated by means of elastic recoil detection (ERD), Rutherford backscattering spectrometry (RBS), weight gain measurement (WGM), and thermal desorption spectroscopy (TDS) techniques. It was found by the ERD and TDS that H and H2O were absorbed into the Pt-coated Li2ZrO3 in air at room temperature and desorbed from it in vacuum at much low temperatures of approximately 317 and 309 K, respectively. In addition, the WGM and TDS spectra revealed that the absorption and desorption characters ofsome gases such as CH4, CO, and CO2including H as well as H2Ointo the Li2ZrO3 bulk were improved by Pt deposition.

A sensitive determination of terbutaline in pharmaceuticals and urine samples using a composite electrode based on zirconium oxide nanoparticles.

PubMed

Baytak, Aysegul Kutluay; Teker, Tugce; Duzmen, Sehriban; Aslanoglu, Mehmet

2016-10-01

An accurate and precise determination of terbutaline has been carried out using a glassy carbon electrode (GCE) modified with a composite of multi-walled carbon nanotubes (MWCNTs) and nanoparticles of zirconium oxide (ZrO2NPs). Energy dispersive X-ray and scanning electron microscopic techniques were utilized for the characterization of the composite layer. Terbutaline exhibited a broad oxidation peak at 770mV on a GCE. However, MWCNTs/GCE presented an electrocatalytic effect toward the oxidation of terbutaline with a better anodic peak at 660mV. Furthermore, the electrochemical behavior of terbutaline has greatly been improved at a GCE modified with a composite of MWCNTs and nanoparticles of ZrO2. The ZrO2NPs/MWCNTs/GCE exhibited a sharp anodic wave at 645mV with a large enhancement of the current response for terbutaline. Square wave voltammetry (SWV) was performed for the determination of terbutaline at ZrO2NPs/MWCNTs/GCE. A linear plot was obtained for the current responses of terbutaline against concentrations in the range of 10-160nM yielding a detection limit of 2.25nM (based on 3Sb/m). Improved voltammetric behavior, long-time stability and good reproducibility were obtained for terbutaline at the proposed electrode. A mean recovery of 101.2% with an RSD% of 1.9 was obtained for the analysis of the drug formulation. The accurate and precise quantification of terbutaline makes the ZrO2NPs/MWCNTs/GCE system of great interest for monitoring its therapeutic use. Copyright © 2016 Elsevier B.V. All rights reserved.

ZrO2 film interfaces with Si and SiO2

NASA Astrophysics Data System (ADS)

Lopez, C. M.; Suvorova, N. A.; Irene, E. A.; Suvorova, A. A.; Saunders, M.

2005-08-01

The interface formed by the thermal oxidation of sputter-deposited Zr metal onto Si(100)- and SiO2-coated Si(100) wafers was studied in situ and in real time using spectroscopic ellipsometry (SE) in the 1.5-4.5 photon energy range and mass spectrometry of recoiled ions (MSRI). SE yielded optical properties for the film and interface and MSRI yielded film and interface composition. An optical model was developed and verified using transmission electron microscopy. Interfacial reaction of the ZrO2 was observed for both substrates, with more interaction for Si substrates. Equivalent oxide thicknesses and interface trap levels were determined on capacitors with lower trap levels found on samples with a thicker SiO2 underlayer. In addition to the optical properties for the intermixed interface layer, the optical properties for Zr metal and unreacted ZrO2 are also reported.

Combinatorial Investigation of ZrO2-Based Dielectric Materials for Dynamic Random-Access Memory Capacitors

NASA Astrophysics Data System (ADS)

Kiyota, Yuji; Itaka, Kenji; Iwashita, Yuta; Adachi, Tetsuya; Chikyow, Toyohiro; Ogura, Atsushi

2011-06-01

We investigated zirconia (ZrO2)-based material libraries in search of new dielectric materials for dynamic random-access memory (DRAM) by combinatorial-pulsed laser deposition (combi-PLD). We found that the substitution of yttrium (Y) to Zr sites in the ZrO2 system suppressed the leakage current effectively. The metal-insulator-metal (MIM) capacitor property of this system showed a leakage current density of less than 5×10-7 A/cm2 and the dielectric constant was 20. Moreover, the addition of titanium (Ti) or tantalum (Ta) to this system caused the dielectric constant to increase to ˜25 within the allowed leakage level of 5×10-7 A/cm2. Therefore, Zr-Y-Ti-O and Zr-Y-Ta-O systems have good potentials for use as new materials with high dielectric constants of DRAM capacitors instead of silicon dioxides (SiO2).

Thermophysical properties of liquid UO2, ZrO2 and corium by molecular dynamics and predictive models

NASA Astrophysics Data System (ADS)

Kim, Woong Kee; Shim, Ji Hoon; Kaviany, Massoud

2017-08-01

Predicting the fate of accident-melted nuclear fuel-cladding requires the understanding of the thermophysical properties which are lacking or have large scatter due to high-temperature experimental challenges. Using equilibrium classical molecular dynamics (MD), we predict the properties of melted UO2 and ZrO2 and compare them with the available experimental data and the predictive models. The existing interatomic potential models have been developed mainly for the polymorphic solid phases of these oxides, so they cannot be used to predict all the properties accurately. We compare and decipher the distinctions of those MD predictions using the specific property-related autocorrelation decays. The predicted properties are density, specific heat, heat of fusion, compressibility, viscosity, surface tension, and the molecular and electronic thermal conductivities. After the comparisons, we provide readily usable temperature-dependent correlations (including UO2-ZrO2 compounds, i.e. corium melt).

Preparation of Si nano-crystals with controlled oxidation state from SiO disproportionated by ZrO2 ball-milling

NASA Astrophysics Data System (ADS)

Okamoto, Yuji; Harada, Yoshitomo; Ohta, Narumi; Takada, Kazunori; Sumiya, Masatomo

2016-09-01

We demonstrate that a SiO disproportionation reaction can be achieved simply by high energy mechanochemical milling. The planetary ball-milling of ZrO2 for a few minutes generated Si nano-crystals. Milling conditions including rotation speed, ball number, milling time, and type of ball material were able to control the oxidation states of Si. The ball-milled SiO powder was tested as an anode of a lithium battery. ZrO2 contamination from the vial and balls was eliminated by dipping the ball-milled SiO powder in (NH4)HSO4 molten salt and heating for 5 min. The disproportionated SiO powder showed characteristics comparable to those of a powder prepared by a conventional heating process taking several hours.

Demonstration of motion control of ZrO2 microparticles in uniform/non-uniform electric field

NASA Astrophysics Data System (ADS)

Onishi, Genki; Trung, Ngo Nguyen Chi; Matsutani, Naoto; Nakayama, Tadachika; Suzuki, Tsuneo; Suematsu, Hisayuki; Niihara, Koichi

2018-02-01

This study aims to elucidate the mechanism that drives dielectric microparticles under an electric field. The driving of microstructures is affected by various electrical phenomena occurring at the same time such as surface potential, polarization, and electrostatic force. It makes the clarification of the driving mechanism challenging. A simple experimental system was used to observe the behavior of spherical ZrO2 microparticles in a nonaqueous solution under an electric field. The results suggest that the mechanism that drives the ZrO2 microparticles under an electric field involved the combination of an electric image force, a gradient force, and the contact charging phenomenon. A method is proposed to control the motion of micro- and nanostructures in further study and applications.

Ligand field splittings in core level transitions for transition metal (TM) oxides: Tanabe-Sugano diagrams and (TM) dangling bonds in vacated O-atom defects

NASA Astrophysics Data System (ADS)

Lucovsky, Gerry; Wu, Kun; Pappas, Brian; Whitten, Jerry

2013-04-01

Defect states in the forbidden band-gap below the conduction band edge are active as electron traps in nano-grain high-) transition metal (TM) oxides with thickness >0.3 nm, e.g., ZrO2 and HfO2. These oxides have received considerable attention as gate-dielectrics in complementary metal oxide semiconductor (CMOS) devices, and more recently are emerging as candidates for charge storage and memory devices. To provide a theoretical basis for device functionality, ab-initio many-electron theory is combined with X-ray absorption spectroscopy (XAS) to study O K edge and TM core level transitions. These studies identify ligand field splittings (ΔLF) for defect state features,. When compared with those obtained from O-atom and TM-atom core spectroscopic transitions, this provides direct information about defect state sun-nm bonding arrangements. comparisons are made for (i) elemental TiO2 and Ti2O3 with different formal ionic charges, Ti4+ and Ti3+ and for (ii) Magneli Phase alloys, TinO2n-1, n is an integer 9>=n>3, and (TiO2)x(HfO2)1-x alloys. The alloys display multi-valent behavior from (i) different ionic-charge states, (ii} local bond-strain, and (iii) metallic hopping transport. The intrinsic bonding defects in TM oxides are identified as pairs of singly occupied dangling bonds. For 6-fold coordinated Ti-oxides defect excited states in 2nd derivative O K pre-edge spectra are essentially the same as single Ti-atom d2 transitions in Tanabe-Sugano (T-S) diagrams. O-vacated site defects in 8-fold coordinated ZrO2 and HfO2 are described by d8 T-S diagrams. T-S defect state ordering and splittings are functions of the coordination and symmetry of vacated site bordering TM atoms. ΔLF values from the analysis of T-S diagrams indicate medium range order (MRO) extending to 3rd and 4th nearest-neighbor (NN) TM-atoms. Values are different for 6-fold Ti, and 8-fold ZrO2 and HfO2, and scale inversely with differences in respective formal ionic radii. O-vacated site bonding defects in TM nano-grain oxides are qualitatively similar to vacant-site defects in non-crystalline SiO2 and GeO2 for ulta-thin films, < 0.2 nm thick, and yield similar performance in MOSCAPs on Ge substrates heralding applications in aggressively-scale CMOS devices.

Effects of pH on heat transfer nanofluids containing ZrO2 and TiO2 nanoparticles

NASA Astrophysics Data System (ADS)

Wamkam, Carine Tchamakam; Opoku, Michael Kwabena; Hong, Haiping; Smith, Pauline

2011-01-01

In this paper, pH influences of zeta potential, particle size distribution, rheology, viscosity, and stability on heat transfer nanofluids are studied. Significant enhancement of thermal conductivity (TC) (>20%) containing 3 wt % zirconium dioxide (ZrO2) and titanium dioxide (TiO2) are observed near the isoelectric point (IEP). Meanwhile, at this IEP (pH), particle sizes, and viscosities of these nanofluids demonstrate a significant increase to maximum values. Experimental results also indicate that the stabilities of these nanofluids are influenced by pH values. The reasonable explanation for these interesting phenomena is that at this IEP, the repulsive forces among metal oxides are zero and nanoparticles coagulate together at this pH value. According to the Derjaguin-Landau-Verwey-Overbeek theory, when the pH is equal to or close to the IEP, nanoparticles tend to be unstable, form clusters, and precipitate. The resulting big clusters will trap water and the structures of trapped water are varied due to the strong atomic force among nanoparticles. Water is packed well inside and volume fraction of the nanoparticles will be larger. In addition, shapes of clusters containing trapped water will not be spherical but rather has irregular structure (like chains). Such structure favors thermal transport because they provide a long link. Therefore, overall TC of nanofluids is enhanced. Some literature results and conclusions related to pH effects of nanofluids are discussed and analyzed. Understanding pH effects may enable exploration of fundamental nature of nanofluids.

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.

The identification of group II inclusions in carbonaceous chondrites by electron probe microanalysis of perovskite

NASA Technical Reports Server (NTRS)

Kornacki, A. S.; Wood, J. A.

1985-01-01

The technique developed by Kornacki (1984) for identifying group II Ca/Al-rich inclusions in carbonaceous chondrites by electron-microprobe analysis of the ZrO2 or Y2O3 content of their perovskite component is demonstrated using material from 20 Allende inclusions. The results are presented in tables and graphs and compared with findings obtained by other procedures. Group II inclusions are found to have perovskites generally containing less than 0.10 wt pct ZrO2 and/or Y2O3 (average of several grains), while those of groups I, III, V, and VI have more than 0.25 wt pct ZrO2. Analysis of data on eight Allende Ca/Al-rich inclusions shows that 75 percent of the fine-grained inclusions belong to group II. The implications of these findings for fractionation processes in the primitive solar nebula are indicated.

Development of graded Ni-YSZ composite coating on Alloy 690 by Pulsed Laser Deposition technique to reduce hazardous metallic nuclear waste inventory.

PubMed

Sengupta, Pranesh; Rogalla, Detlef; Becker, Hans Werner; Dey, Gautam Kumar; Chakraborty, Sumit

2011-08-15

Alloy 690 based 'nuclear waste vitrification furnace' components degrade prematurely due to molten glass-alloy interactions at high temperatures and thereby increase the volume of metallic nuclear waste. In order to reduce the waste inventory, compositionally graded Ni-YSZ (Y(2)O(3) stabilized ZrO(2)) composite coating has been developed on Alloy 690 using Pulsed Laser Deposition technique. Five different thin-films starting with Ni80YSZ20 (Ni 80 wt%+YSZ 20 wt%), through Ni60YSZ40 (Ni 60 wt%+YSZ 40 wt%), Ni40YSZ60 (Ni 40 wt%+YSZ 60 wt%), Ni20YSZ80 (Ni 20 wt%+YSZ 80 wt%) and Ni0YSZ100 (Ni 0 wt%+YSZ 100 wt%), were deposited successively on Alloy 690 coupons. Detailed analyses of the thin-films identify them as homogeneous, uniform, pore free and crystalline in nature. A comparative study of coated and uncoated Alloy 690 coupons, exposed to sodium borosilicate melt at 1000°C for 1-6h suggests that the graded composite coating could substantially reduced the chemical interactions between Alloy 690 and borosilicate melt. Copyright © 2011 Elsevier B.V. All rights reserved.

Chemically stabilized reduced graphene oxide/zirconia nanocomposite: synthesis and characterization

NASA Astrophysics Data System (ADS)

Sagadevan, Suresh; Zaman Chowdhury, Zaira; Enamul Hoque, Md; Podder, Jiban

2017-11-01

In this research, chemical method was used to fabricate reduced graphene oxide/zirconia (rGO/ZrO2) nanocomposite. X-ray Diffraction analysis (XRD) was carried out to examine the crystalline structure of the nanocomposites. The nanocomposite prepared here has average crystallite size of 14 nm. The surface morphology was observed using scanning electron microscopic analysis (SEM) coupled with electron dispersion spectroscopy (EDS) to detect the chemical element over the surface of the nanocomposites. High-resolution Transmission electron microscopic analysis (HR-TEM) was carried out to determine the particle size and shape of the nanocomposites. The optical property of the prepared samples was determined using UV-visible absorption spectrum. The functional groups were identified using FTIR and Raman spectroscopic analysis. Efficient, cost effective and properly optimized synthesis process of rGO/ZrO2 nanocomposite can ensure the presence of infiltrating graphene network inside the ZrO2 matrix to enhance the electrical properties of the hybrid composites up to a greater scale. Thus the dielectric constant, dielectric loss and AC conductivity of the prepared sample was measured at various frequencies and temperatures. The analytical results obtained here confirmed the homogeneous dispersion of ZrO2 nanostructures over the surface of reduced graphene oxide nanosheets. Overall, the research demonstrated that the rGO/ZrO2 nano-hybrid structure fabricated here can be considered as a promising candidate for applications in nanoelectronics and optoelectronics.

Development and fabrication of insulator seals for thermionic diodes

NASA Technical Reports Server (NTRS)

Poirier, V. L.

1972-01-01

Eight different types of cermet seals for thermionic diodes were investigated: (1) 1 micron Al2O3 with Nb spheres; (2) 200 A Al2O3 with Nb spheres; (3) 1 micron Al2O3 with Nb 1% Zr spheres; (4) 200 A Al2O3 with Nb 1% Zr spheres; (5) Pure Y2O3 with Nb 1% Zr spheres; (6) Y2O3 3% ZrO2 with Nb 1% Zr spheres; (7) Y2O3 10% ZrO2 with Nb 1% Zr spheres; and (8) ZrO2 12% Y2O3 with Nb 1% Zr spheres. Investigations were made to determine the most favorable fabrication techniques and the effect of the bonding cycle, (length of bonding time and shutdown sequences). The analysis of the seals included tensile test, vacuum test, electrical test and metallurgical examination. At the conclusion of the development phase, 36 seals were fabricated for delivery for evaluation.

Electron-hole pairs generated in ZrO2 nanoparticle resist upon exposure to extreme ultraviolet radiation

NASA Astrophysics Data System (ADS)

Kozawa, Takahiro; Santillan, Julius Joseph; Itani, Toshiro

2018-02-01

Metal oxide nanoparticle resists have attracted much attention as the next-generation resist used for the high-volume production of semiconductor devices. However, the sensitization mechanism of the metal oxide nanoparticle resists is unknown. Understanding the sensitization mechanism is important for the efficient development of resist materials. In this study, the energy deposition in a zirconium oxide (ZrO2) nanoparticle resist was investigated. The numbers of electron-hole pairs generated in a ZrO2 core and an methacrylic acid (MAA) ligand shell upon exposure to 1 mJ cm-2 (exposure dose) extreme ultraviolet (EUV) radiations were theoretically estimated to be 0.16 at most and 0.04-0.17 cm2 mJ-1, respectively. By comparing the calculated distribution of electron-hole pairs with the line-and-space patterns of the ZrO2 nanoparticle resist fabricated by an EUV exposure tool, the number of electron-hole pairs required for the solubility change of the resist films was estimated to be 1.3-2.2 per NP. NP denotes a nanoparticle consisting of a metal oxide core with a ligand shell. In the material design of metal oxide nanoparticle resists, it is important to efficiently use the electron-hole pairs generated in the metal oxide core for the chemical change of ligand molecules.

Quantum chemistry study of dielectric materials deposition

NASA Astrophysics Data System (ADS)

Widjaja, Yuniarto

The drive to continually decrease the device dimensions of integrated circuits in the microelectronics industry requires that deposited films approach subnanometer thicknesses. Hence, a fundamental understanding of the physics and chemistry of film deposition is important to obtain better control of the properties of the deposited film. We use ab initio quantum chemistry calculations to explore chemical reactions at the atomic level. Important thermodynamic and kinetic parameters are then obtained, which can then be used as inputs in constructing first-principles based reactor models. Studies of new systems for which data are not available can be conducted as well. In this dissertation, we use quantum chemistry simulations to study the deposition of gate dielectrics for metal-oxide-semiconductor (MOS) devices. The focus of this study is on heterogeneous reactions between gaseous precursors and solid surfaces. Adsorbate-surface interactions introduce additional degrees of complexity compared to the corresponding gas-phase or solid-state reactions. The applicability and accuracy of cluster approximations to represent solid surfaces are first investigated. The majority of our results are obtained using B3LYP density functional theory (DFT). The structures of reactants, products, and transition states are obtained, followed by calculations of thermochemical and kinetic properties. Whenever experimental data are available, qualitative and/or quantitative comparisons are drawn. Atomistic mechanisms and the energetics of several reactions leading to the deposition of SiO2, Si3N4, and potential new high-kappa materials such as ZrO2, HfO2, and Al 2O3 have been explored in this dissertation. Competing reaction pathways are explored for each of the deposition reactions studied. For example, the potential energy surface (PES) for ZrO2 ALD shows that the reactions proceed through a trapping-mediated mechanism, which results in a competition between desorption and decomposition of the gaseous reactants, i.e. ZrCl4 and H2O, on the ZrO2 surface. This competition results in relatively low saturation coverage, which consequently leads to a slow growth rate and possibly affects the thickness uniformity and conformality. The insights gained are then used to systematically improve deposition reactions. For instance, from the ZrO2 ALD PES, we are able to suggest the use of high temperature and pressure to obtain higher surface coverage.

Carbon dioxide electrolysis using a ceramic electrolyte. [for space processing

NASA Technical Reports Server (NTRS)

Erstfeld, T. E.; Mullins, O., Jr.; Williams, R. J.

1979-01-01

This paper discusses the results of an experimental study of the electrical aspects of carbon dioxide electrolysis using a ceramic electrolyte. The electrolyte compositions used in this study are 8% Y2O3 stabilized ZrO2, 7.5% CaO stabilized ZrO2, and 5% Y2O3 stabilized ThO2. Results indicate that the 8% Y2O3 stabilized ZrO2 is the best material to use for electrolysis, in terms of current as a function of voltage and temperature, and in terms of efficiency of oxide ion flow through it. The poorest results were obtained with the 5% Y2O3 stabilized ThO2 composition. An electrolysis system which might be employed to reclaim oxygen and carbon from effluents of space manufacturing, assuming that an industry would have to electrolyze 258,000 tonnes of CO2 per year, is predicted to require a total cell area of 110,000 sq m of 1 mm thickness and electrical capacity of 441 MW.

Dielectric Properties of PMMA and its Composites with ZrO2

NASA Astrophysics Data System (ADS)

Sannakki, Basavaraja; Anita

The polymer films of PMMA with different thickness and its composites with ZrO2 at various weight percentages but of same thickness have been studied. The determination of its dielectric properties, dielectric loss, a.conductivity and dielectric modulus were carried out using capacitance measurements of the above samples as a function of frequency, over the range 50 Hz - 5 MHz at room temperature. The films of PMMA and its composites have been characterized using X-Ray Diffractometer. The dielectric permittivity of films of PMMA behaves nonlinearly as frequency increases over the range 50-300 Hz, where as above 300 Hz the values of dielectric constant remains constant. But it is observed that the dielectric constant of PMMA increases as thickness of the film increases. In case of composite films of PMMA with ZrO2 the values of dielectric permittivity decreases gradually up to frequency of around 1 KHz and at higher frequencies it remains constant for all the weight percentages of ZrO2. The complex form of dielectric modulus of PMMA is obtained from the experimentally measured data of dielectric constant and dielectric loss values. The relaxation time of the orientation of dipoles is obtained from the peak value of angular frequency through the plots of imaginary part of electrical modulus as function of frequency. The impedance of PMMA polymer increases as thickness of the films increases. The a c conductivity of PMMA film remains constant up to frequency of 1 MHz and above. It shows a nonlinear phenomenon with peak values at frequency 4 MHz. Shape and size of the nanoparticles of composite film of PMMA with ZrO2 was analyzed by Field Emission Scanning Electron Microscope (FESEM).

Single Crystal Fibers of Yttria-Stabilized Cubic Zirconia with Ternary Oxide Additions

NASA Technical Reports Server (NTRS)

Ritzert, F. J.; Yun, H. M.; Miner, R. V.

1997-01-01

Single crystal fibers of yttria (Y2O3)-stabilized cubic zirconia, (ZrO2) with ternary oxide additions were grown using the laser float zone fiber processing technique. Ternary additions to the ZrO2-Y2O3 binary system were studied aimed at increasing strength while maintaining the high coefficient of thermal expansion of the binary system. Statistical methods aided in identifying the most promising ternary oxide candidate (Ta2O5, Sc2O3, and HfO2) and optimum composition. The yttria, range investigated was 14 to 24 mol % and the ternary oxide component ranged from 1 to 5 mol %. Hafnium oxide was the most promising ternary oxide component based on 816 C tensile strength results and ease of fabrication. The optimum composition for development was 81 ZrO2-14 Y203-5 HfO2 based upon the same elevated temperature strength tests. Preliminary results indicate process improvements could improve the fiber performance. We also investigated the effect of crystal orientation on strength.

A Synergistic Effect of Surfactant and ZrO2 Underlayer on Photocurrent Enhancement and Cathodic Shift of Nanoporous Fe2O3 Photoanode.

PubMed

Shinde, Pravin S; Lee, Su Yong; Choi, Sun Hee; Lee, Hyun Hwi; Ryu, Jungho; Jang, Jum Suk

2016-08-31

Augmenting the donor density and nanostructure engineering are the crucial points to improve solar water oxidation performance of hematite (α-Fe2O3). This work addresses the sluggish water oxidation reaction associated with hematite photoanode by tweaking its internal porosity. The porous hematite photoanodes are fabricated by a novel synthetic strategy via pulse reverse electrodeposition (PRED) method that involves incorporation of a cationic CTAB surfactant in a sulfate electrolyte and spin-coated ZrO2 underlayer (UL) on FTO. CTAB is found to be beneficial in promoting the film growth rate during PRED. Incorporation of Zr(4+) ions from ZrO2 UL and Sn(4+) ions from FTO into the Fe2O3 lattice via solid-state diffusion reaction during pertinent annihilation of surfactant molecules at 800 °C produced internally porous hematite films with improved carrier concentration. The porous hematite demonstrated a sustained photocurrent enhancement and a significant cathodic shift of 130 mV relative to the planar hematite under standard illumination conditions (AM 1.5G) in 1 M NaOH electrolyte. The absorption, electrochemical impedance spectroscopy and Mott-Schottky analyses revealed that the ZrO2 UL and CTAB not only increased the carrier density and light harvesting but also accelerated the surface oxidation reaction kinetics, synergistically boosting the performance of internally porous hematite photoanodes.

A Synergistic Effect of Surfactant and ZrO2 Underlayer on Photocurrent Enhancement and Cathodic Shift of Nanoporous Fe2O3 Photoanode

NASA Astrophysics Data System (ADS)

Shinde, Pravin S.; Lee, Su Yong; Choi, Sun Hee; Lee, Hyun Hwi; Ryu, Jungho; Jang, Jum Suk

2016-08-01

Augmenting the donor density and nanostructure engineering are the crucial points to improve solar water oxidation performance of hematite (α-Fe2O3). This work addresses the sluggish water oxidation reaction associated with hematite photoanode by tweaking its internal porosity. The porous hematite photoanodes are fabricated by a novel synthetic strategy via pulse reverse electrodeposition (PRED) method that involves incorporation of a cationic CTAB surfactant in a sulfate electrolyte and spin-coated ZrO2 underlayer (UL) on FTO. CTAB is found to be beneficial in promoting the film growth rate during PRED. Incorporation of Zr4+ ions from ZrO2 UL and Sn4+ ions from FTO into the Fe2O3 lattice via solid-state diffusion reaction during pertinent annihilation of surfactant molecules at 800 °C produced internally porous hematite films with improved carrier concentration. The porous hematite demonstrated a sustained photocurrent enhancement and a significant cathodic shift of 130 mV relative to the planar hematite under standard illumination conditions (AM 1.5G) in 1 M NaOH electrolyte. The absorption, electrochemical impedance spectroscopy and Mott-Schottky analyses revealed that the ZrO2 UL and CTAB not only increased the carrier density and light harvesting but also accelerated the surface oxidation reaction kinetics, synergistically boosting the performance of internally porous hematite photoanodes.

Co nanoparticle effects on the thermoluminescent signal induced by UV and gamma radiation in ZrO2 powders

NASA Astrophysics Data System (ADS)

Villa-Sánchez, G.; Mendoza-Anaya, D.; Eufemia Fernández-García, M.; Escobar-Alarcón, L.; Olea-Mejía, O.; González-Martínez, P. R.

2014-05-01

Zirconia powders, both pure and doped with Co nanoparticles were prepared by the sol-gel method followed by thermal treatment at 1000 °C. The morphological and crystallographic characteristics were studied by scanning and transmission electron microscopy, X-ray diffraction and the Rietveld refinements method. Analysis of the thermoluminescent (TL) signal induced by UV and gamma radiation was also conducted. According to the results, Co nanoparticles have a strong influence on the growth of ZrO2 particles and favor the formation of monoclinic zirconia. Moreover, an important influence of the added Co nanoparticles was observed on the position of the TL peaks of ZrO2, inducing a shift in the luminescence towards higher temperatures as well as the presence of more TL peaks at higher temperatures.

Milling assisted synthesis of calcium zirconate СаZrО3

NASA Astrophysics Data System (ADS)

Kalinkin, A. M.; Nevedomskii, V. N.; Kalinkina, E. V.; Balyakin, K. V.

2014-08-01

Monophase calcium zirconate (CaZrO3) has been prepared from the equimolar ZrO2 + CaCO3 mixture by two-step synthesis process. In the first step, mechanical treatment of the mixture is performed in an AGO-2 planetary ball mill. In the second step, the milled mixture is annealed to form calcium zirconate. High-energy ball milling of the (ZrO2+CaCO3) mixture results in decrease in the temperature of CaZrO3 formation during annealing at 950 °C. The enhancement of CaZrO3 synthesis is due to accumulation of excess energy by the reagents, decreasing the particle size and notable increase in the interphase area because of “smearing” of CaCO3 on ZrO2 particles during milling. Nanocrystalline calcium zirconate has been produced by controlling the annealing temperature and time.

The influence of ZrO2/20%Y2O3 and Al2O3 deposited coatings to the behavior of an aluminum alloy subjected to mechanical shock

NASA Astrophysics Data System (ADS)

Pintilei, G. L.; Crismaru, V. I.; Abrudeanu, M.; Munteanu, C.; Luca, D.; Istrate, B.

2015-10-01

Aluminum alloys are used in the aerospace industry due to their good mechanical properties and their low density compared with the density of steels. Usually the parts made of aluminum alloys contribute to the structural frame of aircrafts and they must withstand static and variable mechanical loads and also mechanical loads applied in a very short time which determine different phenomenon's in the material behavior then static or fatigue loads. This paper analysis the resilience of a 2024 aluminum alloy subjected to shock loads and the way how a coating can improve its behavior. For improving the behavior two coatings were considered: Al2O3 with 99.5% purity and ZrO2/20%Y2O3. The coatings were deposited on the base material by plasma spraying. The samples with and without coating were subject to mechanical shock to determine the resilience of the materials and the cracks propagation was investigated using SEM analysis. To highlight the physical phenomenon's that appear in the samples during the mechanical shock, explicit finite element analysis were done using Ansys 14.5 software.

Ultrasonic-assisted synthesis of ZrO2 nanoparticles and their application to improve the chemical stability of Nafion membrane in proton exchange membrane (PEM) fuel cells.

PubMed

Taghizadeh, Mohammad Taghi; Vatanparast, Morteza

2016-12-01

Zirconium dioxide (ZrO2) nanoparticles were fabricated successfully via ultrasonic-assisted method using ZrO(NO3)2·H2O, ethylenediamine and hydrazine as precursors in aqueous solution. Morphology, structure and composition of the obtained products were characterized by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), dynamic light scattering (DLS), Fourier transform infrared spectroscopy (FT-IR) and diffuse reflectance spectroscopy (DRS). Then, the synthesized nanoparticles were used to prepare Nafion/ZrO2 nanocomposite membranes. The properties of the membranes were studied by ion exchange capacity (IEC) proton conductivity (σ), thermal stability and water uptake measurements. The ex-situ Fenton's test was used to investigate the chemical stability of the membranes. From our results, compared with Nafion membrane, the nanocomposite membrane exhibited lower fluoride release and weight loss. Therefore, it can concluded that Nafion/ZrO2 nanocomposite exhibit more chemical stability than the pure Nafion membrane. ATR-FTIR spectra and SEM surface images of membranes also confirm these results. Copyright © 2016 Elsevier Inc. All rights reserved.

Tensile and Compressive Responses of Ceramic and Metallic Nanoparticle Reinforced Mg Composites

PubMed Central

Tun, Khin Sandar; Wong, Wai Leong Eugene; Nguyen, Quy Bau; Gupta, Manoj

2013-01-01

In the present study, room temperature mechanical properties of pure magnesium, Mg/ZrO2 and Mg/(ZrO2 + Cu) composites with various compositions are investigated. Results revealed that the use of hybrid (ZrO2 + Cu) reinforcements in Mg led to enhanced mechanical properties when compared to that of single reinforcement (ZrO2). Marginal reduction in mechanical properties of Mg/ZrO2 composites were observed mainly due to clustering of ZrO2 particles in Mg matrix and lack of matrix grain refinement. Addition of hybrid reinforcements led to grain size reduction and uniform distribution of hybrid reinforcements, globally and locally, in the hybrid composites. Macro- and micro- hardness, tensile strengths and compressive strengths were all significantly increased in the hybrid composites. With respect to unreinforced magnesium, failure strain was almost unchanged under tensile loading while it was reduced under compressive loading for both Mg/ZrO2 and Mg/(ZrO2 + Cu) composites. PMID:28809245

Investigation of hydrogen interaction with defects in zirconia

NASA Astrophysics Data System (ADS)

Melikhova, O.; Kuriplach, J.; Čížek, J.; Procházka, I.; Brauer, G.; Anwand, W.

2010-04-01

Defect studies of a ZrO2 + 9 mol. % Y2O3 single crystal were performed in this work using a high resolution positron lifetime spectroscopy combined with slow positron implantation spectroscopy. In order to elucidate the nature of positron trapping sites observed experimentally, the structural relaxations of several types of vacancy-like defects in zirconia were performed and positron characteristics for them were calculated. Relaxed atomic configurations of studied defects were obtained by means of ab initio pseudopotential method within the supercell approach. Theoretical calculations indicated that neither oxygen vacancies nor their neutral complexes with substitute yttrium atoms are capable of positron trapping. On the other hand, zirconium vacancies are deep positron traps and are most probably responsible for the saturated positron trapping observed in yttria stabilized zirconia single crystals. However, the calculated positron lifetime for zirconium vacancy is apparently longer than the experimental value corresponding to a single-component spectrum measured for the cubic ZrO2 + 9 mol. % Y2O3 single crystal. It was demonstrated that this effect can be explained by hydrogen trapped in zirconium vacancies. On the basis of structure relaxations, we found that zirconium vacancy - hydrogen complexes represent deep positron traps with the calculated lifetime close to the experimental one. In zirconium vacancy - hydrogen complexes the hydrogen atom forms an O-H bond with one of the nearest neighbour oxygen atoms. The calculated bond length is close to 1 Å.

The Effect of Sintering Time on the Marginal Fit of Zirconia Copings.

PubMed

Khaledi, Amir Ali Reza; Vojdani, Mahroo; Farzin, Mitra; Pirouzi, Sudabeh; Orandi, Sepideh

2018-01-03

This study analyzed the effect of different sintering times on the marginal adaptation of zirconia ceramic copings. Thirty copings of pre-sintered 3Y-TZP blanks were milled and subsequently sintered in a special furnace for three different durations (n = 10 per group). The sintering time was 1 hour, 15 minutes for IPS e.max ZirCAD, 4 hours 20 minutes for Speed ZrO 2, and 7 hours 20 minutes for the conventional ZrO 2 group. The marginal gaps of specimens were measured at 18 spots on the master die by employing a digital microscope. One-way ANOVA test compared the mean differences among the 3 groups (α = 0.05). The mean values for the marginal gap of the IPS e.max ZirCAD, Speed ZrO 2 , and conventional ZrO 2 groups were 41.06 ± 14.03, 43.03 ± 11.67, and 39.88 ± 15.23 μm, respectively. There was no statistically significant difference among the groups regarding the marginal gap. Different sintering times did not alter the marginal fit of the zirconia copings. The mean values of the marginal gap were within the clinically acceptable level for all three groups. © 2018 by the American College of Prosthodontists.

Experimental and theoretical screening of nanoscale oxide reactivity with LiBH4

NASA Astrophysics Data System (ADS)

Opalka, S. M.; Tang, X.; Laube, B. L.; Vanderspurt, T. H.

2009-05-01

Experimentation, thermodynamic modeling, and atomic modeling were combined to screen the reactivity of SiO2, Al2O3, and ZrO2 nanoscale oxides with LiBH4. Equilibrium thermodynamic modeling showed that the reactions of oxides with LiBH4 could lead to formation of stable Li-bearing oxide and metal boride phases. Experimentation was conducted to evaluate the discharge/recharge reaction products of nanoscale oxide-LiBH4 mixtures. Thermal gravimetric analyses-mass spectroscopy and x-ray diffraction revealed significant SiO2 destabilization of LiBH4 dehydrogenation, resulting in the formation of lithium silicate and boric acid. A smaller amount of lithium metaborate and boric acid was formed with Al2O3. No destabilization products were observed with ZrO2. Density functional theory atomic modeling predicted much stronger LiBH4 interfacial adsorption on the SiO2 and Al2O3 surfaces than on the ZrO2 surface, which was consistent with the experimental findings. Following dehydrogenation, interfacial Li atoms were predicted to strongly adsorb on the oxide surfaces effectively competing with LiH formation. The interfacial Li interactions with Al2O3 and ZrO2 were equal in strength in the fully hydrided and dehydrided states, so that their predicted net effect on LiBH4 dehydrogenation was insignificant. Zirconia was selected for nanoframework development based on the combined observations of compatibility and weaker associative interactions with LiBH4.

The effect of preliminary hydrolysis on the properties of ZrO2-7% Y2O3 powders prepared by hydroxide precipitation

NASA Astrophysics Data System (ADS)

Zhirenkina, Nina V.; Mashkovtsev, Maxim A.; Bereskina, Polina A.; Zakirov, Ilsur F.; Baksheev, Evgenie O.; Bujnachev, Sergey V.; Vereshchagin, Artem O.

2017-09-01

In this study, the effect of preliminary hydrolysis of zirconyl oxysulfate on the properties of ZrO2-7 % Y2O3 powders prepared by hydroxides precipitation at a constant pH of 5 was studied. X-ray diffraction analysis showed the monophasic nature of the samples and the insignificant difference between CSR (coherent scattering regions). Samples differed in particle size distribution, porosity and morphology.

The Composition of Intermediate Products of the Thermal Decomposition of (NH4)2ZrF6 to ZrO2 from Vibrational-Spectroscopy Data

NASA Astrophysics Data System (ADS)

Voit, E. I.; Didenko, N. A.; Gaivoronskaya, K. A.

2018-03-01

Thermal decomposition of (NH4)2ZrF6 resulting in ZrO2 formation within the temperature range of 20°-750°C has been investigated by means of thermal and X-ray diffraction analysis and IR and Raman spectroscopy. It has been established that thermolysis proceeds in six stages. The vibrational-spectroscopy data for the intermediate products of thermal decomposition have been obtained, systematized, and summarized.

Synchrotron X-ray diffraction investigations on strains in the oxide layer of an irradiated Zircaloy fuel cladding

NASA Astrophysics Data System (ADS)

Chollet, Mélanie; Valance, Stéphane; Abolhassani, Sousan; Stein, Gene; Grolimund, Daniel; Martin, Matthias; Bertsch, Johannes

2017-05-01

For the first time the microstructure of the oxide layer of a Zircaloy-2 cladding after 9 cycles of irradiation in a boiling water reactor has been analyzed with synchrotron micro-X-ray diffraction. Crystallographic strains of the monoclinic and to some extent of the tetragonal ZrO2 are depicted through the thick oxide layer. Thin layers of sub-oxide at the oxide-metal interface as found for autoclave-tested samples and described in the literature, have not been observed in this material maybe resulting from irradiation damage. Shifts of selected diffraction peaks of the monoclinic oxide show that the uniform strain produced during oxidation is orientated in the lattice and displays variations along the oxide layer. Diffraction peaks and their shifts from families of diffracting planes could be translated into a virtual tensor. This virtual tensor exhibits changes through the oxide layer passing by tensile or compressive components.

Al2O3-ZrO2 Finely Structured Multilayer Architectures from Suspension Plasma Spraying

NASA Astrophysics Data System (ADS)

Tingaud, Olivier; Montavon, Ghislain; Denoirjean, Alain; Coudert, Jean-François; Rat, Vincent; Fauchais, Pierre

2010-01-01

Suspension plasma spraying (SPS) is an alternative to conventional atmospheric plasma spraying (APS) aiming at manufacturing thinner layers (i.e., 10-100 μm) due to the specific size of the feedstock particles, from a few tens of nanometers to a few micrometers. The staking of lamellae and particles, which present a diameter ranging from 0.1 to 2.0 μm and an average thickness from 20 to 300 nm, permits to manufacture finely structured layers. Moreover, it appears as a versatile process able to manufacture different coating architectures according to the operating parameters (suspension properties, injection configuration, plasma properties, spray distance, torch scan velocity, scanning step, etc.). However, the different parameters controlling the properties of the coating, and their interdependences, are not yet fully identified. Thus, the aim of this paper is, on the one hand, to better understand the influence of operating parameters on the coating manufacturing mechanisms (in particular, the plasma gas mixture effect) and, on the other hand, to produce Al2O3-ZrO2 finely structured layers with large varieties of architectures. For this purpose, a simple theoretical model was used to describe the plasma torch operating conditions at the nozzle exit, based on experimental data (mass enthalpy, arc current intensity, thermophysical properties of plasma forming gases, etc.) and the influences of the spray parameters were determined by mean of the study of sizes and shapes of spray beads. The results enabled then to reach a better understanding of involved phenomena and their interactions on the final coating architectures permitting to manufacture several types of microstructures.

Development of AlN and TiB2 Composites with Nb2O5, Y2O3 and ZrO2 as Sintering Aids

PubMed Central

González, José C.; Rodríguez, Miguel Á.; Figueroa, Ignacio A.; Villafuerte-Castrejón, María-Elena; Díaz, Gerardo C.

2017-01-01

The synthesis of AlN and TiB2 by spark plasma sintering (SPS) and the effect of Nb2O5, Y2O3 and ZrO2 additions on the mechanical properties and densification of the produced composites is reported and discussed. After the SPS process, dense AlN and TiB2 composites with Nb2O5, Y2O3 and ZrO2 were successfully prepared. X-ray diffraction analysis showed that in the AlN composites, the addition of Nb2O5 gives rise to Nb4N3 during sintering. The compound Y3Al5O12 (YAG) was observed as precipitate in the sample with Y2O3. X-ray diffraction analysis of the TiB2 composites showed TiB2 as a single phase in these materials. The maximum Vickers and toughness values were 14.19 ± 1.43 GPa and 27.52 ± 1.75 GPa for the AlN and TiB2 composites, respectively. PMID:28772681

Phase study of SiO2-ZrO2 composites prepared from polymorphic combination of starting powders via a ball-milling followed by calcination

NASA Astrophysics Data System (ADS)

Musyarofah; Nurlaila, R.; Muwwaqor, N. F.; Saukani, M.; Kuswoyo, A.; Triwikantoro; Pratapa, S.

2017-04-01

The effects of SiO2-ZrO2 polymorphic combinations as starting powders and calcination temperature on phase composition of the SiO2-ZrO2 composites were studied. Stoichiometric (1:1 mol%) mixtures of the SiO2-ZrO2 composites were mechanically activated using a ball-milling for 5 h followed by calcinations at 1000, 1100 and 1200 °C for 3 h. The composites used in the present study were a-SiO2+ a-ZrO2, a-SiO2+ t-ZrO2, c-SiO2+ a-ZrO2 and c-SiO2+ t-ZrO2 which were symbolized by AA, AT, CA and CT, respectively. Prefixes a, t and c denote amorphous, tetragonal and cristobalite, respectively. The phase composition was determined by Rietveld analysis of X-ray diffraction (XRD) data using Rietica software. The identified phases for all calcined samples were a combination among t-ZrO2, c-SiO2, m-ZrO2 and zircon (ZrSiO4). Amorphous zirconia formed a transient tetragonal zirconia phase during heating, which reacted with silica to form zircon. The zircon phase was not found to form even at 1200 °C in the AT and CT mixtures and at 1100 °C in the CA mixture. The AA mixture in particular crystallized to form zircon at a lower temperature with more composition fraction than the others, ca 82.9 (14) mol%.

Incorporation of ZrO2 particles in the oxide layer formed on Mg by anodizing: Influence of electrolyte concentration and current modes.

PubMed

Sankara Narayanan, T S N; Lee, Min Ho

2016-02-15

The objectives of the present study are to ascertain, particle incorporation during the initial stages of microarc oxidation (MAO), feasibility of increasing the level of particle incorporation through manipulation of process variables and, the use of MgO-ZrO2 composite coatings either as a pre-treatment or as a post-treatment for MAO coated Mg. Anodic oxide coatings were prepared using 0.3M NaOH+15g/l ZrO2 and 3M NaOH+15g/l ZrO2 at 10V under direct current, pulsed current (PC) unipolar and PC bipolar modes. MAO coatings were prepared using 5g/l NaOH+15g/l Na2SiO3 at 250V under direct current mode for 2min. The study reveals that it is possible to incorporate ZrO2 particles in the anodic oxide layer, suggesting such a possibility during the initial stages of MAO. When the MgO-ZrO2 composite coating is used as a pre-treatment, it helps to reduce the size and density of the pores of the MAO coatings and increased the corrosion resistance. When it is used as a post-treatment, lamellar shaped Mg(OH)2 with a very high surface area is formed on the surface, which would be beneficial to impart a better bioactivity and to facilitate immobilization of biomolecules. Copyright © 2015. Published by Elsevier Inc.

Photoluminescence and cathodoluminescence of Tb-doped Al 2O 3-ZrO 2 nanostructures obtained by sol-gel method

NASA Astrophysics Data System (ADS)

Zawadzki, M.; Hreniak, D.; Wrzyszcz, J.; Miśta, W.; Grabowska, H.; Malta, O. L.; Stręk, W.

2003-07-01

Terbium-doped Al 2O 3-ZrO 2 mixed oxides of 10 wt% zirconia content were prepared by the alkoxide sol-gel method. The obtained samples were characterized by XRD, SEM, thermal analysis, textural and TPR studies. The effect of thermal treatment of Tb-doped Al 2O 3-ZrO 2 samples on photo- and cathodoluminescence spectra was investigated. It was found that the photoluminescence spectrum induced by UV excitation was characterized by a green luminescence pattern arising from the 5D 4 → 7F J ( J=6-0) transitions of the Tb 3+ ion. This photoluminescence became almost completely damped for the samples sintered at 1200 °C. However, these samples have demonstrated an intense cathodoluminescence under high electron accelerating potential (60 kV). Moreover, it was observed that apart of the green luminescence, the blue emission lines arising from 5D 3 → 7F J transitions of Tb 3+ were observed. The nature of such behavior is discussed.

Effect of Dielectric Material Films on Crystallization Characteristics of Ge2Sb2Te5 Phase-Change Memory Film

NASA Astrophysics Data System (ADS)

Nishiuchi, Kenichi; Yamada, Noboru; Kawahara, Katsumi; Kojima, Rie

2007-11-01

Reduction of the film thickness of phase-change film and the adoption of GeN- or ZrO2-based dielectric films are both effective in achieving good thermal stability in phase-change optical disks. It was experimentally confirmed that, at a heating rate of 10 °C/min, the crystallization temperature Tx of the Ge2Sb2Te5 amorphous film when sandwiched by ZnS-SiO2 films markedly increases from 162 to 197 °C, while the thickness of the Ge2Sb2Te5 film decreases from 10 to 3 nm. Tx also slightly increases when ZnS-SiO2 films are substituted for GeN-based films (from 162 to 165 °C) and ZrO2-based films (from 162 to 167 °C). At the same time, the activation energy of crystallization is 2.4 eV for both GeN- and ZrO2-based films, and is higher than 2.2 eV for ZnS-SiO2 films.

Effect of ZrO2 Powders on the Pyrolysis of Polycarbosilanes Coating Under Laser Ablation

NASA Astrophysics Data System (ADS)

Cheng, Han; Chen, Zhaofeng; Tao, Jie; Yan, Bo; Li, Cong; Wang, Liangbing; Zhang, Ying; Fang, Dan; Wan, Shuicheng; Wu, Wangping

Aircrafts hold the outstanding mastery of the sky in modern wars, however the laser beam weapons can carry out laser attacking to aircrafts. The purpose of the present paper is to research on a new type laser protective material. Polycarbosilanes (PCS)/divinylbenzene mixtures containing ZrO2 powders were brushed to the surface of the aluminum alloy plates and then cured at 150°C for 6 h. The PCS-coated plates were ablated by laser for 3 s. The phase identification of as-ablated powders was examined by X-ray diffraction. The results indicated that the as-ablated powders of cured PCS were composed of major phase β-SiC and smaller amounts of free carbon. The PCS composite coating played a certain role of laser ablation resistance. The effect of added ZrO2 powders on the pyrolysis of PCS-coating under laser ablation is conspicuous.

Development of Fe3O4/ZrO2 Composite Powered by Nanographene Platelets (NGP) for Degradation of Water Pollutants via Photo- and Sonocatalysis

NASA Astrophysics Data System (ADS)

Kristianto, Yogi; Taufik, Ardiansyah; Saleh, Rosari

2017-03-01

In this study, a series of Fe3O4/ZrO2/nanographene platelets (NGP) composite, with various weight percent (wt%) of NGP (5%, 10% and 15%), were prepared successfully using ultrasonic-assisted followed by simple hydrothermal method. Their physicochemical properties were fairly characterized by X-ray diffraction, fourier transform infrared and thermal gravimetric analysis. Furthermore, their catalytic activities were investigated toward anionic congo red (CR) and cationic methylene blue (MB) as models of organic pollutant under ultraviolet (UV) and ultrasonic (US) irradiation, respectively. The experimental results showed that the incorporation of NGP in Fe3O4/ZrO2 composite improved its efficiency in degrading CR and MB and became maximum at 10wt% of NGP. In addition, the role of active radicals involved in catalytic activities were discussed.

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.

Growth and characterization of zirconium oxynitride films prepared by reactive direct current magnetron sputtering

NASA Astrophysics Data System (ADS)

Venkataraj, S.; Kappertz, O.; Jayavel, R.; Wuttig, M.

2002-09-01

Thin films of zirconium oxynitrides have been deposited onto Si(100) substrates at room temperature by reactive dc magnetron sputtering of a metallic Zr target in an argon-oxygen-nitrogen atmosphere. To prepare oxynitride films the sum of the O2 and N2 flow was kept at 3.5 sccm, while the relative nitrogen content of this mixture was changed stepwise from 0% to 100%. The film structure was determined by x-ray diffraction, while x-ray reflectometry was employed to determine the thickness, density, and surface roughness of the films. The optical properties have been studied by spectroscopic reflectance measurements. X-ray diffraction (XRD) determines that the as-deposited films are crystalline and do not change their monoclinic ZrO2 crystal structure even for nitrogen flows up to 80%. For pure argon-nitrogen sputtering, on the contrary, cubic zirconium nitride (ZrN) has been formed. Nevertheless, even though the crystal structure does not change with increasing nitrogen flow up to 80%, there is clear evidence from nitrogen incorporation from Rutherford backscattering experiments, optical spectroscopy, XRD, and x-ray reflectometry. The latter technique determines that the film density increases from 5.2 to 5.8 g/cm3 with increasing nitrogen flow from 0% to 80%. Simultaneously, the rate of sputtering increases from 0.17 to 0.6 m/s, while the film roughness decreases upon increasing N2 flow. Optical spectroscopy measurements of the film reflectance confirm that fully transparent films can be prepared up to a nitrogen flow of 80%. For these films, the band gap decreases from 4.52 to 3.59 eV with increasing N2 flow, while the refractive index at 650 nm simultaneously increases from 2.11 to 2.26. For 100% N2 flow, i.e., without any oxygen, films with a metallic reflectance are obtained.

Impact of the oxygen defects and the hydrogen concentration on the surface of tetragonal and monoclinic ZrO2 on the reduction rates of stearic acid on Ni/ZrO2.

PubMed

Foraita, Sebastian; Fulton, John L; Chase, Zizwe A; Vjunov, Aleksei; Xu, Pinghong; Baráth, Eszter; Camaioni, Donald M; Zhao, Chen; Lercher, Johannes A

2015-02-02

The role of the specific physicochemical properties of ZrO2 phases on Ni/ZrO2 has been explored with respect to the reduction of stearic acid. Conversion on pure m-ZrO2 is 1.3 times more active than on t-ZrO2 , whereas Ni/m-ZrO2 is three times more active than Ni/t-ZrO2 . Although the hydrodeoxygenation of stearic acid can be catalyzed solely by Ni, the synergistic interaction between Ni and the ZrO2 support causes the variations in the reaction rates. Adsorption of the carboxylic acid group on an oxygen vacancy of ZrO2 and the abstraction of the α-hydrogen atom with the elimination of the oxygen atom to produce a ketene is the key to enhance the overall rate. The hydrogenated intermediate 1-octadecanol is in turn decarbonylated to heptadecane with identical rates on all catalysts. Decarbonylation of 1-octadecanol is concluded to be limited by the competitive adsorption of reactants and intermediate. The substantially higher adsorption of propionic acid demonstrated by IR spectroscopy and the higher reactivity to O2 exchange reactions with the more active catalyst indicate that the higher concentration of active oxygen defects on m-ZrO2 compared to t-ZrO2 causes the higher activity of Ni/m-ZrO2 . © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

High-Temperature Wettability and Interactions between Y-Containing Ni-Based Alloys and Various Oxide Ceramics

PubMed Central

Li, Jinpeng; Gao, Ming; Li, Qingling; Bian, Weidong; Tao, Tongxiang; Zhang, Hu

2018-01-01

To obtain appropriate crucible materials for vacuum induction melting of MCrAlY alloys, four different oxide ceramics, including MgO, Y2O3, Al2O3, and ZrO2, with various microstructures were designed and characterized. The high-temperature wettability and interactions between Ni-20Co-20Cr-10Al-1.5Y alloys and oxide ceramics were studied by sessile drop experiments under vacuum. The results showed that all the systems exhibited non-wetting behavior. The contact angles were stable during the melting process of alloys and the equilibrium contact angles were 140° (MgO), 148° (Y2O3), 154° (Al2O3), and 157° (ZrO2), respectively. The interfacial reaction between the ceramic substrates and alloys occurred at high temperature. Though the ceramics had different microstructures, similar continuous Y2O3 reaction layer with thicknesses of about 25 μm at the alloy-ceramic interface in MgO, Al2O3, and ZrO2 systems formed. The average area percentage of oxides in the alloy matrices were 0.59% (MgO), 0.11% (Al2O3), 0.09% (ZrO2), and 0.02% (Y2O3), respectively. The alloys, after reacting with MgO ceramic, had the highest inclusion content, while those with the lowest content were in the Y2O3 system. Y2O3 ceramic was the most beneficial for vacuum induction melting of high-purity Y-containing Ni-based alloys. PMID:29735958

High temperature investigation of the solid/liquid transition in the PuO2-UO2-ZrO2 system

NASA Astrophysics Data System (ADS)

Quaini, A.; Guéneau, C.; Gossé, S.; Sundman, B.; Manara, D.; Smith, A. L.; Bottomley, D.; Lajarge, P.; Ernstberger, M.; Hodaj, F.

2015-12-01

The solid/liquid transitions in the quaternary U-Pu-Zr-O system are of great interest for the analysis of core meltdown accidents in Pressurised Water Reactors (PWR) fuelled with uranium-dioxide and MOX. During a severe accident the Zr-based cladding can become completely oxidised due to the interaction with the oxide fuel and the water coolant. In this framework, the present analysis is focused on the pseudo-ternary system UO2-PuO2-ZrO2. The melting/solidification behaviour of five pseudo-ternary and one pseudo-binary ((PuO2)0.50(ZrO2)0.50) compositions have been investigated experimentally by a laser heating method under pre-set atmospheres. The effects of an oxidising or reducing atmosphere on the observed melting/freezing temperatures, as well as the amount of UO2 in the sample, have been clearly identified for the different compositions. The oxygen-to-metal ratio is a key parameter affecting the melting/freezing temperature because of incongruent vaporisation effects. In parallel, a detailed thermodynamic model for the UO2-PuO2-ZrO2 system has been developed using the CALPHAD method, and thermodynamic calculations have been performed to interpret the present laser heating results, as well as the high temperature behaviour of the cubic (Pu,U,Zr)O2±x-c mixed oxide phase. A good agreement was obtained between the calculated and experimental data points. This work enables an improved understanding of the major factors relevant to severe accident in nuclear reactors.

Methane Decomposition and Carbon Growth on Y2O3, Yttria-Stabilized Zirconia, and ZrO2

PubMed Central

2014-01-01

Carbon deposition following thermal methane decomposition under dry and steam reforming conditions has been studied on yttria-stabilized zirconia (YSZ), Y2O3, and ZrO2 by a range of different chemical, structural, and spectroscopic characterization techniques, including aberration-corrected electron microscopy, Raman spectroscopy, electric impedance spectroscopy, and volumetric adsorption techniques. Concordantly, all experimental techniques reveal the formation of a conducting layer of disordered nanocrystalline graphite covering the individual grains of the respective pure oxides after treatment in dry methane at temperatures T ≥ 1000 K. In addition, treatment under moist methane conditions causes additional formation of carbon-nanotube-like architectures by partial detachment of the graphite layers. All experiments show that during carbon growth, no substantial reduction of any of the oxides takes place. Our results, therefore, indicate that these pure oxides can act as efficient nonmetallic substrates for methane-induced growth of different carbon species with potentially important implications regarding their use in solid oxide fuel cells. Moreover, by comparing the three oxides, we could elucidate differences in the methane reactivities of the respective SOFC-relevant purely oxidic surfaces under typical SOFC operation conditions without the presence of metallic constituents. PMID:24587591

A Synergistic Effect of Surfactant and ZrO2 Underlayer on Photocurrent Enhancement and Cathodic Shift of Nanoporous Fe2O3 Photoanode

PubMed Central

Shinde, Pravin S.; Lee, Su Yong; Choi, Sun Hee; Lee, Hyun Hwi; Ryu, Jungho; Jang, Jum Suk

2016-01-01

Augmenting the donor density and nanostructure engineering are the crucial points to improve solar water oxidation performance of hematite (α-Fe2O3). This work addresses the sluggish water oxidation reaction associated with hematite photoanode by tweaking its internal porosity. The porous hematite photoanodes are fabricated by a novel synthetic strategy via pulse reverse electrodeposition (PRED) method that involves incorporation of a cationic CTAB surfactant in a sulfate electrolyte and spin-coated ZrO2 underlayer (UL) on FTO. CTAB is found to be beneficial in promoting the film growth rate during PRED. Incorporation of Zr4+ ions from ZrO2 UL and Sn4+ ions from FTO into the Fe2O3 lattice via solid-state diffusion reaction during pertinent annihilation of surfactant molecules at 800 °C produced internally porous hematite films with improved carrier concentration. The porous hematite demonstrated a sustained photocurrent enhancement and a significant cathodic shift of 130 mV relative to the planar hematite under standard illumination conditions (AM 1.5G) in 1 M NaOH electrolyte. The absorption, electrochemical impedance spectroscopy and Mott-Schottky analyses revealed that the ZrO2 UL and CTAB not only increased the carrier density and light harvesting but also accelerated the surface oxidation reaction kinetics, synergistically boosting the performance of internally porous hematite photoanodes. PMID:27577967

Cubic phase stability, optical and magnetic properties of Cu-stabilized zirconia nanocrystals

NASA Astrophysics Data System (ADS)

Pramanik, Prativa; Singh, Sobhit; Joshi, Deep Chandra; Mallick, Ayan; Pisane, Kelly; Romero, Aldo H.; Thota, Subhash; Seehra, M. S.

2018-06-01

By means of experimental and ab initio investigations, we report on the cubic phase stability of Cu doped zirconia (ZrO2) at room temperature, and further characterize its structural, optical and magnetic properties. Various compositions of Zr1‑x Cu x O2 (0.01  ⩽  x  ⩽  0.25) nanocrystallites of average size  ∼16 nm were synthesized using co-precipitation technique. Thermal analysis and kinetics of crystallization revealed that the cubic phase at ambient temperature can be stabilized by using a critical calcination temperature of 500 °C for 8 h in air and a critical composition of . For x  <  x c , some undigested monoclinic phase of ZrO2 exists together with the cubic structure. However, for x  >  x c , the monoclinic CuO emerges as a secondary phase with shrinkage of unit-cell volume with increasing the Cu content. At x  =  0.05 and 500 °C calcination temperature, we observe a high degree of cubic crystallinity which breaks down into monoclinic phase with increasing calcination temperature beyond 550 °C. Electron magnetic resonance studies provide evidence for the substitution of Cu2+ (2D5/9,3d9) ions at Zr4+ sites with g, g and average g a   =  (  +  2)/3  ∼  2.1. The temperature dependence of magnetic susceptibility measurements from 2 K to 300 K exhibits Curie–Weiss behaviour whose analysis using g a   =  2.1 and spin S  =  1/2 yields x  =  0.028 and x  =  0.068 for the nominal x  =  0.05 and x  =  0.20 samples, respectively. This magnetic analysis confirms the findings from x-ray diffraction that only a part of Cu is successfully doped into cubic phase of Cu-doped ZrO2. The optical bandgap decreases with increasing x, which is due to the emergence of Cu-d states at Fermi-level near the valence bands, thus making Cu-doped zirconia a hole doped (p-type) semiconductor.

Effects of Plume Hydrodynamics and Oxidation on the Composition of a Condensing Laser-Induced Plasma

DOE PAGES

Weisz, David G.; Crowhurst, Jonathan C.; Finko, Mikhail S.; ...

2018-02-01

High-temperature chemistry in laser ablation plumes leads to vapor-phase speciation, which can induce chemical fractionation during condensation. In this work, using emission spectroscopy acquired after ablation of a SrZrO 3 target, we have experimentally observed the formation of multiple molecular species (ZrO and SrO) as a function of time as the laser ablation plume evolves. Although the stable oxides SrO and ZrO 2 are both refractory, we observed emission from the ZrO intermediate at earlier times than SrO. We deduced the time-scale of oxygen entrainment into the laser ablation plume using an 18O 2 environment by observing the in-growth ofmore » Zr 18O in the emission spectra relative to Zr 16O, which was formed by reaction of Zr with 16O from the target itself. Using temporally resolved plume-imaging, we determined that ZrO formed more readily at early times, volumetrically in the plume, while SrO formed later in time, around the periphery. Lastly, using a simple temperature-dependent reaction model, we have illustrated that the formation sequence of these oxides subsequent to ablation is predictable to first order.« less

Palladium-doped-ZrO2-multiwalled carbon nanotubes nanocomposite: an advanced photocatalyst for water treatment

NASA Astrophysics Data System (ADS)

Anku, William Wilson; Oppong, Samuel Osei-Bonsu; Shukla, Sudheesh Kumar; Agorku, Eric Selorm; Govender, Poomani Penny

2016-06-01

The photocatalytic degradation of organic pollutants from water using palladium-doped-zirconium oxide-multiwalled carbon nanotubes (Pd-ZrO2-MWCNTs) nanocomposites is presented. A series of Pd doped-ZrO2-MWCNTs nanocomposites with varying percentage compositions of Pd were prepared by the homogenous co-precipitation method. The photocatalytic applicability of the materials was investigated by the degradation of acid blue 40 dye in water under simulated solar light. The optical, morphological and structural properties of the nanocomposites were evaluated using X-ray powder diffraction, Fourier transformer infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, BET surface area analysis and (UV-Vis) spectroscopy. The Pd-ZrO2-MWCNTs nanocomposites showed enhanced photocatalytic activity toward the degradation of the acid blue 40 dye under visible light compared with bare ZrO2 and ZrO2-MWCNTs alone. The remarkable photocatalytic activity of Pd-ZrO2-MWCNTs nanocomposites in the visible light makes it an ideal photocatalyst for the removal of organic pollutants in water. The 0.5 % Pd-ZrO2-MWCNT was the most efficient photocatalyst with 98 % degradation after 3 h with corresponding K a and band gap values of 16.8 × 10-3 m-1 and 2.79 eV, respectively.

Conversion of CH4/CO2 to syngas over Ni-Co/Al2O3-ZrO2 nanocatalyst synthesized via plasma assisted co-impregnation method: Surface properties and catalytic performance

NASA Astrophysics Data System (ADS)

Rahemi, Nader; Haghighi, Mohammad; Akbar Babaluo, Ali; Fallah Jafari, Mahdi; Khorram, Sirous

2013-09-01

Ni/Al2O3 catalyst promoted by Co and ZrO2 was prepared by co-impregnation method and treated with glow discharge plasma. The catalytic activity of the synthesized nanocatalysts has been tested toward conversion of CH4/CO2 to syngas. The physicochemical characterizations like XRD, EDX, FESEM, TEM, BET, FTIR, and XPS show that plasma treatment results in smaller particle size, more surface concentration, and uniform morphology. The dispersion of nickel in plasma-treated nanocatalyst was also significantly improved, which was helpful for controlling the ensemble size of active phase atoms on the support surface. Improved physicochemical properties caused 20%-30% enhancement in activity of plasma-treated nanocatalyst that means to achieve the same H2 or CO yield, the plasma-treated nanocatalyst needed about 100 °C lower reaction temperature. The H2/CO ratio got closer to 1 at higher temperatures and finally at 850 °C H2/CO = 1 is attained for plasma-treated nanocatalyst. Plasma-treated nanocatalyst due to smaller Ni particles and strong interaction between active phase and support has lower tendency to keep carbon species on its structure and hence excellent stability can be observed for this catalyst.

Furnace Cyclic Oxidation Behavior of Multicomponent Low Conductivity Thermal Barrier Coatings

NASA Astrophysics Data System (ADS)

Zhu, Dongming; Nesbitt, James A.; Barrett, Charles A.; McCue, Terry R.; Miller, Robert A.

2004-03-01

Ceramic thermal barrier coatings (TBCs) will play an increasingly important role in advanced gas turbine engines due to their ability to further increase engine operating temperatures and reduce cooling, thus helping achieve future engine low emission, high efficiency, and improved reliability goals. Advanced multicomponent zirconia (ZrO2)-based TBCs are being developed using an oxide defect clustering design approach to achieve the required coating low thermal conductivity and high-temperature stability. Although the new composition coatings were not yet optimized for cyclic durability, an initial durability screening of the candidate coating materials was conducted using conventional furnace cyclic oxidation tests. In this paper, furnace cyclic oxidation behavior of plasma-sprayed ZrO2-based defect cluster TBCs was investigated at 1163°C using 45 min hot-time cycles. The ceramic coating failure mechanisms were studied using scanning electron microscopy (SEM) combined with x-ray diffraction (XRD) phase analysis after the furnace tests. The coating cyclic lifetime is also discussed in relation to coating processing, phase structures, dopant concentration, and other thermo-physical properties.

Ferroelectric and reliability properties of metal-organic chemical vapor deposited Pb(Zr0.15Ti0.85)O3 thin films grown in the self-regulation process window

NASA Astrophysics Data System (ADS)

Zhao, Jin Shi; Lee, Hyun Ju; Sim, Joon Seop; Lee, Keun; Hwang, Cheol Seong

2006-04-01

Ferroelectric reliability of Pb(Zr0.15Ti0.85)O3 films grown by metal-organic chemical vapor deposition at 570°C on an Ir electrode in the self-regulation process window [constant Pb concentration irrespective of the precursor input ratio (Pb /(Zr+Ti), PIR)] was studied. Although the Pb composition and crystallinity of the films grown under different PIR were almost identical, the film grown under a PIR which was near the center of the process window showed the best ferroelectric performance. X-ray photoelectron spectroscopy showed that the films grown at lower and higher PIR have residual ZrO2 and metallic Pb, respectively, which resulted in reduced remanent polarization and reliability.

Effect of addition of nano-hydroxyapatite on physico-chemical and antibiofilm properties of calcium silicate cements.

PubMed

Guerreiro-Tanomaru, Juliane Maria; Vázquez-García, Fernando Antonio; Bosso-Martelo, Roberta; Bernardi, Maria Inês Basso; Faria, Gisele; Tanomaru, Mario

2016-01-01

Mineral Trioxide Aggregate (MTA) is a calcium silicate cement composed of Portland cement (PC) and bismuth oxide. Hydroxyapatite has been incorporated to enhance mechanical and biological properties of dental materials. This study evaluated physicochemical and mechanical properties and antibiofilm activity of MTA and PC associated with zirconium oxide (ZrO2) and hydroxyapatite nanoparticles (HAn). White MTA (Angelus, Brazil); PC (70%)+ZrO2 (30%); PC (60%)+ZrO2 (30%)+HAn (10%); PC (50%)+ZrO2 (30%)+HAn (20%) were evaluated. The pH was assessed by a digital pH-meter and solubility by mass loss. Setting time was evaluated by using Gilmore needles. Compressive strength was analyzed by mechanical test. Samples were radiographed alongside an aluminum step wedge to evaluate radiopacity. For the antibiofilm evaluation, materials were placed in direct contact with E. faecalis biofilm induced on dentine blocks. The number of colony-forming units (CFU mL-1) in the remaining biolfilm was evaluated. The results were submitted to ANOVA and the Tukey test, with 5% significance. There was no difference in pH levels of PC+ZrO2, PC+ZrO2+HAn (10%) and PC+ZrO2+HAn (20%) (p>0.05) and these cements presented higher pH levels than MTA (p<0.05). The highest solubility was observed in PC+ZrO2+HAn (10%) and PC+ZrO2+HAn (20%) (p<0.05). MTA had the shortest initial setting time (p<0.05). All the materials showed radiopacity higher than 3 mmAl. PC+ZrO2 and MTA had the highest compressive strength (p<0.05). Materials did not completely neutralize the bacterial biofilm, but the association with HAn provided greater bacterial reduction than MTA and PC+ZrO2 (p<0.05) after the post-manipulation period of 2 days. The addition of HAn to PC associated with ZrO2 harmed the compressive strength and solubility. On the other hand, HAn did not change the pH and the initial setting time, but improved the radiopacity (HAn 10%), the final setting time and the E. faecalis antibiofilm activity of the cement.

Terbium content affects the luminescence properties of ZrO2:Tb nanoparticles for mammary cancer imaging in mice

NASA Astrophysics Data System (ADS)

Kaszewski, Jarosław; Borgstrom, Emanuel; Witkowski, Bartłomiej S.; Wachnicki, Łukasz; Kiełbik, Paula; Slonska, Anna; Domino, Malgorzata A.; Narkiewicz, Urszula; Gajewski, Zdzislaw; Hochepied, Jean-François; Godlewski, Michał M.; Godlewski, Marek

2017-12-01

The use of nanoparticles in medicine is a rapidly growing research field with numerous potential applications, especially in the field of cancer diagnosis and therapy. Nanoparticles can be intrinsically diagnostic of therapeutic, or they can be conjugated with diagnostic or therapeutic compounds. Nanoparticles may also passively or actively target tumor cells specifically using the enhanced permeation and retention (EPR) effect, or the addition of targeting ligands to their surface. This may provide a diagnostic or/and therapeutic tools to target primary as well as metastatic tumors. The transport, distribution and toxicity of nanoparticles depends greatly on their size and composition, thus every new formulation needs to be extensively researched. This work was focused on the development of Tb-doped ZrO2 nanoparticles (NPs) for application in cancer imaging. Obtained nanoparticles were below 10 nm with very low influence of Tb concentration on size. Terbium stabilization of ZrO2 had influence on the luminescence properties of obtained material. Partially stabilized zirconium dioxide exhibited broad host related emission peaking at 500 nm, disappearing with the terbium content. We confirmed alimentary absorption and wide distribution of luminescent ZrO2:Tb nanoparticles in mice with their gradual accumulation in the experimentally induced mammary cancers. Furthermore, a high concentration of NPs was found within the lung metastases as opposed to healthy lung tissue, where no NPs-related signal was observed.

Impact of lysozyme on stability mechanism of nanozirconia aqueous suspension

NASA Astrophysics Data System (ADS)

Szewczuk-Karpisz, Katarzyna; Wiśniewska, Małgorzata

2016-08-01

The effect of lysozyme (LSZ) presence on the zirconium(IV) oxide (ZrO2) aqueous suspension stability was examined. The applied zirconia contains mesopores (with a diameter about 30 nm) and its mean particle size is about 100 nm. To determine the stability mechanism of ZrO2 suspension in the biopolymer presence, the adsorption and electrokinetic (surface charge density and zeta potential) measurements were performed in the pH range 3-10. The lysozyme adsorption on the nanozirconia surface proceeds mainly through electrostatic forces. Under solid-polymer repulsion conditions, there is no adsorption of lysozyme (pH < 6, CNaCl 0.01 mol/dm3). The increase of solution ionic strength to 0.2 mol/dm3 causes screening of unfavourable forces and biopolymer adsorption becomes possible. The LSZ addition to the ZrO2 suspension influences its stability. At pH 3, 4.6 and 7.6, slight improvement of the system stability was obtained. In turn, at pH 9 considerable destabilization of nanozirconia particles covered by polymeric layers occurs.

Effect of Zirconia Nanoparticles in Epoxy-Silica Hybrid Adhesives to Join Aluminum Substrates

PubMed Central

Figueroa-Lara, José de Jesús; Torres-Rodríguez, Miguel

2017-01-01

This research presents the interaction of the epoxy polymer diglicydil ether of bisphenol-A (DGEBA) with silica (SiO2) nanoparticles plus zirconia (ZrO2) nanoparticles obtained via the sol-gel method in the synthesis of an epoxy-silica-zirconia hybrid adhesive cured with polyamide. ZrO2 nanoparticles were added to the epoxy-silica hybrid adhesive produced in situ to modify the apparent shear strength of two adhesively bonded aluminum specimens. The results showed that the addition of different amounts of ZrO2 nanoparticles increased the shear strength of the adhesively bonded aluminum joint, previously treated by sandblasting, immersion in hot water and silanized with a solution of hydrolyzed 3-glycidoxipropyltrimethoxysilane (GPTMS). The morphology and microstructure of the nanoparticles and aluminum surfaces were examined by scanning electron microscopy (SEM), and elemental analysis was performed with the Energy-dispersive X-ray spectroscopy (EDS) detector; the chemical groups were investigated during the aluminum surface modification using Fourier transform infrared spectroscopy (FTIR). PMID:28953243

Analysis of the ceramic layer microstructure influence on plasma spray thermal barrier coating performance

NASA Astrophysics Data System (ADS)

Bogdanovich, V. I.; Giorbelidze, M. G.

2017-12-01

This paper outlines the results of analysis and describes the structure of the thermal protection coatings formed by atomic ion stream deposition in vacuum, and plasma thermal spraying method. Crystallite structure features are considered along with the crystallite dimensions, spatial orientation, and position of the boundaries between separate crystallites. Discontinuity, volume, and morphology of the pores has been evaluated. Experimental studies have been accomplished using various fractions of the powder-like material ZrO2 - 8%Y2O3. The influence of the coating microstructure on the coating performance has been analyzed, such as adhesive strength, thermal stability, and thermal conductivity.

Desulfurization from thiophene by SO(4)(2-)/ZrO(2) catalytic oxidation at room temperature and atmospheric pressure.

PubMed

Wang, Bo; Zhu, Jianpeng; Ma, Hongzhu

2009-05-15

Thiophene, due to its poison, together with its combustion products which causes air pollution and highly toxic characteristic itself, attracted more and more attention to remove from gasoline and some high concentration systems. As the purpose of achieving the novel method of de-thiophene assisted by SO(4)(2-)/ZrO(2) (SZ), three reactions about thiophene in different atmosphere at room temperature and atmospheric pressure were investigated. SO(4)(2-)/ZrO(2) catalyst were synthesized and characterized by X-ray photoelectron spectroscopy (XPS), Fourier transformation infrared spectroscopy (FT-IR), X-ray diffraction (XRD) and scanning electron microscope (SEM). The products were detected by gas chromatography-mass spectrometry (GC-MS). XP spectra show that ozone-catalyst system (SZO) have two forms of sulfur element (S(6+) and S(2-)) on the catalyst surface, which distinguished from that of air-catalyst system (SZA) and blank-catalyst system (SZB) (S(6+)). And the results of GC-MS exhibited that some new compounds has been produced under this extremely mild condition. Especially, many kinds of sulfur compounds containing oxygen, that is easier to be extracted by oxidative desulfurization (ODS), have been detected in the SZA-1.5h and SZB-3h system. In addition, some long chain hydrocarbons have also been detected. While in SZO-0.5h system, only long chain hydrocarbons were found. The results show that total efficiency of desulfurization from thiophene with ozone near to 100% can be obtained with the SO(4)(2-)/ZrO(2) catalytic oxidation reaction.

A stable solid acid material: Sulfated ZrO2 dispersed on alumina nanotubes

NASA Astrophysics Data System (ADS)

Feng, Yu; Jiaqi, Chen; Xu, Wang; Rui-Feng, Li

2017-02-01

A tubular solid acid catalyst was designed by loading sulfated zirconia into γ-Al2O3 nanotubes using the method of stepwise deposition. The XRD, N2 adsorption-desorption characterization demonstrated that introducing alumina nanotube and SO4 2- anions have played an important role in stabilizing the metastable tetragonal ZrO2 phase, and the sulfated zirconia on the surface of the γ-Al2O3 nanotube has high dispersion and stability. The catalyst reused repeatedly possesses large amounts of acid sites and good acidity, exhibiting high catalytic activity and stability for isopropylbenzene cracking.

Creep of plasma sprayed zirconia

NASA Technical Reports Server (NTRS)

Firestone, R. F.; Logan, W. R.; Adams, J. W.

1982-01-01

Specimens of plasma-sprayed zirconia thermal barrier coatings with three different porosities and different initial particle sizes were deformed in compression at initial loads of 1000, 2000, and 3500 psi and temperatures of 1100 C, 1250 C, and 1400 C. The coatings were stabilized with lime, magnesia, and two different concentrations of yttria. Creep began as soon as the load was applied and continued at a constantly decreasing rate until the load was removed. Temperature and stabilization had a pronounced effect on creep rate. The creep rate for 20% Y2O3-80% ZrO2 was 1/3 to 1/2 that of 8% Y2O3-92% ZrO2. Both magnesia and calcia stabilized ZrO2 crept at a rate 5 to 10 times that of the 20% Y2O3 material. A near proportionality between creep rate and applied stress was observed. The rate controlling process appeared to be thermally activated, with an activation energy of approximately 100 cal/gm mole K. Creep deformation was due to cracking and particle sliding.

Development of a plasma sprayed ceramic gas path seal for high pressure turbine application

NASA Technical Reports Server (NTRS)

Shiembob, L. T.

1978-01-01

Development of the plasma sprayed graded, layered ZRO2/CoCrAlY seal system for gas turbine engine blade tip seal applications up to 1589 K (2400 F) surface temperature was continued. The effect of changing ZRO2/CoCrAlY ratios in the intermediate layers on thermal stresses was evaluated analytically with the goal of identifying the materials combinations which would minimize thermal stresses in the seal system. Three methods of inducing compressive residual stresses in the sprayed seal materials to offset tensile thermal stresses were analyzed. The most promising method, thermal prestraining, was selected based upon potential, feasibility and complexity considerations. The plasma spray equipment was modified to heat, control and monitor the substrate temperature during spraying. Specimens were fabricated and experimentally evaluated to: (1) substantiate the capability of the thermal prestrain method to develop compressive residual stresses in the sprayed structure and (2) define the effect of spraying on a heated substate on abradability, erosion and thermal shock characteristics of the seal system. Thermal stress analysis, including residual stresses and material properties variations, was performed and correlated with thermal shock test results. Seal system performance was assessed and recommendations for further development were made.

Effect of Surface Forces on the Rheology of Particle-Liquid Systems and the Consolidation of Ceramic Powders

DTIC Science & Technology

1994-01-31

isxeduced by the addition of citric acid, a potential determining ion. The addition of potassium nitrate, an indifferent ion, did not affect the yield...Leong, T.W. Healy, D.V. Boger, "Surface Chemistry and Rheology of ZrO2 Suspensions Containing Polyacrylate : Effects of Molecular Weight and ZrO2...REPORT DOCUMENTATION PAGE Fr 1 940131 ANNUAL REPORT 2/l/93-1/31/94 "EFFECT OF SURFACE FORCES ON THE RHEOLOGY OF PARTICLE-I LIQUID SYSTEMS AND THE

Effect of thermal cycling on ZrO2-Y2O3 thermal barrier coatings

NASA Technical Reports Server (NTRS)

Mcdonald, G.; Hendricks, R. C.

1980-01-01

The paper studies the comparative life of plasma-sprayed ZrO2-Y2O3 thermal barrier coatings on NiCrAlY bond coats on Rene 41 in short (4 min) and long (57 min) thermal cycles at 1040 C in a 0.3-Mach flame. Attention is given to determining the effect of short- and long-duration cycles on ZrO2-Y2O3 coatings, the cause of any cycle frequency effects, and methods to improve tolerance to thermal stress. Short cycles greatly reduced the life of the ceramic coating in terms of time at temperatures as compared to longer cycles, the failed coating indicating compressive failure. The experiments and stress calculations show that repeatedly subjecting a ceramic coating to high rates of initial heating has a more destructive influence on the coating than sustained operation at temperature. The effect of such thermal compressive stresses might be minimized through coating deposition and thickness control and by turbine cycle measurement to keep starting heating rates below critical values.

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

Lemonidou, Angeliki A.; Vagia, Ekaterini C.; Lercher, Johannes A.

Reforming of acetic acid was investigated on Rh supported on CeO2-ZrO2 modified with 3 wt % La. The active catalyst converted acetic acid to H-2-rich gas and hardly formed coke. The low rate of coke formation is concluded to be related to the presence of redox-active oxygen limiting the concentration of coke precursors. Temperature-programmed O-18(2)) isotope exchange measurements showed that the La2O3 and Rh enhanced the mobility of lattice oxygen compared with that of the parent CeO2-ZrO2. Ketonization and decarboxylation of acetic acid are the dominating reactions over the latter up to 600 degrees C, whereas above 600 degrees C,more » steam reforming and water gas shift also contribute. Over 0.5 wt % Rh on La2O3/CeO2-ZrO2, reforming and water gas shift reactions dominate, even below 300 degrees C, producing mostly H-2 and CO2. Using isotope labeling, it is shown that acetic acid adsorbs dissociatively on Rh, forming acetates, which sequentially decarboxylate and form surface methyl groups. The latter are in turn converted to CO, CO2, and H-2.« less

Exhaust gas oxygen sensors

NASA Astrophysics Data System (ADS)

Hetrick, Robert E.; Hohnke, D. K.; Logothetis, E. M.

1981-01-01

Ceramic ZrO2, TiO2 and related oxides with suitable O2-sensitive electrical properties have found important applications in devices for measuring exhaust-gas O2 concentration. For example, such devices are key components in feedback control systems that would maintain the intake air-to-fuel ratio near the stoichiometric value where regulated emissions can be minimized. The physical principles underlying the operation of ZrO2 based O2-concentration cells and TiO2-based resistive devices for the stoichiometric application are described. Finally, a device based on electrochemical O2 pumping is discussed which may be useful for A/F control in the fuel-efficient lean region.

CO 2 hydrogenation over oxide-supported PtCo catalysts: The role of the oxide support in determining the product selectivity

DOE PAGES

Kattel, Shyam; Yu, Weiting; Yang, Xiaofang; ...

2016-05-09

By simply changing the oxide support, the selectivity of a metal–oxide catalysts can be tuned. For the CO 2 hydrogenation over PtCo bimetallic catalysts supported on different reducible oxides (CeO 2, ZrO 2, and TiO 2), replacing a TiO 2 support by CeO 2 or ZrO 2 selectively strengthens the binding of C,O-bound and O-bound species at the PtCo–oxide interface, leading to a different product selectivity. Lastly, these results reveal mechanistic insights into how the catalytic performance of metal–oxide catalysts can be fine-tuned.

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.

Assessment of solid/liquid equilibria in the (U, Zr)O2+y system

NASA Astrophysics Data System (ADS)

Mastromarino, S.; Seibert, A.; Hashem, E.; Ciccioli, A.; Prieur, D.; Scheinost, A.; Stohr, S.; Lajarge, P.; Boshoven, J.; Robba, D.; Ernstberger, M.; Bottomley, D.; Manara, D.

2017-10-01

Solid/liquid equilibria in the system UO2sbnd ZrO2 are revisited in this work by laser heating coupled with fast optical thermometry. Phase transition points newly measured under inert gas are in fair agreement with the early measurements performed by Wisnyi et al., in 1957, the only study available in the literature on the whole pseudo-binary system. In addition, a minimum melting point is identified here for compositions near (U0.6Zr0.4)O2+y, around 2800 K. The solidus line is rather flat on a broad range of compositions around the minimum. It increases for compositions closer to the pure end members, up to the melting point of pure UO2 (3130 K) on one side and pure ZrO2 (2970 K) on the other. Solid state phase transitions (cubic-tetragonal-monoclinic) have also been observed in the ZrO2-rich compositions X-ray diffraction. Investigations under 0.3 MPa air (0.063 MPa O2) revealed a significant decrease in the melting points down to 2500 K-2600 K for increasing uranium content (x(UO2)> 0.2). This was found to be related to further oxidation of uranium dioxide, confirmed by X-ray absorption spectroscopy. For example, a typical oxidised corium composition U0.6Zr0.4O2.13 was observed to solidify at a temperature as low as 2493 K. The current results are important for assessing the thermal stability of the system fuel - cladding in an oxide based nuclear reactor, and for simulating the system behaviour during a hypothetical severe accident.

Photo-, sono- and sonophotocatalytic degradation of methylene blue using Fe3O4/ZrO2 composites catalysts

NASA Astrophysics Data System (ADS)

Kristianto, Y.; Taufik, A.; Saleh, R.

2017-07-01

In the present work, magnetite material Fe3O4/ZrO2 with various molar ratios was prepared by the two-step method (sol-gel followed by the ultrasonic-assisted method). The as-prepared samples were fairly characterized by various characterization methods, such as X-ray Diffraction (XRD), Vibrating Sample Magnetometer (VSM), Fourier Transform Infrared (FT-IR) and Thermal Gravimetric Analysis (TGA). The catalytic performance of the as-prepared samples was evaluated based on the degradation of methylene blue under UV light, ultrasound and combination of UV and ultrasound irradiation. The results revealed that the sample with Fe3O4:ZrO2 molar ratio of 0.5:1 showed the best catalytic performance under UV, ultrasound and UV + ultrasound irradiation. The degradation of methylene blue follows the order: sonophotocatalytic > sonocatalytic > photocatalytic. In addition, the effect of various scavengers has also been studied. Furthermore, all prepared samples could be used as a convenient recyclable catalyst.

Properties of zirconia-toughened-alumina prepared via powder processing and colloidal processing routes.

PubMed

Rafferty, A; Alsebaie, A M; Olabi, A G; Prescott, T

2009-01-15

Alumina-zirconia composites were prepared by two routes: powder processing, and colloidal processing. Unstabilised zirconia powder was added to alumina in 5 wt%, 10 wt% and 20 wt% quantities. For the colloidal method, zirconium(IV) propoxide solution was added to alumina powder, also in 5 wt%, 10 wt% and 20 wt% quantities. Additions of glacial acetic acid were needed to form stable suspensions. Suspension stability was verified by pH measurements and sedimentation testing. For the powder processed samples Vickers hardness decreased indefinitely with increasing ZrO(2) additions, but for colloidal samples the hardness at first decreased but then increased again above >10 wt% ZrO(2). Elastic modulus (E) values decreased with ZrO(2) additions. However, samples containing 20 wt% zirconia prepared via a colloidal method exhibited a much higher modulus than the powder processed equivalent. This was due to the homogeneous dispersion of zirconia yielding a sample which was less prone to microcracking.

Photoemission properties of Eu-doped Zr1- x Ce x O2 (x = 0-0.2) nanoparticles prepared by hydrothermal method

NASA Astrophysics Data System (ADS)

Ozawa, Masakuni; Matsumoto, Masashi; Hattori, Masatomo

2018-01-01

Photoluminescent Eu-doped ZrO2 and Zr1- x Ce x O2 (x = 0-0.2) nanoparticles were prepared by a hydrothermal method. X-ray diffraction and Raman spectra indicated the formation of tetragonal crystals of ZrO2 and its solid solutions with a grain size of less than 10 nm diameter after heat treatment at 400 °C. The photoemission spectra of Zr1- x Ce x O2:Eu3+ nanocrystalline samples showed the typical emission of Eu3+ ions assigned to 5D0 → 7F1 (590 nm) and 5D0 → 7F2 (610 nm) transitions and additional emissions of 5D0 → 7F J with higher J of 3-5. Increasing the CeO2 concentration reduced the emission intensity, and the emission peak shift was affected by a local lattice distortion, i.e., CeO2 concentration. The present study provided fundamental knowledge that is expected to enable the fabrication of ZrO2-based nanocrystal phosphor materials and a measure for controlling the emission peak shift and intensity in oxide fluorite-based phosphor.