Evaluation of CaO-CeO2-partially stabilized zirconia thermal barrier coatings

Plasma sprayable powders were prepared from ZrO2-CaO-CeO2 system using an organic binder and coated onto stainless steel substrates previously coated by a bond coat (Ni 22Cr 20Al 1.0Y) using plasma spraying. The coatings exhibited good thermal barrier characteristics and excellent resistance to thermal shock at 1000 degrees C under simulated laboratory conditions (90 half hour cycles without failure) and at 1200 degrees C under accelerated burner rig test conditions (500 2 min cycles without failure). No destabilization of cubic/tetragonal ZrO2 phase fraction occured either during the long hours (45 h cumulative) or the large number of thermal shock tests. Growth of a distinct SiO2 rich region within the ceramic was observed in the specimens thermal shock cycled at 1000 degrees C apart from mild oxidation of the bond coat. The specimens tested at 1200 degrees C had a glassy appearance on the top surface and exhibited severe oxidation of the bond coat at the ceramic-bond coat interface. The glassy appearance of the surface is due to the formation of a liquid silicate layer attributable to the impurity phase present in commercial grade ZrO2 powder. These observations are supported by SEM analysis and quantitative EDAX data.

Use of S1 nuclease and formamide in combination for the reassociation studies on GC-rich DNA

The optimal parameters in the use of nuclease S1 in DNA reassociation kinetics in the presence of formamide have been determined. The conditions are especially suitable for the study of DNA rich in mole percent GC. A 10-fold dilution of the reassociation samples leading to a decrease in both NaCl and formamide concentrations, consequently resulting in a lowering of Tm by only 1.5°C, and the S1 digestion at temperatures identical to the reassociation assay in order to retain the stability of the duplex, are two important aspects of this system. Under these conditions, the kinetics of reassociation followed the theoretically predicted pattern, while the earlier reported methods have shown lower values.

Noble Metal Ionic Catalysts

Because of growing environmental concerns and increasingly stringent regulations governing auto emissions, new more efficient exhaust catalysts are needed to reduce the amount of pollutants released from internal combustion engines. To accomplish this goal, the major pollutants in exhaust-CO, NOx, and unburned hydrocarbons-need to be fully converted to CO2, N-2, and H2O. Most exhaust catalysts contain nanocrystalline noble metals (Pt, Pd, Rh) dispersed on oxide supports such as Al2O3 or SiO2 promoted by CeO2. However, in conventional catalysts, only the surface atoms of the noble metal particles serve as adsorption sites, and even in 4-6 nm metal particles, only 1/4 to 1/5 of the total noble metal atoms are utilized for catalytic conversion. The complete dispersion of noble metals can be achieved only as ions within an oxide support. In this Account, we describe a novel solution to this dispersion problem: a new solution combustion method for synthesizing dispersed noble metal ionic catalysts. We have synthesized nanocrystalline, single-phase Ce1-xMxO2-delta and Ce1-x-yTiyMxO2-delta (M = Pt, Pd, Rh; x = 0,01-0.02, delta approximate to x, y = 0.15-0.25) oxides in fluorite structure, In these oxide catalysts, pt(2+), Pd2+, or Rh3+ ions are substituted only to the extent of 1-2% of Ce4+ ion. Lower-valent noble metal ion substitution in CeO2 creates oxygen vacancies. Reducing molecules (CO, H-2, NH3) are adsorbed onto electron-deficient noble metal ions, while oxidizing (02, NO) molecules are absorbed onto electron-rich oxide ion vacancy sites. The rates of CO and hydrocarbon oxidation and NOx reduction (with >80% N-2 selectivity) are 15-30 times higher in the presence of these ionic catalysts than when the same amount of noble metal loaded on an oxide support is used. Catalysts with palladium ion dispersed in CeO2 or Ce1-xTixO2 were far superior to Pt or Rh ionic catalysts. Therefore, we have demonstrated that the more expensive Pt and Rh metals are not necessary in exhaust catalysts. We have also grown these nanocrystalline ionic catalysts on ceramic cordierite and have reproduced the results we observed in powder material on the honeycomb catalytic converter. Oxygen in a CeO2 lattice is activated by the substitution of Ti ion, as well as noble metal ions. Because this substitution creates longer Ti-O and M-O bonds relative to the average Ce-O bond within the lattice, the materials facilitate high oxygen storage and release. The interaction among M-0/Mn+, Ce4+/Ce3+, and Ti4+/Ti3+ redox couples leads to the promoting action of CeO2, activation of lattice oxygen and high oxygen storage capacity, metal support interaction, and high rates of catalytic activity in exhaust catalysis.

Facile conversion of electron rich benzylic hydrocarbons to carbonyl compounds by peroxydisulphate and copper ions

A convenient method for the conversion of electron rich benzylic hydrocarbons to carbonyl compounds is reported.

Separation of 5-methylcytosine-rich DNA using immobilized antibody

Anti-(5-methylcytosine) antibodies were immobilized on glutaraldehyde-activated Indion 48-R, a polystyrene resin with amino groups. Immobilized antibody was very stable and could be used several times without any apparent change in the initial binding capacity of the antibody-matrix. Fractions of total DNA from various animal and plant sources were retained on this column and could be eluted quantitatively with 1.0 m NaCl. The bound fraction was further characterized for its 5-methylcytosine content by restriction enzyme digestion patterns.

Experimental investigation of catalytic and non-catalytic surface reactions on SiO2 thin films with shock heated oxygen gas

The present study is to investigate the interaction of strong shock heated oxygen on the surface of SiO2 thin film. The thermally excited oxygen undergoes a three-body recombination reaction on the surface of silicon dioxide film. The different oxidation states of silicon species on the surface of the shock-exposed SiO2 film are discussed based on X-ray Photoelectron Spectroscopy (XPS) results. The surface morphology of the shock wave induced damage at the cross section of SiO2 film and structure modification of these materials are analyzed using scanning electron microscopy and ion microscopy. Whether the surface reaction of oxygen on SiO2 film is catalytic or non-catalytic is discussed in this paper.

Spatiotemporal Organization of AT- and GC-rich DNA and Their Association With Transition Proteins TP1 and TP2 in Rat Condensing Spermatids

Transition protein 1 (TP1) and TP2 replace histones during midspermiogenesis (stages 12-15) and are finally replaced by protamines. TPs play a predominant role in DNA condensation and chromatin remodeling during mammalian spermiogenesis. TP2 is a zinc metalloprotein with two novel zinc finger modules that condenses DNA in vitro in a GC-preference manner. TP2 also localizes to the nucleolus in transfected HeLa and Cos-7 cells, suggesting a GC-rich preference, even in vivo. We have now studied the localization pattern of TP2 in the rat spermatid nucleus. Colocalization studies using GC-selective DNA-binding dyes chromomycin A3 and 7-amino actinomycin D and an AT-selective dye, 4',6-diamidino-2-phenylindole, indicate that TP2 is preferentially localized to GC-rich sequences. Interestingly, as spermatids mature, TP2 and GC-rich DNA moves toward the nuclear periphery, and in the late stages of spermatid maturation, TP2 is predominantly localized at the nuclear periphery. Another interesting observation is the mutually exclusive localization of GC- and AT-rich DNA in the elongating and elongated spermatids. A combined immunofluorescence experiment with anti-TP2 and anti-TP1 antibodies revealed several foci of overlapping localization, indicating that TP1 and TP2 may have concerted functional roles during chromatin remodeling in mammalian spermiogenesis.

Effect of the addition of B2O3 and BaO-B2O3-SiO2 glasses on the microstructure and dielectric properties of giant dielectric constant material CaCu3Ti4O12

The effect of the addition of glassy phases on the microstructure and dielectric properties of CaCu3Ti4O12 (CCTO) ceramics was investigated. Both single-component (B2O3) and multi-cornponent (30wt% BaO-60wt% B2O3-10wt% SiO2 (BBS)) glass systems were chosen to study their effect on the density, microstructure and dielectric properties of CCTO. Addition of an optimum amount of B2O3 glass facilitated grain growth and an increase in dielectric constant. However, further increase in the B2O3 content resulted in its segregation at the grain boundaries associated with a reduction in the grain size. In contrast, BBS glass addition resulted in well-faceted grains and increase in the dielectric constant and decrease in the dielectric loss. An internal barrier layer capacitance (IBLC) model was invoked to correlate the dielectric constant with the grain size in these samples. (c) 2007 Elsevier Inc. All rights reserved.

'Wet N2O oxidation' process and interface state density characterization of nanoscale nitrided SiO2 for flash memory application

In this paper we first present the 'wet N2O' furnace oxidation process to grow nitrided tunnel oxides in the thickness range 6 to 8 nm on silicon at a temperature of 800 degrees C. Electrical characteristics of MOS capacitors and MOSFETs fabricated using this oxide as gate oxide have been evaluated and the superior features of this oxide are ascertained The frequency response of the interface states, before and after subjecting the MOSFET gate oxide to constant current stress, is studied using a simple analytical model developed in this work.

Structural, ferroelectric and optical properties of Bi2VO5.5 thin films deposited on platinized silicon {(100) Pt/TiO2/SiO2/Si} substrates

Bismuth vanadate (Bi2VO5.5, BVO) thin films have been deposited by a pulsed laser ablation technique on platinized silicon substrates. The surface morphology of the BVO thin films has been studied by atomic force microscopy (AFM). The optical properties of the BVO thin films were investigated using spectroscopic ellipsometric measurements in the 300–820 nm wavelength range. The refractive index (n), extinction coefficient (k) and thickness of the BVO thin films have been obtained by fitting the ellipsometric experimental data in a four-phase model (air/BVOrough/BVO/Pt). The values of the optical constants n and k that were determined through multilayer analysis at 600 nm were 2.31 and 0.056, respectively. For fitting the ellipsometric data and to interpret the optical constants, the unknown dielectric function of the BVO films was constructed using a Lorentz model. The roughness of the films was modeled in the Brugmann effective medium approximation and the results were compared with the AFM observations.

The effect of ageing on microstructure and nanoindentation behaviour of dc magnetron sputter deposited nickel rich NiTi films

Nickel rich NiTi films were sputter deposited on p-doped Si left angle bracket1 0 0right-pointing angle bracket substrates maintained at 300 °C. The films were subsequently solution treated at 700 °C for 30 min followed by ageing at 400 and 500 °C for 5 h. The microstructure of the films was examined by TEM and these studies revealed that the NiTi films were mostly amorphous in the as-deposited condition. The subsequent solution treatment and ageing resulted in crystallization of the films with the film aged at 400 °C exhibiting nanocrystalline grains and three phases viz. B2 (austenite), R and Ni3Ti2 whereas the film aged at 500 °C shows micron sized grains and two phases viz. R and Ni3Ti2. Nanoindentation studies revealed that the nature of the load versus indentation depth response for the films aged at 400 and 500 °C was different. For the same load, the indenter penetrated to a much greater depth for the film aged at 400 °C as compared to the film aged at 500 °C. Also the ratio of the residual indentation depth (hf) to maximum indentation depth (hmax) is lower for the film aged at 400 °C as compared to the film aged at 500 °C. This was attributed to the occurrence of stress induced martensitic transformation of the B2 phase present in the film aged at 400 °C during indentation loading which results in a transformation strain in addition to the normal elastic and plastic strains and its subsequent recovery on unloading. The hardness and elastic modulus measured using the Oliver and Pharr analysis was also found to be lower for the film aged at 400 °C as compared to the film aged at 500 °C which was also primarily attributed to the same effect.

Phosphorus Partition between Liquid Steel and CaO-SiO2-P2O5-MgO Slag Containing Low FeO

CaO-SiO2-FeOx-P2O5-MgO bearing slags are typical in the basic oxygen steelmaking (BOS) process. The partition ratio of phosphorus between slag and steel is an index of the phosphorus holding capacity of the slag, which determines the phosphorus content achievable in the finished steel. The influences of FeO concentration and basicity on the equilibrium phosphorus partition ratios were experimentally determined at temperatures of 1873 and 1923 K, for conditions of MgO saturation. The partition ratio initially increased with basicity but attained a constant value beyond basicity of 2.5. An increase in FeO concentration up to approximately 13 to 14 mass pet was beneficial for phosphorus partition.

Modular design of synthetic protein mimics. Crystal structures, assembly, and hydration of two 15- and 16-residue apolar, leucyl-rich helical peptides

Two IS- and 16-residue peptides containing a-aminoisobutyric acid (Aib) have been synthesized, as part of a strategy to construct stereochemically rigid peptide helices, in a modular approach to design of protein mimics. The peptides Boc-(Val-Ala-Leu-Aib),-OMe ( I ) and Boc-Val-Ala-Leu-Aib-Val-Ala-Leu-(Val-Ala-Leu-Aib()11z)- OhaMvee been crystallized.Both crystals are stable only in the presence of mother liquor or water. The crystal data are as follows. I: C78H140N16019~2H20,P2,, a = 16.391 (3) A, b = 16.860 (3) A, c = 18.428 (3) A, p = 103.02 (I)O, Z = 2, R = 9.6% for 3445 data with lFol >30(F), resolution 0.93 A. 11: C7,Hl,,N,S018.7.5H,0, C2221, a = 18.348 ( 5 ) A, b = 47.382 (1 1) A, c = 24.157 ( 5 ) A, Z =8, R = l0,6%, for 3147 data with lFol > 3a(F), resolution 1.00 A. The 15-residue peptide (11) is entirely a helical, while the 16-residue peptide ( I ) has a short segment of 310 helix at the N terminus. The packing of the helices in the crystals is rather incfficicnt with no particular attractions between Leu-Leu side chains, or any other pair. Both crystals have fairly large voids, which are filled with water molecules in a disordered fashion. Water molecule sites near the polar head-to-tail regions are well detcrmined, those closer to the hydrophobic side chains less so and a number of possible water sites in the remaining "empty" space are not determined. No interdigitation of Leu side chains is observed in the crystal as is hypothesized in the "leucine zipper" class of DNA binding proteins.

Stereochemical Analysis of Higher α,α-Dialkylglycine Containing Peptides. Characterization of Local Helical Conformations at Dipropylglycine Residues and Observation of a Novel Hydrated Multiple β-Turn Structure in Crystals of a Glycine Rich Peptide

The peptide Boc-Gly-Dpg-Gly-Gly-Dpg-Gly-NHMe (1) has been synthesized to examine the conformational preferences of Dpg residues in the context of a poor helix promoting sequence. Single crystals of 1 were obtained in the space group P21/c with a = 13.716(2) Å, b = 12.960(2) Å, c = 22.266(4) Å, and β = 98.05(1)°; R = 6.3% for 3660 data with |Fo| > 4σ. The molecular conformation in crystals revealed that the Gly(1)-Dpg(2) segment adopts φ, ψ values distorted from those expected for an ideal type II‘ β-turn (φGly(1) = +72.0°, ψGly(1) = −166.0°; φDpg(2) = −54.0°, ψDpg(2) = −46.0°) with an inserted water molecule between Boc-CO and Gly(3)NH. The Gly(3)-Gly(4) segment adopts φ, ψ values which lie broadly in the right handed helical region (φGly(3) = −78.0°, ψGly(3) = −9.0°; φGly(4) = −80.0°, ψGly(4) = −18.0°). There is a chiral reversal at Dpg(5) which takes up φ, ψ values in the left handed helical region. The Dpg(5)-Gly(6) segment closely resembles an ideal type I‘ β-turn (φDpg(5) = +56.0°, ψDpg(5) = +32.0°; φGly(6) = +85.0°, ψGly(6) = −3.0°). Molecules of both chiral senses are found in the centrosymmetric crystal. The C-terminus forms a hydrated Schellman motif, with water insertion into the potential 6 → 1 hydrogen bond between Gly(1)CO and Gly(6)NH. NMR studies in CDCl3 suggest substantial retention of the multiple turn conformation observed in crystals. In solution the observed NOEs support local helical conformation at the two Dpg residues.

Pt2+ Dispersed in Ce0.83Ti0.15O2-delta: Significant Improvement in PROX Activity by Ti Substitution in CeO2 in Hydrogen Rich Stream

Pt2+ ion dispersed in CeO2, Ce1-xTixO2-delta and TiO2 have been tested for preferential oxidation of carbon monoxide (PROX) in hydrogen rich stream. It is found that Pt2+ substituted CeO2 and Ce(1-x)TixO(2-delta) in the form of solid solution Ce0.98Pt0.02O2-delta and Ce0.83Ti0.15Pt0.02O2-delta are highly CO selective low temperature PROX catalysts in hydrogen rich stream. Just 15% of Ti substitution in CeO2 improves the overall PROX activity.