Effect of post-annealing treatment in oxygen on dielectric properties of K0.5Na0.5NbO3 thin films prepared by chemical solution deposition

K_0.5Na_0.5NbO₃ thin films were prepared on Pt/Ti/SiO₂/Si substrates by chemical solution deposition method with different annealing temperatures of 550 °C, 600 °C, 700 °C. The post-annealing treatment was introduced at 550 °C for 3 min in oxygen ambient. It is found that the films were composed of pure provskite phase, and the post-annealing treatment promoted the crystallization and improved the quality of the films, which resulted in the enhancement of the dielectric property of the films. The effect of the post-annealing on the dielectric properties of the films was also discussed.     

Structural study on Al-26 mass% Si-8 mass% Ni powder

The structure of Al-26 mass% Si-8 mass% Ni alloy, a material used as an input product for manufacturing light weight products via powder metallurgy, was investigated by in situ powder diffraction techniques up to 700°C. Thermal expansion of the dominant phases indicates substitutional alloying of silicon by nickel atoms, forming a solid solution phase stable in the temperature region from 330 to 550°C. The presence of Al, Si, Al₃Ni and Si₃Ni was determined by phase analysis from a sample annealed at 700°C (re-melted) and cooled down to room temperature. EXAFS analysis of as prepared and re-melted samples documented similar local atomic structure around the Ni atoms in both stages.     

Synthesis and properties of platinum-dispersed carbon by pressure pyrolysis of organoplatinum copolymer

Platinum-dispersed carbon was synthesized by pressure pyrolysis of divinylbenzenebis (2-allylphenyl)platinum (APPt) and phenylacetylene-APPt at 550 °C and 125 MPa. The crystallinity of platinum dispersed in the carbon matrix synthesized from phenylacetylene(PA)-APPt was higher than that from divinylbenzene(DVB)-APPt. Platinum particles less than 60 nm were dispersed in the carbon matrix synthesized from DVB-APPt at 550 °C and 125 MPa. The carbon matrix formed from PA-APPt contained platinum particles of about 120 nm. The specific area of platinum-dispersed carbon synthesized at 550 °C and 125 MPa increased on subsequent heat treatments in argon, and reached 90 m² g^–1 after heat treatment at 800 °C for 1 h. The activity of platinum-dispersed carbon for the hydrogenation of cyclohexene increased with increasing specific area. Platinum-dispersed carbon formed from DVBAPPt was more active for hydrogenation reaction than that from PA-APPt. The highly active platinum-dispersed carbon could be synthesized from DVB-APPt at 520 °C. The surface area reached 154 m² g^–1 after heat treatment at 800 °C.     

Structure, hardness and thermal stability of nanolayered TiN/CrN multilayer coatings

Nanolayered TiN/CrN multilayer coatings were deposited on silicon substrates using a reactive DC magnetron sputtering process at various modulation wavelengths (Λ), substrate biases (V_B) and substrate temperatures (T_S). X-ray diffraction (XRD), nanoindentation and atomic force microscopy (AFM) were used to characterize the coatings. The XRD confirmed the formation of superlattice structure at low modulation wavelengths. The maximum hardness of the TiN/CrN multilayers was 3800 kg/mm² at Λ=80  Å, V_B=−150 V and T_S=400°C. Thermal stability of TiN, CrN and TiN/CrN multilayer coatings was studied by heating the coatings in air in the temperature range (T_A) of 400-800°C. The XRD data revealed that TiN/CrN multilayers retained superlattice structure even up to 700°C and oxides were detected only after T_A?750°C, whereas for single layer TiN and CrN coatings oxides were detected even at 550°C and 600°C, respectively. Nanoindentation measurements showed that TiN/CrN multilayers retained a hardness of 2800 kg/mm² upon annealing at 700°C, and this decrease in the hardness was attributed to interdiffusion at the interfaces.     

Synthesis of nickel ferrite-dispersed carbon composites by pressure pyrolysis of organometallic polymer

Nickel ferrite-dispersed carbon could be synthesized by pressure pyrolysis of divinylbenzene (DVB)-vinylferrocene (VF)-nickelocene (Cp₂Ni) polymer in the presence of water under 125 MPa and at temperatures below 700°C. By heat treatment at 550°C with water, nickel ferrite particles could be dispersed finely in the carbon matrix, although a small amount of nickel-iron carbide also began to form above 600°C. The morphologies of the carbon particles formed were observed to be polyhedral, coalescing spherulitic and spherulitic. When 30 wt% H₂O, spherulitic carbons a few micrometres in diameter were prepared, in which nickel ferrite particles from 10–30 nm were dispersed in the carbon matrix. The saturation magnetization of carbon composites formed from DVB-3.0 mol% Cp₂Ni-6.0 mol% VF and 20 wt% H₂O at 550°C was about 30 e.m.u.g^–1 and increased with pyrolysis temperature. The coercive force of the carbon composite was 120 Oe and was affected by the amount of added water using pressure pyrolysis. Thermomagnetic measurement shows that the Curie temperature of nickel ferrite-dispersed carbon was about 580 °C.     

Crystallization behaviour and phase coexistence at morphotrophic phase boundaries in PZT thin films prepared by sol-gel processing

Pb(Zr_0.53Ti_0.47)O₃ (PZT) thin films, prepared by sol-gel techniques and deposited on to Si/SiO₂/Ti/Pt substrates, have been subjected to thermal annealing in a range of temperatures from 550–800 °C. The crystallization behaviour and phase coexistence (tetragonal and rhombohedral) were studied by X-ray diffraction. According to the values of the {110} peak intensity and {110} peak values, the crystallization full-width at half-maximum was more complete at higher temperatures (750, 800 °C). At a fixed Zr/Ti ratio close to the morphotropic phase boundary, the lattice parameters of the two phases changed with the annealing temperature. However, the tetragonality degree had relatively low values and the angular rhombohedral distortion was associated with a narrow angular range. The phase coexistence and the variation of the lattice parameters could be explained by the titanium diffusion through the platinum layer. Thus the formation of a {0 1 1} titanium rich layer at Pt-PZT interface will supply a titanium excess for the nucleation and growth of textured PZT grains.     

The stability of hydroxyapatite in an optimized bioactive glass matrix at sintering temperatures

The stability of sintered hydroxylapatite particles was studied in glass matrices of the system SiO₂-CaO-P₂O₅-Na₂O-Al₂O₃-B₂O₃ at sintering temperatures between 700 and 1000 °C. The results from X-ray diffraction (XRD), scanning electron microscope (SEM), energy dispersive spectroscopy (EDX) analysis, transmission electron microscopy (TEM) and electron diffraction showed that above 700 °C the Na⁺ ions diffuse into the hydroxylapatite particles which then transform into rhenanite. The glass matrix undergoes crystallization yielding wollastonite crystals and a silica rich matrix.     

NO decomposition by ultrafine noble metals dispersed on the rare earth phosphate hollow particles

Novel fine polymer particles containing ultrafine Pd, Pt or Rh metal dispersed on the core-shell [core, poly(styrene-co-acrylamide) or poly(styrene-co-acrylic acid); shell, LnPO₄(Ln = Ce, Nd, Pr, Sm, La)] type microsphere were prepared by the emulsifier-free emulsion polymerization of styrene with acrylamide or acrylic acid followed by the addition of PdCl₂, HPtCl₆, or RhCl₃ and finally by the addition of a mixture of Ln(NO₃)₃ and NaH₂PO₄. Pyrolysis of the resulting polymer particles at 700–900°C provides polymer-free hollow particles (diameter 450–550 nm) composed of noble metals and LnPO₄. The excellent catalytic reduction of NO gas into N₂ and O₂ was observed at 500–700°C using the rersulting particles as catalyst.     

Formation of NiFe2O4 nanoparticles by mechanochemical reaction

Preparation of nanosized NiFe₂O₄ particles by mechanochemical reaction(NiO+α-Fe₂O₃) and subsequent thermal treatment was investigated using X-ray diffraction (XRD). Thermal treatment of the as-milled powder at 700 °C for 1 h led to the formation of NiFe₂O₄ nanoparticles with an average crystal size of about 23 nm. Effect of thermal treatment temperature on the crystal size of the nanoparticles was studied. The mechanism of nanoparticles growth was primarily discussed. The activation energy of NiFe₂O₄ nanoparticle formation during calcination was calculated to be 16.6 kJ/mol.     

Nickel-boron nanolayer evolution on boron carbide particle surfaces during thermal treatment

This study is focused on reduction of Ni₂O₃ and B₂O₃ in the Ni-B nanolayer on B₄C particle surfaces and understanding of the nanolayer composition and morphology changes. Initially, the nanolayer contains Ni₂O₃, B₂O₃, and amorphous boron. After 400 °C thermal treatment in a H₂-Ar atmosphere, Ni₂O₃ is reduced to nickel; the nanolayer morphology is maintained and the coated particles demonstrate magnetism. As the thermal treatment temperature is increased to 550 °C, B₂O₃ is reduced to boron, which reacts with nickel and forms Ni₂B. Simultaneously, the nanolayer evolves into nanoparticles. Thermal treatment temperature increase to 700-900 °C only causes Ni₂B particle growth but does not fundamentally change the composition or phase.     

Nickel nanoparticles inserted in tBuONa matrix deposited on alumina Part II Thermal treatment and nickel content effects on their stabilty and catalytitic activity

Nanoparticles (1 nm–3 nm) of metallic nickel supported on alumina (4.3% Ni–17.9% Ni w/w) were prepared from a colloidal precursor inserted in an organic matrix. Their structural and stability properties have been studied by X-Ray Diffraction (XRD), Electron Paramagnetic Resonance (EPR) and Thermal Gravimetric Analysis (TGA). Benzene hydrogenation at atmospheric pressure in the temperature range of 75 °C–200 °C was used as a test reaction of their catalytic capability. The thermal stability of the particles depended on the nature of the reactive atmosphere. Thus, a growth in size (up to around 20 nm) is observed under H₂ flow at 350 °C or during benzene hydrogenation but not under air flow at 300 °C. The growth may be due to the coalescence of the metal particles during the heating and decomposition of the stabilizing organic matrix. Under oxidative atmosphere, stable nickel oxide particles, firmly attached to the support, are formed. The catalysts pre-treated under H₂/350 °C were active and stable in benzene hydrogenation. The observed activities depended on the reaction conditions and nickel composition.     

Preparation of carbon supported binary Pt–M alloy catalysts (M = first row transition metals) by low/medium temperature methods

Carbon supported Pt alloyed with first row transition elements (Pt–M/C) is being used as improved cathode catalyst for low temperature fuel cells. These catalysts have been usually prepared by deposition of the non-precious metal onto pre-formed carbon supported platinum, followed by alloying at temperatures of the order or above 700 °C. As the thermal treatment at high temperature gives rise to an undesired metal particle growth, synthetic methods based on the simultaneous deposition of Pt and M on the carbon substrate, followed by thermal treatment at lower temperature have been developed. In this paper the formation of Pt–M/C by low/intermediate temperature methods is reviewed.Moreover, to investigate the effect of the conditions used in the synthesis on the Pt:M atomic ratio, the degree of alloying and the particle size, carbon supported Pt–Co electrocatalysts with nominal Pt:Co atomic ratio 75:25 were prepared by a low temperature chemical reduction of the precursors with sodium borohydride at two different temperatures and NaBH₄ concentrations. The physical characterization of these electrocatalysts was performed by energy dispersive X-ray analysis and X-ray diffraction.     

Effects of post-deposition surface treatment on the optical, structural and hydrogen sensing properties of TiO2 thin films

TiO₂ thin films were prepared by DC reactive magnetron sputtering in a mixture of oxygen and argon on glass and oxidized silicon substrates. The effect of post-deposition annealing (300 °C, 500 °C and 700 °C for 8 h in air) on the structural and morphological properties of TiO₂ thin films is presented. In addition, the effect of Pt surface modification (1, 3 and 5 nm) on hydrogen sensing was studied. XRD patterns have shown that in the range of annealing temperatures from 300 °C to 500 °C crystallization starts and the thin film structure changes from amorphous to polycrystalline (anatase phase). In the case of samples on glass substrate, optical transmittance spectra were recorded. TiO₂ thin films were tested as sensors of hydrogen at concentrations 10,000-1000 ppm and operating temperatures within the 180-200 °C range. The samples with 1 nm and in particular with 3 nm of Pt on the surface responded to hydrogen fast and with high sensitivity.     

Synthesis and properties of carbons dispersed with Fe-Co alloy by pressure pyrolysis of organoiron-organocobalt copolymer

Carbons dispersed with Fe-Co alloy were synthesized by the pressure pyrolysis of vinylferro cene-phenylethynylcobaltocene-divinylbenzene copolymer at temperatures below 700° C and at 125 M Pa. As-prepared carbon synthesized at 550° C contained finely dispersed metallic particles of less than 10nm diameter with low crystallinity, which crystallized to form Fe-Co alloy particles with a higher crystallinity by subsequent heat treatment at 800° C. Larger particles of the alloy of more than 50nm diameter were dispersed in the carbon matrix synthesized at 700° C. Thermomagnetization measurement of the as-prepared carbon synthesized from divinylbenzene-2.1 mol% vinylferrocene-4.8mol% phenylethynylcobaltocene copolymer at 550° C and 125 M Pa confirmed that iron formed an alloy with cobalt in the carbon matrix. Fine, superparamagnetic metallic particles in the as-prepared carbon aggregated and crystallized by the heat treatment during the thermomagnetic measurement to increase the magnetization of the alloy-dispersed carbon. The saturation magnetization and the coercive force of alloy-dispersed carbon increased from 128 to 187e.m.u.g^–1 and from a few to 50 Oe, respectively, on increasing the pyrolysis temperature of the starting copolymer from 550 to 700° C. The saturation magnetization of alloy-dispersed carbon from divinylbenzene containing iron and cobalt with a ratio of 52 was higher than that from divinylbenzene including those with a ratio of 25. The carbon with finely dispersed Fe-Co alloy showed a high saturation magnetization of 213 e.m.u.g^–1 and a coercive force of 230 Oe, and the magnetization persisted above 800° C.     

The interaction of oxygen with high loaded Ru/γ-Al2O3 catalyst

The interaction of oxygen with the Ru/γ-Al₂O₃ catalyst comprising metal particle with sizes of 1-16 nm, was examined over a temperature range 20-400 °C. The catalyst loaded with 10.8 wt.% Ru was prepared by incipient wetness from RuCl₃ precursor. The structure of the Cl-containing catalyst and the catalyst after elimination Cl⁻ ions was characterized using H₂ and O₂ chemisorption, O₂ uptake, BET, XRD and TEM. The Cl⁻ ions in the catalyst decreased the H₂ and O₂ chemisorption capacity of Ru and caused large discrepancies between the mean particle size calculated from gas chemisorption and from TEM. Exposure to O₂ at 100-200 °C caused oxidation of small Ru particles, while larger particles were covered with very thin Ru_xO_y skin (undetected by XRD and TEM). The O/Ru ratio increased up to 200 °C implying high affinity of the small Ru particles to oxygen. Oxidation at 250 °C led to the formation of poorly crystalline RuO₂ particles with a mean size of 4 nm, and coverage of large Ru particles with 1.6 nm thick oxide layer. At 300 and 400 °C crystallization of the RuO₂ phase, as well as significant agglomeration of oxide particles was observed. However, even at 400 °C, metallic Ru was detected by XRD, TEM and SAED suggesting that large metal particles were not fully oxidized under the used conditions. Also, the O₂ uptake at 400 °C was lower than expected for oxidation of Ru metal to RuO₂. For the catalyst after elimination Cl ions the O₂ uptake (O/Ru ratio = 1.50) was higher, than for sample with large amount of Cl ions (O/Ru ratio = 1.34), indicating that the presence of Cl inhibits ruthenium oxidation in the Ru/Al₂O₃ catalyst.     

Magnetic properties and microstructures of sputtered epitaxial Co-rich Co-Pt films

Co₃Pt films of various thicknesses were deposited on Pt underlayers by conventional sputtering in order to investigate the effects of Pt underlayers and annealing temperatures on their microstructure and the magnetic properties. XRD and HRTEM analyses reveal perpendicular magnetic anisotropy in films of good epitaxial growth of Co₃Pt (002) on the Pt (111) underlayer when annealed at 300 °C. However, Pt atoms in the Pt underlayer will diffuse seriously into the Co₃Pt layer when the annealing temperature is increased to 375 °C. This changes the compositions to approach equiatomic CoPt, and shows in-plane magnetic anisotropy with soft magnetic properties.     

High temperature reactions between SiC and platinum

Solid state reactions between SiC and platinum have been studied at temperatures between 900 and 1100 °C. In the reaction zones, alternating layers of Pt₃Si and carbon, and Pt₂Si and carbon were formed at 900 and 1000 °C, respectively. Both the Pt₃Si and Pt₂Si phases were stable at respective temperatures. Annealings at 1100 °C, however, produced alternating layers of mixed Pt-silicides and carbon. The formation of platinum silicides gave rise to interfacial melting between SiC and platinum at all the temperature regimes. Laser Raman microprobe indicates that SiC decomposes into carbon and silicon at all the temperatures. The silicon reacts with platinum and forms platinum silicides, while the carbon forms clusters and stays unreacted. Based on the Raman results, the carbon exists in two different crystalline states depending upon its location from the SiC reaction interface. The reaction kinetics between SiC and platinum and the formation of periodic structure, respectively, are discussed based on the decomposition of the SiC and the phase separation of carbon from platinum silicides.     

Textured strontium titanate layers on platinum by atomic layer deposition

Formation of textured strontium titanate (STO) layers with large lateral grain size (0.2-1 μm) and low X-ray reflectivity roughness (~ 1.36 nm) on Pt electrodes by industry proven atomic layer deposition (ALD) method is demonstrated. Sr(t-Bu₃Cp)₂, Ti(OMe)₄ and O₃ precursors at 250 °C were used to deposit Sr rich STO on Pt/Ti/SiO₂/Si ∅200 mm substrates. After crystallization post deposition annealing at 600 °C in air, most of the STO grains showed a preferential orientation of the {001} plane parallel to the substrate surface, although other orientations were also present. Cross sectional and plan view transmission electron microscopy and electron diffraction analysis revealed more than an order of magnitude larger lateral grain sizes for the STO compared to the underlying multicrystalline {111} oriented platinum electrode. The combination of platinum bottom electrodes with ALD STO(O₃) shows a promising path towards the formation of single oriented STO film.     

Fabrication of nanocomposites based on carbon nanotubes containing Pt nanoparticles and TiO<Subscript>2</Subscript>

Using conical multiwalled carbon nanotubes (CNTs), we have prepared Pt/CNT and Pt/TiO₂/CNT nanocomposites with an average platinum particle size of 3–5 nm, Pt/Ti molar ratio on the surface in the range 3.5–4, and C/Pt = 21–22. Titania was deposited onto the CNTs through titanium tetrachloride (TiCl₄) hydrolysis. Platinum particles were produced by reducing chloroplatinic acid (H₂PtCl₆) with sodium borohydride (NaBH₄) in the presence of CNTs. The composition and structure of the composites have been studied using X-ray photoelectron spectroscopy, electron microscopy, X-ray diffraction, and thermogravimetry. The materials have been tested as catalysts for hydrogen oxidation and oxygen reduction. The results demonstrate that the modification of Pt/CNT with titania enhances the catalytic activity of the material.     

Void formation in silica glass induced by thermal oxidation after Zn ion implantation

Thermal annealing effects on Zn⁺ ion-implanted silica glass (a-SiO₂) have been studied in order to control void formation. Void formation in a-SiO₂ with Zn⁺ ion implantation and subsequent oxidation has been observed using transmission electron microscopy (TEM). Zn⁺ ions of 60 keV were implanted into a-SiO₂ to a fluence of 1.0 × 10¹⁷ ions/cm². After the implantation, thermal annealing at 600 or 700 °C for 1 h in oxygen gas was conducted. In as-implanted state, metal Zn nanoparticles (NPs) of 10-15 nm in diameter are formed in the depth region around the projected range. The size of the Zn nanoparticles increases after the annealing at 600 °C in oxygen gas. Annealing in oxygen gas at 700 °C for 1 h caused two processes: (1) the migration of Zn atoms which formed Zn NPs in as-implanted state to the surface of the a-SiO₂ substrate and (2) the transformation to the oxide phase on the substrate. The transportation of Zn NPs to the surface leaves voids of 10-25 nm in diameter inside the a-SiO₂. These results indicate that the oxidation at 700 °C for 1 h causes the migration of Zn atoms to the surface without diffusion and recombination of vacancies which form the voids.