29Si MAS-NMR investigation of the conversion process of a polytitanocarbosilane into SiC-TiC ceramics

A polytitanocarbosilane has been prepared from polycarbosilane and titanium n-butoxide.²⁹Si MAS-NMR was used to characterize the various steps of the conversion process of the polymer into the final ceramic. The reaction of titanium butoxide with polycarbosilane introduces oxygen into the polymer that seems to play an important role in the pyrolysis process. In the first stage up to 1000 ° C, the study reveals the cleavage of Si-C bonds and the formation of SiC_4-xO_x units. In the second stage, above 1000 ° C, the number of Si-O bonds decreases, probably due to a carbothermal reduction process. At 1500 ° C, the product can be described as a mixture of crystalline SiC and TiC with no excess carbon.     

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.     

Deposition of WNxCy thin films for diffusion barrier application using the dimethylhydrazido (2) tungsten complex (CH3CN)Cl4W(NNMe2)

Tungsten nitride carbide (WN_xC_y) thin films were deposited by chemical vapor deposition using the dimethylhydrazido (2⁻) tungsten complex (CH₃CN)Cl₄W(NNMe₂) (1) in benzonitrile with H₂ as a co-reactant in the temperature range 300 to 700 °C. Films were characterized using X-ray diffraction (XRD), Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy and four-point probe to determine film crystallinity, composition, atomic bonding, and electrical resistivity, respectively. The lowest temperature at which growth was observed from 1 was 300 °C. For deposition between 300 and 650 °C, AES measurements indicated the presence of W, C, N, and O in the deposited film. The films deposited below 550 °C were amorphous, while those deposited at and above 550 °C were nano-crystalline (average grain size < 70 Å). The films exhibited their lowest resistivity of 840 µΩ-cm for deposition at 300 °C. WN_xC_y films were tested for diffusion barrier quality by sputter coating the film with Cu, annealing the Cu/WN_xC_y/Si stack in vacuum, and performing AES depth profile and XRD measurement to detect evidence of copper diffusion. Films deposited at 350 and 400 °C (50 and 60 nm thickness, respectively) were able to prevent bulk Cu transport after vacuum annealing at 500 °C for 30 min.     

Polymer-metal chelate precursor reduced its firing temperature and time for preparing yttrium barium cuprate powder

Bulk YBa₂Cu₃O _x was prepared by a polymer chelate precursor method using poly[(N,Ndicarboxymethyl)allylamine] as a chelating polymer of which molecular weights were 3 × 10⁴ (PDAA-L) and 3 × 10⁵ (PDAA-H), respectively. X-ray diffraction (XRD) analysis of the precursor from PDAA-H shows that YBa₂Cu₃O _x (Y123) phase appeared after being calcined at 750 °C for 5 h and the mixture was completely converted to tetragonal Y123 phase after being calcined at 800 °C for 5 h. The phase evolution of the precursor from PDAA-H during isothermal experiment at 800 °C showed that pure tetragonal Y123 was produced even after the polymer chelate precursor was heated for 2 h in air, although a very small amount of BaCO₃ was recognized. This BaCO₃ phase was hardly recognized after 4 h calcination. The precursor prepared from PDAA-L was fully converted to pure tetragonal Y123 after 3 h calcining at 800 °C. On the other hand, the sample prepared from metal nitrate solution without PDAA was not fully transferred to Y123 phase after heating at 800 °C for 10 h. Large amounts of Y₂O₃, BaCO₃ and CuO were observed. These results indicated that the greater homogeneity in the polymer chelate precursor leads to reduced firing times and temperature compared with the metal nitrate precursor.     

Deposition and microhardness of SiC from the Si2Cl6-C3H8-H2-Ar system

We obtained SiC coating layers on a graphite substrate using hexachlorodisilane (Si₂Cl₆, boiling point 144° C) as a silicon source and propane as a carbon source. We examined the deposition conditions, contents of carbon, silicon and chlorine in the deposits, and the microhardness. Mirror-like amorphous silicon layers were deposited in the reaction temperature range 500 to 630° C. well-formed silicon carbide layers with good adherency to the substrate were obtained above 850° C. The lowest deposition temperature of SiC was estimated to be 750 to 800° C. The Vickers microhardness of the SiC layer was about 3800 kg mm^–2 at room temperature and 2150 kg mm^–2 at 1000° C.     

Carbonization of Titanium and Molybdenum by Hexachloroethane

Polycrystalline transition metal carbides (M=Ti, Mo) were deposited by a low-pressure chemical vapor deposition system on quartz and a metal plate. Using C₂C1₆ and the metal plate as the precursors, the carbonization reactions occurred at a temperature exceeding 800°C. The block composition of titanium carbide is Ti/C = 0.66 and that of molybdenum carbide is Mo/C = 1.65. According to our results, the composition of thin films is a mixture of carbon and metal carbide. With respect to the volatile products, in addition to CC1₄, C₂C1₄, and Cl₂, we obtained TiCl₄ while reacting the titanium metal with C₂C1₆. The formation of TiCl₄ implies that titanium metal acts as a reduction reagent. In addition, this compound transfers chlorine from carbon to itself to obtain TiCl, TiC1₂, TiCl₃, and TiC1₄. In this reaction, TiCl₂ and TiCl₃, were freshly prepared and acted as the titanium source of further reaction. The total reaction pathway was studied in detail.     

The properties of polyurethane hybrid materials based on castor oil

The goal of this work was to investigate the properties of environmentally friendly, castor oil based polyurethane hybrid materials with titanium(IV) oxide nanoparticles, as a filler, and different types of diisocyanate (toluene diisocyanate and isophorone diisocyanate). In the sample synthesis, different ratios of the reactive groups (NCO/OH), r, were used (1, 1.15 and 0.92). In the composite preparation, only toluene diisocyanate was used, and the filler particles were premixed in a glass vessel with the castor oil polyol before the reaction with diisocyanate. For all the composite samples, the r value was 1. Polyurethane formation was confirmed by ATR-FT-IR by detecting the urethane band at 1515 cm⁻¹. It was determined that the hydroxyl groups had reacted because the broad band corresponding to the OH groups (3400 cm⁻¹) was not detected or detected at a reduced intensity depending on the r value. As was expected, the presence of the unreacted NCO groups was detected only for samples with r > 1 (band at 2300 cm⁻¹, which corresponds to the existence of these groups). The dynamic mechanical measurements were performed at a temperature range from −50 °C to 100 °C at different frequencies. For investigation of reinforcement effect of filler on polymer matrix, tensile testing was applied. The glass transition temperature, T_g, was determined by DSC measurement. It was estimated that the T_g of the samples decreased as the nanofiller content increased due to the changes in the segmental mobility influenced by the interaction between the nanoparticles and polymer chains.     

Novel ceramic–polymer composites synthesized by compaction of polymer-encapsulated TiO2-nanoparticles

A novel processing route for producing composites from ceramic particles and a thermoplastic polymer with high ceramic content was developed. Via a radical emulsion polymerization reaction in an aqueous suspension, titanium dioxide is encapsulated by a thin layer of poly(methyl methacrylate). Subsequently, the coated particles are compacted by applying high pressure (∼1 GPa) at a temperature above the glass transition temperature of the polymer (∼160 °C). This technique enables producing dense, hard and stiff composites at low processing temperatures. Microstructural investigations of composites by scanning electron microscopy confirm successful coating of titanium dioxide particles by polymer. Compositions were estimated from thermogravimetric measurements. A maximum TiO₂ volume content of almost 70% was achieved. For characterizing mechanical properties, Vickers microhardness as well as flexural strength and elastic modulus were determined. With respect to pure PMMA, composites exhibit a 10-fold increase in microhardness. Furthermore, a strong increase in elastic modulus with TiO₂ contents, up to 40 GPa at 66 vol.% TiO₂ was observed. These moduli are among the highest found in literature for ceramic polymer composites. However, bending strength of the material is still low.     

Synthesis, thermal stability, and photocatalytic activity of nanocrystalline titanium carbide

Titanium carbide (TiC) was prepared via one simple route by the reaction of metallic magnesium powders with titanium dioxide (TiO₂) and potassium acetate (CH₃COOK) in an autoclave at 600 °C and 8 h. Phase structure and morphology were characterized by X-ray powder diffraction (XRD) and Scanning electron microscopy (SEM). The results indicated that the product was cubic TiC, which consisted of particles with an average size of about 100 nm in diameter. The product was also studied by the thermogravimetric analysis (TGA) and its photocatalysis. It had good thermal stability and oxidation resistance below 350 °C in air. In addition, we discovered that the cubic TiC powders exhibited photocatalytic activity in degradation of Rhodamine-B (RhB) under 500 W mercury lamp light irradiation.     

Dielectric relaxation of vegetable-based polyurethane

Vegetable-based polyurethane (PU) was prepared in the thin film form by spin coating. This polymer is synthesised from castor oil, which can be extracted from the seeds of a native plant in Brazil called mamona. This polymer is biocompatible and is being used as material for artificial bone. The PU was characterised by dielectric spectroscopy in a wide range of frequency (10^–5 Hz to 10⁵ Hz) and by thermally stimulated discharge current (TSDC) measurements. The glass transition temperature (T _g = 39°C) was determined and using the initial rise method the activation energy was found to be 1.58 eV.     

Synthesis of Poly(ether ether ketone)s containing tertiary amine

A functional or reactive PEEK-Poly(ether ether ketone)s containing tertiary amine was synthesized. The product was determined by ¹H NMR, ¹³C NMR, IR spectra and elemental analysis. Thermal analysis of the polymer revealed the glass-transition temperatures (T_g = 119.57 °C), a 5% weight loss in air at 386 °C. An M_n of 10.4 kD, M_w of 20.2 kD, Polydispersity of 1.95 was obtained from GPC. The Poly(ether ether ketone)s containing a tertiary amine structure can be synthesized as a scaffolds for post-polymerization reaction.     

PbTiO3 sol-gel process studied by207Pb-NMR,IR, DTA and XRD

PbTiO₃ film and powder materials have been obtained from a sol prepared at room temperature by mixing lead(II) acetate trihydrate (LAT) and tetraisopropylorthotitanate (TPOT) in methoxyethanol. The sol-gel process was studied by means of²⁰⁷Pb nuclear magnetic resonance and infrared spectroscopy, differential thermal analysis and X-ray diffraction measurements. This investigation shows that an interaction between LAT and TPOT occurs immediately on mixing in solution and, as a result of the interaction, the lead and titanium compounds are indistinctly linked togetherthrough bidentate acetate bridging. This linkage remains unchanged during solution reactions and gelation, Pb-O-Ti bonding being absent at this stage. Pb-O-Ti bonding in the sol-gel materials is believed to be first formed between 200 and 350 °C during the decomposition of the OAc group of LAT and its removal from the gel. The gel retains its amorphous state on heating at 370 °C for 1 h. An unidentified primary crystal phase appears after heating the gel at 400 °C for 1 h, and it is transformed into perovskite PbTiO₃ crystals at 500 °C and higher temperatures.     

SAXS/DSC/WAXD study of TiO2 nanoparticles and the effect of γ-radiation on nanopolymer electrolyte

Nanostructured polymer electrolytes are very attractive materials for components of batteries and opto-electronic devices. (PEO)₈ZnCl₂ polymer electrolytes and nanocomposites were prepared using Poly(ethylene oxide) (PEO) γ-irradiated with a selected dose of 529 kGy and with an addition of 10% of TiO₂ nanograins. The influence of the added nanosize TiO₂ grains on the polymer electrolytes and the effect of the γ-radiation from a Co-60 source were studied by small-angle X-ray scattering (SAXS) simultaneously recorded with differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WAXD) at the synchrotron ELETTRA. Infrared (IR) and impedance spectroscopy (IS) were also performed [1]. It was shown by previously performed IS that the room temperature conductivity of the nanocomposite polymer electrolyte increased more than two times above 65 °C, relative to pure composites of PEO and salts. We observed all changes between 20 °C and 100 °C for treated and as prepared polymer electrolyte in the SAXS, DSC and WAXD spectra and especially during the phase transition to the super-ionic phase at 65 °C [2] and [3]. The SAXS/DSC measurements yielded insight into the temperature-dependent changes of the grains of the electrolyte as well as into the differences due to different heating and cooling rates. The crystal structure and the melting and crystallization temperatures of the nanosize grains were revealed by the simultaneous WAXD measurements.     

Formation of compounds by high-flux nitrogen ion implantation in titanium

Polycrystalline titanium was implanted with nitrogen ions at energies from 30 to 60 keV and with doses from 1 × 10¹⁶ to 1.5 × 10¹⁸ N⁺-ions cm^–2 at room temperature. The implanted titanium layers were investigated by high-voltage electron microscopy and transmission high-energy electron diffraction. The formation of titanium nitride, titanium carbonitride and titanium carbide phases were considered in relation to their dependence on nitrogen ion implantation dose. In the dose range from 1 × 10¹⁶ up to 1.5 × 10¹⁸ N⁺-ions cm^–2 the cubic phase -TiN _x was formed. In the dose range between 1 to 2.5 × 10¹⁷ and 1.5 × 10¹⁸N⁺-ions cm^–2 the tetragonal phase -Ti₂N was found in addition to the -TiN _x phase. The lattice structure of these titanium nitride phases is a function of the nitrogen ion implantation dose. Additionally, the presence of titanium carbonitrido TiC _y O _x and titanium carbide TiC _y phases can be proved. The analysed titanium nitride, titanium carbUnitride and titanium carbide phases are represented in a state diagram as a function of implantation dose.     

Layered polymer-kaolinite nanocomposites

Kaolinite (K) was reacted with liquid dimethyl sulfoxide (DMSO) producing K(DMSO)_0.4. Highly ordered polymer/kaolinite materials were obtained by displacement of DMSO molecules in the K(DMSO)_0.4 intercalate by polyethylene oxide (PEO) or bacterial polyhydroxybutyrate (PHB), both in the melt state at 130°C and 180°C, respectively. The hybrid nanocomposites obtained were characterized by powder X-ray diffractometry (PXRD), Fourier Transform Infrared spectrometry (FTIR) and thermal analysis (simultaneous TG/DSC). The obtained results are consistent with the total replacement of DMSO molecules by the macromolecular linear chains that lie flat building a monolayer of the polymer in the interlayer space of kaolinite. The stoichiometry of the compounds estimated from the TG/DSC measurements are: K(DMSO)_0.40±0.02, K(PHB)_0.82±0.02, K(PEO)_3.40±0.02.     

Preparation of TiB2 sintered compacts by hot pressing

A sintered compact of titanium diboride (TiB₂) was prepared by hot pressing of the synthesized TiB₂ powder, which was obtained by a solid-state reaction between TiN and amorphous boron. Densification of the sintered compact occurred at 20 MPa and 1800° C for 5 to 60 min with the aid of a reaction sintering, including the TiB₂ formation reaction between excess 20 at % amorphous boron in the as-synthesized powder (TiB₂ + 0.2B) and intentionally added 10 at % titanium metal. A homogeneous sintered compact of a single phase of TiB₂, which was prepared by hot pressing for 30 min from the starting powder composition [(TiB₂ + 0.2B) + 0.1 Ti], had a fine-grained microstructure composed of TiB₂ grains with diameters of 2 to 3 m. The bulk density was 4.47 g cm^–3, i.e. 98% of the theoretical density. The microhardness, transverse rupture strength and fracture toughness of the TiB₂ sintered compact were 2850 kg mm^–2, 48 kg mm^–2 and 2.4 MN m^–3/2, respectively. The thermal expansion coefficient increased with increasing temperature up to 400° C and had a constant value of 8.8 x 10^–6 deg^–1 above 500° C.     

Surface oxide dissolution in titanium subhydrides studied by Auger electron spectroscopy and X-ray photoelectron spectroscopy

The surface sensitive spectroscopic techniques of Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS) have been applied to the study of oxide dissolution of titanium subhydrides. In an earlier study using AES, it was shown that the rate of oxygen dissolution into titanium increased sharply at ~350° C. These data correlated well with physical property measurements that indicated an exothermic reaction was occurring at these temperatures which corresponded to the reaction of free titanium with atmospheric oxygen. In the present study the work has been expanded to include studies of TiH _x (x=1.15, 1.62). It has been found that dissolution of the native oxide on titanium subhydrides occurs at a temperature substantially higher (~ 500° C) than that required for titanium. It appears that the outward diffusion of hydrogen is inhibiting the inward diffusion of oxygen on the subhydride samples at temperatures below 500° C.Mound Facility is operated by Monsanto Research Corporation for the United States Department of Energy under Contract Number DE-AC04-76-DP00053.     

Plasma-carburization of nickel-based self-fluxing alloy

Surface hardening of Ni-based self-fluxing alloy was carried out using plasma-carburization. The carburization was performed utilizing methane glow discharge plasma on sintered Ni-based self-fluxing alloy (METCO 16C) at 977 °C and 1065 °C for 3.6 ks. The carburized surfaces were characterized by employing optical microscopy, scanning electron microscopy (SEM), electron probe microanalysis (EPMA), transmission electron microscopy and Vickers micro-hardness testing. The SEM and EPMA micrographs show that the thickness of the carburized hard layer increased with increasing temperature, to a depth of approximately 120-200 μm. Hard chromium carbide (Cr₃C₂) was found to precipitate near the surface on carburization at 977 °C more than at 1065 °C. Cr₃C₂ contributes to the surface hardening.     

Combustion synthesis of porous titanium microspheres

The synthesis of titanium porous microspheres by a combustion technique was studied under an argon atmosphere by using a TiO₂ − 2.5Mg reactive mixture. The precursor, a fine TiO₂ powder, was thermally treated in the range 600–1300 °C prior to the combustion experiments. TiO₂ microspheres whose diameters were between 10 and 50 μm were obtained from precursor particles annealed in the range 900–1100 °C. A biphase product consisting of Ti and MgO phases was obtained when the TiO₂ microspheres were reduced with Mg. The spherical morphology of the final particles was retained despite the relatively high combustion temperatures (1630–1670 °C) used in this study. Moreover, porous titanium microspheres were obtained when the MgO particles were dissolved using acid leaching. Scanning electron microscopy (SEM) images of the microspheres suggested that the spherical structure contained ∼0.5–2.0-μm-diameter porous windows. The Brunauer–Emmett–Teller (BET) surface area of the Ti microspheres was determined to be 2.8 m² g⁻¹.     

Ultralow expansion ceramics in the HfO2-TiO2 system synthesized by an hydrolysis and polycondensation technique

Ultra-refractory ceramics from the HfO₂-TiO₂ system in the range 30–40 mol% TiO₂, with a near-zero thermal expansion, have been synthesized by hydrolysis and polycondensation of titanium alkoxide and hafnium dichloride alcoholic solutions and sintered at moderate temperature. Thermal stability, crystallization, density and microstructure of these materials have been examined. The as-prepared powder, amorphous at room temperature, crystallized quickly when heated at 500 ° C. Entire crystallization occurred after treatment at 1000 °C. Sintering at 1500 °C on cold-pressed samples led to ceramics with weak porosity (7%), low expansion coefficient <1×10^–6 °C^– with a minimum for 30 mol% TiO₂ content. SEM examination on sintered materials at 1500 °C reveals a grain size from 2–6 m, increasing with TiO₂ content.