Physicochemical analysis of Ti-Si-B powder aalloys

Titanium alloys of Ti-Si-B system were manufactured by blended elemental powder method using Ti, Si and B powders as starting materials. It was found that uniaxial and isostatic pressing followed by hot pressing at around 1000°C, for 20 minutes, provided good densification of such alloys. The physicochemical studies were performed by means of scanning electron microscopy, X-ray diffraction, atomic force microscopy and microindentation/wear tests. The investigations revealed a multiphase microstructure formed mainly by α-titanium, Ti6Si2B, Ti5Si3, TiB and Ti3Si phases. The phase transformations after pressureless sintering at 1200°C was also studied by X-ray diffraction for the Ti-18Si-6B composition. As stated in some other researches, these intermetallics in the α-titanium matrix provide high wear resistance and hardness, with the best wear rate of 0.2 mm3/N.m and the highest hardness of around 1300 HV. © (2012) Trans Tech Publications, Switzerland.

High-pressure assisted sintering of Ti-20Si-10B and Ti-10Si-5B powders

This work presents the structural characterization of Ti-10Si-5B and Ti-20Si-10B (at-%) alloys produced by high-pressure assisted sintering. Sintering was performed in air at 1100 and 1200°C for 60 s using pressure levels of 5 GPa. Structural evaluation of sintered samples was conducted by means of scanning electron microscopy and energy dispersive spectrometry. Samples were successfully consolidated after sintering, which presented theoretical density values higher than 99%. The microstructures of the sintered Ti-10Si-5B and Ti-20Si-10B alloys revealed the presence of the TiSS, TiB, TiB2, Ti5Si3, Ti5Si4, TiSi, and TiSi2.phases. A small amount of Ti6Si2B was formed after high-pressure assisted sintering of the Ti-20Si-10B alloy (5GPa, 1100°C for 60 s) indicating that equilibrium structures were not achieved during short sintering times. No oxygen and carbon contamination was detected in structures of Ti-Si-B alloys after high-pressure sintering at 1100 and 1200°C without controlled atmosphere. © (2012) Trans Tech Publications, Switzerland.

Growth of calcium phosphate coating on Ti-7.5Mo alloy after anodic oxidation

Titanium and its alloys are widely used as biomaterials due to their mechanical, chemical and biological properties. To enhance the biocompatibility of titanium alloys, various surface treatments have been proposed. In particular, the formation of titanium oxide nanotubes layers has been extensively examined. Among the various materials for implants, calcium phosphates and hydroxyapatite are widely used clinically. In this work, titanium nanotubes were fabricated on the surface of Ti-7.5Mo alloy by anodization. The samples were anodized for 20 V in an electrolyte containing glycerol in combination with ammonium fluoride (NH4F, 0.25%), and the anodization time was 24 h. After being anodized, specimens were heat treated at 450 °C and 600°C for 1 h to crystallize the amorphous TiO2 nanotubes and then treated with NaOH solution to make them bioactive, to induce growth of calcium phosphate in a simulated body fluid. Surface morphology and coating chemistry were obtained respectively using, field-emission scanning electron microscopy (FEG-SEM), AFM and X-ray diffraction (XRD). It was shown that the presence of titanium nanotubes induces the growth of a sodium titanate nanolayer. During the subsequent invitro immersion in a simulated body fluid, the sodium titanate nanolayer induced the nucleation and growth of nano-dimensioned calcium phosphate. It was possible to observe the formation of TiO2 nanotubes on the surface of Ti-7.5Mo. Calcium phosphate coating was greater in the samples with larger nanotube diameter. These findings represent a simple surface treatment for Ti-7.5Mo alloy that has high potential for biomedical applications. © (2013) Trans Tech Publications, Switzerland.

Effects of high temperature plasma immersion ion implantation on wear resistance of Ti-Si-B sintered alloys

Although titanium and its alloys own good mechanical properties and excellent corrosion resistance, these materials present poor tribological properties for specific applications that require wear resistance. In order to produce wear-resistant surfaces, this work is aimed at achieving improvement of wear characteristics in Ti-Si-B alloys by means of high temperature nitrogen plasma immersion ion implantation (PIII). These alloys were produced by powder metallurgy using high energy ball milling and hot pressing. Scanning electron microscopy (SEM) and X-ray diffraction identified the presence of α-titanium, Ti6Si2B, Ti5Si3, TiB and Ti3Si phases. Wear tests were carried out with a ball-on-disk tribometer to evaluate the friction coefficient and wear rate in treated and untreated samples. The worn profiles were measured by visible light microscopy and examined by SEM in order to determine the wear rates and wear mechanisms. Ti-7.5Si-22.5B alloy presented the highest wear resistance amongst the untreated alloys produced in this work. High temperature PIII was effective to reduce the wear rate and friction coefficient of all the Ti-Si-B sintered alloys. © 2013 Elsevier B.V.

Effect of yttrium doping in barium zirconium titanate ceramics: A structural, impedance, modulus spectroscopy study

In the current article, we studied the effect of yttrium [Y3+] ions' substitution on the structure and electric behavior of barium zirconate titanate (BZT) ceramics with a general formula [Ba1-x Y 2x/3](Zr0.25Ti0.75)O3 (BYZT) with [x = 0, 0.025, 0.05] which were prepared by the solid-state reaction method. X-ray diffraction patterns indicate that these ceramics have a single phase with a perovskite-type cubic structure. Rietveld refinement data confirmed [BaO 12], [ZrO6], [TiO6], [YO6] clusters in the cubic lattice. The Y3+ ions' effects on the electric conductivity behavior of BZT ceramics as a function of temperature and frequency are described, which are based on impedance spectroscopy analyses. The complex impedance plots display a double semicircle which highlights the influences of grain and grain boundary on the ceramics. Impedance analyses showed that the resistance decreased with the increasing temperature and resulted in a negative temperature coefficient of the resistance property in all compositions. Modulus plots represent a non-Debye-type dielectric relaxation which is related to the grain and grain boundary as well as temperature-dependent electric relaxation phenomenon and an enhancement in the mobility barrier by Y3+ ions. Moreover, the electric conductivity increases with the replacement of Ba 2+ by Y3+ ions may be due to the rise in oxygen vacancies. © 2013 The Minerals, Metals & Materials Society and ASM International.

Syntheses of bismuth titanate templates obtained by the molten salt method

Bismuth titanate templates (Bi4Ti3O12) were synthesized by the molten salt method in Na2SO4 and K2SO4 fluxes, using an amorphous Bi4Ti 3O12 precursor and a mechanically mixed Bi 2O3+TiO2 mixture as the starting materials. The templates were characterized by means of X-Ray Diffraction, FT-IR, FT-Raman, FEG-SEM and TEM. The templates are free of secondary phases and present orthorhombic structure with orientation in the c-plane. FT-IR suggests no traces of sulfate groups revealing that the molten salt synthesis was beneficial for elimination of inorganic species and for the arrangement of individual nanocrystals into ordered lattices. FEG-SEM analyses of BIT templates revealed that most of the grains were homogeneous with a length of 3.1 μm and a width of 0.3 μm and had plate-like morphology. TEM investigations show that the c-axis of the perovskite units is parallel to the thickness direction of the grains and no liquid-phase was formed during BIT phase formation. © 2013 Elsevier Ltd and Techna Group S.r.l.

Estudo hidrometalúrgico de compostos de titânio proveniente do resíduo do processo Bayer

Estudos realizados no resíduo do processo Bayer, lama vermelha, para reciclagem desse material têm sido intensificados por suas características físico-químicas. O resíduo é constituído por inúmeros óxidos, destes se destaca o óxido de ferro em teores acima de 30% em peso e óxido de titânio em concentrações acima de 5% em peso. Este trabalho estuda a possibilidade de extrair óxido de ferro, objetivando a concentração de compostos de titânio. A extração foi realizada através do processo de calcinação da lama vermelha a 900°C seguida de lixiviação ácida com concentração de H2SO4 a 20% e 30% em volume a 60°C, 80°C e 90°C, com retirada de uma alíquota a cada 30 minutos. Durante o processo de lixiviação, foi observada extração intensa dos compostos de ferro, resultando no aumento da concentração de titânio na lama vermelha, verificado em todos os experimentos, com destaque para os que foram realizados a 90°C e H2SO4 a 30% em v/v, onde houve extração de 95% de ferro e concentração de até 14% de titânio considerando o balanço de massa global. Diante dos dados obtidos, a lama vermelha torna-se um material interessante para ser utilizado como fonte alternativa para obtenção de minerais de titânio, os quais são encontrados na natureza com um percentual em torno de 8%.

Estudo da extração de compostos de ferro da lama vermelha visando a extração e/ou recuperação de compostos de titânio

As principais preocupações com relação à geração de resíduos estão voltadas para os efeitos que estes materiais podem ter sobre a saúde humana e sobre o meio ambiente, uma vez que os resíduos perigosos produzidos pelas indústrias precisam particularmente de atenção e cuidado, pois quando incorretamente gerenciados, tornam-se uma grave ameaça ao meio ambiente. Neste contexto, este trabalho mostra os estudos realizados visando a reciclagem da lama vermelha como matéria-prima para a obtenção de compostos de titânio. O estudo abrange três rotas hidrometalúrgicas: lama vermelha calcinada a 900°C (LV900), lama vermelha sem tratamento térmico (LV-STT) e lama vermelha sinterizada em atmosfera redutora (LV1300). Os experimentos de lixiviação foram realizados com valores de temperaturas de 60, 80 e 90 °C e concentrações de ácido sulfúrico de 20 e 30% em volume. Junto com o estudo de lixiviação foi realizada a modelagem matemática do processo de lixiviação. Os estudos realizados neste trabalho mostram que a lama vermelha pode ser aplicada como fonte de matéria-prima alternativa para a concentração e posterior recuperação de compostos de titânio. A modelagem cinética dos dados das curvas de extração em função do tempo e o modelo matemático desenvolvidos no presente trabalho mostram que a reação química é a etapa que descreve esses ensaios de lixiviação. Os modelos desenvolvidos também possibilitaram a obtenção de parâmetros cinéticos, tais como: energia de ativação e as velocidades das reações químicas do processo de lixiviação.

Bulk rock magnetic measurements and thermomagnetic analyses of sediment core GeoB4901-8 from the southeastern flank of the Niger deep-sea fan

Diagenesis has extensively affected the magnetic mineral inventory of organic-rich late Quaternary sediments in the Niger deep-sea fan. Changes in concentration, grain size, and coercivity document modifications of the primary magnetic mineral assemblages at two horizons. The first front, the modern iron redox boundary, is characterized by a drastic decline in magnetic mineral content, coarsening of the grain size spectrum, and reduction in coercivity. Beneath a second front, the transition from the suboxic to the sulfidic anoxic domain, a further but less pronounced decrease in concentration and bulk grain size occurs. Finer grains and higher coercive magnetic constituents substantially increase in the anoxic environment. Low- and high-temperature experiments were performed on bulk sediments and on extracts which have also been examined by X-ray diffraction. Thermomagnetic analyses proved ferrimagnetic titanomagnetites of terrigenous provenance as the principal primary magnetic mineral components. Their broad range of titanium contents reflects the volcanogenic traits of the Niger River drainage areas. Diagenetic alteration is not only a grain size selective process but also critically depends on titanomagnetite composition. Low-titanium compounds are less resistant to diagenetic dissolution. Intermediate titanium content titanomagnetite thus persists as the predominant magnetic mineral fraction in the sulfidic anoxic sediments. At the Fe redox boundary, precipitation of authigenic, possibly bacterial, magnetite is documented. The presence of hydrogen sulfide in the pore water suggests a formation of secondary magnetic iron sulfides in the anoxic domain. Grain size-specific data argue for a gradual development of a superparamagnetic and single-domain iron sulfide phase in this milieu, most likely greigite.

Room temperature electromechanical and magnetic investigations of ferroelectric Aurivillius phase Bi5Ti3(FexMn1−x)O15 (x = 1 and 0.7) chemical solution deposited thin films

Aurivillius phase thin films of Bi5Ti3(FexMn1−x)O15 with x = 1 (Bi5Ti3FeO15) and 0.7 (Bi5Ti3Fe0.7Mn0.3O15) on SiO2-Si(100) and Pt/Ti/SiO2-Si substrates were fabricated by chemical solution deposition. The method was optimized in order to suppress formation of pyrochlore phase Bi2Ti2O7 and improve crystallinity. The structuralproperties of the films were examined by x-ray diffraction, scanning electron microscopy, and atomic force microscopy. Optimum crystallinity and pyrochlore phase suppression was achieved by the addition of 15 to 25 mol. % excess bismuth to the sols. Based on this study, 17.5 mol. % excess bismuth was used in the preparation of Bi2Ti2O7-free films of Bi5Ti3FeO15 on SrTiO3(100) and NdGaO3(001) substrates, confirming the suppression of pyrochlore phase using this excess of bismuth. Thirty percent of the Fe3+ ions in Bi5Ti3FeO15 was substituted with Mn3+ ions to form Bi2Ti2O7-free thin films of Bi5Ti3Fe0.7Mn0.3O15 on Pt/Ti/SiO2-Si, SiO2-Si(100), SrTiO3(100), and NdGaO3(001) substrates. Bi5Ti3FeO15 and Bi5Ti3Fe0.7Mn0.3O15thin films on Pt/Ti/SiO2-Si and SiO2-Si(100) substrates were achieved with a higher degree of a-axis orientation compared with the films on SrTiO3(100) and NdGaO3(001) substrates. Room temperature electromechanical and magnetic properties of the thin films were investigated in order to assess the potential of these materials for piezoelectric,ferroelectric, and multiferroic applications. Vertical piezoresponse force microscopy measurements of the films demonstrate that Bi5Ti3FeO15 and Bi5Ti3Fe0.7Mn0.3O15thin films are piezoelectric at room temperature. Room temperature switching spectroscopy-piezoresponse force microscopy measurements in the presence and absence of an applied bias demonstrate local ferroelectric switching behaviour (180°) in the films. Superconducting quantum interference device magnetometry measurements do not show any room temperature ferromagnetic hysteresis down to an upper detection limit of 2.53 × 10−3 emu; and it is concluded, therefore, that such films are not mutiferroic at room temperature. Piezoresponse force microscopy lithography images of Bi5Ti3Fe0.7Mn0.3O15thin films are presented.

Electrochemical oxidation of boron containing compounds on titanium carbide and its implications to direct fuel cells

Electrochemical oxidation of sodium borohydride (NaBH(4)) and ammonia borane (NH(3)BH(3)) (AB) have been studied on titanium carbide electrode. The oxidation is followed by using cyclic voltammetry, chronoamperometry and polarization measurements. A fuel cell with TiC as anode and 40 wt% Pt/C as cathode is constructed and the polarization behaviour is studied with NaBH(4) as anodic fuel and hydrogen peroxide as catholyte. A maximum power density of 65 mW cm(-2) at a load current density of 83 mA cm(-2) is obtained at 343 K in the case of borhydride-based fuel cell and a value of 85 mW cm(-2) at 105 mA cm(-2) is obtained in the case of AB-based fuel cell at 353 K. (C) 2011 Elsevier Ltd. All rights reserved.

Amperometric tyrosinase biosensor based on a sol-gel-derived titanium oxide-copolymer composite matrix for detection of phenolic compounds

A new type of tyrosinase biosensor was developed for the detection of phenolic compounds, based on the immobilization of tyrosinase in a sol-gel-derived composite matrix that is composed of titanium oxide sol and a grafting copolymer of poly(vinyl alcohol) with 4-vinylpyridine. Tyrosinase entrapped in the composite matrix can retain its activity to a large extent owing to the good biocompatibility of the matrix. The parameters of the fabrication process and the variables of the experimental conditions for the enzyme electrode were optimized. The resulting sensor exhibited a fast response (20 s), high sensitivity (145.5 muA mmol(-1) 1) and good storage stability. A detection limit of 0.5 muM catechol was obtained at a signal-to-noise ratio of 3.

Titanium Complexes for the Polymerisation of Ethene and Caprolactone

The literature part of the thesis mainly reviews the results of the use of titanium catalysts for ethene and caprolactone polymerisation. The behaviour of titanium catalysts bearing phenoxy-imino ligands has been the focus of more detailed investigations in ethene polymerisation. Reasons for the production of multimodal polyethene for a range of catalysts are also given. The experimental part of the thesis is divided into two sections based on the monomers used in the polymerisations: Part A (ethene) and part B (caprolactone). Part A: Titanium(IV) complexes bearing phenoxy-imino ligands are known to possess high ethene polymerisation activities after MAO activation. Depending on the ligand, the activities of the catalysts in polymerisation can vary between 1 and 44000 kgPE/(mol*cat*h*bar). Depending on the polymerisation temperature and the electronic and steric properties of the catalyst ligands, low to high molar mass values and uni- and multimodal polydispersity values can been observed. In order to discover the reasons for these differences, 22 titanium(IV) complexes containing differently substituted phenoxy-imino derivatives as di- and tetradentate ligands were synthesised with high yields and used as homogeneous catalysts in ethene polymerisations. Computational methods were used to predict the geometry of the synthesised complexes and their configuration after activation. Based on the results obtained, the geometry of the catalyst together with the ligand substituents seem to play a major role in defining the catalytic activity. Novel titanium(IV) complexes bearing malonate ligands were also synthesised. Malonates are considered to be suitable ligand pre-cursors since they can be produced by the simple reaction of any primary or secondary alcohol with malonylchloride, and thus they are easily modifiable. After treatment with MAO these complexes had polymerisation activities between 10 and 50 kgPE/(mol*cat*h*bar) and surprisingly low polydispersity values when compared with similar types of catalysts bearing the O?O chelate ligand. Part B: One of the synthesis routes in the preparation of the above mentioned phenoxy-imino titanium dichloride complexes involved the use of Ti(NMe2)4 with a range of salicylaldimine type compounds. On reaction, these two compounds formed an intermediate product selectively and quantitatively which was active in the ring-opening polymerisation of caprolactone. Several mono-anionic alcoholates were also combined with Ti(NMe2)4 in different molar ratios and used as catalysts. Full conversion of the monomer was achieved within 15 minutes with catalysts having a co-ordination number of 4 while after 22 hours full conversion was achieved with catalysts having a co-ordination number of 6.

Infra-red absorption bands of co-ordinated water in titanium complexes

ORANGE red and amorphous peroxy-titanium complexes of oxalic, malonic and maleic acids1-3, when vacuum-dried, have co-ordinated water molecules firmly bonded to the central titanium atom as shown in formula (I). The peroxy-oxygen from these compounds is slowly lost even at room temperature because of the strained peroxy-group3,4. The compounds, when kept at 95°-100°C. for about three days, give deperoxygenated compounds of the type (II). However, a sample of peroxy-titanium oxalate sealed in a glass tube lost all its peroxy-oxygen in about four years and gave a white crystalline basic oxalate (II). The amorphous nature of the compounds may be due to random hydrogen bonding in the complexes. The crystallinity observed in one of the deperoxygenated titanyl oxalates may be due to the rearrangement of the molecules during ageing for more than four years. The infra-red absorption of these compounds was studied to find out the effect of co-ordination and hydrogen bonding on the infra-red bands of the free water.