Thermoelectric materials: a new rapid synthesis process for non-toxic and high-performance tetrahedrite compounds

The feasibility to synthesize, in large quantity, pure and non-toxic tetrahedrite compounds using high-energy mechanical-alloying from only elemental precursors is reported in the present paper for the first time. Our processing technique allows a better control of the final product composition and leads to high thermoelectric performances (ZT of 0.75 at 700 K), comparable to that reported on sealed tube synthesis samples. Combined with spark plasma sintering, the production of highly pure and dense samples is achieved in a very short time, at least 8 times shorter than in conventional liquid-solid-vapor synthesis process. The process described in this paper is a promising way to produce high performance tetrahedrite materials for cost-effective and large-scale thermoelectric applications.

Thermoelectric properties of TiS2 mechanically alloyed compounds

Bulk polycrystalline samples in the series Ti1−xNbxS2 (0 ≤ x ≤ 0.075) were prepared using mechanical alloying synthesis and spark plasma sintering. X-ray diffraction analysis coupled with high resolution transmission electron microscopy indicates the formation of trigonal TiS2 by high energy ball-milling. The as-synthesized particles consist of pseudo-ordered TiS2 domains of around 20–50 nm, joined by bent atomic planes. This bottom-up approach leads, after spark plasma sintering, to homogeneous solid solutions, with a niobium solubility limit of x = 0.075. Microstructural observations evidence the formation of small crystallites in the bulk compounds with a high density of stacking faults. The large grain boundary concentration coupled with the presence of planar defects, leads to a substantial decrease in the thermal conductivity to 1.8 W/mK at 700 K. This enables the figure of merit to reach ZT = 0.3 at 700 K for x = 0.05, despite the lower electron mobility in mechanically alloyed samples due to small crystallite/grain size and structural defects.

High-temperature hysteresis and magnetization reversal in nanocomposite FeCo plus MnO

The hysteretic behavior of mechanically alloyed nanocomposites FeCo + MnO was studied at high temperatures. These composites present an unusual high and thermally stable coercivity, compared to FeCo milled at equal conditions. Coercivity enhancement was observed in hysteresis loops obtained between room temperature and 750 K. It is attributed to the isolation of the FeCo ferromagnetic particles by the paramagnetic MnO (T(N) = 120 K). The M(rev)(M(irr))(H) curves are clearly linear for the composite, indicating that coherent rotation is the reversal mechanism in these materials. (C) 2008 Elsevier B.V. All rights reserved.

Structural and electrochemical characteristics of Mg((55-x))Ti(x)Ni((45-y))Pt(y) metal hydride electrodes

In recent years, Mg-Ni-based metastable alloys have been attracting attention due to their large hydrogen sorption capacities, low weight, low cost, and high availability. Despite the large discharge capacity and high activity of these alloys, the accelerated degradation of the discharge capacity after only few cycles of charge and discharge is the main shortcoming against their commercial use in batteries. The addition of alloying elements showed to be an effective way of improving the electrode performance of Mg-Ni-based alloys. In the present work, the effect of Ti and Pt alloying elements on the structure and electrode performance of a binary Mg-Ni alloy was investigated. The XRD and HRTEM revealed that all the investigated alloy compositions had multi-phase nanostructures, with crystallite size in the range of 6 nm. Moreover, the investigated alloying elements demonstrated remarkable improvements of both maximum discharge capacity and cycling life. Simultaneous addition of Ti and Pd demonstrated a synergetic effect on the electrochemical properties of the alloy electrodes. Among the investigated alloys, the best electrochemical performance was obtained for the Mg(51)Ti(4)Ni(43)Pt(2) composition (in at.%), which achieved 448 mAh g(-1) of maximum discharge capacity and retained almost 66% of this capacity after 10 cycles. In contrast, the binary Mg(55)Ni(45) alloy achieved only 248 mAh g(-1) and retained 11% of this capacity after 10 cycles. (C) 2010 Elsevier By. All rights reserved.

Preparation of Ni-Ti-Mo and Ni-Ti-Mo-Zr Alloys by High-Energy Ball Milling and Subsequent Hot Pressing

This work discusses on the preparation of Ni-45Ti-5Mo, Ni-40Ti-10Mo and Ni-46Ti-2Mo-2Zr (at-%) alloys by high-energy ball milling and hot pressing, which are potentially attractive for dental and medical applications. The milling process was performed in stainless steel balls (19mm diameter) and vials (225 mL) using a rotary speed of 300rpm and a ball-to-powder weight ratio of 10:1. Hot pressing under vacuum was performed in a BN-coated graphite crucible at 900 degrees C for 1 h using a load of 20 MPa. The milled and hot-pressed materials were characterized by X-ray diffraction, electron scanning microscopy, and electron dispersive spectrometry. Peaks of B2-NiTi and Ni4Ti3 were identified in XRD patterns of Ni-45Ti-5Mo, Ni-40Ti-10Mo and Ni-46Ti-2Mo-2Zr powders milled for 1h. The NiTi compound dissolved small Mo amounts lower than 4 at%, which were measured by EDS analysis. Moreover, it was identified the existence of an unknown Mo-rich phase in microstructures of the hot-pressed Ni-Ti-Mo alloys.

On the Phase Transformation in Mechanically Alloyed Ni-Nb and Ni-Ta and Ni-Nb-Ta Powders

This paper reports on the phase transformation during the preparation of Ni-25Nb, Ni-25Ta, Ni-20Nb-5Ta and Ni-15Nb-10Ta (at-%) powders by high-energy ball milling from elemental powders. The milling process was performed in a planetary ball milling using stainless steel balls and vials, rotary speed of 300rpm, and a ball-to-powder of 10:1. To minimize contamination and spontaneous ignition the powders were handled under argon atmosphere in a glove box. The milled powders were characterized by means of X-ray diffraction techniques. Results indicated that the Ni atoms were preferentially dissolved into the Nb (and/or Ta) lattice at the initial milling times, which contributed to change the relative intensity on the diffraction peaks. After the dissolution of Nb (and/or Ta) into the Ni lattice, the Ni peaks were moved to the direction of lower diffraction angles in Ni-25Nb, Ni-25Ta, Ni-20Nb-5Ta, Ni-15Nb-10Ta powders, indicating that the mechanical alloying was achieved.

Structural Evaluation of Mechanically Alloyed and Heat-Treated Ti-25at-%Si Powders

This work discusses on the structural evaluation of mechanically alloyed and heat-treated Ti-25at%Si powders. The milling process was conducted in a planetary ball mill using stainless steel balls/vials, 200 rpm and ball-to-powder weight ratio of 5:1, whereas the heat treatment was conducted under Ar atmosphere at 1100 C for 4 h. Samples were characterized by X-ray diffraction, differential scanning calorimetry, scanning electron microscopy and energy dispersive spectrometry. The Si peaks disappeared after milling for 30h, indicating that the Si atoms were dissolved into the Ti lattice in order to form an extended solid solution. The Ti peaks were broadened and their intensities reduced for longer milling times whereas a halo was formed in Ti-25Si powders milled for 200h suggesting that an amorphous structure was achieved. The crystallite size was decreased with increasing milling times. A large Ti3Si amount was found in mechanically alloyed Ti-25at%Si powders after heating at 1100 degrees C for 4h.

Study of structural and photoluminescent properties of Ca8Eu2(PO4)(6)O-2

In this work it is presented for the first time the nanostructured hydroxyapatites doped with 0.5, 1.0 and 2.0 wt% of Eu3+ prepared at room temperature by the mechanical alloying technique. X-ray diffraction powder (XRD), infrared (IR) and Raman scattering spectroscopy, scanning electron microscopy (SEM), microhardness measurements as well as luminescent data of Eu3+ were used to investigate the structural and optical properties of these nanomaterials. The electrical and dielectrical analyses were used with the intention of having a better comprehension about the electromagnetic fields in pure and doped hydroxyapatites.

Defect-induced photoluminescence of powdered silica glass

Visible photoluminescence was generated in standard soda-lime-silica glass powder, mechanically milled in a high-energy attrition mill. The broad emission band maximum shows a linear dependence on the exciting wavelength, suggesting the possibility to tune the PL emission. The photoluminescence was attributed to defect generation related to unsatisfied chemical bonds due to the high surface area. Raman scattering and ultraviolet-visible optical reflectance measurements corroborate this assertion. Transmission electron microscopy measurements indicate that the powder is composed by nanocrystallites with about 10-20 nanometers immersed in an amorphous media.

Obtaining NiAl intermetallic compound using different milling devices

NiAl intermetallic compound was synthesized by mechanical alloying technique in planetary and attritor mills. The starting powders consisted of elemental mixtures of Ni and Al at Ni50Al50(at%) composition. In the planetary mill, compound formation occurred gradually during mechanical alloying, while the occurrence of a mechanically induced self-propagating reaction (MSR) can be suggested in the attritor mill. The NiAl obtained in both mill types was partially disordered with long-range order parameter not inferior to 0.66. Quantitative phase analysis using the Rietveld method was performed in as-milled samples, and this method was also employed to estimate changes in crystallite size and lattice strain of the NiAl produced during mechanical alloying. (C) 2011 The Society of Powder Technology Japan. Published by Elsevier B.V. and The Society of Powder Technology Japan. All rights reserved.

Analysis of transport properties of mechanically alloyed [Pb1-xSnxTe]

The work described in this thesis had two objectives. The first objective was to develop a physically based computational model that could be used to predict the electronic conductivity, Seebeck coefficient, and thermal conductivity of Pb1-xSnxTe alloys over the 400 K to 700 K temperature as a function of Sn content and doping level. The second objective was to determine how the secondary phase inclusions observed in Pb1-xSnxTe alloys made by consolidating mechanically alloyed elemental powders impact the ability of the material to harvest waste heat and generate electricity in the 400 K to 700 K temperature range. The motivation for this work was that though the promise of this alloy as an unusually efficient thermoelectric power generator material in the 400 K to 700 K range had been demonstrated in the literature, methods to reproducibly control and subsequently optimize the materials thermoelectric figure of merit remain elusive. Mechanical alloying, though not typically used to fabricate these alloys, is a potential method for cost-effectively engineering these properties. Given that there are deviations from crystalline perfection in mechanically alloyed material such as secondary phase inclusions, the question arises as to whether these defects are detrimental to thermoelectric function or alternatively, whether they enhance thermoelectric function of the alloy. The hypothesis formed at the onset of this work was that the small secondary phase SnO2 inclusions observed to be present in the mechanically alloyed Pb1-xSnxTe would increase the thermoelectric figure of merit of the material over the temperature range of interest. It was proposed that the increase in the figure of merit would arise because the inclusions in the material would not reduce the electrical conductivity to as great an extent as the thermal conductivity. If this were to be true, then the experimentally measured electronic conductivity in mechanically alloyed Pb1-xSnxTe alloys that have these inclusions would not be less than that expected in alloys without these inclusions while the portion of the thermal conductivity that is not due to charge carriers (the lattice thermal conductivity) would be less than what would be expected from alloys that do not have these inclusions. Furthermore, it would be possible to approximate the observed changes in the electrical and thermal transport properties using existing physical models for the scattering of electrons and phonons by small inclusions. The approach taken to investigate this hypothesis was to first experimentally characterize the mobile carrier concentration at room temperature along with the extent and type of secondary phase inclusions present in a series of three mechanically alloyed Pb1-xSnxTe alloys with different Sn content. Second, the physically based computational model was developed. This model was used to determine what the electronic conductivity, Seebeck coefficient, total thermal conductivity, and the portion of the thermal conductivity not due to mobile charge carriers would be in these particular Pb1-xSnxTe alloys if there were to be no secondary phase inclusions. Third, the electronic conductivity, Seebeck coefficient and total thermal conductivity was experimentally measured for these three alloys with inclusions present at elevated temperatures. The model predictions for electrical conductivity and Seebeck coefficient were directly compared to the experimental elevated temperature electrical transport measurements. The computational model was then used to extract the lattice thermal conductivity from the experimentally measured total thermal conductivity. This lattice thermal conductivity was then compared to what would be expected from the alloys in the absence of secondary phase inclusions. Secondary phase inclusions were determined by X-ray diffraction analysis to be present in all three alloys to a varying extent. The inclusions were found not to significantly degrade electrical conductivity at temperatures above ~ 400 K in these alloys, though they do dramatically impact electronic mobility at room temperature. It is shown that, at temperatures above ~ 400 K, electrons are scattered predominantly by optical and acoustical phonons rather than by an alloy scattering mechanism or the inclusions. The experimental electrical conductivity and Seebeck coefficient data at elevated temperatures were found to be within ~ 10 % of what would be expected for material without inclusions. The inclusions were not found to reduce the lattice thermal conductivity at elevated temperatures. The experimentally measured thermal conductivity data was found to be consistent with the lattice thermal conductivity that would arise due to two scattering processes: Phonon phonon scattering (Umklapp scattering) and the scattering of phonons by the disorder induced by the formation of a PbTe-SnTe solid solution (alloy scattering). As opposed to the case in electrical transport, the alloy scattering mechanism in thermal transport is shown to be a significant contributor to the total thermal resistance. An estimation of the extent to which the mean free time between phonon scattering events would be reduced due to the presence of the inclusions is consistent with the above analysis of the experimental data. The first important result of this work was the development of an experimentally validated, physically based computational model that can be used to predict the electronic conductivity, Seebeck coefficient, and thermal conductivity of Pb1-xSnxTe alloys over the 400 K to 700 K temperature as a function of Sn content and doping level. This model will be critical in future work as a tool to first determine what the highest thermoelectric figure of merit one can expect from this alloy system at a given temperature and, second, as a tool to determine the optimum Sn content and doping level to achieve this figure of merit. The second important result of this work is the determination that the secondary phase inclusions that were observed to be present in the Pb1-xSnxTe made by mechanical alloying do not keep the material from having the same electrical and thermal transport that would be expected from “perfect" single crystal material at elevated temperatures. The analytical approach described in this work will be critical in future investigations to predict how changing the size, type, and volume fraction of secondary phase inclusions can be used to impact thermal and electrical transport in this materials system.

Manufacturing of self-passivating tungsten based alloys by different powder metallurgical routes

Self-passivating tungsten based alloys will provide a major safety advantage compared to pure tungsten when used as first wall armor of future fusion reactors, due to the formation of a protective oxide layer which prevents the formation of volatile and radioactive WO3 in case of a loss of coolant accident with simultaneous air ingress. Bulk WCr10Ti2 alloys were manufactured by two different powder metallurgical routes: (1) mechanical alloying (MA) followed by hot isostatic pressing (HIP) of metallic capsules, and (2) MA, compaction, pressureless sintering in H2 and subsequent HIPing without encapsulation. Both routes resulted in fully dense materials with homogeneous microstructure and grain sizes of 300 nm and 1 μm, respectively. The content of impurities remained unchanged after HIP, but it increased after sintering due to binder residue. It was not possible to produce large samples by route (2) due to difficulties in the uniaxial compaction stage. Flexural strength and fracture toughness measured on samples produced by route (1) revealed a ductile-to-brittle-transition temperature (DBTT) of about 950 °C. The strength increased from room temperature to 800 °C, decreasing significantly in the plastic region. An increase of fracture toughness is observed around the DBTT.

The effect of Cu addition and milling contaminations on the microstructure evolution of ball milled Al-Pb alloy during sintering

Al-10 wt.%Pb and Al-10 wt.%Pb-x wt.%Cu (x = 0-7.0) bulk alloys were prepared by sintering the mechanically alloyed powders at various temperatures. The microstructure changes of the as consolidated powders in the course of sintering were analyzed by differential scanning calorimetry, scanning electron microscopy, X-ray diffraction analysis and transmission electron microscopy. It has been found that, with respect to the Al-10 wt.%Pb-x wt.%Cu alloy, CuAl2 and Cu9Al4 phases formed in the milling process, and the amount of CuAl2 phase increased while the Cu9Al4 phase disappeared gradually in the sintering process. In both Al-10 wt.%Pb and Al-10 wt.%Pb-x wt.%Cu alloys, the sintering process results in the coarsening of Pb phase and the growth rate of Pb phase fulfills the Lifshitz-Slyozov-Wagner equation even though the size of the Pb phase was in nanometer range. The Pb particle exhibits cuboctahedral morphology and has a cubic to cubic orientation relationship with the Al matrix. The addition of Cu strongly depressed the growth rate of Pb. Contamination induced by milling has apparent influence on the microstructure of the sintered alloys. Al7Cu2Fe and aluminium oxide phases were identified in the sintered alloys. The cuboctahedral morphology of Pb particles was broken up by the presence of the oxide phase. (c) 2006 Elsevier B.V. All rights reserved.

Densificação e microestrutura de um compósito Mo-Cu preparado a partir de um pó de heptamolibidato de amônia e cobre

The Cu-Mo system is a composite used in the electrical industry as material for electrical contact and resistance welding electrode as well as the heat sink and microwave absorber in microelectronic devices. The use of this material in such applications is due to the excellent properties of thermal and electrical conductivity and the possibility of adjustment of its coefficient of thermal expansion to meet those of materials used as substrates in the semiconductor micoreletrônic industry. Powder metallurgy through the processes of milling, pressing shaping and sintering is a viable technique for consolidation of such material. However, the mutual insolubility of both phases and the low wettability of liquid Cu on Mo impede its densification. However, the mutual insolubility of both phases and the low wettability of liquid Cu on Mo impede its densification. The mechanical alloying is a technique for preparation of powders used to produce nanocrystalline composite powder with amorphous phase or extended solid solution, which increases the sinterability immiscible systems such as the Mo-Cu. This paper investigates the influence of ammonium heptamolybdate (HMA) and the mechanical alloying in the preparation of a composite powder HMA-20% Cu and the effect of this preparation on densification and structure of MoCu composite produced. HMA and Cu powders in the proportion of 20% by weight of Cu were prepared by the techniques of mechanical mixing and mechanical alloying in a planetary mill. These were milled for 50 hours. To observe the evolution of the characteristics of the particles, powder samples were taken after 2, 10, 15, 20, 30 and 40 hours of milling. Cylindrical samples 5 to 8 mm in diameter and 3 to 4 mm thickness were obtained by pressing at 200 MPa to the mixed powders so as to ground. These samples were sintered at 1200 ° C for 60 minutes under an atmosphere of H2. To determine the effect of heating rate on the structure of the material during the decomposition and reduction of HMA, rates of 2, 5 and 10 ° C / min were used .. The post and the structures of the sintered samples were characterized by SEM and EDS. The density of the green and sintered bodies was measured using the geometric method (weight / volume). Vickers microhardness with a load of 1 N for 15 s were performed on sintered structures. The density of the sintered structures 10 ° C / min. reached 99% of theoretical density, how the density of sintered structures to 2 ° C / min. reached only 90% of the theoretical density

Síntese e caracterizações estrutural e magnética das ferritas de cobalto-manganês (Co1-xMnxFe2O4 E Co1,2Fe1,8-xMnxO4)

The cobalt-manganese ferrites (Co1¡xMnxFe2O4 and Co1,2Fe1,8¡xMnxO4) has a mixed structure of spinel type and it has been regarded as one of candidates for petitive wide variety of applications in devices from ultrasonic generation and detection, sensors, transformers, as well as in medical industry. Ferrites cobalt-manganese nanostructured were produced via mechanical alloying with subsequent heat treatment and were characterized by X-ray diffraction, X-ray fluorescence, scanning electron microscopy and magnetization. Samples of Co1¡xMnxFe2O4 and Co1,2Fe1,8¡xMnxO4 were obtained from the precursor powders Fe3O4, Co3O4 and Mn3O4 which were stoichiometrically mixed and ground by 10h and heat treated at 900°C for 2h. The diffraction confirmed the formation of the pure nanocrystalline phases to series Co1,2Fe1,8¡xMnxO4 with an average diameter of about 94nm. It was found that the lattice parameter increases with the substitution of Fe3Å by Mn3Å. The x-ray fluorescence revealed that the portions of metals in samples were close to the nominal stoichiometric compositions. The microstructural features observed in micrographs showed that the particles formed show very different morphology and particle size. The magnetic hysteresis measurements performed at low temperature showed that the saturation magnetization and remanence increased as the concentration of manganese, while the coercive field decreased. The anisotropy constant (Ke f ), was estimated from the data adjustments the law of approaching saturation. It was found that the anisotropy decreases substantially with the substitution of Fe by Mn.