Processing and characterization of PbSnTe-based thermoelectric materials made by mechanical alloying

The research reported in this dissertation investigates the processes required to mechanically alloy Pb1-xSnxTe and AgSbTe2 and a method of combining these two end compounds to result in (y)(AgSbTe2)–(1 - y)(Pb1-xSnxTe) thermoelectric materials for power generation applications. In general, traditional melt processing of these alloys has employed high purity materials that are subjected to time and energy intensive processes that result in highly functional material that is not easily reproducible. This research reports the development of mechanical alloying processes using commercially available 99.9% pure elemental powders in order to provide a basis for the economical production of highly functional thermoelectric materials. Though there have been reports of high and low ZT materials fabricated by both melt alloying and mechanical alloying, the processing-structure-properties-performance relationship connecting how the material is made to its resulting functionality is poorly understood. This is particularly true for mechanically alloyed material, motivating an effort to investigate bulk material within the (y)(AgSbTe2)–(1 - y)(Pb1-xSnx- Te) system using the mechanical alloying method. This research adds to the body of knowledge concerning the way in which mechanical alloying can be used to efficiently produce high ZT thermoelectric materials. The processes required to mechanically alloy elemental powders to form Pb1-xSnxTe and AgSbTe2 and to subsequently consolidate the alloyed powder is described. The composition, phases present in the alloy, volume percent, size and spacing of the phases are reported. The room temperature electronic transport properties of electrical conductivity, carrier concentration and carrier mobility are reported for each alloy and the effect of the presence of any secondary phase on the electronic transport properties is described. An mechanical mixing approach for incorporating the end compounds to result in (y)(AgSbTe2)–(1-y)(Pb1-xSnxTe) is described and when 5 vol.% AgSbTe2 was incorporated was found to form a solid solution with the Pb1-xSnxTe phase. An initial attempt to change the carrier concentration of the Pb1-xSnxTe phase was made by adding excess Te and found that the carrier density of the alloys in this work are not sensitive to excess Te. It has been demonstrated using the processing techniques reported in this research that this material system, when appropriately doped, has the potential to perform as highly functional thermoelectric material.

Nano-engineering of composite material via reactive mechanical alloying/milling (RMA/M)

Attempts to strengthen a chromium-modified titanium trialuminide by a combination of grain size refinement and dispersoid strengthening led to a new means to synthesize such materials. This Reactive Mechanical Alloying/Milling process uses in situ reactions between the metallic powders and elements from a process control agent and/or a gaseous environment to assemble a dispersed small hard particle phase within the matrix by a bottom-up approach. In the current research milled powders of the trialuminide alloy along with titanium carbide were produced. The amount of the carbide can be varied widely with simple processing changes and in this case the milling process created trialuminide grain sizes and carbide particles that are the smallest known from such a process. Characterization of these materials required the development of x-ray diffraction means to determine particle sizes by deconvoluting and synthesizing components of the complex multiphase diffraction patterns and to carry out whole pattern analysis to analyze the diffuse scattering that developed from larger than usual highly defective grain boundary regions. These identified regions provide an important mass transport capability in the processing and not only facilitate the alloy development, but add to the understanding of the mechanical alloying process. Consolidation of the milled powder that consisted of small crystallites of the alloy and dispersed carbide particles two nanometers in size formed a unique, somewhat coarsened, microstructure producing an ultra-high strength solid material composed of the chromium-modified titanium trialuminide alloy matrix with small platelets of the complex carbides Ti2AlC and Ti3AlC2. This synthesis process provides the unique ability to nano-engineer a wide variety of composite materials, or special alloys, and has shown the ability to be extended to a wide variety of metallic materials.

Mechanical alloying of MoSi2 with ternary alloying elements. Part 1: Experimental

Phase evolution during the mechanical alloying of Mo and Si elemental powders with a ternary addition of Al, Mg, Ti or Zr was monitored using X-ray diffraction. Rietveld analysis was used to quantify the phase proportions. When Mo and Si are mechanically alloyed in the absence of a ternary element, the tetragonal C11b polymorph of MoSi2 (t-MoSi2) forms by a self-propagating combustion reaction. With additional milling, the tetragonal phase transforms to the hexagonal C40 structure (h-MoSi2). The mechanical alloying of Al, Mg and Ti additions with Mo and Si tend to promote a more rapid transformation of t-MoSi2 to h-MoSi2. In high concentrations, the addition of these ternary elements inhibits the initial combustion reaction, instead promoting the direct formation of h-MoSi2. The addition of Zr tends to stabilise the tetragonal phase.

Mechanical alloying of MoSi2 with ternary alloying elements. Part 2 - computer simulation

A computer model of the mechanical alloying process has been developed to simulate phase formation during the mechanical alloying of Mo and Si elemental powders with a ternary addition of Al, Mg, Ti or Zr. Using the Arhennius equation, the model balances the formation rates of the competing reactions that are observed during milling. These reactions include the formation of tetragonal C11(b) MOSi2 (t-MoSi2) by combustion, the formation of the hexagonal C40 MoSi2 polymorph (h-MoSi2), the transformation of the tetragonal to the hexagonal form, and the recovery of t-MoSi2 from h-MoSi2 and deformed t-MoSi2. The addition of the ternary additions changes the free energy of formation of the associated MoSi2 alloys, i.e. Mo(Si, Al)(2), Mo(Mg, Al)(2), (Mo, Ti)Si-2 (Mo, Zr)Si-2 and (Mo, Fe)Si-2, respectively. Variation of the energy of formation alone is sufficient for the simulation to accurately model the observed phase formation. (C) 2003 Elsevier B.V. All rights reserved.

Mechanical alloying—a novel synthesis route for amorphous phases

Mechanical alloying (MA) pioneered by Benjamin is a technique for the extension of solid solubility in systems where the equilibrium solid solubility is limited. This technique has, in recent years, emerged as a novel alternate route for rapid solidification processing (RSP) for the production of metastable crystalline, quasicrystalline, amorphous phases and nanocrystalline materials. The glass-forming composition range (GFR), in general, is found to be much wider in case of MA in comparison with RSP. The amorphous powders produced by MA can be compacted to bulk shapes and sizes and can be used as precursors to obtain high strength materials. This paper reports the work done on solid state amorphization by MA in Ti-Ni-Cu and Al-Ti systems where a wide GFR has been obtained. Al-Ti is a classic case where no glass formation has been observed by RSP, while a GFR of 25–90 at.% Ti has been obtained in this system, thus demonstrating the superiority of MA over RSP. The free energy calculations made to explain GFR are also presented.

Microstructure, thermal stability and mechanical properties of the novel (W1-xAlx)C-Co (x=0.2, 0.33, 0.4, 0.5) cemented carbide

Bulk novel cemented carbides (W1-xAlx)C-10.1 vol% Co (x = 0.2, 0.33, 0.4, 0.5) are prepared by mechanical alloying and hot-pressing sintering. Hot-pressing (HP) is used to fabricate the bulk bodies of the hard alloys. The novel cemented carbides have good mechanical properties compared with WC-Co. The density and operating cost of the novel material is much lower than a WC-Co system. The material is easy to process and the processing leads to nano-scaled, rounded, particles in the bulk material. The hardness of (W1-xAlx)C-10.1 vol% Co (x = 0.2, 0.33, 0.4, 0.5) hard material is 20.37, 21.16, 21.59 and 22.16 GPa, and the bending strength is 1257, 1238, 1211 and 1293 MPa, with the aluminum content varying from 20% to 50%. The relationship between the microstructure and the mechanical properties of the novel hard alloy is also discussed.

The mechanical properties of magnesium matrix composites reinforced with 10 wt.% W14Al86 alloy particles

The Mg-based metal matrix composite reinforced by 10 wt.% W14Al86 alloy particles has been prepared by mechanical alloying and press-forming process. X-ray diffraction studies confirm the formation of the composite. Microstructure characterization of the samples reveals the uniform distribution of fine W14Al86 alloy. Mechanical properties characterization revealed that the reinforcement of W14Al86 alloy lead to a significant increase in hardness and tensile strength of Mg and AZ91.

Preparation and mechanical properties of a bulk icosahedral quasicrystalline Ti45Zr35Ni17Cu3 alloy

A bulk Ti45Zr35Ni17Cu3 alloy, which consisted of the icosahedral quasicrystalline phase, was prepared by mechanical alloying(MA) and subsequent pulse discharge sintering. Ti45Zr35Ni17Cu3 amorphous powders (with particle size < 50 mu m) were obtained after mechanical alloying for more than 150 h from the mixture of the elemental powder. The transformation temperature range from amorphous phase to the quasicrystalline phase was from 400 K to 900 K. The mechanical properties of the bulk quasicrystalline alloy have been examined at room temperature. The Vickers hardness and compressive fracture strength were 620 +/- 40 and 1030 +/- 60 MPa, respectively. The bulk quasicrystalline alloy exhibited the elastic deformation by the compressive test. The fracture mode was brittle cleavage fracture.