Methods for melting temperature calculation

Melting temperature calculation has important applications in the theoretical study of phase diagrams and computational materials screenings. In this thesis, we present two new methods, i.e., the improved Widom's particle insertion method and the small-cell coexistence method, which we developed in order to capture melting temperatures both accurately and quickly.

We propose a scheme that drastically improves the efficiency of Widom's particle insertion method by efficiently sampling cavities while calculating the integrals providing the chemical potentials of a physical system. This idea enables us to calculate chemical potentials of liquids directly from first-principles without the help of any reference system, which is necessary in the commonly used thermodynamic integration method. As an example, we apply our scheme, combined with the density functional formalism, to the calculation of the chemical potential of liquid copper. The calculated chemical potential is further used to locate the melting temperature. The calculated results closely agree with experiments.

We propose the small-cell coexistence method based on the statistical analysis of small-size coexistence MD simulations. It eliminates the risk of a metastable superheated solid in the fast-heating method, while also significantly reducing the computer cost relative to the traditional large-scale coexistence method. Using empirical potentials, we validate the method and systematically study the finite-size effect on the calculated melting points. The method converges to the exact result in the limit of a large system size. An accuracy within 100 K in melting temperature is usually achieved when the simulation contains more than 100 atoms. DFT examples of Tantalum, high-pressure Sodium, and ionic material NaCl are shown to demonstrate the accuracy and flexibility of the method in its practical applications. The method serves as a promising approach for large-scale automated material screening in which the melting temperature is a design criterion.

We present in detail two examples of refractory materials. First, we demonstrate how key material properties that provide guidance in the design of refractory materials can be accurately determined via ab initio thermodynamic calculations in conjunction with experimental techniques based on synchrotron X-ray diffraction and thermal analysis under laser-heated aerodynamic levitation. The properties considered include melting point, heat of fusion, heat capacity, thermal expansion coefficients, thermal stability, and sublattice disordering, as illustrated in a motivating example of lanthanum zirconate (La₂Zr₂O₇). The close agreement with experiment in the known but structurally complex compound La₂Zr₂O₇ provides good indication that the computation methods described can be used within a computational screening framework to identify novel refractory materials. Second, we report an extensive investigation into the melting temperatures of the Hf-C and Hf-Ta-C systems using ab initio calculations. With melting points above 4000 K, hafnium carbide (HfC) and tantalum carbide (TaC) are among the most refractory binary compounds known to date. Their mixture, with a general formula Ta_xHf_1-xC_y, is known to have a melting point of 4215 K at the composition Ta₄HfC₅, which has long been considered as the highest melting temperature for any solid. Very few measurements of melting point in tantalum and hafnium carbides have been documented, because of the obvious experimental difficulties at extreme temperatures. The investigation lets us identify three major chemical factors that contribute to the high melting temperatures. Based on these three factors, we propose and explore a new class of materials, which, according to our ab initio calculations, may possess even higher melting temperatures than Ta-Hf-C. This example also demonstrates the feasibility of materials screening and discovery via ab initio calculations for the optimization of "higher-level" properties whose determination requires extensive sampling of atomic configuration space.

Caracterização de juntas soldadas por Arame Tubular com proteção gasosa do aço ferrítico ASTM A335 P91, antes e após situação de duplo reparo.

Pouco se sabe a respeito das consequências da operação de reparo nas propriedades mecânicas e metalúrgicas das juntas do aço ASTM A335 grau P91 soldadas por Arame Tubular. Neste trabalho foi realizado um estudo para analisar e caracterizar juntas de um tubo do aço P91 soldadas pelo processo Arame Tubular com proteção gasosa, antes e após situação de duplo reparo. Foram utilizadas técnicas de microscopia eletrônica de varredura (MEV), análise química semiquantitativa por EDS (Energy Dispersive Spectroscopy), microscopia óptica (MO), além da obtenção de medidas de microdureza Vickers e realização de ensaios de impacto e tração à temperatura ambiente. A macrografia revelou a existência de uma nova zona termicamente afetada formada no centro da junta reparada e a análise micrográfica mostrou que esta zona apresentou uma pequena tendência a formação de grãos menores do que na zona de fusão que sofreu reparo, além disso, a região tinha grãos colunares que não são característicos de uma zona termicamente afetada e quantidade de carbonetos menor comparativamente. Não houve variações significativas nos valores de tração e microdureza. Os ensaios de impacto revelaram baixos valores de energia absorvida na zona de fusão do 2 reparo, no entanto, todas as outras zonas avaliadas das juntas com e sem reparo apresentaram valores dentro das especificações.

Wear of hardfacing white cast irons by solid particle erosion

The response of three commercial weld-hardfacing alloys to erosive wear has been studied. These were high chromium white cast irons, deposited by an open-arc welding process, widely used in the mineral processing and steelmaking industries for wear protection. Erosion tests were carried out with quartz sand, silicon carbide grit and blast furnace sinter of two different sizes, at a velocity of 40 m s-1 and at impact angles in the range 20° to 90°. A monolithic white cast iron and mild steel were also tested for comparison. Little differences were found in the wear rates when silica sand or silicon carbide grit was used as the erodent. Significant differences were found, however, in the rankings of the materials. Susceptibility to fracture of the carbide particles in the white cast irons played an important role in the behaviour of the white cast irons. Sinter particles were unable to cause gross fracture of the carbides and so those materials with a high volume fraction of carbides showed the greatest resistance to erosive wear. Silica and silicon carbide were capable of causing fracture of the primary carbides. Concentration of plastic strain in the matrix then led to a high wear rate for the matrix. At normal impact with silica or silicon carbide erodents mild steel showed a greater resistance to erosive wear than these alloys. © 1995.

A fracture criterion for the notch strength of high strength steels in the presence of hydrogen

High strength steels can suffer from a loss of ductility when exposed to hydrogen, and this may lead to sudden failure. The hydrogen is either accommodated in the lattice or is trapped at defects, such as dislocations, grain boundaries and carbides. The challenge is to identify the effect of hydrogen located at different sites upon the drop in tensile strength of a high strength steel. For this purpose, literature data on the failure stress of notched and un-notched steel bars are re-analysed; the bars were tested over a wide range of strain rates and hydrogen concentrations. The local stress state at failure has been determined by the finite element (FE) method, and the concentration of both lattice and trapped hydrogen is predicted using Oriani's theory along with the stress-driven diffusion equation. The experimental data are rationalised in terms of a postulated failure locus of peak maximum principal stress versus lattice hydrogen concentration. This failure locus is treated as a unique material property for the given steel and heat treatment condition. We conclude that the presence of lattice hydrogen increases the susceptibility to hydrogen embrittlement whereas trapped hydrogen has only a negligible effect. It is also found that the observed failure strength of hydrogen charged un-notched bars is less than the peak local stress within the notched geometries. Weakest link statistics are used to account for this stressed volume effect. © 2013 Elsevier Ltd.

First-principles study of UC2 and U2C3

The electronic structure and mechanical properties Of UC2 and U2C3 have been systematically investigated using first-principles calculations by the projector-augmented-wave (PAW) method. Furthermore, in order to describe precisely the strong on-site Coulomb repulsion among the localized U 5f electrons, we adopt the generalized gradient approximation +U formalisms for the exchange-correlation term. We show that our calculated structural parameters and electronic properties for UC2 and U2C3 are in good agreement with the experimental data by choosing an appropriate Hubbard U = 3 eV. As for the chemical bonding nature, the contour plot of charge density and total density of states suggest that UC2 and U2C3 are metallic mainly contributed by the 5f electrons, mixed with significant covalent component resulted from the strong C-C bonds. The present results also illustrate that the metal-carbon (U-C) bonding and the carbon-carbon covalent bonding in U2C3 are somewhat weaker than those in UC2, leading to the weaker thermodynamic stability at high temperature as observed by experiments.

Hard magnetic properties of Sm3Fe26.7VxN4 and Sm3Fe26.7VxCy

Sm3Fe26.7V2.3N4 nitrides and Sm3Fe26.7V2.3Cy carbides have been synthesized by gas-solid phase reaction. Their hard magnetic properties have been investigated by means of additional ball-milling at room temperature. The saturation magnetization of Sm3Fe26.7V2.3N4 almost decreases linearly with increasing ball-milling time t, but that of Sm3Fe26.7V2.3Cy has no obvious change when the ball-milling time increases from t = 1 to 28 h. As a preliminary result, the maximum remanence B-r of 0.94 and 0.88 T, the coercivity mu(0i)H(C) of 0.75 and 0.25 T, and the maximum energy product (BH) of 108.5 and 39.1 kJ/m(3) for their resin-bonded permanent magnets are achieved, respectively, by ball-milling at 293 K. (C) 1999 Published by Elsevier Science B.V. All rights reserved.

The synthesis of nanostructured W2C on ultrahigh surface area carbon materials via carbothermal hydrogen reduction

Nanostructured tungsten carbides were synthesized, for the first time, with a size distribution of 5-12 nm on ultrahigh surface area carbon material, by carbothermal hydrogen reduction (CHR) at 850degreesC and metal Ni promoted CHR at 650 degreesC.

Fabrication, thermal stability and mechanical properties of novel composite hardmetals obtained by solid-state reaction and hot-pressing sintering

A novel cemented carbides (W0.7Al0.3)C-0.65-Co with different cobalt contents were prepared by solid-state reaction and hot-pressing technique. Hot-pressing technique as a novel technique was performed to fabricate the bulk bodies of the hard alloys. The novel cemented carbides have superior mechanical properties compared with WC-Co. The density, operate cost of the novel material were lower than WC-Co system. The novel materials were easy to process nanoscale sintering and get the rounded particles in the bulk materials. There is almost no eta-phase in the (W0.7Al0.3)C-0.65-Co cemented carbides system although the carbon deficient get the astonished 35% value.

Fabrication, thermal stability and mechanical properties of novel (W0.5Al0.5)C-0.8-Co composite prepared by mechanical alloying and hot-pressing sintering

A novel cemented carbides (W0.5Al0.5)C-0.8-Co with different cobalt contents were prepared by mechanical alloying and hot-pressing technique. Hot-pressing technique as a common technique was performed to fabricate the bulk bodies of the hard alloys. The novel cemented carbides have superior mechanical properties compared to WC-Co. The density, operating cost of the novel material were much lower than WC-Co. There is almost no eta-phase in the (W0.5Al0.5)C-0.8-Co cemented carbides system although the carbon deficient get the value of 20%, and successfully got the nanostructured rounded (W0.5Al0.5)C-0.8 particles.

A novel (W-Al)-C-Co composite cemented carbide prepared by mechanical alloying and hot-pressing sintering

Novel cemented carbides (W0.4Al0.6)C-0.5-Co With different cobalt contents were prepared by mechanical alloying and hot-pressing technique. Hot-pressing technique as a common technique was performed to fabricate the bulk bodies of the hard alloys. The novel cemented carbides have good mechanical properties compared with WC-Co. The density and operation cost of the novel material were much lower than the WC-Co system. It was easy to process submicroscale sintering with the novel materials and obtain the rounded particles in the bulk materials. There is almost no eta-phase in the (W0.4Al0.6)C-0.5-CO cemented carbides system although the carbon deficient obtains the astonishing value of 50%.

Nanostructured novel cemented hard alloy obtained by mechanical alloying and hot-pressing sintering and its applications

A novel cemented carbides (W0.8Al0.2)C-0.7-Co with different cobalt contents were prepared by mechanical alloying and hot-pressing technique. Hot-pressing technique as a common technique was performed to fabricate the bulk bodies of the hard alloys. The novel cemented carbides have superior mechanical properties compared with WC-Co. The density, operate cost of the novel material were much lower than WC-Co system. The novel materials were easy to process nanoscale sintering and get the rounded particles in the bulk materials.

Electronic and mechanical properties of 5d transition metal mononitrides via first principles

The electronic and mechanical properties of 5d transition metal mononitrides from LaN to AuN are systematically investigated by use of the density-functional theory. For each nitride, Six Structures are considered, i.e., rocksalt, zinc blende, CsCl, wurtzite, NiAs and WC structures. Among the considered structures, rocksalt structure is the most stable for LaN, HfN and ALIN, WC structure for TaN, NiAs structure for WN, wurtzite structure for ReN, OsN, IrN and PtN. The most stable Structure for each nitride is mechanically stable. The formation enthalpy increases from LaN to AuN.

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.

Fabrication, microstructure and mechanical properties of novel cemented hard alloy obtained by mechanical alloying and hot-pressing sintering

A novel cemented carbides alloy (W0.4Al0.6)C-0.65-Co were prepared by mechanical alloying and hot-pressing sintering in this work. Hot-pressing (HP) as a common technique was performed to fabricate the bulk bodies of the hard alloys. The hardness, bending strength, density of the novel hard alloy are also tested, and it has superior mechanical properties. The hardness of (W0.4Al0.6)C-0.65-Co hard alloy was very high, and the density, operate cost of the novel material were much lower than WC-Co, more important is the aluminum dissolving is not decrease the strength compared with the WC-Co system. There is almost no eta-phase in the (W0.4Al0.6)C-0.65-Co cemented carbides system even the carbon deficient reaches the astonishing value of 35%. This novel property will give us more choice to design and gain new materials that we needed.