Orientation Selection and Microstructural Evolution in Directionally Solidified Tb0.3Dy0.7Fe1.95

Tb0.3Dy0.7Fe1.95 alloy was directionally solidified by using a modified Bridgman technique at a wide range of growth rates of 5 to 100 cm/h. The directionally grown samples exhibited plane front solidification morphology up to a growth rate of 90 cm/h. Typical island banding feature was observed closer to the chilled end, which eventually gave rise to irregular peritectic coupled growth (PCG). The PCG gained prominence with an increase in the growth rate. The texture study revealed formation of strong aOE (c) 311 > texture in a lower growth rate regime, aOE (c) 110 > and ``rotated aOE (c) 110 > aEuroe in an intermediate growth regime, and aOE (c) 112 > in a higher growth rate regime. In-depth analysis of the atomic configuration of a solid-liquid interface revealed that the growth texture is influenced by the kinetics of atomic attachment to the solid-liquid interface, which is intimately related to a planar packing fraction and an atomic stacking sequence of the interfacial plane. The mechanism proposed in this article is novel and will be useful in addressing the orientation selection mechanism of topologically closed packed intermetallic systems. The samples grown at a higher growth rate exhibit larger magnetostriction (lambda) and d lambda/dH owing to the absence of pro-peritectic (Tb,Dy)Fe-3 and formation of aOE (c) 112 > texture, which lies closer to the easy magnetization direction (EMD).

Formation and structure of composite coating of HDA and micro-plasma oxidation on A3 steel

Composite coatings were obtained on A3 steel by hot dipping aluminum(HDA) at 720 ℃ for 6 min and micro-plasma oxidation(MPO) in alkali electrolyte. The surface morphology, element distribution and interface structure of composite coatings were studied by means of XRD, SEM and EDS. The results show that the composite coatings obtained through HDA/MPO on A3 steel consist of four layers. From the surface to the substrate, the layer is loose Al2O3 ceramic, compact Al2O3 ceramic, Al and FeAl intermetallic compound layer in turn. The adhesions among all the layers are strengthened because the ceramic layer formed at the Al surface originally, FeAl intermetallic compound layer and substrate are combined in metallurgical form through mutual diffusion during HDA process.Initial experiment results disclose that the anti-corrosion performance and wear resistance of composite coating are obviously improved through HDA/MPO treatment.

Effects of La2O3 on Microstructure and Wear Properties of Laser Clad gamma/Cr7C3/TiC Composite Coatings on TiAl Intermatallic Alloy

The effects of La2O3 addition on the microstructure and wear properties of laser clad gamma/C(r)7C(3)/TiC composite coatings on gamma-TiAl intermetallic alloy substrates with NiCr-Cr3C2 precursor mixed powders have been investigated by optical microscopy (OM), scanning electron microscopy (SEM), X-ray diffraction (XRD) and energy-dispersive spectrometer (EDS) and block-on-ring wear tests. The responding wear mechanisms are discussed in detail. The results are compared with that for composite coating without La2O3. The comparison indicates that no evident new crystallographic phases are formed except a rapidly solidified microstructure consisting of the primary hard Cr7C3 and TiC carbides and the gamma/Cr7C3 eutectics distributed in the tough gamma nickel solid solution matrix. Good finishing coatings can be achieved under a proper amount of La2O3-addition and a suitable laser processing parameters. The additions of rare-earth oxide La,03 can refine and purify the microstructure of coatings, relatively decrease the volume fraction of primary blocky Cr7C3 to Cr7C3/gamma eutectics, reduce the dilution of clad material from base alloy and increase the microhardness of the coatings. When the addition of La2O3 is approximately 4 wt.%, the laser clad composite coating possesses the highest hardness and toughness. The composite coating with 4 wt.%La2O3 addition can result the best enhancement of wear resistance of about 30%. However, too less or excessive addition amount of La2O3 have no better influence on wear resistance of the composite coating.

Eutectic MC Carbide Growth Morphologies of a Laser Clad TiC/FeAl Composite Coating

In this paper, eutectic MC carbide growth morphology and its evolution with laser scanning speed were studied comprehensively of a laser clad MC carbide reinforced FeAl intermetallic matrix composite coating. As the laser scanning speed increased, the growth morphology of eutectic MC carbide was found to be needle-aligned annulation, butterfly-like and well-developed dendrite.

Microstructure and mechanical properties of a novel Zr-based bulk metallic glass composite

Zr48.5Cu46.5Al5 bulk metallic glass (BMG) composites with diameters of 3 and,4 mm were prepared through suction casting in an arc melting furnace by modulating the alloy composition around the monothetic BMG composition of the high glass forming ability. Microstructural characterization reveals that the composites contain micron-sized CuZr phase with martensite structure, as well as nano-sized Zr2Cu crystalline particles and Cu10Zr7 plate-like phase embedded in an amorphous matrix. Room temperature compression tests showed that the composites exhibited significant strain hardening and obvious plastic strain of 7.7% for 3 nun and 6.4% for 4 nun diameter samples, respectively.

Microstructure and mechanical properties of Zr-Cu-Al bulk metallic glasses

Zr49Cu46Al5 and Zr48.5Cu46.5Al5 bulk metallic glasses(BMGs) with diameter of 5 mm were prepared through water-cooled copper mold casting. The phase structures of the two alloys were identified by X-ray diffractometry(XRD). The thermal stability was examined by differential scanning calorimetry(DSC). Zr49Cu46Al5 alloy shows a glass transition temperature, T, of about 689 K, an crystallization temperature, T-x, of about 736 K. The Zr48.5Cu46.5Al5 alloy shows no obvious exothermic peak. The microstructure of the as-cast alloys was analyzed by transmission electron microscopy(TEM). The aggregations of CuZr and CuZr2 nanocrystals with grain size of about 20 nm are observed in Zr49Cu46Al5 nanocrystalline composite, while the Zr48.5Cu46.5Al5 alloy containing many CuZr martensite plates is crystallized seriously. Mechanical properties of bulk Zr49Cu46Al5 nanocrystalline composite and Zr48.5Cu46.5Al5 alloy measured by compression tests at room temperature show that the work hardening ability of Zr48.5Cu46.5Al5 alloy is larger than that of Zr48.5Cu46.5Al5 alloy.

Structure and mechanical properties of ceramic coatings fabricated by plasma electrolytic oxidation on aluminized steel

Ceramic coatings were formed by plasma electrolytic oxidation (PEO) on aluminized steel. Characteristics of the average anodic voltages versus treatment time were observed during the PEO process. The micrographs, compositions and mechanical properties of ceramic coatings were investigated. The results show that the anodic voltage profile for processing of aluminized steel is similar to that for processing bulk Al alloy during early PEO stages and that the thickness of ceramic coating increases approximately linearly with the Al layer consumption. Once the Al layer is completely transformed, the FeAl intermetallic layer begins to participate in the PEO process. At this point, the anodic voltage of aluminized steel descends, and the thickness of ceramic coating grows more slowly. At the same time, some micro-cracks are observed at the Al2O3/FeAl interface. The final ceramic coating mainly consists of gamma-Al2O3, mullite, and alpha-Al2O3 phases. PEO ceramic coatings have excellent elastic recovery and high load supporting performance. Nanohardness of ceramic coating reaches about 19.6 GPa. (c) 2007 Elsevier B. V. All rights reserved.

Formation and Structure of Composite Coating of HAD and Micro-Plasma Oxidation on A3 Steel

Composite coatings were obtained on A3 steel by hot dipping aluminum(HAD) at 720 degreesC for 6 min and micro-plasma oxidation (MPO) in alkali electrolyte. The surface morphology, element distribution and interface structure of composite coatings were studied by means of XRD, SEM and EDS. The results show that the composite coatings obtained through HAD/MPO on A3 steel consist of four layers. From the surface to the substrate, the layer is loose Al2O3 ceramic, compact Al2O3 ceramic, At and FeAl intermetallic compound layer in turn. The adhesions among all the layers are strengthened because the ceramic layer formed at the At surface originally, FeAl intermetallic compound layer and substrate are combined in metallurgical form through mutual diffusion during HAD process. Initial experiment results disclose that the anti-corrosion performance and wear resistance of composite coating are obviously improved through HAD/MPO treatment.

Chain-forming zintl antimonides as novel thermoelectric materials

Zintl phases, a subset of intermetallic compounds characterized by covalently-bonded "sub-structures," surrounded by highly electropositive cations, exhibit precisely the characteristics desired for thermoelectric applications. The requirement that Zintl compounds satisfy the valence of anions through the formation of covalent substructures leads to many unique, complex crystal structures. Such complexity often leads to exceptionally low lattice thermal conductivity due to the containment of heat in low velocity optical modes in the phonon dispersion. To date, excellent thermoelectric properties have been demonstrated in several Zintl compounds. However, compared with the large number of known Zintl phases, very few have been investigated as thermoelectric materials.

From this pool of uninvestigated compounds, we selected a class of Zintl antimonides that share a common structural motif: anionic moieties resembling infinite chains of linked MSb₄ tetrahedra, where $M$ is a triel element. The compounds discussed in this thesis (A₅M₂Sb₆ and A₃MSb₃, where A = Ca or Sr and M = Al, Ga and In) crystallize as four distinct, but closely related "chain-forming" structure types. This thesis describes the thermoelectric characterization and optimization of these phases, and explores the influence of their chemistry and structure on the thermal and electronic transport properties. Due to their large unit cells, each compound exhibits exceptionally low lattice thermal conductivity (0.4 - 0.6 W/mK at 1000 K), approaching the predicted glassy minimum at high temperatures. A combination of Density Functional calculations and classical transport models were used to explain the experimentally observed electronic transport properties of each compound. Consistent with the Zintl electron counting formalism, A₅M₂Sb₆ and A₃MSb₃ phases were found to have filled valence bands and exhibit intrinsic electronic properties. Doping with divalent transition metals (Zn²⁺ and Mn²⁺) on the M³⁺ site, or Na¹⁺ on the A³⁺ site allowed for rational control of the carrier concentration and a transition towards degenerate semiconducting behavior. In optimally-doped samples, promising peak zT values between 0.4 and 0.9 were obtained, highlighting the value of continued investigations of complex Zintl phases.

Estudo do efeito magnetocalórico em sistemas magnéticos com terras raras

O efeito magnetocalórico, base da refrigeração magnética, é caracterizado por duas quantidades: a variação isotérmica da entropia (ΔST) e a variação adiabática da temperatura (ΔTS); que são obtidas sob variações na intensidade de um campo magnético aplicado. Em sistemas que apresentam anisotropia magnética, pode‐se definir o efeito magnetocalórico anisotrópico, o qual, por definição, é calculado sob variações na direção de aplicação de um campo magnético cuja intensidade mantém‐se fixa, e é caracterizado por duas quantidades: a variação anisotrópico‐isotérmica da entropia (ΔSan) e a variação anisotrópico‐adiabática da temperatura (ΔTan). O efeito magnetocalórico e o efeito magnetocalórico anisotrópico foram estudados nos compostos intermetálicos formados por terras e outros materiais não magnéticos: RNi2, RNi5, RZn e Gd1‐nPrnAl2. Os cálculos foram feitos partindo de hamiltonianos modelo que incluem as interações de troca, Zeeman, de campo cristalino e quadrupolar.

I. Reactively sputtered Ti-Si-N thin films for diffusion barrier applications. II. Oxidation, diffusion and crystallization of an amorphous Zr_(60)Al_(15)Ni_(25) alloy.

Films of Ti-Si-N obtained by reactively sputtering a TiSi_2, a Ti_5Si_3, or a Ti_3Si target are either amorphous or nanocrystalline in structure. The atomic density of some films exceeds 10^23 at./cm^3. The room-temperature resistivity of the films increases with the Si and the N content. A thermal treatment in vacuum at 700 °C for 1 hour decreases the resistivity of the Ti-rich films deposited from the Ti_5Si_3 or the Ti_3Si target, but increases that of the Si-rich films deposited from the TiSi_2 target when the nitrogen content exceeds about 30 at. %.

Ti_(34)Si_(23)N_(43) deposited from the Ti_5Si_3 target is an excellent diffusion barrier between Si and Cu. This film is a mixture of nanocrystalline TiN and amorphous SiN_x. Resistivity measurement from 80 K to 1073 K reveals that this film is electrically semiconductor-like as-deposited, and that it becomes metal-like after an hour annealing at 1000 °C in vacuum. A film of about 100 nm thick, with a resistivity of 660 µΩcm, maintains the stability of Si n+p shallow junction diodes with a 400 nm Cu overlayer up to 850 °C upon 30 min vacuum annealing. When used between Si and Al, the maximum temperature of stability is 550 °C for 30 min. This film can be etched in a CF_4/O_2 plasma.

The amorphous ternary metallic alloy Zr_(60)Al_(15)Ni_(25) was oxidized in dry oxygen in the temperature range 310 °C to 410 °C. Rutherford backscattering and cross-sectional transmission electron microscopy studies suggest that during this treatment an amorphous layer of zirconium-aluminum-oxide is formed at the surface. Nickel is depleted from the oxide and enriched in the amorphous alloy below the oxide/alloy interface. The oxide layer thickness grows parabolically with the annealing duration, with a transport constant of 2.8x10^(-5) m^2/s x exp(-1.7 eV/kT). The oxidation rate is most likely controlled by the Ni diffusion in the amorphous alloy.

At later stages of the oxidation process, precipitates of nanocrystalline ZrO_2 appear in the oxide near the interface. Finally, two intermetallic phases nucleate and grow simultaneously in the alloy, one at the interface and one within the alloy.

Estudo do efeito magnetocalórico nos compostos da série Gd1-xDyxAl2

Nesta dissertação, foram investigadas as propriedades magnéticas e magnetocalóricas nos compostos intermetálicos de terras-raras Gd1-xDyxAl2 (x = 0, 0.25, 0.50, 0.75 e 1.00) usando abordagens teórica e experimental. Do ponto de vista teórico, a série Gd1-xDyxAl2 foi descrita através de um modelo para o hamiltoniano magnético, incluindo o efeito Zeeman, interação de troca e a anisotropia de campo elétrico cristalino. As entropias da rede e eletrônica foram consideradas nas aproximações de Debye e de gás de elétrons livres, respectivamente. A parte experimental inclui a preparação do material, sua caracterização e medidas das quantidades magnéticas e magnetocalóricas. Os resultados experimentais e os cálculos teóricos da variação adiabática da temperatura (ΔTad) e da variação isotérmica da entropia (ΔS T), sob variações de campo magnético ao longo da direção de fácil magnetização, estão de bom acordo. O efeito da aplicação do campo magnético ao longo de uma direção de difícil magnetização foi estudado e as componentes da magnetização em função da temperatura foram investigadas. Também foi observado que a temperatura de reorientação de spin, TR, diminui quando a intensidade do campo magnético aumenta. Além disso, as concentrações molares ótimas de um material híbrido formado pelos compostos Gd1-xDyxAl2 (x = 0, 0.25, 0.50, 0.75 e 1.00) foram simuladas usando um método numérico de matriz proposto por Smaili e Chahine. O compósito apresenta um bom intervalo de temperatura para um refrigerador magnético de 60 até 170 K.

Investigação do efeito magnetocalórico convencional e anisotrópico no sistema Er(1-y)Ho(y)N

O efeito magnetocalórico, base da refrigeração magnética, é caracterizado por duas quantidades: a variação isotérmica da entropia (ΔST) e a variação adiabática da temperatura (ΔTad) as quais podem ser obtidas sob variações na intensidade de um campo magnético aplicado. Em sistemas que apresentam anisotropia magnética, pode‐se definir o efeito magnetocalórico anisotrópico, o qual, por definição, é calculado através da variação na direção de aplicação de um campo magnético cuja intensidade se mantém fixa. Nos materiais de nosso interesse, o efeito magnetocalórico é estudado teoricamente partindo de um hamiltoniano modelo que leva em conta a rede magnética (que pode ser composta por diversas sub-redes magnéticas acopladas), rede cristalina e a dinâmica dos elétrons de condução. No hamiltoniano magnético são consideradas as interações de troca, Zeeman e campo cristalino (esta ultima responsável pela anisotropia magnética). Recentemente, estudamos o efeito magnetocalórico convencional e o efeito magnetocalórico anisotrópico nos compostos mononitretos com terras-raras, a saber: Ho(y)Er(1-y)N para as concentrações y= 0,1,0.5 e 0.75. Comparações entre nossos resultados teóricos e os dados experimentais para o EMC foram bastante satisfatórias [3,9]. Além disso, diversas predições teóricas como a existência de uma fase ferrimagnética no sistema Ho(y)Er(1-y)N (para a concentração y=0.5) e reorientações de spin nas sub-redes do Ho e Er foram feitas [25].

Identificação da fase sigma em uma junta soldada pelo processo TIG manual autógeno de um aço hiperduplex SAF 2707HD (UNS S32707) por difração de raios-x.

O aço inoxidável hiperduplex possui alta resistência a corrosão por pite em ambientes contendo cloretos, quando comparado a outros aços inoxidáveis comercialmente conhecidos. Possui boas propriedades mecânicas, com limite de escoamento superior a 700MPa e limite de resistência a tração em torno de 1000MPa. Essas propriedades o tornam muito atrativos para aplicações em ambientes contendo cloretos, e por isso tem tido destaque na indústria de óleo e gás, refinarias, plataformas offshore, etc. A liga hiperduplex é composta por uma estrutura bifásica, contendo proporções aproximadamente iguais de ferrita e austenita. Esse material possui boa soldabilidade, mas por ser termodinamicamente metaestável, em altas temperaturas pode ocorrer a precipitação de fases intermetálicas não desejáveis, o que resulta em perda de propriedades mecânicas e diminuição da resistência a corrosão. A fase sigma tem sido fortemente estudada, pois é comum sua precipitação nos aços inoxidáveis da família duplex durante o procedimento de soldagem se este não for muito bem controlado. A fase sigma precipita preferencialmente na fase ferrítica, devido a maior concentração de Cr e Mo, que são os elementos formadores da fase. A resistência a corrosão é reduzida e as propriedades mecânicas do material são alteradas o tornando frágil devido a presença da fase sigma. É formada entre 600C e 1000C e possui uma estrutura tetragonal complexa. O objetivo do trabalho foi identificar a possível presença da fase sigma na junta soldada do aço inoxidável hiperduplex SAF 2707 HD (UNS S32707) pelo processo TIG autógeno manual através da difração de raios-x. Nessa pesquisa, foram analisadas uma junta soldada do material pelo processo TIG autógeno manual com arco pulsado. Complementando o estudo foram analisadas seis amostras do aço inoxidável superduplex, sendo que cinco amostras sofreram tratamento térmico para a proposital formação da fase sigma. O refinamento do resultado da difração das amostras foi feito utilizando o método de Rietveld no software Topas Academic versão 4.1. O resultado da amostra soldada de hiperduplex apresentou as fases austenita, ferrita e alguns prováveis óxidos. Os resultados das amostras de superduplex tratadas termicamente apresentaram a fase sigma, conforme esperado na pesquisa, e as fases austenita e ferrita.

ELECTRONIC AND MAGNETIC-STRUCTURE OF THE TERNARY COMPOUND ND2FE17N

The electronic and the magnetic structure of the Nd2Fe17N1 phase in the family of Nd-Fe-N ternary compounds have been calculated using the first-principles, spin-polarized orthogonalized linear-combination-of-atomic-orbitals method. Results are presented in the form of site-decomposed and spin-projected partial density of states. The occupation sites of the three N atoms are determined by an average radial distribution of all possible N site configurations. Both cases of N occupying the 3b and the 18g sites are studied. The results indicate that the 6c Fe sites have the maximum and the 18h Fe sites have the minimum local moments. This is in good agreement with experiment. It is concluded that the influence on the local moment due to lattice expansion is less important compared to that due to interatomic interaction between the N atom and its neighbors. The results also show the important role of N atoms in raising the Curie temperature of this compound.