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At least 775 records · Page 43

New Effective Material Couple--Oxide Ceramic and Carbon Nanotube-- Developed for Aerospace Microsystem and Micromachine Technologies

The prime driving force for using microsystem and micromachine technologies in transport vehicles, such as spacecraft, aircraft, and automobiles, is to reduce the weight, power consumption, and volume of components and systems to lower costs and increase affordability and reliability. However, a number of specific issues need to be addressed with respect to using microsystems and micromachines in aerospace applications--such as the lack of understanding of material characteristics; methods for producing and testing the materials in small batches; the limited proven durability and lifetime of current microcomponents, packaging, and interconnections; a cultural change with respect to system designs; and the use of embedded software, which will require new product assurance guidelines. In regards to material characteristics, there are significant adhesion, friction, and wear issues in using microdevices. Because these issues are directly related to surface phenomena, they cannot be scaled down linearly and they become increasingly important as the devices become smaller. When microsystems have contacting surfaces in relative motion, the adhesion and friction affect performance, energy consumption, wear damage, maintenance, lifetime and catastrophic failure, and reliability. Ceramics, for the most part, do not have inherently good friction and wear properties. For example, coefficients of friction in excess of 0.7 have been reported for ceramics and ceramic composite materials. Under Alternate Fuels Foundation Technologies funding, two-phase oxide ceramics developed for superior high-temperature wear resistance in NASA's High Operating Temperature Propulsion Components (HOTPC) project and new two-layered carbon nanotube (CNT) coatings (CNT topcoat/iron bondcoat/quartz substrate) developed in NASA's Revolutionary Aeropropulsion Concepts (RAC) project have been chosen as a materials couple for aerospace applications, including micromachines, in the nanotechnology lubrication task because of their potential for superior friction and wearf properties in air and in an ultrahigh vacuum, spacelike environment. At the NASA Glenn Research Center, two-phase oxide ceramic eutectics, Al2O3/ZrO2(Y2O3), were directionally solidified using the laser-float-zone process, and carbon nanotubes were synthesized within a high-temperature tube furnace at 800 C. Physical vapor deposition was used to coat all quartz substrates with 5-nm-thick iron as catalyst and bondcoat, which formed iron islands resembling droplets and serving as catalyst particles on the quartz. A series of scanning electron micrographs showing multiwalled carbon nanotubes directionally grown as aligned "nanograss" on quartz is presented. Unidirectional sliding friction eperiments were conducted at Glenn with the two-layered CNT coatings in contact with the two-phase Al2O3/ZrO2(Y2O3) eutectics in air and in ultrachigh vacuum. The main criteria for judging the performance of the materials couple for solid lubrication and antistick applications in a space environment were the coefficient of friction and the wear resistance (reciprocal of wear rate), which had to be less than 0.2 and greater than 10(exp 5) N(raised dot)/cubic millimetes, respectively, in ultrahigh vacuum. In air, the coefficient of friction for the CNT coatings in contact with Al2O3/ZrO2 (Y2O3) eutectics was 0.04, one-fourth of that for quartz. In an ultrahigh vacuum, the coefficient of friction for CNT coatings in contact with Al2O3/ZrO2 (Y2O3) was one-third of that for quartz. The two-phase Al2O3/ZrO2 (Y2O3) eutectic coupled with the two-layered CNT coating met the coefficient of friction and wear resistance criteria both in air and in an ultrahigh vacuum, spacelike environment. This material's couple can dramatically improve the stiction (or adhesion), friction, and wear resistance of the contacting surfaces, which are major issues for microdevices and micromachines.

Miyoshi, Kazuhisa↗

High temperature thermochemical energy storage materials

Disclosed are thermal energy storage systems and methods that utilize metal carbonate eutectics that can undergo high temperature reversible reactions to form mixtures of metal oxides. The metal oxides undergo an exothermic reaction with carbon dioxide to form the molten metal carbonate eutectics, and the molten metal carbonate eutectics undergo an endothermic decarbonization reaction to form the metal oxides and carbon dioxide. By carrying out the reversible reactions at a temperature above the melting point of the carbonate eutectic, the systems provide high thermal conductivity and reversible stability for thermal energy storage.

25 ENERGY STORAGE↗

Solidification and Re-melting Phenomena During Slurry Preparation Using the RheoMetal™ Process

The melting sequence of the enthalpy exchange material (EEM) and formation of a slurry in the RheoMetal™ process was investigated. The EEM was extracted and quenched, together with a portion of the slurry at different processing times before complete melting. The EEM initially increased in size/diameter due to melt freezing onto its surface, forming a freeze-on layer. The initial growth of this layer was followed by a period of a constant diameter of the EEM with subsequent melting and decrease of diameter. Microstructural characterization of the size and morphology of different phases in the EEM and in the freeze-on layer was made. Dendritic equiaxed grains and eutectic regions containing Si particles and Cu-bearing particles and Fe-rich particles were observed in the as-cast EEM. The freeze-on layer consisted of dendritic aluminum tilted by about 30 deg in the upstream direction, caused by the rotation of the EEM. Energy dispersion spectroscopy analysis showed that the freeze-on layer had a composition corresponding to an alloy with higher melting point than the EEM and thus shielding the EEM from the surrounding melt. Microstructural changes in the EEM showed that temperature rapidly increased to 768 K (495 °C), indicated by incipient melting of the lowest temperature melting eutectic in triple junction grain boundary regions with Al{sub 2}Cu and Al{sub 5}Mg{sub 8}Si{sub 6}Cu{sub 2} phases present. As the EEM temperature increased further the binary Al-Si eutectic started to melt to form a region of a fully developed coherent mushy state. Experimental results and a thermal model indicated that as the dendrites spheroidized near to the interface at the EEM/freeze-on layer reached a mushy state with 25 pct solid fraction, coherency was lost and disintegration of the freeze-on layer took place. Subsequently, in the absence of the shielding effect from the freeze-on Layer, the EEM continued to disintegrate with a coherency limit of a solid fraction estimated to be 50 pct.

36 MATERIALS SCIENCE↗

Role of Titanium, Carbon, Boron, and Zirconium in Carbide and Porosity Formation during Equiaxed Solidification of Nickel-Based Superalloys

This work analyses the effect of Ti in the MC carbide formation and also in the γ/γ´ eutectic promotion in two nickel-based alloys melted under vacuum conditions and solidified into ceramic molds. The role of boron, carbon and zirconium on the porosity level after solidification of both alloys was also investigated; since the alloys were vacuum melted, it is assumed that the observed porosity is due to micro-shrinkage. The chemical compositions for two alloys were: 20.2Cr-13.7Co-4.78Mo-1.19Al-0.69Ti-0.08C-2.34Fe for Alloy 1, and 20.5Cr-15.6Co5.03Mo-1.57Al-3.42Ti-0.15C-1.64Fe-0.076Zr-0.01%B for Alloy 2. Results showed a higher volume fraction of MC carbides and the γ/γ´ eutectic for the Alloy 2 with higher titanium content since this element is a carbide and γ/γ´ eutectic promoter. The porosity level in the Alloy 2, with higher amounts of carbon, boron and zirconium was considerably lower than that for the Alloy 1. These results are discussed in terms of different phenomena caused by the segregating effects of boron, carbon and zirconium towards the interdendritic regions and the formation of zirconium carbides that produce an expansion in volume when they are formed at the end of the solidification process.

36 MATERIALS SCIENCE↗

Effect of Different Heat Treatments on the Microstructural Evolution and Mechanical Properties of Ni-Cr-Si Alloy Fabricated by Laser Additive Manufacturing

Ni-Cr-Si alloy samples were fabricated on mild steel via laser additive manufacturing technology. The microstructural evolution and mechanical properties of the samples were studied systematically in as-deposited conditions and under three different types of heat-treated conditions. The scanning electron microscopy, energy-dispersive x-ray spectroscopy and x-ray diffraction results showed that the structures of the as-deposited samples were mainly dendritic matrices of γ(Ni, Fe), continuous interdendritic eutectics of γ + Ni{sub 3}B and discrete Cr-rich carbides and borides. After solid solution treatment, carbides (Cr{sub 7}C{sub 3}) and borides (CrB) precipitated on the boundary of the eutectic structure, distributing discretely in the matrix. In the solution plus aging heat-treated conditions, the interdendritic eutectics formed Ni{sub 3}Fe intermetallic compounds with a layered distribution. After annealing, the grains were refined, and the hard phases (CrB) were uniformly dispersed along the grain boundary. Among the tested samples, the as-deposited specimens exhibited the highest microhardness and good wear ability at room temperature; however, the wear resistance of the as-deposited sample obviously decreased at 250 °C. The mechanical properties of the specimens were not greatly improved by solution treatment or solution plus aging treatment. The sample subjected to annealing treatment exhibited excellent wear resistance both at room temperature and at a service temperature of 250 °C.

36 MATERIALS SCIENCE↗

Effect of Zr and Sc additions on coarsening- and creep resistance of AlSi10Mg fabricated by laser powder bed fusion

Microstructure and creep properties are studied in a eutectic AlSi10Mg alloy modified with Zr and Sc additions (Al-9.8Si-0.32Mg-0.70Zr-0.23Sc, wt%) manufactured through laser powder-bed fusion (L-PBF). Three types of Zr/Sc-bearing powders - elemental, master-alloy, and pre-alloyed - are employed in the fabrication process, with the pre-alloyed powders providing the highest incorporation of Zr and Sc in the Al matrix. Here, the as-printed alloy exhibits a fine cellular Al-Si eutectic structure which fragments and coarsens into micron-sized Si particles during aging at 300 ºC, leading to a steady drop in alloy microhardness between 0.1 and 1000 h. Coarsening of the eutectic Si phase during aging is not measurably affected by Zr and Sc in solid solution, which precipitate during aging and increases strength, compensating weakening from Si coarsening between 1 and 200 h at 300 ºC. Atom-probe analysis in the peak-aged condition (96 h/300 °C) confirms the presence of Al 3 (Sc,Zr) secondary nano-precipitates with an average radius of 1.0 nm and some Si solubility. Micron-sized grains are present throughout the alloy, with ultra-fine-grained regions at the melt pool boundaries, neither of which coarsen during long-term aging at 300 ºC. Under creep conditions at 300 °C, the Zr/Sc-bearing alloy with Al 3 (Sc,Zr) nano-precipitates exhibits power-law behavior, with a high apparent stress exponent (n a = 9) and a high threshold stress (σ th = 43 MPa), exhibiting nearly double the strength of a Zr/Sc-free AlSi10Mg control alloy (σ th = 22 MPa).

36 MATERIALS SCIENCE↗

Heterogeneous phase transformation pathways in additively manufactured Al-Ce-Mn alloys

Heat treatment of additively manufactured Al-Ce based multicomponent alloys leads to complex microstructure evolution. In this research, the ability to extend the phase transformation theories involving nucleation of a product phase from a heterogeneous multi-phase microstructure typical to that of additively manufactured samples is explored. The Al-10Ce-8Mn (wt%) was used as a model alloy system. Under additive manufacturing conditions different solidification microstructures were obtained due to spatial and temporal variations of thermal gradients (G) and liquid-solid interface velocities (R) within a given melt pool. Near the melt pool boundary (high G and low R, referred as MPB region), initially, Al 20 Mn 2 Ce forms from the liquid followed by a eutectic of FCC Al and Al 11 Ce 3 . In the melt pool interiors (low G and high R referred as ES region) a eutectic structure between FCC Al and Al 20 Mn 2 Ce is observed. During subsequent heat treatments, the MPB and ES regions transform into different sets of microstructures. In the MPB region, a fine globular microstructure containing FCC Al, Al 11 Ce 3 , Al 6 Mn, and Al 12 Mn results from the decomposition of Al 20 Mn 2 Ce. In the ES region a faceted Al 51 Mn 7 Ce 4 plate phase results from the decomposition of Al 20 Mn 2 Ce. The formation of the Al 51 Mn 7 Ce 4 phase within the eutectic microstructure at the boundaries of FCC Al and Al 20 Mn 2 Ce has not been reported in the literature. Further, these two distinct phase transformation pathways are rationalized based on the role of driving force on the nucleation of (Al 6 Mn) and/or metastable intermetallic (Al 51 Mn 7 Ce 4 ) phases at the interface of aluminum (FCC) and the non-equilibrium intermetallic (Al 20 Mn 2 Ce) phases.

36 MATERIALS SCIENCE↗

Phase diagram of the Y–Y{sub 2}Se{sub 3} system, enthalpies of phase transformations

A phase diagram for the Y–Y{sub 2}Se{sub 3} system has been constructed in which the YSe and Y{sub 2}Se{sub 3} phases melt congruently. The daltonide type YSe phase (ST Y{sub 0,75}Se, a=1.1393 nm, melting point=2380 K, H=2200 MPa) forms a double-sided solid solution from 49–50–53 at% Se. In the 50–53 at% Se range, the unit cell parameter increases to 1.1500 nm, the microhardness increases to 4100 MPa and electrical resistivity increases from 0.018 to 0.114 Ω m. These changes are caused by the dominating influx of newly formed structural cationic vacancies arising from the selenium anions that are surplus for the 1:1 Y:Se stoichiometry. The full-valence Y{sub 2}Se{sub 3} composition exists as a low-temperature modification of ε-Y{sub 2}Se{sub 3} (ST Sc{sub 2}S{sub 3}, a=1.145 nm, b=0.818 nm, c=2.438 nm, melting point=1780 K, ∆fusion enthalpy=4±0.4 J/g) and transforms into a modification of ξ-Y{sub 2}Se{sub 3} that does not undergo fixing by thermo-hardening. The eutectic melting point between the YSe and Y{sub 2}Se{sub 3} phases is 1625±5 K, with a eutectic composition that is assumed to be 57.5 at% Se and have an enthalpy of fusion of 43±4.3 J/g. The eutectic for the Y and YSe phases appears at a temperature of 1600 K and 5 at% Se. - Highlights: • Phase equilibria in the Y–Y{sub 2}Se{sub 3} system from 1000 K to melt were studies. • High-temperature polymorphic transition for Y{sub 2}Se{sub 3} were observed. • Singular points in solid solutions areas for YSe and Y{sub 2}Se{sub 3} were found.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Flux growth and magnetic properties of rare earth cobalt germanide, RE{sub 6}Co{sub 5}Ge{sub 1+x}Al{sub 3−x} (RE=Pr, Nd; x≈0.8)

The intermetallic compounds RE{sub 6}Co{sub 5}Ge{sub 1+x}Al{sub 3−x} (RE=Pr{sub ,} Nd) were synthesized from the reaction of germanium and aluminum in RE/Co eutectic flux. These phases crystallize with the Nd{sub 6}Co{sub 5}Ge{sub 2.2} structure type in hexagonal space group P-6m2 (a=9.203(2)Å, c=4.202(1) Å, R{sub 1}=0.0109 for Pr{sub 6}Co{sub 5}Ge{sub 1.80}Al{sub 2.20}; and a=9.170(3) Å, c=4.195(1) Å, R{sub 1}=0.0129 for Nd{sub 6}Co{sub 5}Ge{sub 1.74}Al{sub 2.26}). The structure features chains of face-sharing Ge@RE{sub 9} clusters intersecting hexagonal cobalt nets linked by aluminum atoms. Magnetic susceptibility measurements indicate that both phases exhibit ferromagnetic ordering of the cobalt layers with T{sub C} in the range of 130–140 K. The magnetic moments of the rare earth ions order at lower temperature (30–40 K). Magnetic measurements on oriented crystals of Nd{sub 6}Co{sub 5}Ge{sub 1.74}Al{sub 2.26} show a strong preference of the moments to order along the c-axis. - Graphical abstract: RE{sub 6}Co{sub 5}Ge{sub 1+x}Al{sub 3−x} (RE=Pr{sub ,} Nd) were grown as large crystals from reactions of Ge and Al in RE/Co eutectic melts. Magnetic measurements indicate ordering of the 2-D cobalt nets at 130–140 K, and ordering of the rare earth moments at 30–40 K. Display Omitted - Highlights: • RE{sub 6}Co{sub 5}Ge{sub 1+x}Al{sub 3−x} (RE=Pr{sub ,} Nd) grown as large crystals from RE/Co eutectic flux. • RE{sub 6}Co{sub 5}Ge{sub 1+x}Al{sub 3−x} structure features hexagonal cobalt nets stacked along c-axis. • Cobalt layers order ferromagnetically with T{sub c}=130–140 K. • Rare earth magnetic moments order at low temperature (30–40 K).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effect of carbon content on solidification behaviors and morphological characteristics of the constituent phases in Cr-Fe-C alloys

A combination of transmission electron microscopy, electron backscatter diffraction and wavelength dispersive spectrum has been used to identify crystal structure, grain boundary characteristic and chemical composition of the constituent phases in Cr-Fe-C alloys with three different carbon concentrations. Depending on the three different carbon concentrations, the solidification structures are found to consist of primary {alpha}-phase and [{alpha} + (Cr,Fe){sub 23} C{sub 6}] eutectic in Cr-18.4Fe-2.3 C alloy; primary (Cr,Fe){sub 23} C{sub 6} and [{alpha} + (Cr,Fe){sub 23} C{sub 6}] eutectic in Cr-24.5Fe-3.8 C alloy and primary (Cr,Fe){sub 7} C{sub 3} and [{alpha} + (Cr,Fe){sub 7} C{sub 3}] eutectic in Cr-21.1Fe-5.9 C alloy, respectively. The grain boundary analysis is useful to understand growth mechanism of the primary phase. The morphologies of primary (Cr,Fe){sub 23} C{sub 6} and (Cr,Fe){sub 7} C{sub 3} carbides are faceted structures with polygonal shapes, different from primary {alpha}-phase with dendritic shape. The primary (Cr,Fe){sub 23} C{sub 6} and (Cr,Fe){sub 7} C{sub 3} carbides with strong texture exist a single crystal structure and contain a slight low angle boundary, resulting in the polygonal growth mechanism. Nevertheless, the primary {alpha}-phase with relative random orientation exhibits a polycrystalline structure and comprises a massive high-angle boundary, caused by the dendritic growth mechanism. - Highlights: Black-Right-Pointing-Pointer Microstructures of the as-clad Cr-based alloys are characterized by TEM. Black-Right-Pointing-Pointer EBSD technique has been use to characterize the grain boundary of primary phases. Black-Right-Pointing-Pointer We examine transitions in morphology about the primary phases. Black-Right-Pointing-Pointer Morphologies of primary carbides are polygonal different from primary {alpha}-phase. Black-Right-Pointing-Pointer Solidification structures rely on C concentrations in Cr-Fe-C alloy.

36 MATERIALS SCIENCE↗

Characterization of Cu{sub 6}Sn{sub 5} intermetallic powders produced by water atomization and powder heat treatment

Since the Cu{sub 6}Sn{sub 5} intermetallic shows its importance in industrial applications, the Cu{sub 6}Sn{sub 5} intermetallic-containing powders, produced by a powder processing route with a high production rate, were characterized. The route consisted of water atomization of an alloy melt (Cu–61 wt.% Sn) and subsequent heat treatment of the water-atomized powders. Characterization of the water-atomized powders and their heated forms was conducted by using X-ray diffraction, scanning electron microscopy and transmission electron microscopy. Fine water-atomized powder microstructures consisted of primary hexagonal η-Cu{sub 6.25}Sn{sub 5} dendrites coexisting with interdendritic η-Cu{sub 6.25}Sn{sub 5} + β-Sn eutectic. Solidification of fine melt droplets was governed by surface nucleation and growth of the primary hexagonal η-Cu{sub 6.25}Sn{sub 5} dendrites followed by η-Cu{sub 6.25}Sn{sub 5} + β-Sn eutectic solidification of the remnant liquid. In coarse melt droplets, nucleation and growth of primary ε-Cu{sub 3}Sn dendrites were followed by peritectic reaction (ε-Cu{sub 3}Sn + liquid → η-Cu{sub 6.25}Sn{sub 5}) or direct crystallization of η-Cu{sub 6.25}Sn{sub 5} phase from the undercooled melt. Finally, the η-Cu{sub 6.25}Sn{sub 5} + β-Sn eutectic solidification of the remnant liquid occurred. Heating of the water-atomized powders at different temperatures resulted in microstructural homogenization. The water-atomized powders with mixed phases were transformed to powders with single monoclinic ή-Cu{sub 6}Sn{sub 5} phase. - Highlights: • The Cu{sub 6}Sn{sub 5} intermetallic powder production route was proposed. • Single phase Cu{sub 6}Sn{sub 5} powders could be by water atomization and heating. • Water-atomized Cu–Sn powders contained mixed Cu–Sn phases. • Solidification and heat treatment of water-atomized Cu–Sn powders are explained.

36 MATERIALS SCIENCE↗

Effects of Mo on microstructure of as-cast 28 wt.% Cr–2.6 wt.% C–(0–10) wt.% Mo irons

Microstructures of as-cast 28 wt.% Cr–2.6 wt.% C irons containing (0–10) wt.% Mo with the Cr/C ratio of about 10 were studied and related to hardness. The experimental irons were cast into dry sand molds. Microstructural investigation was performed by light microscopy, X-ray diffractometry, scanning electron microscopy, transmission electron microscopy and energy-dispersive X-ray spectrometry. It was found that the iron with about 10 wt.% Mo was eutectic/peritectic, whereas the others with less Mo content were hypoeutectic. The matrix in all irons was austenite, partly transformed to martensite during cooling. Mo addition promoted the formation of M{sub 23}C{sub 6} and M{sub 6}C. At 1 wt.% Mo, multiple eutectic carbides including M{sub 7}C{sub 3}, M{sub 23}C{sub 6} and M{sub 6}C were observed. M{sub 23}C{sub 6} existed as a transition zone between eutectic M{sub 7}C{sub 3} and M{sub 6}C, indicating a carbide transition as M{sub 7}C{sub 3}(M{sub 2.3}C) → M{sub 23}C{sub 6}(M{sub 3.8}C) → M{sub 6}C. At 6 wt.% Mo, multiple eutectic carbides including M{sub 7}C{sub 3} and M{sub 23}C{sub 6} were observed together with fine cellular/lamellar M{sub 6}C aggregates. In the iron with 10 wt.% Mo, only eutectic/peritectic M{sub 23}C{sub 6} and M{sub 6}C were found without M{sub 7}C{sub 3}. Mo distribution to all carbides has been determined to be increased from ca. 0.4 to 0.7 in mass fraction as the Mo content in the irons was increased. On the other hand, Cr distribution to all carbides is quite constant as ca. 0.6 in mass fraction. Mo addition increased Vickers macro-hardness of the irons from 495 up to 674 HV{sub 30}. High Mo content as solid-solution in the matrix and the formation of M{sub 6}C or M{sub 23}C{sub 6} aggregates were the main reasons for hardness increase, indicating potentially improved wear performance of the irons with Mo addition. - Highlights: • Mo promoted the formation of M{sub 23}C{sub 6} and M{sub 6}C in the irons with Cr/C ratio of about 10. • M{sub 23}C{sub 6} has higher Fe/Cr and Mo/Cr atm% ratios than M{sub 7}C{sub 3}. • Si content and high Mo content over about 9 atm% are characteristics of M{sub 6}C. • No M{sub 7}C{sub 3} was found at 10 wt.% Mo addition, only M{sub 23}C{sub 6} and M{sub 6}C presented. • High Mo matrices and M{sub 23}C{sub 6}/M{sub 6}C aggregates increased iron macro-hardness.

36 MATERIALS SCIENCE↗

Microstructures of ancient and modern cast silver–copper alloys

The microstructures of modern cast Sterling silver and of cast silver objects about 2500 years old have been compared using optical microscopy (OM), scanning electron microscopy (SEM), transmission electron microscopy (TEM), scanning transmission electron microscopy (STEM), energy dispersive X-ray microanalysis (EDX) and electron backscatter diffraction (EBSD). Microstructures of both ancient and modern alloys were typified by silver-rich dendrites with a few pools of eutectic and occasional cuprite particles with an oxidised rim on the outer surface. EBSD showed the dendrites to have a complex internal structure, often involving extensive twinning. There was copious intragranular precipitation within the dendrites, in the form of very fine copper-rich rods which TEM, X-ray diffraction (XRD), SEM and STEM suggest to be of a metastable face-centred-cubic (FCC) phase with a cube–cube orientation relationship to the silver-rich matrix but a higher silver content than the copper-rich β in the eutectic. Samples from ancient objects displayed a wider range of microstructures including a fine scale interpenetration of the adjoining grains not seen in the modern material. Although this study found no unambiguous evidence that this resulted from microstructural change produced over archaeological time, the copper supersaturation remaining after intragranular precipitation suggests that such changes, previously proposed for wrought and annealed material, may indeed occur in ancient silver castings. - Highlights: • Similar twinned structures and oxidised surfaces seen in ancient and modern cast silver • General precipitation of fine Cu-rich rods apparently formed by discontinuous precipitation is characteristic of as-cast silver. • The fine rods are cube-cube related to the matrix in contrast with the eutectic. • The silver-rich phase remains supersaturated with copper. • Possibly age-related grain boundary features seen in ancient cast silver.

36 MATERIALS SCIENCE↗

Heat-affected zone liquation crack on resistance spot welded TWIP steels

In this study, the heat affected zone (HAZ) liquation crack and segregation behavior of the resistance spot welded twinning induced plasticity (TWIP) steel have been reported. Cracks appeared in the post-welded joints that originated at the partially melted zone (PMZ) and propagated from the PMZ through the heat affected zone (HAZ) to the base metal (BM). The crack length and crack opening widths were observed increasing with heat input; and the welding current was identified to be the most influencing parameter for crack formation. Cracks appeared at the PMZ when nugget diameter reached at 4.50 mm or above; and the liquation cracks were found to occur along two sides of the notch tip in the sheet direction rather than in the electrode direction. Cracks were backfilled with the liquid films which has lamellar structure and supposed to be the eutectic constituent. Co-segregation of alloy elements such as, C and Mn were detected on the liquid films by electron-probe microanalysis (EPMA) line scanning and element map which suggests that the liquid film was enrich of Mn and C. The eutectic constituent was identified by analyzing the calculated phase diagram along with thermal temperature history of finite element simulation. Preliminary experimental results showed that cracks have less/no significant effect on the static cross-tensile strength (CTS) and the tensile-shear strength (TSS). In addition, possible ways to avoid cracking were discussed. - Highlights: • The HAZ liquation crack during resistance spot welding of TWIP steel was examined. • Cracks were completely backfilled and healed with divorced eutectic secondary phase. • Co-segregation of C and Mn was detected in the cracked zone. • Heat input was the most influencing factor to initiate liquation crack. • Cracks have less/no significant effect on static tensile properties.

36 MATERIALS SCIENCE↗

Correlative characterization of primary Al{sub 3}(Sc,Zr) phase in an Al–Zn–Mg based alloy

Three-dimensional electron backscatter diffraction, focused ion beam, transmission electron microscopy and energy filtered transmission electron microscopy were employed to investigate the structural information of primary Al{sub 3}(Sc,Zr) phase, i.e. size, shape, element distribution and orientation relationship with the α-Al matrix. It was found that (i) most primary Al{sub 3}(Sc,Zr) phases have a cubic three-dimensional morphology, with a size of about 6–10 μm, (ii) most primary Al{sub 3}(Sc,Zr) phases are located within the α-Al matrix, and exhibit a cube to cube orientation relationship with the α-Al matrix, and (iii) a layer by layer growth was observed within primary Al{sub 3}(Sc,Zr) phases. Al, Cu, Si and Fe are enriched in the α-Al matrix between the layers of cellular eutectic Al{sub 3}(Sc,Zr) phase, while Sc, Ti and Zr are enriched in small Al{sub 3}(Sc,Zr) phases. A peritectic reaction and subsequent eutectic reaction between Al{sub 3}Sc and Al was proposed to interpret the observed layer by layer growth. This paper demonstrates that the presence of impurities (Fe, Si, Cu, Ti) in the diffusion field surrounding the growing Al{sub 3}(Sc,Zr) particle enhances the heterogeneous nucleation of Al{sub 3}(Sc,Zr) phases. - Highlights: • Most fine cubic primary Al{sub 3}(Sc,Zr) phases were observed within the α-Al matrix. • A layer by layer growth within primary Al{sub 3}(Sc,Zr) phase was observed. • A peritectic and subsequent eutectic reaction between Al{sub 3}Sc and Al was proposed. • Impurities in diffusion fields enhance heterogeneous nucleation of Al{sub 3}(Sc,Zr)

36 MATERIALS SCIENCE↗

Grain refinement of cast zinc through magnesium inoculation: Characterisation and mechanism

It was previously found that peritectic-forming solutes are more favourable for the grain refinement of cast Al alloys than eutectic-forming solutes. In this work, we report that the eutectic-forming solute, Mg, can also significantly grain refine cast Zn. Differential thermal analysis (DTA) of a Zn–Mg alloy, in which efficient grain refinement occurred, evidenced an unexpected peak that appeared before the nucleation of η-Zn grains on the DTA spectrum. Based on extensive examination using X-ray diffraction, high resolution SEM and EDS, it was found that: (a) some faceted Zn–Mg intermetallic particles were reproducibly observed; (b) the particles were located at or near grain centres; (c) the atomic ratio of Mg to Zn in the intermetallic compound was determined to be around 1/2. Using tilting selected area diffraction (SAD) and convergent beam Kikuchi line diffraction pattern (CBKLDP) techniques, these faceted particles were identified as MgZn{sub 2} and an orientation relationship between such grain-centred MgZn{sub 2} particles and the η-Zn matrix was determined. Hence, the unexpected peak on the DTA spectrum is believed to correspond to the formation of MgZn{sub 2} particles, which act as effective heterogeneous nucleation sites in the alloy. Together with the effect of Mg solute on restricting grain growth, such heterogeneous nucleation is cooperatively responsible for the grain size reduction in Zn–Mg alloys. - Highlights: • A new eutectic-based grain refiner for the cast Zn was found. • The formation process of an intermetallic compound (MgZn{sub 2}) was characterised. • MgZn{sub 2} can act as potent heterogeneous nucleation sites above the liquidus. • A new OR between MgZn{sub 2} and η-Zn was determined using the CBKLDP technique.

36 MATERIALS SCIENCE↗

Electron microscopy study of direct laser deposited IN718

The microstructure of direct laser deposited (DLD) IN718 has been investigated in detail using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The results confirm that the dendrite core microstructure can be linked to the cooling rate experienced during the deposition. A ~ 100 μm wide δ partially dissolved region in the IN718 substrate was observed close to the substrate/deposit boundary. In the deposited IN718, γ/Laves eutectic constituent is the predominant minor microconstituent. Irregular and regular (small) (Nb,Ti)C carbides and a mixture of the carbides and Laves were observed. Most M{sub 3}B{sub 2} borides were nucleated around a (Nb,Ti)C carbide. Needles of δ phase precipitated from the Laves phase were also observed. A complex constituent (of Laves, δ, α-Cr, γ″, and γ matrix) is reported in IN718 for the first time. The formation of α-Cr particles could be related to Cr rejection during the formation and growth of Cr-depleted δ phase. - Highlights: • Secondary phases in IN718 deposits were identified using electron diffraction and EDS. • MC, M{sub 3}B{sub 2}, γ/Laves eutectic and γ/NbC/Laves eutectic were observed. • Needle-like δ phases were precipitated from the Laves phase. • A complex constituent (Laves, δ, α-Cr, γ″ and γ) was reported for the first time.

36 MATERIALS SCIENCE↗

Low cycle fatigue performance of Ni-based superalloy coated with complex thermal barrier coating

Highlights: • Novel thermal barrier coating (TBC) with YSZ and ZrO{sub 2} + SiO{sub 2} + Al{sub 2}O{sub 3} eutectic ceramic top coat • TBC deposited via atmospheric plasma spraying and a hybrid water stabilized plasma torch spraying • Effect of eutectic ceramic TBC on LCF behaviour at 900 °C • Damage mechanisms in cyclic loading of cast nickel-based superalloy coated with TBC • The dislocation structures of a Ni-base superalloy were observed. - Abstract: Thermal barrier coatings (TBCs) are widely applied to protect high-temperature components against high temperatures in harsh environments. Nineteen cylindrical specimens of Inconel 713LC were manufactured using the investment castings technique, and 10 specimens were subsequently coated with a novel complex thermal barrier coating (TBC) system. The TBC system comprises a metallic CoNiCrAlY bond coat (BC) and a complex ceramic top coat (TC). The TC is a mixture of a near eutectic nanocrystalline ceramic made of zirconia (ZrO{sub 2}), alumina (Al{sub 2}O{sub 3}), silica (SiO{sub 2}) and conventional yttria stabilized zirconia (YSZ) ceramic in the ratio of 50/50 in wt%. Low cycle fatigue (LCF) tests were carried out in a symmetrical push-pull cycle under strain control at 900 °C. Cyclic hardening/softening curves, cyclic stress-strain curves and fatigue life curves of the TBC-coated and uncoated material were assessed. Fatigue life curves in total strain representation showed transient behaviour. Fracture surfaces and polished sections parallel to the loading axis of the TBC-coated and uncoated specimens prior and after cyclic loading were observed by means of scanning electron microscopy (SEM) to study the degradation mechanisms during high-temperature LCF. TBC delamination was observed at the TC/BC interface, and rafting of precipitates occurred after high-temperature exposure. The microstructural investigations further the discussion of the differences in the stress-strain response and the fatigue life of the TBC-coated and uncoated superalloy.

77 NANOSCIENCE AND NANOTECHNOLOGY↗