A Study on Zirconium Rich Uranium–Zirconium Alloys

Uranium–zirconium alloy is the potential candidate materials as metallic fuels for nuclear reactor applications. Along with other properties, volumetric stability is an important issue for these types of fuels. In this work investigations were carried out on the zirconium rich uranium–zirconium alloys (i.e. U–50 wt% Zr, U–60 wt% Zr and U–70 wt% Zr) in as-cast as well as in heat treated conditions. Microstructural and dilatometric studies were carried out along with X-ray diffraction analysis to evaluate the phase content as well as the phase transformation behaviour of these alloys under different heat treated conditions.     

均匀设计-X射线荧光光谱分析铀锆合金中铀和锆的方法探讨

铀锆合金燃料是第4代先进核能系统主要燃料形式,合金成分及含量是燃料性能的关键参数之一,及时、准确地测定铀锆合金中铀(U)、锆(Zr)含量至关重要。常规测量常量水平的铀、锆含量的方法,存在分析过程繁琐或受铀锆元素间基体效应干扰明显等问题。实验通过均匀设计试验方案设置试验点的布置方式,采用均匀设计方案,利用4因素9水平的均匀设计表(U_9~*(9~4))设置试验点,以满足不同铀、锆元素含量的铀锆合金燃料研制需求,建立了X射线荧光光谱(XRF)测定铀锆合金中铀和锆含量的方法。通过实验建立铀、锆信号强度(I)与元素浓度(C)的多元回归模型分别为C_(Zr)=-0.032+0.008 I_(Zr)+2.395×10~(-5)I_(Zr)·I_U,C_U=-0.408+0.03 I_U+1.003×10~(-5)I_(Zr)~2,锆、铀含量分别与锆、铀信号基本呈线性关系。对标准溶液中锆含量分析结果的相对偏差可控制在2.0%内,铀含量分析结果的相对偏差可控制在1.0%内;利用实验方法计算获得的6组铀锆合金中铀锆含量与二元比例方法较为吻合。     

Microstructure and High Temperature Impression Creep Properties of Mg–3Ca–xZr (x = 0.3, 0.6, 0.9 wt%) Alloys

The current study has investigated the influence of zirconium (Zr) addition to Mg–3Ca–xZr (x = 0.3, 0.6, 0.9 wt%) alloys prepared using argon arc melting on the microstructure and impression properties at 448–498 K under constant stress of 380 MPa. Microstructural analysis of as-cast Mg–3Ca–xZr alloys showed grain refinement with Zr addition. The observed grain refinement was attributed to the growth restriction effect of Zr in hypoperitectic Mg–3Ca–0.3 wt% Zr alloys. Heterogeneous nucleation of α-Mg in properitectic Zr during solidification resulted in grain refinement of hyperperitectic Mg–3Ca–0.6 wt% Zr and Mg–3Ca–0.9 wt% Zr alloys. The hardness of Mg–3Ca–xZr alloys increased as the amount of Zr increased due to grain refinement and solid solution strengthening of α-Mg by Zr. Creep resistance of Mg–3Ca–xZr alloys increased with the addition of Zr due to solid solution strengthening of α-Mg by Zr. The calculated activation energy (Q_a) for Mg–3Ca samples (131.49 kJ/mol) was the highest among all alloy compositions. The Q_a values for 0.3, 0.6 and 0.9 wt% Zr containing Mg–3Ca alloys were 107.22, 118.18 and 115.24 kJ/mol, respectively.     

The Preparation of a Haifnium-Free Magnesium-Zirconium Alloy by Process Separation of Hafnium

Abstract

Magnesium zirconium alloy for sheathing uranium elements in gas-cooled reactors was successfully prepared from high-purity magnesiumt and zirconium produced by the magnesium reduction of a crude oxide. Hafnium separation, suggested by a higher ratio Hf to Zr in the sludge than in the melt was considered possible owing to its higher density and melting point and its isomorphous behaviour to the strongly electropositive zirconium which readily forms compounds and exhibits a two-phase melt when added in excess of 0.5 per cent. Precipitation of excess zirconium by settling was aided by the development of a flux of high density and low inclusion-flux interfacial energy. Removal of hafnium and other high neutron capture cross-section impurities was achieved.     

Phase Transformation Studies in U–xZr (x = 2, 5, 10 wt%) Alloys Using Dynamic Calorimetry

The thermo-kinetics aspects of phase transformations in U rich U–xZr binary alloys, with x = 2, 5 and 10 wt% Zr have been investigated using dynamic calorimetry. The on-heating and cooling transformations at controlled scan rates in the range, 1–99 K min^?1, have been monitored and the following transformation sequence is obtained at slow heating (3 K min^?1) of a U–2Zr alloy: (i) α or α′ (distorted orthorhombic martensite) + δ(UZr₂) → α + γ₂ (bcc phase enriched in Zr); (ii) α + γ₂ → β (tetragonal) + γ₂; (iii) β + γ₂ → β + γ₁ (bcc phase enriched in U); (iv) β + γ₁ → γ; (v) γ (bcc) → liquid (melting). Similar transformation sequence for other compositions with varying enthalpy effects has been witnessed for 5 and 10 Zr alloys. The observed transformation characteristics are rationalized for the effect of Zr content and heating/cooling rate variations.     

The Influence of Composition and Heat Treatment on the Phase Composition and Mechanical Properties of ML19 Magnesium Alloy

Samples of ML19 magnesium alloy with composition, wt %, (0.1–0.6)Zn–(0.4–1.0)Zr–(1.6–2.3)Nd–(1.4–2.2)Y have been investigated. The influence of Nd, Y, Zn, and Zr on equilibrium phase-transition temperatures and phase composition using Thermo-Calc software is established. The Scheil–Gulliver solidification model is also used. We show the significant liquidus temperature increase if the zirconium content in alloy is higher than (0.8–0.9) wt %. Thus, a higher melting temperature is required (more than 800°C). This is undesirable when melting in a steel crucible. The change in equilibrium fractions of phases at different temperatures in ML19 magnesium alloy with a minimum and maximum amount of alloying elements are calculated. Microstructures of alloys with different amounts of alloying elements in as-cast and heat-treated condition has been studied using scanning electron microscopy (SEM). We investigate the concentration profile of Nd, Y, Zn, and Zr in the dendritic cell of an as-cast alloy. The amount of neodymium and zinc on dendritic cell boundaries increased. A high concentration of yttrium is observed both in the center and on the boundaries of the dendritic cell. A high zirconium concentration is mainly observed in the center of the dendritic cells. A small amount of yttrium is also present in zirconium particles. These particles act as nucleation sites for the magnesium solid solution (Mg) during solidification. The effect of aging temperature (200 and 250°C) on the hardness of the samples after quenching was studied. Aging at 200°C provides a higher hardness. The change in the hardness of quenched samples during aging at 200°C is investigated. Maximum hardness is observed in samples aged for 16–20 h. The two-stage solution heat treatment for 2 h at 400°C and 8 h at 500°C with water quenching and aging at 200°C for 16 h is performed. This heat treatment enables us to get tensile strength 306 ± 8 MPa and yield strength 161 ± 1 MPa with elongation 8.7 ± 1.6%.     

微量合金元素Zr对Mo合金性能和显微组织的影响

采用粉末冶金方法制备Mo-Zr合金,研究了Zr的添加方式及添加量对Mo的拉伸性能和显微组织的影响.结果表明,添加合金元素Zr大大提高了Mo的力学性能.合金元素Zr以纯Zr形式加入较以ZrH2形式为佳,其添加量在0.1%时,合金性能最高.元素Zr少部分固溶到Mo基体中,大部分与合金中少量氧结合以ZrO2粒子相存在.     

Calcium hydride synthesis of Ti–Nb-based alloy powders

The metallothermic (calcium hydride) synthesis of Ti–Nb alloy powders alloyed with tantalum and zirconium is experimentally studied under various conditions. Chemical, X-ray diffraction, and metallographic analyses of the synthesized products show that initial oxides are completely reduced and a homogeneous β-Ti-based alloy powder forms under the optimum synthesis conditions at a temperature of 1200°C. At a lower synthesis temperature, the end products have a high oxygen content. The experimental results are used to plot the thermokinetic dependences o formation of a bcc solid solution at various times of isothermal holding of Ti–22Nb–6Ta and Ti–22Nb–6Zr (at %) alloys. The physicochemical and technological properties of the Ti–22Nb–6Ta and Ti–22Nb–6Zr alloy powders synthesized by calcium hydride reduction under the optimum conditions are determined.     

Sintering and aging behaviours of Al4CuXMg PM alloy

Sintering and aging behaviours of Al–Cu–Mg powder metallurgy (PM) alloy produced from elemental powders were examined. After evaluating results from thermal analysis, tests were carried out on Al–4Cu alloys with magnesium contents of 0.5, 1 and 2?wt-% and it was found that additions of 1?wt-% Mg was most effective for enhancing the transverse rupture strength (TRS) of the Al–Cu PM alloys for both as sintered and after a heat-treatment conditions. Grain size reduction in the range of 14–45% was achieved by adding magnesium into Al–Cu system. Analyses showed that produced alloys were composed of Al, Al₂Cu, Al₂CuMg and Al₇Cu₂Fe phases. Differential scanning calorimeter and dilatometer analyses revealed that alloys show swelling behaviour after the eutectic melting reaction at 548°C and swelling rates increasing as a function of magnesium content. Both high hardness value (120 HB) and TRS (650?MPa) were achieved via aging of Al4Cu1Mg alloy for 24 hours.     

Influence of the Chemical Composition and Heat Treatment Modes on the Phase Composition and Mechanical Properties of the ZK51A (ML12) Alloy

The objects of investigation are ZK51A (ML12) alloy samples containing from 3.5 to 5.5 wt % Zn and 0.5–0.8 wt % Zr. The influence of Zn and Zr content on phase transition temperatures and the phase composition in equilibrium conditions and when using the Scheil–Gulliver solidification model is established using the calculation of phase diagrams in the Thermo-Calc program. It is shown that a significant increase in the liquidus temperature of the alloy occurs at a zirconium content in the alloy higher than 0.8–0.9 wt %, and an increase in the melting temperature above 800°C is required, which is undesirable when using steel crucibles. The equilibrium content of alloying components in the magnesium-based solid solution at various temperatures is calculated. The microstructure of as cast and heat-treated alloys with various concentrations of alloying components is investigated using scanning electron microscopy. The distribution of Zn and Zr in a dendritic cell of the as cast and heat-treated alloy is investigated. Zinc is concentrated along the dendritic cell boundaries in the as cast state, but its concentration in their center becomes higher than along the boundaries after heat treatment (HT). Zirconium is concentrated in the center of dendritic cells. It is shown that the two-stage solutionizing mode gives the largest increment of this characteristic: 330°C, 5 h + 400°C, 5 h. The influence of the aging temperature (150 and 200°C) on the sample hardness is investigated. It is revealed that it is higher in the case of aging at 200°C, and its maximum is observed under holding for 8?10 h. The HT of the alloy, including solution treatment (330°C, 5h + 400°C, 5 h) with subsequent quenching and aging (200°C, 8 h), made it possible to attain an alloy ultimate strength of 285 ± 13.5 MPa and a elongation of 11.4 ± 1%.     

TiAl预合金粉末制备的研究进展

高品质的预合金粉末是以粉末冶金工艺制备高性能TiAl基合金材料的基础。介绍了目前可用于规模化生产TiAl预合金粉末的各种雾化制备技术,包括惰性气体雾化法、转盘雾化法和等离子旋转电极雾化法,其中惰性气体雾化法又分为等离子感应熔炼定向气雾化法和电极感应熔炼气雾化法。分析了各种雾化制备技术的特点,并对国内外TiAl预合金粉末制备的研究进展进行了综述。     

Investigation into the Fabrication Possibility of the Boron–Aluminum Sheet Rolling of Increased Strength without Using Homogenization and Quenching

Al–Cu–Mn (Zr) aluminum alloys possess high strength and manufacturability without operations of thermal treatment (TT). In order to investigate the fabrication possibility of the aluminum boron-containing alloy in the form of sheet rolling with an increased strength without TT, Al–2% Cu–1.5% Mn–2% B and Al–2% Cu–1.5% Mn–0.4% Zr–2% B alloys are prepared. To exclude the precipitation of refractory boride particles, smelting is performed in a RELTEK induction furnace providing intense melt stirring. The smelting temperature is 950–1000°C. Pouring is performed into graphite molds 40 × 120 × 200 mm in size. It is established using computational methods (Thermo-Calc) that manganese forms complex borides with aluminum and zirconium at the smelting temperature; herewith, a sufficient amount of manganese remains in liquid, while zirconium is almost absent. The formation of AlB₂Mn₂ complex boride is proven; however, the amount of manganese remaining in the solid solution is sufficient to form the particles of the Al₂₀Cu₂Mn₃ phase in amounts of up to 7 wt %. Boron stimulates the isolation of Al₃Zr primary crystals in the alloy with zirconium; in connection with this, an amount of zirconium insufficient for hardening remains in the aluminum solid solution. The possibility of fabricating thin-sheet rolling with a thickness smaller than 0.3 mm with homogeneously distributed accumulations of the boride phase with a particle size smaller than 10 μm is shown. A high strength level (up to 543 MPa) is attained without using quenching and aging due to the precipitation of dispersoids of the Al₂₀Cu₂Mn₃ phase during hot deformation (t = 450°C).     

Settling of undissolved zirconium particles in pure magnesium melts

Zirconium is a remarkable grain refiner for magnesium alloys and is currently introduced into magnesium alloys primarily in the form of a Mg–Zr master alloy (Zirmax^® a Mg–33.3Zr alloy supplied by Magnesium Elektron). Owing to the difficulties of attaining complete dissolution, undissolved zirconium particles are often observed in Zirmax^® alloyed magnesium microstructures in the form of both isolated individual particles varying from submicrometre to greater than 10 μm, and various sizes of clusters that contain a number of zirconium particles. Aimed at improving the alloying efficiency with Zirmax^® and eliminating these undesirable large zirconium inclusions prior to pouring, this paper provides a detailed theoretical and experimental study of the settling behaviour of undissolved zirconium particles in pure magnesium melts. Various characteristics of the settling behaviour of zirconium particles are clarified based on the good agreement achieved between the experimental observations and theoretical predictions. In addition, it is also shown that wet chemical analysis of the total zirconium content in samples taken after different settling times at temperature can be an effective approach for evaluating the settling behaviour of undissolved zirconium particles in pure magnesium melts.     

Effect of small concentrations of zirconium on high temperature oxidation behaviour of Fe-15 Cr-4 Al

Effect of 1% Zr on oxidation behaviour of Fe-15 Cr-4 Al alloy under isothermal conditions in air, O₂ and O₂-10% H₂O environments in the temperature range 1000–1150°C was investigated. The effect of zirconium concentration was studied at 1 200°C in air. Oxidation rate increases with increase in zirconium concentration. Parabolic rate of oxidation was observed. Limited study on cyclic oxidation was carried out at 1150°C in air. The cycle consisted of one hour holding at isothermal temperature followed by half an hour air cooling. The oxidised samples were examined by X-Ray diffractometry, SEM, EDAX. Extensive spalling was observed in the base alloy, Fe-15 Cr-4 Al in all environments. Zirconium additions eliminated the spalling of the scale. The EDAX analysis of a spalled region shows the presence of iron and chromium while the unspalled region is aluminium rich. A common structural feature, localised formation of granules/nodules was observed in the scale of zirconium containing alloys in all the environments. The number of granules increased with increase in zirconium concentration and was observed to be a maximum in 1% Zr and also increases with increasing temperature. The observations reveal that 1% Zr alloy shows lower oxidation rate in O₂-H₂O environment under isothermal conditions. X-Ray diffraction analysis shows the additional presence of Fe₂O₃ and Cr₂O₃ in α-Al₂O₃ scale which have not been detected in the α-Al₂O₃ scale formed in other environments, air and O₂. 0.2% Zr is most effective in increasing oxidation resistance of Fe-15 Cr-4 Al alloy both under isothermal and cyclic oxidation conditions.     

Synthesis and properties of Cu–Al–Ni shape memory alloy strips prepared via hot densification rolling of powder preforms

Abstract

Cu–Al–Ni shape memory alloy strips were successfully prepared by a powder metallurgy route consisting of preparing powder preforms from premixed Cu, Al and Ni powders by cold compaction, stepwise sintering in the range 873–1273 K, followed by unsheathed multipass hot rolling at 1273 K in protective atmosphere. The densification behaviour of the sintered powder preforms during hot rolling has been discussed. Homogenisation of the hot rolled strips was carried out at 1173 K for 4 h. It has been shown that the finished Cu–Al–Ni alloy strip consisted of self-accommodated plates ofβ' and γ' martensites together with a small amount of nanocrystalline Cu₉Al₄ phase. The finished hot rolled Cu–Al–Ni strips had fracture strength of 476 MPa, coupled with 2·5% elongation. The shape memory tests showed almost 100% recovery after 10 thermomechanical cycles in the hot rolled strips at 1 and 2% applied prestrain.     

Melting,Processing and Characterization of Nb-10W-2.5Zr (Cb-752) Alloy

Niobium based alloys are most promising materials for high temperature aerospace and defence applications at temperature above the use of nickel base superalloys (1100 °C). Cb-752 (Nb-10W-2.5Zr) alloy pancakes were prepared by non-consumable arc melting process under argon atmosphere using thoriated tungsten electrode. In view of the very high melting point of tungsten as compared to niobium, it was found necessary to melt the pancake multiple times to ensure complete dissolution of tungsten in the alloy. The temperature of hot forging as well as method for oxidation protection during hot forging was optimised. It was observed that the alloy could be hot forged at 1300 °C. It was further found that the silicide and aluminide coatings, and evacuated stainless steel jacket protected the alloy from oxidation during hot forging. The forged pancakes were cold rolled to 1.5 mm thick sheets. The room temperature mechanical properties of Cb-752 alloy sheet produced from the pancakes were comparable to the data reported in literature.     

Thermodynamics and kinetics analyses of ZrB2 formation in molten aluminium alloys

Smelter grade aluminium can be used as a source for electrical conductor grade aluminium after the transition metal impurities such as zirconium (Zr), vanadium (V), titanium (Ti) and chromium (Cr) have been removed. Zirconium (Zr), in particular, has a significant effect on the electrical conductivity of aluminium. In practice, the transition metal impurities are removed by adding boron-containing substances into the melt in the casthouse. This step is called boron treatment. The work presented in this paper, which focuses on the thermodynamics and kinetics of Zr removal from molten Al–1?wt-%Zr–0.23?wt-%B alloy, is part of a broader systematic study on the removal of V, Ti, Cr and Zr from Al melt through boron treatment carried out by the authors. The thermodynamic analyses of Zr removal through the formation of ZrB₂ were carried out in the temperature range of 675–900°C using the thermochemical package FactSage. It was predicted that ZrB₂ is stable compared to Al–borides (AlB₁₂, AlB₂) hence would form during boron treatment of molten Al–Zr–B alloys. Al–Zr–B alloys were reacted at 750?±?10°C for 60 minutes, and the change in the chemistry and microstructure were tracked and analysed at particular reaction times. The results showed that the reaction between Zr and AlB₁₂/B was fast as revealed by the formation of boride ring at the early minutes of reaction. The presence of black phase (AlB₁₂), i.e. the original source of B, after holding the melt for 60 minutes advocated that the reaction between Zr and AlB₁₂/B was incomplete, hence still not reached the equilibrium state. The kinetics data suggested a higher reaction rate at the early minutes (2 minutes) of reaction compared to at a later stage (2–60 minutes). Nevertheless, a simple single-stage liquid mass transfer controlled kinetic model can be used to describe the overall process kinetic. The analysis of integrated rate law versus reaction time revealed that the mass transfer coefficient (k_m) of Zr in molten alloy is 9.5?×?10^?4?m?s^?1, which is within a typical range (10^?3 to 10^?4?m?s^?1) observed in other metallurgical solid–liquid reactions. This study suggests that the overall kinetics of reaction was predominantly controlled by the mass transfer of Zr through the liquid aluminium phase.     

Preparation,Characterization and Mechanical Properties of Cu-Sn Alloy/Graphite Composites

Ni-B coating was prepared on the surface of graphite particles using the electroless plating method. The Ni-B coating was composed of spherical grains with average diameter of 80 nm. The phases of Ni-B coating were indexed as nanosized crystal Ni phase and amorphous Ni-B phase. Cu-Sn alloy/graphite composites with 0.5, 1.0, 1.5, and 2.0 wt pct graphite contents were synthesized by the powder metallurgy method. Ni-B coating improved the wettability and bonding strength between the Cu-Sn alloy and graphite. The composite with Ni-B coated graphite exhibited higher density, hardness, and compression strength compared with the composites with bare graphite. The crack propagation mechanism of the composites was also analyzed.     

Influence of a Silicon Additive on Resistivity and Hardness of the Al–1% Fe–0.3% Zr Alloy

Isothermal sections of the diagram of the Al–Fe–Si–Zr alloy at temperatures of 450 and 600°C, as well as polythermal sections at concentrations of silicon up to 2 wt % and zirconium up to 1 wt %, are analyzed using computational methods with the help of Thermo-Calc software. It is shown that the favorable phase composition consisting of the aluminum solid solution (Al), the Al₈Fe₂Si phase, and Zr (which completely enters the composition of the solid solution (Al) during the formation of the cast billet) can be attained in equilibrium conditions at silicon concentrations of 0.27–0.47 wt %. To implement the above-listed structural components in nonequilibrium conditions and ensure that Zr enters the (Al) composition, experimental ingots were fabricated at an elevated cooling rate (higher than 10 K/s). A metallographic analysis of the cast structure of experimental samples revealed the desired structure with contents of 0.25 wt % Si and 0.3 wt % Zr in the alloy. The microstructure of the Al–1% Fe–0.3% Zr–0.5% Si alloy also contains the eutectic (Al) + Al₈Fe₂Si; however, the Al₈Fe₂Si phase partially transforms into Al₃Fe. The structure of the alloy with 0.25 wt % Si in the annealing state at 600°C contains fragmented particles of the degenerate eutectic (Al) + Al₈Fe₂Si along the boundaries of dendritic cells. It is established that the Si: Fe = 1: 2 ratio in the alloy positively affects its mechanical properties, especially hardness, without substantially lowering the specific conductivity during annealing, which is explained by the formation of the particles of the Al₈Fe₂Si phase of the compact morphology in the structure. Moreover, silicon accelerates the decay of the solid solution by zirconium, which is evidenced by the experimental plots of the dependence of hardness and resistivity on the annealing step. The best complex of properties was shown by the Al–1% Fe–0.3% Zr–0.25% Si alloy in the annealing stage at 450°C with the help of the optimization function at specified values of hardness and resistivity.     

Effect of Graphite and SiC Addition into Cu and SiC Particle Size Effect on Fabrication of Cu–Graphite–SiC MMC by Powder Metallurgy

Here we have reported individual and combined effect of graphite and SiC into Cu matrix during fabrication of Cu–graphite–SiC hybrid metal matrix composite by powder metallurgy. Mechanical properties of the composites are enhanced by simultaneous addition of 1, 3, 5, 10 and 15 vol. % of graphite along with 2, 5 and 10 wt. % of SiC into pure Cu, whereas electrical conductivity deteriorates. Composites are fabricated by cold compaction of composite powder mixture followed by conventional sintering in a tubular furnace at 900 °C for 1 h in argon atmosphere. For comparison, SiC powder size of 5 and 50 µm are used to study the effect of SiC particle size on microstructure, mechanical and electrical properties of the composites. Optical microscopy and scanning electron microscopy reveal the homogeneous distribution of graphite and SiC in matrix and good compatibility between Cu–graphite and Cu–SiC particles. Hardness of the composites decreases with increase in graphite and increases with increase in SiC content. Composites containing fine SiC particles show higher hardness value as compared to coarse particles. Maximum Vickers hardness value of 75 is obtained for Cu-1 vol. % graphite-10 wt. % SiC composite. Electrical conductivity decreases with increase in both graphite and SiC content. Composites containing coarse SiC particles exhibit higher electrical conductivity than fine SiC.