Zirconium alloys in nuclear power engineering

Results of studies of zirconium alloys É110 and É635 that have served in parts of VVÉR-1000 reactors are presented. The influence of the composition on the properties of alloys É110 and É635 is studied and improved modifications are suggested. The effect of the total content of admixtures in alloy É110 on corrosion and embrittlement of pipes under conditions simulating LOCA is investigated.     

Grain refinement and mechanism of CAl_（0.5）W_（0.5） compound in Mg-Al alloys

The effect of CAl0.5W0.5(CAW) compound on the grain refinement of Mg-Al based alloys was investigated.The results show that CAW compound is an effective and active grain refiner.The grain size of binary Mg-Al alloys is more than 500 μm,and it is changed to about 110 μm with a 1 wt.% CAW addition.The hardness increased with the decease of grain size monotonously.The mechanical properties are improved by the addition.The fine grain size is mainly ascribed to the dispersed Al2CO particles,which are very potent nucleating substrates for Mg-Al alloys.The nucleation cores formed by chemical reaction directly are well-distributed in the matrix.     

Radiation-Induced Phase Transformations in Zirconium Alloys under Long-Term Irradiation

Variation of the phase composition and structure of zirconium alloys É125 and É635 under the action of irradiation is studied by the methods of microscopic x-ray energy dispersion analysis, radiographic analysis, and analytical transmission electron microscopy. Special features of phase transformations in the alloys under the action of long-term neutron irradiation at 290 – 315°C are analyzed.     

High temperature corrosion studies in molten salt-FLiNaK

FLiNaK (LiF–NaF–KF: 46·5–11·5–42 mol.-%) is a promising candidate as high temperature coolant for next generation nuclear reactor coolants. Major technical challenge in implementation is the selection of structural material that can withstand corrosive nature of FLiNaK. Corrosion study of different alloys such as SS-316L, SS-317L, Inconel-625, Incoloy-800H, Hastelloy-B and Ni-201 was performed in FLiNaK salt. The tests were carried out in the temperature range of 650–850°C in graphite crucibles for 60 h under inert atmosphere. Weight loss of the alloy sample due to corrosion was measured, and corrosion rate was estimated. The salt composition after corrosion was analysed by inductively coupled plasma spectroscopy coupled with atomic emission spectroscopy. The surface morphology of the alloy samples was analysed by scanning electron microscopy. Ni-201 and Hastelloy-B showed better resistance to corrosion than other alloys. Corrosion rate was found to increase with increase in Cr content in the alloy.     

Application of texture simulation to understanding mechanical behavior of Mg and solid solution alloys containing Li or Y

The viscoplastic self-consistent model was used to interpret differences in the mechanical behavior of hexagonal close packed magnesium alloys. There are only subtle differences in the compression textures of magnesium and its solid solution alloys containing lithium or yttrium. However, the plane strain compression textures of the alloys showed an increasing tendency for the basal poles to rotate away from the “normal direction” towards the “rolling direction”. Texture simulations enabled these distinctions to be attributed to the increased activity of the non-basal c+a slip mode. The alloys had improved compressive ductilities compared to pure magnesium, and the increased c+a slip mode activity provides a satisfying explanation for this improvement, since it can accommodate c-axis compression within individual grains. Accounting for individual deformation mode hardening enabled the flow curves to be simulated and the anisotropic plastic response of textured wrought alloys to be mechanistically understood and predicted.     

Oxidation of Zirconium Alloys in Oxygen at High Temperatures up to 1600 °C

The oxidation kinetics of the classic pressurized water reactors (PWR) cladding alloy Zircaloy-4 has been extensively investigated over a wide temperature range. In recent years, new cladding alloys optimized for longer operation and higher burn-up are being increasingly used in Western light water reactors (LWR). These alloys were naturally optimized regarding their corrosion behavior for operational conditions. The publicly available data on high temperature oxidation of the various cladding materials are very scarce. This paper presents the results of a first test series with Zircaloy-4 as reference material, Framatome Duplex cladding, Framatome M5^® and the Russian E110 alloy. The first two are Zr–Sn, the latter two Zr–Nb alloys. All materials were investigated in isothermal and transient tests in a thermal balance under argon–oxygen atmosphere. Strong and varying differences (up to 500%) of oxidation kinetics between the alloys were found till 1000 °C, where the breakaway effect plays a role. Smaller but still significant differences (20–30%) were observed at higher temperatures. Generally, the advanced cladding alloys here studied show also a favorable behavior at high temperatures during accident scenarios.     

Ni-Ti形状记忆合金中母相(?)马氏体可逆转变过程的研究SCIEI

用透射电镜对Ni-Ti形状记忆合金中母相?马氏体可逆转变进行了动态观察。利用高分辨电子显微术研究了该合金相变温度上下的结构变化。结果表明,马氏体与奥氏体的取向关系为:[111]_A∥[110]_M,[110]_A∥[001]_M,(110)_A∥(001)_M,(110)_A与(010)_M间夹角为6.5°左右;马氏体的晶体缺陷多为孪晶和层错,新发现有孪晶而为(100)的孪晶。     

REVERSIBLE TRANSFORMATION BETWEEN MATRIX AND MARTENSITE IN Ni-Ti SHAPE MEMORY ALLOYS

The reversible transformation between matrix and martensite in Ni-Ti shape memory alloyshas been dynamically observed under TEM.The orientation relation between martensite andaustenite as well as the structural change near the transition temperature has been also studiedwith the help of HREM SADP.The results show that the orientation relation betweenmartensite and austenite is[(?)11]_A//[(?)10]_M,[110]_A//[001]_M,(110)_A//(001)_M and theangle between((?)110)_A and(010)_M is about 6.5°.The crystal defects of martensite are foundto be twin and stacking fault,and the twin plane as(100).     

Modeling of precipitation hardening in pre-aged AlMgSi(Cu) alloys

A new analytical method to estimate the evolution of the relative volume fraction of precipitates during artificial aging of pre-aged AlMgSi(Cu) alloys in the underaged regime is introduced. The analytical results demonstrate that the precipitation processes in AlMgSi(Cu) alloys are isokinetic in commercially relevant temperature ranges. The theory of transformations is used to model isothermal and non-isothermal aging kinetics in isokinetic systems where the precipitate nuclei pre-exist at the start of aging and definite precipitate contents are reached at the end of transformation. A simple physically based model is also developed for the prediction of the average size of precipitates during artificial aging of pre-aged alloys, when “growth” is the controlling mechanism of precipitation. The microstructural models are combined with a previously developed yield strength model and the evolution of yield strengths during isothermal and non-isothermal aging of AlMgSi(Cu) alloys, with various pre-aging histories, are modeled. The analytical method and the microstructural and yield strength models are validated using experimental results.     

Microstructure and high temperature tensile properties of Al–Si–Cu–Mn–Fe alloys prepared by semi-solid thixoforming

The differences in the microstructure and elevated temperature tensile properties of gravity die cast, squeeze cast, and semi-solid thixoformed Al–Si–Cu–Mn–Fe alloys after thermal exposure at 300 °C were discussed. The results demonstrate that the elevated temperature tensile properties of semi-solid thixoformed alloys were significantly higher than those of gravity die cast and squeeze cast alloys, especially after thermal exposure for 100 h. The ultimate tensile strength (UTS) of semi-solid thixoformed alloys after thermal exposure at 300 °C for 0.5, 10 and 100 h were 181, 122 and 110 MPa, respectively. The UTS values of semi-solid thixoformed alloys were higher than those of heat resistant aluminum alloys used in commercial applications. The enhanced elevated temperature tensile properties of semi-solid thixoformed experimental alloys after thermal exposure can be attributed to the combined reinforcement of precipitation strengthening and grain boundary strengthening due to thermally stable intermetallic phases as well as suitable grain size.     

Formulation and technology research of new silver solder with flux covering

In their eutectic compositions, Au–Si alloys have a melting point of 369°C, and a colour similar to that of high-grade gold. Results of the manufacture of gold alloys with 2.5%, 2.8% and 3.0% silicon, by means of melting in a plasma furnace with an inert argon atmosphere, are presented in this study. Chemical composition characterisation was carried out by energy dispersion spectroscopy and wave dispersion spectrometry, and metallographic and microstructural analysis by optical microscopy, SEM and DRX, Vickers hardness and mircohardness testing, melting point evaluation by DSC and determination of the SCIELab colorimetric coordinates. The results of the hardness and micro-hardness testing gave values around 110HV, presenting an important increase in the mechanical properties with respect to the traditional high purity gold alloys. The melting temperature for the alloys was around 374°C as well as being a heat very close to the values of pure gold.     

Effect of the alloy composition on the grain refinement of aluminum alloys

Experiments were carried out to evaluate the effect of solute elements on grain refinement in aluminum based hypoeutectic alloys. Grain sizes of the as-cast structures were measured. The measured grain sizes were plotted vs. the undercooling parameter, P, the growth restriction factor, Q, and the solidification interval, ΔT, of the alloys. The results indicated that grain sizes decrease monotonically with increasing ΔT over the whole range of the hypoeutectic compositions whereas the relationships between the grain size and P or Q are “V” type curves.     

Designing bulk metallic glass and glass matrix composites in martensitic alloys

To circumvent the limited plasticity of bulk metallic glasses (BMGs), heterogeneous materials with glassy matrix and different type and length-scale of heterogeneities (micrometer-sized second phase particles or fibers, nanocrystals in a glassy matrix, phase separated regions, variations in short-range order by clustering) have been reported. We developed bulk metallic glasses and glass matrix composites in martensitic Zr–Cu-base alloys. Large plasticity can be obtained from microstructure consisting of either a glassy structure, or for alloys with martensitic second phase embedded in a glassy matrix. This type of glasses and glass–matrix composites are able to achieve high strength together with pronounced work-hardening. We explore the possibilities to synthesize such in situ composite microstructures based on shape memory alloys (“M-Glasses”) through metal mold casting.     

Effects of homogenisation conditions on semisolid microstructures of Al–Mg–Si–Mn alloys produced by D-SSF process

Abstract

The effects of different heating rates to a homogenisation temperature on the semisolid microstructure of Al–Mg–Si–Mn alloys are investigated. It is found that the size, morphology and distribution of the α-Al₁₂Mn₃Si₂ intermetallic compound (Mn containing dispersoid) depend on the heating rate in the homogenisation process. Fine spherical and homogeneously distributed Mn containing dispersoid particles are found in the slow heated samples (0˙7°C min^?1), while inhomogeneously distributed coarser particles with a rod-like shape are found in the rapid heated samples (110°C min^?1). The homogenised sample is deformed by 60% cold rolling. It is found that the recrystallised and semisolid grain sizes of the rapid heated sample are smaller than those of the slow heated sample in all conditions. Compared with the M4 alloy (0˙4 mass-%Mn), the M7 alloy (0˙72 mass-%Mn) has much finer semisolid grain size and smaller values of the shape factor close to 1. The Mn containing dispersoid greatly affects the semisolid grain size of the alloys. The results in this work show that the rapid heating in the homogenisation process is useful to produce high quality semisolid products of the Al–Mg–Si–Mn alloys.     

Oxidation of Advanced Zirconium Cladding Alloys in Steam at Temperatures in the Range of 600�C1200?��C

The oxidation kinetics of the classical pressurized water reactors (PWR) cladding alloy Zircaloy-4 have been extensively investigated over a wide temperature range from operational conditions to beyond design basis accident (BDBA) temperatures. In recent years, new cladding alloys optimized for longer operation and higher burn-up are used in Western light water reactors (LWR). This paper presents the results of thermo-gravimetric tests with Zircaloy-4 as the reference material, Duplex DX-D4, M5^® (both AREVA), ZIRLO? (Westinghouse), and the Russian E110 alloy. All materials were investigated in isothermal and transient tests in a thermal balance with steam furnace. Post-test analyses were performed by light-microscopy and neutron radiography for investigation of the hydrogen absorbed by the metal. Strong and varying differences (up to 800%) in oxidation kinetics between the alloys were found at up to 1000 °C, where the breakaway effect plays a role. Less but significant differences (ca. 30%) were observed at 1100 and 1200 °C. Generally, the M5^® alloy revealed the lowest oxidation rate over the temperature range investigated whereas the behavior of the other alloys was considerably dependent on temperature. A strong correlation was found between oxide scale structure and amount of absorbed hydrogen.     

铝合金铸件壁厚对机械性能的影响

研究了铸件壁厚对ＺＬ１０１合金，ＺＬ１０４合金，ＺＬ２０５合金，ＺＬ２０１合金及ＺＬ２０５Ａ合金机械性能的影响。研究表明：这些合金随铸件壁厚的增加机械性能下降。ＺＬ２０１，ＺＬ２０５Ａ合金的机械性能受壁厚的影响比ＺＬ１０１合金，ＺＬ１０４合金和ＺＬ１０５合金的机械性能受壁厚的影响大。     

超疏水铝合金表面的复合制备与性能

铝合金由于易被腐蚀的缺陷限制了其发展,研究表明表面超疏水化能有效地提升其耐腐蚀性能。 文中以铝合金作为基底材料,首先采用激光加工的方法制备微结构表面,然后采用氢氧化钠刻蚀制备超疏水表面。 利用扫描电子显微镜(SEM)、光学轮廓仪、X 射线能谱仪(EDS)、接触角测量仪和电化学工作站对样品表面微观形貌、化学元素组成、 润湿性能和耐腐蚀性能进行表征。 结果表明:激光功率为 30 W,氢氧化钠浓度为 0. 1 M,刻蚀时间为 6 min,该表面的接触角最高为 155. 1°,同时该超疏水表面具有双尺度分层结构,分别是光栅结构与更小一级的蜂窝状结构。 超疏水表面电化学测试表明,腐蚀电位发生左移,为-0. 635 V,自腐蚀电流密度变化更为明显,减小至 1. 68×10^-6 mA·cm^-2 。 该表面耐腐蚀性能显著增加。     

Effect of semisolid microstructure on solidified phase content in 1xxx Al alloys

Melt-spun high purity Al–0.3 wt% Fe–0.1 wt% Si alloys, containing V and Al–5Ti–1B grain refiner, were melted at 2 K/min from 635°C to different temperatures above the solidus in a differential scanning calorimeter (DSC). Quenched and slow cooled (at 2 K/min) microstructures were examined using scanning electron microscopy (SEM). Melting was observed in a hot-stage reflected light microscope. Al–Fe₄Al₁₃ melted first, forming cell boundary liquid films. Rapid coarsening occurred at <4 K above the solidus via motion of these boundaries. Intracellular liquid droplets formed at 4–6 K above the solidus. These droplets have been demonstrated to be sites of metastable Al–FeAl_m formation in V and Al–5Ti–1B containing alloys on solidification. With increasing temperature the liquid cell boundaries thickened and consumed the droplets, until there were none left at 10 K above the solidus, when the microstructure was fully molten. Consequently Al–FeAl_m only formed in V and Al–5Ti–1B containing alloys when solidified following melting to 4–10 K above the solidus.     

Prediction of the effect of second phases embedded in a lead matrix on anodic corrosion

After referring to the research carried out on composite specimens formed by lamellae of “reactive” metals embedded in a lead matrix, an attempt is made to apply the data obtained on penetration of attack into these lamellae to the real case of the anodic corrosion of several two-phase Pb---Sb and Pb---Ag alloys in the as-cast condition.To this end, a theoretical treatment of the effect of a “reactive” second phase on the stability of an alloy is presented. Emphasis is laid on the role which material disintegration may play, provided the second phase particles supply routes for a fast penetration of the localized attack into the alloy structure.     

Effect of Ni content on cracking susceptibility and microstructure of laser-clad FeCrNiBSi alloy

An investigation is reported of the laser surface cladding of self-fluxing Fe---Cr---Ni---B---Si alloys on a medium carbon steel substrate using the preplaced powder method. The cracking susceptibility and microstructure of the laser-cladding layer have been studied in terms of its Ni content, thermal expansion coefficient and wettability on the substrate. With increasing Ni content the cracking susceptibility of the cladding layer decreases and its microstructure changes from a “bamboo leaf” structure to a typical dendritic one.