Grain size and grain-boundary effects on diffusion and trapping of hydrogen in pure nickel

The impact of grain size on hydrogen diffusion and trapping mechanisms has been investigated for a wide range of grain size of non-textured pure nickel. Both aspects depend mainly on the nature of grain boundaries (GBs). In particular, we illustrate the effects of random and special boundaries on the different defects and trapping sites stored in the GBs, and their consequences on hydrogen transport and segregation. The high-angle random boundaries are considered as disordered phase where the hydrogen diffusion is accelerated, while the special boundaries constitute a potential zone for hydrogen trapping due to the high density of trapping sites as dislocations and vacancies. The predominance of one phenomenon over the other depends on several parameters, such as the grain size, the probability of grain boundary connectivity, the grain boundary energy and the excess of free volume. In addition, our experiments confirm that hydrogen promotes vacancy formation probably in GBs.     

New method to diffusion bond superalloys

Abstract

A new method for diffusion bonding nickel base and cobalt base superalloys has been developed, which is based on non-chemical oxide removal before the bonding process. Using this method, diffusion bonds were produced in nickel base and cobalt base superalloys with 'virtually invisible' bond interfaces and compositions very close to the bulk alloys. The bonding time required is about 1 h and the results of severe mechanical tests of the bonded samples, including directionally solidified (DS), single crystal and dissimilar superalloys, are very promising. The new oxide removal method is very rapid, does not require the use of any sophisticated equipment and is not a costly process. The high temperature properties of bonded samples are currently being investigated. European and USA patents have been applied for and the details of this new method are to be published in the future.     

Phase-Field Modeling of Hydrogen Diffusion and Trapping in Steels

Hydrogen embrittlement of steels is directly linked to hydrogen diffusion and trapping in the microstructure,which can hardly be precisely measured by modern experimental techniques.A phase-field model,in which a chemical potential well of hydrogen in the grain boundaries is introduced,is proposed to simulate hydrogen diffusion and trapping in the polycrystal-line iron.It was interestingly found that grain boundaries,as connected trap sites,have a complex influence on the effective diffusivity of hydrogen,which are strongly linked to grain boundary diffusivity and binding energy.     

Diffusion of chromium in nanocrystalline iron produced by means of surface mechanical attrition treatment

By means of surface mechanical attrition treatment (SMAT) to a pure iron plate, a nanometer-grained surface layer without porosity and contamination was fabricated. The average grain size in the top surface layer (of 5 μm thick) is about 10–25 nm, and the grain size stability can be maintained up to 653 K. Cr diffusion kinetics in the nanocrystalline Fe phase was measured by using second ion mass spectrometry within a temperature range of 573–653 K. Experimental results showed that diffusivity of Cr in the nanocrystalline Fe is 7–9 orders of magnitude higher than that in Fe lattice and 4–5 orders of magnitude higher than that in the grain boundaries (GBs) of α-Fe. The activation energy for Cr diffusion in the Fe nanophase is comparable to that of the GB diffusion, but the pre-exponential factor is much higher. The enhanced diffusivity of Cr may originate from a large volume fraction of non-equilibrium GBs and a considerable amount of triple junctions in the present nanocrystalline Fe sample processed by means of the SMAT technique.     

Salzschmelzkorrosion gerichtet erstarrter eutektischer CO-Cr-C-Basis Superlegierungen bei hohen Temperaturen

Corrosion of directionally solidified eutectic Co-Cr-C-Superalloys by molton salts at high temperatures The corrosion behaviour of various directionally solidified 73C-class eutectic alloys (Co-Cr₇C₃) and the conventionally cast nickel base alloy IN 738* were investigated using a eutectic sulphate melt (sodium, calcium, and magnesium with 2% sodium chloride). As these materials are designed for high temperature applications, tests were carried out at 900°, 1000°, and 1100°. The additions to 73C were nickel, aluminium, and manganese. Corrosion surface attack for 73C and IN 738 was found to be similar. The grain boundary formation of sulphides and oxides in IN 738 is shown up as a disadvantage when compared with 73C as 73C has no grain boundaries perpendicular to the surface. This could possibly be compensated by directionally solidifying IN 738. A 10% nickel addition to 73C was found to increase the corrosion resistance, a 2% aluminium addition showed a minor improvement, and a 4.7 or 10% manganese addition to 73C to influence the corrosion resistance considerably.     

Atomistic simulation of hydrogen diffusion at tilt grain boundaries in vanadium

Molecular dynamics simulations of hydrogen diffusion at Σ3 and Σ5 tilt grain boundaries in bcc vanadium (V) have been performed based on modified embedded-atom method interatomic potentials. The calculated diffusivity at the grain boundaries is lower than the calculated bulk diffusivity in a temperature range between 473 and 1473 K, although the difference between the grain boundary and bulk diffusivities decreases with increasing temperature. Compared with that of the other directions, the mean square displacement of an interstitial hydrogen atom at the Σ3 boundary is relatively small in the direction normal to the boundary, leading to two dimensional motion. Molecular statics simulations show that there is strong attraction between the hydrogen atom and these grain boundaries in V, which implies that the role of grain boundaries is to act as trap sites rather than to provide fast diffusion paths of hydrogen atoms in V.     

Three-dimensional simulation of intermetallic compound layer growth in a binary alloy system

We present three-dimensional phase-field simulations of the thickening of intermetallic compound (IMC) layers and their microstructural evolution during soldering and aging in a binary alloy system. The focus was on the grain growth in the IMC layer, since the grain boundary (GB) provides a high-diffusivity path and affects the thickening kinetics of the IMC. The radial grain growth of the IMC was analogous to Ostwald ripening when the phase interface was rounded, while it followed normal grain growth with planar phase interface. The thickening mode of the IMC layer was dependent upon the microstructural evolution within the IMC layer with high diffusivity along the GBs. The simulation results successfully confirm literature models on the effect of GB diffusion on IMC thickening.     

Effect of bonding temperatures on the transient liquid phase bonding of a directionally solidified Ni-based superalloy,GTD-111

The bonding phenomenon and the mechanism involved in the transient liquid phase bonding (TLP Bonding) of directionally solidified Ni-based superalloy GTD-111 was investigated. At a bonding temperature of 1403 K, the liquid insert metal was eliminated by isothermal solidification, which was controlled by the diffusion of B and Si into the base metal. The solids in the bonded interlayer simultaneously grew epitaxially from the mating base metal inward from the insert metal. The number of grain boundaries formed at the bonded interlayer corresponded with those of the base metal. Liquefaction at the grain boundary and dendrite boundary occurred at a temperature of 1433 K. At a bonding temperature of 1453 K which is higher than the liquefaction temperature of the grain boundary, liquids of the insert metal were connected with liquated grain boundaries; this connection extended as far as the grain boundary, which was approximately 1.5 mm from the interface. The composition of this liquid was a mixture of the insert metal and phase that existed at the grain boundary. At extended holding times, liquid phases gradually decreased, and liquids with a continuous band shape develop into distinct islands. However, the liquid phases did not disappear after a holding period of 7.2 ks at 1453K. The extended isothermal solidification process at the bonding temperature, which is higher than the liquefaction temperature for the grain boundary, was controlled by the diffusion of Ti. This resulted in its preferential liquefaction compared to B or Si in the insert metal.     

冶金硅定向凝固法制备太阳能级多晶硅及其微观组织与位错(英文)

以冶金硅为原料,探索采用具有高温度梯度的真空定向凝固技术制备低成本太阳能级多晶硅,并研究其在不同生长条件下的微观组织特征、晶界与晶粒大小、固液界面形貌以及位错结构。结果表明,当凝固速率低于60μm/s时,能获得具有高密度和良好取向的定向凝固多晶硅棒状试样,硅晶粒大小随凝固速率的增大而减小;在控制凝固过程,获得平的固液界面形貌是获得沿凝固方向排列柱状晶的关键;由于硅的小平面生长特性,微观组织中出现了位错生长台阶和孪晶结构;在晶粒中,位错分布呈现不均匀性,并且位错密度随凝固速率的增加而增加;在此基础上,讨论了多晶硅的生长行为以及位错形成机制。     

Preparation and characteristics of thermal resistance polysiloxane/Al composite coatings with low infrared emissivity

The electrochemical hydrogen permeation tests were applied to determine permeability and the effective diffusivity of hydrogen in a plastically deformed FeAl-based alloy. The experimental results reveal that both the hydrogen permeation rate and effective diffusion coefficient are reduced with the increase in plastic working degree. Structural defects induced by preliminary deformation are the main retardation factor for hydrogen transport in iron aluminides.     

螺旋选晶器对单晶高温合金晶粒取向的影响(英文)

对于航天推进和发电燃气轮机,为了实现更高的效率和性能并同时降低成本和排放,需要发展先进的镍基单晶高温合金。随着合金的发展,合金的铸造技术已经从定向凝固(DS)发展到单晶(SX)。单晶取向与择优取向的偏差已经成为单晶高温合金最重要的铸造缺陷之一。在自行设计的高温度梯度定向凝固装置中,采用改进的Bridgeman法,用螺旋选晶器拉制出DZ417G合金的单晶。使用XRD和EBSD对其取向进行分析研究。结果表明:较小角度的螺旋选晶器可以有效地减少单晶取向与择优取向的偏差。     

Diffusion behaviour of hydrogen in nitrogen containing austenitic alloys

Electrochemical permeation technique and thermal desorption spectroscopy were used to evaluate the hydrogen diffusion, solubility, and trapping behaviour in nitrogen containing austenitic alloys. The hydrogen diffusion of all alloys obeyed Arrhenius relationships in the studied experimental temperature range. The apparent diffusion coefficients were determined and the relevant activation energies were estimated. Nitrogen at higher concentration (>0.38 wt.%) as well as chromium decrease the hydrogen diffusion whereas nickel has opposite effect. The thermal analysis of all alloys except Cr18Mn18N0.57 shows a main single peak at different heating rates indicating no significant hydrogen interaction with microstructural defects. The alloy Cr18Mn18N shows a shoulder in addition to the peak which is attributed to nitrogen–hydrogen interaction. The activation energy estimated from the thermal analysis is nearly equal to the activation energy for diffusion obtained from the Arrhenius plots of the corresponding alloys.     

Hydrogen permeation behavior of nickel electroplated AISI 4340 steel

The role of the electroplated nickel layer on hydrogen permeation through AISI 4340 steel was investigated by a electrochemical hydrogen permeation test. The permeation test, composed of three steps, was conducted to measure the hydrogen diffusivity and surface hydrogen concentration. A constant current of 20 mAcm^-2 and a constant potential of -100 mV vs. Ag/AgCl electrode were applied to the hydrogen entry and exit cells, respectively. The thickness of the electroplated nickel layer on AISI 4340 steel increased in a linear fashion with an increase in electroplating time. The nickel coated layer contributed to a decrease in the hydrogen permeability of nickel coated AISI 4340 steel specimens. This is due to the fact that the surface hydrogen concentration and hydrogen diffusivity in nickel coated layer were lower than those of AISI 4340 steel substrate. Especially, low hydrogen diffusivity decreased significantly with hydrogen permeability. The critical effective hydrogen diffusivity for barrier of nickel electroplated AISI 4340 steel specimens was higher than the hydrogen diffusivity of AISI 4340 steel specimen. It is proposed then that the thin nickel layer on AISI 4340 steel acts as a barrier for hydrogen permeation through AISI 4340 steel.     

Modeling Interdiffusion Processes in CMSX-10/Ni Diffusion Couple

A diffusion couple between directionally solidified nickel and the single crystal Ni-base superalloy CMSX-10 was produced by hot pressing in vacuum. The diffusion couples were heat treated at temperatures between 1050 and 1250 °C. The exposed samples were characterized by SEM/EBSD/EPMA. The interdiffusion results in dissolution of the γ′-Ni₃Al in the superalloy and in growth of nickel grains towards CMSX-10. Rapid diffusion of aluminum from the superalloy into pure nickel leads to a significant formation of pores in the superalloy. The interdiffusion processes were modelled using the finite-element simulation software DICTRA with the databases TCNi5 and MobNi2, tailored specially for Ni-base superalloys. The effect of alloying elements on the interdiffusion profiles is discussed in terms of alloy thermodynamics. The calculated element concentration profiles are in good agreement with the EPMA measurements. The interdiffusion modeling correctly predicts the shapes of the concentration profiles, e.g. kinks on the Al and Ti profiles in the vicinity of the original interface in the joint. The calculation predicts with reasonable accuracy the extent and the location of the Kirkendall porosity.     

Wetting of molybdenum grain boundaries by nickel: effect of the boundary structure and energy

The structural effect of the penetration of nickel along symmetrical [101] tilt grain boundaries (GBs) in two different molybdenum bicrystals is investigated. The selection of GBs (Σ=3{121} and Σ=11{323}) is governed by their different energy so that a different penetration behaviour is expected. The temperature of treatment is 1350°C, i.e. above the eutectic temperature. The analysis of the Mo–Ni phase formed on the surface of the bicrystal, the concentration profile along the GB and the identification of the nanophases present at the GB is performed by using several experimental techniques from microscopic to nanoscopic scales. Important differences in the penetration of nickel are found for the two investigated GBs.     

Grain boundary relaxation of hydrogen precharged mild and Cr steels

Internal friction was applied to trace the formation and propagation of the hydrogen-induced degradation of commercial mild and 5% Cr steels. Hydrogen charged and then degassed specimens were subjected to internal friction measurements at the grain boundary relaxation temperature range and the irreversible effects of hydrogen precharging on the grain and phase boundary relaxation processes were studied. From the comparison of the internal friction and the hydrogen permeation data, the critical limits of hydrogen pretreatment corresponding to the different state of the grain boundary degradation were evaluated. At lower critical limit (associated with the minimum of hydrogen apparent diffusivity), the formation of near grain boundary dislocations and the grain boundary decohesion occurred. At critical hydrogen precharging causing the formation of microvoids, annihilation of dislocations and vacancies within the grain boundary voids led to the recovery of internal friction and hydrogen diffusivity. The obtained results agreed with the earlier observed effects of hydrogen precharging on pure iron and low alloy steel, despite the apparent difference in the grain boundary structure and chemistry of those materials.     

定向凝固镍基高温合金的成分因素对涡轮叶片热裂的影响

定向凝固合金可铸性的最重要标志就是它的热裂倾向性，亦即合金的定向凝固过程中产生沿纵向晶界开裂的倾向性，根据一种镍基高压涡轮工作叶片的试制过程中暴露出的严重热裂问题，通过进一步的实验对比与分析，讨论了该合金的成分因素对定向空心叶片热裂的影响。     

V85Ti10Y5和V85Ti10Cu5氢分离合金组织与性能研究

利用高真空非自耗电弧熔炼炉制备了V85Ti10Y5和V85Ti10Cu5氢分离合金。通过SEM、TEM、XRD、氢渗透实验、PCT吸氢实验、恒压缓冷实验,研究了Y、Cu元素的加入对合金氢渗透性能、氢溶解性能及抗氢脆性能的影响。结果表明:铸态V85Ti10Y5和V85Ti10Cu5合金组织均由V-基体和第二相组成,但前者第二相是弥散分布的富Y颗粒,而后者为既在晶内析出又沿晶界连续分布的铜钛金属间化合物。V85Ti10Y5合金中Y2O3的生成及V85Ti10Cu5合金中部分固溶Cu的斥氢作用和Cu2Ti形成使V中Ti的固溶量减少,进而降低合金中的氢浓度,减小氢固溶产生的内应力,提高抗氢脆性能。V85Ti10Y5和V85Ti10Cu5合金在缓冷过程中均未发生氢脆现象,表现出优异的抗氢脆性能,而且在673 K时的氢渗透率分别为0.139×10-6 mol H2 m-1 s-1 Pa0.5和0.174×10-6 mol H2 m-1 s-1 Pa0.5,是Pd77Ag23氢渗透率的5.5和6.9倍,与商用钯合金相比均展现出较高的渗透率。     

晶界状态对定向凝固Al—Cu和Renel25合金热裂倾向的影响

在ＨＲＳ定向凝固设备上进行了合金热裂试验,采用半定量方法评定了定向凝固Ａｌ－Ｃｕ和Ｒｅｎｅｌ２５合金热裂倾向。观察了合金的晶界,并分析讨论了其对合金热裂的影响。用晶界状态分析的结果与试验结果完全一致。证明了晶界状态对热裂纹的形成有重要影响,其影响包括对晶间结合力的破坏作用和对晶界凝固收缩的补偿作用。晶界状态对热裂影响的综合作用取决于晶界低熔点相的分布和数量。     

The oxidation of a directionally solidified cobalt-tungsten eutectic alloy

A study of the oxidation of directionally solidified Co-W alloys were performed at 750, 900, and 1050°C. The study involved a comparison of the oxidation behavior of directionally solidified and as-cast alloys along with the oxidation behavior of the pure components. The study incorporated both thermogravimetric kinetic measurements and morphological studies of the oxides as a function of both temperature and time. Differences were noticed in both the oxidation rate and the oxide morphology and were attributed to differences in alloy microstructure. The directionally solidified Co-W alloy was found to be more spall resistant but also oxidized more rapidly than the conventionally as-cast alloy. Both alloys were more oxidation resistant than the pure components.