High-strength Zr-based bulk amorphous alloys containing nanocrystalline and nanoquasicrystalline particles

Abstract

It was recently found that the addition of special elements leading to the deviation from the three empirical rules for the achievement of high glass-forming ability causes new mixed structures consisting of the amorphous phase containing nanoscale compound or quasicrystal particles in Zr–Al–Ni–Cu–M (M ? Ag, Pd, Au, Pt or Nb) bulk alloys prepared by the copper mold casting and squeeze casting methods. In addition, the mechanical strength and ductility of the nonequilibrium phase bulk alloys are significantly improved by the formation of the nanostructures as compared with the corresponding amorphous single phase alloys. The composition ranges, formation factors, preparation processes, unique microstructures and improved mechanical properties of the nanocrystalline and nanoquasicrystalline Zr-based bulk alloys are reviewed on the basis of our recent results reported over the last two years. The success of synthesizing the novel nonequilibrium, high-strength bulk alloys with good mechanical properties is significant for the future progress of basic science and engineering. © 2000 Published by Elsevier Science Ltd.     

Al-based nanocrystalline composites by rapid solidification of Al-Ni-Sm alloys

Nanophase composites (Al-based materials with α-Al particles dispersed in an amorphous matrix) can be produced by melt spinning and annealing Al₈₈Ni_{12 − x}Sm_x (x = 2 to 10 at%) master alloys. The structures and the thermal stability of the ribbons obtained, asquenched and after annealing, are characterised by X-ray diffraction and differential scanning calorimetry. The mechanical properties of these composites, including hardness and abrasive wear resistance, are measured as a function of the volume fraction of α-Al nanocrystals in the amorphous matrix. The properties of these nanophase composites are compared with other industrial alloys in the aluminium family and show an exceptional hardness and wear resistance.     

Nanoindentation studies on amorphous, nanoquasicrystalline and nanocrystalline Zr8oPt2o and Zr75Pd25 alloys

Nanoindentation studies on rapidly solidified Zr80Pt20 and Zr75Pd25 binary alloys with nanocrystalline, nanoquasicrystalline, and amorphous microstructures are reported. The results indicate that the hardness and elastic modulus are the highest for a mixture of amorphous and nanoquasicrystalline state among the various microstructures studied. Nanoquasicrystalline phase has high hardness and elastic modulus in comparison to amorphous and nanocrystalline phases. The hardness to modulus ratio is close to 0.1 in both the alloys, irrespective of the phase/phase mixture studied indicating that the bonding in these alloys is of covalent nature. In Zr80Pt20, all the phases/phase mixtures have higher hardness and modulus in comparison to similar microstructures in Zr75Pd25 due to higher bond energies caused by more negative heat of mixing in the former case.     

铝基非晶合金的研究与发展

A1基非晶及纳米复合A1非晶合金,作为新兴的工程材料,已经引起人们广泛的关注,近年来发展十分迅速。简述了A1基非晶合金的形成机制、晶化动力学及热稳定性等方面的研究概况及进展,并就其性能与传统A1合金进行了对比。     

铝基准晶的研究进展

概述了铝基准晶态合金的形成机理,其形成存在着相似性原则,具有电子浓度特征.分析了铝基准晶合金的组织与相变特征,铝基准晶的生成通常为包晶、包析反应,其长大速度较慢.综述了铝基准晶合金的性能,铝基准晶具有高的硬度、高的弹性模量及高的强度,室温下塑性小,表现为脆性;铝基准晶具有优良的抗腐蚀性能;铝基准晶具有低摩擦因数和抗摩损的特征.对铝基非晶合金的应用进行了评述.     

铝基非晶合金的制备、性能与应用研究进展

铝基非晶合金因其独特的物理和化学性能在诸多领域具有广泛的应用前景,综述了铝基非晶合金的成分体系、制备方法、性能特点及应用研究进展。首先,介绍了铝基非晶合金的发展历史和成分体系,目前铝基非晶主要分为3大体系：二元、三元和多元体系,以及综合性能和形成能力2大方面,多元体系表现更佳,并逐渐向更多元化发展;其次,系统介绍了铝基非晶合金的制备方法,包括粉末状、薄带状、块体样品的制备,相较于非晶薄带的制备,块体和粉状的制备方法较为丰富,而粉状非晶通常作为铝基非晶涂层的预制材料;随后,详细介绍了铝基非晶合金的性能特点、应用现状及发展趋势,从性能上来看,铝基非晶在强度和硬度以及耐腐蚀性能上表现良好,目前主要以涂层的形式参与应用,除此之外,研究者们也开始对磁性和热塑性展开研究,由于玻璃形成能力的限制,作为结构材料的应用较少;最后,对其未来应用前景进行了展望,认为涂层是目前铝基非晶合金最具应用前景的工程化方式。     

Low-cycle fatigue in Ni3Al-based alloys

The low-cycle fatigue properties of hot-extruded powders of a Ni₃Al-based alloy, IC 218, with nominal composition Ni-16.5Al-8.0Cr-0.4Zr-0.1B (at %) have been evaluated at room temperature. Tests were conducted under total strain conditions in a laboratory air environment. Results indicate that the low-cycle fatigue performance of the PM processed IC 218 nickel aluminide is superior to other structural alloys especially at higher strain amplitudes. These results are explained in terms of the high ductility of the fine-grain material and good crack growth propagation resistance in these alloys. Stress response curves for annealed IC 218 alloys indicate considerable cyclic hardening followed by cyclic softening. The onset of cyclic softening is found to occur at a constant cumulative plastic strain. The critical cumulative plastic strain criteria are verified for step-loaded IC 218 nickel aluminide coupons.     

Dislocation structures in Zr3Al-based alloys

Transmission electron microscopy has been used to investigate dislocation structures in deformed binary and ternary Zr₃Al-based alloys. In the binary alloy deformed at temperatures between 293 and 673 K the dislocations in the Zr₃Al phase consisted of a/31 1 2-type partial dislocations bounding superlattice intrinsic stacking fault on {1 1 1} planes. The {111} a/31 1 ¯2 stacking fault energy was approximately 2mJ m^–2 at 673 K. In binary specimens deformed between 873 and 1073 K cube slip predominated. Dislocations consisted mainly of a/2 1 1 0 pairs separated by antiphase boundary. For this temperature range the {1 0 0} a/201 1 antiphase boundary energy was between 30 and 45 mJ m^–2. Alloying with niobium or titanium was found to increase the {111} a/31 1¯2 stacking fault energy and thus increase the propensity for antiphase boundary-type dissociation.     

铝基非晶材料研究与再制造应用前景

发现于20世纪60年代的铝基非晶合金作为一种低密度材料拥有着较高的比强度,而且与传统晶态材料相比,呈现出长程无序、短程有序的原子排列特点,其内部不存在晶界、位错等较易引发失效的缺陷结构,表现出高硬度和优异的防腐、耐磨等性能,受到了国内外众多学者的广泛关注.起初,这类材料由于受到制备工艺的限制,表现为非晶与纳米晶共存的结构.随着科技发展,科学家们开发了一系列具有完全非晶结构的铝基合金体系.这些材料在具有较高的机械强度的同时能够表现出良好的韧性,使人们对其非晶形成能力、制备方法及应用推广等方面产生了较大的兴趣.对铝基非晶合金非晶形成能力的研究,学者们通常基于块体非晶合金非晶形成能力的经验判据,以及其他一些新提出的判定方法,如蒸发焓、费米层电子态密度、原子扩散以及析出相熔点等.但是,由于铝基非晶合金过冷液相区间较窄以及Al元素化学活性较强,因此铝基非晶合金的非晶形成能力普遍较弱.虽然人们在元素种类及含量变化对铝基非晶合金非晶形成能力的影响等方面做了大量的研究工作,但是目前仍未形成具有普适性的或更加精确的铝基非晶形成能力判定方法,未来仍需借助高性能材料模拟计算和机器学习等技术来进行完善.铝基非晶合金非晶形成能力较弱,以及其对外界条件的影响较为敏感,导致其在制备过程中易发生晶化,从而使获得的材料尺寸维度普遍较低.目前,铝基非晶合金的常见制备方法可按照其形态(粉状、块体、涂层等)来进行划分.粉状铝基非晶合金的制备方法主要为气雾化法和机械合金化法;块体铝基非晶合金的制备方法主要为直接凝固法和粉末冶金法;涂层类铝基非晶合金的制备方法主要包括激光熔覆、爆炸喷涂、冷喷涂、超音速火焰喷涂和电弧喷涂.相对而言,铝基非晶涂层制备技术不会受到工件尺寸的限制,工艺简单、操作方便,且适合于户外大面积施工,在表面防护与再制造工程领域更具应用潜力.尤其是在大型舰船、飞机、海洋设施等高附加值零件的再制造领域里,铝基非晶涂层制备技术的大规模推广应用将会带来巨大的经济效益.本文介绍了铝基非晶合金的发展过程、非晶形成能力、制备方法等内容,总结了铝基非晶涂层在再制造领域的应用前景,并展望了铝基非晶合金的未来研究方向.     

Crystallization of Al-based Amorphous Alloys in Good Conductivity Solution

The corrosion-induced crystallization of Al94 exNixGd6（x=6 and 10, in at.%） metallic glasses as well as phase separation, oxidation and cracking in good conductivity solution has been investigated by various techniques.The transmission electronic microscopy（TEM） result reveals that crystalline intermetallics and oxides present on the electrochemically thinned hole edge, and the phase separation occurs in the matrix of the as-spun ribbons with the circumferential speed Rcof 29.3 m/s. In addition, the bending and cracking of the samples occur after corrosion. The influence of Ni content on the phase separation, bending and cracking can be explained by the fact that the percolation of the backbone clusters in the amorphous alloy melts and glasses is enhanced by increasing the composition of Ni.     

TEM specimen preparation for Al-based amorphous alloys

Transmission electron microscopy （TEM） is usually used to identify the amorphicity. However, some artifacts may be introduced due to improper TEM foil preparation. In this paper, three Al-rich metallic glasses with and without a glass transition were selected for characterizing the effect of the electropolishing condition on the as-quenched structure during TEM specimen preparation. It is shown that the occurrence of the modulated bright-dark structure under TEM observation is closely sensitive to the electropolishing condition, which suggests us being careful about the possible artifacts induced by specimen preparation when examining amorphous alloys under TEM.     

Grain-growth in nanocrystalline zirconium-based alloys

Crystallization and subsequent grain growth in nanocrystalline Fe₃₃Zr₆₇ and (Fe, Co)₃₃Zr₆₇ alloys were studied by TEM, differential scanning calorimetry and X-ray diffraction. The grain-growth data for both alloys obtained over a wide temperature range (about 200 °C) were fitted to different kinetic equations (with different grain-growth exponent, n). The model with n=3 (Equations 4 and 5) was found to predict in the best way the isothermal experimental data. This result gives strong evidence that crystallization (in our case by a polymorphic reaction) is indeed observed of a glass into a nanocrystalline material prior to the coarsening, rather than grain growth in an extremely fine-grained material which was never glassy at all. The activation energies for grain-growth, — 260±25 kJ mol^–1, were found to be practically the same for both systems. Additional information about the crystal growth kinetics of the nanocrystals in the amorphous matrix was obtained for (Fe, Co)₃₃Zr₆₇ glass.     

非晶增强铝基复合材料的微观结构及腐蚀性能

利用扫描电镜(SEM)、透射电镜(TEM)及电化学腐蚀等测试手段对搅拌摩擦加工制备获得的新型非晶增强铝基复合材料的微观组织结构及腐蚀性能进行实验研究.实验结果表明,新型非晶增强铝基复合材料呈现典型的层状结构,且组织呈现一定的纳米级的超细晶结构,主要由α-Al及α Al非晶结构组成的并伴有Al-Cu-Mg系析出相存在,与母材相比抗拉强度得到了较大的提高,而添加非晶形成的复合材料的电化学腐蚀性能相比未添加非晶基体材料加工后的腐蚀性能有所提高,但两种加工条件下材料的抗腐蚀性能均低于母材.     

The formation, structure and properties of nanocrystalline Ni-Mo-B alloys

The structure, structure evolution and microhardness of nanocrystalline Ni-Mo-B alloys were studied by X-ray diffraction, differential scanning calorimetry, transmission and high resolution electron microscopy and microhardness measurements. The nanocrystalline structure was produced by controlled crystallization of amorphous alloys. The annealed samples consist of the FCC nanocrystals with the amorphous regions between them. The grain size of the nanocrystals is about 20 nm and depends on the chemical composition of the alloy. The chemical composition of the amorphous phase between the nanocrystals changes at the annealing. A slight grain growth was observed when the annealing time increases. The diffusion of Mo and B from FCC to the amorphous phase occurs at the annealing. It results in the lattice parameter change. The microhardness of the alloys increases during the annealing. The microhardness values are the same in all alloys before the nanocrystalline structure decomposition. The microhardness is inconsistent with the Petch-Hall equation. The microhardness of the alloys is determined by the microhardness of the amorphous phase bands located between the nanocrystalline grains.     

Edge dislocations in nanoquasicrystalline materials

A theoretical model is proposed which describes energetic characteristics and behavioral features of edge dislocations in coarse-grained and nanostructured quasicrystals. The key point of the model is representation of dislocation-induced phason imperfections as centers of isotropic dilatation (flexes). The special attention in this paper is paid to the influence of the nanoscale structure on both energetic characteristics and behavioral features of edge dislocations in nanostructured quasicrystals (nanoquasicrystalline materials). It is shown, in particular, that the basic grain-size-sensitive contribution of dislocation-induced phason imperfections to the total energy of an edge dislocation varies directly with grain size, in which case the formation of edge dislocations is not suppressed in nanoquasicrystalline materials (in contrast to coarse-grained quasicrystalline materials.     

Amorphous and nanocrystalline silicon growth on carbon nanotube substrates

In this study, smooth and conformal hydrogenated silicon thin films are examined and analyzed on various multi-walled carbon nanotube (MWCNT) substrates. The films are deposited using radio-frequency plasma-enhanced chemical vapor deposition with He dilution and parameters that are heavily in the γ regime. It is proposed that high-energy plasmas with limited penetration depth can induce crystallization to occur on MWCNT substrates of varying active surface areas. The samples presented exhibit properties that are promising for energy applications, including photovoltaics and lithium-ion batteries and have been studied using scanning electron microscopy, Raman spectroscopy, X-ray diffraction, UV-Vis spectrophotometry, four-point probe measurements, and Fourier transform infrared spectroscopy.     

Structure and coercivity of nanocrystalline Fe-Si-B-Nb-Cu alloys

Crystallization behaviour and magnetic properties of melt-spun Fe-Si-B-Nb-Cu alloys have been investigated. It is found that the primary phase changes from α-Fe(Si) to Fe₃Si (DO₃) on increasing the Si content The coercivity of the alloys containing the Fe₃Si phase is significantly lower as compared to the alloy containing α-Fe(Si) phase. A heat treatment temperature-time-coercivity map has been obtained for optimization of the coercivity.     

Precipitation phase transformation in nanocrystalline Fe-Mo alloys

Precipitation phase transformation was studied in nanocrystalline Fe-rich Fe-Mo alloys with the use of X-ray diffraction and M?ssbauer spectroscopy. Alloys up to 5 at% Mo in Fe were synthesized by mechanical alloying and formed in alpha phase bcc solid solutions with average grain sizes in the range of 10-13 nm. The precipitation transformation (alpha-->alpha + lambda) was found to proceed via a Mo clustering that was correlated with the size of the nanograins. This was understood in terms of the Gibbs Thomson effect with a concept of negative surface energy contribution to the Gibbs free energy of mixing in a nanocrystalline alloy with positive internal energy of mixing. This contribution increased the stability of the solid solution for nanosized grains, and the Mo precipitation started once the grains grew beyond a critical size. We argue that the Mo precipitation takes place in the grain boundary regions, and the Mo-rich lambda phase also precipitates directly in the grain boundary regions, in contrast to the microcrystalline alloys, where the Mo clusters formed within the grains and were first dissolved in the Fe matrix before the lambda phase was formed.     

Surfaces of Al-based complex metallic alloys: atomic structure,thin film growth and reactivity

We present a review on recent work performed on periodic complex metallic alloy (CMA) surfaces. The electronic and crystallographic structures of clean pseudo-tenfold, pseudo-twofold, sixfold surfaces will be presented along with the recent findings on CMA of lower structural complexity, i.e. with a smaller unit cell. The use of CMA surfaces as templates for thin film growth and the formation of surface alloy will also be introduced. The reactivity of these complex surfaces and their impact in the field of heterogeneous catalysis will be discussed. Finally, common trends among these systems will be highlighted when possible and future challenges will be examined.