Nanostructured metals are generally unstable; their grains grow rapidly even at low temperatures, rendering them difficult to process and often unsuitable for usage. Alloying has been found to improve stability, but only in a few empirically discovered systems. We have developed a theoretical framework with which stable nanostructured alloys can be designed. A nanostructure stability map based on a thermodynamic model is applied to design stable nanostructured tungsten alloys. We identify a candidate alloy, W-Ti, and demonstrate substantially enhanced stability for the high-temperature, long-duration conditions amenable to powder-route production of bulk nanostructured tungsten. This nanostructured alloy adopts a heterogeneous chemical distribution that is anticipated by the present theoretical framework but unexpected on the basis of conventional bulk thermodynamics.

/pdf/design-of-stable-nanocrystalline-alloys-p52isaf08q.pdf

Design of stable nanocrystalline alloys.

Design of Stable Nanocrystalline Alloys

Forming alloys with impurity elements is a routine method for modifying the properties of metals. An alternative approach involves the incorporation of interfaces into the crystalline lattice to enhance the metal's properties without changing its chemical composition. The introduction of high-density interfaces in nanostructured materials results in greatly improved strength and hardness; however, interfaces at the nanoscale show low stability. In this Review, I discuss recent developments in the stabilization of nanostructured metals by modifying the architectures of their interfaces. The amount, structure and distribution of several types of interfaces, such as high- and low-angle grain boundaries and twin boundaries, are discussed. I survey several examples of materials with nanotwinned and nanolaminated structures, as well as with gradient nanostructures, describing the techniques used to produce such samples and tracing their exceptional performances back to the nanoscale architectures of their interfaces. The incorporation of structural defects, in particular of interfaces, into crystalline lattices results in enhanced material properties. In this Review, different types of boundaries and interfaces are discussed, including high- and low-angle grain boundaries, twin boundaries, nanotwinned and nanolaminated structures, and gradient nanostructures.

Stabilizing nanostructures in metals using grain and twin boundary architectures

The influence of nanocrystalline structure and processing route on corrosion of stainless steel: A review

The limitation of nanograined materials is their strong tendency to coarsen at elevated temperatures. As grain size decreases into the nanoscale, grain coarsening occurs at much lower temperatures, as low as ambient temperatures for some metals. We discovered that nanometer-sized grains in pure copper and nickel produced from plastic deformation at low temperatures exhibit notable thermal stability below a critical grain size. The instability temperature rises substantially at smaller grain sizes, and the nanograins remain stable even above the recrystallization temperatures of coarse grains. The inherent thermal stability of nanograins originates from an autonomous grain boundary evolution to low-energy states due to activation of partial dislocations in plastic deformation.

https://science.sciencemag.org/content/sci/360/6388/526.full.pdf

Enhanced thermal stability of nanograined metals below a critical grain size.

This paper will review the grain growth in nanocrystalline materials with emphasis on the grain size stabilization that can result from solute additions. The grain growth in nominally pure nanocrystalline metals will be presented followed by descriptions of the stabilization of nanocrystalline grain sizes by kinetic approaches and thermodynamic strategies. The descriptions of nanocrystalline grain size by solute additions will be taken from the literature as well as from recent research in the authors’ laboratory. Examples of kinetic stabilization, which involves reduction of the grain boundary mobility, include second phase drag, solute drag, chemical ordering, and grain size stabilization. The thermodynamic stabilization, which is due to the lowering of the specific grain boundary energy by solute segregation to the grain boundaries, will be described for systems including Pd–Zr, Fe–Zr, Ni–W, Ni–P, and Co–P. Recrystallization during grain growth will be presented for the Ti–N system. Finally, a summary of alloys where nanocrystalline grain sizes can be maintained at annealing temperatures close to the melting point will be presented.

Stabilization of nanocrystalline grain sizes by solute additions

Using a modified regular solution model for grain boundary solute segregation, the relative thermal stability of a number of Fe-based nanocrystalline binary alloys was predicted with considerable accuracy. It was found that nanocrystalline iron was strongly stabilized by zirconium, moderately stabilized by tantalum, and not significantly stabilized by nickel or chromium. These findings are fully in line with the aforementioned predictions. This success with iron based alloys highlights the utility of this practical approach to selecting stabilizing solutes for nanocrystalline alloys.

Stabilized nanocrystalline iron-based alloys: Guiding efforts in alloy selection

Nickel-yttrium nanocrystalline alloys with an as-milled grain size of approximately 6.5 nm were synthesized using high-energy cryogenic mechanical alloying. The microstructural changes due to annealing were characterized using x-ray line broadening, microhardness, focused ion beam channeling contrast imaging, and transmission electron microscopy. Experiments demonstrated that increasing yttrium content led to stabilization of the nanocrystalline grain size at elevated homologous annealing temperatures. Additionally, it was found that inadvertent contamination with nitrogen during the milling process caused the formation of yttrium nitride (YN) precipitates, which, in turn, resulted in an additional nonlinear hardening effect beyond the expected hardening due to grain-size reduction. Results reveal that kinetic pinning by YN particles is effective in retaining a nanostructure to relatively high temperatures.

https://www.cambridge.org/core/services/aop-cambridge-core/content/view/0B82C9751C10C6955F12975E9B36CAF8/S0884291413000095a.pdf/div-class-title-thermal-stability-of-nanocrystalline-nickel-with-yttrium-additions-div.pdf

J. E. Semones

Papers

Stabilization of nanocrystalline grain sizes by solute additions

Stabilized nanocrystalline iron-based alloys: Guiding efforts in alloy selection

Thermal stability of nanocrystalline nickel with yttrium additions