Nanocrystalline materials grain size effect

More serious errors may result when the grain-size of a specimen is small compared with the size of an indentation. Then, since all crystals are elastically anisotropic a rigid indenter will produce differing amounts of elastic strain in the grains depending on their orientations. This will create an effective roughening of the surface and increase the friction coefficient. This may result in overestimates of hardnesses. For example, this may underlie reports of nanocrystalline materials being harder than diamond. 

Nanocarbon emitters behave like variants of carbon nanotube emitters. The nanocarbons can be made by a range of techniques. Often this is a form of plasma deposition which is forming nanocrystalline diamond with very small grain sizes. Or it can be deposition on pyrolytic carbon or DLC run on the borderline of forming diamond grains. A third way is to run a vacuum arc system with ballast gas so that it deposits a porous sp2 rich material. In each case, the material has a moderate to high fraction of sp2 carbon, but is structurally very inhomogeneous [29]. The material is moderately conductive. The result is that the field emission is determined by the field enhancement distribution, and not by the sp2/sp3 ratio. The enhancement distribution is broad due to the disorder, so that it follows the Nilsson model [26] of emission site distributions. The disorder on nanocarbons makes the distribution broader. Effectively, this means that emission site density tends to be lower than for a CNT array, and is less controllable. Thus, while it is lower cost to produce nanocarbon films, they tend to have lower performance. 

Nanocrystalline materials have received extensive attention since they show unique mechanical, electronic and chemical properties. As the particle size approaches the nanoscale, the number of atoms in the grain boundaries increases, leading to dramatic effects on the physical properties and on the catalytic activity of the bulk material. Nowadays, there is a wide variety of methods for the preparation of nanocrystalline metals such as thermal spraying, sputter deposition, vapor deposition and electrodeposition. The electrodeposition process is commercially attractive since it can be performed at room temperature and the experimental set-up is less demanding. Furthermore, the particle size can be adjusted over a wide range by controlling the experimental parameters such as overvoltage, current density, composition, and temperature (see Chapter 8). 

It is widely used to synthesize the cost-effective bulk nanocrystalline coating materials. The process is capable of producing materials with a grain size down to 5 ran at room temperature depending on current density used during synthesis. 

In order to investigate the possible differences in oxidation resistance along with any underlying mechanisms, understanding the nanocrystalline structure of a material is essential. This chapter will therefore first describe the structure of nanocrystalline materials, their thermodynamic properties and the possible effects of changes in the material structure (caused by such fine grain size) that may influence the oxidation resistance of a material. 

We expect particularly interesting phenomena in the nanosize range, when the distance between the two interfaces (e.g. grain boundaries in nanocrystalline material) is of the order of magnitude of the Debye length or smaller. If we ignore structmal effects just mentioned (see however Fig. 5.108, page 261) we expect the thermodynamic profiles shown in Fig. 5.82. Nano-size effects will be considered explicitly in Example c. 

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