High energy milling simultaneously influences NiO
powder particle size distribution and surface chemistry.
As such, the evolution of the powder microstructures
upon sintering is a function of the concerted effects of
differences in the powder particle size distributions and
surface chemistries. Typically, fine powders with
uniform size distributions display less rapid grain
growth during intermediate stage sintering [49]. It is
therefore reasonable that the relatively uniform particle
size distributions of NiO powders milled in Vertrel and
methanol result in smaller grain sizes after sintering to
1100 ℃ in comparison to unmilled NiO or NiO milled
with carbon. These effects can be reinforced by the
surface chemical differences imparted by the milling
additives. Notably, it has recently been shown that the
presence of surface bound C–OH or C–O–C groups
hinder surface diffusion and hence sintering of TiO2
nanoparticles [24]. In the present study, the NiO
powders milled in methanol and shown by X-ray
photoelectron spectroscopy and thermogravimetric
analysis to have residual surface bound alkoxy or
alcohol, display a hindered sintering behavior. The
methanol milled powders sintered to 1100 ℃ exhibit
less dramatic grain growth in comparison to the
powders milled with Vertrel and carbon. However, in
the present study, the mechanism of hindered sintering
cannot be connected to hindered surface diffusion
due to the presence of adsorbed species because
thermogravimetric analysis shows that all additives
desorb from the surface before 900 ℃. As such, the
differences in the sintered microstructure are more
likely to be due to the way that additives modify
the surface oxidation state upon desorption. This is
evident for the samples sintered to 1500 ℃, where
carbothermal reduction by carbon and methanol
decomposition products results in metallic nickel
species that undergo melting by 1455 ℃. This melting
transition is observed in differential scanning
calorimetry and manifested in the extreme grain
growth experienced between 1100 and 1500 ℃ for the
powders milled in methanol and carbon. The melting
transition may also be the driving force behind the
significant decreases in porosity between 1100 and
1500 ℃, observed for the NiO milled with carbon and
methanol. Unmilled NiO and NiO milled with an
additive that does not induce carbothermal reduction
(Vertrel XF) show far less pronounced decreases in
porosity between 1100 and 1500 ℃.