Purdue University Graduate School
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posted on 2019-01-17, 03:04 authored by David A. LowingDavid A. Lowing
Ceramic materials are natural or synthetic, inorganic, non-metallic materials incorporating ionic and covalent bonding. Most ceramics in use are polycrystalline materials where grains are connected by a network of solid-solid interfaces called grain boundaries. The structure of the grain boundaries and their arrangement play a key role in determining materials properties. Developing a fundamental understanding of the formation, structure, migration and methods of control grain boundaries have drawn the interest of scientists for over a century.
While grain boundaries were initially treated as isotropic, advances in materials science has expanded to include energetically anisotropic boundaries. The orientation and structure of a grain boundary, determined by this anisotropy, controls the mobility of a grain boundary. The mobility is the controlling factor during grain growth impacting the microstructural evolution of a material.
This thesis covers fundamental research to model how a materials’ equilibrium crystal shape can be used as a grain growth control mechanism. First an overview of ceramic processing and microstructural development is presented with a focus on the role of grain boundaries in determining the properties of a material. The role of anisotropy and related recent work is highlighted setting the foundation for the link between the equilibrium crystal shape and grain growth. A discussion on the selection of the NiO-MgO system for all experimental work is included.
A novel production and processing route for NiO-MgO was developed. Mechanical alloying and milling resulted in significant impurity contamination therefore a chemical production route was used. A modified amorphous citrate process was developed where metal salts containing Ni and Mg were mixed with a polyfunctional organic acid. Rapid dehydration and calcination at 500°C resulted in chemically homogeneous powders. The amorphous citrate production route produced powder with crystallites ranging from 244-393 nm and agglomerates ranging from 20-300 μm with plate-like morphology.
NiO-MgO powders produced via the amorphous citrate method were sintered using various techniques. Conventional sintering was unable to produce fully dense samples peaking with relative densities from 95-96%. The introduction of pressure through spark plasma sintering and hot pressing improved the relative sample density to 97-100%. It was discovered that exposure to the vacuum required for spark plasma sintering and hot pressing resulted in the reduction of NiO. Spark plasma sintering created oxygen depleted regions and hot pressing further reduced NiO to pure nickel metal which precipitated out at the grain boundaries.
Due to the poor sintering behavior of NiO-MgO grain growth experiments were carried out on the large agglomerates formed during the amorphous citrate process. Agglomerates with more than 50 grains with a thickness of at least 1 μm were selected. Grain growth was measured across five compositions with Ni:Mg ratios of 100:0, 75:25, 50:50, 25:75, 0:100. The average grain size and growth rate increased with increasing nickel content with a significant jump between 50% and 75%. Increasing nickel content was also observed to correspond with a higher number of grains exhibiting surface faceting.
The NiO-MgO equilibrium crystal shape as a function of composition was measured previously. To make the equilibrium crystal shape a more viable control for grain growth a quantitative microstructural characterization technique was developed to measure a materials equilibrium crystal shape. Topographic surface information (surface facets measured by atomic force microscopy, AFM) and grain crystallographic orientation (measured by electron back-scattered diffraction, EBSD) were combined to produce the crystallographic topography of a sample surface. Surface crystallographic topography was used to identify the faceting behavior of grains with a range of orientations. Using the combined data, facet stability maps (n diagrams) for NiO-MgO were developed.
Controlling grain growth via the equilibrium crystal shape offers the potential to produce microstructures with a high frequency of desirable grain boundaries (grain boundary engineering) and therefore properties. The combination of using AFM and EBSD to create crystallographic topographical surface data and n-diagrams has been demonstrated. N-diagrams for most materials do not exist, but the technique used here can be applied to a wide range of materials and will expand the ability to control microstructures of ceramic materials.


Degree Type

  • Doctor of Philosophy


  • Materials Engineering

Campus location

  • West Lafayette

Advisor/Supervisor/Committee Chair

John Blendell

Additional Committee Member 2

Wolfgang Rheinheimer

Additional Committee Member 3

Eric Kvam

Additional Committee Member 4

Rodney Trice