FIZIKALNO HEMIJSKE OSNOVE

KERAMIKE
1. PREDAVANJE

DEFINITION

Inorganic, nonmetallic materials processed or consolidated at

high temperature.
Ceramics (ceramic materials) are non-metallic inorganic
compounds formed from metallic (Al, Mg, Na, Ti, W) or semimetallic (Si, B) and non-metallic (O, N, C) elements.
Atoms of the elements are held together in a ceramic structure by
one of the following bonding mechanism: Ionic Bonding, Covalent
Bonding, Mixed Bonding (Ionic-Covalent).
Most of ceramic materials have a mixed bonding structure with
various ratios between Ionic and Covalent components. This ratio
is dependent on the difference in the electronegativities of the
elements and determines which of the bonding mechanisms is
dominating ionic or covalent.

ELECTRONEGATIVITY
Electronegativity is an ability of atoms of the element to
attract electrons of atoms of another element.
Electronegativity is measured in a relative dimensionless unit (Pauling
scale) varying in a range between 0.7 (francium) to 3.98 (fluorine).
Non-metallic elements are strongly electronegative. Metallic
elements are characterized by low electronegativity or high
electropositivity ability of the element to lose electrons.

IONIC BONDING
Ionic bonding occurs between two elements with a large difference
in their electronegativities (metallic and non-metallic), which become
ions (negative and positive) as a result of transfer of the
valence electron from the element with low electronegativity to the
element with high electronegativity.
The typical example of a material with Ionic Bonding is sodium
chloride (NaCl).
Electropositive sodium atom donates its valence electron to the
electronegative chlorine atom, completing its outer electron level
(eight electrons):
As a result of the electron transfer the sodium atom becomes a
positively charged ion (cation) and the chlorine atom becomes a
negatively charged ion (anion). The two ions attract to each other by
Coulomb force, forming a compound (sodium chloride) with ionic
bonding.
Ionic bonding is non-directional.

COVALENT BONDING
Covalent bonding occurs between two elements with low difference
in their electronegativities (usually non-metallics), outer electrons of
which are shared between the four neighboring atoms.
Covalent Bonding is strongly directional.

IONIC- COVALENT (MIXED) BONDING

Ionic-covalent (mixed) bonding with various ratios of the two

fractions (ionic and covalent) occurs in most of ceramic materials.
Degree of Ionic Bonding can be estimated from the following
formula:
I.F. = exp(-0.25*E)
Where
I.F. fraction of ionic bonding;
E difference in the electronegativities of the elements.

DEFINITION
Ceramic materials are inorganic and non-metallic. They are
generally moulded from a mass of raw material at room
temperature, and gain their typical physical properties through a high
temperature firing process.
In contrast, the Anglo-Saxon term "ceramics" also often includes
glass, enamel, glass-ceramic, and inorganic cementitious materials
(cement, plaster and lime).
The German ceramics industry also distinguishes between coarse and
fine ceramics, depending on the particle size in the raw material
(<0,1 mm grain feinkeramik, >0,1 mm grain grobkeramik).
Technical ceramics, tableware, decorative ceramics, ceramic
sanitary ware, wall and floor tiles and
ceramic abrasives belong to the fine ceramics category.
The category of coarse ceramics includes, for example, brick or
conventional refractory materials.

CLASSIFICATION

CLASSIFICATION
TRADITIONAL CERAMICS

ADVANCED CERAMICS

CLASSIFICATION

CLASSIFICATION

Structure of ceramic materials

The following factors affect structure of ceramics:
Balance of electrical charges of anions and cations
Radius Ratio (rc/ra)
Where
rc radius of cation;
ra radius of anion.
Radius Ratio determines Coordination Number (CN) the maximum number
of anion nearest neighbors for a cation.The anion neighbors do not touch each
other.
rc/ra = 0.2250.414(SiO2) CN = 4
rc/ra = 0.4140.732(SnO2, PbO2) CN = 6
rc/ra = 0.7321.0(ThO2) CN = 8
Covalent bonding component, which tends to form tetrahedral coordination, may
affect the Coordination Number.
Ions are packed with maximum density, providing minimum energy of
the structure.

Structure of ceramic materials

Ceramic structures are classified and designated according
to the pattern structures of several natural minerals:
Mineral Name

Formula

Coordination
Number

Structure Characterization

Rocksalt

NaCl

Octahedral unit cell, cubic appearance

Zincblende

ZnS

FCC unit cell with S2- anions at 4

tetrahedral sites

Fluorite

CaF2

8-cation CN
4-anion CN

Corundum

Al2O3

6-cation CN
4-anion CN

Perovskite

CaTiO3

6-cation(Ti) CN
2-anion(O) CN

Silicate

Combination of
SiO44- blocks

FCC unit cell with F- anions at 8 tetrahedral

sites
HCP unit cell with O2- anions at the lattice
sites and Al3+ at interstitial sites
Cubic unit cell with Ti4+ cations coordinated
octahedrally among six oxygen anions
Tetrahedral arrangement with Si4+ cations
at the center bonded to O2- anions at the
apices of the tetrahedron

Examples of some ceramic structures

Examples of some ceramic structures

Examples of some ceramic structures

Tetrahedral silica block (SiO4-4) may form various silicate structures:
Island and DoubleIsland Silicates
Single or two silica blocks, containing other cations, form Island (olivine) or
Double Island Silicates (hemimorphite).
Ring and Chain Structures
Several (3,4,5,6) silica units join each other, forming a chain (orthopyroxenes,
clinopyroxenes, asbestos) or closed ring (beryl).
Sheet (layer) structure
Silica units connect to each other, forming infinite sheet (micas, serpentine,
chlorite, talc).
Framework silicate
Quartz, cristobalite, and tridymite minerals are based on the framework
silicate structure.
Silicates exist in two forms: crystalline and amorphous (glasses).

Key Microstructural Features of Engineering Ceramics

The grains are formed as the compacted grains of ceramic powder try to
reduce their surface area by coalescing together during sintering.
The grain boundaries are formed at the intersection of the grains and
often contain impurities that form glassy phases. The glassy phases
aiding in the sliding process that occurs as the grains coalesce.
Pores are formed due to the inability of the powder compact to sinter to
full density i.e. the theoretical density that can be obtained by the
individual grains eradicating all the pre-existing porosity of the aspressed powder compact.

How Does the Microstructure of a Ceramic Affect Its Performance?

Strength
The strength of an engineering ceramic is typically measured by machining
a bar of material into a solid bar 3x4x45 mm which is the subject to a 3
point bending strength test.
Toughness
The toughness of engineering ceramics in simple terms describes the
ability of the material to withstand the propagation or movement of a crack
throughout the body of the material. It is often measure by using the type
of diamond indenter used in conventional hardness tests.
Hardness
Hardness is perhaps the simplest of all property measurements as it is
generally measured by the depth of penetration of an indenter into the
surface of the material, either a pyramidal indentation in Vickers hardness
or a conical indenter in Rockwell hardness testing.

A typical fracture surface of an alumina ceramic subject to a strength

test is shown in Figure 3. It is easily discernible that the fracture has
proceeded along the weakest points namely the grain boundaries.

The Effect of Machining and Microstructure

The grinding stresses

leads to both surface and
subsurface defects, both
of which may generate
the critical defect at
failure.
Equally, such defects can
also reduce the measured
values of toughness and
hardness.