Ceramic structures

• Because ceramics are composed of at least two

elements, and often more, their crystal structures
are generally more complex than those for metals
• The atomic bonding in these materials ranges
from purely ionic to totally covalent
• Many ceramics exhibit a combination of these two
b di ttypes, the
bonding th degree
d off ionic
i i character
h t b being
i
dependent on the electronegativities of the atoms
• The
Th percentt ionic
i i character
h t ffor severall common
ceramic materials is presented in the table
Crystal structures
g is p
• For those ceramic materials for which atomic bonding predominantly
y ionic, the
crystal structures may be thought of as being composed of electrically charged ions
instead of atoms
• The metallic ions, or cations, are positively charged, because they have given up
their valence electrons to the non-metallic ions, or anions, which are negatively
charged
• Two characteristics of the component ions in crystalline ceramic materials influence
the crystal structure: the magnitude of the electrical charge on each of the component
ions, and the relative sizes of the cations and anions
• With regard to the first characteristic, the crystal must be electrically neutral; that is,
all the cation positive charges must be balanced by an equal number of anion
negative charges
• The chemical formula of a compound indicates the ratio of cations to anions, or the
composition that achieves this charge balance
Crystal structures (continued…)
• For example, in calcium fluoride each calcium ion has +2 charge (Ca+2) an associated with
each fluorine ion, is a single negative charge (F). Thus there must be twice as many F as Ca 2+
ions, which is reflected in the chemical formula CaF2
• The
Th second
d criterion
it i iinvolves
l th
the sizes
i or iionic
i radii
dii off th
the cations
ti and
d anions,
i rC and
d rA
respectively
• Because the metallic elements g
give up
p the electrons when ionized cations are ordinarily
y smaller
than anions and consequently the ratio rC /rA is less than unity
• Each cation prefers to have as many nearest neighbour anions as possible
• The anions also desire a maximum number of cation nearest neighbors
• Stable ceramic crystal structures form when those anions surrounding a cation are all in contact
with
ith that cation,
cation as ill
illustrated
strated in the follo
following
ing fig
figure
re
Crystal structures (continued…)
• The coordination number (i.e., number of
anion nearest neighbors for a cation) is
Linear
related to the cation–anion radius ratio
• For
F a specific
ifi coordination
di ti number,
b th there
is a critical or minimum rc /rA ratio for which Triangular

this cation–anion contact is established

• This ratio may be determined from pure
Tetrahedral
geometrical considerations
• The coordination numbers and nearest-
neighbor geometries for various rc /rA
ratios are presented in the table Octahedral
• For rc /rA ratios less than 0.155, the very
small cation is bonded to two anions in a
linear manner
• If rc /rA has a value between 0.155 and Cube
0.225, the coordination number for the
cation is 3
Crystal structures (continued…)
• This means each cation is surrounded by three
anions
i iin th
the fform off a planar
l equilateral
il t l ttriangle,
i l
with the cation located in the center Linear
• The coordination number is 4 for rc /rA between
0.225 and 0.414; the cation is located at the
Triangular
center of a tetrahedron, with anions at each of
the four corners
• For rc /rA between 0.414 and 0.732, the cation
Tetrahedral
may be thought of as being situated at the center
off an octahedron
t h d surrounded
d dbby six
i anions,
i one
at each corner, as also shown in the table
• The coordination number is 8 for rc /rA between
Octahedral
0.732 and 1.0, with anions at all corners of a
cube and a cation positioned at the center
• For a radius ratio g
greater than unity,
y, the
coordination number is 12
• The most common coordination numbers for Cube
ceramic
i materials
t i l are 4
4, 6
6, and
d8
Crystal structures (continued…)
• The following table gives the ionic radii for several anions and cations that are common ceramic
materials
• The relationships between coordination number and cation–anion radii ratios are based on
geometrical
t i l considerations
id ti and
d assuming
i “h“hard
d sphere”
h ” iions
• Therefore, these relationships are only approximate, and there are exceptions
Crystal structures (continued…)
• For example, some ceramic compounds with rc /rA ratios greater than 0.414 in which the bonding
is highly covalent (and directional) have a coordination number of 4 (instead of 6)
• The size of an ion will depend on several factors
• One of these is coordination number: ionic radius tends to increase as the number of nearest-
neighbor ions of opposite charge increases
• Ionic
I i radii
dii given
i iin th
the ttable
bl iin th
the previous
i slide
lid are ffor a coordination
di ti number
b off 6
• Therefore, the radius will be greater for a coordination number of 8 and less when the
coordination number is 4
• In addition, the charge on an ion will influence its radius
• For example, the radii for Fe2- and Fe3- are 0.077 and 0.069 nm, respectively, which values may
be contrasted to the radius of an iron atom, viz. 0.124 nm
• When an electron is removed from an atom or ion, the remaining valence electrons become
more tightly bound to the nucleus,
nucleus which results in a decrease in ionic radius
• Conversely, ionic size increases when electrons are added to an atom or ion
Example:
AX-type crystal structures
• Some of the common ceramic materials are those in which there are equal numbers of cations
and anions
• These are often referred to as AX compounds, where A denotes the cation and X the anion
• There
Th are severall diff
differentt crystal
t l structures
t t for
f AX compounds
d
• Each is normally named after a common material that assumes the particular structure

Rock Salt Structure

• Most common type of AX compounds is NaCl

• Coordination number is 6

• cation
ti radius/anion
di / i radius
di = 0
0.414
414 – 0.732
0 732

• Unit cell contains FCC arrangement for anions with

one cation situated at the cube center and one at the
center of each of the 12 cube edges

• Two interpenetrating FCC lattices, one composed of

th cations,
the ti th
the other
th off anions
i

• Examples: NaCl, MnS, MgO, LiF and FeO

Cesium Chloride Structure

• Coordination number is 8

• The anions are located at each of the corners of

a cube
cube, whereas the cube center is a single cation

• Interchange of anions with cations produces the

same structure

• This is not a BCC structure because the ions are

yp
of different types
Zinc Blende Structure

• Coordination number is 4

• All corners and the face positions are occupied by S

• The Zn atoms fill the interior tetrahedral positions

• Each Zn atom is bonded to four S atoms, and vice versa

• Example: ZnS, ZnTe and SiC

AmXp-type crystal structures
• If the charges
g on the cations and anions are not the same,, a compound
p can exist
with the chemical formula AmXp, where m and/or p ≠ 1
• An example would be AX2, for which a common crystal structure is found in fluorite
(CaF2)
• The ionic radii ratio rc /rA for CaF2 is about 0.8

Fl
Fluorite
it Structure
St t

• Coordination number is 8 for the cation, 4 for the anion

• Calcium ions are positioned at the centers of cubes

cubes, with
fluoride ions at the corners

• One unit cell consists of eight cubes

• Examples: ZrO2, UO2, PuO2 and ThO2

AmBnXp-type crystal structures
• It is also p
possible for ceramic compounds
p to have more than one type
yp of cation
• For two types of cations (represented by A and B), their chemical formula may be
designated as AmBnXp

Perovskite Structure

• Barium titanate (BaTiO3) having Ba+2 and Ti+4 cations

• At temperatures above 120oC, the crystal structure is

cubic

• Ba+2 ions are situated at all eight corners of the cube,

g Ti+4 is at the cube center,, with O2 ions
and a single
located at the center of the six faces
Ceramic density computations

• It is possible to compute the theoretical density of a crystalline ceramic material from

unit cell data in a manner similar to that for metals

• In this case the density may be determined using the following equation

n   AC   AA 

VC N A

where
n = the number of formula units within the unit cell
∑AC = the sum of the atomic weights of all cations in the formula unit
∑AA = the sum of the atomic weights of all anions in the formula unit
VC = the unit cell volume
NA = Avogadro’s number
Example:
Silicate ceramics

• Silicates are materials composed primarily of silicon and oxygen, the two most abundant elements in the
earth’s crust

• Consequently, the bulk of soils, rocks, clays , and sand come under the silicate classification

• Rather than characterizing the crystal structures of these materials in terms of unit cells, it is more convenient
to use various arrangements of an SiO44 tetrahedron

• Each
E h atom
t off silicon
ili iis b
bonded
d d tto ffour oxygen atoms,
t which
hi h are situated
it t d att th
the corners off th
the ttetrahedron
t h d

• The silicon atom is positioned at the center

• Because
B this
thi iis th
the b
basic
i unit
it off th
the silicates,
ili t it iis often
ft ttreated
t d as a negatively
ti l charged
h d entity
tit
Silica

• Most simple silicate material

• A 3D network is generated when every corner oxygen

atom in each tetrahedron is shared by adjacent tetrahedra

• Material is electrically neutral

• If these tetrahedra are arrayed in a regular and ordered

manner, a crystalline structure is formed

• Three polymorphic forms of silica: quartz, cristobalite and

tridymite

• Their structures are complicated and comparatively

open; atoms are not closely packed together

• As
A a result,
lt these
th crystalline
t lli silicas
ili h
have relatively
l ti l llow
densities (density of quartz is 2.65 g/cm3)

• High melting temperature (1710oC)

Silicate Glass

• Silica can be made to exist as a non-crystalline solid or

glass having a large degree of atomic randomness, which
is the characteristic of a liquid

• Such a material is called fused silica or vitreous silica

• As with the crystalline silica, SiO44 tetrahedron is the

basic unit

• Oxides such as B2O3 or GeO2 also form glassy structure.

These materials (also SiO2) are called network formers.

• Common
C glasses
l which
hi h we use, such h as window
i d glasses
l
and containers, are silica glasses to which CaO or Na2O
are added. These oxides do not form polyhedral network.

• They modify the SiO44 network. They are called network

modifiers.
Silicates

• For the various silicate materials, one, two, or

three of the SiO44 tetrahedra are shared by other
tetrahedra to form some rather complex structures

• Most simple structure involves isolated

tetrahedra (a). For example, forsterite (Mg2SiO4)
has the equivalent of two Mg+2 ions associated
with each tetrahedron in such a way that every
Mg+2 ion has six oxygen nearest neighbors

• The Si2O76 ion is formed when two tetrahedra

share a common oxygen atom. Akermanite
(Ca2MgSi2O7) is a mineral having the equivalent of
two Ca+2 ions and one Mg+2 ion bonded to each
Si2O76 unit

• The positively charged cations such as Ca+2,

Mg+2 and Al+3 serve two roles

• First, they compensate the negative charges

from the SiO44 units so that charge neutrality is
achieved, and second, these cations ionically
bond the SiO44 tetrahedra together
Layered silicates
• A two-dimensional sheet or layered structure can also
be produced by the sharing of three oxygen ions in each
of the tetrahedra
• For
F this
thi structure
t t the
th repeating
ti unitit formula
f l may be
b
represented by Si2O55
• The net negative
g charge
g is associated with the
unbonded oxygen atoms projected out of the plane of the
page
• Electroneutrality is ordinarily achieved established by a
second planar sheet structure having an excess of
cations which bond to these unbonded oxygen atoms
cations,
from the Si2O5 sheet
y
• Such materials are called the sheet or layered silicates,,
and their basic structure is characteristic of the clays and
other minerals
Layered silicates (continued…)
• One of the most common clay minerals, kaolinite, has a relatively
simple
i l ttwo-layer
l silicate
ili t sheet
h t structure
t t
• Kaolinite clay has the formula, Al2(Si2O5)(OH)4 in which the silica
tetrahedral layer is represented by Si2O52
• It is made electrically neutral by an adjacent Al2(OH)42+ layer
• A single sheet of this structure is shown in the figure
e mid-plane
• The d pa eo of a
anions
o s co
consists
ssso of O2 ions
o s from
o the (Si2O5)2
e (S
layer as well as OH ions that are a part of the Al2(OH)42+ layer
• Whereas the bonding within this two-layered sheet is strong and
i t
intermediate
di t iionic-covalent,
i l t adjacent
dj t sheets
h t are only
l lloosely
l
bound to one another by weak van der Waals forces
• A crystal of kaolinite is made of a series of these double layers or
sheets stacked parallel to each other, which form flat plates
typically less than 1 m in diameter and nearly hexagonal
y
• These silicate sheet structures are not confined to the clays
• Other minerals also in this group are talc [Mg3(Si2O5)2(OH)2], and
the micas [e.g., muscovite, KAl3Si3O10(OH)2], which are important
ceramic raw materials