CHAPTER 11

INTRODUCTION TO
CERAMICS MATERIALS

Chapter 12 - 1

Atomic Bonding in Ceramics

Bonding:
-- Can be ionic and/or covalent in character.
-- % ionic character increases with difference in
electronegativity of atoms.

Degree of ionic character may be large or small:

CaF2: large
SiC: small

Adapted from Fig. 2.7, Callister & Rethwisch 8e. (Fig. 2.7 is adapted from Linus Pauling, The Nature of the
Chemical Bond, 3rd edition, Copyright 1939 and 1940, 3rd edition. Copyright 1960 by
Chapter 12 - 2
Cornell University.)

Classification of Ceramics
Ceramic Materials
Glasses

Clay Refractories
products

Abrasives Cements

Advanced
ceramics

-optical
-whiteware -bricks for -sandpaper -composites -engine
-composite -structural high T
-cutting
-structural
rotors
(furnaces) -polishing
reinforce
valves
-containers/
bearings
Adapted from Fig. 13.1 and discussion in
-sensors
household
Section 13.2-8, Callister & Rethwisch 8e.

Chapter 12 - 3

Ceramics Application: Die Blanks

Die blanks:
-- Need wear resistant properties!

Die surface:

-- 4 mm polycrystalline diamond
particles that are sintered onto a
cemented tungsten carbide
substrate.
-- polycrystalline diamond gives uniform
hardness in all directions to reduce
wear.

die
Ao
die

Ad

tensile
force

Adapted from Fig. 11.8(d),

Callister & Rethwisch 8e.

Courtesy Martin Deakins, GE

Superabrasives, Worthington,
OH. Used with permission.
Chapter 12 - 4

Ceramics Application:
Cutting Tools
Tools:
-- for grinding glass, tungsten,
carbide, ceramics
-- for cutting Si wafers
-- for oil drilling

Materials:
-- manufactured single crystal
or polycrystalline diamonds
in a metal or resin matrix.
-- polycrystalline diamonds
resharpen by microfracturing
along cleavage planes.

oil drill bits

blades
Single crystal
diamonds
polycrystalline
diamonds in a resin
matrix.

Photos courtesy Martin Deakins,

GE Superabrasives, Worthington,
OH. Used with permission.
Chapter 12 - 5

Ceramics Application: Sensors

Example: ZrO2 as an oxygen sensor
Ca 2+
Principle: Increase diffusion rate of oxygen
to produce rapid response of sensor signal to
change in oxygen concentration

Approach:

A substituting Ca2+ ion

removes a Zr 4+ ion and
an O2- ion.

Add Ca impurity to ZrO2:

-- increases O2- vacancies
-- increases O2- diffusion rate

sensor
gas with an
unknown, higher
oxygen content

O2diffusion

reference
gas at fixed
oxygen content

voltage difference produced!

Chapter 12 - 6

Advanced Ceramics:
Materials for Automobile Engines
Advantages:
Operate at high
temperatures high
efficiencies
Low frictional losses
Operate without a cooling
system
Lower weights than
current engines

Disadvantages:
Ceramic materials are
brittle
Difficult to remove internal
voids (that weaken
structures)
Ceramic parts are difficult
to form and machine

Potential candidate materials: Si3N4, SiC, & ZrO2

Possible engine parts: engine block & piston coatings
Chapter 12 - 7

Advanced Ceramics:
Materials for Ceramic Armor
Components:
-- Outer facing plates
-- Backing sheet

Properties/Materials:
-- Facing plates -- hard and brittle
fracture high-velocity projectile
Al2O3, B4C, SiC, TiB2
-- Backing sheets -- soft and ductile
deform and absorb remaining
energy
aluminum, synthetic fiber
laminates
Chapter 12 - 8

Ceramic Fabrication Methods (i)

PARTICULATE
CEMENTATION
GLASS
FORMING
FORMING
Blowing of Glass Bottles:
Pressing: plates, cheap glasses
Gob

Pressing
operation

Parison
mold

-- glass formed by application of

pressure
-- mold is steel with graphite
lining

Fiber drawing:
Compressed
air
Suspended
parison

Finishing
mold
Adapted from Fig. 13.8, Callister & Rethwisch 8e. (Fig. 13.8 is adapted from C.J.
Phillips, Glass: The Miracle Maker, Pittman Publishing Ltd., London.)

wind up
Chapter 12 - 9

Sheet Glass Forming

Sheet forming continuous casting
sheets are formed by floating the molten glass on a pool of
molten tin

Adapted from Fig. 13.9,

Callister & Rethwisch 8e.
Chapter 12 - 10

Heat Treating Glass

Annealing:
-- removes internal stresses caused by uneven cooling.

Tempering:
-- puts surface of glass part into compression
-- suppresses growth of cracks from surface scratches.
-- sequence:
before cooling

hot

initial cooling

at room temp.

cooler
hot
cooler

compression
tension
compression

-- Result: surface crack growth is suppressed.

Chapter 12 - 11

Ceramic Fabrication Methods (iia)

GLASS
FORMING

PARTICULATE
FORMING

CEMENTATION

Hydroplastic forming:
Mill (grind) and screen constituents: desired particle size
Extrude this mass (e.g., into a brick)
Ao
force

container

ram

billet

container

die holder
extrusion

die

Ad

Adapted from
Fig. 12.8(c),
Callister &
Rethwisch 8e.

Dry and fire the formed piece

Chapter 12 - 12

Ceramic Fabrication Methods (iia)

GLASS
FORMING

PARTICULATE
FORMING

CEMENTATION

Slip casting:
Mill (grind) and screen constituents: desired particle size
Mix with water and other constituents to form slip
Slip casting operation
pour slip
into mold

absorb water
into mold
green
ceramic

solid component

pour slip
into mold

drain
mold

green
ceramic

Adapted from Fig.

13.12, Callister &
Rethwisch 8e. (Fig.
13.12 is from W.D.
Kingery, Introduction
to Ceramics, John
Wiley and Sons,
Inc., 1960.)

hollow component

Dry and fire the cast piece

Chapter 12 - 13

Typical Porcelain Composition

(50%) 1. Clay
(25%) 2. Filler e.g. quartz (finely ground)
(25%) 3. Fluxing agent (Feldspar)
-- aluminosilicates plus K+, Na+, Ca+
-- upon firing - forms low-melting-temp. glass

Chapter 12 - 14

Drying and Firing

Drying: as water is removed - interparticle spacings decrease
shrinkage .
Adapted from Fig.
13.13, Callister &
Rethwisch 8e. (Fig.
13.13 is from W.D.
Kingery, Introduction
to Ceramics, John
Wiley and Sons,
Inc., 1960.)

wet body

partially dry

completely dry

Firing:
-- heat treatment between
900-1400C
-- vitrification: liquid glass forms
from clay and flux flows
between SiO2 particles. (Flux
lowers melting temperature).

micrograph of porcelain

Drying too fast causes sample to warp or crack due to non-uniform shrinkage
Si02 particle
(quartz)
glass formed
around
the particle

70 mm

Adapted from Fig. 13.14, Callister & Rethwisch 8e.

(Fig. 13.14 is courtesy H.G. Brinkies, Swinburne
University of Technology, Hawthorn Campus,
Hawthorn, Victoria, Australia.)
Chapter 12 - 15

Ceramic Fabrication Methods (iib)

GLASS
FORMING

PARTICULATE
FORMING

CEMENTATION

Powder Pressing: used for both clay and non-clay compositions.

Powder (plus binder) compacted by pressure in a mold
-- Uniaxial compression - compacted in single direction
-- Isostatic (hydrostatic) compression - pressure applied by
fluid - powder in rubber envelope
-- Hot pressing - pressure + heat

Chapter 12 - 16

Sintering
Sintering occurs during firing of a piece that has
been powder pressed
-- powder particles coalesce and reduction of pore size

Adapted from Fig. 13.16,

Callister & Rethwisch 8e.

Aluminum oxide powder:

-- sintered at 1700C
for 6 minutes.

Adapted from Fig. 13.17, Callister

& Rethwisch 8e. (Fig. 13.17 is from
W.D. Kingery, H.K. Bowen, and
D.R. Uhlmann, Introduction to
Ceramics, 2nd ed., John Wiley and
Sons, Inc., 1976, p. 483.)

15 mm

Chapter 12 - 17

Ceramic Fabrication Methods (iii)

GLASS
FORMING

PARTICULATE
FORMING

CEMENTATION

Hardening of a paste paste formed by mixing cement

material with water
Formation of rigid structures having varied and complex
shapes
Hardening process hydration (complex chemical
reactions involving water and cement particles)
Portland cement production of:
-- mix clay and lime-bearing minerals
-- calcine (heat to 1400C)
-- grind into fine powder
Chapter 12 - 18