Ceramic processing

Dr. Ngo Truong Ngoc Mai

Faculty of Chemical Engineering

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Evaluation

Mid term test 20%

Presentation 20%
Final test 60%
References
1. M. N. Rahaman, 2017. Ceramic Processing. 2nd Edition. Taylor and Francis Group
2. W.D. Kingery - Introduction to Ceramics – NXB John Wiley & Sons, Inc. - 1967

3. Ngô Trương Ngọc Mai, Nguyễn Việt Bách, Bài giảng môn học silicat đại cương- Cần Thơ Đại
học Cần Thơ, 2007
Ceramic technology and processing

Chapter 1. Introduction

Dr. Ngo Truong Ngoc Mai

Faculty of Chemical Engineering

 4

outline

1. Ceramic materials: history

2. Classification of ceramic materials
3. Properties of ceramics
4. Application of ceramics nowadays
5. Silicate materials
 Introduction 5

Etymology
The term "ceramic" is derivated from greek "keramos" meaning "clay" or "brick", but also
"the one who went through the fire". The last meaning is connected with greek mythology
and the heroe Keramos. Keramos was the result of a quick affair between Dyonisos, the god
of wine, and Ariadne on the isle of Naxos. Since his youth, Keramos was responsible for the
replacement of the drinking cups, which got broken during his father's binges.

Examples of greek ceramic ware, 1500 B.C.

 6

HISTORY
Ceramic figurines are used for ceremonial purposes (Brno,
28,000 BCE
Czech Republic).
18,000 BCE Chinese pottery appears.
18,000 BCE to 14,000 BCE Ceramic pottery spreads in Eastern Asia.
Ceramic products, such as vases, bricks, and tiles, become
9,000 BCE
popular in the Middle East and Europe.
7,000 BCE Sharp tools made from natural glass appear.
5,000 BCE Phoenician merchants possibly make the first glass.
Simple glass items are fabricated in Mesopotamia and
3,500 BCE
Egypt.
The wheel is invented, which will later be applied in wheel-
3,500 BCE
forming of pottery.
3,000 BCE Glazed pottery is produced in Mesopotamia.
Egyptians start building factories for production of
1,500 BCE
glassware.
 7

700 BCE Ceramic pottery becomes artwork in Attic Greece.

600 CE 600 CE Chinese introduce porcelain.
1400s High-temperature furnaces are developed in Europe for metallurgical use.
High-temperature refractory materials are introduced to build furnaces for
1500s making steel, glass, ceramics, and cements, leading the way to the industrial
revolution.
Mid 1800s Porcelain electrical insulators and incandescent light bulbs are invented.
High-strength quartz-enriched porcelain for insulators, alumina spark plugs,
1920s
glass windows for automobiles, and ceramic capacitors are introduced.
Research on oxide magnetic materials (ferrites) and ferroelectric materials
1940s
begins.
1950s Ceramic capacitors based on barium titanate are developed.
Alumina insulators for voltages over 220 kV are introduced and applications
1960s for carbides and nitrides are developed. The first yttria-based transparent
ceramic is invented. Bioglass is also discovered.
Partially stabilized zirconia is developed. High-performance cellular ceramic
1970s substrates for catalytic converter and particulate filters for diesel engines are
commercialized.
 8

1980s Ceramic high-temperature superconductors are developed.

Multilayer ceramic circuits (low-temperature co-fired ceramics) are

commercialized. Low-fusing ceramics are introduced for dental prostheses.
1990s The first whisker-reinforced alumina composites are fabricated by hot-
pressing. Polycrystalline neodymium-yttrium aluminum garnets for solid-
state lasers are developed.

Late 1990s Nanotechnology initiatives begin proliferating worldwide.

Late 1990s The robocasting process for 3D printing of ceramics is developed.

By creating ZrB2/HfB2-based composites that resist temperatures up to
2,200°C, NASA revives interest in the development of ultrahigh
2000s
temperature ceramics (UHTCs) for fabrication of hypersonic aircraft and
reusable space vehicles.

Various processes are being developed for 3D printing of technical ceramics.

2010s
In 2017 the first hyperelastic bone is created by 3D printing.
 Introduction History of Ceramic Materials 9

7000 BC. First bricks made of dried clay

4000 BC Frist fired bricks (Mesopotamia)
Appearance of potter's wheel and firing kilns (Egypt)
2600 BC First bricks with sumeric cuneiform writings
2300 BC Ziggourat build par Our-Nammon
(‘’The tower of Babylone“)
600 BC Ishtar portal in Babylone build by king Nabuchodonosor (photo)
800 AC Development of porcellain in China
1600 AC Introduction of porcellain manufacturing in Europe (Saxony)
1900 AC First application of non-silicate ceramics, refractories MgO and SiC
1960 AC Introduction of the Bayer process for the manufacturing of alumina
1986 AC Discovery of superconductivity in cuprate ceramics (Müller and
Bednorz, IBM Rüschlikon)
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Classification of Ceramic materials

 11

CLASSİFİCATİON OF CERAMİCS
based on composition

Oxides

CERAMICS Nonoxides

Composite

Oxides: Alumina, zirconia

Non-oxides: Carbides, borides, nitrides, silicides
Composites: Particulate reinforced, combinations of
oxides and non-oxides
12
 13

Non-Oxide Ceramics:

➢Low oxidation resistance

➢extreme hardness

➢chemically inert

➢high thermal conductivity

➢electrically conducting

➢difficult energy dependent

manufacturing and high cost.
Silicon carbide cermic foam filter (CFS)
http://images.google.com.tr/imgres?imgurl=http://www.made-in-
china.com/image/2f0j00avNtpdFnLThyM/Silicon-Carbide-Ceramic-Foam-
Filter-CFS-.jpg&imgrefurl
 14

Ceramic-Based
Composites:

➢Toughness

➢low and high oxidation

resistance (type related)

➢variable thermal and

electrical conductivity

➢complex manufacturing
processes
Ceramic Matrix Composite (CMC) rotor
➢high cost.
http://images.google.com.tr/imgres?imgurl=http://www.oppracing.com/images/
cmsuploads/Large_Images/braketech%2520cmc%2520rotor%2520oppracing
%2520cbr1000rr.jpg&imgrefurl
 15

Classification of ceramics
* based on products
 16

Classification of ceramics
* based on structure

amorphous
CERAMICS
crystalline
Amorphous

✓the atoms exhibit only short-

range order

✓no distinct melting temperature

(Tm) for these materials as there
is with the crystalline materials

✓Na 2 O, CaO, K 2 O,…

Amorphous silicon and thin film PV cells
Crystalline 17

✓atoms (or ions) are arranged in a

regularly repeating pattern in three
dimensions (i.e., they have long-
range order)

✓Crystalline ceramics are the

“Engineering” ceramics
– High melting points
– Strong
– Hard
a ceramic (crystalline) and a glass (non-crystalline)
– Brittle
– Good corrosion resistance
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PROPERTIES
• High hardness
• Electrical and thermal insulating
• Chemical stability
• High melting temperatures
• Brittle, virtually no ductility problems in processing
• Problems in performance
• Some ceramics are translucent window glass (based on silica)
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PROPERTIES The most remarkable property of ceramic

materials is their very high melting, sublimation
MELTING POINTS or dissociation temperatures. Typical ceramic
materials and melting points

MgO 2800 °C HfC 3890 °C

Al2O3 2030 °C HfTa4C5 3940 °C
ZrO2 (stab.Y) 2550 °C WC 2600 °C
TiO2 1840 °C SiC 2250 °C
(diss. elements)

SiO2 1710 °C BN 2400 °C

Mg2SiO4 1810 °C TiN 2950 °C
Al2SiO5 1810 °C AlN 2500 °C
(subl.)
CaSiO3 1540 °C Si3N4 1900 °C
(subl.)
C 3750 °C Si 1421 °C
PROPERTIES 20

BONDING
• Strong covalent or ionic bonding
• Bonding in ceramics compared to metals and polymers:
• More rigid
• Does not permit slip under stress
• Difficult to absorb stress
• For brittle materials fracture stress concentrators are very important.
• Fracture strength enhanced by creating compressive stresses in the
surface region
• Compressive strength: ten times the tensile strength → ceramics
good structural materials under compression (e.g., cement, bricks in
building apartments, stone blocks in the pyramids).
→ tensile test is not used for ceramics → Hard to machine, fail after
0.1% strain.
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ISSUES TO ADDRESS...

• How do the crystal structures of ceramic materials differ

from those for metals?
• How do point defects in ceramics differ from those defects
found in metals?
• How are impurities accommodated in the ceramic lattice?
• In what ways are ceramic phase diagrams different from
phase diagrams for metals?
•How are the mechanical properties of ceramics measured,
and how do they differ from those for metals?
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Review

• Structure of ceramics: AX (RS), AX 2 (Fluorite),

ABX 3 (perovskite) , A 2BO 4 (spinel), Zinc Blend
(diamond), Wuzite,…
• Structure of silicates
• Natural minerals
• Clay minerals
 23

Application of silicate ceramics

Early Ming Dynasty Bowl 14th century Brick wall, Oxford St. Berkeley
http://www.dadums.50megs.com/chinese/fish.html http://www.ma.huji.ac.il

Electric fuses (cầu chì)

http://www.littelfuse.com

Tile pattern, Alhambra, Granada Spain

http://www.ma.huji.ac.il
Application of advanced ceramics 24

BORIDE Inc WC blast nozzle

Kryocera Si3N4 gas turbine rotor

Structural Al2 O3
parts (Reed, 1995)

Kundan MgO refractory bricks

(furnace liners)
 Application: Refractories
• Need a material to use in high temperature furnaces.
• Consider the Silica (SiO2) - Alumina (Al2O3) system.
• Phase diagram shows:
mullite, alumina, and crystobalite as candidate refractories.

2200 3Al2O3-2SiO2
T(°C)
mullite
2000 Liquid
(L) alumina + L
Adapted from Fig. 12.27,
1800 Callister 7e. (Fig. 12.27
mullite is adapted from F.J. Klug
crystobalite alumina and R.H. Doremus,
+L +L + "Alumina Silica Phase
1600 mullite Diagram in the Mullite
Region", J. American
mullite Ceramic Society 70(10),
+ crystobalite p. 758, 1987.)
1400
0 20 40 60 80 100
Composition (wt% alumina)
 Application: Die Blanks
• Die blanks: die Ad
-- Need wear resistant properties! Ao tensile
force
die
Adapted from Fig. 11.8 (d),
Courtesy Martin Deakins, GE Callister 7e.
Superabrasives, Worthington,
OH. Used with permission.

• Die surface:
-- 4 mm polycrystalline diamond
particles that are sintered onto a
cemented tungsten carbide Courtesy Martin Deakins, GE
substrate. Superabrasives, Worthington,
OH. Used with permission.
-- polycrystalline diamond helps control
fracture and gives uniform hardness
in all directions.
 Application: Cutting Tools
• Tools:
-- for grinding glass, tungsten,
carbide, ceramics
-- for cutting Si wafers
-- for oil drilling

• Solutions: oil drill bits blades

-- manufactured single crystal
or polycrystalline diamonds coated single
crystal diamonds
in a metal or resin matrix.
-- optional coatings (e.g., Ti to help
diamonds bond to a Co matrix polycrystalline
diamonds in a resin
via alloying)
matrix.
-- polycrystalline diamonds
Photos courtesy Martin Deakins,
resharpen by microfracturing GE Superabrasives, Worthington,
OH. Used with permission.
along crystalline planes.
 Application: Sensors
• Example: Oxygen sensor ZrO2
• Principle: Make diffusion of ions Ca 2+
fast for rapid response.
• Approach:
Add Ca impurity to ZrO2: A Ca 2+ impurity
-- increases O2- vacancies removes a Zr 4+ and a
-- increases O2- diffusion rate O2- ion.

• Operation:
sensor
-- voltage difference
gas with an reference
produced when unknown, higher gas at fixed
O2- ions diffuse oxygen content O2-
oxygen content
diffusion
from the external
surface of the sensor
to the reference gas. + -
voltage difference produced!
 Alternative Energy – Titania Nano-Tubes
"This is an amazing material architecture for
water photolysis," says Craig Grimes, professor
of electrical engineering and materials science
and engineering. Referring to some recent finds
of his research group (G. K. Mor, K. Shankar,
M. Paulose, O. K. Varghese, C. A. Grimes,
Enhanced Photocleavage of Water Using Titania
Nanotube-Arrays, Nano Letters, vol. 5, pp. 191-
195.2005 ), "Basically we are talking about
taking sunlight and putting water on top of this
material, and the sunlight turns the water into
hydrogen and oxygen. With the highly-ordered
titanium nanotube arrays, under UV
illumination you have a photoconversion
efficiency of 13.1%. Which means, in a nutshell,
you get a lot of hydrogen out of the system per
photon you put in. If we could successfully shift
its bandgap into the visible spectrum we would
have a commercially practical means of
generating hydrogen by solar energy.
 Application of advanced ceramics classified by function 30

Function Class
electrical insulation -Al2O3 , MgO, procelain
ferroelectrics BaTiO3, SrTiO3
piezoelectrics PbZr0.5Ti0.5O3
conductors MoSi2, SiC
fast ionic conductors -Al2O3 , doped ZrO2
superconductors Ba2YCu3O7-x
magnetic soft ferrites Mn0.4 Zn0.6Fe2O4
hard ferrites BaFe12O19, SrFe12O19
nuclear fuel UO2, UO2 - PuO2
shielding SiC, BC4
optical transparent envelopes -Al2O3, MgAl2O4
light memory doped PbZr0.5Ti0.5O3 , LiNbO3
colors doped ZrSiO4, doped ZrO2 , doped Al2O3
mechanical structural refractory -Al2O3 , MgO, Si3N4 , SiC
wear resistance -Al2O3, ZrO2 , Si3N4 , SiC
cutting -Al2O3, ZrO2 , Si3N4 , SiC, WC,
SiAlON
abrasive -Al2O3 , MgO, SiC
construction CaO - Al2O3 - SiO2 , porcelain
thermal insulation -Al2O3, ZrO2 , Al6Si2O13 , SiO2
radiator ZrO2, TiO2, AlN
chemical gas sensor ZnO, ZrO2, SnO2, Fe2O3
catalyst carrier Mg2Al4Si5O18, Al2O3
electrodes TiO2 , SnO2, ZnO, TiB2
filters SiO2, Al2O3
coatings NaO - CaO - Al2O3 - SiO2
biological structural protheses -Al2O3, procelain
Ceramic processing
cements CaHPO4 - H2O N. Rahaman
 31

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.
→ Minerals that have Si as a
component.
• use various arrangements of an SiO 4
tetrahedron to describe structure of
silicates: sp 3 hybridization
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33
 CLASSIFICATION OF SILICATES 34

6 TYPES of silicate:

➢Nesosilicate

➢Sorosilicate

➢Cyclosilicate (silicate vòng – ring silicate)

➢Inosilicate (silicate chuỗi - chain silicate)

➢Phyllosilicate (silicate tấm lớp- sheet silicate)

➢Tectosilicate (Silicat khung- Framework Silicate)

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 36

• Sorosilicates are silicate minerals consisting of double tetrahedral

groups in which one oxygen atom is shared by two tetrahedrons.
• Cyclosilicates, in contrast, are arranged in rings made up of
three, four, or six tetrahedral units.
• Inosilicates show a single-chain structure wherein each
tetrahedron shares two oxygen atoms.
• Phyllosilicates have a sheet structure in which each tetrahedron
shares one oxygen atom with each of three other tetrahedrons.
• Tectosilicates show a three-dimensional network of tetrahedrons,
with each tetrahedral unit sharing all of its oxygen atoms.
 N e s o s i l i c a t e s [SiO4]⁴-
• nesosilicates are minerals whose structure are made up of independent silicate
tetrahedrons.
• In the structure of nesosilicates, SiO4 tetrahedra are not directly connected with mutual
oxygen ion, only by interstitial cations. The simplest structure in nesosilicates have mineral
forsterite Mg2[SiO4].
• Olivine with little iron is closer to forsterite with greenish color. The same with more iron is
closer to fayalite with dark green color.
• Olivine crystallizes in orthorhombic system and hardness of 7-6.5 (depending on the
isomorphous replacement of Mg with Fe). It forms by crystallization of magma at high
temperatures (pyrogen minerals).
• In normal atmospheric conditions, it has low resistance to weathering and easily subjected
to metamorphism in the mineral serpentine (olivine serpentinization), talc or actinolite.

37
 Sorosilicates [Si2O7]6-

• Sorosilicates have isolated double tetrahedra groups with (Si2O7)6-

or a ratio of 2:7. There are no significant petrogenic minerals among
sorosilicates, except epidote, zoisite and vesuvianite

38
 Cyclosilicates [SinO3n]2n-
• Cyclosilicates, or ring silicates, have linked
tetrahedra with (SixO3x)2x or a ratio of 1:3.
These groups of minerals exist as three-
member [Si3O9)6-]. four-member (Si4O12)8-
and six member [Si6O18)12-]. rings.
• 1. Three-member ring Benitoite - BaTi(SiO3)3
• 2. Four-member ring Axinite
{(Ca,Fe,Mn)3Al2(BO3)(Si4O12)(OH)}
• 3. Six- member ring Beryl/Emerald
{Be3Al2(SiO3)6 Cordierite
{(Mg,Fe)2Al3(Si5AlO18)}

39
 Ino s i l i c a t e s
• Inosilicates, or chain silicates, have interlocking chains of silicate tetrahedra with either SiO3,
1:3 ratio, for single chains or Si4O11, 4:11 ratio, for doublechains.
• SINGLE CHAIN- INOSILICATES, PYROXENEGROUP
• The pyroxenes are important rock-forming inosilicate minerals and often exist in many
igneous and metamorphic rocks. They share a common structure of single chains of silica
tetrahedra .
• The group of minerals crystallizes in the monoclinic and orthorhombic systems. Inosilicates
with a single-chain SiO4 tetrahedron of the pyroxene group are very important and
widespread petrogenic minerals . Pyroxenes constitute a related group of silicate minerals
with similar crystallographic, physical and chemical properties.

40
• The Most I m p o r t a n t Pe t r o g e n i c M i n e r a l s f r o m
Pyroxene Group

41
 DOUBLE-CHAIN INOSILICATE/ AMPHIBOLE GROUP
• Amphibole is an important group of generally dark-
colored inosilicate minerals. It is composed of double-
chain SiO4 tetrahedra, linked at the vertices and
generally containing ions of iron and/or magnesium
in their structures.
• Amphiboles crystallize in monoclinic and
orthorhombic system. In chemical composition,
amphiboles are similar to the pyroxenes.
• The differences from pyroxenes are that amphiboles
contain essential hydroxyl (OH) or halogen (F, Cl) and
the basic structure is a double chain of
tetrahedra. Amphiboles are the primary constituent of
amphibolites.

42
The Most Important Petrogenic Minerals of Amphibole Group

43
 Phyllosilicates [Si2nO5n]2n-
• based on interconnected six-member
rings of SiO4 tetrahedra that extend
outward in infinite sheets.
• Three out of the four oxygens from
each tetrahedron are shared with
other tetrahedral.
• The most important minerals among
phyllosilicates: talc- pyrophyllite,
mica, chlorite, vermiculite, smectite
and kaolinitee serpentine.

44
The Most I m p o r t a n t Pe t r o g e n i c M i n e r a l s f r o m t h e
Group P h y l l o s i l i c a t e s

45
46
References

S. K. HALDAR &JOSIP TISLJAR 2013, INTRODUCTION TO MINERALOGY AND PETROLOGY -

Elsevier 225 Wyman Street, Waltham, MA 02451, USA Publishers . 341 p.

Blackburn, W.H. and Dennen, W.H., 1988, Principles of Mineralogy: Iowa, WCB Publishers . 413 p.

47
48
 49

Al: vàng
Mg: xanh da trời
Ion Ca và Na : tím
50
 BENTONITE 51

(Ca 0.5 , Na) 0.7 (Al, Mg, Fe) 4 (Si, Al) 8 O 20 (OH) 4 .7nH 2 O

General structure of calcium montmorillonite. Notice the 2:1

configuration of the silicate tetrahedra and the aluminate octahedra.
 52

Pottery vs. Porcelain

• Various types of clay bodies: porcelain, earthenware, stoneware and
terracotta
• general term ceramic: anything made of clay mixed with water and
earthen elements to shape them into the desired forms. Once shaped,
it is fired and usually glazed. → various types of ceramics
• The main difference between ceramic pottery and porcelain is the ingredients.
• Ceramic pottery articles are made of a mix of natural clay, water
• Porcelain articles are made of a mix of clay, kaolin, silica, quartz, feldspar and various
other materials.
• To look at, porcelain is translucent, whereas pottery is not.

https://mogutable.com /blogs /news /guide -ceramic-pottery-vs-porcelain

 53

Terracotta Earthenware

• used to make many flowerpots, bricks

• the earliest type of pottery
and sculptures.
• slightly porous and coarser than
• may also describe a color which is a stoneware and porcelain
natural brown-orange. • fired at temperatures typically around
1000-1080ºC.
• very porous clay to work with, and a
• it is usually glazed, → watertight.
coat of glaze is needed to make it
• main type of ceramic used for
waterproof.
decoration
→ the kind of ceramic fired at the
lowest temperatures – some have fired
it as low as 600ºC.
 54

Stoneware
Porcelain
• fired at higher temperatures (usually 1150ºC-
1300ºC) • fired at high temperatures – above 1250ºC
• inherently non-porous →watertight. • like stoneware: vitrifies during the firing, → its
surface is watertight naturally.
• can be left unglazed that it will still hold
water inside. • The surface is very smooth and the most
identifying trait of porcelain is its translucence.
• Stoneware is harder, stronger and more
durable than earthenware • after firing becomes very translucent, allowing
light to show through it.
→ mostly preferred for everyday use, found
normally in the kitchen since it can easily go • the sound: ring with a bell-like sound.
into the oven and such.
 55

Compare Pottery How To Determine Whether An Item

Is Porcelain Or Ceramic Pottery?
and porcelain
1. Translucency
2. Density 1. Cost
3. Smoothness 2. Weight
4. Porosity 3. Glaze Examination
5. Texture 4. Sound
6. Durability
56