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A Concise Introduction

to Ceramics
A Concise Introduction
to Cera1l1ics
by
George C. Phillips

~ VAN NOSTRAND REINHOLD


~ ~_ _ _ _ New York
Copyright ('> 1991 by Van Nostrand Reinhold
Softcover reprint of the hardcover 1st ed ition 1991
Library of COnRreSS Catalog Card Number 91·19587
ISBN·13: 978·94·011--6975·2
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rcproduccd or uscd in any form or by any means-graphic. electronic. or meehaniclli.
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Library or Congress Cataloging-in· Publication Data
Phillips. George C .. 1937-
A concise inlrodu!;tion to ceramics/by George C. Phillips.
p. cm.
Includes bibliographical referen!;es and index.
ISBN-13: 978-94-011--6975-2 e-ISBN-13: 978-94-011--6973-8
001:10: 1007/978-94-011--6973-8
I. Cerami!;s. L Tille.
TP807.P53 1991
666-dc20 9 1·19587
C IP
Contents

Preface / ix

Introduction / xiii

PART I-OVERVIEW OF CERAMICS

1. Ceramic Materials / 3
I. I Introduction / 3
1.2 Ceramic Materials / 4
1.3 Terminology / 6
1.4 Formula Notation / 7

2. Ceramic Raw Materials / 8


2.1 Naturally Occurring Minerals / 8
2.2 Manufactured Raw Materials / 10

3. Nature of Clay / 12
3.1 Physics of Clay / 12
3.2 Clay-Water Systems / 15

4. Forming from Powders / 18


4.1 Powder Preparation / 18
4.2 Dry Pressing / 18
4.3 Plastic Forming / 21
4.4 Casting / 22
4.5 Thermal Treatments / 24
v
vi Contents

5. Forming from Melts / 27


5. 1 Cooling Curves / 27
5.2 Glass Forming Methods / 29
5.3 Thermal Conditioning Glass / 30

6. Miscellaneous Forming Techniques / 32


6.1 Coatings / 32
6.2 Single Crystals / 33
6.3 Miscellaneous Formings / 33

7. Traditional Ceramic Industries / 34


7.1 Abrasives / 34
7.2 Refractories / 35
7.3 White wares / 35
7.4 Structural Clay Products / 36
7.5 Glasses / 36
7.6 Porcelain Enamels / 37
7.7 Cements / 38

PART II-THE NATURE OF CERAMIC MATERIALS


(BONDING/CRYST AL CONCEPTS)

8. Atomic Structure / 41
8.1 Background / 41
8.2 Electronic Configurations / 42
8.3 Ionization / 44

9. Bonding and Crystal Chemistry Concepts / 47


9.1 Types of Bonding / 47
9.2 Material Classes / 47
9.3 Pauling's Rules / 48
9.4 Coordination Numbers / 49
9.5 Bond Strength / 52

10. Silicate Stuctures / 53


10.1 Basis / 53
10.2 Types of Silicates / 54
10.3 Layer Minerals / 55

11. Structure of Glass / 60


11.1 Crystalline versus Glassy / 60
Contents vii

11.2 Glass Formers / 61


11.3 Glass Modifiers / 62
11.4 Structure and Composition versus Properties / 63

12. Oxide Crystal Structures / 65


12.1 Basis/65
12.2 ArnXn Compounds / 67
12.3 ABrnXn Compounds / 67

PART III-CHARACTERIZATION OF CERAMIC MATERIALS

13. Analytical Techniques / 71


13.1 Introduction / 71
13.2 Microscopy / 71
13.3 X-Ray Methods / 75
13.4 Surface Measurements / 80

14. Properties and Requirements of Ceramic Materials / 81


14.1 Introduction / 81
14.2 Properties / 81
14.3 Requirements / 84

15. Ceramic Surface Characteristics / 88


15.1 Introduction / 88
15.2 Dry-Pressed Alumina Surfaces / 88
15.3 Surface Variations versus Processing Techniques / 91
15.4 Quantitative Surface Techniques / 95

16. Ceramic Strength Considerations / 102


16.1 Introduction / 102
16.2 Strength Measurements / 103
16.3 Fracture Mechanics / 105

PART IV-HI-TECH APPLICATIONS OF CERAMICS

17. Structural and Electronic Applications / 115


17.1 Introduction / 115
17.2 Structural Applications / 116
17.3 Magnetic Ceramics / 117
17.4 Electronic Applications / 119
viii Contents

18. Integrated Circuit Technology / 122


18.1 Introduction / 122
18.2 Semiconductors / 122
18.3 Integrated Circuit Processing / 123
18.4 Transistor Structures / 125
18.5 Application and Development of Semiconductors / 126

19. Ceramic Packaging of IC Devices / 127


19.1 Introduction / 127
19.2 Package Designs / 128
19.3 Processing of Planar Substrates / 131
19.4 Future Trends in Planar Ceramic Packaging / 136
19.5 Multilayer Ceramics (MLC) / 141

20. The Future of Ceramics / 149

Index / 153
Preface

During the early 1970s, the IBM facility in Endicott, NY, began a signif-
icant development and manufacturing effort to produce both thick- and
thin-film wiring on ceramic substrates for semiconductor packaging. To
fulfill the product mission it was necessary to provide specialized training
in ceramics.
Participants in the resulting 15-week ceramics courses ranged from
manufacturing personnel to engineers with bachelor's, master's, and doc-
tor's degrees. Many were recent college graduates in disciplines ranging
from mechanical engineering to materials science. Their organizational
affiliations included manufacturing, manufacturing engineering, quality
engineering, development engineering, product engineering, product as-
surance, reliability engineering, production control, and purchasing.
Their backgrounds and job assignments were very diverse.
As the ceramics technology spread within IBM, so did the need for
education. As a result, three-day short courses were conducted at the
company's facilities in Burlington, Vermont, and Bromont, Quebec.
More recently, the same basic ceramics course was taught at Broome
Community College and Alfred University in their continuing education
programs. It also was conducted upon invitation for personnel working
at Coors Ceramics in Golden, Colorado.
As the course was developed and refined over a 15-year period, it
became apparent that a textbook was needed to provide a basic introduc-
tion to ceramics. Thus, the basis for this book was established. The
book's general overview of ceramics-what they are, where they come
from, how they are made, and how they are used-came from the au-
thor's undergraduate study at Alfred University. The crystal chemistry
ix
x Preface

concepts are based on his graduate study at Alfred University in crystal


chemistry, clay mineralogy, and structure of glass. Chapters on charac-
terization of ceramic materials resulted from the combination of a mas-
ter's thesis and laboratory investigations. Finally, the hi-tech applications
portion of the book is based on the author's experiences at IBM.
The purpose of this textbook is to provide an introductory overview
of ceramics for people who are working with ceramic materials and for
college students involved with the materials sciences. It is not designed
to replace Kingery, Bowen, and Uhlmann's [I] Introduction to Ceramics.
which is an excellent reference for students or scientists who already
have some background in ceramics. This book provides the necessary
foundation for future studies or involvement with ceramics.
Acknowledgments

I am grateful to the following individuals who played key roles in helping


me formulate the classroom version of A Concise Introduction to Ce-
ramics: Ken Jordan, IBM, Austin, Texas; Charles Quagliata, Broome
Community College, Binghamton, NY; Coral Link, Alfred University,
Alfred, NY; William Flock, Coors Ceramics Company, Golden, CO;
Vivian Harwood Mattox, Materials Research Society; and James CIum,
State University of New York at Binghamton. They each, in their own
way, gave me an opportunity to collect my thoughts, hone my skills, and
teach. Their encouragement provided the impetus for this book.
I also wish to thank Bob Sebesta from IBM for editing the chemistry
section, and David Yetter, a technical editor at IBM, who edited the
manuscript with insight and thoroughness and guided me through the
publishing process.

xi
Introduction

Part I presents a general overview of the field of ceramics, defining what


constitutes a ceramic material and providing examples of the different
types of ceramics. A distinction is made between naturally occuring raw
materials that can be used "as found" and manufactured raw materials
that, because of their unique compositions, require synthesis.
Clay is shown to be the most important ceramic raw material for
traditional ceramic products, possessing unique characteristics that are a
key to ceramic forming techniques. Forming from powders is presented,
based on the ratio of clay to water. The process description continues,
from densification of the initial formed shapes, through high temperature
treatments, to the rocklike condition associated with ceramics.
Glass is shown to differ from other ceramic products more in the
method of manufacture than in its chemical or physical properties.
Glasses are formed from a high temperature viscous state with cooling
that is rapid enough to cause the bulk material to solidify prior to crystal-
lization.
Applications of ceramic materials are highlighted by reviewing the
ceramic industries. Traditional uses are covered, including a variety of
products from dishes to electronic components. The intent is to show that
most applications for ceramics are based on one outstanding character-
istic of the material, such as hardness (abrasives), thermal resistance
(refractories), transparency (glass), or durability (whitewares).
Part II discusses the crystal structures of ceramic materials and their
resulting characteristics. Ceramics are presented as a class of materials
along with metals and plastics. These materials differ from each other in
their properties because of the initial attraction, or bonding, of their
xiii
xiv Introduction

elements. The bonding concepts presented are based on atomic structure


and the consequences of ionization to charged ions, where the ionic bond
in ceramic materials results from the electrostatic attraction of positive
ions (cations) and negative ions (anions).
Differences within a class of materials are due not only to the different
elements but also to the arrangement of the elements. If the arrangement
is regular and reproducible, then the structure is crystalline. Crystal
chemistry concepts are developed by using cations such as silicon, alu-
minum, and magnesium as the reference, and then constructing oxygen
anion tetrahedrons and octahedrons around the cations.
The largest group of ceramic materials is the silicates. This includes
clays, talc, and micas, which are considered to be built by using silicon
tetrahedrons as building blocks. Glass, which also is primarily made from
silicon tetrahedrons, differs from these materials in that its arrangement
is irregular or random. This difference produces unequal bond strengths
in glass, which result in melting "ranges" rather than specific melting
temperatures. It is shown that glassy materials therefore can be formed
in a high temperature viscous state.
The other oxide crystals (nonsilicates) are developed by using the
anion as a reference point, and include the close packed oxygens, such
as body-centered cubic, face-centered cubic, and hexagonal close packed
structures, where the cations occupy interstitial sites that are fourfold
(tetrahedra) and sixfold (octahedra). The unique characteristics of fer-
romagnetics and ferroelectrics, which are related to their close packed
crystal structures, are described.
Part III concerns characteristics of ceramic materials. Analytical tech-
niques such as microscopy, X-ray analysis, and surface analysis are de-
scribed briefly, and properties that dictate the uses of ceramics and
dimensional tolerancing are presented. The effect of ceramic surfaces on
processing is highlighted by using thin-film metal to enhance the differ-
ences. Also, strength considerations are presented, with measurement
techniques and failure analysis from various fracture modes.
Part IV presents some of the high-technology applications for ce-
ramics. This section includes structural or mechanical uses of the newer
materials such as silicon nitride, stabilized zirconia, and aluminum ni-
tride. A discussion of the magnetic behavior of the ferrite materials leads
to some of the unique applications of magnetic ceramic materials. Linear
and nonlinear dielectric applications such as uses in capacitors and trans-
ducers also are explained.
Then an overview of integrated circuit technology-including designs,
manufacture, and applications-is presented as the basis for understand-
ing electronic packaging technologies. Ceramic packaging is described
Introduction xv

from chip connections to package input/output connections. Thick- and


thin-film wiring is illustrated for both planar and multilayer designs. Fi-
nally, future trends in ceramic packaging are presented, including in-
creased I/Os, denser wiring, and electrical and thermal performance
improvements.
The final chapter on the future of ceramics provides some brief
thoughts on growth fields. It focuses on the use of ceramics in hostile
environments where improved thermal and fracture resistance will be
critical, and in hi-tech applications in electronics, fiber optics, and super-
conductivity.
A Concise Introduction
to Ceramics
Part I
Overview of Ceramics
1
Ceramic Materials

1.1 INTRODUCTION
The term ceramics is derived from the Greek word "keramos," which
means "burn stuff." History has not recorded the exact beginnings of
ceramic art and the ceramics industry, but both most likely started thou-
sands of years ago when early humans unknowingly sparked a new sci-
entific field of interest-materials science. That happened when someone
discovered that cooking a clay vessel permanently transformed it into
something different, something rock-hard. There are many examples of
ceramic ware from that early period because the durability of those rock-
like materials allowed them to withstand the ravages of time.
Today, ceramics are riding a new wave of popularity in what some call
the New Stone Age. Much of the attention centers around the basic
knowledge that ceramics are often harder, lighter, stiffer, and more resis-
tant to heat and corrosion when compared to metals-but there is a
penalty to pay. The basic problem with ceramics, as it has been through
the ages, is brittleness. Drop them, and they usually shatter. The problem
is formidable, but engineers and scientists around the world continue to
look for solutions. In the process, they have developed exotic ceramic
compounds and applications that meet very specific, precise require-
ments, as in the field of electronics.
Many dictionaries define ceramics as "the art of making things from
baked clay." The key words here are "art," "baked," and "clay." A
process is considered an art if it can be reproduced with a certain amount
of skill even though it is not completely understood. The word "baked"
is used to describe ceramics because most processing of ceramics in-
3
4 I / Overview of Ceramics

volves high temperature treatment. In fact, ceramics can be considered


to be high temperature chemistry. "Clay" also is used to describe ce-
ramics because clay was an essential ingredient in traditional ceramic
compositions. Clay was added to other ceramic materials as the forming
agent.
As crude as this definition might appear, it was quite an accurate
description of ceramics up until about World War II. But in the early
1940s there was a concentrated effort in materials research to develop
new materials and ways for processing those materials. As a result, the
classical definition of ceramics became too restrictive, and a new defini-
tion took shape.
Ceramics has now become "the art and science of making and using
articles that are essentially composed of inorganic and nonmetallic com-
pounds." In other words, ceramics can be considered a class of materials
that differ from plastic (organics) and metals. The majority of ceramic
compounds are metallic oxides.

1.2 CERAMIC MATERIALS


The metal oxide compounds can be grouped according to the valence of
the metal ion. They include the following groups, with oxygen having a
- 2 valence and M representing the metal:

A. Monovalent metals, or the MzO group, such as:


I. Li 20-lithium oxide
2. NazO-sodium oxide
3. KzO-potassium oxide
B. Divalent metals, or the MO group, such as:
I. MgO-magnesium oxide
2. CaO-calcium oxide
3. NiO-nickeloxide
4. ZnO-zinc oxide
C. Trivalent metals, or the M20 3 group, such as:
I. B 2 0 3-boron oxide
2. Al 20 3-aluminum oxide
3. Fe 20 3-iron oxide
D. Tetravalent metals, or the MO z group, such as:
I. Si02 -silicon oxide
2. Ti0 2-titanium oxide
3. Zr0 2-zirconium oxide
E. Pentavalent metals, or the M20 5 group, such as:
I. As 2 0 5-arsenic oxide
2. Sb 20 5 -antimony oxide
Ceramic Materials 5

Ceramic materials also include mixtures of oxides combined into a


single crystal structure. The most widely occurring group of oxide mix-
tures is the silicates, which can exist in both the hydrated and the anhy-
drous form. Examples of naturally occurring silicates include:

Al cO,·2SiO c·2H cO-hydrated aluminum silicate


MgO'Si0 2 -anhydrated magnesium silicate

The ferroelectric materials are mixtures of titanium oxide and zircon-


ium oxide with divalent metal oxides, such as:

BaO·TiOc-barium titanate
PbO·ZrOc-lead zirconate

The ferromagnetic materials are mixtures of trivalent iron oxide with


a variety of divalent metal oxides that include:

CuO' Fe c0 3-copper ferrite


MnO· Fe c0 3 -manganese ferrite
ZnO· Fe c0 3-zinc ferrite
NiO· ZnO· Fe 20,-nickcl zinc ferrite
MnO·CuO· Fe c0 3 -manganese copper ferrite

The nonoxide ceramic compounds, which are included in the definition


of ceramics as inorganic and nonmetallic materials, include the carbides,
nitrides, borides, and silicides. Examples of these compounds include:

SiC-silicon carbide
WC-tungsten carbide
AlN-aluminum nitride
BN-boron nitride
TiB-titanium boride
MoSi 2-molybdenum disilicide

Cermets are a group of materials sometimes included with ceramic


materials; but, as the term implies, cermets are mixtures of ceramics and
metal that are combined but remain as separate, distinguishable phases.
Examples of cermets include:

WC in cobalt-tungsten carbide (ceramics) in a cobalt (metal) material.


TiC in nickel-titanium carbide (ceramics) in a nickel (metal) matrix.
AlcO, in chromium-aluminum oxide (ceramics) in a chromium (metal)
matrix.
6 I / Overview of Ceramics

1.3 TERMINOLOGY
The nomenclature used to abbreviate ceramic terms can be summarized
by using the various compounds of silicon. The following tabulation
shows the terminology used to represent various chemical formulas for
different combinations with silicon:

Name Formula Type

Silicon Si Metal
Silica Si02 Oxide
Silicate 2A1 20 3 ·3Si02 Mixture of oxides
Silicide MoSi 2 Intermetallic
Silicone SiO(CH 3), Hydrocarbon
Other examples of oxides are:
Alumina Al 20 3 Aluminum oxide
Magnesia MgO Magnesium oxide
Titania TiO, Titanium oxide
Beryllia BeO Beryllium oxide
Other examples of oxide mixtures include:
Titanates BaO·TiO, Barium titanium oxide
Zirconates PbO·ZrO, Lead zirconium oxide

An exception is the ferromagnetic materials, which are referred to as


ferrites such as:

CuO·Pe20 3-copper iron oxide


ZnO· MnO· Pe 20 3-zinc manganese iron oxide

The nonoxide compounds use the "ide" ending. These intermetallics


compounds include the carbides, nitrides, and borides, such as:

WC-tungsten carbide
SiC-silicon carbide
AIN-aluminum nitride
BN-boron nitride
TiB-titanium boride
Ceramic Materials 7

1.4 FORMULA NOTATION


There are different ways of writing chemical formulas. For example, the
chemical formula for the clay mineral kaolinite is:

A chemist would write the formula by listing the symbols for the cat-
ions such as hydrogen, aluminum, and silicon on the left-hand side, and
those for the anions such as oxygen on the right-hand side. The symbols
show the qualitative makeup of the material, and the subscripts show the
quantitative proportions of the elements.
A mineralogist or a geologist would write the formula for kaolinite in
the form of a structural formula:

In this form, the Si2 0 s radical makes it evident that kaolinite is a layer
mineral. This point will become obvious when crystal structures are dis-
cussed.
Finally, a ceramist would write the formula by using oxide groups in
the following order:

The ratio of alumina to silica is apparent here. This is an important


consideration because the kaolinite materials when heated to elevated
temperatures, as they would be in ceramic ware, would release the water,
and the remaining alumina and silica would react to form high tempera-
ture reaction products.
2
Ceramic Raw Materials

2.1 NATURALLY OCCURRING MINERALS


The most commonly occurring elements in the earth's crust are oxygen,
which accounts for approximately 50 percent of the total; silicon, which
is about 25 percent; aluminum, at around 8 percent; and iron, which
makes up 6 percent. Thus, almost 90 percent of the available materials at
the earth's surface are made up of those four elements. The majority of
such raw materials are oxides, specifically silicon oxides or silicates,
which are ceramic materials. Plastics or polymers and most metals (with
the exception of the noble metals) do not exist as raw materials or min-
erals in their natural states.
The types of geological environments that produce ceramic raw mate-
rials include igneous, sedimentary, and metamorphic formations. Igneous
rocks are formed by the solidification of molten lava. The feldspars,
which are anhydrous alkali or alkaline earth aluminum silicates, make up
a large portion of these igneous rocks. Sedimentary rocks are materials
that have been moved from their place of origin, usually by wind or
water, and redeposited in a stable environment such as clay, mica, and
limestone. Metamorphic rocks are materials that have been altered by
the application of pressure, heat, and/or water. Metamorphic rocks are
sources for pegmatites, minerals that have concentrations of the rare
earth elements.
The most commonly occurring minerals are the alumino-silicates, of
which the clay minerals are of prime interest in ceramics. Clays are
weathering products from feldspars, which can be represented by the
following formulas:
8
Ceramic Raw Materials 9

or:

There must be leaching of the potassium (KeO) or other alkali or alka-


line earth. hydration with water (HeO). and discarding of silica (SiO e) to
achieve the formula for kaolinite clay. which is given by:

or:

There are three groups of clay minerals, which are hydrated aluminum
silicates: kaolinite, illite. and montmorillonite. Kaolinite is the clay found
in most white-firing ceramic products; illites are the basis for structural
clay products such as bricks; and montmorillonites, which have expand-
ing lattices, are added to compositions in small amounts to increase the
plasticity of the mixture.
Clay deposits differ from each other in the ultimate particle size of the
clay mineral, the purity of the parent rock, and the accessory minerals
present.
Raw materials are concentrated in nature by various geological pro-
cesses:
• Mechanical separation
• Chemical precipitation
• Chemical leaching
• Thermal alterations
An example of mechanical separation is the extensive washing used to
remove accessory minerals that are softer and less soluble than quartz.
Quartz is very widespread, and thus inexpensive, and is used in most
traditional ceramic and glass products.
Chemical precipitation is a means of concentrating hydroxides and
carbonates, which are stable in a marine environment. These materials
are the primary sources for the alkali and alkaline earth oxides.
The weathering of clay from feldspar (see above) is an example of
chemical leaching, whereas concentration of the rare earth elements is
accomplished by thermal alterations of igneous rocks.
10 I / Overview of Ceramics

2.2 MANUFACTURED RAW MATERIALS


The majority of ceramic products are made from naturally occurring raw
materials. The manufacture of raw materials is driven by a demand for
high purity (alumina) or unique formulations (ferrites, titanates, carbides,
etc.) that do not occur in nature.
Alumina, which is used as the base ingredient in most technical and
electronic ceramic applications, is found in limited quantity as the min-
eral corundum. Most of the raw material alumina comes from bauxite
ore. Bauxite contains mostly aluminum hydroxide, with quartz and he-
matite (iron oxide) as the accessory minerals. Bauxite ore is the primary
source for both the metal aluminum and the oxide of aluminum, which is
the alumina.
The Bayer process [2] is a method for converting bauxite to alumina.
The seven-step process includes:

1. Calcination at the mine to remove volatiles and reduce the weight


for shipment.
2. Grinding to - 70 mesh particle size in order to accelerate chemical
processing.
3. Dissolving in sodium hydroxide to put aluminum in solution.
4. Filtering the suspension in order to remove the accessory minerals
such as quartz (Si0 2) and hematite (Fe 20 3).
5. Cooling the filtered solution to precipitate the aluminum hydroxide
complex.
6. Filtration and washing to clean the aluminum hydroxide (AI(OHh).
7. Calcination of the aluminum hydroxide at 1150°C to convert it to
alumina by the following reaction:

The hydroxides and the carbonates that occur in marine environments


are sources for the alkali and alkaline earth oxides. Examples of calcina-
tion of hydroxides and carbonates to produce an oxide and either carbon
dioxide gas or water vapor are as follows:

Mg(OH)2 - MgO + H 20 (vapor)


CaC0 3 - CaO + CO2 (gas)

The ferrites and titanates used in ferromagnetic and ferroelectric ap-


plications are not found in nature with their exacting compositions. They
Ceramic Raw Materials II

can be produced by reacting their oxides, such as iron oxide or titania,


with the alkaline earth hydroxides or carbonates:

Fe~O, + Zn(OHh ~ ZnO'Fe~O, + H~O (vapor)


TiO~ + BaCO, ~ BaO·TiO~ + CO~ (gas)

The carbides, nitrides, and borides do not occur in nature as minerals.


These raw materials are made by high temperature reactions. For exam-
ple, silicon carbide is made by reacting silica and coke at temperatures
around 2200°C in the following reaction:

SiO~ + 3C ~ SiC + 2CO (gas)

The cost of raw materials varies drastically, depending on the abun-


dance of the materials and the required purity. The silicates are the most
widespread and therefore the least expensive naturally occurring raw
materials. Silica (in the form of the mineral quartz), feldspar, and clay
are widely used in ceramic products and cost just a few cents per pound.
The rare earth oxides, on the other hand, can cost from $50 to $5,000 per
pound. The more common manufactured raw materials such as alumina,
the titanates, and the ferrites vary between $.50 and $5.00 per pound.
3
Nature of Clay

3.1 PHYSICS OF CLAY


The classical definition of ceramics uses the word "clay" to describe
ceramics. Prior to the 1940s most ceramic products used clay as part of
their composition. Clay was a necessary ingredient because it served as
the forming agent that allowed ceramic powders to be shaped from a dry
to a slurry condition. It was not until the clay structure was better under-
stood that substitutions could be made to perform the same role as clay
in the ceramic composition [3].
Clay differs from all other ceramic materials in its physical character-
istics, occurring as an extremely small-size platelike particle (Figure 3-
1).
The sizes indicated in Figure 3-1 are on an atomic scale, and only five
layers of atoms make up the thickness of the clay particle. The clay
platelets, which have a chemical formula given by:

cannot continuously grow in thickness. The surfaces of the clay particles


have a residual stress due to their very small extension. Surface atoms,
in general, tend to pull into the bulk material to minimize the surface
energy; but this distance is so small for the clay particles that the surface
ions cannot pull in but instead become polarized. This polarization sets
up residual positive and negative charges on the surfaces. These charges
can be satisfied by physical absorption of water molecules, which also
can develop dipoles. The physically absorbed water will be attached to
12
Nature of Clay \3

the clay surfaces and will no longer have the mobility to move. It can be
represented as shown in Figure 3-2.
The clay particles could grow continuously in the plane direction: so
the edges of the particles are the result of broken bonds. These are
primary bonds, such as silicon to oxygen or aluminum to oxygen. The
charges from broken primary bonds can be satisfied by chemically ab-
sorbing deionized water. The water molecule can deionize into positive
and negative ions as follows:

These positive and negative ions can attach themselves along the edges
of the clay particles as shown in Figure 3-3.
The surfaces of all materials have physically and chemically absorbed
water molecules. Clay differs from other materials in that it has extremely
small particle sizes and therefore has a considerably greater surface area.
which results in a greater amount of charge on its surfaces. The physical
characteristic of the clay, with its small particle size, produces tremen-
dous amounts of surface charge.
The effect of particle size on surface area can be represented by con-
sidering a cube of unit dimension (Figure 3-4). The surface area of the
cube would be the surface area of each face. which would be 1 x 1
square. times the number of faces (six). Therefore. the total surface area
of the cube would be 6 square units.
If the cube were divided into halves as shown in Figure 3-5, the surface
area for each cube would be 6( 112 x 1/2). There being eight of these
smaller cubes, the total surface area would be 8 x 6 (1/2 x 112). or 12
square units. The surface area doubles when the particle size is reduced
by half.
The clay particle. with its physical dimensions in Angstrom units,
would have an enormous surface area. It also would have a tremendous
amount of surface charge and the ability to retain very large volumes of
physically and chemically absorbed water.
To summarize, the physical properties of clay that make it unique are
as follows:

1. Extremely small particle size.


2. Platelike shape.
3. High surface charges resulting from small extension in one direction
and broken bonds at edges.
4. Ability to retain large volumes of adsorbed water (physically by
dipole bonding: chemically by electrostatic bonding).
14 I / Overview of Ceramics

FIGURE 3-1. Clay particle.

FIGURE 3-2. Physically absorbed water on clay particle surfaces.

FIGURE 3-3. Chemically absorbed water on clay particle edges.

FIGURE 3-4. A unit-dimensioned cube.


Nature of Clay 15

FIGURE 3·5. Unit·dimensioned cube divided in half.

Physically absorbed water retains all the characteristics of the water


molecules, and can be removed by heating above 100°C, which is the
boiling temperature for water. Because the chemically absorbed water
has been deionized, it no longer has the characteristics of the water
molecule and can only be gradually removed at temperatures up to
1000°C.

3.2 CLAY - WATER SYSTEMS


Clay-water systems are the key to ceramic forming methods. At a rela-
tively low water content of less than 10 percent water by weight, there is
not enough water to satisfy all the physical (dipole) and chemical (broken
bond) charges on the clay particles. As a result, the clay particles have
to compete for the water molecules, which thus hold the clay particles
together, as shown in Figure 3-6.
At such a low water content, the clay performs the role of a binder,
holding itself and other particles together. Other materials such as sand
and feldspar would not bond together when mixed with water. Clay thus
became the essential ingredient in forming ceramic powder at low water
content.
At a medium water content of between 15 and 25 percent by weight,
there is enough water to satisfy all the physical and chemical charges on

FIGURE 3·6. Clay particles held together by water.


16 I / Overview of Ceramics

FREE
WATER

FIGURE 3-7. Excess water serving as lubricant between clay platelets.

the clay particles. There even is a little excess water, which acts as a
lubricant between the clay platelets, as shown in Figure 3-7.
In this condition, the clay-water system develops plasticity, which is
the ability of a mass to be formed and to retain its shape after the deform-
ing pressure has been removed. It is this feature that separates clay from
all other ceramic materials. Plasticity allows a potter to shape ceramic
ware on a rotating table. The potter's hands shape the external contours,
which remain intact after the hands are removed.
Characteristics of the "plastic state" are: (1) deformation without rup-
ture, which is basically the definition of plasticity; (2) drying shrinkage,
which occurs as the free and physically absorbed water is removed and
the clay particles move together; and (3) increased strength, which results
from a shortage of water, which requires sharing and thus binding to-
gether.
At a high water content (in excess of 50 percent water by weight), the
physically and chemically absorbed water forms an envelope around the
clay particles. The entire complexes take on exact charges, as shown in
Figure 3-8.
In a slurry with a high water ratio, particles that have the same charges
will repel each other and form a suspension, which prevents the particles
from settling out. When clay is present at a very high water content, the

ADSORBED
WATER

FIGURE 3-8. Enveloped clay particles under high water content.


Nature of Clay 17

solution remains cloudy; clay performs the role of the suspending agent
and is added to other ceramic materials in order to help keep them in
suspension during forming from slurries. Mixtures of nonplastics such as
silica and alumina would not (by themselves) stay in suspension when in
high-water-content systems.
4
Forming From Powders

4.1 POWDER PREPARATION


The considerations for powders are the particle size, which affects the
resulting properties, and the particle size distribution, which affects the
packing density. Smaller-particle-size composItions have higher
strengths because they have more surface area, and therefore more
bonds, than those with larger particles. Increased packing densities can
be achieved by mixed sizing with coarse and fine grains. The porosity
can be minimized, with the finer grains filling the interstitial vacancies
between the larger grains. The ideal mixture is approximately 70 percent
coarse grain and 30 percent fine grain.
A wet process usually is used to prepare the powder for subsequent
forming. Raw materials are wet-milled both to mix the constituents and
to reduce the particle sizes. After screening to remove the grinding
media, and magnetic separation to remove iron contamination, water is
removed to the extent of the forming technique that will be used. The
flow chart for powder preparation is shown in Figure 4-1.

4.2 DRY PRESSING


Dry pressing is the compaction of powders into a smaller volume by
applying pressure; as a result of this pressure, there is particle packing
and particle bonding. Dry pressing is used to make small and sometimes
complex shapes for technical and electronic ceramic applications. The
dry press operation starts with a volumetric fill into a die cavity, as shown
in Figure 4-2.
18
Forming From Powders 19

RAW MATERIALS

MIJING

!
SCREENING

!
MAGNETIC SEPARATION

~
!
SPRAY DRY

~
DRY PRESSING

HGURE 4·1.
1
FILTER PRESS

~
PLASTIC FORMING

A wet process for powder preparation.


I
CASTING

WPUNCH

FIGURE 4·2. Dry press operation: initial phase.

Once the die cavity is filled with powder, the material is compacted by
applying unidirectional pressure through the upper punch and the lower
punch, as shown in Figure 4-3.
Core pins, which can be attached to the lower punches, can be used to
fabricate holes through pressed parts. After pressing, the part is ejected,
and the fill shoe is ready to repeat the operation (see Figure 4-4).
For more complex geometries and for larger length-over-diameter ra-
tios, hydro- or isostatic pressure is used to develop a uniform pressure
against a mold in a pressure chamber (Figure 4-5).
For high alumina compositions, the starting particle size is in the range
of one micron. Powders this fine would be airborne during the die fill,
and also could infiltrate between the die and punches to cause jamming.
20 I / Overview of Ceramics

COMPACTION
...----UPPER
PUNCH

L----LOWER
PUNCH

FIGURE 4-3. Compaction occurs under punch pressure.

EJECTION

I:':":'':':':''~:ot.-_ PART

FIGURE 4-4. After the pressing operation, the formed part is ejected.

CHAMBER-

FIGURE 4-5. Forming in a pressure chamber.

These problems are alleviated by agglomerating the finer particles into


larger granulars in the range of 100 to 150 microns. The resulting micro-
structure from this agglomeration is shown in Figure 4-6.
The voids, which are the limiting features of the surfaces, between the
agglomerates are in the range of 15 to 20 microns, which is considerably
larger than the one micron grain size of the starting powder.
Forming From Powders 21

I<'IGURE 4-6. Micrm,tructure formed by agglomerating fine particles into larger granulars.

4.3 PLASTIC FORMING


Parts formed in the plastic condition utilize the uniqueness of clay in
developing plasticity when mixed with water. The plastic state alIows
deformation or shaping without rupture, and is a technique widely used
by artists to make ceramic ware. Two commercial techniques are used to
form ware in the plastic condition: extrusion and jiggering.
Extrusion involves the forcing of a stiff plastic mix through a die ori-
fice. Compaction occurs by using augers to force the plastic material into
smaller volumes, as shown in Figure 4-7.
Extrusion is used to make parts having a constant cross section, such
as tubing and bricks. Holes can be molded into the ware by attaching
core pins to the ends of the extrusion augers. These holes can have any
type of cross section (i.e. square, round, or triangular), and large and
small holes can be made in the same part.
Jiggering, which is used primarily to make dinnerware, involves a

FIGURE 4-7. Basic process for plastic extrusion.


22 I / Overview of Ceramics

-----\t
r----I.U~~~~~~~. ~-PLASTIC
TOOL

MASS

FIGURE 4-8. Basic process tools for plastic jiggering.

rotating mold to form one surface, whereas the opposite surface is formed
when a soft plastic mass rotates under a contour tool, as shown in Figure
4-8. This technique lends itself to producing round or oblong shaped
objects such as dishes and hollow ware.

4.4 CASTING
Slip casting uses a liquid vehicle, usually water, to transport the powders
during forming. The slip, which is about the consistency of pancake
batter, is poured into porous plaster of Paris molds to remove the water
and thus allow compaction of the powders. Clay is the suspending agent
in clay-based ware where electrolytes can be used to impart charges on
nonplastic powders. The clay keeps the powders in suspension while the
water is being removed by the porous mold.
Slip casting can be used to produce solid ware, as shown in Figure 4-9

DRIED WARE

FIGURE 4-9. Slip casting used to produce solid ware.


Forming From Powders 23

DRY

DRIED

FIGURE 4-10. Slip casting taken a step further to produce hollow ware.

Hollow ware also can be produced by removing the slip from the mold
after an initial layer has dried to form a wall (Figure 4-10).
Slip casting is used to make large complex shapes such as sanitary
ware. It also is used where a limited number of parts or prototype parts
are needed.
Tape casting is used to make large, thin sheets from ceramic powders.
These sheets can be fired and used as thin plates or as a base for applying
thick-film metallization circuitry to the individual sheets. The sheets can
be connected together by means of vias (holes through the sheets), which
are filled with metallization. This technique may be used to make simple
or complex multilayer structures for electronic packaging.
The tape casting process involves forming a slurry with liquid organic
binders, ceramic powders, and plastic binders. The slurry is then coated
onto a thin film tape (Mylar, for example). The coating thickness is deter-
mined by the height that a doctor-blade sets above the film, as shown in
Figure 4-11 .
This technique is sometimes referred to as doctor-blade casting. The
solvents used to carry the powders in the slurry are removed by drying,
after which the ceramic powders are bonded together with the organic
binders. This produces a flexible green sheet through which via holes can

BLADE

HGURE 4-11. Tape casting process using a ~lurry coating.


24 I / Overview of Ceramics

be punched or drilled, and thick-film metallization patterns can be


screened onto the surfaces. Lamination of the individual sheets produces
a monolithic structure with flowing of the organic binders. High temper-
ature thermal treatments remove the organic materials and densify the
ceramic powders and complementary metallization.
Alumina ceramics are used for most electronic packaging in this mul-
tilayer process. The thick-film metallizations that will sinter at the same
temperature as alumina are limited to tungsten and molybdenum.

4.5 THERMAL TREATMENTS


Drying is necessary to remove the excess water from parts made by
plastic forming or slip casting. The different types of water in a c1ay-
water system include:

1. Suspension water from slip casting.


2. Interparticle water from plastic forming.
3. Pore water between particles after shrinking.
4. Physically and chemically adsorbed water on the particles.
5. Lattice water within the crystal structure.

The different stages of drying are represented in Figure 4-12. The


initial removal of the suspension and interparticle water results in shrink-
age, as shown in the figure. The water remaining after this shrinkage is
referred to as pore water because it is in between the grains. This pore
water can be removed at a faster rate once the shrinkage has occurred.
The physically adsorbed water, which is the dipole water molecule, is
removed by heating to temperatures above IOO°C. The chemically ad-
sorbed water, which is made up of ions (H,O+ and OH-), is removed
gradually with temperatures up to IOOO°C. The lattice water, which is the
hydroxide group in the chemical formula, begins to be released at tem-
peratures around 600°C.
Drying results in two significant changes: (I) there is a shrinkage as

(A)
SUSPENSION/INTERPARTICLE
00 (8)
PORE WATER
(C)
DRIED

FIGURE 4-12. Drying process after plastic forming or slip casting.


Forming From Powders 25

the water is removed and the particles come together, and (2) there is an
increase in strength when the remaining water is shared.
Firing or sintering at elevated temperatures is used to densify the
ceramic powders into a coherent mass. During the thermal treatment
there is a reduction in surface area, which is the driving force of the
sintering process; the bulk volume is reduced, so that there is a significant
amount of shrinkage; and there is a considerable increase in strength
because the individual grains are fused together. The result is the rocklike
consistency of the fired ceramic.
Sintering, which is the transfer of material to reduce porosity, is ac-
complished by the following mechanisms:

1. Viscous or plastic flow.


2. Diffusion at grain boundaries and within grains.
3. Vaporization and condensation.
4. Solution and precipitation.

Densification results from the grains fusing together and reducing the
porosity, as shown in Figure 4-13. The left side of the figure represents
grains packed together from the forming techniques. The right side shows
that these grains have fused together at the grain boundaries, and the
porosity between the grains has been reduced. This results in a significant
amount of shrinkage as the grains get closer together and undergo a
transfer of material from each other. It also results in a significant in-
crease in strength because the individual grains are bonded together.
The firing cycle depends upon the formulation of the material, the
physical size of the part, and the properties desired. A typical firing
profile is shown in Figure 4-14.
Firing furnaces can be either the batch type or continuous. Batch
furnaces resemble large boxes that are heated up from room temperature
to the maximum sintering temperature for a prescribed soak period and
cooled back to room temperature to remove the parts. Continuous fur-
naces are similar to long tunnels that have various heat zones. Parts that
are transferred through a tunnel furnace are subjected to increasing-tem-
perature zones, followed by a cool-down to room temperature.

FIGURE 4-13. Densification occurring as grains fuse together and reduce porosity.
26 I / Overview of Ceramics

f
SOAK

TEMPERATURE

TIME ..

FIGURE 4-14. Basic ceramic firing cycle.

The oxide ceramics usually are fired in an air atmosphere, which is


oxidizing. The nonoxide compositions require protective or reducing at-
mospheres to prevent oxidation. The ferroelectrics and ferromagnetics
are heat-treated in controlled oxide atmospheres to develop the desired
properties. Composites of metal and ceramics are fired in a reducing
atmosphere such as hydrogen to protect the metal from oxidizing.
5
Forming From Melts

5.1 COOLING CURVES


The cooling curve representing a crystalline material that cools from a
melt is shown in Figure 5-1. As the material starts to cool, it achieves a
point of constant temperature for a period of time. During this "isoth-
erm," both a liquid and a solid phase are present. At equilibrium, the
material cannot be cooled below this constant temperature until all of the
liquid has solidified. Conversely, it cannot be heated above this temper-
ature until all of the solid has melted. A good analogy to this curve is ice
and water. When in equilibrium, ice water is always at a constant tem-
perature (O°C). The mixture will not get warmer until the ice is gone or
cooler until the liquid has solidified.
Heating a solid crystalline material would produce the same curve.

LIQUID & SOLID

TIM~

FIGURE 5-1. Cooling curve for crystalline material.

27
28 I I Overview of Ceramics

The isotherm, or constant temperature, would represent the melting tem-


perature of the crystal. The reason why crystals have specific melting
temperatures is that all of the bonds have the same strength, as crystals
have a repetitive structure. When energy is added in the form of heat, all
of the bonds will break at the same temperature or melting point.
A cooling curve representing a noncrystalline, or "glassy," material
that cools from a melt is shown in Figure 5-2. Here there is no break in
the cooling curve slope; there is no obvious temperature at which the
liquid has changed to a solid. It is obvious from the nature of the material
that a liquid was present at high temperatures and a solid is present at
low temperatures. It is not obvious when the transition occurred. In
effect, the liquid has achieved sufficient viscosity to be, for practical
purposes, rigid.
Glass products are formed during this transition temperature range.
They are shaped in a high temperature viscous state prior to achieving
high rigidity.
When a glass material is heated, the material does not exhibit a precise
melting temperature; it melts over a range of temperature. Unlike crys-
tals, glassy materials do not have a regular arrangement of atoms. Their
random structure results in unequal bond strengths; so all the bonds will
not break at the same energy. When the temperature is increased, the
bonds break over a range of temperature.
A casual review of the differences between crystalline and glassy
states would seem to indicate that glass is a supercooled liquid. In fact,
the classical definition that Morey [4] gave for glass is "continuous with
and analogous to the liquid state but which as a result of having been
cooled from a fused condition too rapidly has obtained so high degree of
viscosity so as to be for all practical purposes-rigid." However, it has

w
a:
:)

~
a:
w
Q.
::E
w
I-

TIME-

FIGURE 5-2. Cooling curve for noncrystalline material.


Forming From Melts 29

10"
>
I-
iii
a
u~
en en 107
-w
>en
Cl-
00
..Je:. 10"
10" MELTING
RANGE
10'
400 600 800 1000 1200 1400
TEMPERATURE °C

FIGURE 5-3. Various conditions of glassy materials.

been shown [5] on cooling curves of temperature versus volume that glass
can be cooled slowly.

5.2 GLASS FORMING METHODS


Glass products are formed in a high temperature viscous state. A plot of
viscosity versus temperature shows the various conditions of glassy ma-
terials (Figure 5-3).
The forming techniques include:

I. Pressing, used to make dinnerware (Figure 5-4).


2. Blowing, used to make bottles (Figure 5-5). The process shown in
Figure 5-5 actually is a double blowing technique whereby a cavity
is developed in the glassy mass, which is then transferred to a
second mold to determine the external shape.

~
FIGURE 5-4.
-;;ENGLASS

Pressing proce,s for dinnerware production.


..
GLASS PLATE

~
30 I / Overview of Ceramics

MOLTEN

OQAM

FIGURE 5-5. Glass blowing process for bottle manufacture.

3. Rolling and drawing methods, used to produce sheets and plates or


fibers (Figure 5-6). Rollers are used to obtain the desired thickness.
Most flat glass is formed by the Pilkington flotation process where
the molten glass is "floated" on molten tin, thus producing very
flat, parallel sheets.

5.3 THERMAL CONDITIONING GLASS


Glass materials have very low strength characteristics [6]. In fact, glass
has an acceptable working strength of 1000 psi. Its strength is limited
primarily in tension, as glass has about 10 times more compression
strength than tensile strength.
To overcome some of the strength limitation, thermal conditioning is
used to strengthen processed glass. Typically, the surfaces are placed in
compression, which effectively makes the glass appear stronger. The
various types of thermal treatments include:

PLATENS

FIGURE 5-6.
r"OL""
Rolling and drawing process for sheets and plates or fibers.
Forming From Melts 31

1. Annealing: the removal of preexisting thermal stresses caused by


rapid cooling of the glass during the forming process. The stresses
can be removed by heating the glass slightly and cooling it relatively
slowly.
2. Tempering: applying compressive surface stresses by rapid quench-
ing (after annealing, which removes uncontrolled stresses). In order
to break a part that is tempered, the compressive stresses must be
exceeded. When a fracture does occur, the breakage is spontaneous
within the glass because of the stressed condition, and it shatters
into very small pieces.
3. Chemical strengthening: producing compressive stresses on the
glass surface by changing the surface chemistry. The surface crys-
tals have a different thermal expansion from that of the glass, thus
producing compressive stresses. The surface layer is thin enough
that it will not affect the transparency of the bulk glass.
4. Devitrification: The word "vitrify" means to convert into glass: a
material that is so "devitrified" is the opposite of glassy, or crystal-
line. Devitrification is a way to develop compressive stresses within
a glassy material by controlled nucleation and crystallization within
the glass. The crystals that develop within the glassy matrix have a
different expansion from that of glass, thus producing compressive
stresses. It is possible to develop very high strength materials by
controlling which phases crystallize, what the ultimate grain size
will be, and the degree of crystallization.

During chemical and thermal treatment, glasses retain their transpar-


ency. However, crystallized glasses become opaque even though single
crystal oxides are transparent. The reason why polycrystalline materials
are not transparent is that light is scattered at the grain boundaries so that
transmission through the material is prevented. Glasses, on the other
hand, do not have the light-inhibiting grain boundaries, and so are trans-
parent.
6
Miscellaneous Forming
Techniques

6.1 COATINGS
Porcelain enamel coatings are glass coatings applied to metallic base
materials. The process involves refusing powdered glass into a continu-
ous layer on metal surfaces. The glass coatings adhere to oxide layers
that develop from the base metal during the firing operation. The coeffi-
cient of thermal expansion of the porcelain enamel is slightly lower than
that of the metal; this ensures that the coating will be in compression at
room temperature.
Glazes are glass coatings applied to ceramic base materials. They are
used to cover the rough texture caused by polycrystalline grains.
Flame plating produces oxide, carbide, and nitride coatings by feeding
powders into a high temperature arc or flame. The material is melted and
then sprayed as molten drops that solidify as they strike the surface. The
coatings are porous, but very hard. They are used primarily as wear-
resistant surfaces.
Vapor deposition is a way to coat surfaces by melting the material and
allowing the vapor to form stable, high-density, impervious coatings.
These coatings are applied in a controlled environmental chamber.
Cathodic sputtering is a means of producing single-crystal film by
using polycrystalline cathodes. The coatings are produced by energizing
the cathode material so that it will discharge onto a surface in a con-
trolled-temperature/atmosphere chamber.

32
Miscellaneous Forming Techniques 33

6.2 SINGLE CRYSTALS


Single crystals can be produced by flame fusion, fused melts, or hydroth-
ermal solutions. The techniques all require isolating a single nucleus,
which will undergo continuous growth when a thermal gradient is main-
tained.
In flame or zone fusion. a powder fed through a flame is impinged on
the surface of a liquid puddle on the growing surface. The high tempera-
ture gradient from the crystal into the liquid puddle restricts the devel-
opment of additional new nuclei.
In a hydrothermal solution produced by an autoclave, large single
crystals can be grown from polycrystalline starting material. A tempera-
ture gradient is maintained that allows the continuous transfer of material
from the starter to the growth crystals.
Large crystals also can be grown by withdrawing a crystal from a melt
at a rate sufficient to maintain crystal growth at the interface. A high
temperature gradient at the point of crystal growth allows the crystal to
grow continuously without forming new crystal orientations.

6.3 MISCELLANEOUS FORMINGS


Hot pressing is a process for densifying ceramic powders by simulta-
neously applying pressure and heat. It is commonly used for refractory
oxides and carbides that do not form liquid phases or have low atomic
mobility at elevated temperatures. The combined temperature and pres-
sure allow high density and small grain size with a resulting high strength.
Fusion casting is a process of melting and then solidifying nonglassy
refractory ceramics. It allows the achievement of very high-density and
extremely high-purity materials. The disadvantage is minimal control of
grain structure and size because of the low thermal conductivity of ce-
ramic materials. The process is used to produce refractory blocks and
abrasives.
Devitrification is the crystallization of articles that were originally pro-
cessed by glass-forming techniques. The type of crystal structure and the
microstructure that can be obtained in crystallized glasses surpass the
structures made possible by conventional ceramics processes. The tem-
perature of spontaneous nucleation is different from the temperature re-
gion of maximum crystal growth. Therefore. by controlling times and
temperatures it is possible to nucleate different crystals, determine crys-
tal size, and obtain a degree of crystallization.
7
Traditional Ceramic Industries

7.1 ABRASIVES
Abrasives are cutting and grinding media used primarily in the glass and
metal industries to shape consumer products. They are marketed in three
general forms:

1. Bonded abrasives such as wheels and discs.


2. Coatings on paper and cloth.
3. Loose-grain abrasives as polishing pastes.

Abrasives can be categorized as to type of material (alumina, carbide,


etc.), grain size (from coarse to fine), porosity (from dense to open), and
type of bond (such as sintered or resin). In general, for removing large
amounts of material, abrasive wheels would have a large grain size and
an open porous structure, whereas precision machining would require
fine grains and a dense structure.
Materials used for abrasives include naturally occurring minerals such
as corundum, gamet, and emery, along with manufactured raw materials
such as fused alumina, carbides, and nitrides.
The requirements for abrasives are hardness, which determines the
abrasive's effectiveness, toughness against mechanical breakdown, and
resistance to the high temperature resulting from friction forces during
grinding.

34
Traditional Ceramic Industries 35

7.2 REFRACTORIES
Refractories are substances that can withstand high temperatures. Like
abrasives, they are basic materials used in various industries that produce
consumer products. The melting and the refinement of metals and glasses
require refractory containers. Any high temperature processing, such as
sintering of ceramics, requires containment of the heat by refractories.
They can be classified according to their temperature and slag resistance
as follows:

1. Low duty-resistance to 1200°C.


2. Medium duty-resistance to 1500°C.
3. High duty-resistance to 1650°C.
4. Super duty-resistance to both temperature and slag.

Refractories must be resistant to temperature under load bearing of


the refractory wall; to corrosive action from metal and glass slag; and to
disintegration from thermal shock during heating and cooling cycles.
Materials used for refractories include naturally occurring minerals
such as the alumina silicates in fireclay and mullite; pure oxides such as
silica, zirconia, and magnesia; and manufactured raw materials such as
carbides, nitrides, and borides, which are all high temperature materials.

7.3 WHITEW ARES


Whitewares are materials that develop a white fired color. They are used
to make a wide variety of items, such as:

I. Domestic products-tile, sanitary ware, dinnerware, and so on.


2. Electrical products-high and low voltage insulators.
3. Industrial products-items with abrasion and chemical resistance.

These products must be relatively inexpensive to manufacture because


they are competing with other materials, and must be of high purity for
cosmetic reasons because they are used by consumers. Whiteware prod-
ucts can be either glazed (have a glass coating) or used with the as-fired
finish. Most people associate ceramics with whiteware products.
All of the whiteware formulations are made from conventional triaxial
compositions consisting of:
• Clay as the forming agent.
• Feldspar as the fluxing agent.
• Silica as the filler.
36 I / Overview of Ceramics

The purpose of the fluxing agent is to reduce the firing temperature,


and the filler provides stability by not reacting throughout the processing.
This triaxial composition has significant advantages because it is not
sensitive to changes in composition, firing temperatures, or forming
method.

7.4 STRUCTURAL CLAY PRODUCTS


Structural clay products are low-cost ceramic products used primarily in
construction applications such as:
• Building bricks.
• Sewer pipe.
• Ceramic tiles.
The requirements for structural clay products are based on competi-
tion with other building materials. Relatively inexpensive raw materials
and efficient material handling methods are necessary. In contrast to
whiteware compositions, the raw materials usually are unrefined clay
deposits such a shales.

7.5 GLASSES
Glasses differ from other ceramic compositions more in the method of
forming than in the resulting physical or chemical characteristics. Glasses
are formed during cooling of high temperature melts, whereas most other
ceramic materials are formed at room temperature from powders that are
densified at high temperatures.
The outstanding property of glass is its transparency. Although all of
the single-crystal oxides are transparent, most ceramics are formed from
sintering powders and are polycrystalline; and polycrystalline materials
are opaque or translucent because light is scattered at the grain bounda-
ries and is not transmitted through the material. Glass, on the other
hand, is homogeneous, does not have grain boundaries, and thus is trans-
parent.
Silica is the basic ingredient for glass. Although it is the least expensive
of all raw materials, other oxides such as sodium oxide (soda) and cal-
cium oxide (lime) are added to the silica as fluxes to reduce the firing
temperatures. Still, production costs for glassware remain economical.
Glasses may be classified according to their general composition:

1. Soda-lime-silica (Na 20 . CaO . Si02): This is the most widely used


composition.
Traditional Ceramic Industries 37

2. Lead-silica (PbO . SiO z): Lead imparts high reflectivity; lead glass
compositions are used to make crystal glassware.
3. Borosilicate (Bz03 . SiO z): Boron is a network former, and maintains
a high-property glass.
4. Flint (SiO z): This makes a high-property glass, but is also high-cost
because of the higher forming temperature required without the
fluxes.

Another way to classify glasses is based on their end use:

1. Optical glass: uses barium flint glasses.


2. Chemical-based glass: uses borosilicates (Pyrex).
3. Windows and bottles: use soda-lime-silica.

7.6 PORCELAIN ENAMELS


Porcelain enamels are glass coatings applied to metallic base materials,
and serve primarily as protective coatings. Porcelain enamel as a ceramic
is hard and rigid; the coatings are wear-resistant and chemically inert
(providing environmental stability), and they serve as electrical and ther-
mal insulators.
Applications for porcelain enamels include:

1. Domestic uses: appliances and utensils.


2. Architectural uses: signs and paneling.
3. Industrial uses: corrosion and wear resistance.

Porcelain enamels are formulated so that they soften and flow at rela-
tively low temperatures to be compatible with metals. They also have
thermal expansion coefficients that are slightly lower than those of metals
to ensure that the coating will be in compression at room temperatures.
Such compression is desirable because glass is considerably stronger in
compression than in tension.
Metals that can be enameled include the low carbon steels, the 300 and
400 series stainless steels, heat-treatable aluminum alloys, and the noble
metals such as copper, gold, and silver. The steels have to be etched,
either chemicaliy or mechanically, to promote adhesion. The aluminum
alloys require a chromate surface treatment that produces a chrome oxide
layer for adhesion. Copper, gold, and silver require only a clean surface
for adhesion to the enamel.
38 I / Overview of Ceramics

7.7 CEMENTS
Cements are hydraulic bonding agents that are mixed with aggregate
stone to form concrete. Cements are made by reacting clay and limestone
together at high temperatures. The resulting powders are dicalcium and
tricalcium silicates, which when mixed with water form a siliceous bond.
When water is added to cement, it initiates an irreversible process; part
of the water forms a permanent bond, and the excess water is used to
form a slurry that can be poured into a form. The excess water is removed
by drying after bonding has occurred.
Concrete has considerably more strength in compression than in ten-
sion. To overcome its low tensile strength, steel reinforcement is added
to the lower portion of the structure, and absorbs tensile force when there
is loading of the top surface of the concrete.
Part II
The Nature of
Ceramic Materials
8
Atomic Structure

8.1 BACKGROUND
The following postulates, made by Bohr [7], are fundamental to an un-
derstanding of atomic structure:

1. Electrons can move in "discrete" energy states around the nucleus


of an atom without radiating energy. These states can be identified
by a set of integers called quantum numbers.
2. Electrons can pass from one energy state to another with either
emission or absorption of energy.

The simplest atomic structure is that of hydrogen, which has one elec-
tron in orbit around a nucleus containing one proton. The electron has a
negative charge ( - ); the proton has a positive charge ( + ) and contributes
mass (m). The atomic structure of hydrogen can be represented as in
Figure 8-1. This atom has an atomic number of 1, which means that it has
--"""1:~----- ELECTRON H

PROTON (+)
"4t---!r NUCLEUS {
NEUTRON (M)

FIGURE 8·1. Hydrogen atom.

41
42 II / The Nature of Ceramic Materials

...---+-PROTONS (+)
1i---+--NEUTRONS (M)

HELIUM

FIGURE 8-2. Helium atom.

one electron, with a negative charge, in orbit around a nucleus that con-
tains one proton, with a positive charge, and a mass of one.
Elements that make up all of matter can be represented by consecutive
integers called atomic numbers. The atomic numbers indicate the number
of electrons in orbit around corresponding numbers of protons. The dif-
ference between the atomic weight and atomic number is the number of
neutrons contained in the nucleus. Thus for helium, which has an atomic
number of 2 and atomic weight of 4, there would be two electrons in orbit
around a nucleus containing two protons and two neutrons (shown in
Figure 8-2).
As the atomic number increases, it is possible to describe each elec-
tron by a set of integers called quantum numbers. As many as four quan-
tum numbers may be necessary to define an electron, as follows:

1. The first quantum number represents the major energy level of the
electrons, designated 1, 2, 3, etc., or the K, L, M shells.
2. The second quantum number represents the subshells for each
level, designated s, p, d, and f.
3. The third or magnetic quantum number represents the orientation
taken by the electron cloud in a magnetic field; s = 1, P = 3, and
d = 5.
4. The fourth quantum number represents the direction of electron
spin for two electrons (the maximum for each orbit) in the same
orbit, which would be opposite in direction and represented by U.

8.2 ELECTRONIC CONFIGURATIONS


Most ceramic materials are made up of oxygen, silicon, and aluminum,
which all have atomic numbers of 14 or less. The atomic numbers (AN)
from 1 (hydrogen) to 14 (silicon) correspond to the electronic configura-
tions shown in Table 8-1. The number of electrons is represented by the
Atomic Structure 43

TABLE 8-1.
AN Atoms (Symbol) Electronic Configuration

I Hydrogen (H) lsi


2 Helium (He) Is'
3 Lithium (Li) Is' 2s 1
4 Beryllium (Be) Is' 2s'
5 Boron (B) Is' 2s' 2pl
6 Carbon (C) Is' 2s' 2p'
7 Nitrogen (N) Is' 2s' 2p'
8 Oxygen (0) Is' 2s' 2p'
9 Flourine (F) Is' 2s' 2p'
10 Neon (Ne) Is' 2s' 2p6
II Sodium (Na) Is' 2s' 2p6 3s 1
12 Magnesium (Mg) Is' 2s' 2p6 3s'
13 Aluminum (AI) Is' 2s' 2p6 3s' 3pl
14 Silicon (Si) Is' 2s' 2p6 3s' 3p'

exponents. The number (1, 2, 3) in front of the letter (s, p) represents the
major energy level for the electrons, which is the first quantum number.
The letters (s and p) represent the subshells for each major energy level,
which is the second quantum number. The s-subshell has only one orbit,
whereas the p-subshell has three orbits that are along the three dimen-
sional axes; these orbits represent the third quantum number. And, fi-
nally, if there are two electrons in the same orbit that must have opposite
spins, which can be represented by arrows pointing in opposite directions
(it), that represents the fourth quantum number.
The atomic number for each atom or element indicates the number of
protons and the number of neutrons in the nucleus, as well as the number
of electrons in orbit around the nucleus. These electrons can be repre-
sented by the electronic configurations just discussed. For example, oxy-
gen, which has an atomic number of 8 and a molecular weight of 16,
would have eight protons, each with a positive charge (+), and eight
neutrons, which have mass in the nucleus. They are surrounded by eight
electrons in orbit around the nucleus. The electronic configuration in-
cludes two electrons in the first major energy level (ls~) and six electrons
in the second major energy level, with two in the s-subshell and four in
the p-subshell (2s~ 2p4).
When a major energy level is filled with the total number of allowable
electrons, the atom is said to have achieved a noble gas which is the most
stable configuration. The first major energy level is completed with an
atomic number of2, helium, and the second with an atomic number of 10,
44 II / The Nature of Ceramic Materials

that of neon. Both helium and neon, noble gases, are very stable and do
not readily form compounds. The electronic configuration of neon is
shown in Figure 8-3.

8.3 IONIZATION
Atoms other than the noble gases, being less stable, tend to more readily
form compounds by undergoing chemical reactions. During reaction, a
rearrangement of outermost shell electrons takes place; always with a
tendency toward achieving filled shell stability of noble gases. When,
because of this electron rearrangement, an imbalance exists between the
positive nucleus charge and the negative electron charge, the species is
said to have become ionized. This ionization (gaining or losing electrons
to achieve the noble gas configuration) may be represented as shown in
Table 8-2.
For example, in order for oxygen to achieve the noble gas configura-
tion of neon, it must gain two electrons; the oxygen ion has a total of 10
electrons but only eight protons in the nucleus. Because it has two more
electrons than protons, the oxygen ion will always have a - 2 charge.
Above neon in atomic number, aluminum has three more electrons than
the noble gas configuration. When it loses these electrons, an aluminum
ion is produced, with 13 protons in the nucleus but only 10 electrons in
orbit. Thus, the aluminum ion will always have a + 3 charge.

NEON

AN-10

10 ELECTRONS (-)

10 PROTONS (+)

10 NEUTRONS (M)

FIGURE 8-3. Neon atom.


Atomic Structure 45

TABLE 8-2.
AN Atom Ion Protons (+) Electrons ( - ) Net charge

8 Oxygen 0-' 8 8 + 2 = 10 -2
9 Fluorine FI-' 9 9 + I 10 -I
10 Neon Neo 10 10 0
II Sodium Na·' II II - I 10 +1
12 Magnesium Mg-' 12 12 - 2 = 10 +2
\3 Aluminum AI-' 13 13 - 3 = 10 +3
14 Silicon Si -" 14 14 - 4 = 10 +4

Negatively charged ions (e.g., oxygen) are called anions, and posi-
tively charged ions (e.g., aluminum and silicon) are called cations.
These ions, with atomic numbers from 8 to 14, all have the same
electronic configuration, but they differ in the number of protons in their
nuclei. These differences are illustrated by comparing their ionic radii.
Although atoms and ions are not "hard spheres," it is convenient to use
the concept of spheres as a measure of the size of ions. Table 8-3 com-
pares ionic radii.
A size comparison of silicon, aluminum, and oxygen is shown in Fig-
ure 8-4. They all have the same number of electrons in orbit around the

2P

,. 2P

SILICON
ALUMINUM
OXYGEN

FIGURE 8-4. Relative sizes of silicon. aluminum. and oxygen ions.


46 II / The Nature of Ceramic Materials

TABLE8-3.
AN Element Valance Ionic radii

8 Oxygen -2 1.32 Angstroms


11 Sodium +1 0.98
12 Magnesium +2 0.78
13 Aluminum +3 0.57
14 Silicon +4 0.38

nucleus, but they differ in the number of protons in the nucleus (which
attracts the electrons). Therefore, the higher the atomic number, the
smaller the ion within this group.
9
Bonding and Crystal
Chemistry Concepts

9.1 TYPES OF BONDING


The initial attraction of ions determines the type of bonding. There are
three primary types and one secondary type of bonds:
I. Metallic, where one electron is shared by many positive ions, as
shown in Figure 9-1. This arrangement is sometimes referred to as
a "free electron gas."
2. Covalent, where there is a sharing of electrons to attain the noble
gas configuration, as shown in Figure 9-2.
3. Ionic, where an electrostatic attraction exists between oppositely
charged ions, as shown in Figure 9-3.
4. Van der Waals, where secondary bonding originates from electrical
dipoles, as represented in Figure 9-4.

9.2 MATERIAL CLASSES


The classes of materials include metals, plastics, and ceramics. They
differ from each other because of the initial bonding, and the properties
associated with the three different classes are related to the bonding.
Although many compounds are combinations of different types of bond-
ing, it is convenient to consider primary bonding and its effects on prop-
erties:
I. Metals have ions bonded by a gas of electrons that are free to move
and will conduct electricity. With this type of bonding, metals are
relatively soft and have low melting points.
47
48 II / The Nature of Ceramic Materials

FIGURE 9-1. Metallic bonding.

FIGURE 9-2. Covalent bonding.


00

FIGURE 9-3. Ionic bonding.

FIGURE 9-4.
00
Van der Waals bonding.

2. Plastics have ions that are primarily covalent-bonded. Their elec-


tron "sharing" prevents the electrons from moving; therefore, plas-
tics are nonconductors, or insulators.
3. Ceramics have the strongest bonds, which are ionic. Because there
are no free electrons present, these materials are electrical insula-
tors. Ionic materials are characterized by having high melting tem-
peratures and being very hard or rigid. Exceptions include the
nonoxide compounds such as the carbides, borides, and nitrides;
they are primarily covalent, double-bonded for strength.

9.3 PAULING'S RULES


An understanding of the makeup of the silicates, which are the largest
group of ceramic materials, is based on Pauling's rules [7], which were
Bonding and Crystal Chemistry Concepts 49

derived by using the cations as the reference point. Pauling developed


the following rules to explain the crystal chemistry of silicates:

l. A coordinated polyhedron of anions is formed about each cation;


the cation-anion distance is determined by the radius sum, and the
coordination number of the cation is determined by the radius ratio.
2. In a stable coordinated structure, the total strength of the valence
bonds, which reach an anion from all neighboring cations, is equal
to the charge of the anion.
3. The existence of edges, and particularly of faces, common to two
anion polyhedra in a coordinated structure decreases its stability.
4. In a crystal containing different cations, those of high valence and
small coordination numbers tend not to share polyhedron elements
with each other.
5. The number of essentially different constituents in a crystal tends
to be small.

In the following discussions of the crystal structures of the silicates,


these rules will be referred to often.

9.4 COORDINATION NUMBERS


The number of anions surrounding a cation (Pauling's first rule) depends
on the radius ratio of the cation to the anion (rJr,,). The coordination
numbers (eN) are strictly geometric considerations. Examples of the
radius ratios for threefold and fourfold coordination are shown with the
corresponding calculations in Figures 9-5 and 9-6.

~=COS300= ..J3
Ra+Rc 2
2 Ra = v'3(Ra + Rc)
Ra Rc 2 2v'3
Ra + Ra =ra=T
Rc = 2v'3 -1 =1.155-1 =0.155
Ra 3

FIGURE 9·5. Limits for threefold coordination.


50 II / The Nature of Ceramic Materials

Rc + Ra =COS 450 = -J2


2 Ra 2
Rc + 1 =..J2
Ra
Rc = 1.414-1.000=0.414
Ra'

FIGURE 9-6. Limits for fourfold coordination.

FIGURE 9-7. Tetrahedron configuration.

l./-~-ALUMINUM
OR
MAGNESIUM

FIGURE 9-8. Octahedron configuration.


Bonding and Crystal Chemistry Concepts 51

TABLE 9-1.
Radius ratio CN Configuration

0.000-0.155 2 Linear
0.155-0.225 3 Equilateral triangle
0.225-0.414 4 Tetrahedron
0.414-0.732 6 Octahedron
0.732-1.000 8 Body centered cubic
1.000 12 Face centered cubic

The radius ratio ranges, with the corresponding coordination numbers


and geometric configurations, are listed in Table 9-1.
The coordination numbers of the cations of primary interest are those
of silicon, whose CN is 4 (tetrahedron), aluminum, whose CN is 6 (octa-

SILICON (+4)

MAGNESIUM (+2)

ALUMINUM (+3)

FIGURE 9-9. Bond strength representation for silicon. magnesium, and aluminum.
52 II / The Nature of Ceramic Materials

hedron), and magnesium, whose eN is also 6, as shown in Figures 9-7


and 9-8.

9.5 BOND STRENGTH


The bond strength of the cation is equal to the valence divided by the
coordination number. Thus, silicon has a valence of 4 and is in tetrahed-
ron coordination so that each bond from the silicon to oxygen has a
strength of 1; aluminum has a valence of 3 and is surrounded by six anions
so that each bond has a strength of 1/2 ; and magnesium has a valence of 2
and is also surrounded by six anions so that each bond has a strength of
1/3 •

The bond strength can be represented in planar view, as shown in


Figure 9-9.
10
Silicate Structures

10.1 BASIS
The silicate structures are based on the cation silicon, which has a coor-
dination number of 4 so that each silicon ion is surrounded by a tetrahed-
ron of four oxygen ions (Pauling's first rule). This is represented in both
perspective view and cutaway view in Figure 10-1.
Because silicon has a valence of 4, it distributes this charge equally to
the four oxygen ions that are at the corners ofthe tetrahedron. Therefore,
each silicon to oxygen bond has a strength of 1. Because oxygen has a
valence of 2, each oxygen has half of its valence satisfied by the silicon.

FIGURE 10-1. Silicon tetrahedron.

53
54 II / The Nature of Ceramic Materials

SI _1 O..L SI

~AI
S I1- 0 ~
AI
.,.. Mg
SI _1 0 ~Mg
~
........... Mg
FIGURE 10-2. Bonds satisfying oxygen ions.

The remaining valence of the oxygen can be satisfied by either sharing


other silicon ions or utilizing other metal ions (Pauling's second rule).
The oxygen bonded to one silicon would require two aluminum ions, as
the bond strength was previously shown to be Y2. The oxygen would
require three magnesium cations having a bond strength of Y3. A sche-
matic rendering of this bonding is shown in Figure 10-2.

10.2 TYPES OF SILICATES


The types of silicates that may occur can be represented by the number
of shared oxygens, there being oxygens for every silicon tetrahedron.
The different types of structures that may exist for different numbers of
shared oxygens are given in Table 10-1, along with examples of minerals
exhibiting those structures.
These basic structures can be represented as shown in Figures 10-3
through 10-7. It should be noted that the silicon tetrahedrons share only
comers and not edges or faces (Pauling's third rule),
The minerals that have pronounced structures, such as the single and

TABLE 10.1.
Shared oxygen Structure Examples

o Orthosilicate Mg2 Si04


I Pyrosilicate Ca2 MgSi 20 7
2 Metasilicates
• Single chain MgSiO,
• Three-member ring BaTi(Si03)3
• Six-member ring Be,AI2(Si0 3).
2 and 3 Amphibole Ca2Mg,Si.O,,( 0 H)2
3 Disilicate (sheet) Clay, talc, mica
4 Network Quartz, feldspar
Silicate Structures 55

FIGURE 10-3. Orthosilicate.

I<'I(;URE 10-4. Pyrosilicate.

FIGURE 10-5. Single chain.

double chains, as well as the sheet structures, exhibit these shapes. Ex-
amples are the needlelike fibers of asbestos and the platelike shapes of
clay and mica.

10.3 LAYER MINERALS


The layer minerals may be considered to be made up of disilicate sheets
combined with either brucite or gibbsite octahedral sheets, shown in
56 II / The Nature of Ceramic Materials

FIGURE 10-6. Amphilbole.

FIGURE 10-7. Disilicate and network.

expanded profile sketches in Figures 10-8, 10-9, and 10-10. It is important


to note that this is not how the minerals are formed in nature; it is merely
a simple way of representing their structures.
The sketches show that both magnesium and aluminum are in octahed-
ral coordination, with six bonds going to the hydroxide ions (Pauling's
first rule). The bond strength from magnesium is Ij, so that each hydrox-
ide anion is bonded to three magnesium cations (Pauling's second rule).
For aluminum the bond strength is '12 so that each hydroxide is bonded
Silicate Structures 57

FIGURE 10-8. Brucite, Mg(OH),.

FIGURE 10-9. Gibbsite. AI(OHk

FIGURE 10-10. Disilicate. Si,O,.

to two aluminum ions. The silicon cation is in tetrahedral coordination,


with four bonds going to the oxygen ions. The oxygens that bonded to
two silicons are satisfied. The oxygens bonded to one silicon can be
satisfied by sharing either three magnesium or two aluminum ions.
The sharing of the partially satisfied oxygen anions from the disilicate
sheet with the magnesium and aluminum from the octahedral sheets pro-
duces the layer minerals. The end members for the two layers (disilicate
and octahedral) are kaolinite (Figure 10-11) and a magnesium version,
which is crysotile.
Note that in Figure 10-11 the top layer of oxygens and the bottom layer
of hydroxides are completely satisfied. This crystal cannot grow in the
vertical direction; it is obvious that it will produce a platelike structure.
There are only five layers of ions in a distance of only 7 Angstroms,
which is on the atomic scale. This structure accounts for the very small
size of the clay minerals.
There also are three-layer minerals that can be considered to be made
58 II / The Nature of Ceramic Materials

OH-l

OCTAHEDRAL

OH-1/0-2

DISILICATE

FIGURE 10-11. Kaolinite. AI,Si,O,(OH),.

from two disilicate sheets and a central octahedral sheet. The end mem-
bers are talc, shown in Figure 10-12, and the aluminum octahedral pyro-
phyllite.
Again, it should be noted (in Figure 10-12) that the top and bottom
layers of oxygen ions are completely satisfied, and the crystal cannot
grow in the vertical direction. The three-layer minerals are about 10
Angstroms thick.
Isomorphs are materials that have the same structure ("morph" refers
to structure, and the prefix "iso" means "the same"). Isomorphic sub-
stitution into the end members yields a wide range of layer minerals, with
notable differences in physical properties, depending on the amount and
the location of the substitution. The most extensive isomorphic substitu-
tion occurs in the three-layer minerals. The resulting minerals are:

1. Micas, where aluminum substitutes for silicon (1 in 4), and potas-


sium satisfies the charges on the interlayer. Large sheets are pro-
duced with potassium holding the sheets together.

I 0.2

I
DIS ILlCATE SI....

I
OCTAHEDRAL

DISILICATE
0.2

FIGURE 10-12. Talc. Mg,Si,O\O(OH),.


Silicate Structures 59

2. Illite clays, where aluminum substitutes for silicon (l in 6), and


there is less attraction between layers and a smaller size than in
micas because substitution is less regular. Thus a clay material is
produced.
3. Montmorillonite clays, where substitution is in an octahedral sheet,
and sodium on the interlayer becomes hydrated, giving an expanded
lattice characteristic.

A comparison of the properties of the various layer minerals shows


why the clay minerals have very small particle sizes; there is a mismatch
between the octahedral and disilicate sheets. along with a very small
extension (7-10 A) in thickness. Further comparisons show that the end
members of the three-layer minerals pyrophyllite and talc have larger
platelets than the clay minerals because of the symmetry of the two
disilicate sheets; the individual layers only have van der Waals bonding,
and therefore easily slide over each other, giving rise to a lubrication
effect. The micas have large platelets that are held together by the inter-
layer potassium. but can be fairly easily separated. Illites and montmoril-
lites have small sizes because of their less regular substitution, and
therefore have the physical characteristics of clay.
11
Structure of Glass

11.1 CRYSTALLINE VERSUS GLASSY


Polymorphs are materials that have many ("poly") structures
("morphs"), but the same chemistry. An example of polymorphs of silica
is shown in Figure 11-1. Both structures are repetitive, and both are made
from silicon tetrahedrons. They differ, however in their pattern or crystal
structure.
Another example of a polymorph of silica is silica glass, shown in
Figure 11-2. This structure differs from those in Figure 11-1 in that this
pattern is not repetitive; there is no unit cell that reproduces itself like a
crystalline pattern.
This glassy structure has only short-range order ofthe silicon tetrahed-
rons. Because of the lack of a regular arrangement, and therefore equal

o OXYGEN
• SILICON

FIGURE 11-1. Crystalline silica polymorph.


60
Structure of Glass 61

o OXYGEN
• SILICON

FIGURE 11-2. Glassy silica.

distances, the silicon to oxygen bonds have unequal bond strengths. In a


crystalline pattern, the distances are the same and thus the bond strengths
are the same. When energy is transferred to the crystal material by heat,
all of the bonds will break at the same energy or temperature. That is
why crystalline materials have specific melting points. Glass, on the other
hand, does not have a specific melting temperature; it has a melting range
(see Chapter 5 and the cooling curves shown in Figure 5-1 and 5-2 for
crystalline and noncrystalline materials).
Glass is transparent because it is homogeneous and does not have
grain boundaries. Most of the oxide ceramics also are transparent, but
they are formed by sintering powders together. These polycrystalline
materials have grain boundaries that scatter the light and make the ma-
terials appear to be opaque.

11.2 GLASS FORMERS


Most materials cannot exist in the glassy state. The conditions that gov-
ern glass formation, developed by Zachariasen [21], are as follows:

1. Anions cannot be linked to more than two glass-forming cations.


2. The coordination of the cation must be small.
3. Anion polyhedra must share corners, not edges or faces.
62 II / The Nature of Ceramic Materials

4. At least three corners must be shared in order to build a three-


dimensional network.

If anions were linked to more than two cations, the structure would be
too rigid. Small coordination numbers ensure proper linkage. Corners are
shared so that the small cations with high charges can maintain maximum
separation.
The most common glass forming cation is silicon; more than 95 percent
of all glasses have silicon as their glass former. Other cations that can
form glasses are boron, arsenic, antimony, germanium, and phosphorus.

11.3 GLASS MODIFIERS


Although some oxides do not exist in the vitreous or glassy state, they
may be added to glass mixes as modifiers. These oxides have the ability
to modify the properties of the glass by changing the ratio of total oxygen
ions to network-forming cations. As a result, the glass modifiers open up
the three-dimensional framework structure, increasing the fluidity and
thus decreasing the working temperatures. Examples of glass modifiers
are soda, lime, barium oxide, lead oxide, and so on. The effect the mod-
ifiers have on the structure is shown in Figure 11-3.
Note in Figure 11-3 that some silicons are bonded to only one oxygen,
an arrangement that opens up the structure and decreases its melting
point. This is the primary reason why modifiers are added to the silica
glass. The modified glasses are softer and weaker than the non modified
glasses, but they still have transparency, which is one of the major rea-
sons for using glass products. The melting point decreases by as much as
700°C with these modifiers.
High silica glasses can be made by leaching the soda and the lime and
reheating to increase the density of the porous structure. Photosensitive
glasses are made by adding copper oxide as the network modifier and
exposing the glass to radiation, which converts the monovalent copper
ion to a divalent copper ion and metallic copper. The reaction would be
as follows:
radiation C
2 C u+~ u+ 2 + Cuo
Structure of Glass 63

• SODIUM

o OXYGEN

• SILICON

FIGURE 11-3. Soda (Na,O) glass.

11.4 STRUCTURE AND COMPOSITION


VERSUS PROPERTIES
The properties of glasses can be related to the structure of basic silica
glass and the effect of modifiers on the structure. The thermal expansion
of vitreous silica is less than that of crystalline silica. This is so because
some of the ions are closer together, and others are farther apart in the
glassy state; during heating both expansion and contraction occur. The
net effect of the thermal expansion is very small. Consequently, fused
silica, sometimes referred to as fused quartz, is used where thermal shock
or low thermal expansion is required.
The addition of the network modifiers results in an increase in thermal
expansion, a lowering of the viscosity, and thus a lowering of the melting
range, which is the primary reason for the addition. There also is a cor-
responding decrease in mechanical properties because the structure is
more open or weaker, along with variations in the index of refraction and
the density, depending on the cation used to modify the structure.
Although silica is relatively inexpensive, soda and lime often are added
64 II / The Nature of Ceramic Materials

to it to reduce its melting range, and thus allow glass processing at lower
and more economical temperatures. The most common glass products
are windows and containers made from 70 percent silica and 30 percent
soda and lime. Boron is a network former, and when added to silica glass,
it produces a high-property glass that can be used in more demanding
applications such as chemical ware.
12
Oxide Crystal
Structures

12.1 BASIS
In Chapter 10 it was shown that silicate structures use the cation (silicon)
as the reference point and develop anion (oxygen) polyhedrons around
the cation. Oxide structures, excluding silica, can be represented by using
the anion as the reference position. The simpler oxide structures can be
considered as close packed spheres of oxygen and their interstitial sites,
which can be occupied by cations. These close packed systems include
the body-centered cubic (BCC), face-centered cubic (FCC), and hexago-
nal close packed (HCP). The FCC and HCP have the same packing
arrangement, as shown in Figure 12-1. Note the hexagon obtained by
drawing lines from the center of the neighboring anions.

FIGURE 12-1. Close packed structure of anions (oxygen).

65
66 II / The Nature of Ceramic Materials

LAYER 3

LAYER 2

LAYER 1

(A) (8)

FIGURE 12-2. Side view of layers of close packed spheres.

The FCC and HCP differ in the stacking sequence. The FCC has an
AB sequence, such as ABABABAB ... etc.; every other plane of atoms
is in the same reference position. The HCP has an ABC sequence, such
as ABCABCABC ... etc.; every third plane of atoms is in the same
reference position. This staggered package arrangement can be observed
in a side view of the layers of close packed spheres, as shown in Figure
12-2.
It is evident that between the layers there are "voids," perhaps better
described as interstitial sites. There are two types: One with two oxygens
on layer 1 and one oxygen in layer 2 (A), and the other with one oxygen
from layer 1 and two oxygens in layer 2 (B). These same type sites would
be between layers 2 and 3, etc. A top view of two layers is shown in
Figure 12-3, where the clear circles are on layer I and the dark circles
are on layer 2. Observation of this view reveals that three types of inter-
stitial sites would be between these two layers. There are fourfold inter-
stitial sites made up of three clear circles on layer 1 and one dark circle
on layer 2; there are fourfold interstitial sites made up of one clear circle

Layer 1
Layer 2 ---til]

FIGURE 12-3. Top view of two layers of close packed oxygens.


Oxide Crystal Structures 67

on layer 1 and three dark circles on layer 2; and there are sixfold
sites made up of three clear circles on layer 1 and three dark circles on
layer 2.

12.2 AmXn COMPOUNDS


As shown in the discussion of crystal chemistry concepts in Chapter 9,
magnesium and aluminum both occur in octahedral coordination. In a
close packed system the magnesium ions would occupy one-third of the
sixfold sites, whereas aluminum would occupy two-thirds of the sixfold
sites.
The carbides, borides, and nitrides also occur as face-centered cubic
(FCC) and hexagonal closed packed (HCP) systems, but with covalent
bonding (sharing of electrons) evident instead of ionic bonding.

12.3 ABmXn COMPOUNDS


The compound MgAI 2 0 4 , magnesium aluminum oxide, has a normal spi-
nel type structure. In this spinel structure, the oxygen ions form the face-
centered cubic structure; the divalent magnesium ions occupy the four-
fold interstitial sites; and the trivalent aluminum ions occupy the sixfold
interstitial sites.
The compound Fe 30 4 (magnetite) is composed of ferrous ion (Fe+ 2),
which is the divalent iron ion, and ferric ion (Fe+ 3), which is the trivalent
iron ion. These ions form FeO· Fe 20 3 , which is simplified to Fe 30 4 • This
results in an inverse spinel structure where, again, the oxygens ions form
a face-centered cubic structure, the divalent cations occupy sixfold sites,
and the trivalent cations are equally divided between the fourfold tetra-
hedral and sixfold octahedral sites (eight sided polyhedrons with six cor-
ners). Isomorphic substitution occurs with the divalent cations, affecting
the magnetic characteristics of these ferrites.

} - - - - - - - { }+--BARIUM

~+---OXYGEN

'---:~--TITANIUM

FIGURE 12·4. BaTiO, simple cubic structure.


68 II / The Nature of Ceramic Materials

Barium titanate (BaTi03) occurs as a simple cubic structure, shown


Figure 12-4. The oxygen ions are at the faces ofthe cube, the barium ions
are at the comers, and the titanium ions are at the center of the cube and
slightly displaced below the Curie temperature that would produce a
tetragonal structure instead of a cubic structure. This displacement pro-
duces a change in dimension and a resulting dipole with electric charges.
Part III
Characterization of
Ceramic Materials
13
Analytical Techniques

13.1 INTRODUCTION
This chapter presents an overview of analytical techniques that can be
used to investigate ceramics or other materials. It is not intended to give
a detailed description of each of the techniques although an effort will be
made to explain how each method works and what type of information is
revealed by the specific techniques [8].
As will be shown, each of the analytical techniques gives some data
about the material analyzed. In attempts to characterize materials, com-
binations of the techniques usually are employed.
In general, microscopy is concerned with surface, whereas X-ray
methods pertain to composition. Variations of these techniques produce
different information or more exacting analyses.

13.2 MICROSCOPY
Polarizing Microscope
The polarizing or light microscope is used to observe the effects of
light transmission through transparent samples. A sketch of the mic-
roscope parts and the sample with the light source is shown in Figure
13-1.
The polarizing microscope utilizes the fact that the velocity of light in
a medium is slower than its velocity in a vacuum. This velocity varies for
media of different density. When light enters a medium from air, it is
refracted by the change in velocity, as shown in Figure 13-2.
71
r:l
72 III / Characterization of Ceramic Materials

EYE PIECE

} MICROSCOPE
L!JANAL YZER

.......~-r--"!""""~ISAMPLE
"/

\ }LIGHT SOURCE

FIGURE 13-1. Polarizing microscope technique.

The ratio of the velocity of light in a vacuum to the velocity of light in


a medium is referred to as the index of refraction for that medium. Be-
cause different materials have different densities, they also have differ-
ences in their index of refraction. The index of refraction can be
measured by immersing a material in various oil media that have a wide
range of index of refraction values. This index can be used to identify the
material.
In addition to the index of refraction, other effects of light transmission
can be observed. Some crystals are isotropic, which means "the same
path," with the speed of light the same in all directions. There are also
anisotropic crystals, which means "not the same path," in which light
travels at different speed in different crystallographic directions. If the
difference is very significant, it can be used to distinguish between mate-
rials for identification purposes.
The polarizing microscope is useful for characterizing trace materials.
Observations are made on the actual materials, and it is possible to distin-
guish small amounts present on the surface. Most other analytical tech-
niques measure the trace material as a proportion of the total quantity of
material.

AIRr-----~--~----~------__4

MEDIA I--------\r----+------\---------I

AIR 1-------~--...Jo",----~-------1

FIGURE 13-2. Refracted light.


Analytical Techniques 73

Metallograph
A metallograph is used to observe opaque samples. As the name implies,
this technique is used mostly for metals. The metallograph uses a light
source to reflect light off the surface and into a viewer, as shown in Figure
13-3. The light is reflected because of the opaque material, as shown in
Figure 13-4.
The depth of field depends on the magnification. Also, samples usually
are ground and polished to enhance viewing at high magnification. The
metallograph is useful for observing the size and shape of grains and the
phase distribution. The grain outlines usually are highlighted by etching
the grain boundaries.
An example of a high alumina ceramic metallograph is shown in Figure
13-5. The alumina grains are shown as light particles. The glassy phase is
the dark-colored area in between the alumina grains, and the porosity is
shown as the large dark areas.

Electron Microscope
The electron microscope is used to observe surfaces at high magnifica-
tions. The surface topography is obtained by making thin organic replicas

LIGHT SOURCE ~_ E3VIEWER


I'

~ __________~SAMPLE

FIGURE 13-3. Metallograph technique.

OPAQUE
FIGURE 13-4. Reflected light.
74 III / Characterization of Ceramic Materials

FIGURE 13-5. Ninety percent alumina cross section: 480 x magnification .

of the surface, as shown in Figure 13-6. High energy electrons pass


through these replicas and are displayed on a fluorescent screen, as
shown in Figure 13-7.
Contrast is obtained because of differences in thickness of the replicas,
which are caused by the surface roughness. A typical photomicrograph
for a polycrystalline material is shown in Figure 13-8. Smooth surfaces
would show very little difference in contrast. Glass, for example, is
shown in Figure 13-9.
The scanning electron microscope (SEM) bombards actual surfaces
with electrons, and the results are observed directly on a viewer screen,
as shown in Figure 13- 10. Advantages associated with this technique are
as follows: (I) very high magnification is obtained with a large depth of
field, (2) little or no sample preparation is required, and (3) the method is
nondestructive.
The transmission electron microscope (TEM) uses electrons to pass
through thin sections, as shown in Figure 13-11. It can be used to observe
grain boundaries at very high magnifications, as shown in Figure 13-12.

FIGURE 13-6.
=
CONTRAST IN THICKNESS
Surface replica showing differences in thickness.
Analytical Techniques 75

- - - - _ SCREEN

r- . "'1 SAMPLE

~ECTRONS
FIGURE 13-7. Electron micrm,copy schematic.

FIGURE 13-11. Photomicrograph of alumina polycrystalline surface at 2000 x .

The TEM can also be used for electron diffraction (crystal structure).
However, use of this application has been limited because of the tedious
effort involved in preparing the thin (100 nm) sections.

13.3 X-RAY METHODS


X-Ray Transmission
X-ray transmission or radiography is used to investigate internal struc-
ture. The technique is similar to taking medical X rays in that contrast is
obtained because of differences in densities. A schematic of the method
is shown in Figure 13-13. X-ray radiography is useful for observing inter-
nal defects such as cracks. voids. and density variations. It also has the
advantage of being nondestructive.
76 III / Characterization of Ceramic Materials

FIGURE 13·9. Photomicrograph of a glassy surface.

ELECTRONS VIEWER

SAMPLE

FIGURE 13·10. Schematic of SEM .

ELECTRONS - ••----+-----11 VIEWER

THIN SECTION
FIGURE 13·11. Schematic ofTEM.

X.Ray Diffraction
X-ray diffraction is used to identify crystal structure by measuring the
differences between planes within crystals. It is based on Bragg's law of
diffraction, which states that an X ray will be diffracted from planes
within a crystal if the wavelength of the X ray is equal to twice the spacing
Analytical Techniques 77

IJ{

FIGURE 13-12. TEM of alumina grains at 50.000 x magnification.

X-RAY
SOURCE

,..:- ... " ,


FILM - ..
"
~
.......
,....
DENSITY
D
VOID

FIGURE 13-13. Schematic of X-ray transmission.

between the planes (d) times the sine of the angle where diffraction oc-
curs. A representation of the method is shown in Figure \3-14.
The angles of reflection of a crystal depend only on the spacing of
planes. Spacings, in turn. depend only on the dimensions of the lattice,
not on the arrangement of atoms. The spacings are unrelated to the chem-
ical composition. The intensity of the reflection depends on the arrange-
ment of atoms within the crystal. Patterns of a material can be used like
a fingerprint to distinguish it from other crystals and thus identify the
material.
The methods used to obtain diffraction patterns are shown in Figures
13-15 and 13-16. The lines in Figure \3-15 represent the various angles (8)
78 III / Characterization of Ceramic Materials

X-RAYS

FIGURE 13-14. Bragg's diffraction equation.

FILM

PRIMARY
BEAM
--
X-RAY
TUBE CAMERA

FIGURE 13-15. X-ray diffraction by camera technique.

~I

RECORDER
X-RAY SPECIMEN
TUBE

FIGURE 13-16. X-ray diffractometry.

where diffraction occurred. Because the X-ray tube gives a constant


wavelength (A), the d-values can be calculated from Bragg's equation.
The peaks on the strip film chart (Figure 13-16) occur at measured angles
(8) from which, again using a constant wavelength (A) for a given X-ray
tube, the d-values can be calculated from Bragg's equation. The d-spac-
ings are unique to the crystal structure and can be used to identify
the crystalline material. Noncrystalline materials such as glass do not
Analytical Techniques 79

exhibit a diffraction pattern because of the lack of repetition within the


structure.

Fluorescence
X-ray fluorescence or spectroscopy is used to analyze the elements. Pri-
mary X rays are directed toward samples, removing electrons from the
outer shells. These vacancies are filled with electrons from higher energy
shells with the emission of a quantum (specific amount) of energy. This
energy produces secondary X rays that are analyzed in a crystal with a
fixed d-spacing. Therefore, in Bragg's equation the plane spacing (d) is
that of the analyzing crystal. the angle is measured, and the wavelength
is calculated. The emitted wavelength is characteristic for each element,
so the elements can be analyzed. A schematic is shown in Figure 13-17.
Some variations of this basic technique utilize the auger and the elec-
tron microprobe. The auger uses a low energy source, which has a small
depth of penetration and is used for surface analysis. The electron micro-
probe uses an electron source to focus the primary beam at a small size
(one micron). Its schematic is shown in Figure 13-18.
Surface analysis uses lower energy sources than those described
above, so that the interaction with the electronic structure is primarily at
the surfaces. These techniques include:

1'bMM1

RECORDER
ANALYZING
CRYSTAL

FIGURE 13-17. Schematic for X-ray fluorescence.

SPECIMEN

COUNTER
ELECTRON
SOURCE ANALYZING
CRYSTAL

FIGURE 13-18. Electron microprobe ,chematic.


80 III/Characterization of Ceramic Materials

• SIMS-secondary ion mass spectroscopy


• AES-auger electron spectroscopy
• ESCA-electron spectroscopy for chemical analysis
• RBS-Rutherford backscattering spectroscopy
• LIMS-Iaser ionization mass spectrometry

13.4 SURFACE MEASUREMENTS


Surface finish measurements are made with a proficorder, which traces
over the surfaces with a small stylus. Plots of the peaks, valleys, and
centerline averages (CLA) can be made. Surface area determinations are
made by gas adsorption methods. The amount of gas adsorbed is propor-
tional to the surface area.
14
Properties and Requirements
of Ceramic Materials

14.1 INTRODUCTION
The properties of a material are important because they dictate its ulti-
mate usage. Because glasses, for example, are transparent, they are used
primarily for windows and bottles where it is essential to see through the
material. Ceramics, which are well known for their hardness and rigidity.
often are used as abrasives. Other applications take advantage of a ce-
ramic material's electrical and thermal insulation characteristics [9].
In addition to their properties, the basic requirements in using ceramic
materials are dimensional, surface, and strength requirements. Dimen-
sions are important because most ceramic processing involves shrinkage
during thermal treatment; the reproducibility of dimensions or tolerances
can affect the use of the material. Surfaces are important both for contact
applications and when further processing, such as metallization, will be
performed on the part; and strength is important in applications where
the ceramic material is stressed. (Strength is discussed in more detail in
Chapter 16.)

14.2 PROPERTIES
Electrical Properties
Ceramics are commonly used as a base for electronic circuits because
they are dielectric materials. A dielectric or an insulator is a material of
such low electrical conductivity that the flow of current through it can be
neglected. The classes of dielectric materials include:
81
82 III / Characterization of Ceramic Materials

• Ceramics
• Plastics (polymers)
• Liquids
• Gases
Only the first two groups can be used to construct shapes.
There are four important characteristics of dielectrics: resistivity, di-
electric strength, dielectric constant, and the dielectric loss factor.
The resistivity of a material, which is a measure of resistance to cur-
rent flow, is the reciprocal of its conductivity. A comparison of resistivity
values for the different classes of materials is as follows:
• Metals-less than 10- 6 ohm/cm
• Plastics-greater than 10Ic ohm/cm
• Ceramics-greater than IO lc ohm/cm
Because metals are conductors, they have very low resistivities. Plastics
and ceramics are comparable in their resistance to current flow.
The dielectric strength is the maximum voltage gradient that a material
can maintain between electrodes. Ceramics and plastics are comparable
in that their dielectric strength ranges from 50 to 380 volts/mil.
The minimum charge that can be maintained within a material is re-
ferred to as the dielectric constant. Generally this value for ceramics is
relatively small (between 4 and 10). However, there is a group of ceramic
materials, namely the titanates, that have dielectric constants between
100 and 1000. These titanates are used as current storage devices or
capacitors, and the current storage capability is enhanced by using mul-
tilayer structures.
The dielectric loss factor is a measure of the efficiency of the dielectric.
Losses occur from absorption and conduction of moisture. Ceramics, for
the most part, have relatively low (less than 0.002 megacycle/second)
loss factors.

Thermal Properties
The greatest advantages of using ceramics are related to their thermal
properties:
• Thermal resistance. Ceramics are refractory materials and can with-
stand operation at elevated temperatures. For the most part, they
maintain their strength characteristics at higher temperatures.
• Thermal expansion, or the amount that a material expands per in-
crease in temperature. Expansion is important for two reasons:
(1) thermal shock requires low expansion; and (2) when two differ-
ent materials are bonded together, expansion differences can cause
Properties and Requirements of Ceramic Materials 83

considerable stress at the interface. Ceramic materials with rela-


tively high expansions (10 x 10- 6 in'/in./°C) are used to make
ceramic-to-metal seals with steel, whereas materials with relative-
ly low expansion (2 x 10- 6 in'/in./°C) are used for thermal shock
applications.
• Thermal condllctivity, or the amount of heat transfer in calories
through a material of unit thickness per unit area per time in seconds
and per degree centigrade. Ceramic materials. such as beryllium
oxide and aluminum nitride. that have high thermal conductivities
can be used to dissipate heat by transferring it through the material.
Ceramic materials with low thermal conductivities are used as bar-
riers to heat flow.

Mechanical Properties
Ceramics are high-strength materials compared to plastics, but they have
the disadvantage that they fail with a brittle fracture. Comparisons of
stress versus strain for brittle fracture and ductile fracture are shown in
Figure 14-1.
Consider the following mechanical properties of ceramics:
• Modulus of elasticity, which gives a measure of the rigidity of a
material. Ceramics have the highest modulus (50,000,000 psi) and
thus are the most rigid materials.
• Compressive strength. Ceramics exhibit very high compressive
strengths, in excess of 300,000 psi. They very seldom break under
compressive loading, but usually fail from shear or tensile forces.

BRITTLE
z
C(
II:
l-
(/)

STRESS

FIGURE 14-1. Brittle and ductile fracture comparisons.


84 III/Characterization of Ceramic Materials

• Tensile strength. The theoretical tensile strength of a material is


equal to one-tenth its modulus of elasticity. For ceramics having
moduli of 50 million, the tensile strength should be 5 million using
polycrystalline alumina as an example. The actual or measured ten-
sile strength of alumina is about 50,000 psi, which is two orders of
magnitude lower than the theoretical value. This discrepancy is due
to imperfections in the polycrystalline material.

Chemical Properties
Ceramic materials are inert to most chemicals with the exception of hy-
drofluoric acid and the molten alkalies. When fired to high densities, most
ceramic materials are gas-tight. Ceramics can be used to make hermetic
seals in combinations with glass and metals.

14.3 REQUIREMENTS
Dimensional Tolerancing
1. Cartesian coordinates. One way of tolerancing the displacement of
a feature from the reference or basic dimension is to use Cartesian
coordinates (Figure 14-2) for an allowable X-Y displacement. The
center of the feature can vary within the rectangle. If X = Y, then
the boundary would be a square. The worst-case tolerance would
occur on the diagonals, where the displacement could be XV2 (X
times the square root of 2).
2. Radial coordinates. Another way of tolerancing the displacement
from the reference or basic dimension uses radial coordinates. In

+y

-y

-x
FIGURE 14-2. Cartesian coordinates for x-v displacements.
Properties and Requirements of Ceramic Materials 85

the example of Figure 14-2, the center of the feature can vary within a
circle of radius r, as shown in Figure 14-3. When the diameter is the
same as the side of the square, that is, X = r, then the circle is inscribed
within the square, and the worst case would be X, not XY2.

Surfaces
Surface imperfections of ceramics are important both in contacting the
surface and in adding metallization to it. The size and the shape, as well
as the quantity, of surface defects can affect the ability to perform satis-
factorily or to produce acceptable circuit patterns (in an electronic pack-
aging application). Both micro- and macrostructural defects influence
performance:

1. Microstructure-the surface topography or the texture resulting


from the packing of grains or agglomerates. The microstructure
depends on the forming technique used. Some processes disperse
the individual particles prior to compaction so that the microstruc-
ture basically is a grain-to-grain packing. Other forming processes
require the agglomeration of the individual particles into larger
granulars. (These differences will be shown in the next chapter.)
Often, these micro-defects are less than 1 mil in size but are present
in excessive number (> 100 per square inch) on the surface. Such
surface defects can result in voids in thin film coatings and unetched
metal during metal removal in circuit packaging applications.
2. Macrostructure-surface defects caused by powder processing ir-
regularities. These defects include chips, pits, or depressions; ma-
terial buildup or projections; and scratches. Allowable limits are
shown in Figure 14-4. Their sizes are generally greater than 2 mils,
and they occur relatively infrequently (1-3 per square inch).

FIGURE 14-3. Radial displacement.


86 III / Characterization of Ceramic Materials

pATERIAL BUILD-UP

~PITS
~ ...ffllI

FIGURE 14-4. Macrodefects.

Surface Measurements
Surface finish determinations are made with a proficorder, which mea-
sures the grain-to-grain packing. Plots of peaks to valleys can be obtained
and centerline averages determined; the latter are usually in the range of
20 to 30 microinches, as shown in Figure 14-5.
The surface texture and the agglomerate voids can be observed on
SEM photomicrographs at low magnification (50 to 200 x) as shown in
Figure 14-6. The shapes and the sizes of the individual grains can be
observed at higher magnifications (1000 to 2500 x), as shown in Figure
14-7.
Visual observations for macro-defects such as pits and material
buildup require coating the surfaces. A colloidal graphite spray often is
used to improve the contrast of the surface in conjunction with low-angle
lighting. The defects then are observed by scanning the surface at 7 times
magnification and verifying at 30 times magnification.

tPEAKS

~VALLEYS
- SURFACE PROFILE

FIGURE 14-5. Proficorder trace.


Properties and Requirements of Ceramic Materials 87

FIGURE 14-6. SEM of 96 percenl alumina ~urfacc al 100 x magnificalion.

An indirect method has been developed to measure the surface voids ,


which involves using a blanket metallized coating and measuring the light
spots from back-side lighting with an image analyzer. This technique,
which has been used to quantify surface defects , is discussed in Chap-
ter 15.

FIGURE 14-7. SEM of 96 pcn:enl alumina al 1000x magnificalion.


15
Ceramic Surface
Characteristics

15.1 INTRODUCTION
This chapter illustrates the effects of material variations and processing
techniques on polycrystalline ceramic surfaces. Dry-pressed high alu-
mina ceramics are used as the basis for discussion [10]. The changes in
surfaces are observed in thin-film circuit patterns that have been devel-
oped on these alumina surfaces.
Comparisons are made of coarse- and fine-grain compositions; of
as-fired, dry-pressed surfaces and surfaces produced by secondary oper-
ations such as grinding and polishing or glass and fine-grain alumina
coatings; and of surfaces produced by the cast tape forming technique.
Circuit patterns on alumina ceramic substrates are developed by blan-
ket evaporation, or "sputtering," of thin films of chrome and copper,
followed by photolithographic techniques to produce metallized lines.
The morphology of the metal from these thin-film coating methods is an
extension of the ceramic structure.
Changes in surfaces are observed qualitatively with SEM photomicro-
graphs. Efforts to quantify the surface defects are made by measuring
voids produced by back-side lighting through evaporated or sputtered
thin films. Because defects are strength-limiting, cast tape parts prove to
be stronger than dry-pressed parts.

15.2 DRY -PRESSED ALUMINA SURFACES


In making dry-pressed products, the typical starting particle size of the
alumina powder would be about I micron. It is necessary, however, to
agglomerate these fine powders into granules for flow characteristics dur-
88
Ceramic Surface Characteristics 89

HGURE IS-I. Dry-pressed surface with circuit lines at IOOx.

ing dry pressing. These granules are at least 125 microns in size, so that
pits or voids in the range of 12 to 25 microns are produced from the
packing of these agglomerates.
Thin-film metallization reproduces the exact ceramic topography. Ex-
amples of typical dry-pressed surfaces with thin-film circuit patterns are
shown in Figure 15-1 and 15-2 (different magnifications). At the lower
magnification the packing of the granules is apparent. The higher magni-

FIGURE 15-2. Dry-pressed surface with circuit lines of 500 x.


90 III / Characterization of Ceramic Materials

FIGURE 15-3. Dry-pressed void in circuit line at 1000 x magnification.

fication shows that the voids are the result of the granule packing and not
the individual grains, which are much smaller than the granules. These
voids could result in a circuit line discontinuity (shown in Figure 15-3).
The use of finer-grain alumina powders still requires agglomeration for
flow characteristics, and the resulting surface limitations are again related
to the agglomerate packing, as shown in Figure 15-4.
Potential improvements in the dry-press technology using finer starting

FIGURE 15-4. Finer-grain alumina-dry-pressed at 200 x magnification.


Ceramic Surface Characteristics 91

FIGURE 15-5. High alumina composition-dry-pressed at 2()O x magnification.

raw materials or higher alumina compositions are limited because these


materials still must be agglomerated. Although these materials have im-
proved surface finishes as measured by centerline averages (CLA) and
are denser products, they still exhibit the same-size surface defects as
the less dense materials (Figure 15-5).

15.3 SURFACE VARIA TIONS VERSUS


PROCESSING TECHNIQUES
Ceramic surface characteristics relate directly to the processing tech-
niques employed in producing the ceramic part. When changes in sur-
faces are observed quatitatively with SEM photomicrographs, circuit
lines are used to show the advantages of improving the surfaces by mini-
mizing surface defects. Different magnifications are used to illustrate
different features of the ceramic surfaces. At low magnifications (180 x),
defects in the circuit patterns caused by defects in the ceramic surfaces
are evident. At higher magnification (900 x and 4400 x), the individual
grain structure of the alumina ceramic and its replication by the thin-film
circuitry are seen.

As Fired Dry-Pressed versus Machined Surfaces


The packing of the agglomerates is not only a surface effect, as shown in
Figure 15-6; it also causes internal voids (Figure 15-7 for ground surfaces
and Figure 15-8 for polished surfaces).
92 III I Characterization of Ceramic Materials

FIGURE 15-6. SEM as-fired dry-pressed surfaces at 1 80x .900 x .and 4400 x at
45-degree tilt .
Ceramic Surface Characteristics 93

FIGURE 15-7. SEM ground dry-pressed surfaces at 180x . 900 x .and 4400 x at
45-degree tilt.
94 III / Characterization of Ceramic Materials

FIGURE 15·8. SEM polished dry-pressed surfaces at 180 x .900 x •and 1500 x at
45-degree tilt.
Ceramic Surface Characteristics 95

It is evident from these SEM photos that the voids are exposed at the
surface by grinding and polishing. Machining actually produces additional
voids because of grain pullout. Machining voids are not smooth and could
be undercut, rriaking the ceramic more difficult to metallize. Therefore, a
machined surface appears to be worse than an as-fired surface with re-
spect to voids.

Coated Surfaces
Coating the dry-pressed parts covers over the agglomerate defects, as
shown in Figure 15-9 for a glaze or glass coating and in Figure 5-10 for a
coating with an alumina slurry.
The glaze coatings are very smooth and can result in adhesion prob-
lems with thin-film metallization. The alumina coatings are similar to the
original as-fired surface but without the agglomerate structure, and there-
fore do not have voids in the circuit patterns. Because the alumina coat-
ings are still granular they would have the mechanical adhesion
characteristics of the base material.

Cast Tape Surfaces


The cast tape process used to fabricate ceramic parts does not require
the agglomeration of the powders. Surfaces for a 96 percent alumina cast
tape and a 99 percent fine-grain alumina cast tape are shown in Figures
15-11 and 15-12, respectively.
Defects in the cast tape are due mainly to the packing of the individual
grains; so these defects are of a much smaller size than those found
with agglomeration. Using fine-grain compositions in cast tape process-
ing further reduces the defect levels because the starting grains are
smaller.

15.4 QUANTITATIVE SURFACE


TECHNIQUES
Scanning electron microscopes are used to qualitatively observe differ-
ences in surface morphology. In an effort to quantify surface defects, it
has been observed that thin films that are evaporated or sputtered onto
alumina surfaces have voids that are caused by voids on the alumina
surfaces. The voids in the metal films can be seen by back-side lighting
techniques, which will produce light spots against a black background, as
shown in Figure 15-13.
These voids, which can cause open circuits in circuitized patterns, can
96 III I Characterization of Ceramic Materials

FIGURE 15-9. SEM glazed dry-pressed surfaces at 180 x .900 x . and 4400 x at
45-degree tilt.
Ceramic Surface Characteristics 97

FIGURE 15-10. SEM alumina·coated dry-pressed surfaces at H!O x .900 x , and 440() x
at 45-degree tilt.
98 III / Characterization of Ceramic Materials

FIGURE IS-II. SEM 96 percent alumina cast tape surface at 180 x , 900 x , and 4400 x
at 45-degree tilt .
Ceramic Surface Characteristics 99

FIGURE 15-12. SEM 99 percent fine grain alumina cast tape surface at 180 x, 900 x,
and 4400 x at 45-degree tilt.
100 III / Characterization of Ceramic Materials

FIGURE 15-13. SEM 99 percent fine grain alumina cast tape surface at 180 x, 900 x,
and 4400 x at 45-degree tilt.

be quantified with an image analyzer. A plot of the void size versus the
frequency of the void for the various surfaces is shown in Figure 15-14.
As expected, the voids caused by the agglomeration of the powders
are apparent in the dry-pressed samples. Coating of the parts covers the
agglomerate voids, significantly reducing the voids; and because the cast
tape process does not require agglomeration, it yields reduced void lev-
els .
A three-dimensional graph of void area versus metal thickness and
sunace type is shown in Figure 15-15.
It is evident that the void area is related to the type of sunace. There
is an increase in void area with reduced metal thickness because thicker
metal tends to fill in the voids and reduce their sizes.
Ceramic Surface Characteristics 10 I

10,000

1,000
• DRY PRESS
> x COATED DRY PRESS
u o FINE GRAIN COATED DRY PRESS
z
W
::J
o CAST TAPE
ow 100
ex:
u.

10

o .05 MIL 1 MIL


VOID DIAMETER

FIGURE 15-14. Voids versus frequency versus surface type.

STD - DRY PRESS


SIP - COATED DRY PRESS
~ SSIP - FINE GRAIN COATED DRY PRESS

~ I~ ~:S=PE
40000
I'ii 30000
ex:
« 20000
o
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METAL THICKNESS
SURFACE TYPE

HGURE 15-15. Void area versus thickness versus surface type.


16
Ceramic Strength
Considerations

16.1 INTRODUCTION
A major obstacle in the use of ceramic materials is their strength limita-
tions. Ceramic materials will break when subjected to various loading
stresses such as shear, torque, tension (bending), impact, and thermal
shock. This chapter highlights bending, impact, and thermal shock fail-
ures using alumina ceramics as the example [11].
The ultimate strength of a ceramic material is related to its composi-
tion, grain size, and geometry. In general, finer-grain materials have
higher bending strengths than coarser-grain materials because they have
more surface area and thus more bonds. Coarse-grain materials
have more resistance to impact and thermal shock because the flaw
sizes are larger, and therefore the stress to grow the critical crack is
higher.
In considering fracture mechanics, the resistance (fracture toughness)
of a material to failure is proportional to the applied stress, the flaw size,
and the part design or geometric factor. The microstructure plays a key
role in determining the strength characteristics. Internal stresses can be
induced in the ceramic material to significantly increase the effective
ceramic strength.
The study of fractured surfaces (fractography) has been well re-
searched for glasses [12], but polycrystalline ceramics do not have sub-
stantial revealing markings on theirfractured surfaces [13]. However, by
observing polycrystalline alumina fractured surfaces, it is possible to
determine the origin of the fracture, the type of stress involved, and the
relative amount of the applied stress.
102
Ceramic Strength Considerations 103

16.2 STRENGTH MEASUREMENTS


Impact
There are two standard types of impact test. One involves using a ham-
mer to contact the part, and the other involves dropping balls from spe-
cific heights against a ceramic surface. A drop test has been developed to
simulate the impact stresses that would be involved in handling large
volumes of parts. A sketch of the drop test fixture is shown in Figure
16-1.
Parts such as ceramic substrates are placed at the top of the fixture
and allowed to drop at a controlled angle. The amount of stress during
impact is dependent on the height of the drop, the number of parts
(weight) dropped, and the contact area of the impact stress. This contact
area plays a major role in determining the impact shock resistance. As an
example, point contact can generate significant stresses because stress is
equal to the applied force divided by the contact area.

Flexural Strength
The flexural strength of a material can be measured by three-point load-
ing. A sketch illustrating the testing parameters is shown in Figure 16-2.
Parts are tested to complete failure. The modulus of rupture equation
is given below:
3 Load x Span
Modulus of rupture
2 Width x (ThicknessF
From the equation it can be shown that for a given material where the
modulus of rupture would be a constant, and for a given span and width,
the load to failure is directly proportional to the thickness squared, (i.e.,

n = 20 SUBSTRATES

) 2D INCH DROP

FIGURE 16-1. Impact test fixture.


104 III / Characterization of Ceramic Materials

RLOAD

#
:r
THICKNESS~:;:;::===~===:;:;;:::::~~
~I·~--------SPAN--------~·~I
FIGURE 16-2. Flexural test parameters.

load ex: (thickness}2. Therefore, the effective strength of a material can be


increased significantly by increasing its thickness. Conversely, a reduc-
tion in thickness will have a pronounced effect on the force that causes
failure. Thin ceramics break much more readily than thick ones.

Thermal Shock
The resistance to failure from thermal shock is directly proportional to
the thermal conductivity and flexural strength of the material, and in-
versely proportional to the thermal expansion and modulus of elasticity.
Most ceramic materials have thermal shock resistance of less than 200°C.
An expedient means of measuring the thermal shock resistance of a ma-
terial is shown in Figure 16-3.

100%
325

300

m
00 Jl
m
0: 200 ):10
:E
...
w '"m
):10
C)

100

L -_ _ _ _. -_ _ _ _. -_ _- ._ _- ._ _ _ _~ ~k

5 10 15 20
TIME (SEC)

FIGURE 16-3. Breakage versus time/temperature quench.


Ceramic Strength Considerations 105

The time in seconds represents the delay in going from the material's
initial temperature to that of a room-temperature quench bath. In this
delay time, the part is air-cooled. The breakage from this procedure
depends on the size of the part, the design, and the composition of the
material.

Strength Comparison
A comparison of strength measurements of various types of alumina
materials is shown in Table 16-1. The coarse-grain compositions had an
average grain size of 7 microns, whereas the fine-grain compositions had
an average grain size of 3 microns. It is evident that both thermal shock
resistance and impact shock resistance decrease with finer grains and
high alumina composition, whereas flexural strength increases with finer
grains.

16.3 FRACTURE MECHANICS


Cracks
Crack detection is enhanced by using dye penetrants. Cracks caused by
different types of stress-such as impact, bending, and thermal shock-
show definite trends, as illustrated in Figures 16-4, 16-5, and 16-6.

TABLE 16.1. Strength versus composition/grain size of alumina.


96% AI,03 96% AI,03 99%AI,03
coarse grain fine grain coarse grain

Thermal Shock Breakage (N = 24)


5 seconds 100% 100% 100%
10 seconds 100% 100% 100%
15 seconds 33% 100% 100%
20 seconds 0% 62% 100%
25 seconds 0% 4% 33%
30 seconds 0% 0% 0%
Flexural strength (N = 25)
Average 29,000 psi 31,500 psi 28,000 psi
Low 21.800 psi 23,500 psi 17,000 psi
High 36,500 psi 39,300 psi 36,500 psi
Impact Breakage (N = 100)
Drop test 12% 60% 20%
Broken cracks 10% 32% 30%
Total 22% 92% 50%
106 III / Characterization of Ceramic Materials

FIGURE 16-4. Impact type cracks.

FIGURE 16-5. Bending type cracks.

FIGURE 16-6. Thermal shock cracks.

Cracks from impact shock typically show a 45-degree entrance angle


from the contact point. This is so because the maximum shear stress
occurs at 45 degrees.
Cracks from bending originate from tension loading. The crack prop-
agation might exhibit some curvature as the crack moves away from
compressive loading.
Cracks from thermal shock originate at the edge of the part with a 90-
degree entrance angle. The crack propagation is wavy or branching, thus
increasing the surface area of the crack and releasing stored energy
within the part.

Fractured Surfaces
The fractured surface can be used to study the type of fracture (i.e.,
bending, impact, or thermal), origin of the fracture, and the relative
amount of applied stress that produced the fracture. Examples of the
Ceramic Strength Considerations 107

types of features observed on fractured surfaces are shown in Figure 16-


7, 16-8 and 16-9.
Impact fractures usually show ridges radiating from the origin, where
the ridges converge to a point. Bending fractures usually show a series of
waves radiating from the origin, which are due to the tendency of crack
travel to "run away" from the point of tension at the compression sur-
face. The origin of the fracture is at the center of the wave or, in this
case, the bottom surface. Thermal shock fractures do not exhibit ridges
or waves; they have a very smooth surface.
Observations of actual fractured surfaces are made at relatively low
magnification (10 x). Higher magnification (50 x) does not appear to im-
prove the distinguishable features of the various type of fractures. A
colloidal graphite coating on the surfaces eliminates the reflectivity of
white surfaces and allows faster analysis. High magnification (1000 x) are
used to differentiate transgranular and intergranular types of fractures.
Typical fractured surfaces are represented in Figures 16-10 through 16-
14 at low, medium, and high magnifications.
Thus, fractography can be used as a basis for understanding stresses
that cause ceramic breakage. It is possible to determine the origin of the
damage, the type of stress, and the relative amount of the applied stress.

FIGURE 16-7. Impact type fracture surface.

COMPRESSION
\ '=T=E::':N=S:':IO:':'N:-
SIDE VIEW

FIGURE 16-8. Bending type fracture surface.

FIGURE 16-9. Thermal shock type fracture.


108 III / Characterization of Ceramic Materials

FIGURE 16-10. Impact fracture at 5 x, 50 x, and 1000 x magnification . The lower


magnification shows ridges originating from the point of impact. The higher magnifacation
shows that it is a transgranular type of fracture .
Ceramic Strength Considerations 109

FIGURE 16-11. High-stress fractured surface caused by bending , at 5 x ,50 x and


1000 x magnification. This particular sample had a high flexural strength. The markings at
the lower magnification are very pronounced. Higher magnification indicates a
transgranular type of fracture .
llO III / Characterization of Ceramic Materials

FIGURE 16-12. Low-stress fractured surface caused by bending, at 5 x , 50 x and


1000 x magnification. This particular sample had a low flexural strength. The markings on
the fracture surface are barely visible at the lower magnifications. Again, the higher
magnification shows a transgranular type of failure. It is apparent that the amount of stress
applied is related to how pronounced the wave patterns are on the fracture surface.
Ceramic Strength Considerations III

FIGURE 16·13. Bending fracture , at 5 x .50 x and 1000 x magnification . A typical


bending fracture shows the origin of fracture from the bottom surface around the third pin
from the left. A transgranular fracture is apparent at the higher magnification .
112 III / Characterization of Ceramic Materials

FIGURE 16·14. Thermal shock fracture at 5 x ,50 x and 1000 x magnification. Although
the fracture has a wavy feature, the thermal shock fracture is very smooth without any
markings. This makes it easy to distinguish thermal shock from bending and impact
fractures. At high magnification the fracture appears to be intergranular, which means that
it breaks around the grain boundaries.
Part IV
Hi-Tech Applications of
Ceramics
17
Structural and Electronic
Applications

17.1 INTRODUCTION
Ceramic materials exhibit some outstanding characteristics that have led
to applications in "hostile" environments. They are very hard materials,
thus providing wear resistance in applications as wear guides, valves, and
cutting tools. Ceramic materials are very rigid, and therefore mechani-
cally stable; so they are useful as ball bearings and seals. Their high
temperature resistance makes ceramics an attractive material choice for
engine components that run efficiently at high temperatures. Being elec-
trical insulators, ceramics are used for heat sinks and electronic substrate
applications. Also, the use of ceramics in bioceramics (teeth and bone
transplants) is a growing application based on the characteristic of
chemical inertness. The list of general applications for ceramics seems
endless.
In addition to there being general characteristics that make ceramics
the "material of choice" in many familiar applications, there is a growing
list of specific ceramic material compositions with unique properties suit-
able for some oftoday's high-technology applications [14, 15]. Ferroelec-
tric materials have high dielectric constants, making them suitable for use
as capacitors. Similar materials, because of their piezeoelectric proper-
ties, can be used for transducers. Other materials with unique magnetic
characteristics lend themselves to use in memory core and read heads,
and nuclear fuels are being made that use uranium oxide. Also, the re-
cently discovered superconducting materials are based on rare earth cop-
per oxide compositions.
Clearly ceramics will continue to playa critical role in many of today's
115
116 IV / Hi-Tech Applications of Ceramics

emerging technologies, and they also will be chosen for future high-tech-
nology applications.

17.2 STRUCTURAL APPLICATIONS


Silicon Nitride (Si3N4)
U sed as a substitute for metals because of its low density and high
strength, silicon nitride also has high impact resistance and low thermal
expansion, combined with good oxidation and corrosion resistance. In
automobile applications, its low mass reduces inertia, and ball bearings
capitalize on the material's light weight and high rigidity for high-preci-
sion requirements.
Silicon nitride requires sintering aids to promote diffusion and there-
fore densification, or techniques such as hot pressing or hot isostatic
pressing to produce pore-free materials.

Silicon Carbide (SiC)


With the potential to operate at much higher temperatures than metals,
silicon carbide is used for efficient engine operation at elevated tempera-
tures. The material is very hard, and is often used in applications requir-
ing abrasion and corrosion resistance. Silicon carbide is less expensive
then silicon nitride, and has found applications in sandblast nozzles, low-
friction seals, and automotive water pump seals.
Silicon carbide can be pressureless-sintered by techniques developed
by Corborundum, Inc. and General Electric.

Zirconia (Zr02 )
Zirconia, which has been significantly improved for impact resistance
through a unique toughening mechanism that suppresses cracks, occurs
in two crystal phases (tetragonal and monoclinic). Through control ofthe
transformation from one phase to the other, a compressive stress results
that must be overcome before a crack can propagate.
Applications for transformation-toughened zirconia include bearings,
valves, and forming tools that utilize its impact resistance combined with
its excellent wear and corrosion characteristics.

Alumina (AI 20 3 )
The most widely used of all technical ceramics, alumina has excellent
electrical, mechanical, thermal, and chemical properties, and is the
benchmark for comparison with other materials. It is extensively used
Structural and Electronic Applications 117

for substrates, bearings, guides, and seals and in hostile thermal and
chemical environments.
Alumina is formulated in a wide range of compositions (85-100 per-
cent), and is not sensitive to the forming technique or firing temperatures.
Parts made from alumina can easily be glazed or metallized.

Aluminum Nitride (AIN)


Aluminum nitride has found interest as a replacement for alumina as a
substrate material because of its low thermal expansion and higher exter-
nal conductivity.

17.3 MAGNETIC CERAMICS


Magnetic Behavior
Characteristics. Magnetic ceramics are unique in that they have the
electrical resistivities of oxide ceramics but the magnetic permeabilities
of metallic alloys. Small changes in either chemical composition or pro-
cessing methods cause large changes in their magnetic properties.
Magnetic Moments. Pauli's exclusion principle states that only two
electrons can fill any energy level although they must have opposite spin
directions (it), and that their magnetic moments will cancel. Permanent
magnetic moments arise in systems with unpaired electrons (It). Exam-
ples of paired and unpaired electrons are shown in Table 17-1.
The spinel structure produces antiparallel sites (i.e., opposite spins).
For magnesite (iron oxide), the Bohr magnetrons, which are the orbital
contribution to the magnetic moments, and are approximately equal to
the unpaired electrons, would be as follows:
Tetrahedral Fe ( + 3) - 5 Bohr magnetrons
Octahedral Fe ( + 3) + 5 Bohr magnetrons
Octahedral Fe ( + 2) + 4 Bohr magnetrons
Net moment: + 4 Bohr Magnetrons
TABLE 17.1.
Ion Electron/ Electron Number
Charge energy level spin unpaired

Mg (+2) (6) 2p it it it o
AI (+ 3) (6) 2p it it it o
Fe (+2) (6) 3d iti i i i 4
Fe(+3) 5 (3d) i i i i i 5
Ni (+2) 8 (3d) it it it i i 2
118 IV / Hi-Tech Applications of Ceramics

Structural Characteristics. The spinel structure has 32 oxygens in the unit cell
of a face-centered cubic packing arrangement. This produces 64 tetrahedral sites
and 32 octahedral sites. For magnesite, there are eight trivalent (Fe+ 3 ) ions in the
octahedral sites and eight trivalent (Fe+ 3) ions in tetrahedral sites. Because these
sites are antiparallel, the magnetic moments cancel each other. The eight divalent
(Fe+ 2) ions that are in the octahedral sites give rise to all of the magnetic mo-
ments. Substitution of divalent cations such as copper, nickel, magnesium, man-
ganese, and cobalt significantly affects the magnetic properties.
Magnetic Domains. Domains are areas within a crystal in which the magnetic
moments are aligned parallel and oppositely directed, thus giving a zero magnetic
effect. Application of a magnetic field can cause an irreversible change to occur
in these domains. The mechanisms for these changes could be either domain
growth or domain rotation, as shown in Figure 17-1.
Hysteresis Loop. The domain rearrangement can be illustrated by plotting the
magnetization versus the magnetizing force. This plot, called a hysteresis loop
(which means "lag behind"), is shown in Figure 17-2.

~ f[g f~
WITHOUT FIELD

FIGURE 17-1. Domain fields.


DOMAIN GROWTH DOMAIN ROTATION

B 11, - BtH INITIAL PERMEABILITY

(GAUSS) 11m - MAXIMUM PERMEABILITY


B. - SATURATION MAGNETIZATION
B, - PERMANENT MAGNETIZATION
H. - COERCIVE FORCE

H_MAGNETIZING FORCE (OERSTEDS)

FIGURE 17-2. Hysteresis loop.


Structural and Electronic Applications 119

Types of Ferromagnetics
Soft Ferrites. Soft ferrites have high initial permeabilities or thin hys-
teresis loops. They are manganese and nickel-zinc ferrites. These thin-
hysteresis-loop compositions are used for read heads, inductors, tuners,
and antennae cores.
Square Loop. The square or rectangular-shaped hysteresis loop mate-
rials have fast switching speeds and low coercive forces. They are mag-
nesium-manganese and lithium ferrites. These square loop compositions
are used as memory cores for binary information storage and as switching
devices.
Magnetostrictives. The magnetostrictive materials will experience a
change in dimensions when a magnetic field is applied, and, conversely,
an applied force will produce a magnetic output. Therefore, they convert
mechanical to magnetic energy and vice versa. Magnetostrictives are
made from nickel-zinc or cobalt ferrites. They are used for sonar and
ultrasonic devices.
Microwave Ferrites. The microwave ferrite materials have relatively
high resistivities (which reduce dielectric losses) and a very low hyster-
esis loss at microwave frequencies. The ferrites are made from nickel-
aluminum and magnesium-manganese ferrites, as well as yttrium iron
garnet. The microwave materials are used as isolators because of their
ability to isolate the microwave generator from the load, and they also
are used as amplifiers at microwave frequencies.
Hard or Permanent Magnets. The permanent magnets have high coer-
civity and low loss factors, and are made primarily from the barium
ferrite compositions, which have the pervoskite structure. They are used
as permanent magnets in motors and as holding magnets. The advantages
of these ceramic magnets compared to metal magnets include:

1. Higher coercivity and lower permeabilities.


2. Lower specific gravities.
3. Multipolarity on one surface.
4. Ability to be mixed with plastic and rubber to form magnets.

17.4 ELECTRONIC APPLICATIONS


Linear Dielectrics
Linear dielectrics are insulating materials in which the electric displace-
ment increases as a linear function of the applied field. They are used
primarily as insulators or bases for electronic circuits. A variety of com-
positions have been used; for example:
120 IV / Hi-Tech Applications of Ceramics

1. Electrical porcelain made from triaxial compositions of clay (form-


ing agent), feldspar (flux), and silica (filler). They were the principal
insulting materials until about 1930.
2. Steatite (MgO'SiO z), which was the forerunner of electronic ce-
ramics because of its low loss factor. It was made by combining
mixtures of clay and talc.
3. Alumina (Al z0 3), which is used in most electronic substrate appli-
cations because of its excellent properties and ability to be metal-
lized with both thick- and thin-film technologies.
4. Cordierite (2MgO·2AI 2 0 3 ·5Si02), which has a very low coefficient
of thermal expansion (2 x 10- 6 in./in./°C) compared to alumina
(6 x 10- 6 in./in./°C), and thus provides excellent thermal shock char-
acteristics.
5. Forsterite (2MgO·SiO z), which has a very high coefficient of thermal
expansion (10 x 10- 6 in'/in./°C) matching that of steel so that it can
be used to make metal-to-ceramic seals. It does, however, have
very poor thermal shock resistance.
6. Beryllia (BeO), which has a thermal conductivity about five times
that of dense alumina. Used mainly for heat sinking, it is consider-
ably more expensive than alumina because of its fine powder tox-
icity, and its use is not widespread.
7. Glasses, which if alkali-free can be used as a base for electronic
components. For the most part, glasses have poorer mechanical and
thermal properties than other ceramics.

Nonlinear Dielectrics
Nonlinear dielectrics are insulating materials in which the electric dis-
placement increases as a nonlinear function of the applied field. As a
result of this polarization, these materials can be used as capacitors and
transducers.
Capacitors are current-storage devices requiring high-dielectric-con-
stant materials. Barium titanate has a dielectric constant of over 1000,
which permits the use of smaller-size capacitors. Multilayer capacitors
have enhanced current-storage capabilities, compared to nonlayered de-
vices.
Ferroelectrics are materials that have permanent electric dipoles in the
crystal structure so that a unit cell has a net dipole moment. The dipoles
can be oriented by applying an electric field at less than the electric
breakdown strength of the material.
Piezoelectrics are materials that develop a dimensional change from
polarization by an electric field, as shown in Figures 17-3 and 17-4. Pie-
Structural and Electronic Applications 121

FIGlTRE 17-3. Voltage from dimensional changes .

.-----+

L -_ _ _ +
A) CONTRACTION FROM B) EXPANSION FROM C) EXPANSION/CONTRACTION
NEGATIVE VOLTAGE POSITIVE VOLTAGE BY ALTERNATING ACVOLTAGE

FIGURE 17-4. Dimensional changes from voltages.

zoelectrics are widely used as voltage-pressure transducers to measure


such basic functions as force. pressure, displacement, impact. and
stress-strain. Audio applications include phonograph pickups. micro-
phone elements. and hearing aids.
18
Integrated Circuit Technology

18.1 INTRODUCTION
Ceramic materials have played an integral and important part in the evo-
lution of computers. Perhaps the best example of the importance of ce-
ramic materials involves the ceramic processing used, in part, to make
integrated electronic circuits on silicon semiconductor wafers. Such in-
tegrated circuits, which perform the basic operations of a computer, often
are packaged on ceramic substrate materials (described in detail in Chap-
ter 19).

18.2 SEMICONDUCTORS
Semiconductors are materials whose electrical conductivity is less than
that of metals but greater than that of insulators. Conductivity occurs
after electrons in the materials acquire sufficient energy to overcome an
electron gap between the valence energy level and the conduction energy
levels.
The most commonly used semiconductor material is silicon. However,
gallium arsenide has found recent interest because it enables a consider-
able increase in electronic speed. The primary interest in semiconductors
is in the junctions, which have different concentrations of electrons. The
silicon material can be doped with impurities, by way of gas diffusion, to
produce regions that have an excess of electrons or a deficiency of elec-
trons within the solid material. The junction between these areas forms
diodes. These regions can be designated by a "P" for a deficiency of
electrons and an "N" for an excess of electrons. A P/N/P or an N/P!N
structure produces a solid state transistor.
122
Integrated Circuit Technology 123

EMITTER (CATHODE)

P BASE (GRID)

N
COLLECTOR (ANODE PLATE)

FIGURE 18-1. Transistor.

Transistors (see Figure 18-I) are similar to vacuum tubes (see Figure
18-2) in their basic function of amplifying electronic signals. For the solid
state transistor, where the electrons move within a solid material, the
emitter corresponds to the vacuum tube's cathode, the base corresponds
to the grid, and the collector corresponds to the anode.

18.3 INTEGRATED CIRCUIT PROCESSING


Integrated circuit manufacturing involves the following basic steps:

1. Silicon: A single crystal of silicon is grown from a fused melt, with


a diameter of up to 8 inches and a length of about 3 or 4 feet.
Individual wafers are cut perpendicular to the length and are ground
and polished to thicknesses between 15 and 20 mils.
2. Oxidation: An oxide layer is grown over the silicon in order to
passivate it and provide protection from doping operations. This
oxidation can be accomplished by heating the wafer in an air atmo-
sphere.
3. Photolithography. Photolithography, or chemical machining, is
used to create openings through the glass layer for subsequent dop-
ing. This is accomplished by applying a blanket cover of a thin-film

-CONTROL ELECTRON FLOW


GRID

ANODE

FIGURE 18-2. Vacuum tube.


124 IV / Hi-Tech Applications of Ceramics

1====3.'_____ c'=====II-OXIDE ....J1


L....._ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _
~RESIN

..J-SILICON

FIGURE 18-3. Profile of photo-developed region.

resist material, exposing by light a pattern on the resist, developing


and removing the unpolymerized resist, and thus exposing the
glassy layer, which is etched with hydrofluoric acid to the base
silicon, as shown in Figure 18-3.
4. Doping: The diffusion of impurity gases, or doping, is used to tailor
the electrical characteristics of the exposed regions. The diffusion
is accomplished by exposing the wafer to impurity gases, such as
phosphorous, which produces an excess of electrons (N region),
and to boron, which produces a deficiency of electrons (P region).
Bipolar transistors are formed by three sequential doping opera-
tions. A transistor profile is shown in Figure 18-4.
Because of the different thicknesses of the glass layer, the diffu-
sion regions are evident on a wafer.
With this type of processing, it is possible to produce multiple
transistors during the same operations. Advances in density and
numbers have resulted by making the element smaller.
5. Metallization: Thin-film metallization is used to connect or wire the
various elements on the wafer to produce integrated circuits. Typi-
cally, blankets of aluminum are deposited on the wafer, and circuit
lines are developed by photolithography, which involves a process
of resist, expose, develop, and etch to produce the circuitry. Of
primary interest are the PIN junctions. A PIN junction is a diode,
and a P/N/P or an N/P/N configuration represents a transistor. Other
components such as resistors, which are made by diffusing a higher-
resistance impurity in the base material, and capacitors, which are
made by developing an aluminum/oxide/silicon section, also can be
produced during normal processing.

IlW4;f
_ - - - - - GLASS (3)
~ // GLASS (2)
GLASS (1)

SILICON

FIGURE 18-4. Transistor profile.


Integrated Circuit Technology 125

EMITTER

BASi~ I ~ I I ~CILLECTOR

FIGURE 18·5. Profile of bipolar transistor (P/N/P type).

FIGURE 18·6. Profile of MOSFET transistor (N-channel type).

18.4 TRANSISTOR STRUCTURES


There are two basic transistor structures: bipolar and MOSFET (metal
oxide silicon field effect transistor), illustrated in Figures 18-5 and 18-6.
The bipolar also can be an N/P/N type, and the MOSFET also can be
a P-channel, simply by using the opposite diffusion steps. The source for
the MOSFET corresponds to the emitter on the bipolar, with the gate
corresponding to the base and the drain to the collector.
As is evident from the profiles, the bipolar is a vertical structure and
the MOSFET a horizontal structure. The bipolar is current-controlled,
whereas the MOSFET is voltage-controlled. Multi-devices are developed
in the different-type structures, as shown in Figures 18-7 and 18-8.
The bipolar uses a common base and collector, with the emitter being
diffused in multiple regions to develop the multi-transistor designs. The

COLLECTOR
EMITTER
EMITTER
EMITTER
18 BASEl

FIGURE 18·7. Top view of bipolar multi-device.

GATE

GATE

GATE
SOURCE DRAIN

FIGURE 18·8. Top view of MOSFET multi-device.


126 IV / Hi-Tech Applications of Ceramics

MOSFET uses a common source and drain, which are a single diffusion,
and etched multiple gates between the source and drain for the multi-
transistor designs.

18.5 APPLICATIONS AND DEVELOPMENT


OF SEMICONDUCTORS
The importance of semiconductors for computers can be illustrated best
by reviewing the basic parts, or functions, of computers (data processing
systems). There are five main sections in computing systems:

1. Input, which accepts information. The input can be in the form of


computer cards, magnetic tapes, video/keyboard display units, or
voice activation.
2. Memory, which stores information. The information can be stored
on semiconductor chips, and is referred to as part of the computer
hardware. Computers have the advantage of being able to store
enormous amounts of information, along with the ability to recall
that information in fractions of seconds.
3. Logic, which processes information. This processing, which also is
accomplished on semiconductor chips, allows computers to process
calculations very quickly and accurately.
4. Control, which regulates the information within the computer. Such
programming instructions commonly are referred to as computer
software.
5. Output, which feeds information to users. Output devices include
displays, magnetic tapes, and computer cards, as well as printers to
display the processed information on paper.

The ability to store large amounts of information on semiconductor


chips has led to significant improvements in computer performance in
recent years.
Semiconductor technology has evolved from replacing vacuum tubes
with solid state transistors to large-scale integration on semiconductor
devices. The first iteration went from using vacuum tubes to solid state
devices. The second iteration, which was from the device to the chip,
was basically the first level of micro-miniaturization. The next step in the
transition was to combine multiple transistors and other components on
the same chip. Then the fourth and fifth iterations involved the use of
semiconductor technology for memory functions, replacing ferrite cores.
The sixth, and latest, iteration focused on greater complexity in large-
scale integration.
19
Ceramic Packaging of
IC Devices

19.1 INTRODUCTION
This chapter describes ceramic substrate designs used to package in-
tegrated circuits. It includes chip attachment techniques, thick- and
thin-film metallization wiring. planar and multilayer ceramic substrate
designs, and swedged and brazed input/output pin connections [16, 17.
18].
Comparisons are made between solder and wire bond chip attach-
ments on both planar and multilayer ceramic substrate designs. Thick-
and thin-film technologies are compared with the circuit patterns that are
applied to the ceramic substrates. which usually are alumina-based. Pe-
rimeter and array pin connections are illustrated as the input/output (110)
connections to the printed circuit cards and boards.
Future development in ceramic packaging, which is driven by ad-
vances in chip technology, will require increased 1I0s, using either larger
ceramic substrates or reduced grids, as well as denser wiring, by either
finer lines of multilayer structures. Improvements in the electrical perfor-
mance of the circuit patterns require lower-dielectric-constant substrates
along with integral ground planes and resistors/capacitors on the sub-
strates. Also, thermal enhancements to the base alumina materials
require lower coefficients of thermal expansion to minimize substrate-to-
chip mismatch and higher thermal conductivity to dissipate chip power
more effectively.

127
128 IV / Hi-Tech Applications of Ceramics

19.2 PACKAGE DESIGNS


An example of various packaging levels is shown in Figure 19-1, and
includes the chip to substrate, substrate to printed circuit card, and card
to glass laminated board connections. As shown, integrated chips are
attached to the ceramic substrate with solder balls. There is circuitry (not
shown) from the solder pads to the copper input/output (110) pins. These
copper pins, in tum, are soldered into printed circuit cards, which then
are edge-connected into glass laminate boards.
In this type of packaging scheme, the two key connection technologies
that lend themselves to pin grid arrays (PGA) are the C-4 (controlled
collapse chip connector) and the PIH (pin-in-hole) input/output connec-
tions, illustrated in Figures 19-2 and 19-3, respectively.
The controlled collapse, actually a standoff, is achieved by preventing
the solder from wetting away from the chip pads. This is accomplished
by using an oxide layer on the silicon chip and a nonwettable surface
such as chrome (for thin-film technology) or glass (for thick film).
In the PIH process, copper pins are attached to holes in the ceramic
substrates by mechanically deforming the soft copper material around the
hole. An excess of copper, which is needed to fill the hole, is used so that
the portion that does not fit in the hole forms the head; copper also bulges
between the substrate and the die block, mechanically locking the pins
around the bottom of the hole.
An alternate way to attach chips to substrates is with discrete wires,
as shown in Figure 19-4. This is primarily a perimeter type connection as
compared to the arrays with the C-4 type connection.
An example of a wire bond chip carrier design using laminated ce-
ramics is shown in Figure 19-5. In this example, 110 pins are brazed along
the perimeter, as shown in Figure 19-6 for a dual in-line package (DIP).
For more complex multiple-chip modules (MCM), multilayer ceramics
(MLC) are used, as shown in Figure 19-7. The chips are shown connected
as C-4s. The internal metallization includes redistribution layers, signal
distribution, and reference and power distribution. The 110 connections
are brazed pins, which can be an area array design.
The base ceramic for these applications usually is a 90 to 96 percent
aluminum oxide composition. Additives such as silica, magnesia, and
calcia are used as sintering aids. The planar type ceramic structures
usually are dry-pressed, whereas the laminated or multilayer structures
are made by cast tape.
Ceramic Packaging of IC Devices 129

nGUR": 19-1. Packaging leveb.

-------t.~ AFTER REFLOW


P'I"~"""""""~~~
·:·:·:·:SILICON CHIP·:·:·:·::I
OXIDE • SnJPb OXIDE
_/SOLDER~
----S!.-.J. """ ~. Cr

~~-~ CERAMIC SUBSTRATE

nGURE 19-2. C-4 (controlled collapse chip connector) process.

INSERTED PINNED

FIGURE 19-3. PIH (pin-in-hole) process.


130 IV / Hi-Tech Applications of Ceramics

FIGURE 19-4. Discrete wire chip attach.

LAMINATED LAYERS OF CERAMIC LID WIRE BOND

IC CHIP
METALLIZED VIAS
(TUNGSTEN WITH NICKEL AND GOLD PLATING)
FIGURE 19-5. Typical three-layer. co-fired chip carrier construction.

M-3

FIGURE 19-6. Dual in-line package with brazed 110 pins.


Ceramic Packaging of IC Devices 131

DISCRETE WIRING

TOP SURFACE METALLURGY


AND REDISTRIBUTION LAYERS

SIGNAL DISTRIBUTION AND


SIGNAL REFERENCE LAYERS

POWER DISTRIBUTION
AND MODULE 1/0 LAYERS

FIGURE 19-7. Schematic of an MLC module.

19.3 PROCESSING OF PLANAR


SUBSTRATES
Thick-Film Metallization
Thick-film conductors can be applied by screening paste made from metal
powders and glass frit mixed with organic solvents and binders. The paste
is transferred onto the ceramic surface through circuit pattern etching on
metal films and screens. The metal powders that can be used include the
noble metals such as gold. silver. and palladium (which are air-fired),
copper (which requires a nitrogen atmosphere). and molybdenum and
tungsten (which are heat-treated in a reducing atmosphere). During the
thermal treatment. glass frit reacts with the glassy phase in the substrate
to form a chemical bond. and the metal powders sinter together to pro-
duce electrical continuity. This process effectively produces wiring on
the substrate.
In addition to conductor patterns, which are shown in Figure 19-8 for
discrete chips. this thick-film process can be used to produce resistors.
They are applied with lower resistance values than required, and are
trimmed mechanically (by sandblast) or thermally (by laser) to remove
material and thus increase the resistance. An example is shown in Figure
19-9. This thick-film technology is limited to about 5-mil line widths and
spaces.
Glass dams used to control the solder in the chip site are screened and
fired by using the same thick-film techniques. Examples of the circuitry
used for connecting integrated chips, along with the glass dam solder
barrier, are shown in Figures 19-10 and 19-11.
132 IV I Hi-Tech Applications of Ceramics


FIGURE 19-8. Thick-film electrodes on substrate for discrete chips.

FIGURE 19-9. Resistors and conductors on substrate.

FIGURE 19-10. Thick-film electrodes on integrated chips.


Ceramic Packaging of IC Devices 133

FIGURE 19-11. Glass dam (da rke r area) around the chip site area.

Thin-Film Metallization
Thin-film circuitry can be developed on ceramic substrate surfaces by
using photolithography. Using the chrome/copper system as an example,
the process involves evaporating or sputtering a blanket film of chrome/
copper/chrome . The first layer of chrome is for acceptable adhesion to
the base ceramic; the copper is the conductor; and the second or top
chrome layer is used as a solder barrier. analogous to the glass dam for
thick films.
Circuit patterns are produced from the blanket films by wet chemical
processing . This involves a pplying a blanket resist coating. exposing a
pattern on the resist by projection printing with an enlarged master. de-
veloping and removing the resist that has not been polymerized, and then
etching away the unprotected metallurgy (Cr/Cu/Cr) .
The first pass through this photo process produces the circuit pattern ,
or "personability ." This involves removing the excess chrome/copper/
chrome metallurgy. The second pass, or " select, " is used to remove the
top chrome around the I/O pads and chip site pads, thus exposing the
copper. as shown in Figure 19-12 .
This thin-film process is capable of producing I-mil lines and spacings.
thus allowing much greater wiring density than thick films permit.

Attachment Processes
The I/O connections from the substrates to the printed circuit card s are
made through copper pins, which are attached to the ceramic substrate
by deforming soft copper pins around the holes in the substrate. as shown
in Figure 19-13. Because this mechanical deformation does not assure
134 IV / Hi-Tech Applications of Ceramics

FIGURE 19-12. Thin-film circuit pattern.

FIGURE 19-13. Pinned substrate.


Ceramic Packaging of IC Devices 135

contact with the circuit pattern pads, the exposed copper is tinned with
tin lead solder, as shown in Figure 19-14.
In addition to assuring continuity between the 110 pins and the circuit
pattern, the solder is used to attach the chips to the substrates (C-4), as
shown in Figure 19-15 , and the pins to the printed circuit cards or boards.

FIGURE 19-14. Tinned substrate .

FIGURE 19-IS. Complete substrate with attached chip.


136 IV / Hi-Tech Applications of Ceramics

FIGURE 19-16. Encapsulated substrate with gold pins.

Finally, the ceramic modules are encapsulated by using a protective


coating on the chip site, aluminum cans, and an epoxy back seal, as
shown in Figure 19-16.
Typically, the pins are tinned for soldering into printed circuit cards.
The example of the encapsulated substrate shows gold pins used to make
a mechanical connection.

19.4 FUTURE TRENDS IN PLANAR


CERAMIC PACKAGING
Introduction
The need for new packaging techniques is driven by advances in chip
technology. As chips become more complex and demonstrate increased
performance, the packaging technology requires increased I/O connec-
Ceramic Packaging of IC Devices 137

tions, denser wiring, improvements in the electrical performance of the


circuitry, and improved thermal properties of the base ceramics .

Increased 1/0 Connections


Additional I/O connections can be obtained either by increasing the size
of the substrate while maintaining the same 100-mil grid spacings or by
reducing the grid spacing while maintaining the same-size substrate .
These options are shown in Figure 19-17.
The basis for comparison is a 28 mm size on a IOO-mil grid with a 116-
hole pattern , compared to increasing the number of holes with a IOO-mil
grid 36 mm with 179 holes and a 44 mm with 268 holes, or to a 28 mm

FIGURE 19-17. Increased 110, : la rger si zes. reduced grids.


138 IV / Hi-Tech Applications of Ceramics

interstitial grid and a 50-mil grid with a comparable number of holes. The
larger ceramic size puts the implementation burden on the ceramic tech-
nology because the larger size increases the tolerances, thus giving more
uncertainty to the hole locations. The reduced grids put the implementa-
tion burden on the printed circuit cards and boards because of wiring
constraints using pin-in-hole connections. Surface mounting reduces
these constraints.

Denser Wiring
Increases in the wiring density can be produced by using either finer lines
or multilayer designs. Current manufacturing line capabilities produce
minimum line widths of 0.8 mil. Significant reductions in these line widths
will require improvements in the ceramic surfaces. The standard dry-
pressed substrates have surface void sizes in the range of 0.5 mil. Coat-
ings over the dry-pressed surfaces, or alternate forming methods such as
cast tape or mold casting, will give improved surfaces for finer lines. A
comparison of circuitry on dry-pressed versus coated parts is shown in
Figures 19-18 and 19-19. Significant improvements in the surface texture,
and thus the circuit pattern, are obtained with the coated part.
Multilayer wiring designs are being produced by using a polyimide
dielectric between the wiring layers. Figures 19-20 and 19-21 illustrate
the polyimide layer over the first metallized circuit layer and the second
metallized layer on top of the polyimide. The polyimide serves as the
dielectric between wiring layers.

Electrical Performance
Improvements in electrical performance are related mainly to the speed.
Having resistors at the substrate level instead of at the card or board level
decreases the wiring length and thus increases the speed. Thick-film re-
sistors are being used with the noble metal pastes. Sputtered Cermet
resistors have been developed for the thin-film technology. Examples of
thick- and thin-film resistors are shown in Figures 19-22 and 19-23.
Embedded ground or power planes have been designed to reduce the
noise or decoupling between adjacent circuit lines. These buried metal
planes can be made either with thick-film copper paste and a glassy
dielectric or with thin films and polyimide as the dielectric.
An example of a combination of ground and power planes with a glass
dielectric insulator is shown in Figure 19-24. The glass dielectric layer,
which is not apparent, is applied by thick-film screening, as were the
metallized planes. The large squares in the four quadrants are the power
planes, and the ground plane is the remaining common metallurgy.
Ceramic Packaging of IC Devices 139

FIGURE 19-18. Dry-pressed.

FIGURE 19-19. Coated part.


140 IV / Hi-Tech Applications of Ceramics

FIGURE 19-20. Polyimide coverage .

FIGURE 19-21. Top wiring layer.


Ceramic Packaging of IC Devices 141

FIGURE 19-22. Thick-film resistors.

Thermal Performance
There are alternatives to aluminum oxide that will give improved thermal
performance. The two characteristics of interest are low expansion to
match the silicon chips and high thermal conduction for heat dissipation.
Materials that have low expansion around silicon are: mullite, silicon
nitride, cordierite, and aluminum nitride. Materials exhibiting high con-
ductivity include: beryllium oxide, which is toxic; silicon carbide, which
has low resistivity; and aluminum nitride. The prime candidate is alumi-
num nitride, which has both low expansion and high thermal conductiv-
ity.

19.5 MULTILAYER CERAMICS (MLC)


Advantages of MLC Technology
The basis for multilayer ceramic technology is the ability to fabricate a
flexible green or unfired sheet of ceramic that can be processed before
firing. The processing includes making vias through the sheets that can
142 IV / Hi-Tech Applications of Ceramics

FIGURE 19-23. Cermet resistors.

be filled with metal paste, as well as printing the co-fire metal paste with
circuit patterns and laminating individual sheets into a monolithic struc-
ture prior to firing densification.
Advantages of the MLC technology for multichip carriers [19, 20]
include:

I. Reduction in the number of interconnections , which lowers cost


and improves reliability.
2. Reduction in total wiring length , which increases speed and thus
improves performance.
3. Allowance for very large scale integration (VLSI) with multichip
modules.
4. Increased heat dissipation with auxiliary heating designs.
Ceramic Packaging of IC Devices 143

FIGliRE 19-24. Combination ground and power planes.

Green Sheet Considerations


Composition . The green sheets can be made from a ceramic powder
of approximately 90 percent alumina and 10 percent glass frit. An organic
solvent is used to form a slurry, and an organic binder is included to bond
the ceramic powders after solvent removal. The binder makes the sheet
flexible. Prior to firing, the sheet has the characteristics of an organic
material.
Sheet ForminR . The organic/ceramic slurry is deposited or coated onto
a polyester tape film. The coating is applied by moving the polyester with
slurry under a doctor blade preset at a certain height above the polyester
to obtain the desired thickness. The coated film is passed through a dryer
to remove the solvent, leaving the ceramic powders bonded together by
the organic binder. The coating then can be removed from the polyester
carner.
144 IV / Hi-Tech Applications of Ceramics

Multilayer Ceramic Processing


Hole Generation. Holes are put into the green sheets by punching.
Some holes are used to mark the direction of flow because the shrinkage
of the sheets is in a different direction, perpendicular and parallel to the
flow direction. Registration holes are generated, to be used for locating
the sheets during processing prior to firing. Small via holes are made
through the sheets in order to connect the circuit patterns from level to
level.
Metallization. Refractory metals such as molybdenum and tungsten,
which will co-fire with the alumina, are used to fill the vias and print
circuit patterns by means of thick-film pastes. Each sheet has its own
personality, which could include signal, ground, or voltage planes. These
patterns are screened through metal masks.
Lamination. The sheets are stacked alternately to the flow direction
for lamination, which is done at approximately 100°C and 2000 psi for
about 10 minutes. During lamination, the sheets become a monolithic
structure of ceramics with embedded metallization.
Sintering. The firing or densification of the ceramic and the co-fire
metallization are accomplished by using a wet hydrogen atmosphere at
temperatures up to 1600°C. The reducing atmosphere provided by the
hydrogen is necessary to protect the metallization from oxidation. The
densification produces a volume shrinkage of between 16 and 20 percent.
As a result of firing, the ceramic material becomes hermetic and the
metallization continuous.
Secondary Operations. The exposed refractory metals must be plated
to protect them from oxidation as well as produce a surface acceptable
for soldering or brazing. Nickel and gold platings are used. The input/
output pins, which are headed, are brazed onto metallized pads. The chip
attachment uses a solder connection from the chip pads to exposed via
pads on the ceramic surface. An example of a multilayer structure was
shown schematically in Figure 19-7.

Package Configurations
Dual In-Line Packages (DIPs). DIPs are made by using the multilayer
ceramic technology. They are three-layer designs where the bottom layer
is a flat base. The middle layer has a large square hole that will allow the
chip to be set on the base and a metallized pad; this layer also has the
thick-film tungsten co-fired circuitry. The top layer has a larger square
hole than the middle layer to expose the circuit pads for wire bond chip
attachment, and this layer also has a metallized pad around the recessed
Ceramic Packaging of IC Devices 145

FIGURE 19-25. Sketch of dual in-line package (DIP).

i#'7 FLAT PACK


I~
cJ:§ (J
II
II
II

FIGURE 19-26. Sketch of flat pack.

area for attaching a lid or cover. Input/output pins are brazed to nickel
and gold plated pads. These DIPs are used for insertion into printed
circuit cards and boards. A sketch is shown in Figure 19-25.
Flat Packs. The flat pack design (Figure 19-26) is similar to the DIPs
except that the leads are parallel for attachment with solder instead of
insertion into a printed circuit card.
Chip Carriers. Chip carriers have the same basic designs as the three-
layer dual in-line packages except that they do not have leads attached.
They are connected to DIP carriers or printed circuit cards with solder
pads. An example of a leadless chip carrier is shown in Figure 19-27.
Pin Grid Array. The pin grid arrays also have the three-layer multilayer
ceramic design. but with the leads in an area array on the back side. A
design for a PGA is shown in Figure 19-28.
146 IV / Hi-Tech Applications of Ceramics

FIGURE 19-27. Sketch of leadless chip carrier.

FIGURE 19-28. Sketch of pin grid array (PGA).


•••••••
••••• •
••••••••
•••••••
•••••

FIGURE 19-29. From left to right: 35 mm, 50 mm, and 90 mm multichip/multilayer


Ceramic Packaging of IC Devices 147

FIGURE 19-30. Typical chip site.

Multichip Modules (MCM). Multichip modules can be made with up


to 40 layers in thicknesses ranging from 0.17 to 0.28 mm and with via
sizes as low as 0.13 mm on 0.25 mm centers. Examples of IBM's multi-
layer ceramic designs are shown in Figure 19-29.
148 IV / Hi-Tech Applications of Ceramics

FIGURE 19-31. Side view of MLC design.

These designs use the C-4 chip attach technology. A close-up of a


typical chip site is shown in Figure 19-30. A side view of the attached
chips along with the 110 connections is shown in Figure 19-31.
20
The Future of Ceramics

Having withstood the tests of time, ceramic materials are truly the mate-
rials of the ages. Artifacts made of ceramics have been identified with
early civilizations that existed thousands of years ago. The durability of
these ceramic materials has allowed them to bridge the gap between
ancient and modern times. Basic durability sets ceramic materials apart,
and is the primary characteristic that will guarantee them a place in the
future.
Traditional ceramic products such as dishes, sanitary ware, bricks,
and glasses will maintain their share of the market in coming years, based
on improvements in properties, such as those of crystallized glasses, and
more efficient processing techniques. Environmentalists will encourage
the use of ceramics because the materials can be recycled.
The future of ceramics does not rest upon tradition and history alone,
however. Demands for more efficient engines that will operate at higher
temperatures should provide a new market for ceramics as engine com-
ponents. The continuing exploration of space will require ceramic mate-
rials that have extraordinary resistance to high temperatures.
Materials with improved fracture toughness (resistance to fracture),
such as the stabilized zirconia materials, will broaden the base of struc-
tural applications for ceramics. Applications of ceramics for cutting tools,
dies, guides, and seals (limited in the past because of catastrophic failure
characteristics) soon will be feasible, using ceramic materials with en-
hanced strength.
The electronics industry will continue to make use of ceramics as
carriers and packaging materials. Nonoxide ceramics such as the car-
bides, nitrides, and borides will gain acceptance in electro-ceramic appli-
149
150 IV / Hi-Tech Applications of Ceramics

cations that will be driven by the need for higher thermal conductivity,
lower thermal expansion, and lower dielectric constants. The meeting of
those requirements will require improved performance and reliability for
integrated circuit packaging.
The emerging field of fiber optics will expand over the next decade in
communications and electronics applications, and much of the expansion
will incorporate ceramics. Improvements in light transfer will affect home
consumer products as well as hi-tech industries. Also the advantages of
the superconductive materials will be realized in the next few years and
applied to power transmission and computer interconnections.
Ceramic materials have proved themselves over time, filling the
needs of civilization for centuries. From early clay vessels and obsidian
tools to today's hi-tech electronics applications to future applications
in outer space, ceramics seem destined to serve an endless number of
uses.

REFERENCES
1. W. D. Kingery, H. K. Bowen, and D. R. Uhlmann. Introduction to Ce-
ramics, 2nd ed. John Wiley & Sons, New York, 1976.
2. L. H. Van Vlack. Physical Ceramics for Engineers. Addison-Wesley Pub-
lishing Co., Reading, MA, 1964.
3. R. E. Grim. Clay Mineralogy. McGraw-Hill Book Co., New York, 1953.
4. G. W. Morey. The Properties of Glass, 2nd ed. Reinhold Publishing Co.,
New York, 1954.
5. M. Grayson. Encyclopedia of Glass, Ceramics, and Cements. John Wiley &
Sons, New York, 1985.
6. E. B. Sands. Class Engineering Handbook, 2nd ed. McGraw-Hill Book Co.,
New York, 1958.
7. L. Pauling. Nature of the Chemical Bond. Cornell University Press Ithaca,
NY, 1945.
8. G. C. Phillips, R. Sanwald, and J. F. Cain, "Modern Techniques Reveal
Ceramics" Industrial Research, 16(13): 46-50, December 1974.
9. D. W. Richerson. Modern Ceramic Engineering. Marcel Dekker Inc., New
York and Basel, 1982.
10. G. C. Phillips and J. F. Turner, "Characterization of Thin Film Copper
Circuits on Various Ceramic Surfaces," Proc. 31st Electronic Component
Conference, Atlanta, 1981.
11. G. C. Phillips, "Fractography of Metalized Ceramic Substrates," ASTM
Special Technical Publication 827, 1984.
12. L. Orr, "Practical Analysis of Fractures in Glass Windows," Mater. Res.
Stand. 12(ld): 21-23,47, 1972.
13. H. P. Kircnner and R. M. Gruver, "Fracture Mirrors in Alumina Ceramic
Ceramics," Phi/os. Mag. 26(6): 1433-46, 1973.
The Future of Ceramics 151

14. J. E. Hove and W. C. Riley, Ceramics for Advanced Technologies, John


Wiley & Sons, New York, 1965.
15. J. E. Hove and W. C. Riley, Modern Ceramics-Some Principles and Con-
cepts, John Wiley & Sons, New York, 1965.
16. G. C. Phillips, "Planar Pin Grid Arrays Ceramic Packaging," Proc. 38th
Electronic Components Conference, Los Angeles, 1988.
17. B. Schwartz, "Microelectronic Packaging: II," Am. Ceramic Bulletin, 63(4):
577-81, 1984.
18. R. R. Tummala, "Ceramics in Microelectronic Packaging," Am. Ceramic
Bulletin, 67(4): 752-58, 1988.
19. A. J. Blodgett, "A Multilayer Ceramic Multichip Module," IEEE Trans. on
Components, CHMT-3(4): 634-37. 1980.
20. B. T. Clark, "IBM Multichip Multilayer Ceramic Modules for LSI Chips,"
IEEE Trans., CHMT-3 No. (I): 5-8, 1980.
21. W. H. Zachariasen "The Atomic Arrangment in Glass," J Am Chern Soc.
54,3841 (1932).
Index
Index

Abrasives, 34 Computers, 126


Alumina Connectors, C-4, wirebond, 128
applications, 116 Coordination number, 49
chemical properties, 84 Cordierite, 120
dielectric properties, 81 Cracks
mechanical properties, 83 detection of, 100
surfaces, 88 types of. 106
thermal, 82
tolerancing, 84 Devitrification, 33
Aluminum nitride, 117 Dry pressing, 18

Bayer process, 10 Electrical porcelain, 120


Beryllia, 120 Electronic configurations,
Bipolar transistors, 125 42
Bohr postulates, 41 Electron microscope, 73
Bonding, 47 Extrusion, 21
Bond strength, 51
Brazing, 144
Ferroelectric. 120
Ferromagnetic, 4, 20, 67
Capacitors, 120
Flame plating, 32
Casting
Flat packs, 145
slip, 22
Flexural strength, 103
tape, 23
Formula notations, 7
Cements, 38
Forsterite, 120
Ceramic definitions, 3
Fracture mechanics, 105
Chip carriers, 145
Fusion casting, 33
Clay
groups of, 7
physics of, 12 Geological
structure of, 58 environments, 8
water systems, 15 processes, 9

153
154 Index

Glass Polyimide dielectric, 138


composition, 36 Polymorphs, 60
cooling curves, 27 Porcelain enamels, 32,
formers, 61 38
modifiers, 62 Powder processing, 18
structure, 61
uses of, 37 Quantum numbers, 42
Glazes,32
Refractories, 35
Helium atom, 42 Resistors, 138
Hot pressing, 33
Hydrogen atom, 41 Semiconductors, 122
Sheet forming, 143
Impact shock, 103 Silicates
Index of refraction, 72 basis 0[, 53
Ionic radii, 45 as layer minerals, 58
Ionization, 44 structures of, 55
Isomorphs, 59 types of, 54
Isostatic pressing, 18 Silicon carbide, 116
Silicon nitride, 116
Jiggering, 21 Single crystal, 33
Sintering, 25
Kaolinite Spectroscopy, 79
formula for, 7 SpineI, 67
structure, 58 Sputtering, 32
Steatite, 120
Linear dielectrics, 119 Structural clay products, 36
Surfaces
Macrostructures, 85 cast tape, 95
Magnetic moments, 117 coated,95
Magnetite, 67 dry pressed, 88
Metallograph, 73 machined, 91
Metal oxides, 4 polycrystalline, 88
Microstructures, 85 quantitative, 95
Mosfet transistors, 125
Multichip modules (MCM), 147 Terminology, 6
Multilayer ceramics, 141 Thermal shock, 104
Thermal treatments, 24
Neon structure, 44 Thick films, 131
Thin films, 133
Oxide structures, 65 Titanates, 4, 67

Pauling's Rules, 49 Water adsorption, 13


Piezeoelectrics, 120 Whitewares, 35
Pin grid arrays (PGA), 129, 145
Pin-in-hole (PIH), 129 X-ray techniques, 75
Plasticity, 16
Polarizing microscope, 71 Zirconia, 116