Professional Documents
Culture Documents
to Ceramics
A Concise Introduction
to Cera1l1ics
by
George C. Phillips
Preface / ix
Introduction / xiii
1. Ceramic Materials / 3
I. I Introduction / 3
1.2 Ceramic Materials / 4
1.3 Terminology / 6
1.4 Formula Notation / 7
3. Nature of Clay / 12
3.1 Physics of Clay / 12
3.2 Clay-Water Systems / 15
8. Atomic Structure / 41
8.1 Background / 41
8.2 Electronic Configurations / 42
8.3 Ionization / 44
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
xi
Introduction
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
BaO·TiOc-barium titanate
PbO·ZrOc-lead zirconate
SiC-silicon carbide
WC-tungsten carbide
AlN-aluminum nitride
BN-boron nitride
TiB-titanium boride
MoSi 2-molybdenum disilicide
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:
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
WC-tungsten carbide
SiC-silicon carbide
AIN-aluminum nitride
BN-boron nitride
TiB-titanium boride
Ceramic Materials 7
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:
or:
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
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:
FREE
WATER
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
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
RAW MATERIALS
MIJING
!
SCREENING
!
MAGNETIC SEPARATION
~
!
SPRAY DRY
~
DRY PRESSING
HGURE 4·1.
1
FILTER PRESS
~
PLASTIC FORMING
WPUNCH
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
EJECTION
I:':":'':':':''~:ot.-_ PART
FIGURE 4-4. After the pressing operation, the formed part is ejected.
CHAMBER-
I<'IGURE 4-6. Micrm,tructure formed by agglomerating fine particles into larger granulars.
-----\t
r----I.U~~~~~~~. ~-PLASTIC
TOOL
MASS
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
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
(A)
SUSPENSION/INTERPARTICLE
00 (8)
PORE WATER
(C)
DRIED
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:
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 ..
TIM~
27
28 I I Overview of Ceramics
w
a:
:)
~
a:
w
Q.
::E
w
I-
TIME-
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
been shown [5] on cooling curves of temperature versus volume that glass
can be cooled slowly.
~
FIGURE 5-4.
-;;ENGLASS
~
30 I / Overview of Ceramics
MOLTEN
OQAM
PLATENS
FIGURE 5-6.
r"OL""
Rolling and drawing process for sheets and plates or fibers.
Forming From Melts 31
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
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:
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:
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:
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.
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:
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)
41
42 II / The Nature of Ceramic Materials
...---+-PROTONS (+)
1i---+--NEUTRONS (M)
HELIUM
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.
TABLE 8-1.
AN Atoms (Symbol) Electronic Configuration
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)
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
TABLE8-3.
AN Element Valance Ionic radii
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
FIGURE 9-4.
00
Van der Waals bonding.
~=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
l./-~-ALUMINUM
OR
MAGNESIUM
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
SILICON (+4)
MAGNESIUM (+2)
ALUMINUM (+3)
FIGURE 9-9. Bond strength representation for silicon. magnesium, and aluminum.
52 II / The Nature of Ceramic Materials
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.
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.
TABLE 10.1.
Shared oxygen Structure Examples
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.
OH-l
OCTAHEDRAL
OH-1/0-2
DISILICATE
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:
I 0.2
I
DIS ILlCATE SI....
I
OCTAHEDRAL
DISILICATE
0.2
o OXYGEN
• SILICON
o OXYGEN
• SILICON
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.
• SODIUM
o OXYGEN
• SILICON
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.
65
66 II / The Nature of Ceramic Materials
LAYER 3
LAYER 2
LAYER 1
(A) (8)
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]
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.
} - - - - - - - { }+--BARIUM
~+---OXYGEN
'---:~--TITANIUM
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
AIRr-----~--~----~------__4
MEDIA I--------\r----+------\---------I
AIR 1-------~--...Jo",----~-------1
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
~ __________~SAMPLE
OPAQUE
FIGURE 13-4. Reflected light.
74 III / Characterization of Ceramic Materials
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.
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.
ELECTRONS VIEWER
SAMPLE
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{
X-RAY
SOURCE
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
FILM
PRIMARY
BEAM
--
X-RAY
TUBE CAMERA
~I
RECORDER
X-RAY SPECIMEN
TUBE
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
SPECIMEN
COUNTER
ELECTRON
SOURCE ANALYZING
CRYSTAL
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
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
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:
pATERIAL BUILD-UP
~PITS
~ ...ffllI
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
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.
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-
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 15-6. 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.
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
~ I~ ~:S=PE
40000
I'ii 30000
ex:
« 20000
o
o> 10000
~ ~C%>
CIlI> <%l>
SIP TAPE
SSIP
METAL THICKNESS
SURFACE TYPE
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
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
RLOAD
#
:r
THICKNESS~:;:;::===~===:;:;;:::::~~
~I·~--------SPAN--------~·~I
FIGURE 16-2. Flexural test parameters.
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)
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.
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
COMPRESSION
\ '=T=E::':N=S:':IO:':'N:-
SIDE VIEW
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.
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.
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
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:
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
.-----+
L -_ _ _ +
A) CONTRACTION FROM B) EXPANSION FROM C) EXPANSION/CONTRACTION
NEGATIVE VOLTAGE POSITIVE VOLTAGE BY ALTERNATING ACVOLTAGE
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)
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.
ANODE
..J-SILICON
IlW4;f
_ - - - - - GLASS (3)
~ // GLASS (2)
GLASS (1)
SILICON
EMITTER
BASi~ I ~ I I ~CILLECTOR
COLLECTOR
EMITTER
EMITTER
EMITTER
18 BASEl
GATE
GATE
GATE
SOURCE DRAIN
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.
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
INSERTED PINNED
IC CHIP
METALLIZED VIAS
(TUNGSTEN WITH NICKEL AND GOLD PLATING)
FIGURE 19-5. Typical three-layer. co-fired chip carrier construction.
M-3
DISCRETE WIRING
POWER DISTRIBUTION
AND MODULE 1/0 LAYERS
•
FIGURE 19-8. Thick-film electrodes on substrate for discrete chips.
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
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.
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
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.
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:
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
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
•
•••••••
••••• •
••••••••
•••••••
•••••
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
153
154 Index