Fundamentals of Ceramic Materials

Chapter 4
Properties of Ceramic Materials:
Magnetic and Optical Properties
Content for Magnetic Properties
• Brief history
• Introduction
• Sources of e- motion
• Basic equations
• Classification of magnetic materials
• Diamagnetic ceramics
• Superconductors
• Paramagnetic ceramics
• Ferromagnetism
• Anti-Ferromagnetism
• Ferrimagnetism
• Magnetite
• Garnet structure
• Magnetic domains
• Hard and soft ferrites
A Brief History of Magnetic Materials

 The first magnetic material is magnetite (Fe3O4) (lodestone)

 In its naturally occurring state it is permanently magnetized and
is the most magnetic mineral.

 Oxide ceramics can be synthesized with

1. strong magnetic properties
2. high electrical resistivity
3. low losses
ceramics have advantages
over metals, especially in
high-frequency devices

 About 1 million tons of ceramic magnets (developed in 1960s) are

produced each year.
Introduction
The intrinsic magnetic properties of a material are determined by
 the electronic structure,
 the crystal structure,
 the microstructure (domains).
Magnetic forces are generated by moving electrically charged particles.
• e- travel in orbitals with two e- of identical energy in each orbital
• Each e- represents a tiny electrical current rotating around nucleus (+) and
its own axis  produces a magnetic dipole moment.
• The two e- in each orbital spin in opposite directions and produce equal
but opposite magnetic moments that cancel.
Introduction – Magnetic dipole moment

Magnetic dipoles may be thought of as

small bar magnets composed of north
and south poles instead of positive and
negative electric charges.

(arrow designates the

magnetic moment)

magnetic field distributions are

indicated by lines
Introduction – Magnetic or not?

Most crystal structures result in filled e- orbitals where all e- are in

pairs and the magnetic moments are cancelled. These materials are
not magnetic.
Some materials contain e- structures with unpaired e- and have the
potential to be magnetic.
These include;
 metals with conduction e-
 atoms, and molecules containing an odd number of e-
 atoms and ions with partially filled inner-e- shells (especially
important for magnetic ceramic structures)
 Introduction – Magnetic or not?
Elements with partially filled inner-electron shells
include;
 The transition elements (such as Fe, Co, and Mn
that have unfilled shells-d shell partially filled),
-the rare earth elements,
-the actinide elements (5f partially filled).

 Transition metals and lanthanides have unpaired d and f electrons,

respectively  magnetic behavior
Introduction

 Magnetic oxides, especially ferrites such as MgFe2O5

are used in transformer cores, magnetic recording
and information storage devices.
 The magnetic properties are anisotropic.

• γ-Fe2O3 -Recording tapes

• Mn0.4Zn0.6 Fe2O4 -Transformer cores in touch tone telephones
• BaFe12O19 -Permanent magnets in loudspeakers
• Y2.66Gd0.34Fe4.22Al0.68Mn0.09O12 -Radar phase shifters
 Sources of electron motion that can create a magnetic dipole
Generation of atomic magnetic moments by;
1) e- orbital motion around the nucleus 2) e- spin around its axis of rotation

 Small current loop generating a  The magnetic moment

very small magnetic field. is along the spin axis
 The direction of the magnetic
moment is along the orbit axis.

The magnetic moment due to electron spin is dominant over that

due to orbital motion
 Basic Equations
Generation of a magnetic field by current flowing in a coil of wire (A)
in a vacuum, (B) with a material present (material becomes
“magnetized.”)
Current (I) passed through the wire
generates a magnetic field (H)

N: number of turns of wire per meter

The magnetic induction or magnetic flux

density (B), is related to H by
μ0: constant

The magnetic moment produced in the

material by the external field changes B:
Basic Equations
M represents the response of the material to H, which is linear,
and the ratio gives
and

Permeability : B/H : μ

Relative permeability : μr
Characterization of Magnetic Properties

• The magnetometer (magnetic sensor) is a sensor for measuring

magnetic induction (magnetic field intensity)

• It is widely used in many fields such as industry, agriculture,

defense, biology, medicine, aerospace, etc.

• Induction magnometers: Sensors that is based on Faraday’s

electromagnetic induction law.

• Magnetic magnometers (magnetoresistive magnometer): It is

working by the principle that current in the magnetic field can
generate a Lorentz force.
Vibrating Sample Magnetometer (VSM)
• Magnetic properties measurement based
on Faraday’s Law

• Indifferent to mass and size of sample up to

a considerable range

• This device can measure the susceptibility

of material (χ):
χ = M/H
M: magnetization
H: magnetic field

• Analyzing starts from the construction of

vibrations, then continues with the
measurement amplitude of oscillations
Shah, Syed. (2013). Vibrating Sample Magnetometery: Analysis and Construction.
e- configurations and unpaired electrons
 Sources of e- motion that can create a magnetic dipole
When an e- orbital in an atom is filled (all the e- are paired up) both the
orbital and spin magnetic moment are zero.

Mg2+, Al3+ , Zn2+ , and Ti4+ have paired e- and no net magnetic moment
Fe3+ and Mn2+ have 5 unpaired e- and very large magnetic moments

Fe2+, Co3+, Mn3+, Cr2+ have 4 unpaired e- and also have large magnetic moments
 FeO – Magnetic or not?
However, the presence of a magnetic moment in an ion does not
guarantee that the material containing the ion will have a net
magnetic moment.
Often, the ions will align in a structure such that their moments
cancel. FeO is an example. Fe2+ ions in one plane of FeO all contain
e- with spins aligned in one direction, whereas Fe2+ ions in adjacent
planes have e- spins aligned in the opposite direction. The spins in
adjacent planes cancel and the bulk material is not magnetic.

The opposing magnetic moments cancel

one another, the solid as a whole
possesses no net magnetic moment.

antiparallel alignment of spin magnetic

moments for antiferromagnetic MnO
 Classification of Magnetic Materials
 Induced
 Spontaneous

χ: Susceptibility
C: Curie constant (K)
c: Curie temperature (K)
 1) Diamagnetic Ceramics

 Most ceramics are diamagnetic

 The reason is that all the e- are paired during bond
formation, so net magnetic moment = 0 (due to e-
spin)
 Ceramic superconductors are perfect diamagnets
below a critical magnetic field (HC)

Cu, Au, Ag are diamagnetic even though their atoms have unpaired
valence e-
 2) Paramagnetic Ceramics
 The magnetic moment is due to unpaired electron spins.
 (+) magnetic susceptibilities (χ > 0)
 Adjacent magnetic dipoles essentially behave
independently; there is no interaction btw them.
 "No interaction" is the difference of paramagnetic and
ferromagnetic ceramics.

 Most first row transition metals (Ti and

Cr) are paramagnetic because they have
unpaired e- in their 3d orbitals.

 Some oxides containing transition metal or rare earth ions (CeO2

and Cr2O3) are paramagnetic
Paramagnetic Ceramics
 Non-transition metals (Na) may be paramagnetic due to the
alignment of the spin moment of some of the valence e- with
the applied field (Pauli paramagnetism).
 The magnetism is weaker than that due to unpaired 3d e- and
involves e- moving into a higher energy level and changing their
spin direction.
Temperature dependence of paramagnetic susceptibility

Curie law:
 3) Ferromagnetism
 Presence of unpaired e- spins
 There is an interaction between adjacent dipoles (no interaction in
paramagnetic ceramics)
 Fe, Co, Ni are ferromagnetic. Why is Cr paramagnetic not
ferromagnetic?
 The reason is due to a quantum
paramagnetic ferromagnetic mechanical exchange interaction
between the 3d orbitals on adjacent
atoms.
 J: exchange integral.
 If J > 0 there is an interaction btw
adjacent magnetic dipoles causing
Dipole alignments: them to line up and the material is
ferromagnetic (T<C)
 If J < 0 adjacent dipoles are antiparallel
and the material is antiferromagnetic
(below the Neel temperature, N).
 Ferromagnetism
The magnetic susceptibility of a ferromagnetic material varies with
temperature according to the Curie–Weiss law:

Paramagnetic bcs of randomization of the spin magnetic moments

CrO2 is the most important ferromagnetic ceramic → magnetic

media in audio and video recording tapes (doped CrO2)

Rutile structure
a= 0.437 nm and c = 0.291 nm
 4) Anti-Ferromagnetism Dipole alignments:

 Exact cancellation of the magnetic moments.

 Consist of 2 ferromagnetic lattices in which the spin magnetic
moments are equal in magnitude but opposite in direction

 NaCl structure (CN = 6)

 Magnetic dipoles on adjacent {111} are
not parallel.

θN: Néel temperature

 Anti-Ferromagnetism
The magnetic interaction btw the cations occurs indirectly through the
oxygen ions  “superexchange” interaction.

Adjacent Ni ions have

opposed spins (Pauli
exclusion principle)
Antiferromagnetic coupling of spins of d electrons on
Ni2+ ions through p electrons of oxide ions

Ceramics with corundum structure can be anti-ferromagnetic

Chapter 2

Manganate ceramics (have the layered perovskite structure) in the

La1-xAxMnO3 (0 ≤ x ≤ 1; A = Sr, Ca, Ba) system that are anti-
ferromagnetic
 5) Ferrimagnetism
The magnetic moments of one type of ion on one type of lattice
site in the crystal are aligned antiparallel to those of ions on
another lattice site.
Dipole alignments:
The magnetic moments are not of the
same magnitude they only partially cancel
each other and the material has a net M.
M: magnetization (A/m)

Ferrimagnetism is similar to ferromagnetism in that the

cooperative alignment between magnetic dipoles leads to a net
magnetic moment even in the absence of an applied field.

Ferrimagnetism is lost when T > θc θC: Curie temperature

 Most of the ceramics that have useful magnetic properties are ferrimagnetic.
 Ferrimagnetism – Magnetite (Fe3O4)
Inverse spinel structure parallel spin alignment is
related with "double
Feııı(FeııFeııı)O4 in the classic spinel form AB2O4 exchange" mechanism
The Fe2+ ions and half of the Fe3+ ions are in octahedral sites and the
other half of the Fe3+cations are in tetrahedral sites.
Fe ions on octahedral sites have their magnetic
moments all aligned in the same direction
(different magnitude).
Magnetic moments of Fe ions on tetrahedral sites
are aligned in the opposite direction.

Fe ions and spin moments

Ferrimagnetism – Magnetite

e- from the Fe2+ ion (3d6) is transferred to the

oxygen in the face-centered position of the sub cell.
and

Transfer of an e- with parallel spin to the Fe3+ ion

Ferrimagnetic Ceramics
 Yttrium-iron garnet (YIG) – Y3Fe2(FeO4)3
 BaO containing hegzagonal ferrimagnetic ceramics
 Garnet Structures
A unit cell consists of 160 atoms:
96 oxygen, 40 Fe3+, 24 trivalent rare earth
ions (typically Y or Gd).
The trivalent rare earth ions have a CN=8
(interstitial positions)
16 of the Fe3+ are in octahedral sites and 24
are in tetrahedral sites.
As in the spinel ferrites, the Fe3+ ions in
octahedral sites have opposite magnetic
moment to Fe3+ ions in tetrahedral sites.
Thus, the 16 in the octahedral sites cancel
16 in the tetrahedral sites. This leaves 8
Fe3+ in the tetrahedral sites that provide a
net magnetic moment.
The degree of magnetic moment can be
varied in the [garnet] structure by crystal
chemical substitution.
Magnetic Domains
A magnetic domain is a region within a magnetic material in which
the magnetization is in a uniform direction.
The individual magnetic moments of the atoms are aligned with
one another and they point in the same direction.

Magnetic domains and the spin orientations in zero and externally applied
magnetic field (H).
 Magnetic Domains
 Ferromagnetic or a ferrimagnetic material is divided into many
small regions or domains.
 Within each domain the direction of magnetization is the same.
In the boundary region btw the
different domains (domain walls)
there is a gradual change in
magnetic dipole orientation:

 Imaging magnetic domains: SEM, TEM,

Magnetic Force Microscopy (MFM)
 Motion of Domain Walls
 When an external magnetic field is applied to a ferromagnetic or
ferrimagnetic material the domain boundaries begin to move.
Hysteresis loop for hard and soft
magnets:
Hard and Soft Ferrites

Ferrites contain ions with a magnetic moment and retain a net

magnetic moment within the structure.

• Ferrites are often classified according to the nature of

their response to a magnetic field.
• A ferrite that is easily magnetized or demagnetized is
referred to as a "soft" ferrite.
• A ferrite that has permanent magnetization and does not
easily demagnetize is called a "hard" ferrite.
Hard and Soft Ferrites

Hard Ferrites
 Permanent magnets (high Br and high Hc)
 Hard ferrite magnets are found in :
• Starter motors in automobiles
• Loudspeakers • Magnetic strips on credit cards,
• Rotors for cycle dynamos ATM cards, etc.
• Windscreen wiper motors
• Mixed with a flexible polymer in door-catches and decorative
magnets for refrigerators
• DC motors in fuel pumps
• Household appliances such as electric shavers, food mixers, and
coffee grinders B: Magnetic flux density
Soft Ferrites
 High M can be produced using a small H.
 High μ, low Hc
 Soft ferrites should also have high electrical resistivity

Spinel ferrites based on (Mn,Zn,Fe)O4 system are commercially

important soft magnets.
• Magnetic recording and data storage media
• Transformer cores in telephones (transformer cores require the use of
soft magnetic materials, which are easily magnetized and demagnetized. Also
they have relatively high electrical resistivities)
• Numerous applications in radios and televisions, such as line
transformers, deflection coils, tuners, and rod antennas

μ: Permeability
Square-Loop Ferrites

Square-loop ferrites have inverse

spinel or garnet structures.
One of the most important
applications in the past was in
digital computers for data storage.
Currently the predominant
memory and data storage systems
are MOS (metal oxide/silicon),
disks, and tapes. The latter two
use dispersed-ferrite coatings and
magnetic recording heads.
Square-Loop Ferrites
• Ceramic ferrites are used extensively for microwave
applications. Microwaves are used in a wide range of
applications including radar, communications and heating.
Communication applications include transmission of voice,
television, computer data, press copy, and electronic
facsimiles (e.g., telefax).
• Another important application example of ferrites is in
recording tape. Individual single crystals of γ-Fe2O3 are
dispersed in a thin, flexible polymer tape.

• For magnetically based information storage, memory

components should be soft and a certain type of
square-loop.
 Summary
Paramagnetism

Ferromagnetism

Anti-Ferromagnetism

Ferrimagnetism

• A ferromagnetic ceramic has all the magnetic

dipoles aligned in one direction (BaTiO3)
• An antiferromagnetic ceramic has equal but
opposite magnetic dipoles that cancel each
other (FeO)

• A ferrimagnetic ceramic has magnetic dipoles in

opposite directions, but they are not equal and
do not cancel.
• The most important ferrites including [inverse
spinel] and [garnet] structures are ferrimagnetic.
Summary
 TiO, VO and CrO have high conductivity because their d electrons are
delocalised in a partly-filled band, and the absence of localised, unpaired
electrons leads to diamagnetism

 MnO, FeO, CoO and NiO, have localised d-electrons which are more tightly
held to the individual nuclei and the oxides are paramagnetic, in addition to
semiconducting or insulating.
Optical Properties
Introduction
Material’s response to exposure to electromagnetic radiation,
visible light.

• The optical properties of a material include

– absorption
– transparency
– color
• These properties are determined primarily by the level of
interaction btw the incident electromagnetic radiation and
the e- within the material.

• Interaction btw electromagnetic radiation and atoms/ions/e-

Visible light wavelength is ranging btw 0.4 μm
and 0.7 μm.
The spectrum of electromagnetic radiation, including wavelength
ranges for the various colors in the visible spectrum.
• The color is determined by wavelength.
• Radiation having a wavelength of ~0.4 μm appears violet, ~0.5 μm
green, ~0.65 μm red.
Introduction Young
(1803)
Double slit
experiment
Light has both particulate and wavelike characteristics.
• Photon - a quantum unit of light (composed of groups or
packets of energy)

hc
E  h 

E  energy of a photon
  wavelength of radiation
  frequency of radiation
h  Planck’ s constant (6.62 x 10 34 J  s)
c  speed of light in a vacuum (3.00 x 108 m/s)
 Introduction
2 types of interaction btw electromagnetic radiation and
atoms/ions/e-
Distortion of an atomic
e - cloud by an electric
1) Electronic Polarization
field.
2 consequences of this polarization: i) some of the radiation energy
may be absorbed, ii) light waves are retarded in velocity as they pass
through the medium  refraction
2) Electron Transition
e- transitions from one energy state to another
An e- may be excited from an occupied state at energy to a
vacant and higher-lying one, denoted by the absorption of a
photon of energy.
The change in energy (ΔE) experienced by the e-, depends on
the radiation frequency () as ΔE = h
 Light Interactions with Solids
Incident light is reflected, absorbed, scattered, and/or transmitted:

I0  IT  IA  IR  IS

Reflected: IR Absorbed: IA
Transmitted: IT
Incident: I0
Scattered: IS

Optical classification of materials

Transparent
transmitting Translucent
light with Opaque
relatively little
absorption
and reflection
single polycrystalline polycrystalline
crystal dense porous
Introduction
Reflection

 Reflection is the familiar process in which radiation is reflected

off a surface and the angle of incidence equals the angle of
reflection in the case of mirror or specular reflection.
 The reflected beam maintains coherency with the incident beam
and for an individual wave.
 There is no loss of energy in the reflection process.
 Reflection is a major source of color of many materials alongside
absorption and emission.
 Reflection processes are dominant in cases where incident light
interacts with smooth, flat surfaces whose physical dimensions
are much greater than the wavelength of the incident light.
Refraction
• Transmitted light distorts e- clouds.
e- cloud distorts
no
transmitted
transmitted + +
light light

• The velocity of light in a material is lower than in a vacuum.

c (velocity of light in vacuum)

n = index of refraction 
v (velocity of light in medium)

-- Adding large ions (e.g., lead) to glass Material n

decreases the speed of light in the glass.
-- Light can be “bent” as it passes through a
Typical glasses ca. 1.5 -1.7
transparent prism Plastics 1.3 -1.6
PbO (Litharge) 2.67
Diamond 2.41
Selected values from Table 21.1,
Callister & Rethwisch 8e.
Total Internal Reflectance
Example
What is the critical angle c for light passing from diamond (n1 = 2.41) into
air (n2 = 1)?

• Solution: At the critical angle, 1  c

and 2  90
n1 sin 2
Rearranging the equation 
n2 sin 1
n2 n2
sin 1  sin c  sin(90) 
n1 n1
Substitution gives

1
sin c  c  24.5
 2.41
Measurement of Refraction Index

• Refractometers are used for refractive

index measurements.
• The refractive index of the test plate
(disc with a smooth face), referred to
that of the surrounding medium, can
be obtained by measuring the optical-
path differences introduced between
a ray through and a reference beam
outside the plate by two successive
rotations, which change the angle of
incidence.
Becke Line Method-Measurement of Refraction Index

• Method of testing the relative refraction indices in microscopy.

• It is generally used to determine if the crystal has a higher or lower index of

refraction than the surrounding medium.
• This method is applied for transparency in ceramic materials.
When nl < ns, the grain When nl >ns, the grain acts
acts as a convex lens, as a diverging lens,
refracting the light into sending the bright Becke
the grain's center - line into the liquid.
the light Becke moving
into the grain.

• The Becke lines become colored when the dispersion curves for the liquid and
solid intersect in the visible addition to equivalence of their refractive index
Grain acts as a lens
 Liquid or Solid Refractive Index
Water 1.333
Oil 1.467
Window 1.51-1.52
Bottle 1.51-1.52
Vitreous Silica 1.458
Quartz 1.544-1.553
Lead 1.56-1.61
Diamond 2.419
Glass. Retrieved from, https://www.rcboe.org/cms/lib/GA01903614/Centricity/Domain/2900/Unit6_glass_evidence_notes.pdf 2022, October 10th

Optical Properties of Metals
photon absorption for metals in
which an e- is excited into a
higher-energy unoccupied state
Fermi energy: the highest occupied energy
level of a material at 0K.
ΔE is equal to the Reemission of
energy of the photon a photon of light by the
direct transition of an e-
from a high to a low
energy state.

Metals are opaque because the incident radiation having frequencies within
the visible range excites e- into empty energy states. (But, metals are
transparent to high-frequency radiation (X-ray and ϒ-ray))

The incident radiation is absorbed ΔE = h√

Total absorption is within a very thin outer layer (< 0.1 μm). So, only metallic
films thinner than 0.1 μm are capable of transmitting visible light.
Optical Properties of Metals: Absorption
Reflection of Light for Metals
Reflection of Light for Metals

• Reflectivity = IR /I0 is between 0.90 and 0.95.

• Metal surfaces appear shiny
• Most of absorbed light is reflected at the same
wavelength
• Small fraction of light may be absorbed
• Color of reflected light depends on wavelength
distribution
• Example: The metals copper and gold absorb light in blue
and green => reflected light has gold color
Optical Properties of Nonmetals
 Nonmetallic materials may be transparent to visible light.
 Reflection, absorption, refraction and transmission phenomena
should be considered.

Reflection
When light radiation passes from one medium into another having a
different index of refraction, some of the light is scattered at the
interface between the two media even if both are transparent.
The reflectivity (R) represents the fraction of the incident light that is
reflected at the interface
Optical Properties of Nonmetals - Reflection
 Optical Properties of Nonmetals - Absorption
Nonmetallic materials may be opaque or transparent to visible light; if
transparent, they often appear colored.
Light radiation is absorbed by 2 mechanisms:
1) electronic polarization
2) valence band-conduction band e- transitions

leaving
behind a hole in
the valence band
Emission of a photon of light by a
direct electron transition across the
absorption occurs band gap.
 Optical Properties of Nonmetals - Absorption
Maximum possible band gap energy for absorption of visible light by
valence band-to-conduction band electron transitions:

No visible light is absorbed by nonmetallic materials having band

gap energies greater than ~3.1 eV. These materials (with high
purity) will appear transparent and colorless.
Optical Properties of Nonmetals - Absorption
Selected Light Absorption in Semiconductors
 Every nonmetallic material becomes opaque at some
wavelength, which depends on the Eg.

 For example, diamond (Eg= 5.6 eV) is opaque to radiation

having wavelengths less than about 0.22 μm
Optical Properties of Nonmetals - Transmission

Each of the variables R, A, and T depends on light wavelength

 Optical transparency is important in many applications .
• Glass and a variety of ionic ceramics are transparent in
the visible range of the spectrum (400 and 700 nm).
• There are many applications in this range for windows,
lenses, prisms, and filters.
• Transparency in other wavelength ranges is important for
electro-optical and electromagnetic window materials for
tactical and strategic missiles, aircraft, remotely piloted
vehicles, spacecraft, battlefield optics, and high-energy
lasers.
• Metals have many open energy levels for e- movement and
thus are opaque to most wavelengths of electromagnetic
radiation.
• Semiconductors have a small band gap can transmit under
some conditions, but become opaque as soon as enough
energy is present for e- to enter the conduction band.
• Ionic ceramics have filled e- shells comparable to inert gas e-
configurations and do not have energy levels available for e-
movement (e- orbitals are localized around individual ions with
FEW energy levels).

• Most single crystals of ionic ceramics are transparent to the

most electromagnetic wavelengths.
• Covalent ceramics are good insulators and have a large band
gap transmit. Therefore they vary in their level of optical
transmission.
• Optical absorption can also occur due to resonance. This
results when the frequency of the electromagnetic radiation is
comparable to the natural frequency of the material. The
resulting oscillations in the material absorb the radiation and
the material is optically opaque.
• Absorption from extrinsic effects due to scattering by
inclusions, pores, grain boundaries, or other internal flaws.
• If the energy gap is small, incoming photons interact with the
valance e-, the photons give up their energy and may be
absorbed.
• If the energy gap is larger than the incident photons, the
photons may be transmitted.
• In metals, valance and conduction bands overlap; radiation of
any wavelength will be absorbed; metals are opaque.
In most insulators (ionic and covalent ceramics), there is a large energy
gap between valance and conduction bands, if the energy of the photon
is less than the energy gap, no electrons will gain enough energy to
escape to conduction band from valance band, therefore absorption will
no occur. Glass, high purity crystalline ceramics and amorphous
polymers.
E < Eg (no absorption)

E > Eg (absorption)

E < Ea, Ed (no absorption)

E > Ea, Ed (absorption)

• Ionic crystals are transparent in the visible and IR regions (high
energy gaps)
• MgO, Al2O3, and fused SiO2 are transparent in the UV (200 to 400
nm), a portion of the infrared (700 to 3000 nm), and the radar (>
106 nm) ranges.
• MgF2, ZnS, ZnSe, and CdTe are transparent to IR wavelengths
• Si and Ge are transparent in the infrared (IR), but are opaque to
visible light.
• Diamond is transparent to visible and infrared wavelengths.
Opacity results when the scattering is so extensive that virtually
none of the incident beam is transmitted, undeflected, to the
back surface.

Possible sources of light scattering in ceramics: grain

boundaries, pores, impurities, secondary phase.

This internal scattering may result from several different sources.

Polycrystalline specimens in which the index of refraction is
anisotropic normally appear translucent.
Both reflection and refraction occur at grain boundaries,
which causes a diversion in the incident beam. This results
from a slight difference in index of refraction (n) btw adjacent
grains that do not have the same crystallographic orientation.
Scattering of light also occurs in two-phase materials in which one
phase is finely dispersed within the other. Again, the beam dispersion
occurs across phase boundaries when there is a difference in the
refractive index for the two phases; the greater this difference, the
more efficient is the scattering.

Glass–ceramics (crystalline + residual glass

phase) will appear highly transparent if
the sizes of the crystallites are smaller
than the wavelength of visible light, and
when the indices of refraction of the two
phases are nearly identical (which is
possible by adjustment of composition).
Residual porosity  effectively
scatter light radiation.
Color
Color results from the absorption of a relatively narrow wavelength
of radiation within the visible region of the spectrum (400 to 700
nm).
• Color is common in materials containing transition elements having
an incomplete d electron shell (V, Cr, Mn, Fe, Co, Ni, Cu) or
containing rare-earth elements having an incomplete f electron shell.
• Color can also occur due to nonstoichiometry within a structure.
• The oxidation state and bond field are also important in color
formation.
• Ceramic colorants are widely used as pigments in paints and other
materials produced and used at low temperatures.
• At high temperature, ceramics having the spinel structure AB2O4
(such as blue CoAl2O4) are often used in 750 to 850°C temperature
range. Doped ZrO2 and ZrSiO4 are used at higher temperatures (1000
to 1250°C).
 Color of Nonmetals
• Color determined by the distribution of wavelengths:
-- transmitted light
-- re-emitted light from electron transitions
• Example 1: Cadmium Sulfide (CdS), Eg= 2.4 eV
-- absorbs higher energy visible light (blue, violet)
-- color results from red/orange/yellow light that is transmitted
• Example 2:Ruby = Sapphire (Al2O3) + (0.5 to 2) at% Cr2O3
-- Sapphire is transparent and
colorless (Eg > 3.1 eV)
-- adding Cr2O3 :
• alters the band gap
• blue and orange/yellow/green
light is absorbed
• red light is transmitted
• Result: Ruby is deep
red in color
No absorption  colorless
Intense color is caused by lattice defects. Example: Pure Al2O3 crystals are
transparent. If small amount of Cr is added (ruby), color is red.

In the presence of defects there are additional

energy levels above the valence band.
Spectrophotometer (UV-VIS-NIR) NIR: Near Infrared

• It is one of the most basic methods to examine the material properties based on
the interaction with light.
• UV-Vis and UV-Vis-NIR instruments measure the light absorbed, transmitted, or reflected
by the sample across a certain wavelength range.

Some Applications:
• Determination of the optical properties of liquids and solids between 175 nm and
3300 nm
• Quantification of analytes in solutions
• Iron content and valency (Fe2+/Fe3+) determination in glass
• Quality assurance and quality control

Ultraviolet/Visible/Near Infrared Spectroscopy (UV/VIS/NIR) Retrieved from, https://www.eag.com/techniques/spectroscopy/uv-vis-spectroscopy/ on 2022, October 10th
UV-VIS Spectrophotometer curves for hot-pressed glass-ceramics
 Single-Beam
A single beam spectrometric instrument
requires a reference sample to be
measured separately from the test sample.

In a double beam spectrophotometer,

the light from the source is split into two
separate beams after passing through
the monochromator.
One beam is used for the sample, while
the other one is used for reference
Double-Beam
determination.

Color measurements can be made by calculations based on spectral reflectance

measurements by a UV-VIS spectrophotometer.
L* represents lightness from black to white on a scale of zero to 100, while a*
L*a*b* and b* represent chromaticity with no specific numeric limits. Negative a*
corresponds with green, positive a* corresponds with red, negative b*
corresponds with blue and positive b* corresponds with yellow.
The LASER

• The laser generates light waves that are in phase (coherent)

and that travel parallel to one another

• LASER
• Light
• Amplification by
• Stimulated
• Emission of
• Radiation

• Operation of laser involves a population inversion of energy

states process
Operation of the Ruby Laser
A laser produces coherent (in phase) monochromatic (single λ) radiation.
• It consists of the active medium, called the optical cavity, which in the case
of a solid-state laser is an insulating crystal or glass containing a specific
dopant. The optical cavity is typically 10 cm long and 1 cm in diameter. One
end is coated to form a partially transparent mirror while the other end is
fully reflecting.

– Direct electron decay transitions — produce incoherent light

Operation of the Ruby Laser
• The operation of the laser is based on electronic excitation of
the active medium using a source, which is usually a flash lamp
or flash tube.
• The excited e- relax back to the ground state by emitting light.
As light is reflected to and from btw the mirrors it is amplified.
The two most important solid-state lasers are:
• Cr3+ doped Al2O3 (specific wavelength of 694 nm- the ruby
laser),
• Nd3+ doped Y3Al5O12 (specific wavelength of 1006 nm the
yttrium aluminum garnet or YAG laser), and Nd3+ doped glass.

Nd: Neodymium
Operation of the Ruby Laser

• Stimulated Emission
• The generation of one photon by
the decay transition of an e-,
induces the emission of other
photons that are all in phase with
one another.
• This cascading effect produces an
intense burst of coherent light.

• This is an example of a pulsed laser.

• Ideal for medical applications such as
hair and tattoo removal.
Continuous Wave Lasers

• Continuous wave (CW) lasers generate a continuous (rather

than pulsed) beam
• Materials for CW lasers include semiconductors (e.g., GaAs),
gases (e.g., CO2), and yttrium-aluminum-garnet (YAG)
• Wavelengths for laser beams are within visible and infrared
regions of the spectrum
• Uses of CW lasers
1. Welding
2. Drilling
3. Cutting – laser carved wood, eye surgery
4. Surface treatment
5. Scribing – ceramics, etc.
6. Photolithography – Excimer laser
90
References