Ra Module Ii

SRI RAMAKRISHNA ENGINEERING COLLEGE
[Educational Service: SNR Sons Charitable Trust]

[Autonomous Institution, Accredited by NAAC with ‘A’ Grade]
[Approved by AICTE and Permanently Affiliated to Anna University, Chennai]
[ISO 9001:2015 Certified and all eligible programmes Accredited by NBA]
Vattamalaipalayam, N.G.G.O. Colony Post, Coimbatore – 641 022.
Department of Physics
20PH211 - ADVANCED MATERIALS
Dr.S.Deivanayaki / Physics
No. of Credits: 2
03/21/2024 Robotics and Automation 1

PHOTO CHROMIC AND THERMO REFRACTIVE GLASSES
Introduction - Physical principles of

photosensitivity in glasses - Induced
coloration of reversible Photo chromic
glasses - Heterogeneous photo chromic
glasses -Applications.
21/03/2024 ROBOTICS AND AUTOMATION 2

Introduction
Inorganic glasses are the main transparent material –
• windows in buildings
• windshields in cars
• Eyeglasses
• prisms
• lenses in optical instruments
• light delivery (light bulbs, projectors, lasers, optical
fibers)
• fine arts (crockery, bijouterie, jewellery).
The ability of glasses to change coloration after exposure
to sunshine was well known since the last century.
Photochromic glasses
Photochromic glasses that have completely
reversible coloration are made of borosilicate
glasses doped with microcrystals of copper and
silver halides.
These glasses are sensitive to near UV radiation.
Induced coloration is a wide band that covers the

whole visible region.
Photocontrolled waveguides can be fabricated in
photochromic glasses. These waveguides can serve
as attenuators and mode selectors.
Colour centres
• Defect in the regular spacing of atoms within a
solid that absorbs visible light of a particular
colour or infrared or ultraviolet radiation, thus
lending a characteristic colour to the solid.
• Each colour centre involves the absence of an
atom from the place it would normally occupy
in the solid and the relation of an electron with
such an empty place, or vacancy.
• Solids without colour centres may still have
colour if impurity atoms or other structures that
absorb light are present.
Photosensitivity in glasses

Photosensitivity

Photosensitivity

Photosensitivity
Variation in glass properties when
exposed to optical radiation
• Intrinsic absorption (Basic fundamental)
• Extrinsic absorption (dopant)
• Induced absorption (defects)

Intrinsic absorption
• occurs due to electron transition in defect
free substances of stoichiometric
composition
• absorption of alkali silicate glass – 210 nm
(6 eV) – exponential dependence of the
absorption coefficient on photon energy
• Structural units of silicate glass – Si – O –
Na

Extrinsic Absorption
• small additives determines the actual
absorption of commercial silicate glasses in
near IR, visible and near UV
• caused by additional ions distributed in the

glass matrix and by bigger units -
microcrystals

Induced absorption
• By defects in the host substance created by chemical or

physical effect
• Produced by UV and gamma – caused by electrons and

holes at different colour matrix defects
• Photoinduced precipitation
• Colloidal coloration

Induced Coloration of reversible photochromic glass
Photochromic materials – a material which becomes

coloured by optical radiation and restores its
transparency after radiation ceases under specified
operating conditions.
Ex: Glasses doped with microcrystals of Ag and Cu
halides
They show complete reversibility of coloration at
room temperature

• Recently, organic and inorganic compounds have been found that
show reversible color or optical density changes-a property known
as photochromism.
• Reversible materials are activated by a uv source, and the color or
optical density returns to its original state when the source is
removed. The reversal process is not only sensitive to heat
(thermal fading), but also to visible light of relatively long
wavelengths (optical bleaching).
• The degree of color or optical density change depends on the
spectral distribution and the energy density of the total light
incident on the photochromic material. Optimum activating occurs
at wavelengths between 320 nm and 420 nm.
• Optimum bleaching occurs at wavelengths between 550 nm and
650 nm.
• The thermal fading rate increases at higher temperatures and is
relatively slow for some photochromic glasses at room
temperature
• Reversible photochromic glass, on the other
hand, has a host matrix impervious to halogen diffusion and the
released halogens are confined to the immediate vicinity of the
crystallites.
• Thus, gradual recombination can take place after cessation of
the activation irradiation. This process can be enhanced by
exposure to heat or to visible light of relatively long
wavelength.

Characteristics
• Integral and spectral sensitivity
• Darkening degree and rate
• Thermal fading
• Optical bleaching rate

Optical density
The change of optical density (activating or
bleaching) of photochromic glass depends mainly
on the following five parameters:
(1) the size and number of the silver halide
crystallites
(2) the thickness of the photochromic glass plate
(3) the applied light energy density
(4) the light wavelength
(5) the temperature

Optical Density

Main concepts required for photochromic material
characteristics
Light Absorption (Light attenuation)
(Absorption and scattering)
Optical density = - log10 (I transmitted light / I incident light)

Kinetics of photochromic glass darkening under
illumination and fading in the ageing process or the
criterion of relaxation Krel
• Let the optical density of a sample before irradiation (ie)
original absorption , clear glass = D0
• Let the optical density of a sample at the time of exposure
(ie) induced absorption , dark glass = Dexp
• Optical density in time ‘t’ sec of the thermal fading process
(induced absorption, partially relaxed glass) = Dt

Photochromic lenses as sunglasses
i) If a glass has faded completely in that time (time
interval = 180 sec)
Krel = 1
ii) If the induced absorption has not reduced at all (no

fading) Dt = Dexp
Krel = 0
Krel = 0 to 1
Krel - variation in temperature

• When the rate of color generation is
equal to the rate of thermal fading
• Criterion for relaxation characterises
the degree of thermal fading in a certain
time after illumination ceases

PHOTOCHROMIC LENSES
Photochromic lenses are lenses that
darken
visibly and fade indefinitely under
bright and dull light respectively.
Aphotochromic glass lens contains billions

of microscopic crystals of SilverHalide.
When exposed to direct sunlight or

UV light, these crystals absorb energy
and cause the formation of metallic
silver deposit on silver halide crystals..
Photochromic
lenses
Silver halide
Made up of two types of materials;
borosilicate glass and
aluminophospahte glass.
Transmittance range
 Fading rate
 Reaction time
Darkening process of photochromatic lens
• Glass photochromic lens usually come in two
basic colours – grey and brown.
• Technically it is possible to obtain other tint.
COLOR
If glass has
Grey color – absorption (transmission) spectrum is flat in
the visible region
Brown color – absorption in the blue region is greater than

in the red region
This dependence of Dexp and Dt on the time of illumination

or aging are the kinetics of coloration and relaxation

Spectral sensitivity
It is the dependence of the
saturated photoinduced optical
density (Do) on the photon energy
of the exciting radiation – colour
center generation spectrum

• Absorption edge of photochromic
glasses - determines the position of the
color center generation spectrum due to
the absorption of photosensitive
crystals

• Short wavelength edge color – due to decrease of
the thickness of layer containing color centre,
increase of glass absorption coefficient
• Long wavelength edge color is due to decrease in
the absorption and efficieny of photosensitive
centre ionisation

Optical bleaching by visible light
• Process additional to thermal fading
• Accelerates the relaxation of darkened
silverhalide PC glass

Cooperative breeding of color centers
• The long wavelength sensitivity due to
radiation results in generating new
color centres by exciting the same color
centre. This process is called
cooperative breeding of color centres

COOPERATIVE BREEDING OF COLOUR CENTRES
Colouration stimulated by long wavelength
Steps:
• Two colour centres generated by previous short wavelength
irradiation absorb two photons of long wavelength radiation
and are raised to an excited state
• These centres simultaneously transfer the accumulated energy
to a photosensitive centre and return to their ground state.
• The photosensitive centre is ionized and a mobile electron is
released.
• The released electron is localized at a trap that is the 1st stage
in a process of new colour generation.
Such a mechanism is called cooperative sensitization of colour
centre generation or cooperative breeding of colour centres.
 Photo‐thermorefractive glasses that have
irreversible photoinduced refraction are
aluminosilicate glasses doped with silver,
cerium, and fluorine.
 These glasses are sensitive to near UV radiation.
 Their photosensitivity is comparable with the
best organic and inorganic materials, it allows
wide variations of exposure because of image
amplification in the thermal development process
 It has high diffraction efficiency and high
transparency from the UV to the IR region.
Heterogeneous photo chromic glasses
The glasses were divided into two groups as a function
of the nature and state of the active components
inducing the
photochromic effect:
homogeneous
heterogeneous.

Two phases
• Viterous host phase
• Dispersed photosensitive microcrystals
 Microcrystals exhibit reversible PC effect without fatigue

 Attenuation may be due to the absorption of each phase + diff in
refractive indices of the two phases
 Particle size of the microcrystals – advisable to have (10 – 20
nm) – ref index wiil be about 2 – less scattering results
Two groups
Ag halide glass – less conc of Cu, therefore faster relaxation
and low sensitivity
Cu halide glass – less conc of Ag , slow relaxation and high
sensitivity
Photsensitive phase creation
Bottom – up
• Melting
• Rough annealing
• Cooling to RT
• Additional heat treatment
• Final annealing

Photsensitive phase creation
Top – Down
Mass production
Saves heat energy
Glass casting cools down roasting
temperature but not room temperature

• A group of heterogeneous photochromic glasses which
includes both glasses with silver halides and glasses with
copper halides have emerged based on their
physicochemical and photochromic properties in the
current stage.
• This has significantly broadened the concept concerning
the appearance of a microdisperse crystalline phase in a
continuous glassy matrix and the features of their
coexistence which are realized in the physicochemical
properties of the material.

The presence of such photosensitive compounds as silver
or copper halides sensitized with copper or cadmium
additives respectively, in heterogeneous PCG has been
convincingly demonstrated by x-ray phase analysis.

However, the potentialities of modem
methods of investigation have been
restricted in many cases due to both the
amorphous structure of the basic phase
and the freely disperse state and low
volume concentration of the
photosensitive phase.

It was found that the photosensitive
crystals initiate phase separation of the
glassy matrix according to the scheme of a
segregation mechanism and that it is still
very difficult to unambiguously interpret
the data obtained by electron microscopy,
small-angle x-ray scattering etc

1) with Kbas < 0.1, nonphotochromic
2) with Kbas = 0.1-0.28, a linear increase in induced absorption with an increase

in Kbas
3) with Kbas = 0.28-0.58, characterized by constant and high values of the

induced absorption; the photochromic
properties in this region are almost independent of the composition of the glass
and values of Kbas
4) with Kbas = 0.58-1.07, characterized by a decrease in the photochromic

properties from the maximum possible to
zero in the direction of an increase in Kbas;
5) with Kbas > 1.07, totally nonphotochromic.

• The basicity coefficient of the glasses Kbas can be
selected as a criterion capable of characterizing the
combined effect of the acid-base properties of glass
with consideration of possible coordination
transformations.
In the case of copper halide PCG, the following

composition regions can be distinguished on the UV-
induced absorption
curve ~t D620 -Kbas, where zXD620is the induced
absorption at the wavelength of 620 nm in optical
density units (Fig. 1):

Ra Module Ii

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Ra Module Ii

Uploaded by

Copyright:

Available Formats

SRI RAMAKRISHNA ENGINEERING COLLEGE

[Educational Service: SNR Sons Charitable Trust]

03/21/2024 Robotics and Automation 1

Introduction - Physical principles of

21/03/2024 ROBOTICS AND AUTOMATION 2

Induced coloration is a wide band that covers the

21/03/2024 ROBOTICS AND AUTOMATION 6

21/03/2024 ROBOTICS AND AUTOMATION 7

21/03/2024 ROBOTICS AND AUTOMATION 8

21/03/2024 ROBOTICS AND AUTOMATION 9

21/03/2024 ROBOTICS AND AUTOMATION 10

• caused by additional ions distributed in the

21/03/2024 ROBOTICS AND AUTOMATION 13

• By defects in the host substance created by chemical or

• Produced by UV and gamma – caused by electrons and

21/03/2024 ROBOTICS AND AUTOMATION 15

Photochromic materials – a material which becomes

21/03/2024 ROBOTICS AND AUTOMATION 18

21/03/2024 ROBOTICS AND AUTOMATION 26

21/03/2024 ROBOTICS AND AUTOMATION 27

21/03/2024 ROBOTICS AND AUTOMATION 28

21/03/2024 ROBOTICS AND AUTOMATION 29

Optical density = - log10 (I transmitted light / I incident light)

21/03/2024 ROBOTICS AND AUTOMATION 30

21/03/2024 ROBOTICS AND AUTOMATION 31

ii) If the induced absorption has not reduced at all (no

21/03/2024 ROBOTICS AND AUTOMATION 32

21/03/2024 ROBOTICS AND AUTOMATION 34

Aphotochromic glass lens contains billions

When exposed to direct sunlight or

Brown color – absorption in the blue region is greater than

This dependence of Dexp and Dt on the time of illumination

21/03/2024 ROBOTICS AND AUTOMATION 39

21/03/2024 ROBOTICS AND AUTOMATION 43

21/03/2024 ROBOTICS AND AUTOMATION 44

21/03/2024 ROBOTICS AND AUTOMATION 45

21/03/2024 ROBOTICS AND AUTOMATION 46

21/03/2024 ROBOTICS AND AUTOMATION 47

21/03/2024 ROBOTICS AND AUTOMATION 53

 Microcrystals exhibit reversible PC effect without fatigue

21/03/2024 ROBOTICS AND AUTOMATION 56

21/03/2024 ROBOTICS AND AUTOMATION 57

21/03/2024 ROBOTICS AND AUTOMATION 58

21/03/2024 ROBOTICS AND AUTOMATION 59

21/03/2024 ROBOTICS AND AUTOMATION 60

21/03/2024 ROBOTICS AND AUTOMATION 61

2) with Kbas = 0.1-0.28, a linear increase in induced absorption with an increase

3) with Kbas = 0.28-0.58, characterized by constant and high values of the

4) with Kbas = 0.58-1.07, characterized by a decrease in the photochromic

5) with Kbas > 1.07, totally nonphotochromic.

21/03/2024 ROBOTICS AND AUTOMATION 63

In the case of copper halide PCG, the following

You might also like