Glass and Glass Ceramics

MM 353 Smart and Functional Materials

Spring 2021
 Glasses and Glass Ceramics

Glass has a short range network structure

Glass Fibers: Ternary system CaO-Al2O3-SiO2
replacing some SiO2 for B2O3 and some CaO
for MgO. (B2O3 increases the working range)

Glass Ceramics Silica glass Hollow glass fibers

Glass ceramics are fine grained polycrystalline materials which are formed when
glasses of a suitable composition are heat treated and hence undergo controlled
recrystallization (50% – 98%)

Zero porosity, high strength, toughness, translucency or opacity, pigmentation, low

or even negative thermal expansion, high temperature stability, fluorescence,
machinability, ferromagnetism, high chemical durability, biocompatibility,
superconductivity, high resistivity and break down voltage.

A wide variety of glass-ceramic systems exists, e.g., the Li2O-Al2O3-nSiO2 System

(LAS-System), the MgO-Al2O3-nSiO2 System (MAS-System), the ZnO-Al2O3-nSiO2
System (ZAS-System).
Glasses and Glass Ceramics
 Glasses and Glass Ceramics

An oxide glass wets Au with a contact angle of 60o (left), whereas Au does not
wet an ionocovalent solid (right). The contact angle in this case is near 135o.
 Glasses and Glass Ceramics

IR spectrum of LAS parent glass and glass-ceramics

obtained by crystallization at various temperatures. The XRD patterns of a lithium aluminium silicate
Observe the well-defined absorption peaks for LAS-B, glass heat-treated at various temperatures. Note
indicating the more crystalline nature of the sample the amorphous nature of the as-prepared (L0) and
nucleated (L550) glasses.
 Windshields
The automobile industry is also a large consumer of glass for windshields.

These glasses must be transparent, tough and fulfil added functionalities.

To increase their toughness, glass panes are tempered by controlled

thermal treatment, leading to compressive stress at the surface.

Compressive stresses cause it to shatter into small pieces improving safety

Modern shields → Laminate glass → A layer of Polyvinyl Butryl (PVB)

between two layers of tempered glass. Bonded at 70oC in oil bath.

The PVB film can be coloured to give tints to the window and reduce solar
incursion.

Several layers of laminated glass and polycarbonate can be bonded

together to give bullet-resistant glass

Aluminium oxynitrides are light weight bullet proof glasses for large caliber
bullets
 Optical Properties
Glasses are transparent in the visible region owing to the absence of any
grain boundaries that may scatter light and the absence of any molecular
vibration modes corresponding to these frequencies.

Chalcogenide glass is a glass containing one or

more chalcogens (sulfur, selenium and tellurium, but excluding oxygen).
Such glasses are covalently bonded materials and may be classified
as covalent network solids.

Chalcogenide glasses have large molecular masses and as a result do not

show any vibrational transitions in the IR region of the spectrum. These
glasses are therefore transparent to IR radiation over a range of
wavelengths from 1.8 to 12 μm

By careful control of microstructure, the thermal expansion coefficient can

be brought close to zero. Zero expansion glasses/glass-ceramics are
important for telescopic mirrors.
One of the examples of a quartz-solid solution(ss)-based low expansion
glass-ceramic is Zerodur.
 Optical Properties

Transmission spectra of several IR glasses

compared with silica. The two glasses ZBLAN and
BIG are multicomponent fluoride glasses based
on ZrF4 and BaF2 (ZBLAN) and BaF2, InF3, GaF3 (BIG).
The glass 2SG is a selenium-based material Typical window glass with IR
containing the elements Se, Sb, Ge and Ga. The absorption capability to prevent
TeX glass is based on the combination of Te, Se
solar heat ingress into structures.
and I2, whereas the TeXAs is a similar glass with
the addition of As
 Thermal Expansion

A plot of thermal expansion versus temperature for Zerodur. Note the nearly zero CTE over a range of 200 - 450 K

CTE of the glass-ceramics depends upon the phases formed upon heat treatment.

In LZS, it has been seen that the phases depend upon the ZnO/(ZnO + SiO2) ratio

In the expansion-matched seal, the CTE of the glass-ceramic conforms closely with that
of the metal housing. In addition, the glass must wet the metal at the sealing
temperature and adhere to it.
 Glass Ceramic Machinability
Careful optimization of phases and microstructure can also make glass-
ceramics machinable.
This property, normally attributed to metals, allows the glass-ceramic to be
shaped and formed by conventional metal machining tools, greatly
simplifying the shaping process
Fluorine containing magnesium aluminium silicate glass-ceramics can be
heat treated suitably to allow the formation of a fluoropholgopite phase.
 Glass Ceramic Sealants
The property of some glasses and glass-ceramics to wet the metal producing
hermetic and high-pressure seals with different metals.
It has led to the fabrication of a variety of single- and multi-pin feedthroughs
for use in various sophisticated analytical instruments.
For sealing with high-CTE metals such as stainless steel or Ni superalloys,
lithium zinc silicate (LZS - Li2ZnSiO4) glass-ceramics may be used.
 Optical Fibers
Properties
The most important inherent properties of glasses is their transparency.
Transparency is the property of the glass that allows electromagnetic
radiation such as visible light to transmit through it with minimum
attenuation
The refractive index of the fiber material is controlled
by doping with a suitable material.
The central core is a high refractive index glass
surrounded by an outer cladding layer of low
refractive index glass, creating the condition for total
internal reflection.
Advantages of fibers for optical data transmission/communication
1. Light weight
2. Low loss
3. Wide bandwidth
4. Immune to electromagnetic interference
5. Flexibility
 Optical Fibers
Silica with and without doping has shown great promise for drawing optical fibres.
Reasons
1. Matured drawing technology
2. Cost benefits of using silicate glasses,
3. Fibre lengths of several hundred kilometres can be produced

Materials
Glass optical fibers are mostly made of silica,
but some other materials are also used such
as:
• Fluorozirconate glasses
• Fluoroaluminate glasses
• Chalcogenide glasses
• Sapphire (crystalline and used for longer-wavelength A sapphire waveguide
infrared or other specialized applications)

Silica and fluoride glasses usually have refractive indices of about 1.5, but some
materials such as the chalcogenides can have indices as high as 3.
Typically the index difference between core and cladding is less than one percent.
 Optical Fibers
Silica can be drawn into fibers at reasonably high temperatures, and has a fairly
broad glass transformation range.

Properties

Silica fiber has high strength against both pulling and bending (provided that the fiber
is not too thick and that the surfaces have been well prepared during processing).

These also show a high threshold for optical damage.

Silica glass can be doped with various materials to

control of refractive index
• GeO2 and Al2O3 increase refractive index
• Flourine and B2O3 decrease refractive index
Silica has a low solubility for rare earth ions (not
suitable for active fibers).

Hollow fibers
 Optical Fibers

Plastic optical fibers (POF) are commonly step-index

multi-mode fibers with a core diameter of 0.5
millimeters or larger.
POF typically have higher attenuation coefficients
than glass fibers

PMMA (RI 1.49) comprises the core (96% of the cross

section in a fiber 1mm in diameter) and fluorinated
polymers are the cladding material.
Higher performance graded-index (GI-POF) fiber
based on amorphous fluoropolymer (poly(perfluoro-
butenyl vinyl ether) is also widely used. PS is also used.
Polymeric Optical Fibers
Polymer optical fibers are typically manufactured using extrusion
Generally, fiber cladding is made of silicone resin (refractive index ~1.46)
PMMA is commonly used for low-speed, short-distance (up to 100 meters) applications in
digital home appliances, home networks, industrial networks.

The fluorinated polymer fibers are commonly used for much higher-speed applications
such as data center wiring and building LAN wiring.
 Optical Fibers
Fluoride glass is a class of non-oxide optical quality glasses composed of fluorides of
various metals.
ZBLAN fiber (ZrF4-BaF2-LaF3-AlF3-NaF) and AlF3- based fiber (AlF3-BaF2-SrF2-CaF2-MgF2-YF3)

Fluoride fibers have many unique characteristics that are not enabled by silica fiber, such as a
wider operating wavelength range, as well as a higher emission efficiency when doped with
rare-earth elements.

Applications
• Mid-IR spectroscopy
• Fiber optic sensors
• Thermometry
• Imaging
• Guided lightwave transmission
in media such as YAG lasers at
2.9 μm (medical applications
e.g. ophthalmology and
dentistry).
 Optical Fibers
Phosphate glasses can be advantageous over silica glasses for optical fibers with a
high concentration of doping rare-earth ions.
A mix of fluoride glass and phosphate glass is fluorophosphate glass
These are extremely versatile compounds, in that they can be crystalline or
amorphous, metallic or semiconducting, and conductors of ions or electrons.

Glass containing chalcogenides can be used to make fibers for far infrared
transmission.

The cladding is coated by a buffer that protects it from moisture and physical
damage

These coatings are UV-cured urethane acrylate

composite or polyimide materials applied to the
outside of the fiber during the drawing process.

The coatings protect the very delicate strands of

glass fiber (microns in diameter) and allow it to
survive the rigors of manufacturing, proof
testing, cabling and installation.