Glass and Glass‐Ceramics

Glass and Glass Ceramics
Classification of ceramic materials on the 
b i f
basis of application
li i
• solids
solids in which the atomic arrangement is 
in which the atomic arrangement is
more characteristic of liquids
• do not have unique melting points but rather 
do not have unique melting points but rather
soften over a temperature range
• viscosity increases gradually as the 
i i i d ll h
temperature is lowered
 Inorganic Glasses
Non‐crystalline materials especially based on silica (others are based on fluorides, sulfides 
and alloys). Define glass: a metastable material that has hardened and become rigid without 
crystallizing. Below the glass temperature the rate of volume contraction on cooling is 
reduced and material considered glass not undercooled liquid.  

Crystalline 

Undercooled
Glass  liquid
Density 

liquid

Tgg Tm

When silica crystallizes on cooling, abrupt change in the density is observed
 Glass Properties
Glass Properties
•  Specific volume (1/ρ) vs Temperature (T): 

•  Crystalline materials: 
C t lli t i l
Specific volume ‐‐ crystallize at melting temp, Tm
‐‐ have abrupt change in spec.
SSupercooled 
l d Liquid vol at Tm
vol. at T
Liquid (disordered)

Glass 
l • Glasses:
•  Glasses: 
(amorphous solid) ‐‐ do not crystallize
Crystalline 
‐‐ change in slope in spec. vol. curve at 
(i e ordered)
(i.e., ordered)  solid glass transition temperature Tg
glass transition temperature, T
Tg Tm T ‐‐ transparent  ‐ no grain boundaries to 
scatter light
Adapted from Fig. 13.6, 
C lli t & R th i h 8
Callister & Rethwisch 8e. 

5
 GLASS PROPERTIES

• Specific volume (1/ρ) vs Temperature (T):

Specific volume
• Crystalline
C t lli materials:
t i l
Liquid --crystallize at melting temp, Tm
Supercooled (disordered)
Liquid --have abrupt change in spec.
vol.
l att Tm
Glass
(amorphous solid)
Crystalline
• Glasses:
(i e ordered)
(i.e., solid --do not crystallize
Tg Tm T --spec. vol. varies smoothly with T
Adapted from Fig. 13.5, Callister, 6e.
--Glass transition temp, Tg
• Viscosity:
Vi it τ
--relates shear stress & dv
velocity gradient: τ=η glass dv
dy dv
y
dy dy
--has
h unitsit off (Pa-s)
(P ) τ velocity gradient

9
Glass Formation
Kinetics of Glass Formation
critical cooling rate (CCR)
 Criteria for Glass Formation

1 . A low nucleation rate. This can be accomplished by having either a small 
∆Sf or a large crystal/liquid interfacial energy. The lower ∆Sf and/or the 
higher γSL, the higher ∆Gc, and consequently the more difficult the 
nucleation.
2. High viscosity ηm at or near the melting point. This ensures that the
growth rate will be small.
3. The absence of nucleating heterogeneities that can act as nucleating 
g g g
agents, the presence of which can reduce the size of the critical nucleus 
and greatly enhance the nucleation kinetics. 
• Based on items 1 and 2 above, a useful criterion for the formation of a
,
glass is the ratio
Criteria for Glass Formation
 Typical compositions of some common
commercial glasses and their softening points
i l l d h i f i i
•  Basic Unit: 
Glass Structure
Glass Structure
Glass is noncrystalline (amorphous)
•  Fused silica is SiO2 to which no 
4‐ p
impurities have been added 
Si0 4 tetrahedron
•  Other common glasses contain 
Si 4+ impurity ions such as Na+, Ca2+, 
Al3+, and B3+ 
O 2‐
A chemical impurity 
such as Na+ is a 
glass modifier, 
•  Quartz is crystalline Na + breaking up the
breaking up the 
SiO2:  random network 
Si 4+
and leaving 
O 2‐ nonbridging oxygen 
ions

(soda glass)
Adapted from Fig. 12.11, 
Adapted from Fig 12 11
Callister & Rethwisch 8e. 

12
 Glass Properties: Viscosity
Glass Properties: Viscosity
•  Viscosity, η: 
‐‐ relates shear stress (τ) and velocity gradient (dv/dy):
relates shear stress (τ) and velocity gradient (dv/dy):

τ
dy dv τ
glass dv
dy
η=
dv / dy
τ
velocity gradient

η has units of (Pa‐s)

13
Log Glass Viscosity vs. Temperature (viscosity–
p g )
temperature characteristics of the glass)
•  Viscosity decreases with T
• soda‐lime glass: 70% SiO2
balance Na2O (soda) & CaO (lime)
• borosilicate (Pyrex): 
13% B2O3, 3.5% Na2O,  2.5% Al2O3
• Vycor:  96% SiO2,  4% B2O3
• fused silica:  > 99.5 wt% SiO
fused silica: > 99 5 wt% SiO2

10 14 strain point
osity [Paa‐s] 

annealing point
10 10

10 6 Working range: 
Visco

glass‐forming carried out
10 2 Adapted from Fig. 13.7, Callister & Rethwisch 8e. 
Tmelt (Fig. 13.7 is from E.B. Shand, Engineering Glass, 
1 Modern Materials, Vol. 6, Academic Press, New
Modern Materials, Vol. 6, Academic Press, New 
200 600 1000 1400 1800 T(ºC) York, 1968, p. 262.)

14
 Important Temperatures
•Melting point = viscosity of 10 Pa.s
•Working point= viscosity of 1000 Pa.s
•Softening point= viscosity of 4x107Pa.s
Temperature above which glass cannot 
be handled without altering dimensions)
be handled without altering dimensions)
•Annealing point= viscosity of 1012 Pa.s.
•Strain point = viscosity of 3x1013Pa.s 
Fracture occurs before deformation

• Viscosity decreases with T

• Impurities lower Tdeform
1.The melting point corresponds to the temperature at which
the viscosity is 10 Pa-s (100 P); the glass is fluid enough to
b considered
be id d a liliquid.
id

2. The working point represents the temperature at which the

viscosityy is 103 Pa-s ( 104 P);
); the glass
g is easily
y deformed at this
viscosity.

3. The softening point, the temperature at which the viscosity

is 4x106 Pa-s
Pa s (4x107 P),
P) is the maximum temperature at which a
glass piece may be handled without causing significant
dimensional alterations.

4. The annealing point is the temperature at which the

viscosity is 1012 Pa-s (1013 P); at this temperature, atomic
diffusion is sufficiently rapid that any residual stresses may be
removed within about 15 min min.

5. The strain point corresponds to the temperature at which

the viscosity becomes 3x1013 Pa-s (3x1014 P); for temperatures
below the strain point, fracture will occur before the onset of
plastic deformation. The glass transition temperature will be
above the strain point.
 Heat Treating Glass
Heat Treating Glass
•  Annealing:
‐‐ removes internal stresses caused by uneven cooling.
•  Tempering:
p g
‐‐ puts surface of glass part into compression
‐‐ suppresses growth of cracks from surface scratches.
‐‐ sequence:

before cooling initial cooling at room temp.

cooler compression
hot hot tension
cooler compression

‐‐ Result:  surface crack growth is suppressed.

17
 Residual Stresses
Figure 11.33 Residual
stresses in tempered glass
plate, and stages involved in
inducing compressive surface
residual
id l stresses
t ffor iimproved
d
strength.
•Large amount of energy 
stored from residual 
t Æ shatters into 
stresses Æ h tt i t
a large number of 
pieces when broken

•Chemical tempering: exchange of ions in bath of molten KNO3, K2SO4, NaNO3
Æ compressive stresses on the surface
The strength of glass  Tempered Glass
can be enhanced by
can be enhanced by 
inducing compressive 
residual stresses at the 
surface.
surface

The surface stays in 
y
compression ‐ closing 
small scratches and 
cracks.
cracks
 Hardening Processes
Hardening Processes

• Tempering:
– Glass heated above Tg but below the softening point
– Cooled to room temp in air or oil
Cooled to room temp in air or oil
– Surface cools to below Tg before interior
– when interior cools and contracts it draws the exterior into 
compression.
i

• Chemical Hardening:
– Cations with large ionic radius are diffused into the surface
– This strains the “lattice” inducing compressive strains and 
stresses.
 Silicates
– Combine SiO44‐ tetrahedra by having them share 
corners, edges, or faces

Mg2SiO4 Ca2MgSi2O7

– Cations such as Ca2+, Mg2+, & Al3+ act to neutralize & 
provide ionic bonding
 Layered Silicates
• Layered silicates (clay silicates)
– SiO4 tetrahedra connected 
together to form 2‐D plane

• (Si2O5)2‐
• So need cations to balance charge
=
Silicate glasses are most widely used, fused silica made from pure silica has high melting 
point and the dimensional changes during heating and cooling are small. Oxides can be 
classified as glass formers (silica), intermediates (aluminium oxide) and modifiers 
g ( ) ( )
(magnesium oxide) – cause glass to devitrify or crystallize as they break up the network 
structure. 

Modified silicate glasses; 
Modified silicate glasses;
Modifiers break up the network of the silica. When Na2O is added Na+ ions enters the holes 
in the network while O2‐ ions becomes part of the network structure. The O:Si ratio becomes 
large and when it reaches 2.5 glass is difficult to form. Modifiers reduces melting points and 
viscosity of the silica making it possible to produce glass at lower temperatures.

Glass formers – B2O3, SiO2, GeO2, P2O5, V2O3

Intermediates – TiO2, ZnO, PbO2, Al2O3, BeO  

Modifiers – Y2O3, MgO, CaO, PbO, Na
Modifiers – MgO CaO PbO Na2O  O
 Glass manufacturing

At high temperatures and with viscosity controlled so that glass can be shaped 
without breaking. 
Liquid range – sheet and plate glass produced when glass is in a molten state. Liquid 
tin used to form smooth surface on glass.

Working range – shapes for containers or light bulbs can be formed by pressing, 
d
drawing or blowing glass into molds. Glass is heated in the working range so that is 
i bl i l i t ld Gl i h t d i th ki th t i
formable but not runny. 

Annealing range –
Annealing range annealed to reduce residual stresses during forming. Large glass 
annealed to reduce residual stresses during forming Large glass
castings are often annealed and slowly cooled to prevent cracking.

Tempered glass 
Tempered glass – quenching the surface of plate glass with air causing the surface 
quenching the surface of plate glass with air causing the surface
layers to cool and contract. Used in car and home windows shelving for refrigerators, 
ovens, furnitures. 
Laminated glass – consist of two annealed glass pieces with a polymer 
(polyvinylbutyral, PVB) in between used to make car wind shields.  
GLASSES transparent and easily shaped
GLASSES – transparent and easily shaped
Noncrystalline Silicates + oxides (CaO, Na2O, K2O, Al2O3)
E S d li
E.g. Soda lime glass = 70wt% SiO
l 70 % SiO2 + 30% [Na
30% [N 2O (soda) and CaO(lime) 
O ( d ) d C O(li )
Glass SiO2 Al2O3 CaO Na2O B2O3 MgO PbO
Fused silica 99
vycorTM 96 4
PyrexTM 81 2 4 12
Gl
Glass jars 74 1 5 15 4
Window glass 72 1 10 14 2
Plate
ate glass
g ass 73
3 1 13
3 13
3
Light bulbs 74 1 5 16 4
Fibers 54 14 16 10 4
Thermometer 73 6 10 10
Lead glass 67 6 17
Optical flint 50 1 19
Optical crown 70 8 10
E-glass fibers 55 15 20 10
S-glass fibers 65 25 10
Glass Composition – most glass are based on silica, modifiers such as Na2O (soda), 
CaO. Common commercial glass contains approximately 75% SiO2, 15%Na2O and 10% 
CaO = soda line glass. Borosilicate glass – contains 15% B2O3, used in lab glassware, 
glass ceramics and containers for high level radioactive waste. 

Calcium aluminosilicate glass or E‐glass (20% Al2O3, 12%MgO and 3%B2O3) – used for 
general purpose fiber for composite materials such as fiber glass.
l fib f it t i l h fib l

Fused silica – gives best resistance to high temperature, thermal shock and chemical 
attack Photochromic glass darkened by the UV portion of sunlight used for 
attack. Photochromic glass – darkened by the UV portion of sunlight used for
sunglasses. Polychromatic glasses – sensitive to all light not just UV light.   
 Glass coloring and color marking
Obtained by 
Ob i db
1) addition of coloring ions
2) precipitation of nanometer sized colloides (so called striking
2) precipitation of nanometer sized colloides (so‐called striking 
glasses such as "gold ruby” or red "selenium ruby“)
3) by colored inclusions (as in milk glass and smoked glass), 
4) by light scattering (as in phase separated glass), 
5) by dichroic coatings (see dichroic glass), or
6) by colored coatings.
(The addition of oxides, sulfides, salts, and other compounds 
of different metals to molten glass at the time of manufacture
of different metals to molten glass at the time of manufacture 
adds color to glass. The introduction of electrically charged 
ions which are evenly distributed in the glass during 
manufacture also gives glass a characteristic color)
f l i l h i i l )
 Glass Colouring
Metal/Compound Color
Cobalt oxide ((0.025 to 0.1%)) Deepp blue
Pure copper Dark red
Copper oxide, copper compounds (2 to 3%) Turquoise (opaque blue‐to‐green ), light blue, red
Chromium Dark green to black
Chromium,, tin oxide and arsenic Emerald ggreen
Cadmium sulfide Deep yellow
Titanium Yellowish brown
Ferrous oxide, iron oxides Bluish green, greens, browns
g concentration of manganese
High g Amethyst
y (moderate, transparent violet)
( , p )
Nickel with lead crystals Purple
Gold, gold chloride Ruby red/cranberry red, reds
Silver halides Yellowish orange to red
y
Didymium Green or lilac red
Tin oxide and antimony Milky white
Cerric Oxide Brown
Magnesium Oxide Violet
g
manganese oxides deepp amber,, amethyst,
y , decolorizer
selenium compounds ruby red
carbon oxides amber/brown
mix of mangnese, cobalt, iron Black
antimony y oxides white
uranium oxides ((0.1 to 2%)) yellow green (glows!)
sulfur compounds amber/brown
lead with antimony yellow
 Glass ceramics
• Polycrystalline materials produced by the 
controlled crystallization of glass
controlled crystallization of glass 
• Composed of randomly oriented crystals with 
some residual glass typically between 2 and 5
some residual glass, typically between 2 and 5 
percent, with no voids or porosity.
• most attractive attribute of this class of 
t tt ti tt ib t f thi l f
materials is the ease with which they may be 
f bi t d
fabricated
Glass ceramic
Glass–ceramic

Scanning electron micrograph

showing the microstructure of a
glass–ceramic
glass ceramic material. The long
acicular blade-shaped particles
yield a material with unusual
strength and toughness. (65,000 x).
(Ph t
(Photograph h courtesy
t off L.
L R.
R
Pinckney and G. J. Fine of Corning
Incorporated.)
Glass ceramics – are crystalline materials derived from amorphous glasses. Glass‐ceramics have a 
substantial level of crystallinity (>70 – 99%). Formability and density of glass becomes important. Glass is 
crystallized using heterogeneous nucleation by such oxides such as TiO2 and ZrO2. In making glass ceramics 
– first step is to assure that no crystallization during cooling from the forming temperature.      
first step is to assure that no crystallization during cooling from the forming temperature

Cooling must be rapid to avoid the start of crystallization. Isothermal and continuous cooling values for 
lunar glass The rate of nucleation of precipitates is high at low temperatures whereas rate of growth is
lunar glass. The rate of nucleation of precipitates is high at low temperatures, whereas rate of growth is 
high at higher temperatures

Heat treatment profile for glass‐ceramic fabrication. 
Melting
1600
liquidus Forming
1250 ‐4 x 104

poise)
Teemperaturee (°C)

Growth 
900
Softening 
Softening

Viscosity µ(p
Nucleation ‐107.6
point 800

Annealing 650 1013.4

‐1013 4

point

Time
Nucleation of the crystalline phase is controlled in two ways; first the glass contains agents  such as 
Nucleation of the crystalline phase is controlled in two ways; first the glass contains agents such as
TiO2, that react with other oxides and form phases that provides the nucleation sites. Second heat 
treatment is designed to provide number of nuclei, the temperature should be relatively low in order 
to maximize the rate of nucleation. 
 Continuous cooling transformation diagram 
for the crystallization of a lunar glass
for the crystallization of a lunar glass

cooling rate represented by curve 2 is much greater than that for curve 1.
curve 1, crystallization begins at its intersection with the upper curve, and progresses
as time increases and temperature continues to decrease; upon crossing the lower
curve, allll off th
the original
i i l glass
l h
has crystallized
t lli d

cooling curve (curve 2) just misses the nose of the crystallization start curve. It is the
minimum cooling rate for which the final room-temperature
room temperature product is 100% glass
A nucleating agent (frequently titanium dioxide) is often added to glass to promote
crystallization. It shifts the begin and end transformation curves to shorter times.
 Sheet Glass Forming
Sheet Glass Forming
• Sheet formingg – continuous castingg
– sheets are formed by floating the molten glass on a pool of molten tin

Adapted from Fig. 13.9, Callister & 
Rethwisch 8e. 

35
 Pressed Glass Processingg

Softened
Gob
 Blow Molding
Blow Molding

Softened
glass
 Glass Tubingg
Figure 11.29 Manufacturing
process for glass tubing. Air is
blown through the mandrel to
keep the tube from collapsing.
Source: Corning Glass Works.

•Mandrel: rotating
Air is blown through the 
•Air is blown through the
mandrel ÅÆ tube 
collapse

•Drawing of continuous fibers: multiple orifices with speeds as high as 500 m/s
Æ fibers as small as 2㎛
•Short glass fibers: by centrifugal spraying process
 Steps in
Manufacturing a
Glass Bottle
: Blowing

Figure 11.30 Stages in

manufacturing an ordinary glass
bottle. Source: F.H. Norton,
Elements of Ceramics. Addison-
Wesley Publishing Company, Inc.
1974.
Glass Molding
Figure 11.31
Manufacturing a
glass item by
pressing glass in a
mold. Source:
Corning Glass
Works.

Figure 11.32 Pressing

glass in a split mold.
Source: E.B. Shand,
Glass Engineering
Handbook. McGraw-Hill,
1958.
 Centrifugal Glass 
C i
Casting
Figure extra Centrifugal
Fi C if l casting
i off
glass. Television-tube funnels are made
by this process. Source: Corning Glass
Works.

•TV picture tubes
•Missile nose cones