Section 11:

PROPERTIES AND USE

OF GLASS

1
 Glass structure
Glasses exhibit an AMORPHOUS STRUCTURE:
• they have a disordered structure (non-crystalline);
• there is no long-range atomic order;
• there is short-range atomic order.

Crystalline SiO2 Non-crystalline

(quartz) (silica glass)

• Si atom
o O atom

Note that in silica glass the short-range order is only represented by the [SiO4]4-
2
tetrahedral unit (1 atom of Si surrounded by 4 atoms of O, forming a “pyramid”)
 Glass solidification Crystal solidification

Tg

Glasses do not solidify in the same sense of crystalline materials: upon cooling,
glasses become more and more viscous and there is no definite temperature at
which the liquid transforms into solid as for crystalline materials.

GLASSES:
CRYSTALLINE SOLIDS:
glass transition temperature Tg
above which glass melting temperature Tm
progressively softens 3
 Bonds in amorphous solids (e.g.
glasses) do not break all
together at a certain
temperature Tm: an exact
melting point cannot be defined,
but the amorphous solids
soften step by step.

Tg can be practically viewed as the temperature at which glass starts to

change from a rigid state to a “gum-like state”.

In glasses, we can define Tm as “liquid temperature”, i.e. the temperature

above which the material becomes a stable liquid (it completely changes
4
from a “gum-like” state to a liquid state).
 Glass formation
Glass-forming liquids: upon cooling, viscous molten material (mixtures of
inorganic oxides such as SiO2, CaO, Na2O, MgO…) reaches a temperature
below the solidification temperature without crystallization there is no time
for crystalline structure formation during conventional cooling of a glass-
forming liquid.

This occurs as atomic arrangement in liquid material is blocked by high

viscosity: the random atomic structure of the liquid is “frozen” in the solid state
out of thermodynamic equilibrium.

Example: viscosity of SiO2 fused at 1720 °C is about 109 times higher that
that of H2O at 20 °C!!!

Amorphous structures are thermodynamically metastable (they do not

represent the configuration at the lowest energy); therefore, they
progressively will move into crystalline structures according to
thermodynamic and kinetic conditions (DEVITRIFICATION can take several
thousands of years at room temperature, but this process can be accelerated
by thermal treatment below Tm). 5
 Glasses vs. ceramics?
Note that glasses formally belong to the class of CERAMIC
MATERIALS.

In fact, we can divide ceramics into 3 sub-families:

• FULLY CRYSTALLINE CERAMICS (e.g. most of rocks and stone

materials used in construction, that can be considered as “natural
ceramics”; cements, that can be considered “artificial ceramics”;
advanced or technical ceramics such as alumina and zirconia);

• GLASSES (completely amorphous, non-crystalline materials);

• GLASS-CERAMICS, in which one or more crystalline phases are

embedded in an amorphous matrix of residual glass; devitrification can
be deliberately carried out on starting glasses by thermal treatment to
impart better properties to the material (for instance, glass-ceramics
exhibit superior mechanical properties, such as strength, hardness and
stiffness, in comparison to their parent glasses). 6
 Glass constituents (inorganic oxides)

NETWORK
FORMERS: NETWORK
MODIFIERS:
(e.g. SiO2, B2O3):
oxides able to form (e.g. CaO, Na2O):
glassy structure oxides that are not able
to form glassy
(polyhedral) networks
INTERMEDIATES: but their cations are
incorporated into the
(e.g. TiO2, Al2O3): oxides
glass network (e.g. in
that do not form the network
the SiO2-based one)
but can substitute atoms of
the forming network, thereby
becoming part of the network
and stabilizing it
7
NETWORK FORMERS

NETWORK MODIFIERS

8
 Network of a
quaternary (4-oxide) glass
belonging to the
SiO2-Al2O3-NaO-CaO
system

9
 Glass synthesis
The most commonly used method used for making glasses is the
melting-quenching route

Reagents mixing in a
crucible (e.g. SiO2, Melting in high- Pouring in moulds (e.g.
carbonates of Na and temperature furnaces for windows) or in water
Ca, Al2O3…) (typically above 1000 °C) for very rapid cooling

Furthermore, upon cooling, soft glass can undergo pressing and/or air blowing (for
instance to produce bottles) or be drawn in fibres (for instance to be used as
reinforcing phase in polymer-matrix composites). 10
Float glass production use of a melted TIN bath

11
 Mechanical properties of glasses
Usually glasses are not used as structural materials, but they can sustain
loads (windscreen and glass windows are exposed to wind, impacts…)

Glasses are brittle materials!

Stress concentration near pores or
macroscopic defects (cracks, flaws)
brittle materials show better
strength under compressive load

Mechanical properties of glasses, together with other

physical properties (e.g. optical properties, transparency…)
STRONGLY depend on GLASS COMPOSITION (= the type
and amount of the oxides we use for making the glasses)

12
ELASTIC MODULUS: 50-90 GPa. It depends on oxide composition
alumina (intermediate oxide) makes the glass stiffer

HARDNESS: about 6 of Mohs’s scale

(Note: CRYSTALLINE silica or quartz grade 7 of Mohs’s scale)

FATIGUE RESISTANCE
Over time mechanical strength of a glass decreases and this trend is
emphasized by water and by sudden changes of T
Stress-corrosion occurs at the crack tip of a glass in water, as water
favours crack propagation thereby destroying the glass network
water Si-O-Si + H2O 2SiOH (hydration)

13
 Typical features of glasses

Density: 2.2-6.3 g/cm3; for common glasses 2.5 g/cm3

Hardness: 5.5-6.5 Mohs (for instance higher than metals, but lower than
quartz and granite)
Elastic (Young’s) modulus: E = 75 GPa
Compressive strength: σ = 1000 MPa
Tensile/flexural strength: σ = 40 MPa for common glasses; up to 200
MPa for special glasses
Thermal expansion coefficient: 9×10-6 K-1 (lower than metals but quite
high: for instance, a 2-m long glass fiber shows elongation of 0.72 mm
because of heating of 40 °C)
Thermal conductivity: very low
Thermal shock resistance: low for common glass, good for silica glass
Refractive index: n = 1.5 for common glasses 14
The most common glasses are silica-soda (SiO2-Na2O
system) glasses:
• Low cost
• Easy processing and forming
• Good resistance to devitrification and stability in water
• Al2O3 addition increases glass durability
• Uses: house windows, car/train windows, windscreens,
light bulb…
• Poor resistance to heat and to sudden changes of
temperature

15
 Coloured glasses
We can add chromophore ions in form of small quantities of special metal oxides
to the basic glass composition

16
Actually, colour in glass may be obtained in 2 ways:
(1) by addition of metal ions or metal oxides in the basic glass composition, in
which they will be homogenously distributed;
(2) by precipitation of fine particles (e.g. nano-sized magnetite, Fe2O3).

Ordinary silica-soda-lime (SiO2-Na2O-CaO) glass, that is usually employed for

making window glasses, appears colourless to the naked eye when it is thin,
although FeO impurities of up to 0.1 wt% may produce a pale green tint which
can be viewed in thick pieces or with the aid of scientific instruments.
Further FeO and Cr2O3 additions may be used for the production of green
bottles.
Sulphur, together with carbon and some iron salts, is used to form iron
polysulfides and produce amber glass ranging from yellowish to almost black.
Mn2O3 can be added in small amounts to remove the green tint given by FeO or
to impart a red to violet tint to the material.

In all these cases the glass remains transparent to visible light; however,
some cromophore ions may also act as opacyfing agent inducing
crystallization of one or more phases partial devitrification with formation
of an opaque GLASS-CERAMIC. 17
 Roman “cage cup” found in Cologne (4th century AD)
Fe2O3 was added to the silica-soda-lime composition to
impart the yellow colour.

Rose window of Northern front in Notre

Dame de Paris
(Late Gothic period, 15th century)
Some glass tesserae are original, but the
majority of them were apposed in the
course of restoration in the 19th century. 18
 Glass use in modern buildings
Glass for building is primarily used due to its TRANSPARENCY, as it allows
light to enter into rooms, thereby illuminating enclosed spaces, floors,
objects and framing an exterior view through a window.
Glass is also used as a material for internal partitions and external
decorations (glass-derived coatings obtained by glazing on external
claddings of the buildings fronts less expensive than stone materials).

Glass internal partition.

Glass-ceramic opaque standard or custom-made tiles, 19

that can be assembled to compose decorative motives.
 Special glasses for solar control or thermal insulation

These glasses mitigate the effects of continuous, intense and direct

solar irradiation

absorbent glass and reflective glass (summer)

and/or improve the thermal insulation of the windows

insulating glass and low-emission glass (winter)

General purpose: to reduce the costs of summer conditioning and

/ or winter heating

20
Absorbent glasses are coloured glasses due to the introduction of
coordinated metal oxides in the raw materials they partially stop incident
radiation through absorption

They emit some of the energy absorbed inwards, and the whole
transmittance curve is lowered compared to a clear glass, so that the
absorption of visible light may make artificial white lighting necessary even
during the day. 21
Transmittance curve

22
Reflective glasses mitigate the excessive solar irradiation by reflecting a
large fraction of the incident solar light towards the outside of the window.

They are produced by deposition of metals and / or metal oxides on their

surface:

Sputtering 23
Insulating glasses: presence of an airspace
If special gases are used better insulating effect (e.g. Ar, k = 0.016 W/mK)

Low-emitting glasses: coating with high reflectance in the IR (e.g.

multilayered coating of Ag and ZnO obtained by sputtering) 24
 Energy balance

In construction, the glass surfaces (e.g. windows) are crossed by

important thermal flows that affect energy consumption both in winter
(heating) and in summer (air conditioning).

These flows are:

a) THERMAL DISPERSIONS from the inside to the outside, controlled by the

transmittance U of the window;

b) SOLAR THERMAL FLOWS

from the outside to the inside,
controlled by the solar factor of
the glass window

25
 Winter energy balance

The thermal/energy balance of the glass surfaces (windows) is the algebraic

sum between the heat loss (negative sign) and the solar thermal
contributions (positive sign) calculated over the period considered (day,
month, season, year).
For the winter season it can be expressed by:

EB = S(-U ⋅ Gh + It ⋅ FS) , where

EB = energy balance in Watts (W)

S = glass window surface in m2 for given exposure
U = transmittance of the insulating glass in [W/m2 ⋅ K]
Gh = seasonal basic product = DD (day degrees) x 24 h
It = average solar irradiation for given exposure
FS = solar factor of the insulating glass used

26
 Example

You are required to determine the energy balance of the glass surfaces of an
apartment located in MILAN with independent heating and windows on the
north facade = 15 m2 and on the south facade = 10 m2.
The use of three types of glass is taken into consideration:
a) simple glass;
b) common insulating glass;
c) CLIMALIT-type insulating glass with Eko Plus (insulating material with
low-emissivity and argon layer).

The following climatic data are known:

DD (day degrees) in Milan: 2404
Internal temperature = 20 °C for 24 h

We can also calculate from the Tables in the next slides:

It N Northern exposure (from 15/10 to 15/04) = 94.289 W/m2
It S Southern exposure (from 15/10 to 15/04) = 309.573 W/m2
27
Notes:

DD (day degrees) = sum of the deviations of the average temperature T,

accumulated during the year, from an appropriate reference T, usually equal to
18.5-19 °C.

Only negative deviations are considered (winter).

From suitable tables (on engineer’s manuals and on the internet) you can see
the T deviation for each day and the sum of all the deviations for every year.

Examples: DD of Bologna = 2411, DD of Rome = 1578.

Based on the DD, the maximum duration in hours of heating is determined.

For places with DD between 2100 and 3000, a maximum of 14 h of heating
per day is allowed.

28
October and April: ½ month is considered (from 15/10 to 15/04) 29
October and April: ½ month is considered (from 15/10 to 15/04) 30
It =(It N ⋅ 15 m2 + It S ⋅ 10 m2 )/25 m2 =
= 180386 W/ m2 season (avg solar irradiation)
(seasonal
Gh = DD ⋅ 24 h = 2404 ⋅ 24 = 57696 K/season basic product)
Known characteristics for the glass windows:
(a) (b) (c)
Transmittance U = 5.90 2.90 1.90
Solar factor FS = 0.85 0.76 0.70
From the general formula of EB:
EB = S(-U ⋅ Gh + It ⋅ Fs) , we will have these 3 cases:
A) EB = 25 ⋅ (-5.9 ⋅ 57696 + 180386.6 ⋅ 0.85) =
= - 4676.596 W/season dispersed
B) EB = 25 ⋅ (-2.9 ⋅ 57696 + 180386.6 ⋅ 0.79) =
= - 755.305 W/season dispersed
C) EB = 25 ⋅ (-1.9 ⋅ 57696 + 180386.6 ⋅ 0.70) =
= + 416.216 W/season earned 31
Conclusions:

The EB of the glass surfaces examined highlights the

remarkable advantages already obtained by the use of
common insulating glass windows.

If low-emissivity windows are used, the EB becomes

POSITIVE, i.e. the heat flow entering through the glass of the
windows is greater than that the glass itself has let out (thermal
dispersions).

32
 Safety glasses

Designers must choose glasses taking into account some severe

rules.

Glass sheets can be subjected to:

• Dynamic loads (wind, pressure of the crowd)
• Static loads (own weight, snow, hydrostatic pressure)
• Accidental loads (hail, vibrations, torsion, seismic phenomena)
• Impact with soft body (people and animals, usually accidental and
with low intensity)
• Impact with hard body (stones, burglary tools)
• Impact with projectile (fire-arms)
• Thermal shocks (fire)
33
 ARMOURED GLASS

Glass containing inside a metallic

network.
Mechanical strength is not particularly
enhanced (slight increase of bending
resistance) but there is flame
propagation delay in case of fire
if glass softens or breaks, metallic
network allows to maintain glass in its
position for certain period.
TEMPERED GLASS

Using physical or chemical

processes, permanent compressive
stress on the surface and tensile
stress in the core are induced
superior resistance to mechanical
impacts in windows
34
 MULTILAYERED GLASS

Float glass

Tempered glass

- Good shock resistance

- Rupture is localized
- Glass fragments remain attached to the
polymeric sheet 35
Multilayered glass
Foamed glass (or cellular glass)

Used for thermal and acoustic insulation, it has a cellular,

water-proof and gas-proof structure.

Main features: good insulation ability, low density, high chemical

stability, satisfactory mechanical performances (adequate
compressive strength).

It is characterized by a high amount of small, closed (non-

interconnected) PORES suitable for thermal and acoustic
insulation (air is a bad heat and sound conductor).

It is used for civil building (load-bearing substructures for roof,

paving, walls) and industrial use (high- or low-temperature
plants, gas tanks, chimneys, tunnels).
36
Commercial name:
FOAMGLAS® cell

Major constituents:
SiO2 65.77 %wt. strut
Na2O 13.44 %wt.
CaO 5.83 %wt.
Al2O3 5.58 %wt.

Minor constituents:
Fe2O3 ,MnO, K2O, SO3,
BaO, TiO2 , SrO, carbon
< 9.38 %wt. Others
SiO2
37
Attractive properties for use of FOAMGLAS® in building:
cheap, ease of processing, eco-friendly

FOMAGLAS® is an excellent material for civil construction and insulation

purposes. It is a lightweight, extremely fine-pored expanded glass with
millions of hermetically sealed pores. Since no diffusion can take place,
the material is watertight and achieves an efficient barrier against soil
humidity and vapour (NO PROBLEMS RELATED TO WATER
ENTRANCE, such as FREEZING-THAW CYCLES).

Besides the outstanding mechanical and thermal properties of the product,

foamed glass manufacture is an exemplary process for WASTE
RECYCLING on an industrial basis. Foam glass can be manufactured fully
out of waste glass, with only a minimum of virgin additives.

Foamed glass grain is the product of choice wherever a finely grained,

free-flowing bulk material is required. It is especially suitable for thin-walled
thermal insulations, such as for window frames, cement bricks and
insulating plasters (FOAMGLAS® is often joined to another “traditional
38
”material).
Foamed glass is prepared by gas
blowing in a glass melt upon cooling,
or by introducing in the starting glass
composition particular components
that, upon heating (reagents melting)
can decompose developing gas.

Foamed glass processing is eco-

friendly: the majority of the starting
raw material is constituted by glass
from broken windscreen, recycled
glass and silica sandstone.

Starting glass scraps are molten, and

the produced glass is ground and
milled with coal powder.

This glass/coal blend is then

introduced in appropriate moulds that
are only partially filled; the moulds are
sealed and thermally-treated in a
temperature range within 600-800 °C.

Upon heating, glass powders

sinter and gas bubbles develop
(coal burning-out), thus the mass
39
occupy the whole mould volume.
 FOAMGLAS® applications
in Building Engineering

Thermal insulation of:

• Basement walls and floors

in dry soil and groundwater

• External (and also internal

if necessary) walls

• Flat roofs, also covered by

vegetation and subjected to
vehicles weight

• Roofs of complex shape

(slopes, curvatures), for
instance if coated by metal
40
tiles
• FOAMGLAS® is mainly fabricated in form of plates or panels (=
assembled plates), but can be also modelled in complex shapes.
• The plates and panels are normally put in place with the aid of
molten bitumen (= blend of petroleum-derived natural
hydrocarbons) or by means of synthetic adhesives.
• FOAMGLAS® is manually cut and requires no special tools for
installation or for the protection of the operator.

41
Isolation of external walls by using glass-coated
panels of foamed glass

Bitumen to fix
the foamed glass
panel to the wall
The FOAMGLAS®
panel can be
coated with
coloured glass

Compact glass layer (also imparting

nice aesthetic effect to the wall or acting
as a substrate for the application of other materials)

EASE OF FOAMGLAS®
INSTALLATION! 42
 “Self-cleaning” glass surfaces

Layer of TiO2: under UV exposure photocatalysis (degradation of organic

contaminants) + improved hydrophilicity 43