Glass 8 Mech

• The fracture behavior of glass is controlled by mainly environmental
factors not be the inherent strength of the bonds forming the

amorphous network.
• The fracture strength of glass varies with
• Prior surface treatment
• Chemical environment
• Method of strength measurement.
Other mechanical properties such as elastic modulus, may to some
extent be controlled by the inherent properties such as
• individual bond strength,
• structure of the network.
Elastic modulus
• Glasses exhibit nearly perfect Hookian behavior on application of stress.
• The ratio of strain, resulting from the application of a stress is constant
which is known as elastic modulus or Young’s modulus, is defined by the
expression:
δ = Eἐ
• If the tensile strength stress is applied to a specimen in x-direction, the
specimen will elongate in that direction.
• This elongation will be accompanied by contraction in y and z-directions.
• The ratio of transverse strain to axial strain is called Poisson’s ratio.
• For oxide glasses this ratio varies between 0.2 to 0.3; vitreous silica is 0.17
• Young’s modulus, shear modulus and Poisson’s ratio are related by the
expression:
G= E/2(1+γ), where γ = Poisson’s ratio.
• The elastic modulus of a material arises from the relation
between an applied force and the resultant changes in the
average separation distance of the atoms which form structure
of that material.
• If we consider the Condon-Morse curve for force F, as function of
atomic separation distance, r, we can write an equation :
F= -a/r n + b/r m
a,b,m and n are constants.
• The curve shows variation of force with distance of separation,
passes through a distance ro, which is the equilibrium spacing of
the atoms.
• Application of macroscopic force will increase the average
spacing an amount,
E =r-r0/r0, where r is the strained interatomic distance.
• The elastic modulus is equal to the slope of the force-distance
curve at r0.
• This simple model based on the Condon-Morse curve applies
quite well to highly ionic, close packed structures.
If the structure of glass is considered, it is found that the modulus is also influenced by
• Dimensionality and
• Connectivity.
• Connectivity of a structure with a trend towards increasing elastic moduli as the structure changes from a chain
structure to a layered structure to a fully connected three-dimensional network.
• Weak bonds between chains or layers effectively offset the influence of strong bonds between atoms within
the building blocks of the structure and allow easier distortion of the structure.
• The presence of breaks in the linkage within the structure, such as NBO, allows easier displacement of atoms
and reduces the elastic modulus.
• Replacement of modifier ions by Al3+ ions, which reduces NBO concentration and increase the connectivity of
the network, increases the elastic modulus of silicate structure.
• The highest elastic modulus for oxide glasses are found in glasses such as rare earth or yttrium alumino silicate
glasses which shows strong bonds and high packing density.
• Elastic modulus of inorganic glasses varies between 10 to 200MPa. Silica glass has 70MPa.
• Nitriding of these glasses, which provide 3-co-ordinated N2 linkages between tetrahedra, further increases the
elastic modulus.
• SIALON (silicon aluminium oxynitride) system shows very high value of elastic modulus.
• As elastic modulus is influenced by the bond strength, glass with high Tg usually has high elastic moduli. Glass
with low thermal expansion co-efficient value often have high elastic modulus.
• Hardness of glass is usually defined in terms of either the scratch hardness
using Mohs scale or indentation hardness using a Vickers indenter.
• Oxide glasses lie in the range of 5-7 on Mohs scale as they will scratch
apatite (hardness 0f 5) but will not scratch crystalline quartz (hardness 7).
• The Vickers hardness of oxide glasses ranges from 2 to 8 Gpa, with values
over 11GPa for nitride glass.
• These values are much lower than the Vickers hardness of diamond, which
is ~100GPa.
• Borate, germanate and phosphate glasses are softer than silicate glasses.
• Chalcogenide glasses are much softer with Vickers hardness values in the
range of 0.3GPa for vitreous selenium to over 2.0GPa for 3-dimensional
structures found in Ge-As-S glasses.
• In general, the effect of glass composition on hardness is parallel to the
elastic modulus.
Fracture strength of glass is usually much less than their theoretical strength.
• This strength can only be described in forms of distribution function and does not exhibit
a single value characteristics of a given glass composition.
• The reduction in strength is attributed to surface flaws which severely weaken the glass
structure.
Theoretical strength of a material is given by the force which must be applied to overcome
the maximum restorative force predicted in the previous equation.
Once the interatomic separation distance exceeds the distance corresponding to the
maximum restorative force, continued application of force will extend the bond distance
until the bond is broken and a crack can propagate through the material.
Orowan proposed that the stress necessary to break a bond is determined by the energy
necessary to create two new surfaces due to the fracture.
The Orowan stress is given by δm= √Eγ/ r0;
Where γ, fracture surface energy is the value in the range of 2 to 4 J/m-2.
It we put the values of E=70GPa, surface energy 3Joule/m2 and r0= 0.2nm into the
expression, theoretical strength of 32GPa for a silicate glass can be obtained.
Since terms in the expression are all independent of glass composition, glass has the
strength in the range of 1 to 100GPa, regardless of the composition.
Practical strength of glasses:
The strength calculated in the above expression are much higher than
those found in the practical applications of bulk glasses.
The reduction of strength is attributed to the presence of flaws in the
structure of glass.
These flaws act as stress concentrators, increasing the local stresses to
the levels exceeding theoretical strength and causing fracture of the
glass.
Griffith treated this problem in detail and derived the expression:
• c is the critical crack length for crack growth.
• Attainment of the critical length is only condition for crack
growth.
• It is also necessary for the stress at the crack tip to exceed the
theoretical strength of the material before the crack will grow
spontaneously.
• Orowan argues that any applied stress sufficient to exceed
Griffith criterion is usually sufficient to cause fracture.
• Flaws that are introduced by external factors, are not intrinsic
to the material.
• Flaw lengths are determined by prior treatment of the surface
and vary over several orders of magnitude.
• It follows that the inherent strength of a glass is usually of little
importance in determining the practical strength.
• Hardness of a glass can influence the practical strength through
its influence on the resistance to flaw formation, i.e. scratch
resistance.
The Sources of flaw and their removal:
How the critical or Griffith flaws are introduced into the glasses?
• Contact with any material which is harder than glass causes a flaw.
• Abrasion with hard material degrades the strength of the glass
• Contact with another piece of the same glass or with metal objects used to
handle glass is sufficient to generate flaws.
• Chemical attack can also generate flaws.
• Touching of glass with a fingertip will generate flaw through the attack on
the surface due to the NaCl deposition from the skin.
• Thermal stresses induced during rapid cooling of a glass introduce flaws
through thermal shock.
• Heating glasses for prolonged times – reduce their strength by formation of
a small number of surface crystals or by bonding of dust particles to the
glass surface.
Protection of glass surfaces from flaw formation is very difficult
• The surface of a freshly produced glass has a very high co-efficient of
friction for contact against other materials.
• Flaw generation can be reduced if a lubricant is applied to the fresh glass
surface before any flaws are formed.
• Lubricating coatings are often applied to the surface of glass containers just
after they exit from the annealing lehr.
• This coating must be resistant to wear, since any contact which penetrates
the coating will result in flaw formation on the underlying glass.
• Flaws can be removed by removing the outer surface of the material by
chemical etching or mechanical polishing.
• Etching blunt the flaw tip and reduces the flaw length, while polishing
simply reduces the length of the flaws to below the Griffith criterion.
• Flame polishing removes flaws through viscous flow in the near-surface
regions.
Strengthening of glass
The strength of the glass can be increased mainly by 2 methods :
1. By preventing formation of flaws
2. By removing those which do form
Removal is only effective for short times since new flaws are readily formed.
Preventing their formation by coating has proven to be limited value.
We have to accept the fact that flaws will be present, we have to
concentrate on the prevention of crack growth.
Since crack growth requires presence of tensile stress at the flaw tip,
creation of a near-surface compression region should prevent crack growth.
No growth will occur until the applied stress is large enough to overcome the
residual compressive stress and produce a tensile stress at the crack tip.
Compressive stress can be produced by the following processes:
1. Ion-exchange-exchange of alkali ions can be used to strengthen glass by producing a
compressive layer near surface region.
• If the exchange is carried out at temp well below Tg, very little relaxation will occur
during the exchange process.
• Special silicate glasses having high Na diffusivities have been developed for ion
exchange strengthening. These glasses have composition containing roughly equimolar
concentration of soda and Al2O3, where both Tg and Na-mobility are high.
Commercial borosilicate Practical strength of glasses:
The strength calculated in the above expression are much higher than those found in the
practical applications of bulk glasses.
The reduction of strength is attributed to the presence of flaws in the structure of glass.
These flaws act as stress concentrators, increasing the local stresses to levels exceeding
theoretical strength and causing fracture of the glass.
Griffith treated this problem in detail and derived the expression:
• Glasses do not strengthen significantly due to their low Na2O content, while relaxation
during exchange prevents the development of large compressive stresses.
2. Thermal tempering: it involves formation of a compressive layer by
rapidly cooling a glass from at or above the upper limit of glass
transformation range.
• Since interior of the glass will cool more slowly than the surfaces, the
fictive temp of the interior will be lower than that of the surface and
equilibrium density will be greater than that of surface region.
• As the interior and surface regions are bonded together, elastic
strains must arise to counter the difference in equilibrium densities.
• The surface region is placed in compression, while interior is placed in
tension.
• Differenced in fictive temperature is function of the differences in
cooling rate between interior and surfaces of glass, so that magnitude
of compressive stress increases with increasing cooling rate and glass
thickness.
• Thermal tempering is not very effective for very thin wall container or
fibres because only a small difference in cooling rate occurs, or
• For low expansion glasses such as vitreous silica or many commercial
borosilicate glasses where volume difference as function of fictive
temperature difference is small.
Application or formation of compressive coating:
• A compressive surface layer can be formed if a thin layer of material having a lower thermal expansion
co-efficient than the bulk glass can be created.
• Cooling the composite will create a compressive surface layer with a balancing tension region in the bulk glass.
• Application of a glaze can be carried out by fusing a thin sheet of glass with a lower Tg to the surface of a bulk
glass or by more traditional glazing methods involving application of a low melting glass frit.
• A variation of ion exchange method using an ion which is smaller that initially present in glass can also produce
a surface region of low thermal expansion co-efficient.
• If exchange of Na from the glass with Li+ from a bath occurs at temperature above Tg of the glass, relaxation
will occur, and chemical stuffing stress will not exist.
• Since the surface region now consists of Li+ rather than Na+, thermal expansion co-eff will usually be reduced in
this region.
• Cooling the glass will force the lower expansion region into the compression, while bulk glass in tension.
• The exchange of Li for Na offers another route to strengthening of glasses by formation of a surface crystallized
region. If the glass is an alkali alumino silicate, it may be possible to crystallize only the exchanged region,
forming a very low thermal expansion such as virgilite / spodumene.
• Cooling the material will place the crystallized region in compression and the substrate in tension.
• Formation of region which can be crystallized may also be possible
after in implantation of Mg2+ ions or by exchange of Ag+ for Na+ to
form a region with a nucleation density where crystallization will
occur more readily than in the bulk glass.
• Low expansion region can be obtained by removal of alkali from
surface region of soda-lime-silicate glasses.
• Exposure to SO2 vapor, which is often carried out to improve
chemical durability, leaches alkali ions from the surface, producing a
silica rich near surface region.
• Reduction in alkali concentration reduces the thermal expansion
co-eff and produces a compressive layer after cooling the glass.
Most acceptable measurement of is diamond indenter where
a square pyramid shaped small diamond indenter is pushed
into the material under a known load.
The size of the indentation is generally of the order of a few
microns under 5 to 1000gm load.
Vickers hardness number, VHN=1.854F/D2kgf/mm2

Glass 8 Mech

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• The fracture behavior of glass is controlled by mainly environmental

factors not be the inherent strength of the bonds forming the

Vickers hardness number, VHN=1.854F/D2kgf/mm2

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