MIT 3.

071
Amorphous Materials
2: Classes of Amorphous Materials

Juejun (JJ) Hu

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Network formers, modifiers and intermediates

 Glass network formers

 Form the interconnected backbone glass network
 Glass network modifiers
 Present as ions to alter the glass network
 Compensated by non-bridging oxygen (NBO) in oxide
glasses
 Usually reduce glass network connectivity
 Intermediates
 Can function as network formers or modifiers depending on
glass composition

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Network formers, modifiers and intermediates

O O

O Si O Si O Na2O

O O
Bridging oxygen
O O
Silicon:
glass former
O Si O- Na+ Na+ O- Si O
Sodium:
network modifier
O Non-bridging oxygen O

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  Glass former: high valence
state, covalent bonding with O
 Modifier: low valence state,
ionic bonding with O

Network modifiers Glass formers Intermediates

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Silica glass (SiO2)
 A 3-D glass network predominantly consisting of corner-sharing
SiO4 tetrahedra interconnected by bridging oxygen (BO)
 High network connectivity: high softening point, low diffusion
coefficient, small coefficient of thermal expansion (CTE)

Cristobalite

Image of vitreous silica removed

due to copyright restrictions.

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Volume anomaly in silica glass

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Alkali silicate glass
 Each alkali ion creates one non-bridging oxygen
 Reduced network connectivity: viscosity decreases (compared to
silica at the same T), diffusion coefficient and CTE increases
 Increased ionic conductivity, reduced chemical resistance

Invert glass
Increasing alkali concentration 7
Structural determination in alkali silicate glass
 Y : the average number of corners
shared per SiO4 tetrahedron Viscosity isotherms
 In a glass with molar composition:
Y=2
x Na2O · (1-x) SiO2
 Number of NBO per mole: 2x

log10(viscosity)
 Number of BO per mole: 2-3x
 Number of corners shared per
mole: (2-3x) × 2 = 4-6x
 Number of tetrahedra per
mole: 1-x
 Y = (4-6x) / (1-x)
 Onset of inverted glass structure:
Y = 2, x = 0.5
Y
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Alkali-alkaline earth-silicate glass
 Each alkaline earth ion creates two NBOs

Si O Si CaO Si O- Ca2+ O- Si

 Increased network connectivity compared

to alkali silicates: stabilized glass network,
improved chemical resistance
 Approximate composition of commercial
soda-lime glass (window glass):
 16Na2O·10CaO·74SiO2

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Borate glass
 B2O3: the glass former consisting of corner-sharing BO3 triangles
connected by bridge oxygen

B O

O B

B O

Boroxol rings: basic structural

unit in boric oxide glass

B2O3 crystal

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Borate glass
 B2O3: the glass former consisting of corner-sharing BO3 triangles
connected by bridge oxygen
 Alkali borate glass:
NBO formation
O O

B O 1/2 Na2O B O- Na+

O O

O O O

B O 1/2 Na2O B- Na+

O O O
B3 → B4 conversion

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 The Boron anomaly
Fraction of 4-fold coordinated boron

Initial addition of
alkali ions increases
B3 → B4 network connectivity,
conversion NBO formation reduces CTE and
enhances thermal &
chemical resistance

Molar fraction of alkali (%)

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Various properties of lithium borate glass

More than two

structural
transformations
contribute to the
boron anomaly

Further reading:
Shelby Ch. 5

J. Non-Cryst. Sol. 351, 1103-1112 (2005).

Courtesy of Elsevier, Inc., http://www.sciencedirect.com. Used with permission.
Source: Mazurin, O.V. "Glass Properties: Compilation, Evaluation, and Prediction."
J. Non-Crystalline Solids 351 (2005): 1103-1112.
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(Alkali) borosilicate glass
 Borosilicate glass: x M2O · y B2O3 · (1 - x - y) SiO2
 SiO2 and B2O3 : glass formers
 Alkali ions (M+) converts B3 to B4 states (when x / y < 0.5)
 Each additional alkali ion creates one NBO (when x / y > 0.5)
 The original Pyrex™ recipe: 4Na2O·13B2O3·2Al2O3·81SiO2

Image of space shuttle tile courtesy of the Science Museum London on Wikimedia Commons.
License CC BY-SA. Glassware images © Pyrex. All rights reserved. This content is excluded from
our Creative Commons license. For more information, see http://ocw.mit.edu/help/faq-fair-use/.

Space shuttle tile coating

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(Alkali) aluminosilicate glass

 Aluminosilicate glass: x M2O · y Al2O3 · (1 - x - y) SiO2

 SiO2 : glass former
 Al functions as a glass former in the form of AlO4 groups
(when x > y)
 Each excess Al atom creates three NBOs (when x < y)

y=x
Activation energy for
DC conductivity

y/x
Al3+ in an oxygen octahedron
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Chalcogenide glass (ChG)

 Reduced mechanical strength ACerS Bull. 94, 24-29 (2015).

 Low softening temperature
 Low phonon energy (infrared transparency)
 Enhanced optical (Kerr) nonlinearity
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Amorphous semiconductors
 Tetrahedral glasses
 a-Si, a-Ge, a-Si:H (hydrogenated amorphous silicon)
 Vapor deposition: plasma enhanced chemical vapor deposition
(PECVD), sputtering, electron beam evaporation

Dangling
bonds
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Metallic glass (amorphous metal, glassy metal)

Polycrystalline Amorphous
metal metal

Grain
boundaries

 Inoue’s empirical rules for bulk metallic glass (BMG) formation

 Multicomponent systems consisting of three or more elements
 Significant difference in atomic size ratios (> 12%)
 Negative enthalpy of mixing

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Other glass groups and glass formers
 Phosphate glass: P2O5
 Heavy metal oxide (HMO) and transition metal oxide glass
 TeO2, PbO, Bi2O3, V2O5, TiO2, etc.
 Halide glass and alloys
 e.g. ZBLAN: ZrF4-BaF2-LaF3-AlF3-NaF
 Chalcohalide, oxyhalide, etc.
 Amorphous minerals
 Opal, biominerals

and many others…

Amorphous calcium
carbonate in lobster
carapace

“The Formula for Lobster

Shell,” Max Planck Research
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Representation of glass composition

 In oxide glasses, the convention is to list the glass

network modifiers in increasing valence order ending
with glass network formers
 Example: K2O·CaO·5SiO2
 In mole fraction: 14.3K2O·14.3CaO·71.5SiO2
 By weight: 20.9K2O·12.4CaO·66.7SiO2 (wt%)
 In metallic glasses, the listing is usually done in
decreasing order of content
 Example: Zr41.2Be22.5Ti13.8Cu12.5Ni10.0 (Vitreloy-1)

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Summary
 Glass formers, network modifiers, and intermediates
 Silicate glass chemistry
 Corner-sharing tetrahedra
 Bridging and non-bridging oxygens
 Different modifiers: alkali, alkali earth
 Borates and boron anomaly
 Impact of network connectivity on glass properties
 Other glass systems
 Chalcogenides: weak bonds
 Tetrahedral glasses: passivation of dangling bonds
 Amorphous metals: w/o grain boundaries

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Summary of oxide glass chemistry

SiO2 (silicate) B2O3 (borate)

Structural unit: SiO4
Structural unit: BO3
No NBOs, low or negative CTE,
No modifier No NBOs, corrugated layered
high softening point, low
structure
diffusivity
Each ion creates 1 NBO; large
Each ion creates 1 B4 group or
CTE, low softening point, poor
Alkali oxide 1 NBO; extremum in glass
chemical durability, ionic
properties (boron anomaly)
conductivity
Each ion creates 2 NBOs;
Each ion creates 2 B4 groups
Alkaline earth similar effects as alkali ions
or 2 NBOs; extremum in glass
oxide although some network
properties (boron anomaly)
connectivity is preserved
Each ion creates 3 NBOs; in the B2O3 and Al2O3 both serve as
Alumina (Al2O3) presence of alkali ions Al3 → Al4 glass formers; glass is stable
conversion occurs only with high B2O3 content

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3.071 Amorphous Materials

Fall 2015

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