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Answers to 2nd Edition Questions

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Chapter 1
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id
qu
Li
id ed
qu ol
ation

Li erco
f or m
ns
s Tra nge

p
Su
G las
Ra
Enthalpy

C o ole d Glass
Fast
ss
C o o led Gla l
Slow Crysta

Tf T Tm
Slow fFast
Temperature
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Chapter 2
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1.

Tm
Temperature

Tn

1%
<CCR
1 ppm
>CCR CCR

tn
! Time of Heat Treatment
2.
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Tm
Metastable Zone of Undercooling
Tc

Growth Rate
Temperature

Nucleation Rate

Tg

! Rate
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A. Thermodynamics supports an increase in rates as the temperature decreases due to an
increase in G. Kinetics lead to a rate decrease as the temperature decreases due to decrease
in ion mobility (diffusion coefficients decrease).
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B. Growth can occur at any temperature below the melting point (Tm) provided a nucleus is
present from any source, i.e. either homogeneous or heterogeneous sources. Nuclei do not
have to be precipitated from the melt.
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C. Critical radius size is a result of competing terms. Gv (formation of volume) reduces the free
energy of the system, while (formation of surface) increases the free energy. The
net effect must be a decrease in free energy for formation of a stable nucleus. It follows that
there must exist a zone of metastability for nuclei.
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3.
A. CCR = 100/103 = 0.1 K/s
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B. CCR = 100/104 = 0.01 K/s
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4. The high viscosity at the melting point indicates a large kinetic barrier to crystal growth (low
diffusion coefficients). Since the atoms cant rearrange from the liquid structure to form a
crystalline network, a glass will form. Even if nuclei are present, growth is too slow to all
significant crystal formation.
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5. In this case, the viscosity is low at the melting point, which would allow growth to occur if the
melt were held in this temperature region and nuclei were present. However, the
rapid increase in viscosity with decreasing temperature means a rapid increase in the kinetic
barrier to nuclei formation with decreasing temperature and a very slow nucleation rate
by the time the temperature decreases below the critical temperature for stable nuclei.
Homogeneous nucleation hence does not contribute to crystallization. If no heterogeneous
nuclei are present, growth does not occur.
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Chapter 3
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1. (a) Glassforming oxide
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The oxide which forms the structural network of the glass and makes glass formation possible.
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SiO , B O , GeO , P O
2 2 3 2 2 5
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(b) Modifier oxide (flux)
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Oxides which do not participate in network formation, but serve primarily (in silicate melts) to
lower the temperature needed to produce a fluid melt.
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Na O, Li O, K O, PbO
2 2 2
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(c) Property modifier oxide
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Oxides which are used primarily to adjust properties of the final glass to meet commercial
requirements. They often partially counteract the fluxing contribution of the modifier
oxides.
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CaO, MgO, Al O , BeO, ZnO
2 3
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(d) Colorant
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Oxides which alter the color of the glass. These oxides are often added in very small quantities
and have little effect on the other properties of the glass.
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Transition metal oxides (FeO, Fe O , CoO, CuO, Mn O , Cr O )
2 3 x y 2 3
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Rare earth oxides (Pr O , Nd O , Er O , etc.)
2 3 2 3 2 3
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Elements which can form colloids (Au, Ag, Cu)
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(e) Fining agent
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Agents added in small quantities to aid in removal of bubbles from the melt. These oxides also
have little effect on the common properties of the glass.
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As oxides, Sb oxides, Na2SO4, NaCl, NaNO3, KNO3, etc.
2. Calculate the batch weights of each component needed to yield 50 grams of glass for each of
the following compositions. The raw materials to be used are SiO2, Na2CO3, CaO, Al2O3,
PbO, PbF2, and H3BO3. Indicate the total batch weight, the molecular weight of the glass, and
the weight of each component for each case.
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(a) Na O - 2SiO
2 2
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M.Wt of glass = 60.71 grams/mole Na2CO3 = 29.09 grams
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Total wt of batch = 62.08 grams SiO2 = 32.99 grams
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(b) 15 Na O - 10 CaO - 75 SiO
2 2
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M.Wt of glass = 59.97 grams/mole Na2CO3 = 13.26 grams
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Total wt of batch = 55.51 grams CaO = 4.68 grams
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SiO2 = 32.99 grams
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(c) 2Na O - Al O - 6SiO
2 2 3 2
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M.Wt of glass = 65.13 grams/mole Na2CO3 = 18.08 grams
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Total wt of batch = 57.52 grams Al2O3 = 8.70 grams
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SiO2 = 30.74 grams
(d) 20 PbO - 80 B2O3
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M.Wt of glass = 100.33 grams/mole PbO = 22.25 grams
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Total wt of batch = 71.56 grams H3BO3 = 49.31 grams
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(e) 20 PbF2 - 80 B2O3
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M.Wt of glass = 104.73 grams/mole PbF2 = 23.41 grams
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Total wt of batch = 70.64 grams H3BO3 = 47.23 grams
3. Convert the following glass compositions from wt% to mol% or vice versa (depending upon
which is given).
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(a) 25 mol% K2O - 75 mol% SiO2
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34 wt% K2O 66 wt% SiO2
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(b) 25 wt% K2O - 75 wt% SiO2
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17.5 mol% K2O 82.5 mol% SiO2
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(c) 20 mol% Na2O - 80 mol% SiO2
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20.5 wt% Na2O 79.5 wt% SiO2
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(d) 12 soda - 9 lime - 3 magnesia - 2 alumina - 74 silica (all given in wt%)
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11.5 mol% Na2O 9.5 mol% CaO 4.4 mol% MgO
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1.2 mol% Al2O3 73.3 mol% SiO2
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(e) 20 PbO - 80 B2O3 (mol%)
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44 wt% PbO 56 wt% B2O3
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4. Express the following compositions in stoichiometry formulae. (example - Li2Si2O5 for
lithium disilicate)
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(a) Na2O - 3SiO2 Na2Si3O7
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(b) 15 Na2O - 10 CaO - 75 SiO2 Na30Ca10Si75O175 = Na6Ca2Si15O35
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(c) Na2O - 2SiO2 Na2Si2O5
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(d) NaF - 2GeO2 NaGe2O4F = NaGe2FO4
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(e) As0.33S0.67 AsS2
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(f) 33 BaF2 - 17 AlF3 - 50 ZrF4 Ba33Al17Zr50F317
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(g) Na2O - Al2O3 - 4 SiO2 Na2Al2Si4O12 = NaAlSi2O6
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5. Write the general oxide formula for a series of glasses where
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(a) Silica is replaced by soda
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xNa2O-(100-x)SiO2 or xNa2O-(1-x)SiO2
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(b) Boric oxide is replaced by lime
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xCaO-(100-x)B2O3 or xCaO-(1-x)B2O3
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(c) Soda is replaced by alumina while maintaining a constant 75 mol% silica in all the glasses
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(25-x)Na2O-xAl2O3-75SiO2
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(d) Soda is replaced by alumina in a series of soda aluminosilicate glasses while maintaining a
constant 25 mol% soda in all the glasses
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25Na2O-xAl2O3-(75-x)SiO2
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(e) A constant ratio of Na2O to CaO of 1.0 is maintained while the total silica concentration
decreases.
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Na2O-CaO-xSiO2
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(f) Arsenic is replaced by sulfur
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As(1-x)Sx
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6. Why is there an optimum size for the sand used in glass melting, i.e. what problems occur if
the sand is (a) too coarse or (b) to fine?
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(a) If the sand is too coarse, the dissolution of the grains will be very slow, and the regions of
silica-rich melt will be very large, resulting in an inhomogeneous melt. The batch-free
time will be too long.
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(b) If the sand is too fine, agglomeration will occur, which prevents the more fluid portions of
the melt from reaching the inner regions of the agglomerates. This effectively slows the
melting process and again leads to inhomogeneous melts and long batch-free times.
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7. Describe the process of dissolution of a grain of sand in a glass in which the batch contains
NaCO3.
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(1) Na2CO3 = Na2O + CO2
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Decomposition of the carbonate to form very fluid Na2O plusCO2gas. The release of gas
causes foaming and stirring of the melt. The stirring action can improve homogeneity.
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(2) Na2O + 2SiO2 = Na2Si2O5
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Reaction of sodium oxide at the surface of sand grains produces very fluid sodium
silicate liquid.
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(3) This liquid continues to react with the sand grains. The melt gradually becomes more
viscous as the silica content of the liquid increases. Melting rate slows.
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(4) All sand is finally dissolved. With time, diffusion results in a homogeneous melt.
Stirring by convection, bubbles rising, or mechanical means speeds the homogenizing
process.
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8. Calculate the volume in liters of CO2 released during the preparation of 1 kilogram of a glass
with the composition 25 Na2O - 75 SiO2. Use Na2CO3 and SiO2 as the raw materials.
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Volume = 92.6 liters (STP) (601 liters at 1500C)
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9. Why does replacement of sodium carbonate by NaOH accelerate melting of a soda-lime-
silicate batch?
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2NaOH = Na2O + H2O
Sodium hydroxide decomposes at relatively low temperatures to yield sodium oxide and
water. The sodium oxide reacts with the sand as discussed in question 2. Water acts as a strong
flux, reducing the melting temperature of the sand and other refractory components of the
batch. Water vapor also forms bubbles, which rise to the surface. The rising bubbles stir the
batch and aid in homogenization and fining.
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10. State WHY the following reduce alkali volatilization losses from melts.
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(a) Reduction in temperature
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Rate of loss of alkali is a function of temperature, which decreases with decreasing
temperature. This process is similar to evaporation of a liquid, e.g. water, which has a similar
temperature dependence.
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(b) Covering the melt with a lid
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Covering the melt increases the partial pressure of alkali vapor in the atmosphere above the
melt. Once the partial pressure of alkali vapor reaches the equilibrium value for the melt
composition and temperature, alkali will leave and re-enter the melt at equal rates. If the melt
is not covered, the alkali vapor is continuously removed from the vicinity of the melt surface
and evaporation of alkali continues.
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11. Discuss the use of As2O5 as a fining agent. Describe how this oxide serves to both increase
the rate of bubble rise and to increase dissolution of gases from bubbles. Indicate the
conditions under which each process occurs.
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As2O5 = As2O3 + O2
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Arsenic is usually added to melts in the form of As2O3. A nitrate, e.g. KNO3 is usually also
added to these batches. During the initial heating of the batch, the nitrate decomposes,
oxidizing the arsenic to the pentavalent state. Release of O2 and NOx during this process
produces bubbles, which stir the melt and sweep smaller bubbles to the surface. Continued
heating to a higher temperature shifts the equilibrium described by the equation above toward
trivalent arsenic, releasing more oxygen, This oxygen diffuses into nearby bubbles, increasing
their diameter and thus increasing their rise rate. Lowering the temperature after
homogenization of the melt shifts equilibrium back toward the pentavalent state, which results
in absorption of oxygen from the melt to bond to the arsenic. Nearby bubbles shrink until they
are no longer stable, at which point they will disappear.
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12. Calculate the rate of rise of a bubble 2 mm in diameter in a melt with a viscosity of 130 Poise
(the cgs units of the poise are gm/cm-s). The melt density is 2.4 gm/cm3. (Use Stokes Law).
WATCH YOUR UNITS!!!
Rate = ____0.04___cm/s
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13. Discuss the rationale for bubbling helium through a glass melt as an aid in removing bubbles.
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Bubbling helium will produce large bubbles which rise rapidly, sweeping smaller bubbles to
the surface. Helium also diffuses rapidly in melts, so that it can enter existing bubbles and
increase their diameter. After bubbles are removed, any remaining helium can diffuse rapidly
to the surface and be removed without forming additional bubbles or leading to reboil.
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14. List and describe the 4 major sources of bubbles in glass forming melts.
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(a) Trapping of atmospheric gases during melting
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Bubbles contain atmospheric gases (N2, O2, Ar, CO2, H2O). These gases are trapped between
particles as the melt is formed. Their volume is limited to the free spaces between batch
particles. They contribute to foaming during the early stages of melt formation.
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(b) Decomposition of carbonates and other batch components
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Release of carbon dioxide, nitrous oxides, halides, water vapor, etc. from decomposing batch
materials usually results in far more gas than that simply trapped between melting particles.
These gases are reactive and can bond to the network in the form of carbonate, hydroxyl, etc.,
which makes them very difficult to remove. They produce foaming during the early stages of
melting, which may actually improve initial fining. At later times, however, the tend to
become supersaturated, which results in the formation of new bubbles in a bubble-free melt.
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(c) Supersaturation of the melt with a specific gas
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Supersaturation can occur by several methods. The term indicates a change in conditions
whereby a gas which was originally present in concentrations below its solubility limit now
exceeds its solubility limit. Carbon dioxide, for example, is very soluble in alkali-rich liquids,
but much less soluble in silica-rich liquids. The sodium oxide and high sodium silicates
produced during the initial stages of melting can thus contain a large concentration of carbon
dioxide. As the sand dissolves into this liquid, the solubility of carbon dioxide decreases until
the amount present exceeds the solubility limit and carbon dioxide precipitates into the melt
and forms bubbles. Changes in the oxidation state of polyvalent cations can change the
solubility of oxygen in the melt. Changes in furnace atmosphere can change the solubility of
sulphur in melts.
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(d) Reboil due to a change in temperature (a special case of supersaturation)
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The solubility of a few gases is very temperature dependent.This is especially true for sulphur
compounds. If the solubility is high at a high temperature, the gas will be dispersed through
the melt and not occur in bubbles. If cooling the melt reduces the solubility, the gas will
become supersaturated, precipitate from the melt, and bubbles will form. This frequently
occurs during reheating of soda-lime-silicate glasses.
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