5.

60 CHAPTER FIVE

FIGURE 5.38 Logarithm of the permeability of helium gas versus 1000/T for various glasses. (After
F. J. Norton, J. Amer. Ceram. Soc., vol. 36, p. 90, 1953.)

5.16 ELECTRICAL CONDUCTION

5.15.1 Introduction

As stated in the earlier section, ionic motion is the dominant diffusion phenomenon in sil-
icate glasses. Of these, conduction by alkali ions makes up 99 percent or better of the
electrical transport in common silicate glasses. Hence, ions are the most mobile charge car-
riers. Since ions are less mobile than electrons, the silicate glasses are basically electrical
insulators relative to the metals, where electrons are the dominant charge carriers. There
is some electronic conduction in silicate glasses, particularly in those that have a signifi-
cant amount of transition metals, such as Fe, Mn, and V, displaying multivalency in glass.
Electronic conduction is predominant in elemental glasses, such as silicon, germanium, and
the chalcogenides, where such conduction is, in fact, responsible for the semiconductor
properties, and, perhaps, for much of the modern electronic industry. Glasses containing
fluoride ions display anionic conduction based on the transport of F −. Some silver- and
copper-containing glasses display fast ion conduction based on transport of charge by Ag+
and Cu+ ions.
The basic equation describing electrical conduction is Ohm’s law, according to which
the resistance Re (ohms) is given by
Re = V/I (5.46)
 INORGANIC GLASSES 5.61

V is the electrical potential (volts) applied across the conductor and I is the current (in
amperes) that flows. The resistance for a conductor having a cross-sectional area A and
length L is given by
Re = ρL/A (5.47)

where ρ is called the resistivity. Appropriate units for ρ are Ω · cm (in cgs) or Ω · m (in SI).
Conductivity σ is the reciprocal of resistivity; the units are often written as mho/cm or S/m
(siemens per meter). Conductivity is related to the diffusivity through the Nernst-Einstein
relation:

n( ze)2 D z 2 F 2 DC
σ= = (5.48)
H R kBT H R RT

where n is the number of charge carriers per unit volume, e is the electronic charge, z is the
valency, kB is the Boltzmann constant, R is the gas constant, C is the concentration in
mols/volume, and F is the Faraday unit of charge. HR is the Haven ratio, which correlates
charge conduction to the atomic motion in successive jumps. Often D/HR is written as Dσ .
The value of the Haven ratio for diffusion by a vacancy mechanism may be shown to be
approximately 0.4.

5.15.2 Temperature Dependence

The temperature dependence of resistivity is given by the empirically obtained Rasch-

Hinrichsen equation, which is
log rρ = A + [B/T ] (5.49)

where A and B are constants. The equation is essentially the Arrhenius equation of the form
valid for diffusion. For conductivity
σ ≅ σ 0 exp(−∆H/RT ) (5.50)

where the activation energy ∆H is essentially the same as that for diffusion.

5.15.3 Application of DC Potential across Glass

When a dc potential is applied across a thin disk of a silicate glass, the mobile alkali cations
(e.g., Na+) migrate from the anode region to the cathode region. The two nonbridging
oxygen anions, to which the two Na+ were attached, recombine to form one bridging oxygen
and release one O2−, which moves toward the anode. Glass is thus gradually electrolyzed.
The electrode reactions are

Cathode region: 2Na + + 2e → 2 Na 0

1 (5.51)
Anode region: O 2 − → 2e + O 2 ↑
2

Thus, metallic sodium is deposited on the cathode plate and oxygen is outgassed from the
anode region. The depletion of ions near each electrode builds a polarization field, which
causes a rapid decrease of current. In time, the current stops flowing. Oxygen outgassing
5.62 CHAPTER FIVE

FIGURE 5.39 Guard ring arrangement to measure dc conductivity.

and the motion of alkali ions, both under the influence of electric field, are a serious prob-
lem when glass is bombarded by charged particles, such as electrons in a television picture
tube or in instruments such as an electron microscope or an electron probe analyzer.

5.15.4 Measurement of Electrical Conductivity

Electrical conductivity of a glass may be measured by using a “guard ring” arrangement

(see ASTM C657-93) and an ac bridge circuit. Metallic electrodes, often as thin as approx-
imately 300 Å, are vacuum deposited on both sides of a glass disk. On one of the sides, the
deposition is carried out by using a ring mask—the outer ring thus acts as a guard against
surface conduction along the edge surface (see Fig. 5.39). Both the center and the guard
ring are held at the same potential (voltage), but the current is measured only through the
center electrode. Use of the alternating current in place of the direct current avoids the elec-
trode polarization effects mentioned above. One measures the complex impedance (Z*) of
the specimen as a function of the ac frequency. The plot of the imaginary part (Z″) of the
complex impedance against the real part (Z′) generally has the shape of a semicircular arc.
The intercept of the arc (or its extrapolation) with the Z′ axis directly yields the dc resistance.
Since the electrodes do not provide a supply of the ions into glass, such a method is often
termed the blocking electrode method.
 INORGANIC GLASSES 5.63

FIGURE 5.40 Nonblocking electrode method to measure dc conductivity. 1 = furnace, 2 = controller,

3 = thermocouple, 4 = platinum electrodes, 5 = thermometer, 6 = dc power supply, 7 = ammeter, 8 = recorder,
9 = U-tube, 10 = steel shield, 11 = fused salt, 12 = specimen. (After V. Jain, A. Varshneya, and P. Bihuniak,
Glastech. Ber. vol. 61, p. 321, 1988.)

For a nonblocking electrode method, the disk of glass may be sealed into a tube in a
way that separates the two arms of a glass U tube (of matching thermal expansion coeffi-
cient, so that fusion is successful). Alkali salts, e.g., NaNO3, are filled into the arms of the
tubes and the tube is placed in a vertical orientation inside a furnace. After a sufficiently
high temperature is reached, platinum electrodes are inserted into the arms, a dc potential
applied, and the current is measured with a sensitive electrometer (see Fig. 5.40).
Surface conductivity of glass or of thin films on glass is often measured in terms of sheet
resistance Rsh (ohms per square, or Ω/) using a four-point probe technique. Electrically
contacting point probes are placed at the four corners of a square on the surface or the film.
A current I is allowed to pass through two adjacent probes, and the potential difference V
developed across the other two probes is measured. Sheet resistance in this arrangement is
calculated as
2π   V 
Rsh = 
 ln 2   I  (5.52)

5.15.5 Composition Dependence

Electrical conductivity of silicate glasses is extremely sensitive to chemical composition.

In general, the higher the Na and Li content, the higher the conductivity. As expected, con-
ductivity increases rapidly with increasing temperatures, closely following the Arrhenius
relation, with an activation energy of about 20 kcal/mol (80 kJ/mol), the same as that for
5.64 CHAPTER FIVE

FIGURE 5.41 Variation of dc resistivity at 25°C of 15Na2O ⋅ 85SiO2 (wt%) glass with progressive
replacement of SiO2.

the sodium ion diffusivity. The effect of replacing silica by other oxides on resistivity at
25°C in a 15Na2O · 85SiO2 (wt%) glass is shown in Fig. 5.41. Addition of CaO and B2O3
appears to raise resistivity greatly. Dependence on the cationic radius of the added oxide is
indicated in Fig. 5.42. Shown in Table 6.2 (Chap. 6) are values of the electrical resistivity
of some commercial compositions at 25°C. Šašek and Knotek10 have offered the follow-
ing additivity calculations for the soda-lime-silicate glasses:

σ = Σ σi pi /100 (5.53)
where pi is the wt% of the oxide and σi is the factor given in Table 5.6 at three different
temperatures. The reader must, however, be cautioned against using additivity factors to
calculate the electrical conductivity. The most dramatic departures from the additivity rela-
tionship are displayed by diffusivity and ionic conductivity in mixed alkali glasses. This
is shown, for instance, in Fig. 5.43 for Na+ and Cs+ ions in mixed Na2O-Cs2O-SiO2 glasses
at 480°C as a function of the mixed alkali ratio. It is noted that the self-diffusivity of Na+
ions (measured by tracer isotopes) decreases dramatically with increasing Cs content
and actually becomes lower than that of the Cs+ in the pure Cs2O-SiO2 glass. Likewise, the
self-diffusivity of Cs+ ions decreases with increasing Na content and crosses over to
unmeasurable values. The measured conductivity is far from being the linear sum of the
conductivities in the end compositions: It shows a dramatic negative deviation, 4 orders
of magnitude difference, from an additivity behavior. The minimum in conductivity is not at
 INORGANIC GLASSES 5.65

FIGURE 5.42 DC resistivity of 2R′2O⋅R′′Ο ⋅7SiΟ2 as a function of alkaline earth ionic radius rR′′.
(After H. Wakabayashi, R. Terai, and H. Watanabe, J. Ceram. Soc. Japan, vol. 94, p. 677, 1986; vol. 94,
p. 948, 1986.)

the diffusivity crossover; rather it is a bit toward the more mobile cation (around the 0.6
mixed alkali ratio). In glass science, this phenomenon is called the mixed-alkali effect, and
remains the most intriguing of all the unsolved mysteries. (One may not be called a glass
scientist if one did not indulge in trying to unravel at least some aspect of it.) It does appear
that one alkali somehow affects the motion of the other. From a practical application point
of view, the mixed alkali effect has been beneficially utilized in developing very low electrical
5.66 CHAPTER FIVE

TABLE 5.6 Factors σi for Determining Electrical Conductivity (in S/cm)

of Soda-Lime-Silicate Glass Melts at Different Temperatures

σi for T in °C

Oxide 1200 1320 1400

SiO2 −0.413 −0.576 −0.701
Al2O3 −0.654 −0.908 −1.10
Fe2O3 −0.311 −0.439 −0.537
MgO −0.168 −0.100 −0.019
CaO −0.243 −0.088 −0.087
Na2O +3.61 +4.93 +5.92
K2O −0.582 −0.458 −0.282
Source: After L. Šaˇsek and M. Knotek, Chem. Technol. Silik., vol. L13, pp. 91–106,
1985.

conductivity glasses to insulate current leads in high-wattage lamps. The mixed alkali effect
is of concern in properties other than electrical conductivity as well. For instance, the mixed
alkali effect has been shown responsible for the undesirable drift in mercury-glass ther-
mometers during a temperature measurement (otherwise known as the thermometer effect).
Hence, precision glass thermometers are now made out of single-alkali glasses.

5.17 DIELECTRIC PROPERTIES

When a dc voltage V is applied to a large parallel plate capacitor having a narrow vacuum
gap d between the plates, then the plates are charged with +q and −q charges per unit area
immediately. The electric displacement flux D0 that develops may be given by:
D0 = q (5.54)
The electric field strength E is defined by
D0 = ε0E and E = V/d (5.55)
where ε0 is called the absolute permittivity (dielectric constant) of the free space, and has
a value 8.854 × 10−12 F/m. The capacitance C0 per unit area between the parallel plates is
given by
C0 = ε0/d (5.56)
If we replace vacuum by a dielectric such as glass, the new capacitance C and electric dis-
placement are given by
C = εsC0 and D = εs D0 (5.57)
where εs is called the static relative permittivity (or the relative dielectric constant).
Thus,
D = εs ε0 E = ε E (5.58)
where ε is called the electric permittivity of the medium.
In an alternating field, we may write
D* = ε*ε0 E* (5.59)
 INORGANIC GLASSES 5.67

FIGURE 5.43 Diffusivity and electrical conductivity in

Na2O-Cs2O-SiO2 glasses at 480°C. Dσ is the diffusivity
calculated from the measured conductivity by the Nernst-
Einstein relation. The deep minimum in Dσ (actually the
electrical conductivity) represents the mixed-alkali effect.
(After R. Terai, J. Non-Cryst. Sol., vol. 6, no. 2, p. 121, 1971.)

where the asterisk is used to represent complex numbers. Thus, the complex dielctric con-
stant has the form
ε * = ε ′− j ε ″ (5.60)
where j = (−1)1/2. The real part ε ′ is the dielectric constant, and the imaginary part ε″ is the
dielectric loss factor. The ratio
ε ″/ε ′ = tan δ (5.61)
5.68 CHAPTER FIVE

is termed the loss angle, where δ is the phase difference angle between the electric field E*
and the electric displacement flux D*. Dielectric properties are measured as a function of
the applied frequency by ac bridges or other electronic equivalents.
All dielectrics suffer from breakdown when the applied voltage exceeds the dielectric
strength. The breakdown usually results in a changeover from an insulating to a conducting
behavior, often because of a large dielectric loss factor. Dielectric constants are important
for many applications. Large capacitors require high dielectric constants. On the other hand,
in integrated circuit applications, the substrates are required to have low dielectric constants
to allow a high interconnect signal speed.
The dielectric constant of glasses is generally 4 to 11 at 1 MHz and 20°C. Typical values
for soda-lime-silicates are 7 to 9. Some internally nucleated glass-ceramics in the B2O3-
P2O5-SiO2 system have values as low as 3.8 to 4.5, suggesting potential applications as micro-
electronic substrates, replacing alumina for which the dielectric constant is 9. The loss
angle, tan δ, is strongly related to the conductivity σ. Values are generally 10−3 and increase
with the amount of alkali ions, again mitigated by the mixed-alkali effect. Presence of heavy
metal ions, such as Pb, causes a decrease in tan δ.

5.18 CHEMICAL DURABILITY

5.18.1 Introduction

The high chemical durability or the resistance of glass to a large number of corrosive media
has been one the primary reasons why glass is a preferred material in a variety of applica-
tions. Glasses are preferred over plastics for beverage containers primarily because the
sintering aids used in the manufacture of the latter impart undesirable taste to the contained
fluid. Plastics also adsorb some of the taste-generating organics in the beverages. (Addi-
tionally, the permeation of oxygen through most plastics causes the oxidation of alcohols
to aldehydes and ketones, which has also been deemed undesirable.) However, glasses are
not altogether inert to most fluids. Even water attacks glass gradually over long periods,
causing it to develop a white surface deposit. Silicate glasses are readily dissolved by
hydrofluoric acid (HF). Phosphoric acid (H3PO4) attacks most silicate glasses at tempera-
tures exceeding about 200°C. Caustic alkalis are also able to attack most silicates, albeit
generally slowly.
There are two primary mechanisms of chemical attack on silicate glasses:

1. Leaching, where the mobile alkali ions such as Na+ in the glass interstices are gradually
leached out and replaced by H+ (or the hydronium ion, H3O+) on a no net transfer of
charge basis. The reaction may be represented by
Si-O−Na+ + H+OH− → Si-O−H+ + Na+OH− (5.62)

which is an interdiffusion reaction. The extracted mass of alkali is directly proportional

to the square root of time.
2. Dissolution, where the corrosive medium attacks the Si-O primary bond and may be rep-
resented by
Si-O-Si + Na+OH− → Si-O−Na+ + HO-Si (5.63)
The result is the breakup of a bridging bond to form a more gel-like structure. With time,
more and more of the bridging bonds are broken, causing the network to essentially fall
apart. The extent of corrosion generally increases linearly with time.