Max

Mersch

05/12/13

Diffusion of Ag ions in Soda-Lime Glass

Abstract:
This laboratory investigated the diffusion coefficient of silver in soda lime glass
with the method of inductively coupled plasma and optical emission
spectrometry. A sample of glass was chemically toughened; corroded using a
diluted HF solution and finally the concentration of silver ions in the used
etchant solution was measured. The inter-diffusion coefficient was found to be
3.064*10-14 m2s-1, which was lower than the given value for the sodium self-
diffusion coefficient (2.4*10-14 m2s-1). This did not comply with the Stokes-
Einstein theorem and therefore the possible errors were discussed.

Introduction:
Due to its low cost of manufacturing and optical properties, glass is becoming
and increasingly popular material in a large range of applications. However, to
overcome the limitations coming from its brittleness, glass is often chemically or
thermally toughened.
To thermally toughen glass, it is quenched in cold air jets after having been
heated to 680C (1). The outside surface of the glass cools rapidly and does not
undergo a change in structure. The middle of the glass solidifies at a slower rate
and therefore a displacive transformation will occur (2). This transformation
leads to a smaller volume inside the glass, which will be in tension.
Simultaneously, the outside surface will be under compression, which reduces
the crack width and therefore increases the required force for fracture.

On the other hand, chemical toughening works by replacing cations on the
surface of the glass with cations of larger atomic radius. This substitution also
leads to a compression of the surface of the glass and thus smaller crack widths.
To substitute the larger cations into the glass surface, it is immersed in a high
temperature molten salt bath.

This laboratory investigates a method of chemical toughening by replacing Na+
ions with Ag+ ions in soda-lime glass. To understand the process and the rate of
ion exchange in chemical toughening (allows to manipulate the mechanical
properties), the glass was etched in hydrofluoric acid (HF) over several stages.
To measure the number of Ag+ ions that had diffused to different depths, the
etchant was analysed through inductively coupled plasma and optical emission
spectrometry (ICP OES).

ICP OES is a spectrometry method developed to overcome the issues with
emission spectroscopy, which could not clearly differentiate interference free
spectral lines in complex spectra of heavy elements such as Ca, Al and Ag (3). ICP
OES works by injecting a liquid sample into an argon plasma. At very high
temperatures (around 7000K), this sample is dried, vaporized and energized
through collisional excitation. The atomic emission from this plasma is then
analysed with optical emission spectrometry (4). By breaking up the various
molecules into their individual atoms, the characteristic wavelengths of the
elements can be differentiated.

Max Mersch

05/12/13

The ion exchange rate is mainly driven by the diffusion coefficients of the ions.
The Stokes-Einstein equation relates the diffusion coefficient to the temperature
and then atomic radius of the particles:

!
=

6
Equation 1
Where kB = Boltzmann constant, T = Temperature (Kelvin), =Viscosity of liquid
and r = radius of particle.

From equation 1 it can be deduced that the Na+ ions will have a greater diffusion
coefficient than Ag+ ions due to their lower radius. Therefore glass containing
silver ions will be less affected by HF etching, which concludes that as the
samples is etched repetitively, the rate of corrosion is increases as the Ag+
concentration decreases.

The concentration of silver ions that will substitute with sodium ions at a certain
depth can be found with equation 2:

!
!
=
. exp

4
(. . )
Equation 2
Where C = Concentration of Ag at depth of x metres, D = diffusion coefficient and t =
diffusion time (seconds).

By re-arranging equation, it can be seen that an approximate value for the
diffusion coefficient can be found by plotting ln(C) against x2. The gradient will
be equal to -1/4Dt. This will be used in the results to calculate the diffusion
coefficient of silver in soda-lime glass.

Experimental:
The dimensions of four samples of soda-lime glass had their dimensions
measured using an electric vernier calliper. The density of each sample was
calculated after their weight had been measured on an electric scale, and the
average density of soda lime was determined. Sample 1 cleaned with deionised
water and acetone, and then placed in a platinum holder. It was placed in a
crucible containing AgNO3-KNO3 eutectic melt (60% AgNO3 and 40% KNO3). It
was heated for 17 minutes. The temperature increased from 604K to 650K over
the 17-minute time period.
After washing the sample with water and acetone to remove the remaining salt
on the surface, it was weighted again with the platinum wire. The sample was
then etched in a 2.5wt% HF solution for 3 minutes and then eight consecutive
times for 2 minutes. Each etch was done in a different beaker and then remaining
solution was preserved. The sample was also weighted after each etch.
After the etching was completed, the etchant solutions were all individually
poured into 50ml beakers, which were then filled all the way to 50ml with
deionised water. The concentration of Ag+ ions in the solutions was then
measured through ICP OES.

Max Mersch

05/12/13

Results:
The results measured during the experiment can be found in tables 1, 2 and 3
below:
Table 1 Dimensions and densities of 4 samples
Sample
1
2
3
4

Mass
0.001523
0.001638
0.001326
0.001379

L (m)
0.0249
0.0246
0.02485
0.02452

T (mm)
0.95
1
0.8
0.84

W (m)
0.02445
0.02503
0.0248
0.0248

Volume (m3)
Density (Kg/m3)
5.78365E-07
2633.286347
6.15738E-07
2660.222367
4.93024E-07
2689.524242
5.10801E-07
2699.683383
Average Density:
2670.679085

The change in thickness was found by dividing the change in volume by the area
of the sample (considering that the corrosion on the sides of the sample was
negligible). The values for x were calculated as the sum of the changes in
thickness of all the previous etchings plus half of the current etching.

Table 2 Changes in mass of samples and concentration results
Etching
Time
(min)
0
3
2
2
2
2
2
2
2
2

M (kg)

Mass
(Kg)

Volume
(m3)

Thickness
(m)

x2

0.0041715
0.0041668
0.0041623
0.0041610
0.0041600
0.0041550
0.0041530
0.0041485
0.0041460
0.0041450

-
4.70E-06
4.50E-06
1.30E-06
1.00E-06
5.00E-06
2.00E-06
4.50E-06
2.50E-06
1.00E-06

-
1.7599E-09
1.6850E-09
4.8677E-10
3.7444E-10
1.8722E-09
7.4887E-10
1.6850E-09
9.3609E-10
3.7444E-10

-
1.4453E-06
1.3838E-06
3.9977E-07
3.0752E-07
1.5376E-06
6.1504E-07
1.3838E-06
7.6879E-07
3.0752E-07

-
7.227E-07
2.137E-06
3.029E-06
3.383E-06
4.306E-06
5.382E-06
6.381E-06
7.458E-06
7.996E-06

-
5.223E-13
4.568E-12
9.176E-12
1.144E-11
1.854E-11
2.897E-11
4.072E-11
5.562E-11
6.394E-11

The values for the concentration of Ag+ ions were found by passing the different
diluted etchants through the ICP OES machine.

Table 3 Concentration of Ag+ ions in every etchant
Etchant
1
2
3
4
5
6
7
8
9

Concentration of Ag+ ions (ppm)

29.21
19.23
14.22
13.7
14.6
11.39
10.56
12.3
9.982

Max Mersch

05/12/13

Using equation 2 and the results above, a graph of ln[Ag+] vs. x2 was plotted (this
plot excluded the first etch as the sample was etched for 3 minutes instead of 2):

3.2
3

ln[Ag+]

2.8
y = -8E+09x + 2.7868

2.6
2.4
2.2
2
0

1E-11

2E-11

3E-11

4E-11

5E-11

6E-11

7E-11

x2 (m2)

Graph of ln[Ag+] vs. x2

The gradient of the line was found to be -8*109. Using equation 2, this is
equivalent to 1/4Dt. The time (t) was 17 minutes (1020 seconds), which leads to
the result of D = 3.064*10-14 m2s-1.


Discussion:
The results of the experiment were used to arrive at the inter-diffusion
coefficient of silver of 3.064*10-14 m2s-1. This was found to be lower than the self-
diffusion coefficient of sodium (2.4*10-14 m2s-1 at 563K). This does however not
fit with expectations based on the chemical theory of diffusion. According to
equation 1, the diffusion coefficient (D) should decrease with larger atoms and
with lower temperature. This is because larger atoms will have more difficulties
diffusing through a lattice and lower temperature translates to a lower available
energy for the diffusion process. In this experiment the silver has a larger atomic
radius (126pm) than sodium (102pm)(5), and the experiment was conducted at
550K (13K lower than the sodium experiment). So both parameters that affect D,
should have pushed it to increase.

This error could have been induced by human mistakes while measuring the
dimensions of the samples or while diluting the etching solutions. The second
part was done fairly approximately and the cleaning of the samples could have
lead to a loss of some silver ions. It is also important to note that the electrical
scale was fluctuating a lot and always increased after the sample was positioned
(possibly due to currents in the fume cupboards). To minimize this error the
reading was always taken at the very beginning when the sample had just been
placed. The sample was also found to have a relatively large crack (possibly

Max Mersch

05/12/13

induced by the platinum wire). The final error that was not taken into account is
the fact that the sample was also corroded on its sides and thus the results are
only an approximation. This could have been corrected by re-measuring all the
dimensions after each etch.

In the diffusion process, the Na+ ions only exchanged with Ag+ ions as they have
the same charge and are similar in size. They do not exchange with K+ or with
Ca2+ unless the sample is heated to very high temperatures to increase the
diffusion coefficients. Ca2+ ions can only difficultly substitute the Na+ ions
because of the charge difference. It would require two Na+ ions to be removed to
accommodate for one Ca+2. Potassium has an atomic radius of 138pm, which is
much larger than Na at 102pm (5). For this reason, the silver atoms (126pm) are
more likely to exchange with the sodium atoms (higher diffusion coefficient and
thus lower energy required). It is important to note that even the exchange with
silver had to be pushed through the immersion of the sample in a high
temperature molten silver bath.

During the experiment it was observed that after the glass sample was removed
from the salt bath, salt crystals were starting to nucleate at the corners and
where the samples was in contact with the platinum wire. This lead to a
complete opaque layer covering the sample, which disappeared after cleaning
with deionised water and acetone. Only a yellow tint remained inside the sample,
which was probably a result of the Ag+ ions in the sample.

Conclusion:
It was concluded that the diffusion coefficient of silver ions in soda lime glass
was 3.064*10-14 m2s-1. This was lower than the self-diffusion coefficient of
sodium (2.4*10-14 m2s-1), which does not follow the theory. The possible errors
in the experiment included human errors, high fluctuations on the electrical
scale and in-accurate assumptions about the corrosion of the sample. It was also
noted that the exchange of Ag+ ions in soda lime glass gave the sample a yellow
tint.

References:

[1]- Fraser Wigley, 104 Notes (Pg.15), Imperial College London
[2]- Fraser Wigley, 104 Notes (Pg.3), Imperial College London
[3]- A R Date & A L Gray, 1989, Inductively Coupled Plasma Mass Spectrometry(Pg.1), Blackie.
[4]- Xiandeng Hou, Bradley Jones, Inductively Coupled Plasma/Optical Emission Spectrometry,
Encyclopedia of Analytical Chemistry
(http://www.wfu.edu/chemistry/courses/jonesbt/334/icpreprint.pdf)
[5]- http://environmentalchemistry.com/yogi/periodic/ionicradius.html