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In-Line Oxygen Sensors for the Glass Melt and the Float Bath

Article in Advanced Materials Research · April 2008

DOI: 10.4028/www.scientific.net/AMR.39-40.443

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 ON-LINE OXYGEN SENSORS FOR THE GLASS MELT AND THE TIN BATH
AND MODELLING OF OXIDATION STATE OF GLASS MELTS

Paul Laimböck* Oscar Verheijen and Ruud Beerkens

Read-Ox & Consultancy B.V. TNO Science & Industry, Glass Group
de Kuiper 14, 5591 MZ Heeze, P.O.Box 6235, 5600 HE Eindhoven,
the Netherlands the Netherlands

SUMMARY
Measuring curves from on-line oxygen sensors for the glass melt and tin bath (in float lines) are
presented, showing the high value of these sensors in understanding and improving the industrial glass
melting process.
A so-called feeder sensor is used for the measurement of the redox state of the glass melt in the feeder
(container glass), fore hearth (fibre glass) or canal (float glass). The sensor is used for redox monitoring and
control, especially in furnaces melting a high share of recycling cullet or during a colour conversion.
Besides the feeder sensor, a so-called batch sensor has been developed for the redox state of the glass
melt under the batch blanket in the charging area. Results of a simultaneous measurement with feeder and
batch sensor show the enormous potential for redox control. Both sensors can be used in combination with a
redox model, translating the sensor signals to fining and foaming behaviour or predicting the colour of the
final product.
By monitoring the oxygen activity of the tin bath in float glass production lines, oxygen related surface
defects such as bloom, tin pick-up and tin dripping can be reduced. Moreover, the sensor can be used for
saving expensive hydrogen gas.

INTRODUCTION
Over the past decades the glass industry has succeeded to reduce operational costs and to
improve product quality significantly as a result of improved production technology methods and
materials. However, ever increasing energy prices, tougher competition due to globalisation and
stricter environmental regulations (imposed by the authorities) urge the glass industry to seek for
more opportunities to increase its production efficiency.

Research programs during the past decennia have shown that the oxygen activity of the glass
melt and the tin bath are key parameters determining many physical and chemical properties of
these melts. The use of on-line oxygen sensors is now recognised by an increasing number of glass
producers as an effective tool to obtain more information about the chemistry of the melt during
production, significantly increasing the understanding, controllability and of the production process
efficiency.

*
To whom correspondence should be adressed, e-mail: info@readox.com
 Presently, however, only the temperature of the glass melt and tin bath is measured continuously.
Chemistry of the melt is usually only monitored by a periodical analysis of samples. The lack of
commercially available on-line oxygen sensors is due to the technical difficulty of an accurate
oxygen activity measurement in a hot and corrosive melt for extended times. For this reason, Read-
Ox has developed innovative oxygen sensors for the glass melt and the tin bath during the past
years. These sensors are now successfully applied in several industrial furnaces. They are practical
in use and are relatively inexpensive, making an on-line oxygen activity measurement very
accessible for the glass producing industry.

The measuring principle of both the glass melt redox sensor and the tin bath oxygen sensor is
based on an electrochemical cell. A detailed theoretical background of the measuring principle has
been given elsewhere [1,2]. In the following the glass melt redox sensor and the tin bath sensor will
be discussed in separate sections. The emphasize will be on the discussion of measuring curves
obtained from industrial furnaces to illustrate the merits of on-line oxygen sensors for the glass
industry. For the glass melt redox sensor a software model was developed to assist the furnace
operator with the interpretation of the sensor signal in relation to process and product properties
such as, e.g., fining and foaming behaviour and colour of the final product.

1. GLASS MELT REDOX SENSORS

The oxygen activity of the glass melt determines the equilibrium state of multivalent elements in
the glass melt. Melts with a low oxygen activity contain more reduced species such as Fe2+, S2-,
Sb3+ and Cr3+ and melts with a high oxygen activity contain more oxidised species such as Fe3+,
SO42- Sb5+ and Cr6+. The amounts of the various multivalent species in the melt affect many
important process and/or product properties. Without going into detail, following properties are
affected by the redox state of the glass melt:

Radiative heat transfer from the burner flames and superstructure refractories into the glass
melt bath. Fe2+ has a broad absorption band around 1050 nm in the near infrared range.
Consequently, a higher concentration of Fe2+ in more reduced melts decreases the free path of
heat radiation, resulting in a poorer heat conduction of the glass melt
Fining and foaming behaviour of the melt by gas producing reactions between multivalent
elements such sulfur and iron[3]. Sufficient gas must be produced in the melt for a good
fining. Too much gas production, however, may lead to a foam layer on the melt, which
blocks the heat transfer (see also section 1.4).
Forming process as a result of a colour dependent cooling rate by radiant heat transfer from
the gob and perform. For example, a high Fe2+ concentration will result in faster cooling of the
surface area but slower cooling of the interior of the gob or perform
Glass colour and other optical glass properties such as UV or IR absorption/transmission. For
example, iron gives the glass the typical slight green colour. Depending on the redox state of
the glass, the green will have a more bluish cast (reduced, more Fe2+) or a more yellowish cast
(oxidised, more Fe3+). Another example is the redox dependent amber coloration, caused by
the Fe3+-S2- chromophore in reduced container glasses
 For the industrial glass production process it means that the glass melt redox affects both
variable and fixed costs such as energy consumption (good or bad heat transfer into the glass melt
bath), furnace lifetime (overheating of the superstructure by bad heat transfer into the glass melt)
and reject numbers (seed count, colour, forming defects). Due to a limited experience with reliable
on-line redox measurement in industrial furnaces, not all effects are fully understood yet. However,
the above given items show the enormous potential of on-line oxygen sensors in pursuing cost
reduction.

From the eighties on there have been many attempts to develop reliable on-line sensors with
targeted lifetimes of usually more than one year. Such long lifetimes require a robust design
containing heavy corrosion resistant ceramic parts with thick platinum wiring and electrodes,
making the sensor very expensive. The customer’s risk of losing his investment is large.
Circumstances in the furnace are usually not so well controlled as one would wish and the
expensive sensor may already be lost by a small incident such as a minor variation of the glass melt
level. In most cases, as budget does not allow another investment, the joy of having an on-line
redox sensor is usually confined to an experience of a few weeks.

Figure 1 shows a schematic representation of the

redox measuring system developed by Read-Ox. It
consists of water-cooled lance (2), an insert core
containing the wiring (3) and a disposable redox
sensor (4). It is ideal for measurement in the feeder
(container glass), the fore hearth (fibre glass) or
canal (float glass). The sensor can be connected
easily to the contact block on the insert core. The
water-cooled lance is positioned in the furnace so
that its lower end is about 8 to 10 cm above the
glass melt level. The redox sensor extends partially
out of the water-cooled and is dipped with its
ceramic measuring tip in the glass melt

Figure 1 Schematic representation of the glass melt redox sensor.

(1) lance holder unit, (2) water-cooled lance, (3) insert core, (4) disposable redox sensor for
the feeder.
 By this simple concept the system is very flexible. The water-cooled lance can be made in
various lengths, depending on the furnace design at the particular measuring location. As the lance
bridges the (from furnace to furnace variable) distance in the hot furnace atmosphere, the disposable
sensor can be kept small and can always have the same dimension, irrespective of the measuring
location. The small and standardized sensors are therefore low in cost price.

As it is very difficult to make a reliable sensor for extended times, a disposable sensor concept
has been developed. The sensor tip is made of alumina and zirconia ceramics and will slowly
dissolve in the hot and corrosive melt. After a certain operation time the sensor must be exchanged
for a new sensor. Sensor exchange is easy, because of the convenient connector system and takes
only 10 minutes. The lifetime of a single sensor is approximately 4 weeks in a container glass melt
at 1200°C. In case of unforeseen accidents in the furnace the loss will usually be limited to only one
disposable sensor.

The system can be used for a continuous redox monitoring, e.g., for glass types melted from a
high share of foreign recycling cullet like most commercially produced container glasses.
Moreover, because of the disposable sensor concept, the system is also very suitable for occasional
measurements. For example, for trouble shooting, during a colour conversion or in a six sigma
program to decrease operational costs and/or to increase product quality.

1.1 Experiences in a green container glass furnace melting a high share of recycling cullet
Figure 2 shows a schematic drawing of a U-flame fired green container glass furnace melting
about 320 tons per day. In this furnace a batch sensor and a feeder sensor were installed. Using this
setup, the oxygen activity in the melt under the batch charging area and in the feeder channel could
be measured simultaneously.

Feeder sensor

Feeder 1
Refiner 1
Firing

Feeder 2

Refiner 2

Doghouse Feeder 3

Batch sensor
Figure 2 Schematic overview of a U-flame fired green container glass furnace and the positioning of the
glass melt redox sensors in this furnace.
1.2 Feeder sensor
Figure 3 shows the partial oxygen pressure measured by the redox sensor in the feeder. The daily
measured Fe2+/Fetot-ratio of the final product by means of an optical spectrometer is also given in
this Figure. It can be seen that there is a very good correlation.

-4.75 25
-4.70
24
-4.65
-4.60 23
log (pO2 (bar))

Fe2+/Fetot (%)
-4.55
22
-4.50
-4.45 21
-4.40
20
-4.35
-4.30 19
29 mei
30 mei
31 mei

1 jun
2 jun

3 jun

4 jun

5 jun
6 jun
7 jun

8 jun

9 jun

10 jun
11 jun
12 jun
Figure 3 log pO2 (♦ feeder sensor) versus daily analysed Fe2+/Fetot ratio (line)

In addition, the continuously available partial oxygen pressure provides the furnace operator
much more information for active control of the redox state. This is illustrated by the following
example: The redox set point was an Fe2+/Fetot-ratio of 0.20. On Friday June 7 the redox trend was
upward according to the daily iron ratio measurement at 7 am. Based on these optical analyses
addition of an oxidising agent to the batch must be considered during the weekend in order to
prevent a too reduced glass melt (too high iron ratio). However, during the day the oxygen sensor
already indicated a clear decreasing trend showing that a batch redox correction was not necessary
anymore.

Due to the better monitoring and control of the glass melt redox using the on-line redox sensor
the furnace operator was able to increase the recycling cullet share from 87% to 92%. Recycling
cullet costs about 5-10 Euro less than raw materials per ton of produced glass and about 0.25%
energy is saved per 1% of extra recycling cullet share in the batch. The present energy cost is about
25 Euro per ton produced glass. For this particular furnace melting daily 320 ton green container
glass, this represents an annual saving of about 80,000 Euro. Additionally, because of the
continuous monitoring, bad recycling cullet batches with a higher COD than specified by the cullet
supplier can be recognised easily as temporary dips. These inferior batches can be traced back in
time very accurately for optimal feedback to the cullet supplier.
 The policy of the plant is to melt the green glass at a relatively high oxidation state (set point
2+
Fe /Fetot = 0.20) by adding a relatively large amount of sulphate to the batch. In this way the
appearance of amber cords in the glass product is prevented. These may appear in the glass product
due to large redox dips as a result of incidental very dirty recycling cullet batches, having a much
too high COD value. The glass melt may become so reduced that the amber chromophore Fe/S2-
complex can be formed.

On the other hand, during a six sigma program the seed count of the product was measured as a
function of the iron ratio (Figure 4). A lower seed count was found at a more reduced glass melt for
this particular furnace. However, melting at a lower oxidation state (e.g. Fe2+/Fetot = 0.40) would
also mean a higher risk of brown cords as a result of incidentally too dirty recycling cullet batches.

40

30
seed count (-)

20

10

0
30 32 34 36 38 40 42 44
2+
Fe /Fetot (%)

Figure 4 Seed count as a function of the daily analysed Fe2+/Fetot ratio.

A redox sensor, especially in the batch charging area (see section 1.3), will be very helpful,
enabling faster batch redox correction when dirty recycling cullet has entered the furnace (for
example by adding more sulphate to the batch). This will reduce the risk of the formation of amber
cords, even when the glass is melted at a higher iron ratio. The redox sensor can be a helpful tool to
find the optimum redox state with a low seed count on the one hand and a minimal risk of drifting
out off colour specifications on the other hand.

Figure 5a shows the bottom temperature in the melting tank and the oxidation state of the melt in
the feeder channel expressed in millivolt (mV). A higher mV value corresponds to a more oxidised
melt and a lower mV value corresponds to a more reduced melt. There is a clear relation between
the bottom temperature and the sensor’s mV value (Figure 5b). In this particular green container
glas furnace the bottom temperature clearly increases when the melt becomes more reduced. This
trend contradicts the earlier discussed relation of a reduced heat conduction of more reduced melts
by a shorter free path of the heat radiation. This would lead to lower bottom temperatures at more
reduced melts. However, the foam layer in the hot spot area (blocking heat transfer) is usually
thicker on a more oxidised sulphate fined melt than on a more reduced sulphate fined melt (see also
section 1.4). The observed trend may therefore be explained by an increased foaming tendency of
more oxidised melts.
a. b.
210 1215 1215
Feeder sensor signal (mV)

Bottom temperature (°C)

Bottom temperature (°C)
220 1213 1213

230 1211 1211

240 1209 1209

250 1207 1207

260 1205 1205

0 50 100 150 200 260 250 240 230 220
Time (hrs) Feeder sensor signal (mV)

Figure 5 a. Feeder sensor signal (◊) and bottom temperature (●) in time
b. Relation between bottom temperature and feeder sensor mV at approx.1200°C (R2 = 0.7995)

When bottom temperatures cool down below a certain (furnace dependent) temperature, the
furnace operator must take action to prevent cold bottom flows carrying insufficiently fined melts
with usually high seed count. The most obvious action would be to increase the expensive electrical
boosting in the batch charging area. Disadvantage of this solution is that electrical boosting is much
more expensive than overhead firing in most countries. Increase of overhead firing alone is no
option as superheating of the superstructure will be risked, because of the reduced heat transfer into
the glass bath.

However, by the use of the on-line redox sensor, the empirical relation of a higher bottom
temperature at a more reduced melt was established in this particular furnace (see Figure 5).
Decrease of the redox number of the batch [4] to a more reduced melt in combination with
increased overhead firing may therefore be considered. Bottom temperatures will increase again
without risking overheating of the superstructure and saving expensive electrical boosting. This
example shows that the new insights obtained from the on-line redox sensor enables a more
economical management of the glass melting process.

1.3 Batch sensor

A new development is the ability to measure the oxidation state of the glass melt under the batch
blanket in the charging area by means of a so-called batch sensor. This sensor is based on similar
measuring system as the feeder sensor, using a water-cooled lance and a disposable redox sensor.
However, as the glass melt temperature is usually higher in this area than in the feeder section and
the incompletely reacted glass melt is much more corrosive, the sensor must be more robust to
obtain a reasonable lifetime of a few weeks.
Figure 6a shows a simultaneous measurement in a green container glass furnace. It can be
recognised immediately that:
the redox in the feeder follows the same trend as the redox in the batch charging area
the batch redox is about 8 to10 hours in advance on the feeder redox
as a result of glass melt mixing in the melting tank, very pronounced redox dips in the batch
charging area (dirty recycling cullet) appear later as more smeared peaks in the feeder
a. b.
-2.5 0.18
-3.0 1 0.15
log(pO2(bar))

-3.5 0.12

frequency
-4.0 0.09

-4.5 3 0.06
2 0.03
-5.0
timeshift of 8-10 hrs
-5.5 0.00

0-2

4-6

8-10

12-14

16-18

20-22
6-8-2003 8-8-2003 10-8-2003 12-8-2003 14-8-2003 16-8-2003
date
time (hours)
Figure 6 a. simultaneous measurement in a green container glass furnaces
(1) pO2 batch area (approx. 1300°C, with 1 hr moving average),
(2) pO2 feeder (approx. 1200°C),
(3) feeder response signal calculated from batch signal
b. impulse response h(τ )

Looking at these results it hardly needs saying that the batch sensor has an enormous potential
for very effective redox control. Using the batch sensor one has a considerable time gain compared
to the feeder sensor and especially compared to the (presently applied) daily analysis of the cold
product by means of an optical spectrometer.
The relation between the batch sensor signal x(t) and the feeder sensor signal y(t) is given by the
convolution integral over time of the batch sensor signal x(t) and the impulse response h(τ).
∞
y (t ) = ∫ h(τ ) ⋅ x(t − τ ) dτ (eq.1)
0

The impulse response h(τ) represents the time distribution (or mixing) of glass melt flowing
from the batch sensor location to the feeder sensor location. As both the feeder sensor signal y(t)
and the batch sensor signal x(t) were measured simultaneously, the impulse response h(τ) could be
calculated (see Figure 6b).
Knowing the mixing behaviour of the furnace h(τ), the glass melt redox in the feeder (or the
redox state of the product) can be predicted 8 to 10 hours in advance from measured batch sensor
signal at any time using eq. 1. This feeder redox prediction is presented by line 3 in Figure 6a. In
this way batch redox corrections can be made in an early stage in order to move the predicted feeder
redox value back to the desired set point value.

1.4 Use of oxygen sensors in combination with a redox model

Even more information from the glass melt oxygen sensors can be obtained when they are used
in combination with a redox model. For this purpose a redox model was developed which calculates
a. the equilibrium state of multivalent species (such as
0.45
0.40 ferrous (Fe2+) and ferric iron (Fe3+), sulfide (S2-),
0.35 sulfur dioxide (S4+) and sulphate (S6+)) in the glass
Fe /Fetot (-)

0.30
0.25 melt as a function of the temperature starting from a
0.20 certain initial partial oxygen pressure.
2+

0.15
0.10 When using such a model in combination with
0.05 an on-line oxygen sensor, the gas production of the
0.00
melt, iron ratio and sulfur retention (wt% SO3) in
1250 1300 1350 1400 1450 1500
Temperature (°C) the melt can be calculated. From these equilibrium
data process and product properties such as the
b.
0.45 radiant heat transfer of the glass melt, fining and
0.40
0.35
foaming behaviour and the colour of the final
product can be calculated in sub-models.
SO3 (wt%)

0.30
0.25
Figure 7 shows the calculate iron ratio (a), the
0.20
0.15 sulphate retention (b), and the gas production (c) as
0.10 a function of the temperature of two sulphate-
0.05
0.00 saturated glass melts heated from 1250°C to
1250 1300 1350 1400 1450 1500 1500°C. This situation may correspond very well to
Temperature (°C) the freshly melted glass under the batch blanket at
c. 1250°C (measured by the batch redox sensor!) and
9.00
8.00 which will flow to the hotspot at 1500°C.
7.00 One of the melts is more oxidised with an initial
Vgas (m3/m3glass)

6.00
5.00 iron ratio at 1250°C of 0.20 (corresponding to a
4.00 partial oxygen pressure at 1250°C of 10-3.85 bar),
3.00
the other melt is more reduced with an initial iron
2.00
1.00 ratio at 1250°C of 0.40 (corresponding to a partial
0.00
oxygen pressure at 1250°C of 10–5.56 bar). The total
1250 1300 1350 1400 1450 1500
iron content of the glass melts is 0.35 wt%, which
Temperature (°C)
is a representative value for green container glass.

Figure 7 Glass melt properties resulting from a redox model calculation (a) iron ratio vs. temperature,
(b) sulphate retention vs temperature, (c) gas production vs temperature,
─ oxidised melt, ─ reduced melt
Table 1 lists the properties of these melts. It can be seen that the equilibrium sulphate level in the
oxidised melt is much higher than that of the more reduced melt.

Table 1 Glass melt and glass product properties resulting from a redox model calculation
1250°C 1500°C Optical properties
2+ 2+
Fe /Fetot pO2 SO3 Fe /Fetot pO2 SO3 Vgas DWL B P
3 3
(-) (bar) (wt%) (-) (bar) (wt%) (m /m glass) (nm) (%) (%)
Oxidised melt 0.20 10–3.85 0.346 0.10 10–0.52 0.209 8.52 557.57 66.6 20.41
Reduced melt 0.40 10-5.56 0.049 0.28 10-2.61 0.027 0.97 555.46 65.3 18.93

Figure 7a and b show that both the iron ratio and the sulphate level decrease during heating up.
This is caused by the reduction of sulphate by Fe2+, producing SO2 gas according to:
SO42-(melt) + Fe2+(melt) → Fe3+(melt) + SO2(gas) Reaction 1

It is believed that this iron-sulphate interaction is responsible for a proper fining of the melt.
However, it can be seen in Figure 7c that the oxidised melt starts to produce a large amount of gas
above about 1450°C. This gas production is generated by the so-called thermal decomposition of
sulphate in the melt according to:
SO42-(melt) → SO2(gas) + ½ O2(gas) + O2-(melt) Reaction 2

Excessive foaming in the hot spot area is attributed to a too abundant SO2 and O2 gas production
by this reaction. It is may clear that glass tanks melting more oxidised sulphate fined melts have
more foaming problems in the hotspot area at around 1500°C.

Table 1 shows also the optical properties of 2 mm thick cold glass samples calculated from the
two glass melts using a sub-model. This sub-model calculates the optical transmission spectrum
from the equilibrium concentrations of multivalent ions in the glass*. From the optical transmission
spectrum the Dominant Wave Length (DWL), Brightness (B) and Purity (P) of the samples can be
calculated. It is assumed that iron ratio of the cold glass sample is equal to the iron ratio at 1500°C.
This is a reasonable assumption as the gasses produced by the glass melt according to Reaction 1
and 2 have left the melt by fining and foaming, so that the reactions cannot shift back during
cooling down of the melt. Moreover, the physical solubilities of SO2 and O2 gas in the glass melt
are too small to cause a significant change in the iron ratio during cooling at a total concentration of
0.35 wt% Fe2O3.

*
For the calculation of the optical properties a (for green container glass representative) Cr2O3 concentration of
0.25 wt% was taken. The chromium ions are assumed to be completely in the trivalent state.
 The above given model calculation shows that an on-line oxygen sensor in the bath charging area
the in combination with a redox model may predict the expected foaming situation in the melting
tank, the expected bottom temperatures (based on predicted radiant heat transfer calculated from
iron ratio of the melt) and the expected the colour. Based on the predicted values, (batch redox)
corrections can be implemented in an early stage.

2. TIN BATH OXYGEN SENSOR

Nowadays the so-called float process is applied for the industrial production of most types of flat
glass. Molten glass from the melting tank is spread out on a tin melt in the so-called float bath
(Figure 8). In this way a glass ribbon of high homogeneity and highly controllable thickness is
produced continuously. A major concern in the operation of the float glass production line is to
prevent oxygen contamination or even oxidation of the metallic tin in the bath. The float bath
atmosphere is therefore continuously flushed with so-called forming gas, a mixture of roughly 95%
nitrogen and 5% hydrogen gas. However, oxygen may enter by air leaks through open or leaking
furnace joints , by diffusion of oxygen from the glass ribbon or by oxygen traces in the
nitrogen . Oxygen impurities exceeding only a few ppm in the tin bath may already lead to float
glass surface defects, risking the rejection of large production volumes.

Upper
Forming gas (5% H2, 95% N2 + traces of O2 3) plenum

Lower
plenum
Vent Heating elements
Oxygen
Tweel Coolers
Tin leaks 1
Lipstone Glass

Refractory in metal casing

Oxygen from
glass 2

Figure 8 Schematic cross section of the float bath

Two types of oxygen related surface defects can be distinguished:

1. Bottom surface defects such as:
- tin pick up by dross
- formation bloom formation during post processing heat treatments
(tempering or bending)

2. Top surface defects such as:

- tin drips
- cassiterite particles (SnO2)
 In order to minimize or even prevent the occurrence of these surface defects, accurate monitoring
and control of the oxygen level in the molten tin has therefore become a necessity in modern float
glass production lines. For this purpose, a sensor has been developed especially for the continuous
measurement of the oxygen activity and oxygen content of the molten tin in the float bath. Besides
preventing surface defects, the sensor can also be used to reduce the consumption of expensive
hydrogen gas. In addition, it can be of great help during the application of high added value
coatings. A minimal distortion of the surface chemistry may already lead to coating quality
problems.

The probe’s geometry and dimension is similar to that of a normal thermocouple (see Figure 9)
allowing simple replacement along the entire length of the float bath. Installation of the probe can
be easily done by a furnace technician. The built-in K-type thermocouple takes over the temperature
measurement in the molten tin at the measuring spot

Sensor head

4b

Stainless steel
protection tube 4a

4c

Alumina housing tube

Ceramic meas

Figure 9 Read-Ox tin bath sensor: (1) Din A sensor head, (2) Stainless steel protection tube
(3) Alumina housing tube, (4) Ceramic measuring tip.
Insert: 4a) Zirconia oxygen cell, 4b) Alumina sheated K-type t/c, 4c) Bath contact

Figure 10 shows an example of an oxygen content measurement (ppm O) during several ribbon
thickness changes. When a thinner ribbon is produced at the same pull, more surface area of glass is
transported though the float bath per time unit. As a result, more oxygen diffuses from the glass
ribbon into the molten tin underneath and consequently a higher oxygen content of the tin bath is
measured. Maintenance actions such as a short sidewall opening and a filter exchange are detected
by the sensor as distinct peaks.
 5 8
Opening sidewall
Filter change
7
4

glass sheet thickness (mm)

Oxygen level (ppm)
6
3
5
2
4

1
3

0 2
10 jul

14 jul

18 jul

22 jul

26 jul

30 jul

3 aug

7 aug
Figure 10 Oxygen content measured with the tin bath oxygen sensor at mid bath position (approx. 740°C)

2.1 Float Bath Chemistry

Hydrogen in the forming gas atmosphere over the tin bath reacts with oxygen according to:
H2 (g) + ½ O2 (g) ' H2O (g) Reaction 3

As reaction kinetics are especially fast in the hot end area, all oxygen ingress is converted rapidly
into water vapour. The water/hydrogen vapour equilibrium acts as buffer preventing too high
oxygen activities in the bath. Oxygen dissolves in the tin melt following Sievert´s law :
O2 (g) ' 2 O (tin) Reaction 4

The higher the partial oxygen pressure in the atmosphere (determined by the H2O/H2 buffer
ratio), the more oxygen will be dissolved in the tin melt. The maximum oxygen solubility is defined
as the amount of oxygen dissolved in the molten tin at the partial oxygen pressure given by the
Sn/SnO2 equilibrium:
Sn (l) + O2 (g) ' SnO2 (s) Reaction 5

No more oxygen will dissolve in the tin bath at a partial oxygen pressure higher than given by
the Sn/SnO2 equilibrium. SnO2 will be formed on the tin bath in that case, which is usually referred
to as dross. Figure 11 shows that the maximum oxygen solubility (solid line) is very temperature
dependent, ranging from below 10 ppm at cold end temperatures (approx. 600°C) to more than
1000 ppm at the hot end temperatures (approx. 1100°C). The dashed lines represent equilibrium
oxygen solubilities in the tin melt at various pH2O/pH2 ratios of the atmosphere. In addition, oxygen
contents are given, which are measured with the oxygen sensor in various tin baths around the
world during normal operation.
 4
Dross Sn-SnO2
3 pH2O/pH2
1

l
2
log (ppm O) Dross in exit end 0.1

l
1
0.01

l
0

-1

-2
600 700 800 900 1000 1100 1200
Temperature (°C)

Figure 11 Maximum oxygen solubility in tin (solid line), oxygen solubility in tin in equilibrium with
various pH2O/pH2 ratios of atmosphere (dashed lines), maximum oxygen solubility in the cold
end at 600°C (dotted line), and measured oxygen contents in various float furnaces (symbols).

2.2 Bottom surface defects

2.2.1. Dross formation
Molten tin is transported along with the floating glass ribbon from the hot end to the cold end,
and returns to the hot end via the open flow (not covered with glass) on both sides of the bath. Flow
simulations performed by Ler [5], showed that complete recirculation of a bath takes place in only
25 minutes. Smaller or larger amounts of oxygen may enter the float furnace atmosphere as a result
of oxygen leaks or a bath emergency when sidewalls have to be opened. In the hot end area, where
reaction kinetics are fast and the oxygen solubility is high, large amounts of oxygen may dissolve
rapidly in the tin bath. During cooling down of the oxygen rich tin melt flowing under the glass
ribbon to the cold end, the oxygen may be expelled from the tin bath as dross when the maximum
solubility is exceeded. Oxygen release to the atmosphere is impossible under the ribbon. The dross
may easily adhere to the bottom surface of the glass ribbon (see Figure 12).

Cold end
SnO2 Glass ribbon
SnO2
↑
Sn + 2O Tin bath (Sn)

Figure 12 SnO2 (dross) formation in the cold end, adhering to the glass ribbon bottom surface.

Despite of the high oxygen solubility at hot end temperatures, Figure 11 shows that the measured
oxygen contents in various float baths do not exceed the maximum solubility at the cold end of
about 10 ppm (dotted line), along the entire length of the bath. This observation is in agreement
with a proper float bath management, as dross formation will not occur when the tin cools down
flowing from the hot end to the cold end at oxygen levels below 10 ppm.

In case oxygen contents above the dotted line (see Figure 11) are measured, a higher hydrogen
level or an increased venting of the float bath atmosphere may be considered. Alternatively,
hydrogen could be saved when oxygen contents are much lower than required for dross free
operation. Nevertheless, one should be cautious, as at the exit end where the glass ribbon leaves the
float bath, the curtain like sealing is less effective. Although oxygen contents may be sufficiently
low in the hotter parts of the bath, oxygen ingress at the exit end may also contribute to dross
formation in the cold end area. In addition, also near-saturation oxygen contents underneath the
glass ribbon in the cold end area appear to cause problems. Molten tin of high relative oxygen
saturation seems to have a higher affinity to the glass ribbon than tin at low relative oxygen
saturation values. Consequently, the ribbon moving from the bath into the annealing lehr may pick
up molten tin. The tin will solidify on the water-cooled steel rollers in the annealing lehr and may
easily damage the bottom surface of the glass ribbon.

2.2.2. Bloom formation

Bloom originates from the diffusion of tin from the tin bath into the glass ribbon. As metals are
usually insoluble in oxides, metallic tin must first be oxidized to an Sn2+ ion (SnO), before it may
diffuse into the glass ribbon. Reheating of the glass in air (during post processing steps such as
tempering or bending) results in oxidation of SnO in the surface area of the glass sheet to SnO2.
This oxidation is accompanied with a volume increase [6], causing in a wrinkling of the glass
surface. The wrinkled surface is experienced by the eye as a haze on the glass surface.

Glass ribbon Tin oxidation at the glass surface may be

possible by a simultaneous reduction of
Tin bath
reducible glass oxides such as Na2O, FeO,
Glass ribbon Glass ribbon Fe2O3 or SO3, promoting the dissolution of
metal components such as sodium and iron or
elementary sulfur in the tin bath [7] (see Figure
Sn2+ O2- Fe2+ Sn2+ + O2- 13a).
Sn + O However, Hayashi et al. [8] suggested that
Sn Fe
tin might also be oxidized by oxygen dissolved
Tin bath Tin bath
in the tin bath (see Figure 13b).
Figure 13 Diffusion of tin into the glass sheet.
a) oxidation of tin by reducible glass oxides
b) oxidation of tin by dissolved oxygen in the tin bath.
 Figure 14 shows that a good relation was found between the oxygen level measured by the
oxygen sensor in the hot end (at 1000°C) and the daily measured so-called tin count value. The tin
count is determined by X-Ray Fluorescence and is a measure for the amount of tin that diffused into
the glass ribbon. Short bath openings for maintenance resulted in both high tin oxygen levels and
high tin count values. These results support the mechanism proposed by Hayashi et al. [8] and show
the potential benefit of using an oxygen sensor in the hot end to prevent bloom.

15 1450
Nov.21
Relative oxygen saturation (%)

Nov.9 1400
Cameras in and out Exchange of
spout 1350
Nov.10
10 1300

Tin Count (-)

Cleaning of coolers
1250
1200
5 1150
1100
1050
0 1000
Oct.31 Nov.4 Nov.8 Nov.12 Nov.16 Nov.20 Nov.24

Date
Figure 14 Relation between tin count value (XRF) and oxygen content of the tin bath in the hot end
(approx. 1000°C) measured by the tin bath oxygen sensor.

2.3 Top surface defects

2.3.1. Tin Drips and Cassiterite Particles
At temperatures above about 900°C in the hot end, the reaction of molten tin with dissolved
oxygen in the tin or with water vapour in the atmosphere forming gaseous SnO becomes significant:

Sn(tin) + O (tin) ' SnO (g) Reaction 6

Sn(tin) + H2O (g) ' SnO (g) + H2 (g) Reaction 7

The reaction product SnO evaporates easily from the tin bath surface, due to its high vapor
pressure. When an atmosphere containing gaseous SnO comes in contact with colder parts of the
roof or water-cooled equipment like overhead glass coolers or top rollers, Reaction 7 shifts back to
the left side and liquid tin condenses (Figure 15). The tin will accumulate and may eventually drip
down on the ribbon where it may cause surface defects (so-called top specks) [9]. Especially in the
hot end area, where the glass surface is still deformable, tin drops may be very problematic as they
are more difficult to remove and may leave small pits in the glass surface.
 Forming gas (H2, N2 )
IIII III I I II I II II
Sn (l) Cold(er)
roof
SnO (g) + H2 → Sn (g) + H2O (g)

Cooler

Cooled
SnO (g)
Glass ribbon toproller
O
Tin bath

H2O
SnO (g) + H2(g) SnO (g)

Sn Sn +
Sn +OO

Tin bath Tin bath

Figure 15 Tin dripping mechanism in the float bath atmosphere

At very high oxygen activities (represented by high water vapour levels in the atmosphere),
cassiterite (SnO2) may also be formed on the colder roof parts or on cooled equipment above the
glass ribbon according to:
SnO (g) + H2O (g) ' SnO2 (s) + H2(g) Reaction 8

This may happen during a bath emergency when parts of the sidewalls have to be removed for
repair and air may freely flow in the float bath atmosphere. Figure 16 shows the oxygen level
during a shut down and start-up, measured by a sensor installed at a mid bath position (approx.
740°C).
80 900
Closing of the bath
850
Dissolved oxygen (ppmO)

Tin bath temperature (°C)

60
Short opening
Opening 800
for starting up

40 750

700
20
Shutdown,
short bath opening
650

0 600
13 june 13 june 13 june
Time 13 june
(date hh:mm) 14 june
00:00 10:56 14:08 17:20 00:00
Figure 16 Increase of the oxygen level in the tin bath as a result of sidewall removal for a start-up after a
shut down.
 It can be seen that sidewall openings resulted in large peaks of increased oxygen levels in the tin
bath. During the start-up, oxygen levels increased even above the maximum oxygen solubility in tin
at approx. 740°C (= 40 ppm). Dross (SnO2) will be formed locally on the bath surface at these high
oxygen levels, and also a lot of SnO gas will evaporate from the surface. SnO gas may condense on
colder parts in the furnace as molten tin (Reaction 7) or deposit as solid cassiterite particles
(Reaction 8). After restoring the reducing forming gas atmosphere the cassiterite particles will be
(partially) reduced again to molten tin. The molten tin, and also cassiterite particles may eventually
come lose and will drip or fall on the ribbon. The reduction reaction of the solid cassiterite particles
to tin with hydrogen gas is a slow process, because it involves a surface reaction. After severe bath
emergencies, during which large amounts of SnO2 deposits were formed, tin dripping and cassiterite
particle deposition may continue up to even several days after the accident took place.

CONCLUSIONS
Examples given of on-line oxygen measurements in glass production furnaces show the
enormous potential of these sensors to improve the understanding, controllability and efficiency of
the industrial glass production process. For the first time, relative inexpensive on-line oxygen
sensors have become available to give continuous information about the glass melt and tin bath
chemistry. Using these sensors relations between (undesirable) oxygen balance changes and process
and product properties are revealed much easier than with the conventional methods of a periodical
off-line analysis of samples.
Especially furnaces melting a high share of recycling cullet will profit optimally from an on-line
glass melt redox sensor. Redox variations from the batch charging area to the final product can be
monitored using a batch sensor and a feeder sensor simultaneously. Controllability of the glass
melting process improves considerably when redox variations can be detected in an early stage and
minimized by faster batch corrections. A redox model links the glass melt oxidation state to
properties such as heat transfer, fining, foaming, forming, colour and seed count. This will help the
furnace operator to take the right corrective measures.
Continuous monitoring of the tin bath oxygen content using the sensor enables operators to
respond much earlier to dangerously high oxygen levels of the tin, limiting or preventing surface
defects. For example, air leaks in the bath perimeter can be detected earlier or sidewall openings for
maintenance or repair can be carried out in a more controlled way to prevent the formation of too
much overhead condensates. In addition, hydrogen usage can be optimised in order to produce the
highest quality at the lowest costs
Finally, now on-line redox sensors for the glass melt and the tin bath have become easy
accessible, they will be implemented in more and more glass production furnaces. It is expected that
relations between the oxidation state of the melt, process parameters and product properties will be
understood better and new relations will be found in the near future further improving the efficiency
of the industrial glass production process.
 REFERENCES

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Melting Tanks”, Ceram. Engin. Sci. Proc. 23(1) 27-44 (2002).
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Production Lines” in ´66th Conference on Glass Problems´ edited by W.M. Kriven, Wiley, Amsterdam,
in press.
3 P.R. Laimböck, “Foaming of Glass Melts”, Ph.D. Thesis, Eindhoven University of Technology, 1998.
4 W. Simpson, and D.D. Myers, “The redox number concept and its use by the glass technologist”, Glass
Technology 19(4) 82-85 (1978).
5 B.-C. Ler, “Turbulent flow in a shallow rectangular cavity caused by a long mobile wall”, Ph.D. Thesis,
University of Liverpool, 1976.
6 S. Takeda, R. Akiyama, and H. Hosono, “Precipitation of Nanometer-sized SnO2 Crystals and Sn Depth
Profile in Heat-treated Float Glass”, J. Non-Cryst. Solids 311 273-280 (2002).
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68C1 15-19 (1995).
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