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SURFACE AND INTERFACE ANALYSIS
Surf. Interface Anal. 2001; 31: 87–92

Surface characterization of float glass related to

changes in the optical properties after reheating
Yasuo Hayashi,1∗ Ryoji Akiyama1 and Masahiro Kudo2
1
Research Centre, Asahi Glass Co. Ltd, 1150 Hazawa, Kanagawa-ku, Yokohama 221-8755, Japan
2
Department of Applied Physics, Seikei University, 3-3-1 Kitamachi, Kichijyoji, Musashino 180-8633, Japan

Received 10 May 2000; Accepted 9 September 2000

Commercial soda-lime float glass samples, exhibiting different levels of their haze indices after reheating,
have been investigated in terms of their surface morphology and surface composition. Scanning electron
microscopy (SEM) and atomic force microscopy (AFM) observations confirm that the origin of the increase
in the haze indices is due to the formation of roughness on the bottom face of the glass, which has
been described as ‘wrinkling’. Tin depth profiles in the bottom face of the float glass, with and without
reheating, were measured by means of SIMS and XPS. It was found that a tin-enriched layer was formed at
the surface, due to the migration of tin towards the surface during reheating. There was a linear correlation
between the amount of tin enriched at the surface and the haze index after reheating. This observation
indicates that the wrinkling is caused by the surface segregation of tin. Furthermore, SIMS depth profiles
of iron at the bottom face have revealed that the amount of tin enriched at the surface is inversely correlated
to the surface iron concentration. The surface iron concentration is dependent not only on the concentration
in the bulk glass but also on the iron concentration in the tin bath and on the atmosphere used during the
float process. In particular, iron as an impurity in the tin bath can penetrate into the bottom face of float
glass. These analytical results, which have led to the successful improvement of the thermal durability of
float glass, are discussed in detail. Copyright  2001 John Wiley & Sons, Ltd.

KEYWORDS: float glass; optical haze; reheating; surface segregation of tin; surface iron concentration

INTRODUCTION different faces. It is known that the surface in contact with

A high transparency and a smooth surface that can be
shaped arbitrarily and maintained stably are among the most
important properties of glass. Because of these properties,
glass has been used increasingly in new technological
applications such as optoelectronic or display devices.
In general, the surface composition and structure of the
glass, which is often significantly different from the bulk,1
sensitively influences a number of its properties. Owing to
the importance of the glass surface, we have studied the
mechanisms of various surface-related phenomena using
various analytical techniques.
Present-day plate glass is generally produced using
the float method, in order to provide optically flat and
distortion-free surfaces.2 In the float process, molten glass
is floated on a bath of molten metallic tin at ¾1100 ° C
in the presence of an N2 /H2 reducing atmosphere where
it is formed into a continuous ribbon. The glass ribbon
is cooled down while advancing on a bath of molten tin
and is then lifted off the bath at ¾600 ° C. Subsequently, it
enters an annealing lehr to remove thermal stresses. As a
consequence of the float process, the glass has two distinctly
Ł Correspondence to: Y. Hayashi, Research Centre, Asahi Glass Co.
Ltd, 1150 Hazawa, Kanagawa-ku, Yokohama 221-8755, Japan.
E-mail hys@agc.co.jp
tin (bottom face) exhibits different properties from those of
the opposite surface (top face). For example, the durability
of the bottom face is observed to be significantly higher
than that of the top face with respect to environmental
weathering,3 which can result in optical dimming of
the glass.
Optical haze can be produced by reheating at ¾600 ° C or
above during the manufacture of thermally toughened glass
or bending flat glass used for automotive or architectural
windows. The phenomenon is known as ‘bloom’ and is
observed to be due to wrinkling at the bottom face caused by
the reheating. It has been postulated that this phenomenon
is associated with the oxidation of tin from the Sn2C to
the Sn4C state,2,4 the tin having penetrated into the glass
during the float process. However, the precise reason for
the formation of the wrinkling roughness has not yet been
clarified.
In this study, changes in the tin depth profile of
the float glass induced by reheating are measured. It is
found that the tin, which has penetrated into the glass
during the float process, is enriched at the surface by
the reheating. The mechanisms for the formation of the
wrinkling roughness and factors governing the thermal
durability will be discussed in terms of the surface seg-
regation of tin.

Copyright  2001 John Wiley & Sons, Ltd.

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88 Y. Hayashi, R. Akiyama and M. Kudo

EXPERIMENTAL RESULTS AND DISCUSSION

Sample preparation Origin of changes in the optical properties

Commercial soda-lime float glasses of four different grades Table 1 shows haze index measurements (which represent
of thermal durability were selected as samples in this exper- thermal durability) for the series of glass samples following
iment. All the analysed samples, which were manufactured reheating. It is confirmed that the haze indices of all samples
increases following reheating at 700 ° C for 30 min in air,
on the same float line but on different dates, had essentially
because the haze index of every sample without reheating is
the same bulk composition, including the iron content. The
0%. It is also shown that there are differences in the haze index
samples also had the same thickness of 3.5 mm. Heat treat-
amongst the series of glass samples after reheating. Each of
ments were carried out at 700 ° C for 30 min in air using a
the glass samples is numbered S1–S4 in order of their haze
tube furnace with a large constant-temperature zone.
index. In order to clarify the reasons for the increase in the
The diffusion behaviour of iron at the interface between
haze index by reheating, the surface morphology of all the
the glass and the molten tin was examined using a laboratory-
samples was examined. Figure 1 shows SEM photographs for
scale float apparatus. A low-iron soda-lime glass (<0.01 wt.%
the top and bottom faces of glass sample S1 after reheating,
iron) was floated on the molten tin, which was within an
which has the greatest haze index amongst the four glass
aluminous porcelain crucible, at 700 ° C for 10 min. The glass
samples. A wrinkling roughness was observed only at the
was subsequently cooled down and lifted from the molten
bottom face, as reported previously,2 and its peak-to-trough
tin at 500 ° C. The atmosphere in the laboratory-scale float
height was estimated to be >100 nm from AFM observations.
apparatus, which comprised a glove-box furnace, was kept
Consequently, the reasons for the increasing haze index due
in a reducing condition by means of N2 /H2 gas flow. Iron
to reheating can be explained by light scattering due to the
was added as an impurity to the molten tin and was adjusted
formation of wrinkling roughness on the bottom face.
to a concentration of 500 or 1000 ppm.
Formation mechanisms of the wrinkling roughness
In order to investigate the reason for the formation of
Analytical procedure
wrinkling roughness by the reheating, the depth affecting
The grade of thermal durability was evaluated by haze index
the formation of wrinkling roughness on the bottom face
measurements using a haze meter (Tokyo Denshoku, TC-H
of the float glass was analysed. The surface layer of glass
III type). The haze index was defined as the percentage of
sample S1 was removed in steps of 100–200 nm by an etching
transmitted scattered light relative to the total transmitted
treatment with 0.5% HF aqueous solution and then further
light. The surface morphology of the glass was observed
reheating were carried out. As a result, it was found that
by SEM and atomic force microscopy (AFM) measurements. the wrinkling roughness was observed on glass sample S1
The SEM observation was performed on a Hitachi S-800 field-
emission-type instrument and the sample surface was coated
Table 1. Haze index for a series of glass samples following
with Pt–Pd (¾5 nm thick) to make the surface conductive.
reheating at 700 ° C for 30 min in air
The AFM measurements were carried out using a model
SPI3700 instrument from Seiko Instrument Inc. Haze index (%) Bulk iron content (wt.%)
The depth profiles of tin and iron were measured by
Glass S1 15.3 0.09
SIMS with an Atomika 6500 instrument, where positive
Glass S2 12.0 0.10
secondary ions of 120 SnC and 54 FeC were detected using
Glass S3 9.5 0.08
8 keV O2 C primary ions with a current of 100 nA. The
Glass S4 7.2 0.09
incident angle of the primary ions was 60° to the sample
surface normal and an area of 100 µm ð 100 µm on the
sample surface was sputtered. An electron beam of 1 keV
was used to compensate for the positive charging of the
sample surface. The time to depth conversion was carried
out by the measurements of the crater depth using a surface
profilometer (Sloan DEKTAK II A type).
For depth profiling of tin in the near-surface region at
150 nm, XPS was used with ArC ion sputtering. The XPS
spectrometer employed in the present experiment was a PHI
Quantum 2000 instrument with a monocromatized Al K˛
x-ray source. The detection angle of the x-ray photoelectrons
was set to 45° from the sample surface and an area of
100 µm in diameter on the sample surface was measured.
Both electron showers of 30 eV and ArC ion showers of 5 eV
were used to compensate for the charging of the sample
surface during the XPS measurements. The samples were Figure 1. Scanning electron micrographs photographs of the
sputtered by an ArC ion beam of 1 keV at an incident angle top (a) and bottom (b) faces of glass sample S1 following
of 45° , which was rastered across an area of 2 mm ð 2 mm. reheating at 700 ° C for 30 min in air.

Copyright  2001 John Wiley & Sons, Ltd. Surf. Interface Anal. 2001; 31: 87–92

when the surface was etched off by a thickness of up to
300 nm. However, it was not formed when the surface was
etched off by >500 nm. This result indicates that only the
relatively near-surface layers on the bottom face are related
to the formation of the wrinkling roughness.
The major differences in composition between the top
and the bottom faces lie in the amount of tin that has
penetrated into the glass during the float process.5 It is
known, however, that the grade of thermal durability cannot
be explained solely by the overall penetrated tin content.
Therefore, changes in the depth profiles of tin caused by
the reheating were analysed in this study. The SIMS depth
profiles of glass samples S1 and S4 at the bottom face are
shown in Fig. 2. When both samples were not reheated, there
was no significant difference in their tin depth profiles. A
tin-enriched inner layer exists at a distance of ¾5 µm from
the surface, which is called a ‘hump’ or a ‘bump’ in previous
papers.6,7
It is shown in Fig. 2 that the tin depth profile changes
drastically following reheating, namely tin is enriched at
the surface due to the migration of tin atoms, which
are located primarily at depths less than the tin-enriched
inner layer. On the other hand, there are no significant
changes in the tin depth profiles at depths deeper than the
tin-enriched inner layer. From previous observations the
depth affecting the formation of the wrinkling roughness is
<500 nm, therefore depth profiles of tin in the near-surface
region were analysed in detail by XPS. As shown in Fig. 3, a
Figure 2. The SIMS depth profiles of tin at the bottom face of
glass sample S1 (a) and glass sample S4 (b), with (solid lines)
and without (dashed lines) reheating.
Figure 3. The XPS depth profiles of tin at the bottom face of
glass sample S1 (a) and glass sample S4 (b), with (solid lines)
and without (dashed lines) reheating.
Copyright  2001 John Wiley & Sons, Ltd.
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Surface characterization of float glass 89
difference in the tin depth profiles in the near-surface region
after reheating is seen between the two glass samples, which
have different grades of thermal durability. Namely, in the
case of glass sample S1 with a high haze index, a larger
amount of tin exists at shallower depths on the bottom face
compared with that of glass sample S4 with a low haze
index.
Figure 4 shows the relationship between the haze index
after reheating and the average tin concentration in the
surface layer at a depth of <50 nm, obtained from the XPS
depth profile measurements of the series of glass samples.
There is a linear relationship between both factors and this
result suggests that the surface segregation of tin is related
to the formation of wrinkling roughness, which causes the
increase of haze index. Figure 5 shows XPS depth profiles
of tin after reheating for glass sample S1 after removing
surface layers of 100 and 500 nm using the HF etching
treatment. From previous observations, this corresponds
to the situation with and without the observed wrinkling
roughness, respectively. It is also confirmed that the thickness
of the tin-enriched layer at the surface is obviously greater in
the glass with the wrinkling roughness compared with the
glass without the wrinkling roughness.
To show definitively that the wrinkling roughness is
caused by the existence of a tin-enriched layer at the surface,
reproducible experiments were carried out as follows. Both
the top and bottom surface layers of glass sample S4 were
Figure 4. Relationship between the haze index and the
average tin concentration in the bottom surface layer at a
depth of <50 nm after reheating.
Figure 5. The XPS depth profiles of tin at the bottom surface
of glass sample S1 after surface layers of 100 nm (a) and
500 nm (b) have been removed by HF etching and with (solid
lines) and without (dashed lines) reheating.
Surf. Interface Anal. 2001; 31: 87–92
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90 Y. Hayashi, R. Akiyama and M. Kudo

removed to a depth of >1 µm by mechanical polishing

and then a single side of this sample surface was coated
with a sputtered SnO2 –SiO2 film containing 50 mol.% SnO2 .
Subsequently, the samples were heated at 700 ° C for 30 min
in air. The results, shown in Fig. 6, reveal that the wrinkling
roughness is observed on the samples with an SnO2 –SiO2
film of thickness 50 nm or above. It is confirmed that the
wrinkling roughness is related to the existence of a tin-
enriched layer at the surface.
On the basis of these results, a mechanism for the
formation of the wrinkling roughness is deduced as follows.
Relatively large amounts of tin, penetrating into the bottom
face of the float glass during the float process, subsequently
migrate in the direction of the surface during reheating in
air, so that a tin-enriched layer is formed at the surface. The
difference in the thermal expansion coefficients between the
tin-enriched surface layer and the tin-deficient subsurface Figure 7. The SIMS depth profiles of iron from the top (dashed
layer may become sufficiently large to cause the formation line) and bottom (solid line) faces of glass sample S1 without
of the wrinkling roughness. It is also deduced that the grade reheating.
of thermal durability can be attributed to the amount of
tin enriched at the surface after reheating through the same
mechanism.

Factors governing the surface segregation of tin

Figure 7 shows depth profiles of iron from the top and bottom
faces of glass sample S1 measured by SIMS. In the case of the
bottom face, the iron concentration in the depth region up to
10 µm, except for the surface, is lower than the bulk, whereas
it is extremely high at the surface. The mechanism for this
will be discussed in the next section. Secondary ion mass
spectrometry was used to evaluate the iron concentration
in the surface layer up to 100 nm in depth for the series of
glass samples without reheating, as shown in Fig. 8. In this
figure, the intensity ratio of 54 FeC /30 SiC , which represents the
first-order approximation of the relative iron concentration,
is plotted against the surface tin concentration as shown in
Fig. 4. It was revealed that there was an inverse correlation Figure 8. Relationship between the average tin concentration
between both factors, namely the amount of tin enriched in the surface layer at a depth of <50 nm after reheating and
at the surface increased with a decrease in the surface iron the relative iron concentration of the bottom surface layer at
concentration. <100 nm before reheating.
The reason for the surface tin segregation dependence on
the surface iron concentration can be explained in terms of a
and Sn4C . The Fe3C acts as an oxidizing agent against Sn2C , so
redox reaction and the relative diffusion coefficients of Sn2C
that it can convert Sn2C to Sn4C .8,9 In the case of reheating in
the air, all of the iron in the surface layer up to 100 nm exists
in the Fe3C state10 and hence the surface Fe3C concentration is
estimated to a few mole.%, which is comparable to the Sn2C
concentration in the near-surface region. Consequently, the
oxidation state of tin in the near-surface region is strongly
influenced by the surface iron concentration.
Changes in the oxidation state of tin are thought to
affect the migration of tin, because the diffusion coefficient
of Sn4C is regarded as relatively small compared with that
of Sn2C . This is because the Sn4C acts as network formers,
whereas the Sn2C acts as network modifiers in the glass
structure. Accordingly, the amount of tin enriched at the
Figure 6. Scanning electron micrographs obtained after surface due to the migration of tin is dependent on the
reheating of glass sample S4 coated with SnO2 –SiO2 films surface iron concentration. The surface iron concentration
of 10 nm (a), 50 nm (b) and 100 nm (c) thickness. The reheating governs the concentration of Sn2C , which exhibits a relatively
was carried out at 700 ° C for 30 min in air. large diffusion coefficient. It should be to mentioned that the

Copyright  2001 John Wiley & Sons, Ltd. Surf. Interface Anal. 2001; 31: 87–92

migration of tin atoms located at depths shallower than the
tin-enriched inner layer could also be interpreted as being
due to differences in the diffusion coefficient related to the
oxidation state of the tin. Namely, it has been reported that
tin located at depths shallower than the tin-enriched inner
layer exists mainly in the Sn2C state, whereas the tin located
at the deeper side exists as the Sn4C state.11 The oxidation
of tin from Sn2C to Sn4C , which has been deduced as the
origin of changes in the optical properties, may be merely
the result of a redox reaction between Sn2C and Fe3C in the
glass.
It is concluded that changes in the optical properties
due to reheating are caused by the surface segregation of
tin. Moreover, the amount of tin enriched at the surface
by reheating is governed by the surface iron concentration.
Therefore the control of the surface iron concentration in the
bottom face of the float glass, which is dependent on the iron
content in the bulk glass and a number of additional factors,
has important industrial consequences.
Surface segregation mechanisms of iron
The depth profile of iron in the bottom face of float glass
exhibits a characteristic concentration distribution, as shown
already in Fig. 7. The formation of a relatively low iron
concentration region up to 10 µm can be considered to be
due to the diffusion of Fe2C into the tin bath during the float
process.8,12 There are two possibilities for the existence of a
high iron concentration at the surface. One is the migration
of iron from the bulk during the annealing lehr process after
the glass emerges out of the float bath. The other possibility
is the penetration of iron into the glass from the tin bath,
which could occur at the cool end of the float bath. A
surface enrichment of iron is, however, not observed in the
iron profile of the top face, as shown in Fig. 7. This result
indicates that the contribution due to migration from the
bulk during the annealing lehr process is small, because the
top and bottom faces are exposed to the same environments
during this process. Therefore, it is suggested that the iron
diffuses from the glass into the tin bath at the hot end of the
float bath and subsequently re-penetrates the glass from the
tin bath at the cool end of the float bath.
The penetration of iron from the molten tin through the
glass was tested experimentally with the laboratory-scale
float apparatus. Figure 9 shows SIMS depth profiles of iron
obtained from a glass surface that was in contact with a
molten tin bath containing iron. A high iron concentration at
the surface is observed in all the glass samples. It is confirmed
that the iron, which exists as an impurity in the molten tin,
penetrates through the glass at a temperature corresponding
to the cool end of the float bath. Furthermore, it is found that
the amount of iron penetrating through the glass increases
with an increase in the iron concentration in the molten tin
and decreases as a function of the hydrogen concentration
in the atmosphere. Accordingly, it can be considered that
the surface iron concentration on the bottom face of the float
glass is dependent on the above float bath conditions, in
addition to the iron content in the bulk glass.
The surface iron concentration has been found to affect
not only the thermal durability, as described in this paper,
Copyright  2001 John Wiley & Sons, Ltd.
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Surface characterization of float glass 91
Figure 9. The SIMS depth profiles of iron from the glass
surface in contact with the molten tin containing iron in a
reducing atmosphere. (a) 1000 ppm iron, N2 /H2 D 90/10
atmosphere; (b) 500 ppm iron, N2 /H2 D 90/10 atmosphere,
(c) 1000 ppm iron, N2 /H2 D 98/2 atmosphere.
but also the adsorption properties of the float glass surface,
which will be reported in a future publication. The surface
iron concentration appears to be one of the most important
factors for controlling the surface properties of float glass.
CONCLUSION
In this paper, the mechanisms behind changes in the optical
properties of float glass caused by reheating have been
discussed. The origin of the increased haze index is ascribed
to the formation of ‘wrinkling’ roughness on the bottom face
of the glass. It has been found that the wrinkling roughness
is caused by the formation of a tin-enriched layer at the
surface, due to the migration of tin towards the surface
during reheating.
Differences in the haze index amongst a series of glass
samples are explained as being due to the amount of tin
enriched at the surface after reheating and they are inversely
correlated to the surface iron concentration. It has been
shown that iron, which exists as an impurity in the tin bath,
can also penetrate through the bottom face of float glass.
The surface iron concentration in the bottom face is therefore
dependent on the iron concentration in the tin bath and the
atmosphere during the float process, in addition to the iron
content in the bulk glass.
The results of this analysis are expected to be useful
in improving the thermal durability of float glass and to
contribute towards further applications of float glass as new
functional materials.
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