Adapted Heat Treatment for Phase

Transformation of NiS Inclusion in the

Session 1

Heat Strengthened and Tempered Glass

Dr. Chihiro Sakai* and Masashi Kikuta**

*Nippon Sheet Glass Techno-Research Co.Ltd.
**Nippon Sheet Glass Co.Ltd.

Keywords:
1 = Tempering 2 = Nickel sulfide
3 = Heat soak 4 = Phase transformation

Abstract (1)(2)(3)(4). The formation of crystalline NiS in the

soda-lime-silicate glass (so called float glass) has
To avoid spontaneous breakage of heat- been explained by the reaction between metal
strengthened and tempered glass is one of most and alloy particles with the Ni components and
important subjects of glass products in buildings molten glass, or chemical absorption of the Ni
and automobiles. Several attempts have been so components, including burner flame, during the
far made for empirical basis of heat treatment or glass-making process.
phase transformation of NiS by many authors. It is very difficult to reduce the NiS stones in
However, we found few investigations into the the glass-making process; therefore, the heat-
nucleation frequency of the phase transformation soak treatment of glass products is employed to
of NiS inclusions, although there are many studies exclude the NiS defects. The nickel sulfide in the
of the rate of transformation with respect to the glass is composed of several crystalline phases
holding temperature and time. of NiS with different chemical compositions. The
Effective frequencies of nucleation and crystal transitional temperatures from the alpha to beta
growth of NiS inclusion depend on the rate of the phases can be changed by varying amount of
temperature increase in the heat soak process of sulfur in the NiS. Different kinetic parameters have
tempered and heat-strengthened glass. They also been found for different compositions of NiS
depend on the composition of crystalline NiS (the (1)(2)(3).
compositional ratio of Ni and S and additional Researchers have previously explained that the
elements such as Se and Fe in NiS). Maintaining phase transformation of NiS is strongly dependent
the temperature and time of NiS at the maximum on the holding temperature and time at the
temperature affects the growth rates of trans- maximum temperature during the heat soak test.
formation from the alpha to beta phases of We have investigated phase transformations of
crystalline NiS. New technical methods, i.e. the crystalline NiS with different compositions of Ni
heat treatments necessary to transform from the and S in glass products for several years, and
alpha to beta phases of NiS, are described in this suggested a reliable heat-soak process to make
paper. high-quality, heat-strengthened and tempered
glass. In this paper, the kinetics of the phase
transformations of NiS and a new technology of
Introduction heat-soak treatments are provided, based on
Heat-soak treatment serves to prevent several experimental results.
spontaneous breakage of heat- strengthened
and tempered glasses in many glass-making Experimental procedure
companies (1)(2). Spontaneous failure of the glass
is caused by volumetric expanding of the phase We studied the phase transformations of NiS
transformation (from the alpha, in a high- in glass using a polarizing optical microscope
temperature form, to beta phases in the low attached to thermocouples on the glass surfaces,
temperature form) of nickel sulfide (NiS) with which were controlled from 25°C (room tem-
different compositional ratios of Ni and S perature) to 500°C. NiS particles of several grain

Glass Processing Days, 13–16 June ’99

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sizes in the glass were collected from the defects Table 1. Comparison of temperature of phase transformations
of NiS.
in the float glass products. Measurements were
repeatedly performed under differing rates of

Session 1
increasing and decreasing temperatures while the
time at the maximum temperature was maintained.
We used more than twenty glass samples in the
experiments.
The transformations of NiS from the alpha to
beta phases were confirmed, on the basis of the
intensities of the interference colors, which were
formed by the compressive stress around the
particle, under crossed-nicol conditions with a 530
nm sensitive color plate (compensator) at a
diagonal position. The heat-soak treatment
procedure which we adapted, was determined
using the results of the experiments, and the
performance of the NiS heat-soak process
was established by comparison with several
productive processes.

Results
Phase transformations of NiS
Figure 2. Perfectly transformed beta phase of NiS in the glass
NiS particle in the glass showed spherical or after heat soak treatment.
sometimes ellipsoidal forms (Fig.1). They were
composed of several crystalline phases of nickel
Figure 3 shows time-temperature-transfor-
sulfides, i.e. Ni3S2, Ni7S6, NiS, NiS1.01, and Ni2S3.
mation (T-T-T) diagrams, which clarify the
The crystalline form of the NiS can be detected
reversible transformation from alpha to beta
by the analytical data of micro X-ray camera
phases of the crystalline NiS particle in the glass.
patterns. The transitional temperatures of each NiS
The beta NiS start to nucleate at 140°C (the open
phase differed among the different associations of
circle shows incomplete state of the interference
the crystalline phases. Therefore, the rates of the
color), at a low rate of increasing temperature
phase transformations from the alpha to beta
(about 10°C/min). The stable temperature of the
phases of NiS in glass are dependent on the
beta phase of the NiS ranges from 200°C to 300°C
amounts of Ni7S6, NiS, and NiS1.01 in the particle
under the same conditions (temperature and
( see Table 1).
time).

Figure 1. NiS particle after spontaneous failure of tempered Figure 3. Time-temperature-transformation (T-T-T) diagram of
glass. crystalline NiS.

We can confirm the transformation of the NiS

by the intensity of the interference colors under a Figure 4 shows the T-T-T diagram from the
thermally controlled microscope. The maximum alpha to beta transformations of the NiS in the
degree of interference color and growth of micro glass. The stable area of the beta-phase differs
cracks around the NiS particle indicate the beta due to the different rate of rising temperature in
phase of NiS (Fig.2). the heat-soak treatment. The temperature of

Glass Processing Days, 13–16 June ’99

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 nucleation and crystal growth of the beta NiS at spontaneous breakage. We can automatically
a low rate of increasing temperature is lower than perform the heat-soak process, and effectively
that at a high rate of temperature increase. The reducing production costs.
Session 1

stable area of the temperature of the beta NiS is

wider under the lower rate of temperature
increase. The stable area (temperature and time)
Conclusions
of the beta phase of the NiS is wide; therefore, we Our investigations of the phase transformation
can perform heat treatment of the NiS at a lower from the alpha to beta phases of crystalline NiS
temperature (from 200°C to 250°C) at a low rate and reduction of NiS defects have been
of temperature increase (less than 10°C/min). conducted for several years. The results obtained
regarding NiS defects are as follows.
1) The rates of phase transformations from the
alpha to beta phases of NiS in glass depend
on the amounts of crystalline Ni7S6, NiS, and
NiS1.01. They also strongly depend on the
heating rate of the glass products.
2) The conditions of the heat-soak treatment (the
rate of temperature increase and the holding
time at the maximum temperature) can be
determined in time-temperature-transformation
(T-T-T) diagrams, which have been determined
by the experimental procedure.
3) We can realize low cost heat-soak treatment
Figure 4. T-T-T diagram of NiS at the different rate of rising using the new technique, which maintains a
temperature.
constant temperature immediately after the
quenching of tempered glass. We can achieve
The NiS defects which contain other elements shortening of heat treatment of the NiS and
such as selenium (Se) and iron (Fe) in the colored- cost down of the operating.
glass (brownish or greenish colored glass) , can
transform from the alpha to beta phases at a lower
References
rate of temperature increase (less than 10°C/min).
(1) F.Bordeaux and A.Lasper: Reliable and shorter heat
soak test to avoid spontaneous fracture of heat
Low cost heat soak treatment strengthened and tempered glasses. Glass Processing
Days, 13–15, 1997.
The heat soak treatment of NiS is expensive in (2) F.Bordeaux, A.Kasper and L.Duffrene: A shorter heat
soak test to avoid spontaneous failure of heat
terms of personnel, electric power and equipment strengthened and tempered glasses. ICG Conference
costs. We must reduce these costs in the newly in San Francisco, 1998.
adapted heat treatment technique. (3) M.V.Swain: A fracture mechanism description of the
microcracking about NiS inclusions in glass, J.Non
Figure 5 shows the schematic diagrams of the Crystalline Solids, 38 and 39, 451–456, 1980.
new heat-soak treatment technique that maintains (4) M.V.Swain: Nickel sulfide inclusions in glass: an
the temperature from 150°C to 300°C immediately example of microcracking induced by a volumetric
expanding phase change, J.Mat.Science, 16, 151–158,
after quenching process of heat-strengthened or 1981.
tempered glass. The stable alpha phase of NiS
continuously transforms to stable beta crystals in
the glass, so that the defects can be removed by

Figure 5. Schematic diagrams of new heat soak treatment.

Glass Processing Days, 13–16 June ’99

ISBN 952-91-0885-0
78 fax +358-3-372 3180