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Enhancing mechanical endurance of chemical-tempered thin soda-lime

silicate float glass by ion exchange

Article · June 2019

DOI: 10.1007/s41779-019-00375-x

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Journal of the Australian Ceramic Society
https://doi.org/10.1007/s41779-019-00375-x

RESEARCH

Enhancing mechanical endurance of chemical-tempered thin

soda-lime silicate float glass by ion exchange
Aydın Süleyman Güzel 1,2 & Meryem Sarıgüzel 1 & Melis Can Özdemir Yanık 1 & Esin Günay 1 & Metin Usta 1,2 &
Yusuf Öztürk 1

Received: 27 September 2018 / Revised: 3 February 2019 / Accepted: 18 May 2019

# Australian Ceramic Society 2019

Abstract
The aim of this study is to determine the mechanical properties differences in between the air and tin surfaces of thin soda-lime
silicate float glasses that subjected to ion exchange using KNO3 salt bath. The ion exchange process was carried out at different
times and temperatures. Chemically tempered glasses were investigated by means of compressive stress (CS), microhardness
measurements, cracking probability, fractographic analysis, and flexural strength. The relationship among these properties was
also discussed. The Weibull distributions of the samples were determined for a better understanding of the strength results. The
AFM was used to determine the surface roughness. The weight of glass samples was increased gradually with increasing ion
exchange time and temperature due to the inter-diffusion of K+–Na+ ions. The fracture load of chemically strengthened glass with
ion exchange at 435 °C-8 h showed an increase of ~ 4.4 times that of untreated glass (raw glass), and it was selected as the
optimum process conditions. The number of broken pieces was increased by increasing flexural strength, and smaller pieces were
obtained with a great deal of branching. The air side always has greater compressive stress than the tin side. The maximum
hardness value was reached with ion exchange at 435 °C for 12 h on a tin surface was 8.25 GPa with an increase of ~ 18% with
respect to the raw glass. The crack resistance of chemically tempered glasses showed an increase in the range of 410–1290% and
241–1895% for air and tin surfaces, respectively. According to the AFM analysis, surface roughness of the samples after ion
exchange did not change dramatically. SEM-EDS analysis revealed that the surface potassium concentration and diffusion depth
increase with temperature.

Keywords Chemical tempering . Ion exchange . Soda-lime float glass . Mechanical strength . Indentation . Compressive stress

Introduction thermally tempered glass, and thermal tempering cannot be

The Ultra-Thin Glass Market was estimated to be USD 9.73
billion in 2017 and is foreseen to reach USD 16.99 billion by
2022, at a CAGR (Compound Annual Growth Rate) of 11.8%
from 2017 to 2022 [1]. The decrease in glass thickness re-
duces the mechanical strength of the glass, and the thin glasses
cannot theoretically reach the appropriate mechanical strength
through thermal tempering. In addition, any surface treatment
(such as cutting, drilling, or shaping) cannot be performed on
* Yusuf Öztürk
ozturk.yusuf@tubitak.gov.tr
1
TÜBİTAK, Marmara Research Center, Materials Institute, Gebze,
Kocaeli, Turkey
2
Material Science and Engineering, Gebze Technical University,
Gebze, Kocaeli, Turkey
used for strengthening complex-shaped or for low thermal
expansion glasses [2–4]. All of these reasons will be led the
world’s leading glass companies to focus on improving the
chemical tempering process (strengthening) of glass [5–7].
Increasing its mechanical strength by modifying its surface
with a chemical tempering process, glass has started to be used
progressively in applications such as computers, tablets, mo-
bile phones and television screens, cover glasses used in solar
cell panels, automotive glasses, and many other industrial uti-
lization [8].
In the chemical strengthening process by ion exchange,
alkali ions on the glass surfaces are replaced with alkali ions
in the salt when a glass is immersed in the molten salt bath
under the glass transition temperature [9–11]. The radius of
the ions diffused into the glass surface is greater than that of
the ions coming out of the glass surface, thus the glass is
strengthened by creating compressive stress [12]. Besides

submerging in a molten salt bath, there are many different ion
exchange application techniques, such as exposing to salt va-
por, spraying the salt solution onto the glass surface, and coat-
ing the surface of the glass by tempering the salt solution into
paste consistency [13, 14].
Ion exchange method, which is generally used for the im-
provement of mechanical strength, also increases the thermal
shock resistance, stiffness, and scratch resistance of glass and
can change the optical, electrical, chemical, and physical prop-
erties of glass, such as refractive index, electrical conductivity,
and chemical composition [15–18].
The glass bending strength is determined by the geometry,
depth, distribution, and density of glass flaws, which consid-
erably reduce the theoretical strength of the glass [19, 20]. For
this reason, it is important to limit the formation and propaga-
tion of cracks by creating compressive stress on the glass
surface through ion exchange in order to increase the mechan-
ical strength of the glass [21, 22].
There are many papers and patents on strengthening glass
through ion exchange, and in these studies, the effects of ex-
perimental parameters, such as process time and temperature,
glass composition and thickness, and salt type and concentra-
tion, were investigated [23, 24].
Many flat glasses used for automotive and architectural
applications and large-sized glass products are produced
by the float glass production process, which was discov-
ered by Pilkington [25]. In this production process, glass is
produced by floating on the molten tin, and during produc-
tion, one surface of the glass is in contact with molten tin.
Due to tin diffusion to one surface of the glass, chemical
compositions of glass surfaces are differed from each other
and are called as air and tin surfaces [26]. The composition
and structural differences between the two sides can lead to
different compressive stress, depths of stress layers, and
dissimilar diffusion characteristics, which can affect the
properties of glasses [27–29].
As a result, the diffusion behavior of K+–Na+ ions on both
surfaces is very important for controlling the properties of
float glasses. However, the difference between the diffusion
characteristics of the K+–Na+ ions on the tin and air surfaces
of float glass is not still clear yet [30]. Moreover, the hardness,
compressive stress, and surface roughness change differences
between the air and tin surfaces of the chemically tempered
soda-lime silicate float glasses are still uncertain.
This paper clarifies the difference between the compressive
stresses (CS) and depths of stress layers (DOL) of air and tin
surfaces of float soda-lime silicate glasses and determines the
effect of process conditions to the final mechanical perfor-
mance of two surfaces. The effect of the ion exchange behav-
ior (strengthening process) of the tin and air surfaces of float
soda-lime silicate glass was examined systematically, and the
optimum results were obtained that are thought to provide an
important contribution to literature.
J Aust Ceram Soc
Experimental
A ŞİŞECAM soda-lime silicate (SLS) float glass which
has a thickness of 1.1 mm and 60 × 60 mm2 surface area
was used in this study. The chemical composition and the
transition temperature BT g ^ of the glass are given in
Table 1.
The glass samples were cleaned in ethanol and deionized
water for 5 min, respectively, by using an ultrasonic cleaner
before the ion exchange process. The same cleaning process
was carried out after the ion exchange to remove salt residues
from the glass surface. The glass samples were preheated for
1 h at 180 °C and then were placed in the molten KNO3 salt
solution. The schematic workflow diagram of the ion ex-
change process and all experimental conditions are given in
Fig. 1.
The tin surfaces of the glass samples were placed in
contact with the bottom of the steel tank. The glass
weight/salt weight ratio was kept constant at 1/5, so the
results did not influence by the change in the salt amount.
In this study, the Sigma Aldrich KNO3 salts were used
(purity > 99%), and the glass samples were immersed into
100% the molten KNO3 salt bath in an electric furnace
(Protherm Chamber Furnace) at different temperatures
(375 °C, 400 °C, 425 °C,435 °C, 450 °C, and 475 °C)
for different times (4, 8, and 12 h).
Weight increases of the ultrasonically cleaned samples be-
fore and after the ion exchange process were measured by a
digital scale weighing device with 1-mg measurement
precision.
The flexural strength of chemically strengthened glass
samples was measured by a ring-on-ring test with loading
and support diameters of 20 mm and 40 mm, respectively.
The biaxial flexural test fixture was measured according to
the EN1288-5 norm. Tests of all glass samples were carried
out by applying loads on the air side and specimens were
taped on the tin side before the test to hold fragments
together.
Afterwards, the fracture load distributions were studied
using a conventional two-parameter Weibull approach [31].
Vickers hardness measurements of the glass samples
were performed before and after ion exchange treatment.
The indentations were created by using CSM Instrument
Micro Hardness Tester with a loading capacity ranging
Table 1 Chemical composition and transition temperature (Tg) of
untreated (raw) soda-lime silicate glass
XRF glass composition, wt% Tg (°C)
SiO2 Al2O3 Fe2O3 TiO2 CaO MgO Na2O K2O SO3
72.33 0.99 0.09 0.054 8.43 4.40 13.45 0.06 0.20 560
J Aust Ceram Soc
Fig. 1 Schematic workflow diagram of the ion exchange process and all experimental conditions
from 1 g (0.0098 N) to 10,000 g (98 N) for 7-s dwell time.
Observation of the indentations and measurement of diag-
onal lengths were made using an optical microscope
(Nikon MB 10) connected to the Vickers Micro Hardness
Tester. The air and tin sides were examined separately.
Microhardness measurements were performed at 0.49 N.
In addition, the Vickers Indentation method was used to
evaluate the crack resistance and the crack formation proba-
bility in glass. The percentage of crack formation probability
was obtained by dividing the number of corners where radial
cracks are formed by the total number of the corners indenta-
tions. The applied load was elevated incrementally, and twen-
ty Vickers hardness indentations were performed for each ap-
plied load (total 80 corners). From the crack initiation proba-
bility (%) versus the indentation load (N) graph, the indenta-
tion load corresponding to 50% crack initiation probability
was determined as Bcrack resistance.^ Both the air and tin
sides were examined separately [18, 32].
The AFM was used to determine the surface roughness.
The AFM measurements were carried out using a model
Quesant Ambios AFM Q-Scope (Nano Scope Tapping
Mode TM). The per scans of a surface region of 40 × 40 μm
were investigated. The measurements were repeated for each
sample on different spots of the surface.
After the ion exchange process, compressive stress (CS),
depths of stress layers (DOL), and central tension (CT) of the
samples were determined by birefringence stress analysis
(FSM-6000LE model surface stress meter, ORIHARA,
Japan). Five different measurements of both the air and tin
surfaces were performed for each glass sample. The average
CS and DOL values and standard deviation calculations were
obtained to verify the reproducibility of the measurements.
Phase characterizations of samples were carried out by
using Shimadzu™ XRD-6000 X-ray diffractometer in the
2θ range of 2–70° with the step size of 0.02° using a Cu
radiation tube (wavelength 1.5405 Å).
After the ring-on-ring test, some fragments were select-
ed from the clean-flat surfaces of broken samples and then
coated by sputtering Platinum (Pt). The K/Na ratios were
determined from sodium and potassium concentration pro-
files with a point analysis at 1-micron intervals (about
30-μm long) by using the JEOL JSM-6510-LV scanning
electron microscopy (SEM) and Oxford Instruments Inca
Energy Dispersive Spectroscopy (EDS). All the analyses
were performed for each glass sample on the air and tin
sides separately to investigate the different diffusion per-
formance of the two sides.
All data are presented as mean ± standard deviation(S).
STDEV.S uses Eq. 1:
vffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
ffi
u  2
u ∑ x−x
t
ð1Þ
ðn−1Þ
where x is the sample mean average (data 1, data 2,…), and n
is the sample size.
 J Aust Ceram Soc

Results and discussions
Weight increase results and evaluation
Since potassium is a heavier alkali ion than sodium, the weight
increase occurred as a result of the inter-diffusion of Na+ ions
in the glass with K+ in the molten salt bath. The weight in-
crease of the samples is given in Fig. 2 as a function of tem-
perature and time.
The weight of glass samples increased gradually with in-
creasing process temperatures (Fig. 2a) and times (Fig. 2b). A
total of 25 °C increment at ion exchange temperature caused
weight gain of about 2.5 mg, but the weight gain rate was
higher at 450 °C (Fig. 2a). The analyses, as stated by Gy [2]
and Erdem et al. [18], showed that the weight of the samples
increased with rising temperature and time. Also, according to
Gy [2], the measurement of the weight increase in glass de-
pending on the temperature and time provides a quick and
useful way to define a constant inter-diffusion coefficient.
The principle of this method is based on the weight change
in glass samples as a result of the ion exchange process since
the ionic weight of potassium (39,0983 u) is greater than the
sodium atomic weight (22,9897 u) [2, 33]. After the ion ex-
change, the total mol amount (Q) of incoming ions can be
calculated from the weight increase in the glass specimens
(ΔW) and incoming ions per unit surface area of this glass
(Sıx) (Eq. 2). This relation will allow the determination of
the mass average diffusion coefficient, Da (cm2/s) (Eq. 3)
[33, 34]. Thus, it is possible to reconstitute the concentration
depth profile using the value of the mass average diffusion
coefficient and assess the depth of the ion exchange layer.
ΔW
Q¼
S ðMa−M bÞ
rffiffiffiffiffiffiffiffiffiffiffiffiffiffi
Da  t
Q ¼ 2  Cs
π work restructures so that new places for the larger ions are
where Ma, Mb is the molecular mass of the ion-exchanged ions
(g/mol); Cs is the surface concentration per unit volume, and t
is process time.
Weight increase which has an important role in the fast
detection of possible errors, especially because the ability to
quickly and easily measure for industrial applications follow-
ing the determination of the optimum process parameter is
necessary.
Strengthening (failure load) results and evaluation
In order to analyze the strengthening provided to the glass
surface by ion exchange, the ring-on-ring test was preferred
because, in this test set up, a large tensile stress is not imparted
to the processed edges of the test sample. Besides, the Weibull
distribution was used to understand the strength values better
and to represent the statistical approach of the depth of distri-
bution of the surface defects (cracks). Weibull modulus (m),
characteristic strengths (σ0), and bending strength values are
presented in Table 2, and the graphs are shown in Figs. 3, 4,
and 5.
Systematic experimental studies have been carried out on
the 12-h constant process time to determine the effect of the
ion exchange temperature on the fracture load (Fig. 3a). After
ion exchange, the increase in mechanical strength can be
clearly observed at all temperature and time parameters (Fig.
3a, b). The results obtained showed that the fracture load in-
creased continuously with increasing temperature in the range
of 375–435 °C, and the fracture load decreased at tempera-
tures above 435 °C. This result can be explained by the fact
that the glass shows a stress relaxation at temperatures above
ð2Þ 435 °C. The decrease in strength is attributed to the stress
relaxation behavior of glass in the case of long ion exchange
times at the high temperatures. Glass network relaxation oc-
curs when larger ions are introduced in the glass, as the net-
ð3Þ

16 16
(a) (b) 425˚C
14 14 435˚C
450˚C
Weight increase, mg

Weight increase, mg

12 12

10 10

8 8

6 6
4 4
2 2
0 0
350 375 400 425 450 475 500 0 4 8 12 16
Temperature, °C Time, h
Fig. 2 Weight increase of ion-exchanged samples for a varying temperatures (for 12 h) and b varying times
Table 2 All experimental data with standard deviation values
J Aust Ceram Soc

Sample Weight increase, Failure load, m (Weibull modulus) σ0, N % load of failure Surface Compressive stress, Depths of stress layer, Central tension, Microhardness, Crack resistance,
mg N possibility, N MPa μm MPa GPa N

%1 %0.0001

Raw – 501.51 ± 269.67 1.88 597.45 52.02 0.39 Air – – – 7.02 ± 0.26 1.08
Tin – – – 7.26 ± 0.48 0.68
375–12 0.67 ± 0.60 1314.80 ± 397.00 3.40 1470.80 380.05 25.26 Air 807.09 ± 51.23 4.96 ± 1.18 18.51 ± 10.79 7.35 ± 0.32 14.51
Tin 648.02 ± 42.83 4.59 ± 0.87 6.64 ± 0.45 7.30 ± 0.30 10.07
400–12 2.73 ± 0.79 1467.54 ± 474.05 3.14 1655.63 382.54 20.32 Air 653.02 ± 3.28 6.76 ± 0.05 5.45 ± 0.13 7.13 ± 0.28 13.58
Tin 621.56 ± 5.74 5.55 ± 0.25 4.58 ± 0.20 7.33 ± 0.36 3.76
425–12 5.00 ± 0.60 1532.52 ± 246.96 7.26 1692.95 898.37 252.45 Air 567.51 ± 9.39 12.24 ± 0.36 7.67 ± 0.16 7.73 ± 0.45 13.67
Tin 556.59 ± 10.87 11.40 ± 0.28 6.64 ± 0.07 7.65 ± 0.31 6.37
435–12 6.50 ± 1.00 1784.30 ± 249.46 5.83 1924.99 874.03 179.91 Air 544.15 ± 35.91 13.46 ± 1.56 8.52 ± 0.77 8.12 ± 0.39 12.95
Tin 494.32 ± 34.35 12.86 ± 0.98 6.83 ± 0.63 8.25 ± 0.18 12.95
450–12 7.42 ± 0.67 1307.69 ± 133.51 11.20 1362.85 903.93 397.12 Air 469.45 ± 27.35 17.89 ± 0.21 11.45 ± 4.18 7.57 ± 0.21 10.90
Tin 456.05 ± 6.72 14.97 ± 0.8 7.80 ± 0.12 7.36 ± 0.44 6.30
475–12 12.75 ± 0.97 1148.58 ± 391.49 3.90 1400.86 430.09 40.38 Air 373.07 ± 51.79 23.62 ± 1.57 11.24 ± 3.21 7.06 ± 0.26 5.51
Tin 373.10 ± 4.88 23.40 ± 0.54 10.39 ± 0.17 7.16 ± 0.47 2.32
425–4 3.00 ± 0.85 1543.00 ± 361.00 4.90 1682.62 658.06 100.34 Air 617.59 ± 6.94 6.82 ± 0.10 4.87 ± 0.11 7.35 ± 0.25 15.02
Tin 601.87 ± 15.92 5.06 ± 0.46 4.23 ± 0.58 7.77 ± 0.34 13.57
425–8 4.08 ± 0.52 1529.00 ± 447 4.51 1692.08 610.16 79.07 Air 595.26 ± 17.00 9.67 ± 0.32 6.41 ± 0.30 7.57 ± 0.86 11.76
Tin 565.59 ± 23.67 7.84 ± 0.82 5.67 ± 0.23 7.84 ± 0.51 8.66
435–4 3.33 ± 1.30 1493.30 ± 197.17 3.29 1672.38 413.14 25.10 Air 603.96 ± 19.26 7.16 ± 0.62 5.27 ± 0.16 7.77 ± 0.21 11.93
Tin 573.44 ± 13.41 5.38 ± 0.83 4.43 ± 0.26 7.50 ± 0.27 9.64
435–8 5.16 ± 0.93 2226.50 ± 249.46 10.63 2332.13 1512.90 635.79 Air 579.64 ± 13.97 10.88 ± 1.13 6.98 ± 0.37 7.59 ± 0.30 11.08
Tin 535.64 ± 32.99 9.63 ± 1.45 5.83 ± 0.51 7.16 ± 0.12 10.71
450–4 4.42 ± 0.67 1259.54 ± 370.89 3.33 1389.43 349.21 21.96 Air 502.22 ± 25.41 11.10 ± 1.97 5.80 ± 0.63 7.62 ± 0.24 4.76
Tin 498.50 ± 22.54 9.86 ± 1.54 5.77 ± 0.37 7.40 ± 0.28 3.75
450–8 6.50 ± 0.80 1357.84 ± 155.36 10.23 1415.35 902.60 366.54 Air 488.16 ± 11.86 14.69 ± 0.86 8.11 ± 0.03 7.58 ± 0.33 7.42
Tin 486.40 ± 18.36 13.55 ± 0.32 7.14 ± 0.04 7.19 ± 0.41 3.84
 J Aust Ceram Soc

2800 2800
(a) (b)
2400 2400 425˚C
2000 2000 435˚C
Failure load, N

Failure load, N
450˚C
1600 1600

1200 1200

800 800

400 400

0 0
Raw 375 400 425 435 450 475 Raw 4 8 12
Temperature, ˚C Time, h
Fig. 3 Failure loads of raw and ion-exchanged glasses for a increasing temperature (for 12 h) and b increasing time

created [18, 35, 36]. Similarly, Varshneya [37] reported that
elastic deformation occurs when a smaller ion is substituted by
a larger ion, and subsequent plastic deformation occurs due to
the readjustment of non-bridging oxygens or displacement
and bond bending of bridging oxygens. A total of 435 °C
was evaluated as the optimum temperature, since the fracture
load of chemically strengthened glass showed an increase of
~ 3.5 times (1784.30 N) that of raw glass (Fig. 3a).
The results of the simultaneous examination of ion ex-
change temperature and the effect of time are given in Fig.

2 12
(a) (b)
1
10
m (Weibull Modulus)

0
8
lnln [1 / (1-F)]

-1
Raw 6
-2 375˚C
400˚C 4
-3 425˚C
435˚C
-4 2
450˚C
475˚C
-5 0
4.00 5.00 6.00 7.00 8.00 9.00 Raw 375 400 425 435 450 475
lnσ (N) Temperature, ˚C
2700
(c)
2400
2100
1800
σ0 (N)

1500
1200
900
600
300
0
Raw 375 400 425 435 450 475
Temperature, ˚C
Fig. 4 Effect of increasing temperature on a the two-parameter Weibull distribution fitted, b m, and c σ0 of ion-exchanged glasses
J Aust Ceram Soc

2
12
(a) (b)
1
10 425°C

m ( Weibull modulus)
435°C
0 450°C
8
lnln [1 / (1-F)]

-1 Raw
425-4 6
-2 425-8
425-12
435-4 4
-3 435-8
435-12
-4 450-4 2
450-8
450-12
-5 0
4.00 5.00 6.00 7.00 8.00 9.00 Raw 4 8 12
lnσ (N) Time, h

2700
(c)
2400 425°C
2100 435°C
450°C
1800
σ0 (N)

1500
1200
900
600
300
0
Raw 4 8 12
Time, h
Fig. 5 Effect of increasing process time on a the two-parameter Weibull distribution fitted, b m, and c σ0 of ion-exchanged glasses

2b. For 425 °C and 450 °C, it is understood that increasing the where F (σ, V) is the probability of fracture, V is the volume of
ion exchange time from 4 to 12 h did not cause a significant the material, V0 is the normalization volume, and σ is the
change in the fracture strength. But at 435 °C, while a rela- homogeneously applied stress. σ0 is a scaling parameter that
tively more pronounced effect was observed, ~ 2227 N, the is called the characteristic strength identified as the stress at
highest fracture load reached at 8 h of ion exchange. fracture probability of 63.2%. The Weibull modulus, m, is an
The effect of the ion exchange process on the standard indication of the strength distribution. Since the samples are
deviation values is not clear, as it provides a significant in- equal in size, V = V0 is assumed, and the exponential Weibull
crease in the strength of the glass. Additional defects and modulus was transformed into the linear form by taking the
irregular distribution of the ion-exchanged layer can be con- natural logarithm twice (Eq. 5):
sidered as the factors affect negatively to the standard devia-  
tion especially during the preparation of the samples. The 1
lnln ¼ lnV þ mlnðσ−σ0Þ−mlnσ0 ð5Þ
lowest standard deviation is obtained for glasses ion ex- 1− F
changed at 450 °C for 12 h.
Strength measurements were applied to 10 specimens for In such a procedure, a fracture probability (F) is required
each condition, and fracture load distributions were calculated for each test sample, and Eq. 6 is used:
using the conventional, two-parameter Weibull distribution
(Eq. 4): i−0:5
F¼ ð6Þ
     N
V σ m
F ðσ; V Þ ¼ 1−exp − ð4Þ
V0 σ0 where N is the total number of tested samples, that i is the
sample sequence in order of increasing stress [38].

When Fig. 4a–c and Table 2 are examined, it is seen that the
Weibull modulus (m) and the characteristic strength (σ0)
values of ion-exchanged glasses increased with the process
temperature. No direct relationship was obtained between
the ion exchange temperature and the Weibull modulus.
When the characteristic strength values (σ0) are taken into
consideration, the bending strength is similar to σ0 measure-
ments. The Weibull modulus increased with temperature in-
crease from 375 to 425 °C, while it decreased at 435 °C, where
the maximum fracture load was obtained, and increased again
at 450 °C (Fig. 3b). The highest Weibull module was reached
at 450 °C as 11.20. Similarly, it has been understood that there
is no relation between the fracture load and the Weibull mod-
ule. These results give priority to the glass which ion-
exchanged at 450 °C in terms of reproducibility. The charac-
teristic fracture load increased steadily with increasing tem-
perature, and after reaching the maximum point of ~
1924.99 at 435 °C, it tended to fall at temperatures above
435 °C due to stress relaxation (Fig. 4c). With this aspect, it
showed a similar behavior to the relationship between fracture
load and temperature. Depending on the application area, it
may be desirable to determine under which load the specific
rupture rates can be achieved [39]. From this point of view, the
fracture load values for 1% and 1 ppm fracture probabilities
are calculated (Table 2) and the highest results were obtained
for ion-exchanged glass at 450 °C as 903.93 and 397.12 N,
respectively, for 1% and 1 ppm fracture probabilities.
It is estimated that the mechanical strength values of
400 °C are scattered and distant from each other that shows
the defect rate in these glasses is higher than those at other
temperatures. At 450 °C, it can be assumed that the defect
ratio is homogeneous and less than other temperatures, and
this glass is reliable for certain strength value ranges.
Moreover, these values are in good agreement with the stan-
dard deviations of strength measurements of ion-exchanged
glasses [40].
From Fig. 5b, when the temperature and the time were
evaluated together, the Weibull module increased with in-
creasing ion exchange temperature except for 435 °C-12 h
process conditions. It can be concluded that Weibull modulus
(m) were high due to the better filling of surface defects in
glass (e.g., flaw, crack) by increasing ion exchange tempera-
ture [41].
The highest Weibull modulus is obtained for 450 °C-12 h
process. The Weibull module of 435 °C-8 h process is also
Table 3 Raw, only heated raw samples, and 435-8 samples
Failure load
Raw 501.51 ± 269.67
Only heated raw samples (435 °C-8 h) 580.20 ± 293.79
435-8 2226.50 ± 249.46
J Aust Ceram Soc
close to the highest value. At the same time, it was determined
that the optimum process condition was 435 °C-8 h because of
both lower temperature and time requirements, and also, it has
a higher characteristic fracture load. The highest σ0 value with
a fracture load value of 2332.13 N is observed for the glass
treated for 435 °C-8 h.
The 425 °C-8 h and 435 °C-8 h samples of ion exchanged
showed 63.2% a probability of fracture with σ0 values
1692.08 and 2332.13 N, respectively. Also, the highest values
were obtained under 450 °C-8 h and 435 °C-8 h process con-
ditions for 1% and 1 ppm load of failure probabilities.
In order to confirm the effect of the annealing (heating) of
the raw glass on the mechanical properties, after the raw sam-
ples were only heated, the fracture load values were examined.
The heating process was performed at 435 °C-8 h, which was
determined as the optimum process parameter. Only the heat-
ed samples (without the presence of KNO3), the raw glass, and
the 435-8 samples are compared in Table 3. A significant rise
in the failure load values of samples of only the heating pro-
cess was not observed. In addition, a slight decrease was cal-
culated in the Weibull modulus value. As a result, no ion
exchange process was carried out, so a close value was ob-
tained with the raw samples. Furthermore, heating samples are
significantly lower than the mechanical properties of the ion-
exchanged 100K-435-8 sample. For these reasons, only the
heating process was not performed at the other temperature
parameters for raw glasses.
Fractographic results and evaluation
It is known that there is a relationship between glass fracture
behavior and glass strength. The fractured specimens were
photographed and examined for fracture behavior after the
ring-on-ring test. The fracture fragments between the outer
ring and the glass edges were counted as shown in Fig. 6
and Table 2, and the relationship between the number of frag-
ments after the fracture test and the fracture strength was
established.
Fragmentation is a dynamic process in which rapid crack
branching or multiple crack initiation and propagation occurs
during the fracture of a highly strained material [42]. During
the bending, it was seen that in the central region where the
stress was applied, the fracture pattern called the inner ring
was formed, and the fracture pieces expanded towards the
edges of the sample. Since the number of cracks is a function
m (Weibull modulus): σ0 (N)
1.88 597.45
1.20 829.66
10.63 2332.13
J Aust Ceram Soc

Fig. 6 Images of fracture pattern (a) (b)

for ion-exchanged glass with dif-
ferent exchange times and tem- Number of
peratures. a Representative sam- Sample code
fractured part
ple. b Number of fracture part
Raw 42
375-12 65
400-12 78
425-12 82
435-12 97
450-12 67
475-12 69
425-4 95
425-8 78
435-4 71
435-8 112
450-4 65
450-8 63

of the magnitude of elastic energy that is released at the mo-
ment of fracturing, the total number of cracks is less in a glass
of low fracture strength. Conversely, the number of cracks
increases as more elastic energy is necessarily applied to crack
the strengthened glasses [41, 42].
The highest number of broken pieces of glass showing the
highest fracture strength value was reached at 435 °C-8 h (112
fragments) (Fig. 6b). It is also apparent that the ion exchange
process carried out at a constant temperature of 450 °C in a
100% KNO3 salt bath does not have a significant effect on the
number of fragments in a similar manner to that of the time.
The number of broken parts of the reference glass was also
determined to be lower than that of the glasses obtained from
the other ion exchange processes, similar to the mechanical
strength value.
The role of internal central tension, which causes fragmen-
tation, is well known for thermally tempered glasses, and in
these studies, it was assumed that internal central tension pre-
dominates influence in fragmentation and its value was con-
nected to the fragment numbers [43, 44]. Hill and Donald [45]
studied on ion exchange properties of a lithium aluminosili-
cate glass, and they reported that the higher strength samples
had smaller fragments after biaxial bending loading in frag-
mentation of the glass. Bouyne and Gaume [46] predicted that
to make identical fragmentation levels, the tensile stress in
chemically tempered glass could be considerably less than in
thermally tempered glass.
In our study, similarly, the number of broken pieces in-
creased by increasing the flexural strength, and smaller pieces
were obtained by branching. As a possible reason for this, the
effect of the sum of the center tensile stress and the surface
compressive stresses were interpreted. It has a significant ef-
fect on mechanical strength that the glass sample already had
pre-existing defects and occurred during sample preparation
[41, 42, 47]. All these results show that the number of broken
pieces increased in parallel with the increase in strength so in
accordance with the literature.
Compressive stress and depths of stress layer results
and evaluation
Surface compressive stress (CS), depths of stress layer
(DOL), and center tensile stress (CT) on the air and tin
sides resulting from ion exchange process were deter-
mined by the FSM-6000 LE instrument. The measure-
ments were taken from five different points for each of
the air and tin surfaces of the samples, and the results are
given in Table 2 and Fig. 7. In the process conditions,
during which the 100% KNO3 melt salt solution and the
12 h ion exchange time were kept constant, it was seen
that as the ion exchange temperature increased, the com-
pressive stresses in the glass air and tin surfaces de-
creased, and the depths of stress layer increased (Fig.
7a, b). By increasing the ion exchange time and tempera-
ture, the amount of K+ ions that were diffused to the glass
surface continuously increased; thereby, the DOL was in-
creased. Increasing the time and temperature of the ion
exchange process can generate stress relaxation and, thus,
decreases compressive stress [28, 30, 48, 49]. The DOL
of the samples is a minimum of 4.6 μm, and the CS
values range from ~ 373 to 807 MPa. The depth of the
stress layer, with every 25 °C increase in temperature, was
found to provide regularly a ~ 6-μm depth increase on the
surface of the air. The general tendency was similar on tin
surfaces.
The depth of stress layer was always found to be larger on
the air side than the tin side. Since tin is known to increase the
network connectivity of the glass, and presence of tin in glass
blocked the K+ diffusion and, thus, it may cause a decrease in
depth of stress layer. It was also reported that compressive
 J Aust Ceram Soc

Fig. 7 CS (compressive stress) 1000 30

Atm.
and DOL (depth of stress layer) (a) Atm.
Tin
(b) Tin
900
on air and tin sides of ion- 25

Compressive stress, MPa

exchanged specimens. a CS at 800
different exchange temperatures 20
700
for 12 h. b DOL at different ex-
change temperatures for 12 h. c 600 15
CS at 425–435–450 °C for dif-
ferent exchange times. d DOL at 500
10
425–435–450 °C for different 400
exchange times
5
300

200 0
375 400 425 435 450 475 375 400 425 435 450 475
Temperature ,˚C Temperature ,˚C

1000 30
Atm-425˚C
900
(c) Tin-425˚C (d) Atm-425˚C
Tin-425˚C
Atm-435˚C 25 Atm-435˚C
Compressive stress, MPa

Tin-435˚C Tin-435˚C
800 Atm-450˚C Atm-450˚C
Tin-450˚C 20 Tin-450˚C
700

600 15

500
10
400
5
300

200 0
4 8 12 4 8 12
Time, h Time, h

stress is generally greater on the tin side than on the air side for
aluminosilicate (ALS) float glasses [28, 50]. Unlike this, our
results also show that the air side has greater compressive
stress than the tin side for soda-lime silica glass. It was report-
ed that the tin is diffused from the surface towards the interior
by the ion exchange process. Due to the ion exchange process,
tin vacancies formed on the surface by diffusion of tin towards
to inner layers, and this may cause lower compressive stress
than the air side. SLS glass has a lower density than ALS glass
and has more non-bridging oxygen [51]. As a matter of fact, it
is thought that the different network structure of both glasses
can cause the air surface to have higher compressive stress
values than the tin surface. In the literature, the compressive
stress behavior of SLS glasses on the air and tin surfaces has
not been examined up to now, and from this aspect, our study
also carries its own authenticity.
As to ensure a reliable strength, the depth of a compressive
layer must generally be greater than the size of typical surface
flaws [36]. While there is no clear relationship between com-
pressive stress and fracture load, it is considered that the opti-
mum depths of stress layer are about 9.5–11 mm depending on
fracture loads (for 425 °C-8 h and 435 °C-8 h). Because the
reproducibility of these experiments (425 °C-8 h and 435 °C-
8 h) has been tested and similar fracture load values, CS,
DOL, and CT have been obtained.
Microhardness results and evaluation
The results of the microhardness measurements are given in
Table 2, and the comparative graphs are shown in Fig. 8. After
all ion exchange process conditions, the hardness of air sur-
faces of glasses was increased. In the ion exchange experi-
ments at different temperatures for the 12-h time, the hardness
values increased until 435 °C and then gradually decreased
with increasing temperature for both surfaces (Fig. 8a). The
maximum hardness value was obtained as 8.25 GPa with an
increase of ~ 18% with respect to the raw glass on the tin
surface at 12 h-435 °C process conditions (Fig. 8b). When
examining the difference between air and tin surfaces, it was
seen that the increase in the air surface is greater, but there is
no clear relationship between the hardness values of the two
surfaces. Also, hardness values generally increased with in-
creasing ion exchange time on the air surfaces (Fig. 8c), but
more complicated results were obtained on the tin surfaces
(Fig. 8d). It is noteworthy that ion exchange enhanced the
hardness.
The non-bridging oxygen (NBO) size in glass is closely
associated with the contending shear and densification defor-
mation mechanisms, and SLS glass contains plenty of NBOs,
which results in increased subsurface shear damage as inden-
tation load increases [22, 52].
J Aust Ceram Soc

Fig. 8 Effect of increasing ion 9 9

exchange temperature on (a) (b)
hardness; a air, b tin surfaces.
Effect of increasing ion exchange

Hardness, GPa

Hardness, GPa
time on hardness; c air, d tin 8 8
surfaces

7 7

6 6
Ref. 375 400 425 435 450 475 Ref. 375 400 425 435 450 475
Temperature, ˚C Temperature, ˚C

12.00 12.00
425°C (c) 425°C (d)
435°C 435°C
10.00 450°C
10.00
450°C
Hardness, GPa

Hardness, GPa
8.00 8.00

6.00 6.00

4.00 4.00

2.00 2.00

0.00 0.00
Raw 4 8 12 Raw 4 8 12
Time, h Time, h

When the effect of the glass composition on the hardness
was examined, it is reported that the hardness of the Na-
containing glass is higher than the K-containing glass with a
similar composition [4, 32]. Filling potassium into the glass
surface with ion exchange produces a compressive stress
against the penetration of the Vickers pyramidal tip and also
can increase the elastic recovery when the load is withdrawn
[9, 53]. For this reason, the increase of hardness in glass
strengthened with ion exchange is not due to the composition-
al change but related to the filling effect induced by the pass-
ing of K+ ion in place of the Na+ ion that was caused by
increased compressive stresses and density.
Kolluru et al. [54] reported that tin on the tin surface can
increase the network connectivity of the glass. This in-
crease in network connectivity will prevent the diffusion
of K+ ions and reduce the depth of the stress layer [28]. It is
worthy to note that the hardness of the raw glass tin surface
is higher than air side, and the hardness of the air surfaces
can be higher after ion exchange. As mentioned above, the
compressive stress on the air surface after ion exchange is
always greater than on the tin surface, and the compressive
stress can lead to a higher hardness (Fig. 7a, c). For this
reason, the larger CS on the air surface may be one of the
reasons for the hardness being greater than the tin surface.
On the other hand, perhaps one of the most significant
causes is the glass chemical composition differences be-
tween the air and tin surfaces [50, 55].
Another reason for the increase in hardness is the increase
in density because of the filling of larger K+ ions into the glass
matrix. However, it is evident that ion exchange in 100%
KNO3 molten bath enhances the resistance of our glass versus
radial/median crack formation during Vickers indentation.
The most important factors determining the strength of the
glass are seen as crack initiation and crack propagation. It is
known that the glass exhibits high theoretical strength, and
when a crack occurs on the glass surface, the stress concen-
tration at the crack tip accumulates, and the catastrophic frac-
ture occurs at strengths much lower than the theoretical
strength. Therefore, Bcrack resistance analysis^ is proposed
as a method of evaluating crack initiation and crack propaga-
tion (BCracking resistance results and evaluation^ section)
[56–58].
Cracking resistance results and evaluation
In this section, in the interest of clear assessments on the
hardness alterations among ion-exchanged samples, further
comparisons of crack probability were evaluated. Figure 9
shows the cracking probabilities of ion-exchanged specimens
for air and tin surfaces, and the cracking resistance data are
given in Table 2. When ion-exchanged samples compared
with the raw glass at all temperature and time conditions, the
possibility of cracking formation on both surfaces was deter-
mined to occur at higher loads and the crack resistance
 J Aust Ceram Soc

100 100
(a) (b)
80 80

Cracking probability, %
Cracking probability, %

60 60

40 40 Raw
Raw
375˚C 375˚C
400˚C 400˚C
425˚C 20 425˚C
20 435˚C
435˚C
450˚C 450˚C
475˚C 475˚C
0 0
0 2 4 6 8 10 12 14 16 18 20 22 24 0 2 4 6 8 10 12 14 16 18 20 22 24
Load, N Load, N
100 100
(c) (d)
Cracking probability, %

80

Cracking probability, %
80

60 60
Raw Raw
425-4 425-4
425-8 425-8
40 425-12 40 425-12
435-4 435-4
435-8 435-8
20 435-12 20 435-12
450-4 450-4
450-8 450-8
450-12 450-12
0 0
0 2 4 6 8 10 12 14 16 18 20 22 24 0 2 4 6 8 10 12 14 16 18 20 22 24
Load, N Load, N
Fig. 9 Cracking behavior of ion-exchanged glasses after Vickers indentation-cracking possibilities (%) the effects of a temperature on air surface, b
temperature on the tin surface, c time (hour) on air surface, d time (hour) on the tin surface

increased. On the air surface, the cracking probabilities in-
creased with increasing temperature, and a more complicated
layout was exhibited on tin surfaces (Fig. 9a, b). There were
no apparent differences in the microhardness results of the air
and tin surface (BMicrohardness results and evaluation^ sec-
tion), but the cracking resistance results clearly showed the
superiority of the air surface over the tin surface for all process
conditions (Table 2).
When we look at the process times, it is generally de-
termined that the cracking probability decreased with in-
creasing time, and correspondingly, the cracking resistance
increased (Fig. 9c, d). An improvement of about 13.9 times
on the air surface of the chemical-tempered samples and
19.95 times on the tin surfaces was calculated with respect
to raw glass.
The Vickers indentation-cracking test is used to measure
resistance to crack formation in a rigid configuration under
controlled/repeatable test conditions [59]. It has been reported
that when K+ replaces Na+, the network connectivity increases
due to the increase in density, which also supports network
rearrangement [32].
Indentation crack formation behavior depends on pre-
existing defects on the glass surface and residual stresses in
the glass [22]. The purpose of compressive stress created on
the glass surface is to beat residual tensile stresses induced by
the Vickers indenter and to discontinue crack initiation and
propagation [60, 61]. As mentioned in previous studies, the
ion-exchanged generated compression stress on the glass sur-
face for all specimens’ crack resistance and therefore the crack
initiation loads were developed, which improves the mechan-
ical behavior [18, 62].
Kese et al. [15] and Koike et al. [32] investigated the effect
of stress on hardness in soda-lime glass by hardness measure-
ment during the bending strength test and deduced that stress
slightly affected hardness, and in their analysis results, the
hardness was not much improved by the compressive stress.
As a result, surface compression has a small effect on the
measured crack resistance (and hardness) in the chemically
tempered glass. As can be seen in other studies, it could be
evaluated that viscoelastic relaxation in the glass structure
occurs near the glass transition temperature at high tempera-
tures, which affects mechanical properties such as hardness
J Aust Ceram Soc
Fig. 10 AFM image of an ion exchange process. a Raw glass. b 435 °C-8 h
and cracking resistance [45, 63]. In addition, when we com-
pare our crack resistance values with our mechanical strength
(fracture load) values, it is observed that the difference ratio in
cracking resistance between air and tin surfaces of our ion-
exchanged glasses is lower in high mechanical strength. This
is an important point for both surfaces in terms of mechanical
strength and cracking resistance analysis.
However, there was no clear relationship among the com-
pressive stress, hardness and cracking resistance values, and
this requires further investigation. Generally, glass is impor-
tant for the development of the ion exchange process to create
a much better surface, since the micron and submicron flaws
(crack, defect) that occur during and after production signifi-
cantly affect the mechanical strength of the glass material.
Production conditions and glass composition are also impor-
tant influences on ion exchange research.
AFM (surface topography) results and explanation
Figure 10 illustrates the surface topography images of AFM to
raw and 435 °C-8 h process and Figs. 11 and 12 show the
AFM numerical results. The surface of the raw and ion-
1.0
(a)
0.8
0.6
Ra, nm
0.4
0.2
0.0
Ref. 375 400 425 435 450 475
Temperature, ˚C
Fig. 11 On the surface roughness of the air surface. a The effect of the ion exchange temperature at a fixed time of 12 h. b The effect of the ion exchange
time at 425 °C, 435 °C, and 450 °C
exchanged glasses was smooth and no buckling pattern was
found. Ra values range from 0.28 to 1.18 nm.
An improvement in surface roughness was observed for all
process conditions (Figs. 11, 12). In the 12-h studies, the sur-
face roughness increased on air and tin surfaces of glass with
increasing temperature (Figs. 11a, 12a). In studies carried out
at 425 °C and 435 °C with 4, 8, and 12-h waiting times, it was
observed that generally, the surface roughness increased with
increasing waiting time (Fig. 11a, b). It was also observed
after ion exchange studies that the surface of the tin is always
rougher than the air [64], because it is known from previous
studies that tin increases surface roughness. Since our me-
chanical strength tests are made only on the air surface, it is
not possible to say exactly what the effect of surface rough-
ness on mechanical strength is.
As the diameter of each potassium ion is larger than the
diameter of the sodium ion, pre-existing microcracks on the
glass surface are filled by potassium ions and a smoother
surface is obtained [65]. In this study, the ion exchange depths
of stress layer (DOL) range from 4.59 to 23.62 μm, and it is
understood that potassium ions diffuse deeper from the sur-
face with increasing temperature and time. Considering in this
manner, it can be said that the increase in surface roughness
1.0
(b) 425
435
0.8 450
0.6
Ra, nm
0.4
0.2
0.0
Ref. 4 8 12
Time, h
 J Aust Ceram Soc

1.5 1.5
(a) (b) 425
435
1.2 1.2 450

0.9 0.9
Ra, nm

Ra, nm
0.6 0.6

0.3 0.3

0 0.0
Ref. 375 400 425 435 450 475 Ref. 4 8 12
Temperature, ˚C Time, h
Fig. 12 On the surface roughness of the tin surface. a The effect of the ion exchange temperature at a fixed time of 12 h. b The effect of the ion exchange
time at 425 °C, 435 °C, and 450 °C

due to the increase in temperature may be caused by reason of
the fact that the potassium ion is not deeply filled with the
defects (or microcracks) in the surface. At lower temperatures,
the ion exchange process had a surface roughness reducing the
effect, since potassium ions may remain on the surface layer
and can result in the better filling of surface defects
(microcracks). It should also be noted that the changes in
surface roughness values of the ion exchange process are very
small ranges.
K/Na concentration profile and explanation
Developing mechanical properties in glasses is directly related
to the amount of compressive stress on the surface and the
depth profile, which is linked to the ion concentration amount
entering into the surface and the ionic diffusion depth [4, 11,
18, 21]. In addition, the other important parameter is the effect
combination of stress and structural relaxation in glasses. It is
important to minimize the behavior of the glass while creating
a high-stress profile and compressive stress during ion ex-
change [3, 18, 66].
Figure 13 shows the K/Na concentration profiles ratio on
the air and tin sides of the ion-exchanged glasses at 12 h for
different exchange temperature.
The surface potassium concentration and diffusion depth
increase with temperature. In all samples, while the potassium
ion concentration decreases continuously from the surface to
the depth, the sodium ion concentration increases. The potas-
sium ion concentration on the air side is always greater than
that on the tin side, and these are parallel to the depths of stress
layer (DOL) results. As the depth is progressed, irregular for-
mations occur due to the glass structure and SEM-EDS point
analysis error margin (Fig. 13).
During ion exchange, it is known that structural relaxation
occurs at high temperatures close to the glass transition tem-
perature and for an extended period of time, and a higher
diffusion rate was expected with increasing temperature/time.
In the SEM-EDS K/Na ratio depth profile analysis, the

45 40
Air Tin
40 35
375-12 375-12
35 400-12 30 400-12
425-12 425-12
% K/Na rao

30
% K/Na rao

435-12 25 435-12
25 450-12 450-12
475-12 20 475-12
20
15
15
10 10

5 5
0 0
0 2 4 6 8 10 12 14 16 18 20 0 2 4 6 8 10 12 14 16 18 20
Depth, μm Depth, μm
Fig. 13 K/Na concentration profile for different temperature
J Aust Ceram Soc
Fig. 14 X-ray diffraction patterns
of raw and 475 °C-12 h ion-
exchanged glass samples
Intensity (counts)
diffused potassium ion to the sample increased with tempera-
ture (coming out of Na ions increased) and progressed with
time and this is also shown in the weight increase measure-
ments (Fig. 13).
With regard to the effect of the temperature, a deeper
profile obtained at a higher surface potassium concentra-
tion or at higher temperatures does not always mean better
mechanical performance [18, 30, 66]. This is due to the
glass relaxation behavior which overcomes the stress
forming process at temperatures close to the glass transi-
tion temperature during ion exchange [3, 4, 18]. Therefore,
the very high diffusion rate remains insignificant and the
concentration profile and the compressive stress profiles
do not coincide.
Moreover, XRD analyses were performed to verify that
there was no crystallization at the raw and the highest temper-
ature ion-exchanged glass (475-12). XRD patterns of untreat-
ed glass, 475 °C for 12 h ion-exchanged glass are shown in
Fig. 14.
The raw glass and ion-exchanged sample were determined
no crystalline phase, high-temperature ion-exchanged glass
(475 °C-12 h) still being amorphous as the raw sample (Fig.
14).
Conclusion
The mechanical behavior of chemical-tempered soda-lime sil-
icate glass using the ring-on-ring test and Vickers indentation
has been investigated, and the relation between compressive
stress and depth of stress layer of mechanical behavior has
been evaluated. The weight of glass samples increased grad-
ually with time and temperature increase due to the inter-
diffusion of K+–Na+ ions. For the 375 °C and 475 °C ion
exchange temperature ranges, the rate of weight increase
2000
Raw
1800
1600 475-12
1400
1200
1000
800
600
400
200
0
10 20 30 40 50 60 70
2 theta (degree)
varied from 0.007 to 0.144%, respectively. The results of the
ring-on-ring test showed that the mechanical strength was best
at 435 °C-8 h (4.4 times) and that the mechanical strength of
the chemical-tempered soda-lime silica glass decreased due to
stress relaxation at high temperatures and long process times.
The statistical Weibull module was found to be a reliable glass
of chemical-tempered glass at 450 °C, but the highest fracture
strength (63.2% fracture probability) was achieved at 435 °C-
8 h. As the mechanical strength increased, the accumulated
elastic energy in the chemically tempered glass increased; the
samples, consequently, were broken into too many pieces.
Compressive stress decreased with increasing temperature,
and the air side always had greater compressive stress than
the tin side for soda-lime silica glass. These results also im-
proved the mechanical strength of the glass. Chemical tem-
pering improved the hardness of float soda-lime silicate
glasses to about 18%. For the chemically tempered glass sam-
ples, it was determined that the crack resistance increased by
13.9 times at the air side and 19.95 times at the tin side. The
AFM surface roughness increased with increasing tempera-
ture and time; lower values were also obtained according to
raw glass. SEM-EDS concentration profile ratios showed that
the potassium ion concentration decreases continuously from
the surface to the depth, but the sodium ion concentration
increases.
Acknowledgments Many thanks to Bilal ALCAN for his contributions to
the experimental studies from the TUBITAK Marmara Research Center
Materials Institute. The authors are thankful to ŞİŞECAM Science and
Technology Center.
Funding information The authors of this study are grateful to the
Scientific & Technological Research Council of Turkey (TUBITAK)
for the financial support under the project entitled and numbered as
BThird-Generation Glass Toughening: Ultra Strong Sheet Glass For
Large-Area Applications Through Super-Efficient Side-Selective Ion
Exchange-215M127.^

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