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CERAMICS
INTERNATIONAL

Ceramics International 42 (2016) 76267631

www.elsevier.com/locate/ceramint

Characterization of ceramic tiles containing LCD waste glass

Kidong Kima,n, Kicheol Kima, Jonghee Hwangb
a

Department of Materials Science and Engineering, Kunsan National University, Chunbuk, Republic of Korea
b
Korea Institute of Ceramic Engineering and Technology, Jinju, Republic of Korea
Received 31 October 2015; received in revised form 14 January 2016; accepted 25 January 2016
Available online 2 February 2016

Abstract
In the present work, the application of LCD waste glass as a ux material substituting for the traditional feldspar in ceramic tiles was studied.
The viscosity of LCD glass at the sintering temperature of the ceramic tile was found to be optimal for the dense solid that is obtained from the
sintering of the glass powder. The sintered body containing LCD waste glass showed a dense microstructure due to the rich liquid. Even for full
replacement of feldspar, neither pyroplastic deformation nor liquid exudation was observed. Overall, properties such as water absorption and the
thermal expansion coefcient were positively affected by LCD waste glass substitution. Moreover, the mullite content in the sintered body was
almost unchanged. These results were discussed in terms of the apparent viscosity and glass composition.
& 2016 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Keywords: Ceramic tile; LCD waste glass; Feldspar; Viscosity; Glass composition

1. Introduction
LCD glass is composed of SiO2, Al2O3, B2O3, and alkaline
earth oxides. Because this glass is used for LCD panels, its
homogeneity and the resulting physicochemical properties are
very different from those of traditional glass [1]. A large amount
of waste glass (hereafter designated as LPWG: LCD process waste
glasses) equal to approximately 80 kt/y is currently produced by
LCD panel manufacturers in four Asian countries. LPWG is
contaminated by thin lm transistors (TFT), indium tin oxide
(ITO) conductors, polarizers and colour lters. Furthermore, the
composition of LPWG occasionally exhibits considerable uctuation because it consists of glass products from three different
manufacturers. Therefore, unlike the LCD cullet recycled as a raw
material in the E glass industry [2,3], the recycling of LPWG is
difcult for an industry that is sensitive to compositional change.
There have been several studies on LPWG recycling for use
in clay ceramic tiles [4], glassceramics [57], foamed glass
[8] and cement [911]. In particular, recently, the present
authors have reported a full replacement of feldspar by LPWG
n

Corresponding author. Tel.: 82 63 469 4737; fax: 82 63 462 6982.

E-mail address: kdkim@kunsan.ac.kr (K. Kim).

http://dx.doi.org/10.1016/j.ceramint.2016.01.172
0272-8842/& 2016 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

in traditional porcelain sanitary ware [12]. It is well known that

in porcelain ceramics such as vitreous white ware, the feldspar
plays the role of a uxing agent penetrating into the alumina
silicate ceramic powders by viscous ow during sintering and
the rest of the liquid phase is solidied without active crystallization during cooling. Therefore, several studies have investigated the use of soda lime silicate (SLS) glass [1315] or
alkali alkaline earth silicate CRT glass [16,17] derived from
commercial products as a substitute for feldspar in conventional porcelain stoneware. However, because these glasses
exhibit low viscosity at the sintering temperature, their content
is limited to only 1020 wt% of the total feldspar depending
on body composition.
In the present work, gradual replacement of feldspar by
LPWG was examined for ceramic tiles, a typical application of
traditional porcelain ceramics. The sintered specimens were
characterized and the obtained results were discussed.
2. Materials and methods
The ceramic oor tiles in the original batch obtained from a
tile manufacturer consist of 36 wt% clay, 18 wt% quartz and
46 wt% feldspar. Up to 40 wt% of the 46 wt% concentration of

K. Kim et al. / Ceramics International 42 (2016) 76267631

3. Results and discussion

The compositions and crystalline phases of the starting raw
materials obtained by XRF and XRD analyses, respectively,
are presented in Table 1. Andesine (Na0.70.5Ca0.30.5Al1.3
1.5Si2.72.5O8: a kind of plagioclase minerals and mixture of
albite and anorthite) and quartz are present, and no kaolinite
was found in the clay used in the present work. In addition to
the quartz, the raw quartz material contains magnesioferrite
(MgFe2O4). The feldspar consists of albite (Na2OAl2O36SiO2)
and quartz. Both clay and quartz supplied from local mines
seem to be naturally contaminated with another mineral,
leading to the presence of the unusual crystalline phases such
as andesine and magnesioferrite. The three raw materials
contain higher concentrations of Fe2O3 than LPWG. The
normal sintered specimen therefore showed a deep reddish
brown colour, which became less pronounced after the

Table 1
Compositions (wt%) and identied crystalline phases of raw materials.
Component

Clay

Quartz

Feldspar

LPWG

SiO2
Al2O3
TiO2
B2O3
Na2O
K2O
MgO
CaO
SrO
BaO
Fe2O3
Crystalline phase

66.91
22.71
0.78

1.01
2.27
1.30
0.28

4.43
Q, A

66.83
20.01
0.66

0.22
5.77
0.58
0.07

5.38
Q, Ma

65.52
18.19
0.64

2.16
3.74
3.05
0.76

5.41
Ab, Q

5864 (60.1)
1520 (16.8)

711 (10.3)

04 (0.44)
38 (7.6)
08 (4.2)
05 (0.48)
0.025

Q: quartz, A: andesine, Ma: magnesio-ferrite, and Ab: albite.

(): the average composition of LPWG used in the present work.

16

LCD glass
SLS glass
CRT glass

14

Viscosity (log in dPas)

feldspar in the batch is replaced by LPWG powder ned

partially via milling in a glass processing plant. LPWG is a
waste glass generated from the edge trimming process of LCD
and thus free from organic thin lms; the number at the end of
LPWG specimen code species wt% of LPWG in total batch.
For all powders, the particle size was in the 550 m range.
To examine the effect of viscous ow due to glass powder
during sintering, the temperature dependence of the LPWG
viscosity was determined based on the DIN 52312 and ASTM
C338 standards at high and low temperatures, respectively.
The body mix of each batch composition was prepared by
milling the three raw materials specied above and LPWG in a
zirconia ball mill. Based on the actual ceramic tile production
conditions, the disk-shaped green compacts prepared by uniaxial
pressing with 500 kg/cm2 were heated at a rate of 5 1C/min in
an electric box furnace and sintered for 1 h at 1100 1C or
1150 1C. After sintering the specimen was cooled naturally to
room temperature. It took about 10 h for heating, isothermal
sintering and cooling. All the sintered bodies showed neither
pyroplastic deformation nor rough surfaces due to the rich liquid
or the exudation of the glass phase. Properties such as bulk
density, water absorption and thermal expansion coefcient
were measured for the resulting sintered body according to
ASTM C373 and E831, respectively. The bulk density was
determined using special kit (P/N77402-00, Ohaus, USA) based
on Archimedes principle. The water absorption was measured
for the boiled specimen. Thermal mechanical analysis (TMA
4100S, Bruker AXS, Germany) was used to determine the
thermal expansion coefcient. The details for some of the
measurement procedures are described in the literatures
[12,18,19,21]. The composition and crystalline phases of the
raw materials and sintered bodies were analysed by XRF (ZSX
Primus II, Rigaku, Japan) and HR-XRD (EMPYREAN, PANalytical, Netherlands), respectively. A quantitative analysis of the
phases existing in the sintered body was carried out using the
Rietveld-RIR method with PANalytical Highsco-plus in which a
Si crystal was used as the standard phase. Data were recorded in
the 2 range of 5751 under the condition of 0.0261 step size
and 21/min step scan speed.

7627

12
10
8
Sintering range of

to a solid body

glass powder

6
4
2
400

600

800

1000

1200

1400

1600

Temperature ( C)
Fig. 1. Temperature dependence of the viscosity of LPWG inclusive of
conventional two glasses (SLS and CRT) and a description of the sintering
range of glass powder only.

introduction of LPWG containing approximately 250 ppm

Fe2O3. The viscosity curves of LPWG and the conventional
SLS and CRT glasses in Fig. 1 show different temperature
dependences. The LPWG is an alkali-free alumino-borosilicate
glass, and its viscosity is therefore much higher than those of
SLS and CRT glasses that include alkali oxide, alkaline earth
oxide and silica. For LPWG, the temperature corresponding to
106 dPas, where a dense microstructure can be obtained by
sintering the glass powder [20], lies in the 10801120 1C
range. Moreover, the viscosity behaviour in this range is
similar to that of Na feldspar suggested by Andreola et al.
[21]. On the other hand the corresponding temperature for SLS
and CRT glass is 840 1C, which is much lower than the normal
sintering temperature. The ceramic tile sintering range of
11001150 1C corresponds to 105105.6 dPas for LPWG.
Therefore, it is expected that compared to SLS and CRT
glass, LPWG can be an excellent substitute for feldspar.
The bulk density (D) of the specimens sintered at 1100 1C
and 1150 1C as a function of LPWG content is shown in Fig. 2.
Irrespective of the sintering temperature, similar dependences of

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K. Kim et al. / Ceramics International 42 (2016) 76267631

2.6
o

1100 C
o
1150 C

D (g/cm )

2.4

2.2

2.0

1.8
0

10

20

30

40

LPWG Content (wt%)

Fig. 2. Bulk density (D) of the sintered specimens.

14

1100 C
o
1150 C

12

WA (%)

10
8
6
4
2
0
0

10

20

30

40

LPWG Content (wt%)

6.0

1100 C
o
1150 C

5.8

-6

TEC (10 /?C)

5.6
5.4
5.2
5.0
4.8
4.6
4.4
4.2
0

10

20

30

40

LPWG Content (wt%)

Fig. 3. (a) Water absorption (WA) and (b) thermal expansion coefcient
(TEC) of the sintered specimens.

D on the LPWG content are obtained. The D values show an

overall decrease with increasing LPWG content. At the initial
introduction of LPWG, D shows an approximately constant
value, but an abrupt decrease in D is observed in the 1015 wt%
range. D values are again constant for LPWG contents greater
than 25 wt%. Two factors contributing to the change in D upon

substitution for feldspar by LPWG can be suggested: one is the

volume shrinkage difference that increases D, and the other is
the density difference between LPWG (2.45 g/cm3) and feldspar
(2.552.76 g/cm3) that decreases D. A viscous ow of LPWG
during sintering strongly affects the volume shrinkage. Nevertheless, the results in Fig. 2 imply that the latter factor is
dominant. Fig. 3 shows the results of the water absorption (WA)
and the thermal expansion coefcient (TEC) measurements.
While at 1100 1C, the obtained WA is greater than 0.5 up to
LPWG35, at LPWG40 it approaches the 0.5 value, which is
marked by an arrow in Fig. 3. By contrast, at 1150 1C, all
specimens except LPWG0 show almost 0 WA, satisfying the
requirement (ISO 13006) of WAo0.5 for the dry-pressed
ceramic tiles Group Bla. Regarding the TEC, unlike the alkali
aluminosilicate feldspar, LPWG is an alkali-free glass, and its
TEC under the glass transition temperature is 3236  10  7/1C,
which is much lower than those of the feldspar glasses [22].
This is the origin for the decrease in the TEC of the sintered
specimen with increasing LPWG content. Therefore, better
thermal shock resistance is expected for the ceramic tiles
containing LPWG.
Analysis of SEM micrographs of samples with increasing
LPWG contents (Fig. 4) demonstrates the behaviour observed
in a previous study of porcelain sanitary ware [12]. Comparison of the micrographs shows that the evolution of the
microstructure depends on the LPWG content. The sintered
body with LPWG shows a soft and dense microstructure due to
the rich liquid phase derived from the pure glass. Such a
tendency is clearly shown by LPWG40, which is sintered at
1150 1C but exhibits large closed pores. Conversely, the
LPWG0 has a rough microstructure due to a small quantity
of liquid phase derived from the partially melted feldspar.
Fig. 5 shows the shapes of the sintered specimens consisting of
only ux with feldspar and LPWG:feldspar 1:1; the results
conrm that differences between feldspar and LPWG affect the
sintering of the green compact. The differences in the sintering
mechanisms of feldspar and LPWG in the green compact can
be described as follows: while for the feldspar (LPWG0), the
sintering may proceed by diffusion via slightly viscous ow of
the partially melted feldspar, for the LPWG, diffusion via full
viscous ow of the glass may be dominant. Finally, the
sintering reaction results in the formation of a quasi-liquid
consisting of a liquid and non-melted crystalline phase.
Because the uidity of a quasi-liquid depends on the content
of the crystalline phase [23], its apparent viscosity at the
sintering temperature decreases with increasing LPWG content. The constant D in the 3040 wt% range shown in Fig. 2
may be due to the large closed pores trapped in the quasi-liquid
with low viscosity obstructing body shrinkage [13,14].
XRD patterns of some specimens sintered at 1100 1C are
shown in Fig. 6. In addition to quartz and mullite, the presence
of andesine derived from the clay was observed in these
sintered specimens. The contents of these three crystalline
phases and the glass phase in the body sintered at 1100 1C are
quantitatively described as a function of LPWG content in
Fig. 7. The contents of the four phases are almost constant for
all sintered specimens containing LPWG. In particular, the

K. Kim et al. / Ceramics International 42 (2016) 76267631

7629

LPWG0

LPWG20

LPWG40

LPWG0

LPWG20

LPWG40

Fig. 4. SEM micrographs of specimens (  1000) at (a) 1100 1C and (b) 1150 1C.

100

Glass phase
Mullite
Quartz
Andesine

90

(a)

Content of Phase, wt%

80

(b)

70
60
50
40
30
20
10

Fig. 5. Shape of the sintered specimens of (a) feldspar only and (b) LPWG:
feldspar 1:1 at 1150 1C.

0
0

10

15

20

LPWG Content, wt%

Fig. 7. Dependence of the phase content of the sintered specimens on the
LPWG content at 1100 1C.

M
Q

Intensity (arbitrary)

Table 2
Mullite content (wt%) of specimens sintered at 1100 or 1150 1C determined by
the Rietveld-RIR method and its resulting range of numerical statistical
indicators (Rwp, Rp) and goodness-of-t (s) showing the quality of renement.

LPWG0

M
Q

LPWG5

LPWG10

LPWG15

LPWG20

Q
M
Q
Q
M
Q
Q
M
Q
Q

10

20

30

40

50

60

70

80

2
Fig. 6. XRD patterns of specimens sintered at 1100 1C. Q: Quartz, M: Mullite,
and A: Andesine.

Item

LPWG0

LPWG5

LPWG10

LPWG15

LPWG20

1100 1C
1150 1C
Rwp (%)
Rp (%)
s

4.6
5.2
3.09.5
2.13.8
4.17.4

4.1
5.3

4.2
5.3

4.5
5.4

4.5
5.9

mullite content for LPWG5LPWG20 is approximately 4

6 wt%, which is nearly the same as that of LPWG0 at each
sintering temperature, as shown in Table 2. In other words,
there is no signicant change in the mullite content despite the
replacement of the feldspar by LPWG. It is well known that

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K. Kim et al. / Ceramics International 42 (2016) 76267631

Table 3
Average compositions of several sintered bodies (wt%).
Component

LPWG0

LPWG10

LPWG20

LPWG30

LPWG40

SiO2
Al2O3
B2O3
Na2O
K2O
MgO
CaO
SrO
BaO
TiO2
Fe2O3

66.25
20.14

1.39
3.58
1.98
0.46
0.04
0.06
0.69
5.05

65.65
19.95
1.05
1.18
3.20
1.71
1.16
0.50
0.10
0.63
4.51

65.04
19.84
2.09
0.96
2.82
1.43
1.86
0.96
0.15
0.56
3.96

64.44
19.70
3.14
0.75
2.45
1.16
2.57
1.43
0.20
0.50
3.42

63.84
19.55
4.18
0.53
2.07
0.89
3.27
1.89
0.24
0.44
2.88

mullite strongly inuences the maintenance of the mechanical

strength of the nal ceramic body. Therefore, the mullite
content is very important in these ceramics. There could be
several possible explanations for the lack of dependence of
mullite content on the LPWG content. Comparison of the
present results with those of other studies using waste glass
such as SLS [13] and CRT glasses [16] shows that LPWG
exhibits two remarkable differences from other waste glasses:
(1) the Al2O3-rich composition and (2) viscosity with optimal
uidity at sintering temperature. Table 3 shows the average
compositions of several selected sintered bodies. Because the
Al2O3 content of LPWG is similar to that of the feldspar, as
shown in Table 1, the replacement of the feldspar by LPWG
hardly inuences the Al2O3 concentration of the nal sintered
specimens. As indicated above based on Fig. 5, the apparent
viscosity at the sintering temperature will decrease with the
replacement of feldspar by LPWG because the viscosity of
LPWG is smaller than that of feldspar. Therefore, active
diffusion of the corresponding components of LPWG via
viscous ow during sintering can be expected. These two
features of LPWG are certainly contributing factors for the
maintenance of the mullite content [12].
Normally, the green bodies of ceramic tile prepared from the
present batch are sintered at 1150 1C during industrial production. However, the results of the present work show that
depending on LPWG content the required ceramic tile properties can be achieved even at 1100 1C. This means that the
energy consumption and the feldspar usage in the tile industry
can be reduced by the introduction of the LPWG.

4. Conclusions
In the present study, the effects of feldspar substitution by
LPWG in ceramic tiles on some properties of the sintered body
were investigated. The properties such as WA and TEC
including microstructure showed a positive tendency for
ceramic tile up to almost complete replacement of feldspar
by LPWG. Moreover, there was no signicant change in the
mullite content in the sintered body containing LPWG. It can
be concluded that the viscosity and composition of LPWG

play decisive roles in determining the properties of the nal

product.
However, the present positive results for LPWG are not
valid for the current end LCD waste glasses generated from the
end-of-life LCD devices. Such end waste glasses derived from
the glass product before 2010 contain mostly toxic components
such as As2O5 and Sb2O5 [24] that preclude their active
recycling. From the perspective of the WEEE directives of the
EU [25], various attempts for positive use of the end LCD
waste glasses are necessary.
Acknowledgements
This study was supported by the R&D Center for Valuable
Recycling in the Institute for Advanced Engineering (GlobalTop Environmental Technology Development Program) and
was funded by the Ministry of Environment, Republic of
Korea (Project no. 2014001170002).
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