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Ceramics International
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A R T I C L E I N F O A B S T R A C T
Keywords: The recovery and reuse of industrial wastes are of great importance to the environment. Today, a large amount of
Ceramic waste is produced due to marble production, and it is extremely important to bring such wastes to the ceramic
Glaze industry, to solve the pollution problem and to provide cost-efficient ceramic production. In this study, marble
Marble waste
waste was used for ceramic earthenware glaze and body formulations. Marble waste was used in two different
Masse
formulations as glaze and body. Chemical analysis, morphological features, crystallographic information of
Raw material
different formulations were made with XRF, SEM and XRD, respectively. When the hardness test results of the
ceramic body and glazed samples were examined, the hardness values of the marble waste added samples
increased by 1.9% compared to the standard samples. According to the results obtained, it has been seen that
using marble waste in the ceramic industry is very important for both economic and environmental reasons.
* Corresponding author.
** Corresponding author.
E-mail addresses: labaratuar@keramika.com.tr (F. Gol), fatihsen1980@gmail.com (F. Sen).
https://doi.org/10.1016/j.ceramint.2022.02.096
Received 30 January 2022; Received in revised form 9 February 2022; Accepted 9 February 2022
Available online 13 February 2022
0272-8842/© 2022 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
F. Gol et al. Ceramics International 48 (2022) 15622–15628
Fig. 1. Process diagram of ceramic glazes prepared using CoCaM/marble powder wastes.
formed in the production process [22–24]. These wastes cause envi and used in production was taken as reference. CoCaM, was removed
ronmental pollution and cause energy losses (Science, n.d. [28] [24]; from the formulation and replaced with waste marble powder at the
Tabit, n.d. [29]). The introduction of waste into recycling processes will same rate. In addition, another glaze formulation (F2) has been prepared
contribute to reducing environmental pollution and making the energy to determine the different effects that will occur on the glaze surface.
and natural resources used in production sustainable [25]; Gülmez, n.d. The prepared formulations were ground in a jet mill for 15 min. The
[27]; [26]. The aim of this study is to investigate the availability of glaze samples obtained were sieved with a 325 mesh sieve. The glaze
marble waste in earthenware ceramics. mixture prepared was applied to the ceramic body by dipping method.
In this study, the usability of marble waste powders in glaze and Then it was fired at 1100–1200 ◦ C in a rapid firing roller oven. The
masse formulations instead of calcium oxide-containing raw materials flowchart of the process is shown in Fig. 1.
was investigated. In this direction, instead of raw materials containing In addition, waste marble powders were used instead of CoCaM in
CoCaM (Commercially available Ca-Based materials), marble waste ceramic body formulations. For the preparation of ceramic body for
powders containing high levels of calcium oxide were used in the for mulations, clay, quartz, feldspar, CoCaM/waste marble powders were
mulations. The formulations were determined, marble waste powder ground together with water for 45 min in jet mills and sieved with a 200
additions were added in the same weight percentages, and relevant mesh sieve. The resulting mixtures were shaped in plaster molds and
analyzes were made. The results were compared with the standard made suitable for tests. Firstly, chemical analysis of CoCaM and waste
sample in terms of technical properties. It is thought that the dissemi marble powders with XRF was carried out to determine their chemical
nation of R&D studies on these issues will create a roadmap for the composition. The water absorption test was performed on the samples
development of environmentally friendly formulations. obtained and the results were observed. In addition, shrinkage values
were compared with the reference ceramic body. The surface properties
2. Material and method of glazed and body samples and CIE L*a*b* values were investigated
with X-rite brand spectrophotometer. In addition to these, crystallo
In this study, the use of waste marble dust as an alternative raw graphic and morphological properties were examined with FE-SEM
material in the ceramic industry was investigated. Due to the similar (scanning electron microscope) and hardness test was performed with
chemical structures, waste marble powder has been used in two different Duroline-M brand device.
formulations as ceramic glaze and ceramic body. The waste marble
powder was used with a grain size of 0.5 μm. First, a glaze formulation
(F1) containing CoCaM (Commercially available Ca-Based materials)
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F. Gol et al. Ceramics International 48 (2022) 15622–15628
Table 1 brightness decreases with the addition of CoCaM, and the brightness
CaO amount of the CoCaM and marble waste (wt %). increases on the surface with the addition of waste marble powder. Due
Component CoCaM (%) Waste Marble Powder (%) to the fact that the values in F2 are between 10 and 70 GU, the surface is
called semi-glossy. It is observed that the brightness decreases with the
CaO 57.90 58.71
addition of CoCaM, and the brightness increases on the surface with the
addition of waste marble powder.
3. Results and discussion A water absorption test was applied to the glazed samples and the
results were calculated. According to the CoCaM-containing sample, the
In this study, the availability of waste marble powders instead of values of the waste-added sample increased by 0.08%. This value is
CoCaM used in ceramic glaze and body formulations was investigated. tolerable under operating conditions.
As seen in Table 1, calcium oxide (CaO) contents of CoCaM and waste In addition to these, the behavior of glazes against heat was
marble dust are similarly high. This situation supports the usability of
waste marble powder instead of CoCaM. Also, due to the compounds Table 2
contained in these wastes, when used instead of CoCaM, it can provide CIE L*a*b* values of glazed samples.
technical features to the structure.
F1 F2
The surface images of the samples are given in Fig. 2. It is seen that
the color intensities of the pigments used in glaze formulations without L* a* b* L* a* b*
CoCaM addition (Fig. 2. (a) and (d)) are more vivid. Glaze formulations CoCaM-Free/Marble 38.55 0.45 1.75 70.99 7.59 10.11
prepared with CoCaM and waste marble powders showed similar effects waste- Free
Standard Sample 43.15 75.72 6.15 15.19
on the surfaces. It has been observed that both formulations create ¡3.79 ¡1.95
Sample containing 39.11 ¡2,91 ¡1,59 76.33 6 12.9
artistic effects on the surface and similarly create differences in color marble waste
tones. These results are supported by the CIE L*a*b* values in Table 2.
CIE L*a*b* values give information about optical parameters of objects.
It is seen that the whiteness (L*) increased and the redness (a*) value
Table 3
decreased with the addition of CoCaM and waste marble powder in glaze Glossmeter (GU) values of F1 and F2.
formulations. In Formulation-1 (F1), it is seen that the green and blue
F1 F2
colors decreased in glazes without CoCaM, and the redness and yel
lowness increased in the sample containing waste marble powder. In 20⁰⁰ 60⁰⁰ 85⁰⁰ 20⁰⁰ 60⁰⁰ 85⁰⁰
High Semi Low High Semi Low
Formulation-2 (F2), it was observed that yellowness (b*) increased with
Gloss Gloss Gloss Gloss Gloss Gloss
the addition of CoCaM and waste marble powder. This is due to the fact
that different glaze formulations form different compounds during CoCaM-Free/ 25.9 76.1 44.2 14 39.4 30
Marble
firing. waste- Free
Table 3 shows the glossmeter values for F1 and F2. The brightness Standard 18.7 63.5 55.7 12.7 31.2 17.2
measurement of the samples was performed with a three-angle 3nh Sample
brand glossmeter. In order to determine the most suitable measurement Sample 34.9 76.6 60.3 11.2 37.3 17.1
containing
angle, measurement was started with an angle of 60◦ . When the results
marble
were examined, the values in 20◦ were also examined because the values waste
measured in F1 were greater than 70 GU. It is observed that the
Fig. 2. Surface images of glazed products; (a) CoCaM-free F2; (b) CoCaM added F2; (c) Waste marble powder added F2; (d) CoCaM-free F1; (e) CoCaM added F1; (f)
Waste marble powder added F1.
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Table 4 investigated. It was observed that the standard sample and the waste
Viscosity values of F1 and F2. marble powder sample flowed at approximately the same rates, and the
F1 F2 CoCaM-free sample flowed at a rate of 11.57% less.
In Table 4, flows of the same density of CoCaM-free, CoCaM and
density viscosity density viscosity
waste marble powder-formed glazes are given. As can be seen, CoCaM
CoCaM-Free/Marble waste- 1530 g/l 12.8 1530 g/l 12.4 and waste marble powders tend to reduce the flow of glaze. It is believed
Free
Standard Sample 1530 g/l 11.95 1530 g/l 11.95
that this is due to the ratio of calcium oxide (CAO) and magnesium oxide
Sample containing marble 1530 g/l 11.86 1530 g/l 11.88 (MgO) contained in CoCaM and waste marble dust.
waste The XRD results of the F1 sample are shown in Fig. 3. When the
analysis results were examined, the formation of Quartz, Anorthite,
Mullite, Albite phases was observed. The quartz peak was observed to be
the intensity peak in all samples. It was determined that the albite ratio
was lower in the CoCaM/waste marble powder-free sample compared to
the other samples.
SEM images of the F1 standard sample are given in Fig. 4. Fig. 4(a)
when the EDX results in were examined, Si, Al, O, Ca elements were
detected in high concentrations in certain regions, and these structures
indicate the presence of anorthite phase. In addition, mullite blocks
were found in the structure. XRD analysis results in Fig. 3 support this
situation. In Fig. 4 (b), dendritic structures were formed with the
decrease of melting point together with the presence of K-Feldspar and
Cl in the glaze formulation.
SEM images of samples with F1 waste marble powder added are
given in Fig. 5. Similar to the standard sample, the presence of anorthite
phase, mullite blocks and dendritic structures were found.
SEM images of the samples without F1 CoCaM/waste marble powder
addition are given in Fig. 6. When the EDX results in Fig. 6 (a) were
examined, Cr2O3 showed a nucleation center effect. Also, when the EDX
results are examined, it is seen that the blocks in Fig. 6 (b) contain high
levels of Cl2O, K2O and SiO2, and dendritic structures begin to form from
the corners of these blocks. It was observed that these dendritic struc
tures were clearer than the sample containing CoCaM and waste marble
powder.
Vickers measurement method, which is used for hardness measure
ment of ceramic materials, was applied to the glazed samples of
Fig. 3. X-ray diffraction patterns of F1.
Formulation 1. Measurement values are given in Table 5. CoCaM-free/
marble waste-free, standard sample, a sample containing marble waste
samples were examined under the same load. The hardness values
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F. Gol et al. Ceramics International 48 (2022) 15622–15628
decreased with the addition of CoCaM. It was observed that the hardness formulations.
was better than CoCaM in the addition of waste marble powder. This The images of ceramic body are given in Fig. 7. It has been observed
increases its usability potential. The presence of decreased dendritic that the waste marble powder used is more polluted than the standard
structures in the formulation using CoCaM in SEM images shows that its sample. But it is possible that this pollution will be tolerated under
mechanical strength also decreases. operating conditions. At the same time, CIE L*a*b* was examined; It was
Waste marble powder has also been used as a substitute for CoCaM in observed that the whiteness and redness decreased and the yellowness
the ceramic body. The CoCaM used in ceramic glaze and body formu increased according to the body with the addition of waste marble
lations is different. It is observed that CoCaM and waste marble powder powder of the standard body. This situation can be cited as the reason
contain similar proportions of CaO as shown in Table 1. This situation why ceramic bodies are dirty. Table 6 shows the CIE L*a*b* values.
also supports its availability as an alternative to CoCaM in ceramic body When the physical characteristics of the body were examined, no
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F. Gol et al. Ceramics International 48 (2022) 15622–15628
Table 5 ZnO and CaO in the structure caused the formation of a white covering
F1 Vickers Micro Hardness measurement values of glazed samples. called ‘boron tulle’. Along with the addition of waste marble powder, an
F1 improvement in hardness and water absorption test results was
observed. When SEM, XRF, and XRD analyses were examined, it was
HRV HV D1 D2 Ort. Diagonal
(μm) (μm) (μm) observed that CoCaM and marble waste have similar contents and sur
face morphology. The inclusion of marble waste in earthenware pro
CoCaM-Free/Marble 57 624.93 38.5 38.55 38.53
waste- Free
duction provides support for the production of environmentally friendly
Standard Sample 56.33 604.43 39.56 38.79 39.18 products in recycling processes. At the same time, the use of waste in
Sample containing 56.67 615.96 39.33 38.34 38.83 production processes tends to reduce costs when assessed in an eco
marble waste nomic context.
Evaluation of Waste Marble Powder in Ceramic Body. It is envisaged that this study will support the development of
alternative glaze compositions using waste and new studies.
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