Accepted Manuscript

Industrial ceramic waste in Pakistan, valuable material for possible applications

Mohammad Saleem Khan, Mohammad Sohail, Noor Saeed Khattak, Murtaza Sayyed

PII: S0959-6526(16)31295-1
DOI: 10.1016/j.jclepro.2016.08.131
Reference: JCLP 7923

To appear in: Journal of Cleaner Production

Received Date: 26 August 2016

Accepted Date: 26 August 2016

Please cite this article as: Khan MS, Sohail M, Khattak NS, Sayyed M, Industrial ceramic waste in
Pakistan, valuable material for possible applications, Journal of Cleaner Production (2016), doi: 10.1016/
j.jclepro.2016.08.131.

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1 Industrial ceramic waste in Pakistan, valuable material for possible applications

2 Mohammad Saleem Khan*1, Mohammad Sohail1, Noor Saeed Khattak1, Murtaza Sayyed2

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3 National Center of Excellence in Physical Chemistry, University of Peshawar (25120), Pakistan

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4 Chemistry Department, COMSATS Institute of Technology, Abbottabad (Pakistan)

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5 Abstract: In Pakistan, ceramic industry has been known to produce large quantities of waste that

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6 have become an environmental concern due to their misplace disposal. Solutions to reuse and

7 incorporate industrial ceramic waste can be rewarding for many reasons, specifically for

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8 environmental, economic and technical aspects. In the present study, three ceramic waste
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9 collected from the premises of ceramic factories located in Hayatabad industrial zone, Peshawar,

10 KP, Pakistan are characterized. Chemical composition of this waste was determined by energy
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11 dispersive X-rays spectroscopy (EDX) which showed that the waste is the mixtures of various

12 metal oxides. The effect of chemical composition was observed in the variation of physical
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13 properties of the materials. Many physicochemical parameters such as thermo gravimetric

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14 analysis (TGA), scanning electron microscopy (SEM), dielectric properties and rheology were

investigated in detail. TGA confirmed that the materials are thermally stable up to 700°C with a
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16 little weight loss. Extensive dielectric properties such as dielectric constant, dielectric loss,
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17 capacitance and conductivity in the frequency range from 1 MHz - 3 GHz at ambient
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18 temperature showed that ceramic waste will be best alternatives for application in embedded

19 capacitors. Absorption behavior of the ceramic waste was checked for methyl orange dye based

20 waste water. All the samples succeeded in removing the dye from the water with absorption

21 efficiency in the range 30-60%. Rheology studies showed that the materials are mechanically

22 rigid and stiff drawing attention to the reusability of these waste in mechanically tough

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1 composites. Microstructures and chemical composition of the waste were found to have key

2 factors for rheological characteristics.

3 Key words: Ceramic waste. TGA. Dielectric properties. Ac conductivity, Dye absorption.

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4 Rheology.

5 Corresponding author: *Mohammad Saleem Khan

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6 E-mail: saleemkhan@upesh.edu.pk

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1 1. Introduction

2 In the modern worldwide economic scenario, business societies are asked to mitigate

3 undesirable impacts of their activities on the environment (Tikul, 2014). This is particularly right

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4 for those industrial organizations that generate adverse global environmental impacts. Ceramic

5 industries produce large amount of waste which are discarded without any further treatment.

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6 These solid waste lead to severe environmental pollution and significant land occupation

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7 (Mohammad et al., 2014). Waste materials produced are about one third of the total ceramic

8 production. The ability to cope with these waste depends on sector and geographic location of

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9 the industry, resource availability, company size and strategic attitude (Gonzalez-Bentio J and
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10 Gonzalez-Bentio O, 2006). Huge amount of ceramic waste (in the form of pellets and powder) is

11 produced in different stages such as grinding, cutting, dressing and polishing inside the industrial
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12 plant. They pose severe environmental problems (Tozsin et al., 2014). Natural resources are

13 facing a decline with time due to abandoned uses. It is worth noticing that progress in concrete
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14 technology might be a useful way to reduce the use of natural resources by recycling the ceramic
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15 waste coming out from the industries (Chen et al., 2003). Recycling and reuse of waste materials

16 suggest energy saving, cost reduction, possibly superior products and less or no hazards to the
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17 surrounding environment.
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18 It has been observed that ceramic waste are hard, durable, extremely resistant to
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19 chemical, physical and biological degradations and highly thermally stable (Pacheco-Torgal and

20 Jalali, 2010). Due to an increase in heaping up ceramic waste, there is a pressure on the

21 producers for their valuable disposal. A lot of work has been done in reprocessing and reusing of

22 the waste materials obtained from marble and ceramic industries. Many researchers have

23 investigated the possible use of these waste in different areas such as building materials, cement

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1 additives (Aruntas et al., 2010), infiltration (Davini, 2000), bricks (Senturk et al., 1996),

2 desulphurization techniques (De Bresser et al., 2005), polymer based composites (Guru et al.,

3 2005), clay based materials (Acchar et al., 2006) and mortar additives (Arslan et al., 2005).

4 Waste ceramics as an efficient alternative have been utilized for the synthesis of geo-polymers

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5 (Sun et al., 2013). Red-mud/Polyaniline composites have been prepared and their thermal and

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6 electrical properties were examined (Gok et al., 2007). Polymer based waste ceramic composites

7 were proposed for high voltage outdoor performance (Aman et al., 2013).

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8 Different countries in the world are trying to reduce the load of solid waste by exploiting

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9 them in a better way. In the specific case of Pakistan, there are seven ceramic industries,
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10 manufacturing ceramic products such as tiles, stoneware, porcelain/pottery and bricks (Kaisar

11 and Akbar, 2011)]. Large quantities of ceramic waste are produced in the form powders, pellets
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12 and cakes during quarrying and processing procedures. It has been observed that the most

13 common destination of this waste is landfill disposal. Although notified vicinities have been
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14 identified for the disposal of waste near the industrial units, however, most of them discard away
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15 the waste into the nearby ditches or open spaces. Consequently, serious environmental impacts

16 occurred due to this misplaced dumping while lodging a vast land area. Environmentally, it is a
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17 fact that by recycling ceramic waste, landfilling is reduced while more natural resources are
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18 protected (Kelestemure et al., 2014). Therefore, the integration of this stable ceramic waste for
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19 some useful applications like capacitors, heaters and adsorbents may offer economic, technical as

20 well as environmental benefits.

21 Most of the ceramic producing units in Pakistan are medium and small enterprises and there

22 is lack of investigating environmental impacts ascending from this industry. Up to best of our

23 knowledge in the perspective of Pakistan, no attention has been given to the better disposal and

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1 recycling of the waste producing by these plants. The immense impacts of this waste are

2 increasing day by day which alternatively damage the environment and hence public health. The

3 present research work is dedicated to find an appropriate solution for the clearance of this waste.

4 This study focuses on the reusability and hence proper disposal of the ceramic waste collected

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5 from the premises of three different industries located in Hayatabad, Peshawar, Pakistan as

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6 shown in Fig.1. Thermal, dielectric, viscoelastic and dye removal properties of the collected

7 waste were determined. Reusing ceramic waste in different areas such as capacitors, ceramic

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8 heaters, tough composites and purification of municipal waste water could be a win-win

9 approach. That is on, one hand by solving the problem of waste generating by the industries and

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at the same time their recycling in places where natural resources face decline.
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11 2. Materials and methods
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12 Ceramic waste samples were collected from three different ceramic industries (1. Fort
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13 Ceramics, 2. Marble Complex and 3. Rehman Marbles) located in the North-West region
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14 (Peshawar) of Pakistan. They were used to denote the most common ceramic waste discarded by

15 these industries. Three waste samples composed of powder, pellets, tiles and stones were
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16 gathered form inside and surroundings of three selected companies along with information about

17 ceramic waste management. It was detected that outside the industrial units, deposits with large
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18 quantities of ceramic waste have been accumulated over time. The hardness of the waste reveal
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19 that it was not degraded and thus generating long term problems of waste management. In

20 addition, tape as well as double distilled water was used for washing purposes. Methyl orange

21 dye (96%) was obtained from Sigma Aldrich (USA) for evaluating the dye absorption properties.

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1 The waste samples were first washed with tap water for removing the apparent soil and dust

2 particles attached with the materials during dumping. After drying, the samples were ground

3 properly to powder form. Further the samples were washed with double distilled water two times

4 so as to eliminate the contaminants like adsorbed dust particles and organic matter. All the three

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5 samples were then kept in an electric oven at 60 °C for 12 h After cooling to room temperature,

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6 the dried samples were again crushed appropriately in an agate mortar. Subsequently, the powder

7 samples were then passed through 200, 220 and 240µ mesh consecutively in order to get

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8 powdered particles in the same micro dimensions. Finally, the samples were coded with CW-F,

9 CW-M and CW-R for Fort Ceramics, Marble Complex and Rehman Marbles respectively.

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10 Energy dispersive X-ray spectroscopy (EDX) was performed to analyze the elemental

11 compositions of the ceramic waste. For this purpose X-ray Philips diffractometer attached with
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12 SEM (USA) was used. Waste samples with 50 mm diameter and 20 mm thickness were loaded

13 in the X-ray chamber. Thermo-gravimetric analysis (TGA) in the range from 30-800 °C was
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14 accomplished with Diamond TG/DTA, Perkin Elmer (USA) while loading 5-8 mg of each
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15 sample. An automatic furnace under N2 atmosphere was used for heating the samples at the rate

16 10 °C per minute. RF Impedance material analyzer, Agilent E4 997A (USA) was used to
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17 investigate the dielectric properties of the materials. Pellets of samples with 5-10 nm diameters
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18 were prepared by a hydraulic press machine under 5 t hydraulic pressures. Before subjecting
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19 between the electrodes, all the pellets were sintered at 300°C for 5 h. Viscoelastic properties

20 were studied by Anton Paar Rheometer, Physica MCR 301 (Germany). About 5 mg of each

21 sample was applied between the plates under internally controlled thermal conditions. Color

22 index analysis was used to investigate dye removal properties of the waste from water.

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1 3. Results and discussion

2 EDX analysis showed the elemental composition of CW-F, CW-M and CW-R ceramic

3 waste as evident from the spectra given in Fig.2a, b and c. It is seen that the major elements

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4 present in CW-F are Si, Al, K, Ca, Fe, Ti and Mg in their corresponding oxidized forms i.e. SiO2,

5 Al2O3, CaO, Fe2O3, TiO2 and MgO (Faria and Holanda, 2012). According to the relative

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6 information gathered from the industry, Fort ceramics are produced from five different types of

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7 clays transported from the different regions of the country. It is assumed that the clays would

8 have the same metallic oxides composition as predicted in EDX analysis of CW-F. EDX

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9 spectrum for CW-M shows peaks for Ca, Mg, Si and C. Metals are present in their respective
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10 oxide and carbonated forms such as CaCO3, SiO2 and MgCO3 (Lavat et al., 2009). CW-R is

11 composed of only Ca and C as the major elements present in CaCO3 and CaO forms. SEM
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12 micrographs represent globular and agglomerated morphology of the samples. The elemental

13 weight% composition of CW-F, CW-M and CW-R is shown in Table 1.

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14 From Table 1, it is evident that the chemical composition of waste varied significantly

15 from CW-F to CW-R. The variation is based on the constituents that have been utilized by the
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16 industries in the fabrication of ceramics. It was noted that Fort ceramic manufacturer’s use five

17 various types of clay minerals mined from the earth’s crust located in different regions of the
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18 country. The clays consist of mainly natural minerals such as feldspar with minute amount of
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19 magnetite and titania additives. It was found that feldspar is used to lower the quantity of other

20 chemical additives and firing temperature necessary during tiles shaping process. The chemical

21 composition of CW-M and CW-R samples is rather different and consists of low quantities of

22 constituent elements. It is due to the fact that minerals used by the two industries are

23 beneficiated or refined nearby the mine before their shipment to the ceramic plant. It also

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1 depends upon the final product of each manufacturer that what type of chemical composition

2 they required; this is why the chemical composition of each waste is different from the other.

3 Various physical properties of the waste samples are listed in Table 2. It is obvious that

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4 CW-F shows relatively large values for some of the properties which are attributed to the type

5 of atoms present, bonding between the atoms and the way different atoms are packed together in

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6 the ceramic composition. Generally, ionic bonds are present between the metal and non-metal

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7 atoms which results in the attraction of opposite charge sites but the presence of transition

8 elements (Fe and Ti) in CW-F offers some strong metallic bond environment. Consequently,

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9 more close packing and hence enhancement of properties occurs. However, general physical
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10 properties are approximately the same for all samples.

11 TGA curves for CW-F, CW-M and CW-R are given in Fig. 3. During the experiment, all
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12 the three samples were subjected to a temperature range from 30 °C to 800 °C under N2
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13 atmosphere. No mass changes occur in the first thermal cycle where the mass is almost stabilized
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14 however, in the second heating cycle mass changes occurred. All the waste was thermally stable

15 in the temperature range from 660°C to 700°C. It is attributed to strong inter-ionic interactions
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16 between the metal ions present in these ceramics. At the preliminary stage (80-100°C), no weight

17 loss was observed due to water/moisture contents. It is attributed to the thermal activation of the
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18 waste before subjecting to TG analysis. A slight disintegration above 660°C in CW-F with about
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19 10% weight loss, at 670°C in CW-M with 7% mass loss and at 697°C in CW-R with 15% weight

20 loss is ascribed to the complete de-intercalation of residual water and other additives. The

21 residues of all the three waste at 800°C represent the diffused form where the grain boundaries of

22 the constituents in the ceramics are dispersed away (Li et al., 2015). Thermal stability of ceramic

23 waste up to 700°C suggests these materials as better alternatives for application in thermal

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1 protective coatings (TPC). Automotive, oil exploration and aerospace industries use electronic

2 components which can work at temperature > 200 °C. Being dielectric materials, the ceramic

3 waste understudy may be a best option for these industries. The decomposition temperatures and

4 corresponding weight losses for all samples are shown in Table 3.

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5 Dielectric properties are associated with the storage and dissipation of electrical energy in

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6 materials. Frequency dependence dielectric parameters such as dielectric constant (ε′), dielectric

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7 loss (ε″) and loss tangent (tanδ) were measured in the frequency range from 1MHz to 3 GHz at

8 300K by using the following equations (Javed et al., 2010).

9   = /
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 = 1/2  (2)
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 (3)
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12 where C is the capacitance of the pellets, d is the thickness, A is the cross-sectional area,
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13  is the constant of permittivity, f is the applied field frequency, Cp is the equivalent parallel

14 capacitance and Rp is the equivalent parallel resistance. Fig. 4, 5 and 6 show the variation of ε′,
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15 ε″ and tanδ as a function of frequency for CW-F, CW-M and CW-R respectively. It was

16 observed that for these parameters, all the samples exhibit frequency dependent phenomena that
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17 is their values decrease with increasing applied field frequency and become constant at certain
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18 specific frequency (1.6 x 108-1.8 x 109 Hz). This can be described on the basis of space charge

19 polarization due to electron displacement. According to Maxwell/Wagner model (Ashiq et al.,

20 2009), space charge polarization appears due to the presence of inhomogeneity in the dielectric

21 structure of the material where the strong conducting grains are separated by poor thin

22 conducting boundaries. This results in the well-up polarization of the dipoles in low frequency
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1 regions thus enhancing dielectric properties of the materials. In dielectric materials, polarization

2 is the sum of dipolar, ionic, electronic and interfacial polarization. At low frequency regions,

3 these four phenomena respond easily to the varying electric field however, with increase in

4 frequency of the applied electric field different polarization contributions filter out. Consequently

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5 the net polarization of the material decreases which leads to the drop in the value of ε′. In our

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6 case, the collected ceramic waste are composed of inhomogeneous grains and species as

7 confirmed by the SEM/EDX studies and hence show high values for dielectric parameters at low

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8 frequency as listed in Table 5. At low frequency, high ε′ value reflects the presence of

9 dislocations, voids and other defects in the ceramic waste. For all samples, ε′, ε″ and tanδ show

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decrease in their values with increasing frequency. This is due to the decrease in space charge
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11 polarization at high frequency. It has been reported by many researchers (Ashiq et al., 2009; Bos

et al., 2012; Malana et al., 2016), that in a dielectric material, space charge carriers need finite
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13 time to align themselves parallel to an applied electric field and if the electric field frequency is
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14 increased, a point reaches where the space charge carriers are unable to adjust with the
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15 alternating field hence resulting in the decrease of ε′, ε″ and tanδ. This indicates that at further

16 high frequency space charge carriers make no contribution in the polarization of the materials.
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17 Generally, dielectric losses represent conductivity measurements where materials with high

18 losses exhibit high conductivity and vice-versa. The appearance of extra peaks in ε′, ε″ and tanδ
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19 curves at about 2 GHz is attributed to the fact that electron hopping frequency becomes equal to
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20 the applied field frequency which results in exhibiting a resonance type behavior by the materials

21 at high frequency. The presence of extra peaks in the spectra of ε″ and tanδ suggests the existing

22 of relaxing and non-relaxing dipoles in these materials (Khuershid et al., 2015). The penetration

23 depth of electromagnetic waves is decreased due to high ε′ via increasing skin effect. So the

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1 smaller ε′ (5.50-5.51) obtained for ceramic waste permits their application at high frequencies.

2 Frequency dependence tanδ is an imperative parameter and it must be as low as possible in an

3 ideal capacitor. In this regard, the ceramic waste will be suitable candidates for applications in

4 capacitors due to their low tanδ magnitudes as shown in Table 5. The large ε′ value for CW-F as

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5 compared to other two samples signifies the presence of Fe+2 and Ti+3-site vacancies which help

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6 in improving ε′. The slight decrease in the ε′ value of CW-M and CW-R is attributed to their

7 relatively denser microstructures as shown in Fig. 2.

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8 Fig. 7 shows the variation of capacitance with increasing frequency at 300K for CW-F,

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9 CW-M and CW-R. It is seen that CW-F has highest capacitance (4.45 pF) at I MHz as compared
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10 to CW-M (3.07 pF) and CW-R (2.19 pF). High value of capacitance at low frequency is ascribed

11 to the reduction of space charge regions at electrodes surfaces. Comparatively less capacitance of
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12 CW-M and CW-R may be due the wide space charge regions in these materials and also the non-

13 existence of Fe ions as verified by EDX spectra. At about 2.14 GHz, an immediate fall appears in
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14 the capacitance of all materials which is due to the presence of partially blocked charge carriers
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15 near the electrodes. The highest values of capacitance for each material are listed in Table 5.
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16 Frequency dependence Ac conductivity ( ) of all the samples was measured by using

17 the following relation;

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19 where ω = 2πf and ε0 is the permittivity of free space. The data obtained was plotted

20 against applied field frequency as shown in Fig. 8. It is seen that conductivity of all the three

21 samples is increasing linearly with frequency and at about 2.45 GHz the samples exhibit highest

22 value which is considered to be the dominant conductivity dispersion region. The increase in AC

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1 conductivity is usually due to hopping and tunneling of electrons between the localized states. In

2 the present study, the conductivity enhancement is especially due the translational hopping of

3 electrons in conductivity dispersion regions as reported earlier (Shi et al., 2016). A decline in

4 conductivity of the samples occurs beyond 2.43 GHz which is ascribed to the loss in hopping of

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5 electrons due the presence of oxygen vacancies present in these samples (Naceur et al., 2013). A

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6 further boost in conductivity at high frequency for all samples may be due the reorientation of

7 well-localized electrons hooping. The highest conductivity achieved by each material is given in

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8 Table 5. The dielectric properties and Ac conductivity values of the samples make them useful in

9 miniaturizing microwave devices.

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10 The collected ceramic waste was checked for rheological properties such as viscosity,

11 storage modulus and loss modulus in order to find their durability in different areas. Flow curves
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12 which represent shear rate versus viscosity plots for CW-F, CW-M and CW-R are shown in Fig.

13 9a, b and c. The data was recorded at three different temperatures i.e. 30, 40 and 50°C. It is seen
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14 that viscosities of all the samples decreased with increase in shear rate indicating shear thinning
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15 or non-Newtonian behavior. This implies the existence of an aggregated (no flocculation)

16 structures in the materials (Tanurdijaja et al., 2011). Strong metallic and weak dipolar
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17 interactions are responsible for holding together the particles of ceramic waste however, with
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18 increasing shear rate, interactions among the particles become weak which results in the decrease
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19 in resistance to flow and hence viscosity decreased. It was also observed that increasing

20 temperature from 30-50°C has no appreciable effect on the viscosity of ceramic waste.

21 Rheological models such as Bingham plastic model, Modified Bingham and Ostwald

22 power law (Yahia and Khayat, 2001) were applied to the data obtained in the flow curves

23 rheograms. The corresponding plots for CW-F, CW-M and CW-R are shown in Fig. 10a, b and c

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1 respectively. The flow index (n) value in Ostwald power law model indicates the rate of change

2 of structure with increasing shear rate. Bingham plastic model is useful in assessing the yield

3 stress which is the least stress applied before the material under investigation starts to flow. It is

4 supposed to be a good indicator in characterizing solids/semisolid systems while affecting their

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5 retention and spreadibility. Modified Bingham model explains the shear thinning and plastic

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6 viscosity of CW-F, CW-M and CW-R. It is obvious from the plots that all the samples show best

7 fit to modified Bingham and power law models at low shear rate with R2 value in the range 0.93-

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8 0.99 as shown in Table 4. The n values were estimated from Ostwald power law model are

9 n(CW-F) = 0.03, n(CW-M) = 0.5 and n(CW-R) = 0.4. The values are significantly lower than 1

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which shows the shear thinning behavior of these materials. For stronger materials the value of n
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11 is smaller. In this sense, CW-F ceramic waste is the strongest among the three materials. Angular

frequency dependent storage modulus (G′) and corresponding loss modulus (G″) plots for the
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13 samples are shown in Fig 11a, b and c. It is evident that with increasing angular frequency, both
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14 viscoelastic properties (G′ and G″) increase which is due to the shear thinning behavior of these
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15 materials as shown in the flow curves. This also describes the rigidity of the all the three samples

16 due to which these materials exhibit high thermal stability. It was found that with increasing
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17 temperature from 30°C to 50°C, G′ improves for both CW-F and CW-R as compared to CW-M

18 which may be due to the thermal stability of these two samples that enabled the materials to trace
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19 the increasing temperature (Faiz et al., 2016). CW-F achieved highest G′ value of 6.49 x 103 Pa
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20 relative to CW-M (5.51 x 103 Pa) and CW-R (5.50 x 103 Pa. This shows that CW-F is

21 mechanically more rigid material than the other two. The corresponding G″ is comparable for all

22 the samples recorded at one specific temperature. This indicates the stiffness of the ceramic

23 waste which is very useful for the implementation of these materials in polymer based tough

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1 membrane composites (Ferry, 1980). Different viscoelastic properties of the materials are listed

2 in Table 5.

3 All the three ceramic waste were investigated regarding their capacity to remove methyl

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4 orange dye from waste water. It was found that all samples absorb the dye with different

5 efficiencies as shown in Fig. 12. CW-R sample exhibited 60% dye absorbance efficiency while

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6 the other two CW-F and CW-M showed the absorbance of methyl orange in the range 30-35%.

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7 The contact time was between 2-5 h. It has been reported in literature (Ahmed et al., 2013) that

8 ceramic based polymer core-shell composites show effective dye removal up to 90% from waste

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9 water due to the presence of different polar sites along the polymer chains. Polymeric chains
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10 have the ability to lift the oily stains and dyes while acting as detergent molecules in these

11 composites. In this regard, the ceramic waste if utilize as fillers in polymeric composites would
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12 be able to achieve more absorbance efficiency for dyes and other waste. This could make the

13 waste to recycle in a better way for purifying municipal and industrial waste water.
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14 4. Conclusions

15 Ceramic waste collected from three different local ceramic producing industries were
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16 characterized via different physicochemical techniques. The chemical compositions investigated

17 with EDX showed that the ceramic waste is composed of normal and some transition metal
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18 oxides. CW-F was found to contain a large number of elements among the three waste. Different
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19 physical properties of the waste were found to vary according to their chemical composition.

20 Ceramic waste was found to have thermal stability up to 700°C with least weight loss ~15%. The

21 materials exhibited dielectric characteristics with highest value of ε′ = 9.35 and lowest tanδ =

22 0.034 which refer the waste ceramics for possible application in capacitors. Rheological

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1 properties of the materials revealed their worthy elastic nature with G′ = 6.49 x 103 (Pa) and G″

2 = 2.2 x 103 (Pa). The three materials differ in various features based on their composition. On the

3 basis of these properties, ceramic waste studied are suggested to be possibly used in protective

4 coatings, high temperature sensors, embedded capacitors and tough membranes. The waste

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5 adopted dye absorption efficiency in the range 30-60% from waste water. This also signifies the

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6 best disposal of ceramic waste rather their extra burden and pollution in the environment.

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7 Acknowledgments

8 The authors are thankful to the National Center of Excellence in Physical Chemistry,

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9 University of Peshawar (Pakistan) for providing facilities and financial support for this research
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10 work. The administration and supporting staff of ceramic industries are also acknowledged for

11 their cooperation during the visit and providing necessary information.

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12 References
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13 Acchar, W., Vieira, F., Hotza, D., 2006. Effect of marble and granite sludge in clay materials.
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14 Mat. Sci. Eng. A 419, 306-309.

Ahmed, M.A., Khafagy, R.M., Bishay, S.T., Saleh, N.M., 2013. Effective dye removal and water
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17 core–shell nanocomposites. J. Alloy. Comp. 578, 121-131.

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18 Aman, A., Yaacob, M.M., Alsaedi, M.A., Ibrahim, K.A., 2013. Polymeric composite based on

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20 Arslan, E.I., Aslan, S., Ipek, U., Altun, S., Yazicioglu, S., 2005. Physico-chemical treatment of

21 marble processing wastewater and the recycling of its sludge. Waste. Manage. Res. 23, 550-

22 559.

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14 Faiz, S., Anis, A., Luqman, M., Al Zahrani, S.M., 2016. Studies on thermal, mechanical,
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15 morphological, and viscoelastic properties of polybenzimidazole fiber reinforced high

16 density polyethylene composites. Polym. Compos. 37, 5-13.

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17 Faria, K., Holanda, J., 2012. Using SEM/EDS for characterization of clay ceramic bearing

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19 Ferry, J.D., 1980. Viscoelastic properties of polymers. John Wiley & Sons.
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20 Gök, A., Omastová, M., Prokeš, J., 2007. Synthesis and characterization of red mud/polyaniline

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Khursheed, T., Islam, M.U., Asif, I.M., Ali, I., Shakoor, A., Awan, M.S., 2015. Synthesis and
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11 characterization of polyaniline-hexaferrite composites. J. Magnet. Mag. Mate. 393, 8-14.

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15 titanate for polyvinylidene fluoride composites with high dielectric constant and ultralow

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17 Malana, M.A., Qureshi, R.B., Ashiq, M.N., Ehsan, M.F., 2016. Synthesis, structural, magnetic

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19 pseudoplastic grout. Cem. Concr. Res. 31, 731-738.

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Table 1 Chemical composition of the collected ceramic wastes.

Waste Sample Elemental composition Weight%

Codes Si Al K Ca Fe Ti Mg Na C O

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CW-F 23.65 8.64 1.36 4.46 3.55 0.40 2.46 0.35 --- 55.14

CW-M 0.31 --- --- 36.63 --- --- 0.30 --- 10.80 51.69

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CW-R --- --- --- 37.94 --- --- --- --- 10.15 51.92

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Table 2 TGA data for collected ceramic wastes samples.

Single step degradation

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Samples T (°C) Wt (%) Residues (Weight %)
CW-F 660 10 90
M

CW-M 670 07 93
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CW-R 697 15 85
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Table 3 The values of different parameters measured for CW-F, CW-M and CW-R samples.

Samples ε′ ε″ tanδCp (pF) σ (Ω.cm)-1 η (Pa.s) G′ (Pa) G″ (Pa)

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CW-F 9.35 1.56 0.609 4.45 0.034 31.1 6.49 x 103 2.0 x 103
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CW-M 8.81 1.15 0.133 3.07 0.068 03.8 5.51 x 103 2.2 x 103

CW-R 7.72 1.03 0.034 2.19 0.050 28.9 5.50 x 103 2.1 x 103
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Table 4 Application of different rheological modles.

Sample ID Bingham Modified Bingham Ostwald power law Flow index value

R2 R2 R2 n

PT
RI
CW-F 0.680 0.987 0.931 0.03

CW-M 0.800 0.895 0.964 0.55

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CW-R 0.861 0.958 0.995 0.42

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Table 5 The values of different parameters measured for CW-F, CW-M and CW-R samples.

Samples ε′ ε″ tanδ Cp (pF) σ (Ω.cm)-1 η (Pa.s) G′ (Pa) G″ (Pa)

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CW-F 9.35 1.56 0.609 4.45 0.034 31.1 6.49 x 103 2.0 x 103
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CW-M 8.81 1.15 0.133 3.07 0.068 03.8 5.51 x 103 2.2 x 103

CW-R 7.72 1.03 0.034 2.19 0.050 28.9 5.50 x 103 2.1 x 103
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CEP
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Fig. 1.
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(a)

PT
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(b)
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C
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PT
RI
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(c)

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Fig. 2.
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120

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100
CW-F

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% Weight Loss

80

Single-step
60 decomposition CW-M

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40

20
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0
0 200 400 600 800
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Temperature (°C)
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Fig. 3.
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PT
1.00E+01

RI
9.00E+00

8.00E+00 CW-F
Dielectric Constant

SC
CW-M
7.00E+00
CW-R

6.00E+00

5.00E+00
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AN
4.00E+00
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3.00E+00
1.00E+06 1.00E+09 2.00E+09 3.00E+09
Frequency (Hz)
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Fig. 4.
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1.60E+00

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1.40E+00

1.20E+00

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1.00E+00
Dielectric loss

8.00E-01

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6.00E-01 CW-F
CW-M
4.00E-01
CW-R

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2.00E-01
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0.00E+00

-2.00E-01
1.00E+06 1.00E+09 2.00E+09 3.00E+09
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Frequency (Hz)
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Fig. 5.
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7.00E-01

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6.00E-01

5.00E-01

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4.00E-01
Tan Loss

3.00E-01 CW-F
CW-M

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2.00E-01
CW-R
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1.00E-01

0.00E+00
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-1.00E-01
1.00E+06 1.00E+09 2.00E+09 3.00E+09
Frequency (Hz)
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Fig. 6.
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4.00E-12

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3.50E-12
Capacitance (pF)

3.00E-12 CW-F

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CW-M
2.50E-12
CW-R
2.00E-12

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1.50E-12
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1.00E-12
0.00E+00 1.00E+09 2.00E+09 3.00E+09
Frequency (Hz)
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Fig. 7.
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8.00E-02
7.00E-02

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Conductivity (Ω.cm)-1

6.00E-02
5.00E-02

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4.00E-02 CW-F
3.00E-02 CW-M
2.00E-02

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CW-R
1.00E-02
0.00E+00
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-1.00E-02
-2.00E-02
0.00E+00 1.00E+09 2.00E+09 3.00E+09
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Frequency (Hz)
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Fig. 8.
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100

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(a)
10
Viscosity (Pa.s)

30 °C

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1 40 °C
50 °C

SC
0.1

0.01

0.001
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0.01 0.1 1 10 100
Shear rate (1/s)
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10
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(b)
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1
Viscosity (Pa.s)

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0.1 30 °C
40 °C
50 °C
0.01
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0.001
0.01 0.1 1 10
Shear rate (1/s)
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100
(c)
10

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Viscosity (Pa.s)

1
30 °C
0.1 40 °C

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50 °C
0.01

0.001

0.0001
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0.00001
0.01 0.1 1 10
Shear rate (1/s)
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Fig. 9.
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y = -1.6445x2 + 0.7319x + 0.6034

(a)
0.69 R² = 0.9873
0.68 (Modified Bingham)
Shear stress (Pa)

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0.67
y = 0.7096x0.0354
0.66 R² = 0.9314
0.65 (Power law)

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y = 0.1831x + 0.6253
0.64 R² = 0.6802
0.63 (Bingham)
0.62

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0.61
0.6
0 0.05 0.1 0.15 0.2 0.25 0.3 0.35

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Shear rate (1/s)
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(b) y = 1.0977x0.5594
0.6 R² = 0.9648
(Power law)
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y = 1.2779x + 0.0932
0.5
R² = 0.8004
Shear stress (Pa)

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(Bingham)
0.4
y = -5.3738x2 + 2.7965x + 0.0593
0.3 R² = 0.8957
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(Modified Bingham)
0.2
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0.1
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0
0 0.1 0.2 0.3 0.4
Shear rate (1/s)
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(c)

45 y = 0.0131x + 7.7606

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R² = 0.8615
40 y = -7E-06x2 + 0.0277x + 5.484 (Bingham) y = 1.3816x0.4215
R² = 0.9584 R² = 0.9956
35
Shear stress (Pa)

(Modified Bingham) (Power Law)

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30
25

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20
15
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10
5
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0
0 5 10 15 20 25 30
Shear rate (1/s)
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Fig.10.
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(a)
7.00E+03

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6.00E+03
5.00E+03 30 °C
40 °C

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4.00E+03
G′ (Pa)

3.00E+03 50 °C

2.00E+03

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1.00E+03
0.00E+00

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-1.00E+03
0 100 200 300 400 500 600
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Angular Frequency (1/s)
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(b)
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6.00E+03

5.00E+03

4.00E+03
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30 °C
G′ (Pa)

3.00E+03 40 °C
2.00E+03 50 °C
C

1.00E+03
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0.00E+00

-1.00E+03
0 100 200 300 400 500 600
Angular Frequency (1/s)
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PT
6.00E+03 (c)

5.00E+03

RI
4.00E+03

SC
30 °C
G′ (Pa)

3.00E+03
40 °C
2.00E+03 50 °C

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1.00E+03
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0.00E+00

-1.00E+03
0 100 200 300 400 500 600
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Angular frequency (1/s)

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Fig. 11.
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PT
120
100%
(colour index analysis)

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100

80
% Colour

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35% 38%
60
60%
40

20
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0
Standard metyl CW-F CW-M CW-R
orange solution
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Fig. 12.
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Highlights:
• Ceramic Waste collected from different Ceramic Industries was studied
for different properties and reuse.

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• Thermal, dielectric and rheological properties were determined.

• Chemical composition of the ceramic influences the properties of wastes.

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• Dye absorption efficiency of the wastes is in the range from 30-60%.

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• Ceramic wastes have potential applications in thermal protective

coatings, tough membranes and capacitors.

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