Arab J Sci Eng (2014) 39:453–459 DOI 10.1007/s13369-013-0917-2
RESEARCH ARTICLE - EARTH SCIENCES
Synthetic White Marble-Like Material Produced from Natural Raw Materials Mohammed A. Binhussain · Esmat Hamzawy
Received: 20 July 2013 / Accepted: 31 October 2013 / Published online: 3 December 2013 © King Fahd University of Petroleum and Minerals 2013
Abstract An alternative natural marble (such as Thassoss marble, Greek) was synthesized and produced using natural raw materials, namely silica sand, magnesite, limestone, phosphate and fluorspar. A ceramization casting of glass powder was employed to produce a similar tile to the common natural marble with outstanding properties. Different batch compositions subjected to mixing, melting, quenching, pulverizing, casting and sintering were employed. X-ray diffraction analysis and scanning electron microscopy were used for characterization. The physical and mechanical properties of the produced synthetic samples were investigated. These properties include density, water absorption, porosity, hardness, compression and flexural strength. Some of these properties of synthetic marble are better than the common tile similar to marble or granite. Keywords Sintered glass–ceramic · Microstructure · Strength measurements
M. A. Binhussain (B) KACST, PO Box 6086, Riyadh 11442, Saudi Arabia e-mail:
[email protected] E. Hamzawy National Research centre, Dokki, Cairo 12622, Egypt
1 Introduction Natural marble (such as Thassos marble from Greece) is an ideal material for the manufacture of floor tiles, as it is not affected by environmental temperature variations. However, natural stone deposits are not sufficient to fulfil the requirements of the building and construction industry, and it is therefore necessary to investigate alternatives to natural marble. Over the world, synthetic marble is rapidly replacing natural marble. Its properties are almost the same or better than those of the natural product. Furthermore, it exhibits high strength, low shrinkage, minimal water absorption, high resistance to corrosion by aggressive chemicals and to ageing and the effects of weather, easy maintenance and high abrasion resistance [1–10]. Synthetic marble can be prepared by crystallization or sintering of glass powder or by direct ceramization [7–12]. Recently, the Kingdom of Saudi Arabia has started investigating the use of its local resources for this purpose, with related achievements being seen in the glass–ceramics and ceramics fields [11–14]. An alternative to natural marble, synthetic marble, has been prepared in the market, without the use of heating, from dolomite and other natural minerals admixed with epoxy polymers [15–17]. However, very little research has focused on the utilization of local raw and waste materials in the preparation of synthetic building products. It is well known that the mechanical properties of ceramics are important for determining their uses and applications [18]. It is also obvious that the composition of the raw materials used in ceramics manufacturing has a bearing on the properties of the final products. This paper describes the manufacture and properties of synthetic marble produced using local raw materials such as
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Table 1 Results of chemical analysis of raw materials (new)
Raw material
Chemical composition (wt%) SiO2
IL ignition loss a Pre fired at 600 ◦ C
Al2 O3
Fe2 O3
TiO2
MgO
CaO
Na2 O
K2 O
P2 O5
IL
Magnesitea
2.15
0.30
0.04
0.01
91.10
1.65
0.09
0.11
–
4.55
Limestone
2.28
0.86
0.26
0.02
0.57
52.72
0.02
0.07
–
43.19
Sandstone
98.92
0.61
0.01
0.04
0.01
0.01
0.08
0.01
–
0–30
Clay–Kaolin
49.68
31.11
1.49
2.82
0.26
1.25
0.17
0.12
–
13.10
2.21
0.15
0.08
<0.01
0.31
54.81
0.15
0.02
29.52
12.75
Phosphate
materials were considered in the calculation of the batch composition.
Table 2 Constituents of batches (new) Batch no. Raw materials (wt%) Silica Magnesite Limestone Clay Phosphate CaF2 23
51.15 20.21
23.03
–
0.93
4.67
24
49.83 29.36
8.51
8.10
0.95
3.81
25
51.10 35.46
–
8.69
4.76
–
silica sand, clay, limestone, dolomite and phosphate. The synthetic marble thus produced is efficient and economical with better properties and is an environmentally friendly alternative to natural marble and granite tiles.
2.3 Grinding, Mixing and Melting Process The raw materials were ground and mixed for 2–3 h in a planetary ball mill to achieve homogenization of each batch. The well-mixed samples were melted in alumina crucibles for 2 h between 1,400 and 1,500 ◦ C with a swirl interval of 30 min. The glass melt was then quenched in water and the produced glass frits were dried in a dryer.
2.4 Discs and Bars Samples 2 Methods and Testing 2.1 Raw Materials Local raw materials from Saudi Arabia were used, namely silica sand, magnesite, limestone, phosphate and fluorspar (or commercial CaF2 ). Clays were also added in small quantities. The chemical analysis of the raw materials was carried out at KACST and checked by the A.L.S. Chemical Laboratory, Canada, as per ASTM methods. The compositions of these materials in terms of oxides are shown in Table 1.
The dried glass frit was then pulverized in the ball mill to particle sizes between <100 (0.149 mm) and >200 (0.047 mm) mesh. Discs and bars were prepared by dry pressing samples from each batch. Samples were placed into disc-forming stainless steel dies of 31 and 48 mm diameter, compressed by a steel plunger and finally ejected by a bottom plunger. The bar specimens were of about 3 mm × 3 mm × 40 mm in size. The operating force for compression was as high as 50 kN for different moulds. Uniaxial force was maintained with a precision of ±7–10 N. 2.5 Sintering and Characterization
2.2 Batching The batch composition was based on the stoichiometric formulae of diopside (CaMgSi2 O6 ) and enstatite (MgSiO3 ). For each batch, Table 2 shows the constituents and Table 3 the batch in oxide composition (wt%). Major oxides of the raw Table 3 Chemical composition of batches
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Batch no.
Powdered glass samples were subjected to sintering in an electric furnace at 700–1,350 ◦ C for 1 h, at a rate of 10 ◦ C/min. The casted samples were subjected to sintering at 100 ◦ C intervals between 700 and 1,350 ◦ C for an hour at every temperature. The developed crystalline phases, after sinter-
Chemical composition (wt%) SiO2
Al2 O3
Fe2 O3
TiO2
MgO
CaO
Na2 O
K2 O
P2 O5
CaF2
23
57.85
0.34
0.16
0.01
21.87
14.92
24
61.32
0.23
0.12
0.01
32.46
5.75
0.03
0.05
4.76
–
0.04
0.045
1.00
25
57.71
0.16
0.09
0.01
35.64
0.64
0.04
4.00
0.05
0.09
4.71
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Fig. 1 XRD analysis of 23, 24 and 25 samples sintered up to 1,350 ◦ C
ing, were characterized by XRD and SEM. The crystalline phases were determined by X-ray powder diffraction (XRD) (Bruker D8 Advance, Karlsruhe, Germany, Cu K α radiation,
0.15418 nm, Germany) and the scanning electron microscope (SEM) (Philips XL30 ESEM, Eindhoven, Netherlands) was used to study the microstructure.
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Fig. 2 SEM micrographs of 23, 24 and 25 samples sintered up to 1,350 ◦ C/2 h
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2.6 Physical Testing The flexural and compression strength σ0 was measured by bending bar specimens of about 3 mm × 3 mm × 40 mm in size until fracture, using a four-point flexural test technique (30 mm outer span, 8 mm inner span) using an Instron 1121 UTS instrument (Instron, Danvers, MA). The bending load was applied at a rate of 1 mm/min until rupture. The bar specimens were also used for the determination of the geometric density and, according to the requirements of the UNI EN ISO10545-3 standard, for water absorption WAB determination using the boiling method. For hardness determination, Vickers hardness was measured by applying a 5 N force using a diamond indenter in the form of a square-based pyramid (Shimadzu HMV 2000Japan). The apparent and true densities were calculated using bulk samples and powdered samples, respectively, employing a helium gas pycnometer (Micromeritics AccuPyc 1330, Norcross, GA). The porosity (as volume percentage) was calculated from the density values. The linear coefficient of thermal expansion α was measured using a dilatometer (NETZSCH DIL 402 PC, Geratebau GmbH, Selb, Germany) with a heating rate of 10 ◦ C/min).
3 Results and Discussion Transparent white glass frits were produced after water quenching and subjecting to drying, pulverizing, casting and sintering. The present experiments showed that the formulation was suitable for producing strong and dense materials. The processing conditions promoted the formation of embedded crystalline phases in glassy matrix, similarly to what happens in conventional porcelain or stoneware products. X-ray diffraction analysis (Fig. 1) of the samples sintered up to 1,350 ◦ C/2 h indicates that very effective crystallization occurs upon the sintering process, and this is confirmed by the true density values. MgO was the main constituent in the composition after SiO2 ; however, sample 23 incorporated the limestone with higher CaO content. The produced glasses are within MgO–SiO2 and CaO–MgO–SiO2 systems. Clinoenstatite (MgSiO3) was the main phase developed in all samples, i.e. 23, 24 and 25; however, incorporation of CaO in sample 23 led to the formation of augite [Ca(Mg0.85 Al0.15 )Si1.70 Al0.30 O6 ]. A little protoenstatite (MgSiO3 ) was also developed, which reflects a change in the crystal system. A part of residual MgO was crystallized into forsterite [Mg1.867 Fe0.133 SiO4 ] in both 23 and 24 samples containing high MgO wt%. The later results of X-ray diffraction show the role of composition in the formation the crystalline phases. The presence of both protoenstatite and clinoenstatite means that the stable protoenstatite (orthorhombic– prismatic) formed at high temperature (up to 1,350 ◦ C) and
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transformed into the metastable clinoenstatite (monoclinicprismatic) during cooling of the sample [19]. Inversion of protoenstatite into clinoenstatite may be clear in this equation:
Transformation of protoenstatite to clinoenstatite accompanied by 4 % volume shrinkage. This was observed when the samples displayed an excessive viscous flow, resulting in loss of the original disk shape. Taking into account the optimized crystallization and the retention of shape, the desirable crystal changed into clinoenstatite. This shrinkage attends to micro cracks that may be attractive as pores to keep moisture from the atmosphere. In other words, such transformation associated with lamellar twinning and cleavage is key to the toughness in clinoenstatite [10]. The presence of P2 O5 and CaF2 plays an important role in the formation of either phase separation or heterogenous nucleation that is responsible for subsequent crystallization. The SEM microscopy of the polished and unpolished samples is shown in Fig. 2. The surfaces of the samples were observed using SEM; in low magnification, the porosity (cracks) due to transformation of protoenstatite to clinoenstatite appears in all samples (Fig. 2). At high magnification (Fig. 2), twinned clinoenstatite crystals can be seen on the Table 4 Engineering properties of samples fired at up to 1,300 ◦ C for 2h Sample Property
23
24
25
HV (GPa)
6.30
6.45
6.55
3.99
3.44 1.19
Compression stress (KN) WAB (wt%)
0.95
1.85
σf (MPa)
84.95
41.64
40.35
ρg (g/cm3 )
2.68
2.69
2.61
ρapp (g/cm3 )
2.87 ± 0.003
3.19 ± 0.003
3.22 ± 0.003
ρt (g/cm3 )
3.24 ± 0.003
3.25 ± 0.004
3.23 ± 0.001
OP (vol%)
6.7
15.7
19.2
CP (vol%)
10.6
1.5
0.1
TP (vol%)
17.3
17.2
19.3
α(25–500) ◦ C−1
10.02 × 10−6
10.29 × 10−6
10.29 × 10−6
α(25–1000) ◦ C−1
11.96 × 10−6
11.32 × 10−6
10.26 × 10−6
HV vickers microhardness, WAB water absorption, σf flexural strength, ρg geometric density, ρapp apparent density, ρt true density, OP open porosity, CP closed porosity, TP total porosity, α(25–500) linear coefficient of thermal expansion from 25 to 500 ◦ C, α(25–1000) linear coefficient of thermal expansion from 25 to 1,000 ◦ C
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Table 5 Comparison of engineering properties of synthetic marble with those of natural common marble, Thassos marble and granite (new)
a
Reference [20] b Reference [21]
Samples
Properties (average) Density (g/cm3 )
Water absorption (%)
Average porosity (vol%)
Vickers microhardness (GPa)
Compression Compression
Flexural strength (MPa)
Synthetic marble
2.8–3.25
0.95–1.85
10.90
6.45–6.55
344–399
40.0–85.0
Natural common marblea Thassoss marbleb
2.65
0.30
4.60
5.0–5.5
220
33.9
2.80
0.23
0.37
3.2–5.60
160
31.4
Granitea
2.70
0.35
4.30
∼6.00
295
45.0
ence of a significant amount of open porosity of the order of 19 vol%. Part of the porosity is open, as testified by the remarkable water absorption of 1.8 % and illustrated in Fig. 3 confirming the substantial microstructural similarity. 4 Conclusions
Fig. 3 Typical synthetic marble sample
unpolished surfaces of sample 24, whereas on the polished surface they slightly appear in the enstatite faces in 23 and 25 samples (compare high magnification photos in Fig. 2. The crystals are clearly impregnated in the glassy matrix, with interspersed pores. The surfaces are rough, with high degrees of crystallization in some areas. Some physical properties were measured and are mentioned in the table. Density of the synthetic sintered glassceramics was between 2.606 and 2.693 gm/cm3 (Table 3) which is within that of commercial tiles, common marble and granite tiles (Table 4). Vicker’s microhardness values were between 645 and 655 kg/mm2 that were higher than those of commercial tiles, 500 to 600 kg/mm2 . Also for compression strength, the values of our synthetic glass ceramic (339–344 KN) were better than those of commercial ones (160–295 KN). In consequence, the flexural strength is higher in synthetic marble (40.00–85.00 MPa) than in the common natural ones (3.19–45.00 MPa). The aforementioned results show that the values of the strength of the produced synthetic tiles are higher than the natural ones; however, other measurements that concern porosity and water absorption were higher than those of common marble (Table 5). In fact, the crystallization of clinoenstatite, formed due to inversion from protoenstatite, causes micropores, which can be explained primarily by the pres-
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From natural raw materials, the experiments reported here have shown that it is possible to produce artificial marble similar to the common natural marble. This suggests that synthetic marble can replace traditional materials for covering walls, floors and sanitary products. The production of this material involved the conversion of relatively common raw materials through the melt quench route (comprising 95–100 % of the initial composition, with less than 5 % additives) and then subjecting to pluverizing, casting and sintering into valuable polycrystalline materials. The prepared synthetic materials have outstanding physical properties as micro-hardness, compression and flexural strength, which are better than the common natural one. However, other properties such as porosity and water absorption depend upon grain size and casting condition. Acknowledgments The authors would like to thank King Abdul-Aziz City for Science and Technology (KACST) for Research Grant No. 72632. Thanks go to Professor Paolo Colombo, University of Padova, Italy, and his group for further analysis and discussions. Thanks are also due to the technical staff at the National Centre for Building Systems at KACST.
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