Scholarly article on topic 'Review on the elaboration and characterization of ceramics refractories based on magnesite and dolomite'

Review on the elaboration and characterization of ceramics refractories based on magnesite and dolomite Academic research paper on "Materials engineering"

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Abstract of research paper on Materials engineering, author of scientific article — Chaouki Sadik, Omar Moudden, Abdselam El Bouari, Iz-Eddine El Amrani

Abstract One of the most important elements of furnaces, boilers and other heating units is the structure (lining), usually made of silica–alumina, basic or special refractories. The basic refractories are materials that are increasingly in demand and whose manufacturing involves necessarily the use of MgO and CaO. In this article, the description and characterization of magnesite (MgCO3) and dolomite (Mg,Ca(CO3)2) and their contribution in industrial ceramics-refractories have been reviewed.

Academic research paper on topic "Review on the elaboration and characterization of ceramics refractories based on magnesite and dolomite"

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Journal of Asian Ceramic Societies xxx (2016) xxx-xxx Contents lists available at ScienceDirect

Journal of Asian Ceramic Societies

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Review Article

Review on the elaboration and characterization of ceramics refractories based on magnesite and dolomite

Chaouki Sadik3'*, Omar Mouddenb, Abdselam El Bouaria, Iz-Eddine El Amranic

a Laboratory of Physical Chemistry of Applied Materials (LPCMA), Department of Chemistry, Faculty of Sciences Ben Msik, University Hassan II, Casablanca, Morocco

b Laboratory of Structure and Rehabilitation (LSR), Casablanca, Morocco

c Department of Earth Sciences, Geomaterials and Geo-Environment Team (Geo M&E), Scientific Institute, University Mohammed V, Rabat, Morocco

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ARTICLE INFO

ABSTRACT

Article history:

Received 29 April 2016

Received in revised form 13 June 2016

Accepted 25 June 2016

Available online xxx

Keywords:

Dolomite

Magnesite

Firing

Ceramics

One of the most important elements of furnaces, boilers and other heating units is the structure (lining), usually made of silica-alumina, basic or special refractories. The basic refractories are materials that are increasingly in demand and whose manufacturing involves necessarily the use of MgO and CaO. In this article, the description and characterization of magnesite (MgCO3) and dolomite (Mg,Ca(CO3 )2) and their contribution in industrial ceramics-refractories have been reviewed.

© 2016 The Ceramic Society of Japan and the Korean Ceramic Society. Production and hosting by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/

licenses/by-nc-nd/4.0/).

Contents

1. Introduction.............................................................................................................................................00

2. Materials................................................................................................................................................00

3. Process routes...........................................................................................................................................00

4. Magnesia ceramics......................................................................................................................................00

5. Doloma ceramics........................................................................................................................................00

6. Conclusion..............................................................................................................................................00

References..............................................................................................................................................00

1. Introduction

Different mixtures of geomaterials (kaolin clay, red clay, marl, andalusite, perlite, pozzolana, schist, silica sand, magnesite, forsterite, etc.), and additives (natural and synthetic) are used for the elaboration of ceramics and refractories [1]. These industrial minerals and rocks are the raw materials of economic value that are not classified as metallic minerals, fossil fuels or precious stones.

* Corresponding author. Tel.: +212 6 45405676. E-mail addresses: schawki37@gmail.com (C. Sadik), o.moudden@gmail.com (O. Moudden), elbouari@gmail.com (A. El Bouari), izdinelamrani@yahoo.fr (i.-E. El Amrani).

Peer review under responsibility ofThe Ceramic Society ofJapan and the Korean Ceramic Society.

Shaped and unshaped basic ceramics-refractories, based on magnesite and dolomite are produced worldwide for lining industrial furnaces, especially primary and secondary steel furnaces [2]. Actually, there are two methods to produce refractory by using dolomite and magnesite as materials, one is fired in rotary or shaft kilns up to dead burning temperatures of 1500-1800 °C, the other is produced by electric smelting furnace with a temperature over 2500 °C, for example burned magnesite (i.e. fused magnesia) and electrocast spine are produced by electric smelting furnace. The behavior of these elaborated materials in high temperature has been investigated through the use of complementary methods of characterization: structural (X-ray diffraction), microstructural (scanning electron microscopy (SEM)), macroscopic (optical and polarized microscope), technological (porosity, water absorption, density, flexural strength, and shrinkage), thermal (DTA, expansion, shock, and conductivity), and chemical (resistance toward acid attack) [2].

http://dx.doi.org/10.1016/jjascer.2016.06.006

2187-0764 © 2016 The Ceramic Society ofJapan and the Korean Ceramic Society. Production and hosting by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

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Fig. 1. Schema of the fourtextural elements of a refractory.

Refractory materials can be divided into several classes: chemical composition (acid, basic and special), method of implementation (shaped and unshaped), method of manufacture (fused and sintered), and porosity content (porous and dense). They are supposed to be resistant to heat and are exposed to different degrees of mechanical stress and strain, corrosion from liquids and gases, and mechanical abrasion at high temperature. The application fields of refractory are multiple and depend on the properties of each type. In fact, the performance of a refractory (good resistance to heat and thermal shock) is directly related to its texture and its richness in refractories minerals such as mullite, corundum, periclase, doloma, spinel and alumina [1]. Generally, every refractory is composed of four major structural elements that are depicted in Fig. 1 as the following; (1) aggregates (mean grain size: 1000-2500 mm) [3,4]; (2) matrix or filler materials smaller than 150 |im; (3) binder, bond, or cement; (4) pores.

The basic refractories are materials that are increasingly in demand and whose manufacture involves necessarily the synthesis of periclase, spinel and doloma. The primary attributes that make magnesia (MgO) an attractive choice are its high melting point (2800°C) and excellent resistance to attack by iron oxides, alkalis and high lime content of flakes formed at the working temperature of steel melting furnaces [5]. Moreover, it does not suffer from issues of hydration like dolomite and lime, while also being non-toxic. Today, magnesia for refractory production is obtained from three basic sources [2] as the following: (a) natural magnesite, (b) extraction from sea water, and (c) extraction from inland brine. Basic refractories have the attributes of being relatively inexpensive compared to other bricks (special carbon refractories, zircon, zirconia, fused-cast refractory). In addition, they can be used in several applications as the following: coating of laboratory furnaces, refractory supports, thermal insulating, industrial ceramics, concrete, chemical producers and especially in the steel sector.

Several research studies have investigated the use of magnesite and dolomite in building materials and ceramics. The behavior of minerals (quartz, potassium feldspar, sodium feldspar, kaolinite, illite, calcite, dolomite, siderite, pyrite and apatite) in an improved ash fusion test was studied by Reifenstein et al. [6]. Arvanitidis [7] published a paper in 1998 on Northern Greece's industrial minerals. He studied the production and the environmental technology developments. The thermal analysis studies on the decomposition of magnesite and dolomite were studied respectively in 1993 and 1990 by Sheila [8] and Mclntosh et al. [9]. The effect of rate of heating on the decomposition reactions of some raw materials (kaolinite; CaCO3; dolomite; magnesite; and mixes of these) was studied in 1984 by Ibrahim et al. [10]. In 1975, Khalifa et al. [11] studied rapid and quite reliable procedures for analysis of

phosphate, quartzite and fluorspar minerals, as well as chromite, chrome-magnesite and magnesite-chrome bricks-basic refractories.

This review is intended to provide a large overview of the current status of this type of basic ceramics-refractories and to provide a summary of recent information concerning the elaboration and the characterization of refractories elaborated from magnesite and dolomite.

2. Materials

Basic refractories are manufactured using forsterite, spinel, cordierite, magnesite and dolomite. They will refer, somewhat arbitrarily, to common crystalline compounds with melting temperatures of at least 2000°C [5]. In this work, we are interested only with magnesite and dolomite.

Magnesite is a well-known raw material widely used for making magnesia refractories. Magnesite is the mineral name for magnesium carbonate, MgCO3, and was one of the original sources for magnesium oxide used in refractory products. Its theoretical composition is as follows: MgO: 47.7%; CO2: 52.3%, with traces of Fe; Mn; Ca; Co; N and organic compounds. Magnesite is usually white or yellowish with compact appearance. It does not melt but decomposes at 700°C. The residual MgO forms at the bottom at 2800 °C. The decomposition of magnesite in an inert N2 atmosphere can be represented as follows: MgCO3 ^ MgO + CO2.

Magnesite is delivered in three forms as the following: (1) Brute; (2) Calcined at 850 °C; (3) Dead burned and agglomerated (bricks at 1500-1800 °C). Magnesite occurs in nature in three distinct textures as the following: macrocrystalline rich in MgO (MgO content greater than 43%); microcrystalline with inclusions of dolomite (MgO content is between 39 and 43%); macrocrystalline but containing many impurities and having a MgO content of less than 39% [12].

The different methods used for the enrichment of magnesite are based on techniques such as optical or manual sorting, magnetic separation, gravity and flotation. These operations are used depending on the nature and texture of the mineral accompanying magnesite. Treatments show that the obtained concentrate has a good quality, considering the high content of MgO (exceeding 47%), and has low impurity content. The semi-industrial tests are focused on the manufacture of magnesia and magnesium sulfate from the concentrates obtained from raw magnesite.

Production of caustic magnesia and dead burned magnesia from magnesite Boudkek (north of Morocco) was carried out at 850 °C for the first and between 1650 and 1800 °C for the second. The obtained contents during these operations are as the following for the caustic magnesia: 95% MgO, 3% CaO, 0.3% Fe2O3, 0.12% A12O3, and 1.2% SiO2; and as the following for the dead burned magnesia: 96.5% MgO, 1.5% CaO, 0.6% Fe2O3, 0.6% A12O3 and 0.75% SiO2 [12].

In order to produce magnesium sulfate from magnesite, Boudkek tests were performed on representative samples whose average chemical composition is as follows: 44.16% MgO, 3.80% CaO, 0.26% Fe2O3, 0.35% SiO2, 1.12% Al2O3 and 50.00% Lol. The treatment method is an acid attack allowing the transformation from the magnesium carbonate (magnesite) to sulfate. Three techniques were tested as the following: (1) direct attack on the raw magnesite at room temperature; (2) direct attack with heating; and (3) attack after roasting magnesite. Only the acid attack after magnesite roasting at 700 °C presents advantages, especially a coarse grain size (1 mm), and instant reaction and very high efficiency up to 99%. The obtained magnesium sulfate is of the hydrated kind (MgSO4-7H2O) comparable to the commercial sulfate.

Dolomite is a carbonate sedimentary rock that contains more than 50% of carbonate, half of which is at least in the

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Fig. 2. XRD patterns: (a) magnesite and (b) dolomite.

form of dolomite (double carbonate of calcium and magnesium (Ca,MgXCO3)2). The CaO and MgO contents are 30.4% and 21.7%, respectively. Metals may accompany magnesium and calcium in the structure, and the most common is Fe. Mn, Pb and Zn are often present in trace amounts. The thermal decomposition of dolomite has been widely studied. The decomposition of dolomite in an inert nitrogen (N2) atmosphere occurs in a single step and can be depicted by the following reaction: CaMg(CO3 )2 ^ CaO-MgO + 2CO2.

Dolomite is presented in solid form recalling the limestone. It is distinguished by the absence of effervescence with dilute hydrochloric acid. It is often grainy and light-colored, but can be powdered. Its density, when it is pure, varies from 2.8 to 2.9 g/cm3, and its mechanical properties are identical to those of limestone. It does not melt but decomposes from 900 °C losing its CO2 [2].

Varying amounts of impurities including SiO2, Al2O3 and Fe2O3 are present in dolomite. The amounts and types of these impurities may have a large effect on the extent of densification. Dolomite was traditionally used as fettling material for the hearth of furnaces. Dolomites are, as magnesite, used as refractories bricks after being subjected to calcination and sintering at 1600-1700 °C. Dolomite

bricks are used in basic soil converters (electric furnaces). Their disadvantage is to present an irregular expansion curve, related to calcium flux content. Dolomite is also used in the glass; it increases the weather resistance of the glass and prevents devitrification. Dolomite is also used as a flux in the manufacture of steel. Dolomite is harder than limestone; it is an excellent building material and can enter in the manufacture of concrete and reconstituted products [2].

The chemical composition of natural dolomite of Morocco is as follows: 36.11% MgCO3 and 57.80% CaCO3. Result indicates that the Moroccan dolomite is relatively pure with an impurity content of around 4.58 wt.%. The mineralogical composition of the two raw materials (magnesite and dolomite) was analyzed using X-ray diffractometer (XPERT DATACOLLECTER software) operating at 40 kV and 40 mA and using CuKa radiation (Fig. 2). The magnesite rock is mainly composed of magnesite mineral, in addition to a small amount of dolomite [20: 33.5; 40.5; 50] and quartz [20: 26.5]. The dolomitic rock is characterized by the presence of appreciable amount of antigorite mineral [20: 23.5], calcite [20: 29.5], quartz [20: 26.5], and pyrite [20: 50.5] beside the major dolomite mineral.

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Table 1

Room temperature properties of samples sintered at 1300 °C.

Total shrinkage (%) Porosity (%) Water absorption (%) Apparent density (g/cm3)

Magnesite rock 12.3 21.5 14.4 2.1

Dolomite rock 4.1 13.4 5.9 2.6

The fired properties of the samples were evaluated and are given in Table 1. The apparent density, water absorption and open porosity were measured according to ASTMC373-88 [13-15].

3. Process routes

Several efforts have been made by various researchers to improve the high temperature properties of magnesite and dolomite by engineering the microstructure like modification of the grain morphology, amount and distribution of low melting phases and also by changing the chemical and physical nature of bonds. It is evident from a literature survey of about 120 recently published papers that the basic bricks can be used in many industrial applications requiring temperatures greater than 1500 °C. Table 2 summarizes the process conditions, the synthesis/firing temperatures and the characterization of the elaborated basic refractory of various research teams.

4. Magnesia ceramics

Magnesite refractory exhibits various advantageous high temperature properties like high-softening point and excellent chemical endurability in basic condition, and thus the demand for this material has been significantly increased for high temperature applications over the years. Magnesite refractories are widely used in ferrous, non-ferrous and cement industries. They have been extensively used in the steel converter, electric arc furnace and ladle lining in steel-making processes [2]. The primary source for magnesia is natural magnesite along with sea water and inland brine containing the soluble compound magnesium chloride (MgCl2); these final products are referred to as synthetic magnesia. A secondary source of magnesium oxide is from the mining and sintering of brucite deposits; this mineral is composed of magnesium hydroxide (Mg(OH)2) and has a theoretical MgO of about 70 wt.%.

A magnesia refractory is defined by the American Society for Testing and Materials (ASTM) as "a dead-burned refractory material consisting predominantly of crystalline magnesium oxide (MgO)". Also, ASTM defines basic refractories as "refractories whose major constituent is lime, magnesia, or both, and which may react chemically with acid refractories, acid slags, or acidic fluxes at high temperatures". Basic refractories exhibit excellent chemical resistance to other basic refractories, basic slags, or basic fluxes at high temperatures. Magnesium oxide has a very high melting point of about 2800 °C. This characteristic, together with its resistance to basic slags, ubiquitousness, and moderate cost, makes magnesium oxide products the choice for heat-intensive, metallurgical processes such as for the production of metals, cements, and glasses.

As mentioned in the introduction, a chemical analysis of a magnesite will yield the following principal impurities: SiO2 (silica); CaO (lime); Al2O3 (alumina); Fe2O3 (iron oxide); and B2O3 (boric oxide). These impurities combine together and/or with MgO to form minerals that, under equilibrium conditions, can be predicted from phase equilibrium relationships in the MgO-CaO-SiO2-Al2O3-FeO-Fe2O3 system and generally confirmed by X-ray diffraction analyses. Some incorporate suitable additives, which can react with these impurities, convert them into some other high melting phases and thus minimize the amount of low melting phases.

It was reported that TiO2 reduces the formation of low melting phases [100]. Compacted green pellets and bars of magnesite containing 0-5 wt.% TiO2 were sintered in the temperature range of 1500-1600°C with 2h soaking at peak temperature. It was observed that TiO2 slightly increased the apparent porosity and decreased the bulk density by reducing the formation of low melting phases. High temperature flexural strength increases with TiO2 content up to 3 wt.% followed by slight decrease in strength after further increase in the amount of additive. The microstructure of magnesia-zirconia refractories has been studied [112]. It was observed that addition of ZrO2 reduces the formation of low melting CMS at higher temperature and improves the flexural strength at 1200 °C. Periclase grain shape also changed from rounded to subrounded in the presence of zirconia.

Preparation and characterization of porous MgO-Al2O3 refractory aggregates from magnesite and Al(OH)3 as starting raw materials were studied by Yan et al. [106]. The results showed that the Al2O3 contents in the porous refractory aggregates strongly affected the spinel formation, change of the neck bonds between the particles, pore structure (porosity, average pore size and pore size distributions), and then affected the strengths. The porous MgO-Al2O3 refractory aggregates of 62-72 wt.% Al2O3 showed the best combination of high apparent porosities of 42.1-44.2%, high compressive strengths of 51.1-52.0 MPa, high flexural strengths of 17.7-18.6 MPa and small average pore size of 10.81-12.07 | m.

Porous magnesium aluminate spinel (MgAl2O4) ceramic supports were fabricated by reactive sintering from low-cost bauxite and magnesite at different temperatures ranging from 1100 to 1400°C and their sintering behavior and phase evolution were evaluated [107]. The supports prepared at 1300 °C showed a homogeneous pore structure, exhibited high flexural strength and excellent chemical resistance.

Other researchers [103] have used hydromagnesite (basic magnesia carbonate) and fumed silica to produce forsterite via solid-state reaction. Liu et al. [79] have studied the thermal decomposition kinetics of magnesite from thermogravimetric data. Thomaidis and Kostakis [108] have prepared cordieritic materials using raw kaolin, bauxite, serpentinite/olivinite and magnesite. The ceramic materials resulted after firing were investigated regarding their phases composition and physical properties of technological interest. By this way, the creation of materials having interesting combinations of properties such as shrinkage, porosity, density, sufficient compressive strength and low coefficient of expansion at high temperatures was achieved. Processing of cordierite-based ceramics from alkaline-earth aluminosilicate glass, kaolin, alumina and magnesite was studied by Tulyaganov et al. [30]. Microstructural changes, porosity evolution and properties of cordierite-based composites have been studied as a function of cordierite-anorthite ratio in modeled ceramic systems. The model systems were composed of alkaline-earth-aluminosilicate glass powder, kaolin, alumina and magnesite. Suitable densification levels of investigated compositions are attained in a narrow temperature range and relatively high residual porosity levels are observed. These features were attributed to the role of the liquid phase during high temperature sintering. Cordierite, anorthite or mixtures of each with mullite are the formed crystalline phases when maximum densification levels are achieved. Their properties are correlated to the processing route and to the composition of sintered materials.

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Table 2

Table comparing various research works published between 2000 and 2016.

Research team

Year of publication

Title of paper

General characterization

Gal'yanov et al. [16]

Alvaradoet al. [17]

Warren [18]

Tsirambides [19]

Shatilovet al. [20]

Gropyanov and Gropyanov[21] 2001

Kashcheev [22]

Samtani et al. [23] Zawrah [24]

Khaliletal. [25] Darweesh [26]

Sato and Katsura [27]

Samtani et al. [28]

Cunha-Duncan and Bradt [29] 2002

Tulyaganov et al. [30]

Kalpakli et al. [31]

Serry et al. [32]

Preparation of magnesite ore in mining

Preparation and characterization of MgO powders obtained from different magnesium salts and the mineral dolomite

Dolomite: occurrence, evolution and economically important associations

Industrial applications of the dolomite from Potamia, Thassos Island, N. Aegean Sea, Greece A study of the kinetics of decarbonization of magnesite concentrated by flotation

Sintering kinetics of MgO studied on magnesite of provenance from the Chita Deposit

Ways toward improving the technology of refractories based on powdered periclase

Thermal analysis of ground dolomite, confirmation of results using an X-ray powder diffraction methodology Characterization and sinterability of chemically precipitated phosphate-bearing magnesia grains

Aluminous cements containing magnesium aluminate spinel from Egyptian dolomite

Building materials from siliceous clay and low-grade dolomite rocks

Experimental investigation on dolomite dissociation into aragonite + magnesite up to 8.5 GPa

Isolation and identification of the intermediate and final products in the thermal decomposition of dolomite in an atmosphere of carbon dioxide Synthesis of magnesium aluminate spinels from bauxites and magnesias

Processing of cordierite-based ceramics from

alkaline-earth-aluminosilicate glass, kaolin, alumina and magnesite Effect of binder type and other parameters in synthesis of magnesite chromite refractories from process waste

Characterization of Egyptian dolomitic magnesite deposits for the refractories industry

It is shown that the chemical composition of the mined magnesite ore is interrelated with its lumpiness. The results have made it possible to use the effect of segregation for primary preparation of the ore in the mining stage.

The decomposition of the precipitated Mg(OH)2 was analyzed by DTA/TGA and XRD. The variation of the properties with the nature of the precursors at 960 °C was studied. The microstructural differences between the MgO agglomerates were examined by SEM at different temperatures.

Dolomite is not a simple mineral. Dolomite is a metastable mineral, early formed crystals can be replaced by later more stable phases with such replacements repeated a number of times during burial and metamorphism.

The authors present a detailed characterization and applications of the used dolomite.

The kinetics of decarbonization of magnesite concentrated by the method of flotation is studied under various conditions (stationary unblown layer, fluidized layer, and layer mixed in a rotary furnace). Typical features of the process of decarbonization of magnesite are determined.

An equation is derived that provides an adequate description of the kinetic features of MgO sintering.

Away toward obtaining high-quality powers involves reducing the concentration of SiO2 in magnesite to 0.2-0.5% and increasing the calcination temperature to 2000-2100 °C to prepare coarse-grained periclase with a crystal size larger than 140 |xm. To investigate if grinding had detrimental effects, a detailed study was carried out using dolomite as the material to be ground.

The precipitated powders were characterized for their chemical and mineralogical compositions, thermal analyses and particle size distribution as well as particle morphology. The effect of P2O5 was discussed.

The results indicated that the mineralogical compositions were refractory MA spinel, in addition to CA and/or CA2 phases depending on the composition of the starting materials. Results showed that the thermal interaction between the constituents of clay and dolomite at 750 °C ensures better and relatively high mechanical strength for the resulting products. The XRD and DTA analyses indicated that the produced articles are composed mainly of carbonates and new formations of calcium silicates, calcium aluminates and MgO in amorphous or fine crystalline state. The fired products after hydraulic hardening at a dried environment recorded the highest mechanical properties. This study suggests that the equilibrium line of the dolomite = aragonite + magnesite reaction could be very useful in addition to phase transformation of quartz-coesite and graphite-diamond to constrain P-T conditions for the metamorphism of dolomite-bearing ultrahigh-pressure rocks. The intermediate products were found to be dolomite, calcite and periclase, while the final products were calcium oxide and periclase. Using these results a mechanism of thermal decomposition for dolomite is proposed. Four different alumina sources and four different magnesia sources were investigated. The periclase reacts with the free corundum of the bauxite to produce Mg-Al spinel. The periclase then reacts with the mullite in the bauxites to yield additional spinel and also some forsterite.

Control of the porous structure through manipulation of heating rate was found feasible and easy to implement.

The optimum sintering temperature was found at 1750 °C.

XRD, SEM, DTA, DTG, TG and wet chemical analysis methods were applied. According to the research output, pure magnesites with the addition of MgO and/or Fe2O3-rich materials are recommended for the production of unshaped MgO-CaO refractories.

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Table 2 (Continued)

Research team

Year of publication

Title of paper

General characterization

Mustafa etal. [33]

Samtani et al. [34]

Kashcheev et al. [35] 2003

Demir et al. [3б]

Beruto et al. [37]

Antonov et al. [38]

Serena et al. [39]

Yeprem et al. [40]

Haldaret al. [41]

Chen and Tao [42]

Suvorov et al. [43]

Aksel et al. [44]

Kalaitzaki et al. [45]

Othman and Nour [4б]

Pokrovsky et al. [47]

Sintering and microstructure of spinel-forsterite bodies

Comparison of dolomite decomposition kinetics with related carbonates and the effect of procedural variables on its kinetic parameters

Synthesis of spinel from caustic magnesite and alumina dust

Calcination kinetic of magnesite from thermogravimetric data

Solid products and rate-limiting step in the thermal half decomposition of natural dolomite in a CO2(g) atmosphere

Stabilized dolomite refractories

Corrosion behavior of MgO/CaZrO3 refractory matrix by clinker

A quantitative-metallographic study of the sintering behavior of dolomite

Effect of compositional variation on the synthesis of magnesite-chrome composite refractory

Effect of solution chemistry on notability of magnesite and dolomite

A high-density water-resistant magnesia-lime material based on dolomite

Investigation of parameters affecting grain growth of sintered magnesite refractories

Hydraulic lime mortars for the restoration of historic masonry in Crete

Recycling of spent magnesite and ZAS bricks for the production of new basic refractories

Dissolution kinetics of calcite, dolomite and magnesite at 25 °C and 0-50 atm pCO2

The spinel-forsterite phase mixtures formed by the addition of different proportions of alumina to forsterite grog's mixes, showed a good compromise of high-density, cold crushing strength and microstructure after firing at 1450 and 1500°C. Forsterite was first prepared from talc and calcined magnesite at 1400 °C/2 h. The thermal behavior and the kinetics of decomposition were studied using the Arrhenius equation applied to solid-state reactions. It was found that calcite and dolomite supposedly decompose via a zero-order mechanism while magnesite decomposes via a first-order process.

The sintering of a mixture of a caustic dust and an alumina dust collected from electric filters taken in MgO/Al2O3 ratios of 0.1, 0.28, 0.5, and 0.75 at 1650 °C is studied. Materials with superior physicomechanical properties are obtained: open porosity, 1.2-8.4%; density, 3.5g/cm3, and compressive strength, 160-410 MPa. High-density pellets (free of additions) are prepared at a MgO/Al2O3 ratio of 0.75, with compressive strength as high as 160 MPa.

It was observed that the process fitted a first-order kinetic model and the values ofthe activation energies decreased with decreasing particle size, which can be attributed to the increasing particle internal resistance to the escape of CO2 as the grain size increased. Natural dolomite powders obtained from caves, which give unusual high-resistance building materials, have been decomposed in a Knudsen cell at high CO2 pressures in the temperature range of 913-973 IK XRD traces for the final solid products, after the first halfthermal decomposition, have shown that beside the XRD patterns for the calcite and MgO, the existence of a new structure with major peaks at 20 equal to 38.5° and 65°. This finding has been ascribed to a solid solution of MgO in calcite. A technology of environment-friendly refractories based on briquetted dry-ground dolomite, magnesia-silicate raw materials, and stabilizing additives has been developed. The potential use of the newly designed refractories as an alternative to chromite-periclase refractories is emphasized. The attack mechanism to substrates of 80% MgO and 20% CaZrO3 (wt.%) obtained from dolomite and ZrO2 mixtures and MgO and presintetized CaZrO3 mixtures is established. Grain growth of the MgO phase during sintering of natural dolomite was studied. For comparison purposes, iron oxide (98.66% mill scale) was added up to 1.5%. The compositions of the phases formed during sintering were studied using XRD and SEM. Magnesite-chrome composites have been prepared by utilizing sintered magnesite and friable chrome ore in presence of titania as additive. The physical properties as well as thermomechanical properties and microstructural studies of the sintered aggregates have been evaluated.

The present study was undertaken to investigate effects of dissolution rate, species distribution, solubility, surface conversion phenomenon, and surface electrical properties on notability of magnesite and dolomite.

A method for preparation of water-resistant magnesia-lime granules of high density (95-98%) is developed using dolomites and dolomitized magnesites. The use of granulated materials for manufacture of water-resistant clinker, powders, and magnesia-lime refractories with superior performance and economical characteristics is discussed.

The parameters influencing grain size of sintered magnesite such as temperature, time, cooling rate and various particle size were investigated using different sintering regimes to improve grain growth. The effects of impurities (SiO2, CaO, Fe2O3, and CaO/SiO2 ratio) on grain growth were also evaluated by EDX analysis. This study presents the results of the physicochemical characterization of original mortars and plasters and the evaluation of the repair ones prepared with natural hydraulic lime (NHL) as binding material and siliceous sand and crushed brick as aggregates.

The results revealed that, the addition of spent ZAS up to 5.0 wt.% to spent magnesite enhanced the physicomechanical, refractory and thermal properties due to the development of highly refractory phases MA spinel and MgO ZrO2 solid solution. The obtained results demonstrate that carbonate mineral dissolution rates are not proportional to H2CO3(aq) and depend only weakly on pCO2. For dolomite and magnesite, the surface complexation model (SCM) predicts dissolution rates up to 50 atm pCO2 with a good accuracy.

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Table 2 (Continued)

Research team

Year of publication

Title of paper

General characterization

Diazet al. [48]

Lingling and Min [49] Shchekina et al. [50]

Solodkii and Shamrikov [51]

Ye and Troczynski [52]

Kangal and Guney [53] Gonzalez et al. [54]

Ghosh et al. [55]

Yeprem [56] Mako [57]

Diaz and Torrecillas [58] Kurama et al. [59]

Kalpakli [60]

Diazet al. [61]

Peiwei et al. [62]

Aksel'rod et al. [63]

Alumina-rich refractory concretes with added spinel, periclase and dolomite: a comparative study of their microstructural evolution with temperature

Dolomite used as raw material to produce MgO-based expansive agent

Use of magnesian-dolomite mixtures in steel-melting furnace hearths and the mechanism of their wear in service. 1. Study of hearth refractory mixture

The ural mineral raw-material base for the ceramics, refractory, and glass industry

Hydration of hydratable alumina in the presence of various forms of MgO

A new industrial mineral: huntite and its recovery

Copper matte penetration resistance of basic refractories

Effect of MgO and ZrO2 additions on the properties of magnesite-chrome composite refractory

Effect of iron oxide addition on the hydration resistance and bulk density of doloma

The effect of quartz content on the mechanical activation of dolomite

Phase development and high temperature deformation in high alumina refractory castables with dolomite additions Investigation of borax waste behavior in tile production

Investigation ofTiO2-added refractory brick properties from calcined magnesite raw material

Room temperature mechanical properties of high alumina refractory castables with spinel, periclase and dolomite additions

Using a new composite expansive material to decrease deformation and fracture of concrete Refractory materials and methods for increasing the life of converter linings from experience of OOO Gruppa Magnezit

The evolution of the phases and microstructure was studied as a function of T°C and the processing route for both refractory concretes and their corresponding matrices (<125 |xm).

The expansion of pastes depends on the making condition and dosage of MgO-based expansive agents greatly. MgO particles burned at lower temperature are bigger than those at high temperature, and resulting in expansion at early age. The results of mineralogical-petrographic analysis of magnesian-dolomite refractory mixture used in the hearths of steel-melting furnaces are described. The variation regularities of its phase and chemical composition are identified and the mechanism of its wear in service at the metallurgical works in is considered.

Brief information is reported on the promising deposits of clays and kaolins, feldspars and their substituents, quartz minerals, carbonate rocks, pyrophyllites and kyanites, magnesia and magnesia-silicate materials, and many other types of raw materials for the ceramics, glass, and refractories industry. The results revealed significant difference in the hydration products between the hydratable alumina-reactive magnesia mixture and the hydratable alumina-fused magnesite or dead burnt magnesite mixtures under the hydration conditions. Characterization of huntite ores was made and separation conditions for huntite from the associated mineral, magnesite were investigated.

The effects of oxygen potential and matte grade on burned magnesite-chrome brick and spinel direct-bonded brick were studied using operating conditions typical of copper converters, and their relative performance was evaluated using high-grade and low-grade matte at oxygen potentials of 10-7 and 10-6 atm. The reactivity of magnesia was found to play an important role in the final properties of samples. Introducing less reactive sintered magnesia improved all the properties of the aggregates. ZrO2 was found to be a good sintering aid in the magnesite-chrome composites.

According to the results of experiments with 15 sintered samples, sintering temperature, soaking time and increase of mill scale amount were found to increase the bulk density and thus decrease the observed apparent porosity.

The increased quartz content accelerated the mechanochemical deformation and amorphization of dolomite phase. After grinding the dolomite/quartz mixtures, the thermal decomposition of dolomite showed a four- or three-step weight loss, instead of the original two- or one-step one.

A correlation between the microstructural phase evolution and the creep behavior with temperature was established.

The addition of TSW appeared to improve liquid phase development with better physical properties compared to those of standard composition for the firing regime involved. The results indicated a prospect for using the waste as a co-flux in wall tile formulations.

90% magnesite-10% chromite composition was used as a brick composition. Compaction pressure, sintering temperature, ratio of TiO2 addition, and influence of bonding type on refractory properties were examined. Experiments show that using a magnesite particle size of-10-3 m and a chromite particle size of -63 x 10-6 m affects the properties of the product in a positive way.

From room temperature to 1000°C the refractory castables present a pronounced non-linear stress-strain behavior both in the uniaxial tensile and compressive modes, as a result of damage to the microcrack network. Above 1000 °C the refractory castables begin to sinter owing to a transitory liquid phase, the crystallization of calcium aluminate cement phases and the self-forming spinel phase.

Using minerals of dolomite, serpentine and magnesite produce a new composite material, which provides an expansive stress to decrease deformation and fracture of hydraulic concrete. Experience of using Gruppa Magnezit refractory materials in the lining of acid converters in Russia and the Ukraine is summarized briefly.

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Table 2 (Continued)

Research team

Year of publication

Title of paper

General characterization

Prokofev et al. [64] Rabah and Ewais [65]

Siadati and Monshi [66]

Martinez etal. [67] Adriano et al. [68]

Das et al. [69]

Yamamoto et al. [70] Szczerbaand Pedzich[71]

Mahadi and Palaniandy [72]

Hojamberdiev et al. [73]

Hojamberdiev et al. [74]

Khater [75]

Obregon et al. [76]

Khater and Morsi [77]

Urvantsev and Kashcheev [78]

Physical-chemical phenomena occurring during the production of sorbent from a clay-dolomite composition

Multi-impregnating pitch-bonded Egyptian dolomite refractory brick for application in ladle furnaces

Acidic and basic binders for magnesite-based aggregate in plaster oftundish

Sintering behavior of periclase-doloma refractory mixes

Microscopic characterization of old mortars from the Santa Maria Church in Evora

Microstructural and densification study of natural Indian magnesite in presence of zirconia additive

Antibacterial characteristics of CaCO3-MgO composites

The effect of natural dolomite admixtures on calcium zirconate-periclase materials microstructure evolution Mechanochemical effect of dolomitic talc during fine grinding process in mortar grinder

Characterization and processing of talc-magnesite from the Zinelbulak deposit

Processing of refractory materials using various magnesium sources derived from Zinelbulak talc-magnesite

Influence of Cr2O3, LiF, CaF2 and TiO2 nucleants on the crystallization behavior and microstructure of glass-ceramics based on blast-furnace slag

MgO-CaZrO3-based refractories for cement kilns

Glass-ceramics based on spodumene-enstatite system from natural raw materials

Magnesite enrichment by a dry method

It is shown that kaolinite plays a decisive role in the formation of the porous structure of granules and dolomite determines the strength of the articles produced.

Dolomite brick samples containing 10 wt.% coal tar pitch and pressed at 108 MPa have high hydration resistance compared to the hydration resistance of the commercial. The prepared brick samples have acceptable density, chemical stability, outstanding resistance and good mechanical properties would meet the requirements of ladle furnace (LF) for steel-making industry. Cold crushing strength at different heat treatments is measured. Apparent porosity of samples without pulp and bulk density together with pH of the binder solution is evaluated and XRD and SEM studies are performed.

The analyzed mixes mainly contain periclase and doloma, with iron oxides. Sintering began at temperatures higherthan 1200°C and was associated to liquid phase formation. The characterization methodology involved a multidisciplinary set of chemical, physical, microstructural and mechanical techniques, and gave special attention to the use of microstructural characterization techniques, particularly petrographical analysis and SEM for the identification of the mortar's constituents as well as in the evaluation of the state of conservation. The sintering and microstructural evaluation of magnesite was carried out in presence of zirconia. A crystalline phase, magnesio-zirconate, was identified at the triple point regions of the direct-bonded periclase grains.

Composite powders contributing to oral hygiene application, i.e. nano-scale MgO crystallite dispersed in CaCO3 grain, were fabricated by the thermal decomposition of dolomite. The material obtained from the mixture of zirconium oxide and natural dolomite with the high impurities content has the highest densification level at 1500 and 1600°C.

Dolomitic talc was milled in a mortar mill by varying the milling time, solid content, and vertical stress. The milled samples exhibited massive particle size reduction and came to a threshold value around 4 |im, with wider particle size distribution. Petrographic analysis confirmed the presence of magnesite and breunnerite. The dressability of the Zinelbulak talc-magnesite was tested using conventional gravity concentration, flotation and electromagnetic separation. Subsequent flotation and magnetic separation techniques could further increase the yield of high-quality magnesite and talc. Refractory samples prepared by heating the separated magnesite at 1600 °C for 2h met the State Standards for refractory materials.

A series of refractory materials were prepared on the basis of these magnesium sources, and their effects on physicomechanical properties and microstructures were investigated as a function of sintering temperature, molding pressure, and the particle size of magnesium sources.

Glass-ceramics based on blast-furnace slag (56.78 wt.%) were prepared by mixing quartz sand, dolomite, limestone, and clay as other batch constituents.

Two series of refractory materials have been designed taking into account the phase equilibrium relationships to obtain MgO-CaZrO3-Ca2SiO4-Ca3Mg(SiO4)2 or MgO-CaZrO3-Ca3Mg(SiO4)2-c-ZrO2 as final crystalline phases. Specimens have been fabricated by reaction sintering of natural dolomite and zircon and with dead burned magnesia aggregates. Different relationships between the proportion and sizes of the fines and the aggregates have been explored. Glasses ofcompositions (wt.%) corresponding to 50-90 spodumene and 50-10 enstatite were prepared depending on natural raw materials and Li2CO3 as small ingredient. The crystallization behavior was studied using DTA and XRD. The effect of addition of the nucleating agents (LiF) to a selected glass was also examined.

Results are provided for enrichment of low-grade magnesite deposit (MgO 43.1%) by electric separation.

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Table 2 (Continued)

Research team

Year of publication

Title ofpaper

General characterization

Liuetal. [79]

Ghosh and Tripathi [80] 2012

Dwarapudi et al. [81] 2012

Lampropoulou et al. [82] 2013

Choetal. [83]

Macris et al. [84]

Othman [85]

Sasaki et al. [86]

Wangetal. [87]

Tian et al. [88]

Soltan et al [89]

Charalampides et al. [90]

Fu et al. [91]

Gao et al. [92]

Thermal decomposition kinetics of magnesite from thermogravimetric data

Sintering behavior and hydration resistance of reactive dolomite

Effect of MgO in the form of magnesite on the quality and microstructure of hematite pellets

New periclase-spinel refractories from densely sintered high-purity magnesite and new synthetic compositions based on spinel. Part 1. Study of mineral composition, microstructure, thermal expansion, and ultimate strength in compression Air gasification of mixed plastic wastes using calcined dolomite and activated carbon in a two-stage gasifier to reduce tar

Experimental determination of equilibrium magnesium isotope fractionation between spinel, forsterite, and magnesite from 600 to 800 °C

Effect of talc and bauxite on sintering, microstructure, and refractory properties of Egyptian dolomitic magnesite

Effect of natural dolomite calcination temperature on sorption of borate onto calcined products

New synthetic route to Mg-Al-CO3 layered double hydroxide using magnesite

An experimental study on thermal decomposition behavior of magnesite

Densification and resistance to hydration and slag attack of ilmenite-doped MgO-dolomite refractories in relation to their thermal equilibrium and microfabric The contribution of industrial minerals to sustainable recovery of Greek Economy

Kinetics of extracting magnesium from mixture of calcined magnesite and calcined dolomite by vacuum aluminothermic reduction

Characteristics of calcined magnesite and its application in oxidized pellet production

Thermal decomposition kinetics of magnesite were investigated using non-isothermal TG-DSC technique at heating rate (8) of 15, 20, 25,35, and 40 Kmin-1. A new multiple rate iso-temperature method was used to determine the magnesite thermal decomposition mechanism function, based on the assumption of a series of mechanism functions.

Sintering of raw dolomite and hydroxides derived from dolomite was carried out in the temperature range 1350-1650 °C. Hydration resistance was related to densification and grain size of sintered dolomite.

it was observed that with increasing MgO, swelling characteristics of pellets were found to be improved. Reducibility of the pellets improved substantially in the range of 0.5-1.5% MgO. Formation of magnesioferrite phase and high melting point slag formed during induration could be attributed to the improved quality of pellets. Sintered magnesite and synthesized spinel properties are provided. On the basis of petrographic criteria, and also linear thermal expansion coefficient (LTEC) and ultimate strength in compression for final materials, the authors of this article propose a most suitable material with respect to quality for testing in high temperature branches of industry.

Stable gasification of mixed plastic wastes was conducted in a two-stage gasifier. Strong tar removal was achieved with the combination of activated carbon and dolomite. Increasing amount of activated carbon resulted in less tar and high hydrogen production. Chlorine in feed material was mainly transferred to char or captured by activated carbon.

The authors performed experiments at 600, 700, and 800°C and 1 GPa to establish the equilibrium magnesium isotope partitioning between forsterite (Mg2SiO4) and magnesite (MgCO3) and between spinel (MgAl2O4) and magnesite, making use of the carbonate as an isotope exchange medium to overcome sluggish diffusion-limited magnesium isotope exchange between spinel and forsterite.

Mineralogical composition and microstructure, pore size distribution, and mechanical and refractory properties of samples were investigated. Most samples showed high refractoriness under load, good spalling resistance, better mechanical properties than current refractories, and compact microstructure. The sorption density of borate was greater with the calcined products at 700 °C than 800-900 °C and under an Ar gas flow system rather than for static air at the same temperatures. The surface reactivity of the calcined dolomite with borate in the aqueous phase was affected by CO2 emitted in the decarbonation at higher temperatures.

The crystal morphology of the prepared LDH displays platelet-like structure with a hexagonal shape, which is agreed with the LDH produced by industrial chemicals. Thermal analysis indicated that the total weight loss was 43.8% in the range of 20-8500C. Thermal decomposition of magnesite is investigated by using a TG-MS. Different kinetic methods including Coats-Redfern, Flynn-Wall-Ozawa, and Kissinger-Akahira-Sunose are used to investigate the thermal decomposition kinetics of magnesite. It was observed that the activation energy values obtained by these methods are similar.

This work aims at studying rate of densification, resistance to hydration and slag attack of 0.0-2.0 wt.% ilmenite-doped MgO-dolomite refractories fired at 1400-1700 0C, in relation to their thermal equilibrium and microfabric. XRF, XRD, SEM, EDAX and mercury intrusion were used to characterize the fired samples. Occurrences and industrial mineral deposits, primarily in North Greece, are examined in relation to their uses, such as feldspars, pozzolan, pumice, kaolin, zeolites, quartz, gypsum, and white carbonates.

The results indicate that the reduction rate is increased with increasing temperature, content of aluminum and pellet forming pressure. The XRD patterns confirm that the reduction process can be roughly classified into three stages: the formation of MgAl2O4, and Cai2 Ali4O33 phases; the phase transformation from MgAl2O4 and C12A7 to CaAl2O4; the formation of CaAl4O7 phase. Experimental resulting indicated that the best calcination condition was 850 0C and 1 h. Under this condition, the hydration activity of the calcined magnesite was 88.56%.

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Table 2 (Continued)

Research team

Year of publication

Title ofpaper

General characterization

Valle-Zermeno [93]

Huang et al. [94]

Fuet al. [95]

Ghosh et al. [96]

Gadikota et al. [97]

Zhang et al. [98] Liu et al. [99]

Kumar etal. [100] Lavat etal. [101]

Kipcakand Isiyel [102] 2015

Chenet al. [103]

Wangetal. [104]

Chenet al. [105]

Yanetal. [106]

Reutilization of low-grade magnesium oxides for flue gas desulfurization during calcination ofnatural magnesite: a closed-loop process Effects ofcalcite and magnesite application to a declining Masson pine forest on strongly acidified soil in Southwestern China

Mechanism of extracting magenesium from mixture of calcined magnesite and calcined dolomite by vacuum aluminothermic reduction

Studies on densification, mechanical, microstructural and structure-properties relationship of refractory aggregates prepared from Indian magnesite by changing lime-silica ratio Morphological changes during enhanced carbonation of asbestos containing material and its comparison to magnesium silicate minerals Reaction kinetics of dolomite and portlandite

Experimental investigation on the properties and microstructure of magnesium oxychloride cement prepared with caustic magnesite and dolomite

Effect of titania on the microstructure evolution of sintered magnesite in correlation with its properties The firing steps and phases formed in Mg-Zr-Al refractory dolomite-based materials

Magnesite tailing as low-cost adsorbent for the removal of copper(II) ions from aqueous solution

Low temperature synthesis of forsterite from hydromagnesite and fumed silica mixture

Role of MgxCa1-xCO3 on the physical-chemical properties and cyclic CO2 capture performance of dolomite by two-step calcination Influence of MgO precursors on mechanically activated forsterite synthesis

Preparation and characterization of porous MgO-Al2 O3 refractory aggregates using an in situ decomposition pore-forming technique

Three different by-products from the calcination of natural magnesite were selected in order to evaluate their desulfurization capacity.

Both calcite and magnesite additions caused a significant increase in pH and a decrease in dissolved inorganic monomeric aluminum concentration of soil water. Calcite addition may further decrease the Mg2 + availability in soil water, thereby exacerbating Mg2 + deficiency in the acidified forest soils of southern and southwestern China.

The first stage included the direct reaction between calcined dolomite or calcined magnesite and Al with 12CaO7Al2O3 and MgOAl2O3 as products. The CA phase was mainly produced in the second stage and the overall reaction rate was determined by both the diffusion of Ca2+ with molten Al and the chemical reaction. The CA2 phase was mainly produced in the third stage and the reaction process was controlled by the diffusion of Ca2+. The sintered material has been characterized in terms of bulk density, apparent porosity, true density, relative density, cold modulus of rupture, hot modulus of rupture, thermal shock resistance, structural properties by XRD in terms of phase identification and evaluation of crystal structure parameters of corresponding phases by Rietveld analysis. Formation of phases such as dolomite ((Ca, Mg)(CO3)2), whewellite (CaC2O4H2O) and glushinskite (MgC2O42H2O) and a reduction in the chrysotile content was noted.

Pressed pellets of dolomite develop calcite at both exterior surfaces and in the interior, where calcite develops as a secondary phase but is not morphologically well-formed crystals. The results indicated that MOCs (magnesium oxychloride cements) prepared with caustic magnesite and dolomite obtained a good engineering performance.

It was observed that TiO2 slightly increased the apparent porosity and decreased the bulk density by reducing the formation of low melting phases.

This study was carried out in order to determine the feasibility of using Argentine dolomites in the preparation of CaZrO3-MgAl2O4 by solid-state reaction. The thermal and structural changes which occur during the firing of the batches up to 1425 °C were studied by the combination of diffractometric and infrared spectroscopic data at the most remarkable reaction steps. The final product is composed mainly by MgAl2O4, CaZrO3, and Ca2SiO4 phases and the optimal synthesis temperature would be 1425 °C. The removal of Cu(II) ions from aqueous solution using magnesite tailing was investigated. Batch kinetic and equilibrium experiments were conducted to study the effects of initial pH, adsorbent dosage, contact time, initial concentration and temperature. The results showed that magnesite tailing is a suitable adsorbent for the removal of Cu(II) ions from aqueous solutions.

The phase development and morphology evolution of the hydromagnesite and hydromagnesite-fumed silica mixture during heat treatment were characterized by SEM, BET nitrogen-gas adsorption method, and XRD. Monolithic forsterite was synthesized after calcination of the hydromagnesite-fumed silica mixture at 1100°C.

Two-step calcination treated dolomite sorbent was prepared and characterized. An intermediate phase (MgxCa1-xCO3) was observed by TG and XRD results.

Brucite-fumed silica and hydromagnesite-fumed silica mixtures were used to investigate the influence of MgO precursors on mechanically activated forsterite synthesis. The changes in morphology, chemical bond and phase composition of the ground and calcined mixtures were examined with SEM, XPS and XRD. The porous MgO-Al2O3 refractory containing 30-92wt.% Al2O3 were prepared via an in situ decomposition pore-forming route using magnesite and Al(OH)3. The results showed that the Al2O3 contents in the porous refractory aggregates strongly affected the spinel formation, change of the neck bonds between the particles, pore structure and then affected the strengths.

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Table 2 (Continued)

Research team Year of publication Title ofpaper General characterization

Wangetal. [107] 2015 Preparation and characterization of porous MgAl2O4 spinel ceramic supports from bauxite and magnesite The effects of sintering temperature on the pore structure, size and distribution as well as on the main properties of spinel ceramic supports such as flexural strength, nitrogen permeation flux and chemical resistance were investigated.

Thomaidis and Kostakis [108] 2015 Synthesis ofcordieritic materials using raw kaolin, bauxite, serpentinite/olivinite and magnesite The ceramic materials resulted after firing, were investigated regarding their phases composition and physical properties of technological interest.

Albhilil et al. [109] 2015 Thermal and microstructure stability of cordierite-mullite ceramics prepared from natural raw materials - Part II The refractoriness of samples is found to be higher. XRD shows that heating-quenching procedure has led to crystallization of cordierite and mullite phases.

da Cruz and Braganca [110] 2015 Evaluation of the protective C2S layer in the corrosion process of doloma-C refractories C2S layer samples were characterized by analyzing their chemical composition, phase formation and microstructure.

Temiz etal. [111] 2015 Influence of blast-furnace slag on behavior of dolomite used as a raw material of MgO-type expansive agent Volume expansion of paste samples increased with increasing dolomite content. However, it decreased with addition of BFS. Length change samples containing dolomite + BFS was less than one containing sole dolomite but more than reference samples.

Burhanuddin et al. [112] 2015 Effect of zirconia on densification and properties of natural Indian magnesite ZrO2 was added to reduce the formation of low melting phase in order to improve the hot strength.

Booth etal. [113] 2015 Effect of impurities and sintering temperature on properties of MgO-CaZrO3 ceramics The influence of the different mineralogy of the dolomites and sintering temperatures on the properties of the composites was investigated. Ceramics had porosity of 20-30%, the representative microstructure as determined using SEM-EDX was constituted by CaZrO3, MgO grains containing some m-ZrO2 grains.

Raza et al.[114] 2015 Leaching of natural magnesite ore in succinic acid solutions The results indicated that the extraction of magnesium depends on acidic strength, reaction temperature, ore particle size, stirring rate and liquid solid ratio.

Debska[115] 2015 The effect of exposition conditions on the durability of cement concrete with dolomite aggregate sourced near Krakow, Poland The observation of linear extension as well as changes in compressive strength and surface alteration due to corrosive exposition conditions were the key diagnostic features adopted for this examination.

Li etal. [116] 2015 Low temperature synthesis of Calcium-hexaluminate/magnesium-aluminum spinel ceramic

calcium-hexaluminate/magnesium-aluminumomposites were synthesized at 1450 ◦ C for3 h using a precursor

spinel composite ceramics from dolomite and industrial aluminum hydroxide through a 200 0C hydrothermal treatment, which was 100 0C lower than the traditional process.

Formosa et al. [117] 2015 Magnesium phosphate cements formulated with a low-grade MgO by-product: physicomechanical and durability aspects MPC formulated with LG-MgO by-product were selected from preliminary study. Durability studies show good durability and repairing properties.

Sifre etal. [118] 2015 Effects of temperature, pressure and chemical compositions on the electrical conductivity of carbonated melts and its relationship with viscosity Evidence for a relationship between melt electrical conductivity and melt viscosity. Less than 0.2% of carbonated melt explains electrical conductivity below Brazilian craton.

Xie et al. [119] 2016 The thermochemical activity of dolomite occurred in dolomite-palygorskite The decomposition temperature of dolomite occurred in DPC started at 500 0C and ended at 780 0C, with a maximum peak at 7450 C. The decomposition temperature of dolomite in DPC was found to be 50 0C lower than that of common dolomite.

Chenet al. [120] 2016 Comparison of the chemical corrosion resistance of magnesia-based refractories by stainless steel-making slags under vacuum conditions This study evaluates commercially available magnesia-chromite, magnesia-carbon and magnesia-doloma bricks for their use in a vacuum oxygen decarburisation ladle. The corrosion behavior of these bricks by stainless steel-making slags is, therefore, investigated through crucible tests in a vacuum induction furnace at elevated temperatures and low oxygen partial pressures. The results reveal that magnesia-carbon bricks are severely corroded due to the high dissolution of MgO, while magnesia-chromite and magnesia-doloma refractories exhibit an excellent corrosion resistance.

Gautieretal. [121] 2016 Magnesite growth inhibition by organic ligands: an experimental study at 100,120 and 146 0C The authors show the influence of three organic ligands: oxalate, citrate and EDTA on magnesite growth in alkaline conditions and at hydrothermal temperatures (100,120 and 146 0C) using mixed flow reactors.

Masindi and Gitari [122] 2016 Simultaneous removal of metal species from acidic aqueous solutions using cryptocrystalline magnesite/bentonite clay composite: an experimental and modeling approach The overall aim of the present study was to fabricate cryptocrystalline magnesite and bentonite clay composite and evaluate its application for simultaneous removal of Co(II), Cu(II), Ni(II), Pb(II) and Zn(II) from wastewater in a single step.

Masindiet al. [123] 2016 Synthesis ofcryptocrystalline magnesite-bentonite clay composite and its application for neutralization and attenuation of inorganic contaminants in acidic and metalliferous mine drainage The capacity of the composite to neutralize acidity and remove toxic chemical species from synthetic and field AMD was evaluated at optimized conditions. Interaction of the composite with AMD led to an increase in pH (pH > 11) and lowering of metal concentrations.

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Forsterite was prepared from Egyptian talc and calcined magnesite at 1400 °C/2 h [33]. The material shows good density but the microstructure contains cracks along the grain boundaries affecting the mechanical properties. The sintering and mechanical properties are improved through the addition of alumina. Thermal and microstructure stability of cordierite-mullite ceramics prepared from kaolin, magnesite, quartz and Al(OH)3 was studied by Albhilil et al. [109]. X-ray diffraction (XRD), scanning electron microscopy and mercury intrusion porosimetry (MIP) have been used to characterize the samples before and after heating-quenching test. The refractoriness of samples is found to be higher. XRD shows that heating-quenching procedure has led to crystallization of cordierite and mullite phases.

Magnesite-chrome composites have been prepared by utilizing sintered magnesite and friable chrome ore in presence of titania as additive [41]. Three types of batch compositions containing 5% Cr2O3, 18% Cr2O3 and 30% Cr2O3 have been selected for developing mag-chrome composites. The physical properties as well as thermomechanical properties and microstructural studies of the sintered aggregates have been evaluated.

The parameters influencing grain size of sintered magnesite such as temperature, cooling rate and various particle size were investigated by Aksel et al. [44]. For the samples sintered at 1700 °C, the decrease in the cooling rate from 10 to 5 °Cmin-1 and the increase in the dwell time from 19 to 50 min enhanced grain size significantly.

The reutilization of low-grade magnesium oxides for flue gas desulfurization during calcination of natural magnesite was also studied by Zermeno et al. [93]. Magnesium oxychloride cements with different amounts of active magnesium oxide were prepared with caustic magnesite and dolomite [99]. The fluidity, compressive and flexural strength were measured. The results indicated that the prepared materials with caustic magnesite and dolomite obtained a good engineering performance. Siadati and Monshi [66] have studied the effect of nature of binders for magnesite-based aggregates. In their work, sulfate binders, such as sulfamic acid, H2NSO3H; aluminum sulfate, Al2(SO4)3; ammonium sulfate, (NH4)2SO4; magnesium sulfate, MgSO4; calcium sulfate, CaSO4; sodium sulfate, Na2SO4; and potassium sulfate, K2SO4, are investigated. Cold crushing strength at different heat treatments of room temperature, 110 °C, 1100 °C, and 1400 °C is measured. Apparent porosity of samples without pulp and bulk density together with pH of the binder solution is evaluated and XRD and SEM studies are performed. Among these sulfate binders, MgSO4 was found to be the best. It is acidic in nature and develops strong bonds to the basic aggregate, MgO, at low temperatures. At high temperatures, it dissociates from MgO(s) and SO3(g) and the remaining portion of MgO is the same as host oxide, with no corrosion and easy deskulling. Basic binders such as calcium sulfate, sodium sulfate and potassium sulfate could not strongly bond the MgO aggregates.

5. Doloma ceramics

The term "doloma" refers to the calcined dolomite. Doloma consists of a phase mixture of lime (CaO) and periclase (MgO). Doloma is the semi-product used to produce dolomite refractory. They have extremely high melting points, as the eutectic for the CaO-MgO binary system occurs at 2370°C. Doloma is a material that is susceptible to hydration and thus its free lime ratio must be lower than a critical value. A usable doloma should have a bulk density greater than 3 g/cm3. Varying amounts of other impurities, including SiO2, Al2O3, and Fe2O3, are usually present. The amounts and types of the accessory oxides may have a large effect on the extent of densifica-tion, as it has been established that with these impurities sintering may occur by a liquid phase mechanism. It has been reported that the trivalent oxides, especially Fe2O3, enhance the sintering

during the commercial manufacturing process. Doloma is one of the attractive steel-making refractories because of its potential cost effectiveness and worldwide abundance [124].

Doloma is an excellent refractory for use in many steel-making applications since it is thermodynamically stable to slags and metal. The two major constituents of doloma, CaO and MgO, are among the more stable of the refractory oxides [5]. A doloma refractory containing less than 1% SiO2 is far more thermodynamically stable than high alumina or even magnesite refractories.

Refractory-grade doloma typically contains less than 2.5% impurities (silica, iron oxide, and alumina) and greater than 97.5% CaO + MgO. Most high-purity dolomite deposits are difficult to calcine and sinter to high density and usually require special methods to yield an acceptable refractory-grade doloma. The carbonate (dolomite) is converted to the oxide (doloma) and sintered to the required density in either a rotary kiln or a shaft kiln operating at 1850 °C or greater. There are basically two different production routes: single-pass process and double-pass process [124].

The good slag-resistant characteristics of doloma are a result of the presence of free lime not found in other refractories of lower basicity. In contact with slags not fully saturated with lime, a dense layer of recrystallized lime and dicalcium silicates forms on the hot face of the brick, limiting further slag penetration. Basically, the slag's reaction with the lime stops penetration, slowing down overall wear. However, slags deficient in lime but high in R2O3 oxides can be quite aggressive to a doloma brick. This is due to the formation of calcium aluminates and/or ferrites that have melting points significantly below 1600 °C.

Lingling and Min [49] have used dolomite as raw materials to produce MgO-based expansive agent. On the characteristics of decomposition of dolomite, the authors think it is possible to use dolomite as raw material, but the silica-bearing mineral is considered to combine the CaO released from dolomite to form silicate. The phases of MgO-based expansive agent are mainly MgO, C2S and a little amount of CaO. Yeprem et al. [40] have studied the effect of iron oxide addition on the hydration resistance and bulk density of doloma. The resulting bulk densities and apparent porosities of the sintered doloma are investigated. According to the results of experiments with 15 sintered samples, sintering temperature, soaking time and increase of mill scale amount were found to increase the bulk density and thus decrease the observed apparent porosity. In hydration resistance tests, it seemed that the same characteristics also increased the resistance. Natural dolomite powders obtained from caves, which give unusual high-resistance building materials, have been decomposed at high CO2 pressures in the temperature range of 1176-1246°C [37]. XRD traces for the final solid products, after the first half thermal decomposition, have shown that beside the XRD patterns for the calcite and MgO, the existence of a new structure with major peaks at 29 equal to 38.5° and 65°. This finding has been ascribed to a solid solution of MgO in cal-cite. Xie et al. [119] have studied the thermochemical activity of dolomite that occurred in dolomite-palygorskite (DP). The phase, microstructure, and morphology of DP were characterized before and after calcination using X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), and transmission electron microscopy (TEM). Additionally, the process of thermal decomposition of DPC was determined by thermal gravity (TG) and differential thermal gravity (DTG) analysis and was compared with that of common dolomite. The results showed that the decomposition temperature of dolomite that occurred in DPC started at 500 °C and ended at 780 °C, with a maximum peak at 745 °C.

Due to the open pore microstructure, MgO-CaZrO3 refractory composites are considered useful materials in various industrial applications. However, the reactivity of the MgO limits its utilization in acid conditions. Lavat et al [101] have used dolomite in the preparation of CaZrO3-MgAl2O4 by solid-state reaction. The

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thermal and structural changes that occur during the firing of the batches up to 1425 0C were studied by the combination of diffrac-tometric and infrared spectroscopic data at the most remarkable reaction steps. The final product is composed mainly by MgAl2O4, CaZrO3, and Ca2SiO4 phases and the optimal synthesis temperature would be 1425 0C. Tomba Martinez et al. [67] have studied the sintering behavior of periclase-doloma refractory mixes. Results showed that the analyzed mixes mainly contain periclase and doloma, with a wide granulometric distribution and different content of minor components (mainly, iron oxides). Material sintering began at temperatures higher than 1200 0C and was associated to liquid phase formation. Differences in sintering mechanisms with distinct amounts of liquid phase involved were determined in the analyzed materials and related to their iron oxides contents. Well-sintered specimens with higher room temperature mechanical strength and lower porosities were obtained from the mix with highest iron oxide content.

Mixes of calcium aluminate cements containing MA spinel were prepared using appropriate mixtures of Egyptian dolomite (MgO, 20.16% and CaO, 31.32%) with active alumina (99.50%) [25]. The cement mixes were prepared at 1600 0C using the sintering method. The results indicated that their mineralogical compositions were refractory MA spinel, in addition to CA and/or CA2 phases depending on the composition of the starting materials. The prepared cements exhibited a compromise between considerable strength and higher refractoriness.

Building bricks could be prepared from mixtures of low melting clay and low-grade dolomite rocks after firing at a relatively low firing temperature of 7500C [26]. Results showed that the thermal interaction between the constituents of clay and dolomite at 750 0C ensures better and relatively high mechanical strength for the resulting products. The XRD and DTA analyses indicated that the produced articles are composed mainly of carbonates and new formations of calcium silicates, calcium aluminates and MgO in amorphous or fine crystalline state. The fired products after hydraulic hardening at a dried environment recorded the highest mechanical properties.

A method of preparation of multi-impregnated pitch-bonded dolomite refractory brick for ladle furnace was described by Rabah and Ewais [65]. Brick samples were prepared from blend of calcined dolomite mineral and coal tar pitch. The blend was hot mixed and pressed under a compression force up to 151 MPa. Green bricks were baked for 2 h at temperatures up to 1000 0C. Voids in the baked bodies were filled with carbon by multiple impregnations using low-softening point coal tar pitch. Each impregnation step (30 min) was followed by calcination at 1000 0C. Brick samples containing 8-12 wt.% coal tar pitch binder and pressed under 108-151 MPa acquired quantify crushing strength. However, multi-impregnating favored the mechanical strength of the baked brick samples and improved their hydration resistance (>45 days). Dolomite brick samples containing 10 wt.% coal tar pitch and pressed at 108 MPa gave high hydration resistance (more than 60 days in normal condition) compared to the hydration resistance of the commercial bricks (30 days). The prepared brick samples have acceptable density, chemical stability, outstanding resistance and good mechanical properties that would meet the requirements of ladle furnace (LF) for steel-making industry.

Sintering behavior and hydration resistance of reactive dolomite was studied by Ghosh and Tripathi [80]. The hydroxide derived from dolomite was developed through precalcination of dolomite followed by its hydration. For hydroxide development, after pre-calcination, one sample was air-quenched and the other powder was furnace cooled before hydration. The air-quenched samples showed better densification than that of the furnace cooling process at the same temperature. Fe2O3 addition enhances sintering by liquid formation at higher temperature. The grain size of doloma

with Fe2 O3 addition is bigger than that without additive. Hydration resistance was related to densification and grain size of sintered dolomite.

The effect of natural dolomite admixtures on calcium zirconate-periclase materials microstructure evolution was studied by Szczerba and Pedzich [71]. In the materials synthesized from natural dolomites and ZrO2, two main phases were present - calcium zirconate and periclase. During firing of CaZrO3-MgO materials at lower temperatures, the presence of transient phases was detected (mainly ferrites and calcium aluminates, 4CaO-Al2O3-Fe2O3 or 2CaO-Fe2O3). These phases disappeared at higher temperatures. This is probably related to the dissolution of impurities in the main phases of CaZrO3-MgO. The material obtained from the mixture ofzirconium oxide and natural dolomite with the high impurities content has the highest densification level at 1500 and 16000C.

Diaz et al. [48] have studied the evolution of the phases and microstructure as a function of temperature and the processing route of alumina-rich refractory concretes elaborated from spinel, periclase and dolomite. Some authors have studied room temperature mechanical properties of high alumina refractory castables with spinel, periclase and dolomite additions [61]. The mechanical properties of refractory castables at room temperature are critical parameters for selecting suitable operating conditions for the structural design of refractory components. Bending strength studies at room temperature under several thermal treatments and the analysis of the elastic modulus of the refractories and their matrices point to two different mechanical behaviors. From room temperature to 10000C, the refractory castables present a pronounced non-linear stress-strain behavior both in the uniaxial tensile and compressive modes, as a result of damage to the microcrack network. Above 1000 0C, the refractory castables begin to sinter owing to a transitory liquid phase, the crystallization of calcium aluminate cement phases and the self-forming spinel phase. At higher firing temperatures, the sintering process leads to a strengthening of the mechanical properties.

Corrosion behavior of MgO/CaZrO3 refractory matrix by clinker was studied by Serena et al. [39]. The attack mechanism to substrates of 80% MgO and 20% CaZrO3 (wt.%) obtained from dolomite and ZrO2 mixtures and MgO and presintetized CaZrO3 mixtures is established. The studied matrix presented a clinker layer with good adherence that could prevent the corrosion of the refractory brick in work conditions, improving the corrosion resistance. The good corrosion behavior of the studied materials supports their use as a matrix in magnesia chrome-free bricks for the burning zone of rotary cement kilns.

Kalpakli et al. [31] have studied the effect of binder type and other parameters in synthesis of magnesite chromite refractories from process waste. The results of the experiments revealed the optimum type and content of the bond as MgSO4-7H2O and 8%, and optimum pressing pressure of the materials containing raw magnesite at 250 MPa. It was observed that when the chromite content of the material composition increased from 10% to 28% and 50%, the cold crushing strength (CCS) of the material has decreased, yet its porosity (P%) increased. This improves when the sintering temperature increased from 1450 to 15500C and 17500C. Four spinel-containing matrix compositions in the high-alumina region of the Al2O3-MgO-CaO ternary diagram were selected and prepared by using dolomite additions. The creep behavior of these matrices was studied in the temperature interval ranging from 1000 to 1400 0C [58].

6. Conclusion

Basic ceramics are an important class of refractories materials that enable processes to exploit extreme environments. In

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recent decades, tremendous efforts have been devoted to innovative processing of basic refractory ceramics and investigation of properties and their application in suitable fields. Because of the large number of papers in this field, this review mainly focuses on the processing and special conditions of the research works. Different processing routes for refractories ceramics have been developed for specific applications to satisfy the associated requirements for porosity, refractoriness, flexural strength and thermal properties. This paper provides a historical perspective on the elaboration of basic refractory from magnesite and dolomite, reviews typical processing routes and summarizes the properties of these materials.

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