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ScienceDirect Procedia Engineering 153 (2016) 118 – 123

XXV Polish – Russian – Slovak Seminar “Theoretical Foundation of Civil Engineering”

Controlled process of liquid-phase sintering due to low-fusible melt forming Natalya G. Chumachenkoa*, Vladimir V. Tyurnikova, Ekaterina V. Petrovaa a

Samara State University of Architecture and Civil Engineering, 194 Molodogvardeyskaya St., Samara, 443001, Russia

Abstract The article presents the analysis results of known state-transition diagrams of two- and three-component systems. Triple aluminosilicate and silicate systems have been investigated. Considering two-component systems the ɋɚɈ ones have been analysed. Oxides, providing binary and ternary low-fusible eutectic are defined. Fluxing power of fluxing oxide in aluminosilicate systems, including argillous raw material is determined. Compositions in three-component silicate system are defined, providing the formation of low-fusible melt at less than 500 0ɋ, that is 2000ɋ lower than low-fusible clay. The results are used for controlled process of liquid-phase sintering: ceramic material production; composition development of raw batches, which neutralize harmful influence of carbonated impurities. © by Elsevier Ltd. by This is an open © 2016 2016Published The Authors. Published Elsevier Ltd.access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/). Peer-review under responsibility of the organizing committee of the XXV Polish – Russian – Slovak Seminar “Theoretical Peer-review responsibility of the organizing committee of the XXV Polish – Russian – Slovak Seminar “Theoretical Foundation Foundation under of Civil Engineering. of Civil Engineering”. Keywords: liquid-phase sintering; state-transition diagrams; ceramic materials; neutralization of carbonated impurities.

1. Introduction A large group of construction materials is produced with the process of heating raw materials or special raw batch. For some materials heating provides obtaining of active elements from dissociation of raw material. These materials include: gypsum binder, lime, magnesian binder. Heating is essential for forming new elements and a necessary structure for many materials. These construction materials include: ceramic brick, tile, roof tile; portlandcement clinker and alumina cement. For above-listed ceramic materials the formation of ceramic body starts with solid-state sintering and continues with liquid-phase sintering. ________ * Corresponding author. Tel.:+7-927-745-0464 E-mail address: [email protected]

1877-7058 © 2016 Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license

(http://creativecommons.org/licenses/by-nc-nd/4.0/). Peer-review under responsibility of the organizing committee of the XXV Polish – Russian – Slovak Seminar “Theoretical Foundation of Civil Engineering”.

doi:10.1016/j.proeng.2016.08.090

Natalya G. Chumachenko et al. / Procedia Engineering 153 (2016) 118 – 123

2. The factors influencing liquid-phase sintering The main factors influencing liquid-phase sintering are: chemical and mineral composition; dispersability and degree of raw material homogenization, granulometric distribution; degree of densification; heating temperature; atmosphere; retention time, etc. The defining factor is melt quantity . If 20...35 % of melt is formed with heating, then there are partially sintered materials, such as: ceramic brick; wall tile; drain pipes. Such amount of melt is enough for contact adhesive bonding of refractory elements and fractional void-filling there. Heated materials have opened porosity of more than 5 %. Fully sintered materials are characterized by 35...50 % melt enough for void–filling and formation of a singlepiece die. Water absorption capacity of materials from this group is less than 5 %: ceramic roof tile, floor and building tile - 2-5 %; clinker brick, stoneware drain < 2 %. And sintering degree is increased due to increasing quantity of new-forming melt. Pyroplastic mass is formed if there are more than 50 % of melt. If there is gas evolution in this phase, bloating of mass can occur, that is possible while producing keramzite gravel. If there is no gas evolution, then melting of heated pieces takes place with a loss of form. It is possible to calculate the quantity of melt for two- and three-component systems in homogeneous mass using the known data of state-transition diagram [1, 2]. Binary and triple state-transition diagrams can be used to define: temperature of initial eutectic melt formation ; interrelation between the melt and a solid phase at any temperature; temperature of system transition into melt. Eutectics with more than four components cannot exist in homogeneous masses. The formation of two- and three-component eutectics which are well-studied is more possible. The analysis of more component systems has purely applicable nature and can be applied only in a few fields of industry. Amount of melt for multi-component homogeneous aluminosilicate systems can be calculated with the suggested method [3-5]. This method also allows to define melt composition and undissolved residue composition in ceramic batches while heating. The method is based on usage of known state-transition diagrams of triple aluminosilicate systems [1] and on the results of numerous researches on phase transformation of aluminosilicate raw materials at a wide range of temperatures. The researche was first conducted by U.D. Kingeri and A.I. Augustinik, then continued by S.P. Onatsky, V.F. Pavlov, V.V. Eremenko [6-11]. This method is also based upon theoretical and practical research made by G.V. Kukolev, A.Ⱥ. Novopashin, etc. [12-18]. 3. Fluxing power of fluxing oxides 3.1 Fluxing power of fluxing oxides in aluminosilicate systems Alkaline oxids are usually found in argillous raw materials. The quantity of initial eutectic melt for homogeneous systems is defined by the type of fluxing oxides and their amount. If Ʉ 2 O oxide is present in raw material, then the first aluminosilicate melt is formed at 710 0ɋ. With the lack of Ʉ 2 O oxide, oxide Na 2 O provides the formation of initial eutectic melt at 740 0ɋ. If the temperature is increased up to 985 0ɋ (for K-containing systems) or up to 1050 0ɋ (for Na- containing systems), compositions of alkaline melts will be varying according to eutectic lines in corresponding systems Ʉ 2 O - Al 2 O 3 - SiO 2 or Na 2 O - Al 2 O 3 - SiO 2 [1]. Fluxing power of fluxing oxides in aluminosilicate systems is given in Table 1. It is suggested to divide fluxing oxides according to fluxing power: the first group - high fluxing power , the second- low fluxing power. The first group - K 2 O (Ʉ+) ɢ Na 2 O (Na+). The second one - CaO (Ca2+), MqO (Mq2+) and Fe 2 O 3 (Fe2+). K 2 O (Ʉ+) has the highest fluxing power. The presence of 1 % K 2 O oxide in chemistry of aluminosilicate raw material can provide the formation of 15 % alkaline aluminosilicate melt at 985 0ɋ. The second one is Na 2 O. The other fluxing oxides can provide a lot lesser quantity of melt. Fe 2 O 3 (Fe2+) has the least fluxing power (2,20 %). Table 1.Fluxing power of fluxing oxides

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Group according to fluxing power

Oxide / Basis Ion K 2 O Ʉ+

Calculated eutectics [5]

Temperature of forming eutectic melt, 0ɋ

15,00

K2

985

12,50

Na 2

1050

Quantity of melt, %, on 1 % oxide

High +

Na 2 O / Na

CaO / Ca2+ Low

3,77

C1

1170

2+

MqO / Mq

3,40

M1

1345

Fe 2 O 3 / Fe2+

2,20

F1

1073

3.2 Fluxing power of fluxing oxides in silicate systems In aluminosilicate systems the most low-fusible eutectics can be formed at 710 0ɋ with K 2 O. The analysis of presented state-transition diagrams[1] has proved that it is impossible to form much more lower-temperature melt in known aluminosilicate systems. At the same time the production of ceramic materials is considered to be one of the most energy-intensive technologies. The decrease of baking temperature is the main factor that saves energy and helps to turn to energysaving technologies. As a liquid-phase sintering is the basic process for ceramic body formation for fabrication of construction ceramics, then the search for compositions providing more low-fusible melt is of great importance. The analysis of triple silicate systems has shown that the most low-fusible eutectics is formed in the system Na 2 O - FeO- SiO 2 [1] at lower than 500 0ɋ. 4. Liquid-phase sintering control for fabrication of ceramic materials In the process of heating clays a liquid phase takes place because of more low-fusible eutectics in systems (R,R 2 )O-Al 2 O 3 -nSiO 2 . Having used the developed methods [3-5] compositions of sintered ceramic aggregate [18], high-tensile ceramic aggregate [19-20] have been designed. Achievement of higher tensile properties has been reached by the purposeful modification of argillous raw materials with compounds from industrial waste that improves liquid-phase sintering [21-26]. Computer modelling has been applied while designing raw batches [27,28]. Raw mixture for wall ceramics (ceramic brick, stone and building blocks) has been developed. It provides more strength at lower heating temperature [29, 30]. Suggested raw mixture provides forming of melt at lower heating temperatures, than in low-fusible clays. Such clays without additives are characterized by the initial melt at 710740 0ɋ because of more low fusible eutectics of K 2 O-AI 2 O 3 -SiO 2 ɢ Na 2 O-AI 2 O 3 -SiO 2 systems [3]. The sequence of low-fusible eutectics formation is shown in Fig/ 1. Compound additive containing liquid glass, pyrite cinders, diatomite and coal provides much more low-fusible melt at lower than 500 0ɋ due to low-fusible eutectics of Na 2 O-FeO-SiO 2 system [1]. Interrelation between the listed-above components is calculated in such a way that at the beginning there is a reduction of Fe oxide from pyrite cinders in reductive conditions, created by the coal and then , Na 2 O, FeO and SiO 2 oxides form low-fusible melt of the composition,. %: Na 2 O - 12,2; FeO - 25,8; SiO 2 - 62 [27, 28].

Natalya G. Chumachenko et al. / Procedia Engineering 153 (2016) 118 – 123

Fig. 1. The sequence of low-fusible eutectics formation.

5. Control of liquid-phase sintering for developing composition of raw batches neutralizing harmful effects of carbonated impurities The majority of low-fusible bricked and roof-tiled clays contain carbonated impurities, causing such defect as blisters [31]. One of the ways to reduce harmful effects of carbonates is «encapsulation» with ɋɚɈ layer, formed with additives [32]. The additives are used to form low-fusible melt with calcium-containing base.

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Binary calcium-containing state-transition diagrams have been analyzed to define the types of additives [2]. It is determined, that the formation of binary low-fusible melt with only Cr 2 O 3 ɢɊ 2 Ɉ 5 is only possible up to 1100 0ɋ (average temperature of brick heating) – see Fig. 1. ɋɚɈ forms the melt with other oxides at much higher temperatures. Eutectics of CaO-Cr 2 O 3 , system is of special interest because of formation temperature of 1022 0ɋ. This temperature is a little higher than the temperature of CaCO 3 dissociation, but is lower than the temperature of construction ceramics heating . In triple calcium-containing systems the most low-fusible melt can be formed at 1440 0ɋ [1], but it can`t be applied in industrial construction ceramics. Soitisofnovalue. 6. Summary 1. The analysis of present binary silicate and triple silicate and aluminosilicate state-transition diagrams is made. The most low –fusible double and triple eutectics are defined. 2. The fluxing power of fluxing oxides in aluminosilicate systems including argillous raw materials is determined. It is suggested to divide fluxing oxides according to their fluxing power into 2 groups: with high and low fluxing power correspondingly. The first group is K2O (Ʉ+) and N a2 O (Na+). The second one - CaO (Ca2+), MqO (Mq2+) and F e2O3 (Fe2+). 3. The obtained data on the fluxing power of fluxing oxides allows: • to predict the quantity of eutectic melt according to the chemistry of aluminosilicate raw material; • to predict dynamics of melt formation while increasing the heating temperature by the calculated method • to control and regulate the quantity of forming melt due to reasonable choice of type and amount of additives; • to regulate the degree of liquid-phase sintering and physical-mechanical properties of heated ceramic materials correspondingly; 4. It is possible to form low-fusible melt in the Na 2 O-FeO-SiO 2 system at lower than 500 0ɋ because of the most low-fusible eutectic, that is 200 0ɋ lower than in low-fusible clays. 5. It is possible to form low-fusible melt in ɋɚɈ-Cr 2 O 3 system at 1022 0ɋ. Low-fusible argillous raw material with high level of carbonated impurities modified by chrome-containing additives will allow to create a layer on the ɋɚɈ surface and reduce blisters. References [1] State-transition diagrams of silicate systems: Reference guide. Volume. 3. Triple systems / N.Ⱥ. Toropov, V.P. Burzakovsky, V.V. Lapin .: Nauka, Leningrad, 1972. 488 p. [2] State-transition diagrams of silicate systems. Reference guideVolume. 1. Binary systems / N.Ⱥ. Toropov, V.P. Burzakovsky, V.V. Lapin, N.N. Kurtseva,.: Nauka, Leningrad, 1969, 822 p. [3] Ⱥ.Ⱥ. Novopashin, Ⱥ.Ⱥ. Shentyapin, N.G. Chumachenko, Defining the quantity and melt composition, formed by heating ceramics. 'HSRVLWHGPDQXVFULSWʋ7KHKDQGERRNRIXQSXEOLVKHGDQGGHSDUWDPHQWDOSDSHUVȼɇɂɂɗɋɆ. Volume 11. Glass and glass pieces. Ceramic materials and pieces. Nonmetallic and non-PHWDOOXUJLFDOPDWHULDOV9ROXPHʋS [4] N.G. Chumachenko, Ⱥ.N. Chudin, New graphic-calculated methods for predicting the quality of construction ceramics // Collection of research papers: Urban planning, modern construction structures, technologies, engineering systems. Magnitogorsk: MSTU, 1999. pp. 219229. [5] N.G. Chumachenko, Method calculating the quantity and melt composition, formed by heating ceramics, with state-transition diagrams of alumosilicate systems // Works of XXII Rusian-polish-slovak workshop «Theoretical basics of construction». Section «Composition materials, technologies and management of construction production», Procedia Engineering, T. 91. 2014. pp. 381-385. [6] Ⱥ.Y. Augustinik, Ceramics. 2-nd edition. L.:, Leningrad. 1975. 592 p. [7] U.D. Kingeri, Introduction to ceramics. 2-nd edition. Ɇ.: Stroyizdat, 1967. 499 p. [8] V.V. ȿremenko, Research on raw material quality calculation of optimal banch composition based on state-transition diagrams of vitreous (glass) systems // Collection of research papers of All-Soviet Union workshop for workers of expanded clay production. Kyibishev, 1978. pp. 77-78. [9] S.P. Onatskiy, Expanded clay production. 2-nd edition. Ɇ.: Stroyizdat, 1971. 312 p. [10] V.F. Pavlov, Physico-chemical basics of construction ceramics heating. Ɇ.: Stroyizdat, 1977. 240 p. [11] V.F. Pavlov, V.S. Mitrokhin, Investigation of phase modification in clays of various mineral composition in the process of continuous heating // Works of RI of Construction Ceramics. 1975. Volume 40-41. pp. 204-221. [12] G.V. Kukolev, Silicon chemistry and physical chemistry of silicates. Ɇ.: Vysshaya Shkola, 1966. 464 p.

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