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Corrosionerosion wear of refractory

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Article in Engineering Failure Analysis November 2014
DOI: 10.1016/j.engfailanal.2014.09.003

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Engineering Failure Analysis 46 (2014) 188195

Contents lists available at ScienceDirect

Engineering Failure Analysis

journal homepage: www.elsevier.com/locate/engfailanal

Corrosionerosion wear of refractory bricks in glass furnaces

A.M. Guzmn a,, D.I. Martnez a, R. Gonzlez b
a
Faculty of Mechanical and Electrical Engineering, Autonomous University of Nuevo Leon, Pedro de Alba S/N, Cd. Universitaria, San Nicols de los Garza,
Nuevo Len 66451, Mexico
b
Faculty of Civil Engineering, Autonomous University of Nuevo Leon, Pedro de Alba S/N, Cd. Universitaria, San Nicols de los Garza, Nuevo Len 66451, Mexico

a r t i c l e

i n f o

Article history:
Received 25 August 2014
Received in revised form 10 September 2014
Accepted 11 September 2014
Available online 30 September 2014
Keywords:
AZS
Corrosion
Molten glass
Wear

a b s t r a c t
This paper presents the failure analysis of aluminazirconiasilica (AZS) refractory bricks
located in the glass level in the tank of a furnace for melting glass, since is the region where
there is greater wear respect to the base. The wear of the refractory was evaluated after
4 years of campaigning, under thermal and mechanical loading during the glass manufacture. The analysis by scanning electron microscopy shows high porosity and the presence
of alkalis is also detected from the glass composition, being the phase aluminazirconia
silica (AZS),the one that shows better resistance to erosion wear by displacement of the
molten glass. The analysis yielded the following mechanisms of chemical wear, removal
of the vitreous phase toward the surface of the sample due to the increase in temperature
of the furnace, and therefore attack by vapors through the porosity caused by the exudation of the vitreous phase, as well as deterioration of the microstructure of the refractory
due to the formation of cracks. Because it is considered as the main problem in these types
of furnaces, the erosion wear is related to the ows of convection currents within the tank,
this occurs at the level of the glass, as it is at this point, where it has concentration of
thermal and mechanical loads due to movement of the molten glass.
2014 Elsevier Ltd. All rights reserved.

1. Introduction
Nowadays, refractory materials are important components in the equipment used for the production of glass; refractory
materials are considered mechanically and chemically high performance, being chemically inert at temperatures above
1400 C. The requirements to be met in the glass manufacturing industry are good physical and mechanical resistance to
the thermal shock of the working temperatures, and resistance to attack by molten glass which can dissolve the refractory,
modifying its properties [14]. The glass industry has made signicant progress regarding the type of materials used to
manufacture it, this is undoubtedly due to the change of clay-based refractory materials and prepared by pressing and electrocast materials sintering, this change in the manufacturing process was introduced by Fulcher in 1925 based on research
conducted at Corning Glass Co. A characteristic of the electro melted manufacturing is that the materials have a minimum
porosity (12%), this is of great importance to the refractory, since this minimizes the glass-refractory interface [58].
Additionally to the typical defects that cause rejections in the glass production like inclusions, bubbles, cracks, etc. are
also the failures in the refractory linings. Therefore an alternative in the materials used in the glass production furnaces
are aluminazirconiasilica (AZS) refractory because the ZrO2 has a high melting point and it is also a thermodynamically
stable oxide. These are widely used, although few have been reported about its failure mechanisms, so this paper reports
the failure mechanisms of electrocasted refractory type AZS [913].
Corresponding author.
E-mail addresses: anmgh@yahoo.com (A.M. Guzmn), dorairma@yahoo.com (D.I. Martnez), rhodio@hotmail.com (R. Gonzlez).
http://dx.doi.org/10.1016/j.engfailanal.2014.09.003
1350-6307/ 2014 Elsevier Ltd. All rights reserved.

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2. Experimental
The evaluation was made in new AZS refractory bricks and AZS bricks extracted from a furnace after 4 years campaigning,
Fig. 1a shows a furnace in use during the glass melting process, and the 1b indicates the placement of the samples took for
this research.
2.1. Materials
The new refractory was characterized by chemical analysis, X-ray diffraction, physical properties were determined and
penetration testing was performed, also a molten glass attack was carried out by the ASTM C621 [14]. The molten glass
attack was carried out by a penetration test placing 5 g of sodalime glass on the sample, the sample was placed inside
of an electric furnace to a temperature of 1450 C at a heating rate of 10 C/min, keeping this temperature in a lapse of
4 h, subsequent a slow cooling inside the furnace. Samples attacked were cut across and prepared for their observation
by SEM (Scanning Electron Microscope) in order to make a comparison with the attack observed in the refractory with
4 years campaigning.
Evaluation of the refractory used in the glass furnace.
In samples from areas where attack occurs (Fig. 2a) microstructural observations were made, through light and electron
microscope (JEOL-SEMJSM-6510LV) with semi quantitative EDS (energy dispersive spectrometry) phase analysis.
Subsequently, cubic cuts were performed to determine physical and mechanical properties of the refractory according to
the penetration prole of molten glass (Fig. 2b)
The material (glass) in contact to the brick walls was sodalimesilica commercial glass its typical composition is 71.16%
SiO2, 7.8% Na2O, 7.14% CaO, 0.92 Al2O3, 0.23 K2O and 0.16 MgO. The furnace temperature was 12001600 C.
2.2. Determination of surface wear
Surface images were taken using a stereographic microscope to determine the wear, hot face exposed to uid (see Fig. 1b).
Coupons of 5 by 5 cm2 were cut from the surface and the images were taken at a 50 magnication, observing cavities and
deformation of the material in the liquid glass ow direction, the volume wear was determined through image analysis of
the attacked zone, calculating the average loss of wall thickness on each section, once wear was determined in the samples, a
correlation between the nal microstructure and mechanical properties of the refractory was made.
3. Results and discussion
3.1. New refractory
The chemical analysis results obtained by the atomic absorption technique are presented at Table 1, mineral phases were
determined by X-ray diffraction founding alumina as corundum and zirconia as baddeleyite (see Fig. 3), physical property

Fig. 1. (a) Glass furnace, during melting process. (b) Brick sample extracted from the furnace (glass ow zone).

Fig. 2. (a) Transversal cut of the brick and (b) samples analyzed.

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Table 1
Chemical composition.
Oxide

% Weight

Al2O3
SiO2
ZrO2

43
20
37

Fig. 3. X-ray diffraction of a AZS refractory (B = baddeleyite, C = corundum).

Fig. 4. Overall electrofused product microstructure.

results indicate a density of 3.57 g/cm3 and a porosity of 3.5%, a low value compared with sintered refractory which porosity
percentages are around 15% [2].
The microstructural analysis of the new refractory has a matrix composition of SiO2Al2O3, in it, a gray phase was found
as ordered needles its composition indicates the presence of ZrO2 with low content of Al2O3 and SiO2, also some clear particles of ZrO2 or ZrO2SiO2 were located, Fig. 4.
The microstructural characterization of the refractory after static test indicates the presence of a glass interface (Fig. 5),
where the glass presents a normal chemical composition, clear phases of ZrO2SiO2 are observed and dark phases of
Al2O3ZrO2 as ordered needles (Fig. 6), alkalis penetration from the glass was detected, also the formation of phases of
SiO2Al2O3Na2O, EDS (energy dispersive spectrometry) analysis indicates the presence of Na2O and in the matrix are
detected also some composition phases SiO2Al2O3CaONa2OZrO2, which means penetration by molten glass.
The microstructural analysis shows that once the molten material enters an interface glass-refractory composition is
formed, which acts as a barrier to the penetration of molten material in contact to the refractory. The high density and
thereby low porosity of the electro fused refractory minimizes the surface area and the penetration by the molten glass
[15,16].

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Fig. 5. General image where the glass-refractory interface is observed.

Fig. 6. General image of the sample penetrated by alkalis glass.

Fig. 7. Stereoscope images: (a) glass, (b) side view image of the glass and impregnated refractory and (c) attack and high porosity of material.

3.2. Microstructural analysis of campaigning refractory

3.2.1. Visual inspection
The side views of the refractory cuts show the presence of a surface layer of glass (Fig. 7a), penetrated in the refractory
(Fig. 7b, transversal view), toward the end of the cut it is observed a microstructure attacked by the glass and with high
porosity (Fig. 7c).
3.2.2. SEM evaluation and semi-quantitative analysis (EDS)
The overall observation of the sample shows the presence of dendritic type formations [17], the white particles showed a
composition corresponding to zirconia (Z), the gray areas correspond to aluminazirconia (AZ), and also the presence of a
dark siliceous phase composition corresponding to the glass phase (G) with cracks along the entire sample. The chemical
analysis obtained by EDS indicates the presence of alkalis from the glass (see Figs. 8 and 9).
The evaluation of the region that was not in contact with the molten glass, but with the backup brick (second refractory
layer), shows the presence of sodium from the glass, which corroborates that the wear of the refractory is of the type
corrosionerosion as indicated earlier (see Fig. 10).

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Fig. 8. Microstructure of the sample penetrated by alkalis glass as can be seen by EDS.

Fig. 9. Overall microstructure of the sample.

Fig. 10. Chemical analysis of the nal sample in contact with the backup refractory.

3.3. Physical and mechanical properties

Considering the cuts shown in the gure, cubic samples were taken to determine density of the porosity and mechanical
strength following the molten glass penetration prole in the furnace according to Fig. 11.
In Fig. 12 are shown the results of density and porosity of the coupons identied as 1, 2, 4, 5 and 7 for the zones identied
as A, B and C, where is important to underline that the zone identied as B that corresponds to the coupon with white

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193

coloration of the refractory presents the lowest values of porosity which can be attributed to the densication of the matrix
due the attack by alkalis from the glass composition.
This can be corroborated with the results of the cold compressive strength test (CCS) presented in Fig. 13 corresponding to
the coupons identied as 3 and 6, and where it is observed that the region identied as B which corresponds to the white
region of the refractory has very high strength values respect to the other sections due to the almost null porosity of the zone,
which can be attributed to a higher density due the diffusion of alkalis from the glass.

Fig. 11. Sample cuts for determination of physical and mechanical.

Fig. 12. Densityporosity chart of coupons from different areas.

Fig. 13. Compressive strengths chart of the coupons from different zones.

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Fig. 14. Effect of the molten glass in the deterioration of the refractory [19].

3.4. Mechanism of corrosionerosion wear [18]

The mechanism of corrosionerosion wear observed at the walls of the refractory bricks can be described in four stages:
1. The penetration of alkalis from the glass occurs among the phases of the refractory AluminaZirconia (AZ) and
Zirconia (Z), combining with alumina mainly.
2. A layer of sodium aluminosilicate is formed (see EDS Fig. 8), enriched with Al2O3, has high surface tension, this occurs
at the interface or at the waterline of the molten glass. The high temperature causes the glass phase exudation, leaving
the appearance of cavities.
3. The formation of cavities between the phases AZ and Z on the refractory, caused by the exudation of the glassy phase,
produces the weakening of the link between them, causing cracking of the glassy phase and on the microstructure in
general.
4. Once initiated the chemical weathering process, mechanical wear due to erosion exerted by the uid glass, that
travels in high temperature at a constant velocity, accelerates the degradation of the refractory, peeling the fragile
material (removal of the vitreous phase) from the surface, leaving the appearance of large cavities, that get accentuated or scattered by the continuous movement of uid and the furnace temperature, as shown in Fig. 14.
All has been previously reported by Fueyo-Garcia [19], where reference is made about the creeping of the glasses in contact, the uid located in the oven and the one penetrated into the surface of the refractory; is due to the difference in surface
tension between the glasses in contact, where the one having the lowest surface tension gets dragged by the other one, this
phenomenon occurs in the meniscus of the water line of a molten glass bath, as observed in this research [20].
We have studied the failure analysis according to the theory of plasticity in refractory based on the model of Drucker and
Prager which concludes that the main cracks in AZS refractory bricks are due to the transformation phase from tetragonal to
monoclinic during thermal shocks, these allotropic changes create tensions that begin when temperatures drop below
1000 C, this causes the elastic dilatation near the center of the refractory element, these tensions can exceed the rupture
tension of the material, cracks are formed when the rupture tension is exceeded, large opening displacements are present
due the viscous ow at the high temperatures mentioned before [16].

4. Conclusions
From the obtained results can be conclude that:
1. The refractory AZS presents severe wear from the hot face (region in contact with the glass) that to the other side (cold
face) since the presence of alkalis from the glass phase is observed in the material, as well as cracking of the glass
phase due to the presence of these compounds.
2. The white appearance region of the refractory (zone B) presents resistance values greater than 448 MPa respect to
other sections due the almost null porosity of the zone, which can be attributed to the greater densication due
the alkalis diffusion from the glass.
3. The wear mechanism present was the type corrosionerosion showing four stages: penetration, exudation of the glass
phase, cracking of the glass phase and nally the erosion of the refractory surface.

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