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The Mechanism of Thermal Spalling in the

Wear of the Pierce-Smith Copper Converter

Article in Journal of the Ceramic Society of Japan August 2006

DOI: 10.2109/jcersj.114.672

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 Paper
Journal of the Ceramic Society of Japan 114 [ 8 ] 672675 (2006)

q j~ q~ p~ t~
m
p ` `

Pierce Smith


 
Christian GONI,
Vanesa BAZAN,
Mara Florentina BARBES, Elena BRANDALEZE,
Roberto PARRAand Luis Felipe Verdeja Gonz alez
Departamento de Ingeniera Metal urgica. Universidad Cat olica del Norte. Avda. Angamos 0610. Antofagasta. Chile


Instituto Argentino de Siderurgia IAS . Avda. Central y Calle 19 Oeste. San Nicol as. Provincia de Buenos Aires. Argentina



Universidad de Concepci on. Departamento de Ingeniera Metal urgica DIMET . Edmundo Larenas 285. Concepci on. Chile




Universidad de Oviedo Escuela de Minas. Siderurgia. Independencia 13. Oviedo 33004. Spain

The Nodal Wear Model
NWM constitutes a working tool that may be employed to study the processes of
differential corrosion in the Pierce-Smith converter
PSC with the aim of achieving significant improvements in
duration and productivity of the diverse lining alternatives that may be used. Both knowledge of the wear
mechanisms as well as the definition of the corrosion equations are necessary to apply the NWM to the PSC. By
means of the NWM, the outputs of corrosion in the tuyere zone of the PSC may be interpreted. The present
paper analyzes the wear mechanism for thermal spalling. An equation is proposed which, as well as justifying the
damage occasioned in the refractory bricks, it can also be used in the development of new designs.

Received August 15, 2005; Accepted June 15, 2006

Key-words : Pierce-Smith converter, Wear, Nodal wear model NWM , Thermal spalling

1. Introduction Table 1. Physical-Chemical and Mechanical Characteristics of the

One of the basic processes of copper pyrometallurgy con- Refractory of Magnesite-Chrome
sists in the treatment of copper matte or the white metal to
obtain blister copper copper saturated in oxygen in Pierce-
Smith converters PSC.1
A sound basis for increasing
productivity in copper-producing pyrometallurgy installations
is the transformation of discontinuous operations in continu-
ous workings or the increase of the average temperature of the
melts that take part in the processes.
Under these circunstances, the materials used for the linings
have to be able to guarantee a minimum number of working
hours under conditions of maximum thermal stress.
The Nodal Wear Model NWM has previously been used
as a tool in the interpretation and quantitative dynamic simu-
lation of the differential corrosion processes of the wall-plates
of electrical furnaces or in blast furnace hearths.2
4

For three years, the Copper Group DIMETOviedo has
been working on the adaptation of the NWM from theory to
copper pyrometallurgy operations. In particular, the differen-
tial corrosions that take place in the linings of the PSC have boundary conditions of the problem, may be measured ex-
been studied. The mechanisms and equations of corrosion that perimentally, Figs. 2 and 3. Another necessary contour condi-
affect the most punished zone of the PSC the tuyere zone tion for the solution of the thermal problem is the global
have been developed.5
Table 1 presents the physical-chemical transport coefficient, hg, between the melt and the refractory
characteristics of the customary material used in copper metal- lining. This coefficient may be calculated empirically, for ex-
lurgy for the linings of the PSC in the tuyere zone: direct ample, if the values that the temperature reaches at the differ-
bonded magnesite-chrome bricks.6
,7
ent heights of the lining are known. Using these data, the con-
The contribution of thermal fatigue was determined in the ductivity of the materials, the heat flow in the refractory and
corrosion of the PSC for the first time. Finally, with the nodal therefore the heat that is transmitted from the melt to the
corrosion equations, proposals can be made for new PSC refractory are determined in the stationary state.
coatings which enable operation temperatures and the oxygen However, the phenomenon of corrosion modifies the geo-
blowing into the tuyere air to be increased simultaneously. metry of the system. Hence, the solution of the thermal
problem after a period Dt or a number of cycles Nof of refin-
2. The nodal wear model
NWM: theoretical foundations ing is not valid, since a new distribution of temperature has
The stationary state determination of the thermal profile of been consolidated throughout the refractory material of the
the refractory lining of a converter allows the temperature in PSC. The calculation of the new geometry is obtained by ap-
the nodal meltrefractory interface to be known, given the plying the corresponding corrosion equation to each of the
conditions limits, Fig. 1. The temperature or heat flow nodes of the interface of the refractory lining with the melt.
throughout the external shell of the PSC, which is one of the This characteristic equation, which depends on the controlling
672
 Christian GO NI
et al. Journal of the Ceramic Society of Japan
Fig. 1. Cross-sectional of a PSC. Position of the thermocouple of
measure.
Fig. 2. Evolution of time with the averages temperature of ther-
mocouples TCA; TCB y TCC of the Fig. 1, in one PSC with 150
mm of average wear in the zone of tuyeres cycle No. 120 .
mechanism of the wear process, is determined phenomenolog-
ically or semi-empirically. On the other hand, the corrosion
equation is actually a function of the nodal temperature, the
temperature difference between node i and its adjacent nodes,
DTi, or between node i of the considered interface and the
temperature of the melt, T
Ti , Fig. 4. That is to say, the
speed of corrosion in node i of the interface, expressed in units
of length by time unit,:24
ncorrosionifTi; DTi; T
Ti 1
Even though the corrosion mechanisms that occur in the blast
furnace hearth or in a copper converter can not be compared,
from a general view of a process analysis, the velocity of cor-
rosion both in the blast furnace hearth as in the CPS is a varia-
ble function indicated in Eq. 1.
3. Mechanism of thermal spalling
In order to study the mechanism of thermal spalling in the
PSC, we need to consider:
114 [ 8 ] 2006 673
Fig. 3. Flow of heat Wm
2 . A In the interfase refractory-gas.
B In the influence zone of melt, both for one PSC with 120 cycle of
Fig. 2.
a The cyclical character of the operations during the
process of formation of fayalite slag, Fig. 2 for each conver-
sion operation, tap to tap, the refractory supports three to
four thermal cycles.
b The melt matte or slags penetrates through the open
porosity of the refractory, giving rise to a crust whose thick-
ness, ec, Fig. 4, is a function of the position of the solidus
isotherm of the melt within the refractory the situation of the
isotherm can be calculated using Finite Element Models
FEM, which best fit the conditions reflected by the ex-
perimental data, Fig. 1.
The derivation of the equation that represents the magni-
tude of the advance of a crack in the crust-refractory inter-
face, Fig. 4, from a preexisting defect in the material pores,
Table 1, Da, is based on an energy balance. The energy need-
ed to create a new solid-gas interface which depends on
the value of the surface energy, geffect, and on the microstruc-
ture, AVref, the area-volume of the matrix and disperse
components of the refractory is equal to the work of the
forces developed in the crust-refractory interface that appear
as a result of the thermal cycles of the system, N, and of the
different thermal-mechanical properties of the materials that
make up the crust and the refractory:5,6

H1 a
N
aN| B 0 2
N
1
where B is a nodal function that depends on the temperature-
position of the node i, and on the microstructural characteris-
tics of the refractory:
B Ca ag DT E e ee 
c r c c c 1
3
effect r i


A
V ref
C is a constant of cogoverning adimensional proportionality
of all the simplifications introduced in the derivation of ex-
pression 2, ac and ar are, respectively, the coefficients of ex-
pansion of the crust and the refractory, Ec, the elastic module
of the crust, DT the magnitude of the thermal jump, er and ec,
are, respectively, the thickness of the refractory and crust and
finally a0 is the mean size of the preexisting structural defects
of the material Table 1.
 674 The Mechanism of Thermal Spalling in the Wear of the Pierce-Smith Copper Converter

Fig. 4. Temperature's profile along of the interface melts-refractory-steel-air.

During the first refining operation in the PSC, when N1

remember that three thermal cycles exist in the operation of
conversion of the copper matte, the size of the structural
defects, a1, is equal to:
a120 mmB 4
where 20 mma0, is the mean size of the structural defects
present in the refractory, Table 1.6
,7

Whereas for cycle N:
B
aNaN1 5
N

4. Results and discussion

The following experimental findings were verified for a PSC
in which a material presenting the characteristics given in
Table 1 was installed in the tuyere zone, with a thickness er
609.6 mm,:5

a Around cycle 62, 102 mm of refractory became
detached. In this case, the thickness of the crust, ec, is identi-
fied with the 102 mm of detached refractory.
b In cycle 118, 80 mm of refractory became detached.
As in the previous case, ec, is identified with the thickness the
detached refractory.
c Finally, from cycle 118 to 450 five operations per
day, detachment of 30 mm of refractory took place for each
of the 58 production cycles of copper blister. In this last situa-
tion, no identification exists between the thickness of the
produced crust caused by infiltration of melt and the magni-
tude of the detached refractory.
From these experimental data and bearing in mind the
thermal-mechanical model developed in Eqs. 2 and 3,
Figure 4 and Fig. 5, the values of constants B and a0 in Eq.
2 were calculated
1 From the first cycle to cycle 62: B346 mm and a020
Fig. 5. Variation of thickness' refractory in the tuyere N
15 central
position for different tests nine linings. The solid line is the ex-
perimental correlation tests. The dashed line is the simulation by
means of NWM.
mm.
2 Between cycles 62 and 118: B346 mm and a045
mm.
3 From cycle 118 to 350, four stages are considered:
The first from 118 to 176: B341 mm and a070 mm.
The second from 176 to 234: B337 mm and a095 mm.
The third from 234 to 292: B333 mm and a0120 mm.
And finally, the last stage, from cycle 292 to 350: B328
mm and a0145 mm.
From cycle 350 until the end operation 450, the penetra-
tion of the melt in the refractory is so small that, during the
one hundred last processes of refining, the wear mechanism of
the refractory would be identified with chemical corrosion. To
 Christian GO NI
et al. Journal of the Ceramic Society of Japan
quantify the importance of the thermal-mechanical mechan-
ism in the corrosion of the PSC, it can be concluded that 35 construction of the linings.8

of the total wear of the refractory may be attributed to chemi-
cal processes, whereas the remaining 65 would be the conse-
quence of the thermal spalling experienced by the lining.
With the aim of applying the NWM to the corrosion of the
PSC, it must borne in mind that the crust layer below node i or
above node ic-r in the tuyere zone, Fig. 4, disappears when
aN2030 mm the critical fracture size that may be attained by
the defects according to the data in Table 1.
The possible formation of unstable accretions in Fe3O4,
Fig. 4, is a hypothesis that has not been experimentally tested.
It may be that, if one uses a PSC design that allows a very
reduced, Ti, for example: using air-water external refrigera-
tion or placing a line of carbonaceous refractories of high
thermal conductivity between the magnesite-chrome bricks
and the steel plate, Fig. 4 this might result in forming stable
crusts, with Fe3O4, as the main component.8

The smaller the value of Ti, the greater the viscosity of the
molten metal that is in contact with node, i, and the lesser the
capacity of infiltration of the fluid in the refractory. The value
of constant B decreases, Eq. 3, when the nodal temperature
Ti is lower.
As the high-conductivity carbonaceous material 2550 W
is given on the contribution of chemical corrosion 35  and
m1
K1  in contact with the magnesite-chrome bricks
small-conductivity, Table 1 provoke an increase in the heat-
flow, the value of Ti decreases global heat transport
coefficient, hg, and temperature, T, remain constant.
Therefore, the high-conductivity carbonaceous material 25
50 Wm1K1 , decrease the B constant in Eq. 3 but do
not affect the different values that constant, a0, might have in
Eq. 4 in the formation of the six crusts that they create and
which come off during the copper refining in the PSC, Fig. 5.
The presence of second phases that are perpendicular in the
direction of the contra-refractory interface steel fibres or
fused MgO with large sized crystals: 1000 mm increase the su-
perficial energy of the material fracture, geffect, and therefore
decrease the value of B, in Eq. 3.
Finally, in the Fig. 5 results are given of a series of ex-
perimental measures corresponding to the wear undergone by
the refractory in the zone nearest a PSC nozzle. Together with
the continuous adjustment correlation, the analysis according
to NWM is given describing the damage incurred from the
chemical corrosion caused by thermal spalling.
5. Conclusions
The NWM constitutes a valid alternative for the study of the
differential corrosions that are observed in the refractory
linings of the PSC in the tuyere zone, Fig. 1. By means of the
application of the NWM to the PSC, different alternatives to
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114 [ 8 ] 2006 675
magnesite-chrome bricks may be studied and simulated for the
The first consequences of the research work of the Copper
Group in the application of the NWM to the PSC aimed at
increasing the number of cycles while maintaining the MgO
Cr2O3FeO system as the refractory system, are the following:
a To situate a carbon product of high conductivity
2550 Wm1K1  below the working refractory in contact
with the steel shell. When increasing the thermal conductivity
of the coatings, the nodal temperature drops, Ti Fig. 4, and
therefore the corresponding thickness of the stable scab, ec, or
the value of the B constant in the Eq. 3 also drops.
b To use a magnesite-chrome system reinforced with
radially-oriented steel fiber perpendicular to the crust for
the refractory in the tuyere zone. By means of this operation,
the surface energy of fracture, geffect, increases and it conse-
quently causes a decrease in the B constant obtained, Eq. 3,
with the corresponding decrease in the damage of the coating
refractory.
The paper reveals for the first time a quantitative analysis of
the corrosion process of the refractory in zones close to the
PSC nozzle area. Apart from studying the influence of the
variables that intervene in the wear process, a first evaluation
of thermal spalling 65  in the damage undergone by the
refractory.
Acknowledments The authors wish to thank the Ministry of
Education, Science and Technology Spain
MAT200300502,
the Chagres smelting plant, Anglo-America, Chile, and the
Argentine Iron and Steel Institute for the help received in the
development of this research work.
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