Professional Documents
Culture Documents
Charles R. Beechan
Program Chairman
May 5-9, 1985
ISSN 0196-6219
Published by
The American Ceramic Society, Inc.
65 Ceramic Drive
Columbus, Ohio 43214
@The American Ceramic Society, Inc., 1986
Editor
William J Smothers
Director of Publications
Donald C. Snyder
Production Coordinator
Carl Turner
The American Ceramic Society assumes no responsibility for the statements and opinions advanced by t h e contributors to its publications. o r by the
speakers at its programs.
01970. The fee for articles published before 1986 is also $2.00 per copy. This
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Preface
This issue of Ceramic Engineering and Science Proceedings features papers
from the Refractories Division 1985 technical programs. The 29 papers cover
the wide interests of our Division, including processing and properties of raw
materials and their effect on physical properties of refractories made from
them. Statistical process control is discussed in two papers. Recently developed
methods of using X-ray computed tomography are discussed. Design,
modeling, and application of refractories are covered in several papers. Use
of refractories in the steel industry, one of the largest applications, is the subject of 10 papers. Other uses in glass, petrochemical, and cement industries
are covered. Also, several of the papers are by authors from overseas. As
chairman of the Program Committee for the Refractories Division, I want
to thank the authors and session chairmen who contributed to the meetings
and in the preparation of this publication.
Charles R. Beechan
Program Chairman
Refractories Division
American Ceramic Society
iii
Table of Contents
The Deming System After One Year: One
Companys Experience ......................................
14
27
40
.........................................
52
................................
58
75
79
100
Thomas H. Elmer
Zircon Processing
K. K. Cheang
K. Kurata
131
145
167
Charles A. Schacht
.....................
185
196
209
220
229
M. A. Stett
Charles A. Schacht
Curtis E. Zimmer
. . . 236
243
261
............................
267
.......................
....... 277
269
284
vi
........................................
301
314
H N 0 3 , and H,SO,
James P. Bennett
vii
This diagram helps us to focus on the potential causes of the inherent process
variability. Only management can make the necessary changes in these areas
to improve performance, and it is only by making changes that we can reduce
the chances of making defective product. Once we understand what composes
our process, we can make required improvements with minimal capital expenditures. Not every process requires expensive new machinery. Yet, even in these
cases, the charts give us a solid basis for selling such a need to upper
management.
The Deming philosophy basically requires: (1) to get the process stable,
(2) to get the process comfortably within valid specifications, and (3) to make
the probability of producing defectives approach zero while spending the least
amount of money necessary.
How We Have Implemented the Program
Our initial exposure to the Deming approach occurred in November 1983
when our vice-president of manufacturing attended a five-d seminar which
outlined what upper management must do to implement a Deming program.
In February 1984, the quality control manager, the manufacturing engineer,
and a process engineer were sent to another five-d seminar on SQA within
a Deming approach. Primarily, we were to learn the Deming system while
refreshing our SQA skills. Essentially, we were being trained on how to push
the program to the test of the company.
In May 1984, we officially kicked off the program. Upper management
informed the entire management team of the new philosophy, its importance,
and how everyone would fit into the new program. A preliminary outline of
the required training was presented. The first seminar was to be conducted
by an outside consulting firm while all others would be led by our own personnel. Also at the kick-off, management announced the formation of four
levels of committees, ranging from upper management to floor operators.
Figures 2-5 summarize the structures of these committees. Basically, these committees form Quality Circles where the problems of quality and productivity
are addressed in detail and where strategies for improvement are developed.
Upon each committee sits at least one person well trained in statistics who
serves as an advisor.
Upper management plus the heads of each corporate staff department
form the first level or steering committee which establishes overall policy and
oversees its implementation. Naturally, it was the first to meet and continues
to meet on an approximately monthly schedule.
The second level consists of upper plant management plus all manufacturing department heads. This committee develops, on a plant level, policies and
programs for achieving the objectives established by the steering committee.
In theory, this committee should meet at least quarterly; however, it meets
less often.
All manufacturing supervision, divided by product area, forms the third
level committees. This level actually puts into practice the bulk of the program. These committees discuss the particular problems within each department, how these problems affect other departments, and how we can best
attack and solve them. Generally, these committees meet every two to three
weeks.
The final level consists of the entire individual department, including the
supervisors, all assistants, and all operators. Although this level has not started
3
to meet, these committees will function much like the more common Quality
Circles. Here, each department will discuss its particular quality and productivity problems as well as possible solutions. The supervisor, assisted by a statistician and engineers, evaluates and implements these suggestions in a systematic
manner.
The committee structure provides a formal and systematic basis for communicating quality problems to and within management. In different ways,
each committee seeks: (1) to identify our major problem areas, (2) to isolate
the causes of these problems, and (3) to correct these causes in the most cost
efficient way. The supervisors use control charts as tools to identify what the
major problems are and when they occurred. The committee structure provides a basis for communicating these problems to the level of management
required to correct the situation.
Naturally, a committee structure by itself does not correct problems. We
have expended a great deal of effort to train our people in both the philosophy
and the techniques of this program. To date, a consulting firm has conducted
one seminar on our plant site for all departmental supervisors. An in-house
team has conducted three other seminars for groups ranging from upper
management to assistant supervisors. Before we are finished, all employees
will receive some form of training in this program. Seminars, however, only
plant the seed. Three of us have had to nurture the further growth by one-onone follow-up instruction, particularly on how to sample, how large a sample
to take, how often to sample, how to chart, how to read the charts, and how
to use the charts as management tools.
Presently, all departments have ongoing SQA projects. Generally, we have
the management team establish in the third level committees what problem
area to attack. First, the supervisor in that departmetn works with an operator
to collect the samples, which the supervisor grades or measures and then charts.
Later, the operator will begin to grade the sample. Ultimately, the operator,
once he or she is familiar with the routine, charts the information as well.
In many departments, we have achieved this final step with some operators.
Yet, in all cases, we are using the charts to make fundamental decisions.
Areas Of Progress
We have seen significant improvements in many areas of our operation;
however, two require special mention. In our ceramic pencil lead process, we
have reduced our reject rate from over 10% in 1984 to less than 3% for 1985
to date. In essence, we have increased by more than 7% the productivity of
this department without spending any extra money. Consequently, an area
where we could not produce enough, now produces to excess.
Principally, we have achieved this improvement by working closely with
our suppliers. By monitoring when we begin to use new shipments of raw
materials, the important characteristics of these materials, and the process
variability that results in the important lead characteristics, we have been able
to establish meaningful raw material specifications. Certainly, raw materials
are not our only problem. Yet, with our SQA program in place, we have
operated this department at reject rates of less than 1'70 for significant periods
of time. We hope to beat this rate consistently by the end of the year.
Our injection molding department had been the worst area in our operation in terms of both quality and productivity for years. Performance was never
Problem Areas
Of course, this program has not been all peaches and cream. We have
encountered several problems, which we have summarized as follows:
(1) Resistance to the program from our people,
(2) The amount of time,
(3) Less than total commitment from our management, and
(4) Lack of understanding the true intent of the program.
Naturally, people tend to resist new programs, particularly ones that they do
not fully understand and which require a significant change in routine. Our
people have been no different. Some still hope that this program will simply
disappear so they can get back to their more familiar routines. However, most
people realize: (1) the program is not going away any time soon, (2) it really
is not that complicated, and (3) it really makes everything run better in the
long run. As people become more aware of what the program will do for them,
their resistance breaks down.
The amount of time the program requires presents two problems. First,
our supervisors have had to spend a great deal of their time learning the
methods, applying them, and finally constructing control charts. Much of the
present resistance comes from the lack of time many of our supervisors have
to give to it. However, getting the charts to the operators does free back much
of their time. Unfortunately, we usually start another project in that department soon thereafter, and the cycle begins anew.
Second, the program itself takes several mo before one can begin to see
tangible results. Even then, the first significant improvements are always the
easiest to achieve. Consequently, one must wait several more mo before seeing
more improvement. People are impatient beings. Particularly when you invest
a great deal of time and effort, you expect to see progress quickly. Unless
you are careful and persistent, either people become frustrated and lose interest
or the charts become ends in themselves rather than tools for improvement.
In either case, the program is almost certainly doomed to stagnate.
This last point illustrated how important total management commitment
is to this program. Without constant pressure and support from above, as well
as some pushing from within, this program ultimately stagnates. Companies
who give this program its highest priority, without rushing the process, will
see more dramatic results in less time. Our management has been inconsistent
in how it rates this programs priority. We have been fortunate, though, since
management has always supported our program and has been patient in seeing
results. However, there have been times when management should have sent
more consistent signals about the programs importance. As a result, we are
making slow and steady progress which could be improved.
The final major problem actually underlies all of the others. In the final
analysis, only a few of us really understand the true intent of this program.
Too often people view our attempts as just one more thing that has to be done,
as just one more meeting to be attended. Too often people only get their charts
up-to-date in order to get ready for the next SQC meeting, rather than using
them as management tools. As soon as the meeting is over, the charts are
forgotten about until the time comes for the next meeting. Management, rather
than using the charts as a basis for defining and discussing problems, often
times forgets that they even exist. For this program to bear its fullest fruit,
everyone involved must learn to live by the charts and to die by them. The
program challenges us to manage in a new and different way. Only when we
6
accept and understand this fact can we really expect any SQA program to fly
as it is intended.
Conclusions
SQA, rightly understood and implemented, is the only way to manage
any process. However, it does require a lot more than running control charts.
SQA demands that we learn to listen to, and later to communicate with, our
process. Statistics provides us with a very efficient and effective tool, but like
any tool, we must learn how to use it. In so doing, we can improve both our
quality and our productivity. If we do not, we, as corporate entities, may not
survive.
Goals and slogans do not solve problems. Only people solve problems.
Certainly goals and slogans affect peoples attitudes, but people really need
the proper tools to solve problems, hence, the need for training and management support.
iv. Closely examine the impact of work standards. Do they consider
quality or help anyone do a better job?
In most cases, work standards provide a rigid measure of ones performance. Get out so many parts each shift, or else! Such an attitude betrays
a complete disregard for the quality of ones performance. Even the attitude
of get out so many good quality parts, if rigidly enforced, leads to severe
quality and morale problems when breakdowns in the system occur. Further, rigidly enforced work standards tend to lower productivity in the long
run since no reason exists to try to break them. Ultimately, work standards
can cause more problems than they supposedly cure.
4. On Outside Suppliers
i. Reduce the number of multiple source suppliers. Price has no meaning without an integral consideration for quality. Encourage
suppliers to use statistical process control.
No two vendors, no matter how good they are, make identical products.
Each will have slight but definite differences which do have some impact
on the final assembly. Each additional vendor compounds the problem.
Similarly, the lowest price supplier may or may not be the lowest cost supplier when all factors are considered, including rejects your company suffers
due to the poor quality of the raw materials. A supplier who provides consistent parts with good quality may seem to cost more, but, when all cost
factors are considered, including rejects, may actually cost less. Further,
suppliers who use SPC ultimately will supply a better part at a lower price
than those who do not. Everyone benefits from such a program.
References
W. E. Deming, Quality, Productivity, and Competitive Position, MIT Center for Advanced
Engineering Study, 1982, p. 90.
W. E. Deming, ibid., pp. 17-50.
Bibliography
A. J. Duncan, Quality Control and Industrial Statistics, 4th ed., Richard D. Irwin, 1974.
very good text on approximately a junior level. Good balance of theory and applications.
I highly recommend it.
E. L. Grant and R. S. Leavenworth, Statistical Quality Control, 5th ed., McGraw-Hill, 1980.
very good text on approximately a sophomore level. Emphasizes applications. Definitely
one of the standard SQC texts.
K. Ishikawa, Guide to Quality Control, revised 2nd ed., Asian Productivity Organization, 1982.
a popular presentation of the Japanese approach to SQC. Written on approximately a
sophomore level. Personally, I feel there are better texts available.
MATERIALS
METHODS
MEASUREMENT
>
MACHINES
PEOPLE
10
--_____-_---------I
DIRECTOR O F
Fig. 2. Faber-Castellquality/productivitysteeringcommittee.
II
!-!
/_I
MKER
SUPERVISOR
Fig. 4.
I
!
i 1
L_/
TIPPING
SUPERVISOR
12
UCL = 35.52
CL = 33.24
UCL = 32.66
CL = 3 1 . 7 1
LCL = 30.96
LCL = 3 0 . 7 5
UCL = 30.70
CL = 29.77
UCL = 28.67
LCL = 28.83
CL = 27.73
UCL = 27.26
CL = 27.08
LCL = 26.91
LCL = 26.79
13
R. A. LANDY
North American Refractories Co.
3127 Research Dr., State College, PA 16801
The method of measurement or analysis is not perfectly repeatable and the material
is not perfectly homogeneous so repeat analyses and samples will difer among
themselves. One needs to carry out multiple measurements or analyses on more than
one sample from a rational subgroup in order to &timate the two types of errors that
arise due to analysis and sampling. Techniques are presented by which variations
associated with defned sources may be isolated and estimated.
1 n process control, key process variables are sought out that are related to,
and, thus can predict, response variables. With the recent emphasis on
statistical process control, those responsible for carrying out the process studies
need to reflect on the quality of measurements they are using for making
decisions about the process.
Measurements are required to be made of both types of variables. A
measurement consists of the sum of two components: one component being
related to the value of the item or characteristic measured, and the other being
related to the testing process of the measurement. The first component directs
us to the realm of sampling, while the second is involved with testing. Let
us discuss each in further detail.
Everybody uses sampling experiments as a means of gaining information
in order to make decisions. Holes are drilled in rocks to obtain samples of
ore bodies. Incoming shipments are inspected to develop a quality level. Opinion polls are carried out from segments of our population to gain an insight
into our likes and dislikes. From the examination of a relatively small number
of observations, inferences are made about a much larger number of units.
A finite sample from an infinite population will not allow us to determine
exactly what the population values are; however, we can obtain estimates (sample estimates of population parameters), and make inferences about the infinite population.
Sources of variation can contribute to the inaccuracy of such inferences.
We would be free of this problem if the materials we decided to sample were
homogenous. But they arent.
There are possible effects that need to be evaluated. Let us assume that
were interested in a response variable of a burned refractory produced in a
14
batch operation-type process (Fig. 1). It is highly probable that the product
will not receive identical heat treatment from one firing to the next, or possibly
different lots of raw materials will cause slight variation from one batch to
the next. The individual pieces within any burn or batch may be somewhat
different from one another. To estimate the quality of the refractory pieces,
several small samples need to be taken from the bodies. A mathematical model
for a measurement from this example may be described as:
Y .=p+fl + T I ( ) + &
(1)
where Y is the measurement, p is the overall mean value, the fl represent
the variation in the true response variable due to firing or batches; the n ( )
represent the fluctuations among the pieces from each of the firings or batches;
and the E,. are random errors* not identified or previously assigned. Effects
due to variations in samples taken from individual refractory bodies are
assumed to be zero in this model.
However, as we said earlier, sampling errors are only one group of sources
of variations. Inherent test errors result from the lack of repeatability in the
test equipment or test personnel. Many of you are familiar with the work being
done by the various committeesof ASTM on this subject. A major thrust in
ASTM these days is in regard to test errors. The concepts of ruggedness
and interlaboratory studies or round-robins are important to understanding test errors. It is not so much the actual data and results being developed
by ASTM as it is the consideration that errors of measurement will be made
in testing. Allowances must be made for these. Sources of variation due to
variations in test conditions, abound; operators, laboratories, materials, equipment, and days are some of the factors to be considered. In general, at least
two replications by each operator of each material on each piece of equipment in each laboratory are needed to be able to estimate this overall effect.
Our measurement may now be mathematically described by:
(2)
Y g a = V + P + n ( ) + X x ( ) + E a ( x)
The additional effects, X, ), represent variation due to positional effects
within a plug; we would like to assume that the refractory piece is uniform,
but the fact is that there can be variations in mineralogy and phases as a
function of grain sizing, shape, composition and texture of the body; the
E % ( .)
represent the differences between duplicates attributed to procedures,
apparatus, operator and unassigned errors.
The total variation has now been segregated into, in this case, three
identifiable sources, and a source which we have not specified further, experimental error. Variation will be estimated as variance (standard deviation
squared), and, fortunately, there is a statistical technique to treat the data
known as the analysis of variance. The experimental design used to handle
and estimate these specific variance components at each level of sampling is
frequently described as nested.
As an example of this model weve developed, consider the following
experimental design which is depicted in Fig. 2. Four consecutive batches of
fired, high-alumina porous plugs were identified. Approximately 64 plugs of
a size of about 28 cm (1 1 in.) in length were in each batch. Five plugs were
randomly selected from each batch. Finally, five 50-m3samples or cubes were
diamond-cut from each plug. The cubes were numbered so as to preserve their
identity. Each cube was measured twice. This latter step afforded an estimate
15
of the analytical or experimental error. The five samples or cubes per plug
allowed an estimate of the variation between samples from a plug. The five
plugs yielded an estimate of the variation with one batch, and the four batches,
of the process.
The order of measuring the cubes was established as follows. Two hundred
slips of paper of the same size were prepared; the identity of each cube was
marked on a separate slip, and this procedure was then repeated. The 200 slips
were well mixed in a box, and the sequence of analysis for each cube was determined by randomly drawing a slip from the box.
The response variable selected for measurement for this study was
permeability. The permeability of a material to a gas is defined as the rate
at which the gas in question will pass through the material under a definite
difference of pressure.
The measuring procedure was adapted from British Standard 1902: Part
1A: 1966. A schematic diagram of the permeability apparatus is shown in Fig.
3. Water from a constant head supply flows into a large bottle which forces
air into a large separatory funnel from which air is driven through the test
piece at a pressure indicated by a manometer. The 50-mm3test piece is placed
in a rubber mold and sealed in a metal vessel. Depending on the permeability
of the test piece, the duration of the test varies between three to six min. The
permeability, in centidarcies, is defined by the following equation:
K=
vx
TxAxP
x 1888
(3)
02
+ oxz+ up (02= 0)
(5)
54 550 + 83 568 7 7 3 0 ~
145 848
(6)
54 550
4x2
83 568
+-----4
0,=6819+20 892+7730
uT2= 188
+7730
(9)
(10)
The F value for 24 and 100 degrees of freedom is approximately 1.65; there
is no reason to reject the hypothesis that these two variances are equal. We
conclude that the testing procedure was in statistical control (with the one
outlier removed) during the experiment.
Additional care in laying out the experimental design can result in other
findings. For example, in this investigation the location of the cubes selected
from the plugs was maintained and not just randomly derived. Five positions
were identified with Position 1 being at the small end of the plug; Position
2 was located adjacent to Position 1 and towards the large end of the plug;
etc. Figure 8 summarizes the cube location within a plug, and Fig. 9 outlines
the new design of the experiment. The permeability measurement may now
be described by the equation:
Here the d, position effects become fixed effects and represent the variation
due to the plug positions and the 6' and A (. ) are interaction effects. The
analysis of variance for this particular model is displayed in Table 111.
Significance tests of the components of variance are made by forming approximate variance ratios as we did previously. We find all the variances are
significant with the exception of a: the batch x position interaction is not
significantly different from zero.
Figure 10 shows the deviations of the measurements from each cube
position average irrespective of batches or plugs. The differences in position
averages are related to difficulties in forming the plugs in a deep die cavity;
apparently, there is an overall consistency in filling the die which gives rise
to a rather stable structural pattern where Position 4 has the lowest permeability
within each plug.
Plotting the average permeability of each position by batches, Fig. 1 1 ,
also shows the same pattern where Position 4 has the lowest permeability for
all batches; although there is some overlapping of trend lines, we earlier had
concluded from the second analysis of variance that the batch x position interaction term was not significant (a: = 0).
However, when we examine, see Fig. 12, the permeability from position
to position for each plug, there is a noted inconsistency in the permeability
response; this is what the plugs x positions interaction is telling us (ox2#O).
So, although, the positional effect is a strong main effect (across batches and
plugs) and remains consistent through the batches, this condition becomes
inconsistent in examing the permeability pattern for each individual plug.
When you are ready to start your SPC endeavors, be careful to understand
the variations introduced by the operations of sampling and testing which are
common to any measurement. Hopefully, our example has given you clues
as to how to go about identifying sampling subunits or rational subgroups.
Obviously, as we illustrated, capricious sample selection might have signaled
that changes needed to be made to the process when it might have been in
18
Degrees
of
freedom
Sum of
squares
Between batches
3
1 868
Between plugs
16 3 778
within batches
Between cubes
within plugs
80 17 503
and batches
Between determinations
100 5 454
within cubes, plugs
and batches
Totals
199 28 604
Mean
square
Components of variance
or expected mean square
500;
54 550 u2
827
Table 11. Estimates of the Variance Components for the Completely Nested
Design
Source
Component
Batches
Cubes
Measurements
7730
83 568*
54 550
19
Between batches
Between plugs
within batches
Between positions
Batches x positions
interaction
Plugs x positions
interaction
(within batches)
Between
determinations
within batches, plugs
and positions
Totals
Degrees
of
freedom
Sum of
squares
Mean
square
Components of variance
or expected mean square
1 868 069
16
3 778 664
500;
12
2 487 234
64
10 574 051
100
5 454 972
+ 100,2
PROCESS
SAMPLE
1 2
SAMPLE
1 2
SAMPLE
1 2
20
LOT
LOT
LI
I 2 3 4 5
SAMPLE
ABCDE
1 1 1 1 1
f-l
MEASUREMENT
P P
WATER SUPPLY
RUBBER MOLD
I(= l V x H l / ( T x A x P l xi888
21
4000
'GI
c>
3000
2000
1000
BATCH 1
A AMEASUREMENT 1
BATCH 2
BATCH 3
BATCH 4
0 OMEASUREMENT 2
Fig. 4.
-.
il
..I
-1000
z
w
I
w
Y
-2000
L
7
.
-c
-3000
BATCH 1
BATCH 2
BATCH 3
BATCH 4
Fig. 5. Needle plot of the 100 differences in measurements for the cubes.
22
IOGO
0-
-1000
-2000
-3000
t *
N O R M A L
P R O B A B I L I T Y
Fig. 6 . The 100 differences in measurements for the cubes plotted on normal
probability paper.
11/
I
3000
1000 -f
I
BATCH 1
BATCH 2
BATCH 3
BATCH 4
23
El
El
POSITION
POSITION
r
LOT
nk
LOT
LOT
LOT
mm
I 2 3 4 5
I 2 3 4 5
1 1 1 1 1
MEASUREMENT
P P
24
3500
3000 2500 -
2000
15001000 I
CUBE 1
CUBE 2
CUBE 3
CUBE I
CUBE 5
2200
P-
--mI
fa
W
n
16001400-BATCH
x---xBATCH
1200- D-*BATCH
o.**...**BATCH
1000
2
3
4
25
2600 -
2400-
2
2
2200-
2000-
F
z
>-
c-
1800-
16001400-
1200
POSITION NUMBER
26
Introduction
1 n recent years there has been a significant increase in the usage of carboncontaining, and other improved/advanced refractories for steelmaking
applications. One specific new refractory type that has had extremely rapid
success is the magnesia-carbon compositions, ranging from low to high carbon
content. The rapid increase in usage of magnesia-carbon refractories in a period
of only 5 yr, between 1979 and 1982, is shown in Fig. 1'. Initially magnesiacarbon refractories were used mainly in electric arc furnaces, especially in the
hot-spot regions. Based on ongoing research and development, and increased
use experience, magnesia-carbon refractories are now being used successfully
in other steelmaking applications. With the practical successes achieved to date,
coupled with the ongoing product improvements, it can be expected that there
will be continued growth in the market for magnesia-carbon refractories. The
knowledge and experience gained from these refractories will also be useful
in improving and developing other refractory products and types.
The excellent performance of magnesia-carbon refractories is the result
of various outstanding properties, including excellent (high) refractoriness, high
thermal conductivity, excellent thermal shock resistance, and good erosion and
penetration resistance, especially to FeO-rich slags. From the refractory
producers' standpoint, a major benefit is the low energy required for production. But magnesia-carbon refractories commonly degrade by hot face oxidation/decarbonization in service, which increases their susceptibility to attack.
To overcome this problem there is continuing research worldwide to better
understand and further improve the oxidation resistance and performance life
of magnesia-carbon refractories. One of the various topics of this research
is the development of a dense MgO zone in the hot face region of magnesiacarbon compositions. The possible service benefits due to dense MgO zone
formation are still controversial, as the various studies to date have suggested
both positive and negative effects.
21
Literature Review
Pickering and Batchelor2 found that the strength of magnesia-carbon
refractories decreased in association with magnesia volatilization and carbon
oxidation at 1500-16000C.They also noted that firing at 1600C in air resulted
in the formation of a dense impervious MgO zone near the hot face; the
impervious nature of the dense zone resulted in pressure buildup in the brick
interior and eventual deformation/fissuring of the brick to relieve the pressure.
The various reactions in magnesia-carbon refractories were indicated to be
possible contributors to wear under steelmaking conditions. This study was
followed by others3-4that addressed the thermodynamics of oxidation/reduction reactions in magnesia-carbon refractories and considered the formation/
microstructure of a dense MgO zone in both laboratory compositions and used
brick. Carnighas conducted a fundamental study of the thermodynamics and
kinetics of reactions in BOF refractories and concluded that the rate of dense
zone formation would be slower than the typical rate of wear of the brick
(hot face) caused by physical and chemical degradation effects on the thin
decarbonized hot face zone. Other author^^.^ reported the presence of a slaglimiting dense MgO zone in used magnesia-carbon refractories from a BOF
and also compared the dense MgO zone microstructure developed in both
laboratory samples and used BOF brick. Kim, et aI.* reported the protective
effect of a dense MgO zone in resisting attack by several steelmaking slags.
Mikami and Martinet9 reported that carbon-MgO reactions invariably
produce evidence of secondary MgO, but that a uniform, continuous dense
MgO zone is not commonly found in used brick from either a BOF or EAF.
It was concluded that the predominant wear mechanism was by hot face erosion
of a thin decarbonized zone and that the MgO volatilization/oxidation reaction was only a minor factor in either wear or protective action. Jackson and
Webster'O noted that used magnesia-graphite bricks from an electric arc
furnace had a thin decarbonized zone at the hot face, with occasional evidence
of a magnesia dense layer; likewise, brick from BOF service also occasionally
show evidence of a magnesia dense layer near the hot face. They indicate that
the MgO-C reactions are mainly detrimental because ongoing oxidation of
carbon would clearly result in increased porosity and slag wettability. Although
used brick samples have not yet shown evidence of a uniform, thick and
impervious dense MgO zone, Jackson and Webster note that if conditions
would permit the formation of such a layer, that could be maintained intact,
the degradation of the hot face region might be slowed. In a related study,
to improve the performance character of magnesia-carbon refractories,
Watanabe, et al." found that the addition of A1 and/or Si improved both the
hot strength and oxidation resistance; the work showed no dense MgO zone
but there was secondary formation of matrtix-bonding Al,C3. Brezny and
Semler12compared two commercial magnesia-carbon refractories (a conventional type and an improved Mg metal-~ontaining'~
type); firings at 1650C
showed uniform dense zone formation around the brick perimeter for both
products, with the Mg-containing type showing the thickest dense zone, the
least carbon oxidation, and no bloating or deformation.
Background
The firing of magnesia-carbon refractories in air initiates the following
decarbonation reaction:
MgO(s) + C ( S )= Mg(v) + CO(v)
(1)
28
(2)
Experimental Procedure
Sample compositions of 90 wt% MgO and 10 wt% graphite were chosen
for study; four sample variations were evaluated, the only difference being
their particle sizing. The sample compositions studied represented arbitrary
coarse, intermediate (2 variations), and fine particle sizing, as detailed in Table
I.
The raw materials used were 98 grade sea water magnesia* and reagent
grade powdered graphite.+ The specified amount of size-graded material for
each batch formulation was carefully weighed and mixed manually to achieve
homogeneous dispersal. Test pellets of 1.3-cm (%-in.) diameter and 0.6-cm
(%-in.) height were made by pressing (hydraulic) at 83 MPa (12 OOO psi),
without any binder. Before firing, the dimensions and weight were determined
for each sample (pellet). Four samples of each of each size grading were fired
together in a MoSi,-heated electric furnace. To limit the oxidation of the
samples during firing, and also to enhance the magnesia dense zone formation, the samples were placed on an alumina plate and covered with a formed
alumina cover 1.9-cm diameter x 1.3-cm high (%-in. diameter x % -in. high).
The samples were heated to 1600C in 1 h after which one pellet of each type
was sequentially removed after soak times of 15, 30, 60, and 90 min at
temperature. The fired samples were measured and weighed to give the weight
and density change. One-half of each pellet (cut across the diameter) was
29
30
play a controlling role over the key reactions, although that effect was not
evaluated in this study. Future work needs to be conducted to clearly document the influence of firing atmosphere on dense MgO zone development.
Such information will be needed to improve our understanding of the criteria
that control the presence or absence of a dense MgO zone in refractories used
in steelmaking furnaces.
Figure 6 shows the relationship of sample particle sizing and dense zone
thickness development for the different experimental firing times. For a short
firing time, the dense zone thickness is greater for a coarse-grained body, but
as the firing time increases there is a progressive change, with the dense zone
thickness becoming greater for a fine-grained body. This relationship could
provide initial guidance in future work where there is a desire to promote or
minimize dense zone formation as a function of refractory particle size grading,
firing atmosphere, and startup heat treatment/curing in service.
Figure 7 shows the measured sample weight loss for increasing time. The
results suggest that there are two reaction schemes contributing to the observed
effects, with the coarser-grained samples showing greater weight loss than the
finer samples. Certainly the inter-relationships between sample particle sizing,
formation rate and integrity of the dense zone, diffusion mechanisms and rate,
and firing atmosphere, all have a contributory role. Figure 8 likewise indicates
a difference between the coarse and finer samples; the plot shows that there
are two broad classes of effective diffusion character. The slope of the lines
represents the effective diffusion coefficient; it can be seen that the two coarser
samples have a lower effective diffusion coefficient than the two finer-grained
samples that have a higher effective diffusion coefficient. The observed diffusion effects show the same correlation with sample particle sizing as the
weight loss data, i.e., a dual regime in which the two coarser and the two finer
sample formulations each exhibit similar behavior.
Figure 9, shows the oxidized sample area (070) vs firing time, also illustrates
a dual regime in which the oxidation of the coarser samples is much higher
(to 100%) than that of the finer samples (< SOYO).
Based upon the data in Figs. 7 and 9, it seems apparent that the finergrained samples develop a protective dense zone sooner than the coarsergrained samples, which limits the graphite oxidation and thereby reduces the
weight loss. The fact that the finer-grained samples show a higher effective
diffusion coefficient (Fig. 8) establishes a technical basis for the early development of a protective dense zone. This effect is significant because it indicates
that control of carbon loss (within limits) can be realized by manipulation of
the refractory composition and particle sizing, along with the firing variables
(time, temperature, and atmosphere).
Figure 10 shows the relationship between the oxidized sample area (90)
and the quality index. Although the quality index is only a relative indicator
of dense zone integrity, it can clearly be seen that as the quality index increases,
there is less carbon loss (oxidation). This observation indicates that, at least
within the experimental limits of this study, the quality index can be used as
a relative indication of the integrity (protection potential) of the dense zone.
From these data it is again apparent that the particle size grading of the refractory, in conjunction with the firing atmosphere, can be used to control the
oxidation of magnesia-graphite compositions. Although sample composition
and additives were not considered in this study, they are key factors that must
be included in any related future research. Further experimental work is needed
31
Conclusions
This study of a controlled series of four size-graded MgO-graphite compositions, containing no metal additions, has provided new experimental data
regarding the formation of a dense MgO zone. A series of photomicrographs
is presented showing the dense MgO zone development in the different sizegraded samples as a function of firing time. The quality index (Q.I.), used
as a measure of the dense zone uniformity, also gave a general indication of
the dense zone integrity. As the firing time was increased (up to 90 min) for
a given sample particle sizing, the quality index and the dense zone thickness
increased. The experimental data for weight loss, oxidized area, and effective
diffusion coefficient, all showed dual regimes in which the two coarser samples
had similar results, and the two finer samples performed similarly. The higher
effective diffusion coefficient in the finer samples correlated with lower weight
loss and significantly lower carbon loss, which must be attributable to enhanced
dense MgO zone formation. The particle sizing of a refractory formulation
clearly has a direct effect on dense zone formation, and thus carbon loss, but
there are other controlling factors as well, like material composition, firing
temperature, and atmosphere that need to be thoroughly evaluated in further
studies. Along with the potential benefits of dense zone formation in the outer
32
References
Table I.
Raw Materials
Coarse
45
45
10
148
33
Sample, WtVo
intermediate
1
2
45
45
90
10
275
10
361
Fine
90
10
469
QUALITY INDEX
100
80
60
40
2o
COARSE
100
GRAIN
INTER.GRAIN
300
200
FINE GRAIN
400
(Sq.
500
Ctn/g)
Fig. 5. Quality index vs sample grain sizing after firing for 15,
30,60, and 90 min at 1600OC.The lines shown represent a least
squares fit of the data. In all cases the quality index increases with
decreasing grain size (average) of the samples.
220
200
180
160
: y
9D MI?-
__--_ _ - - - -_
- _---
- - - - _ - - -_ _ - -
60 MIN
............................
.!!.!!!!_
-.._
_ _ _ _ _ _ . ~ _ ~ ~ _ _ ~ _ ~
15 M I N
140
120
1NTER.GRAIN
COARSE GRAIN
36
FINE M A I N
WEIGHT LOSS ( X I
INTER GRAIN I
10 -
COARSE GRAIN
goo
iaoo
2700
3600
5400
4500
Fig. 7. Sample weight loss (%) vs firing time for the four
differentsize-gradedsample compositionsstudied. Two weight
loss regimes are indicated, with the coarser samples showing
more weight loss than the finer samples.
5-
4 -
INTER GRAIN
3 -
2 -
FINE GRAIN
goo
moo
2700
3600
4500
5400
37
OXIDATION ( X AREA1
100
80
70
INTER GRAIN I
INTER GRAIN 11
1800
900
-_ - - - -_ _ - -
3600
2700
FIRING T I M E (seconds)
4500
5400
111 1NTER.GAAIN I
80
70
60
50
L!
INTER GRAIN I1
40 -
Q
A
A
Li
30 .
L?
20 .
FINE GRAIN
10 20
30
40
60
50
70
80
90
100
38
Honeycomb Structures
THOMAS
H. ELMER
Corning Glass Works
Corning, New York 14831
The thermal expansion of extruded cordietite honeycomb structures is sign$cantly
lowered by leaching. The resulting bodies have a markedly greater thermal shock
resistance than untreated structures. Alumina and magnesia are selectively remowd
from the extruded cordiente (2MgO .2A& .5SiOJ, ceramics. Scanning electron
microscopic examination revealed that the shape of the cordiente crystallites is not
altered on leaching, indicating that the leaching process is topotaxial. Ewtremely high
surface areas are obtained by totally leaching such cordietite monoliths. The high surface
area is due to microporous silica formed on leaching. Amorphous silica and traces
of spinel and aluminum titanate were detected in the totally leached material. Partially
leached structures have excellent thermal stability, showing no signs of degrading, euen
after long-time exposure to elevated temperatures.
Introduction
C eramic cordierite bodies have been synthesized and studied by many workers,
notably Singer, Cohn,2 Geller and I n ~ l e y ,Lamar,4
~
Basta and Said,5
Gugel, Vogel and Osterried,6 and others. In recent years extruded cordierite
ceramics have found large-scale use in the form of honeycomb structures as
substrates for automotive exhaust catalysts. Such monolithic structures must
have a low thermal expansion and relatively high refractoriness to perform
dependably in a gasoline engine exhaust environment. Lachman, Bagley and
Lewis have shown that orientation of the cordierite crystallites on extrusion
accounts for the lower-than-average thermal expansion observed in such thinwalled monoliths.
This paper shows that the thermal shock resistance of extruded cordierite
honeycomb ceramic bodies can be improved by selective leaching. It includes
information on thermal expansion, surface area, porosity, X-ray diffraction
analysis, chemical composition, and SEM micrographs of these unique
monoliths.
Experimental
41
Chemical Analyses
Table VIII summarizes chemical analyses results for both unleached and
leached cordierite monoliths. Both alumina and magnesia are extracted from
the cordierite phase by the acid, leaving a silica-rich product. The 6 wt%
A1,0,, 1.2 wt% MgO and 0.6 wtVo TiO, are assumed to be associated with
the minor crystalline phases observed by X-ray analysis, namely spinel
(MgA1,0,) and aluminum titanate (A1,O,.TiOz), both of which are acid
resistant.
Micrography
Electron microscopic examination of the cordierite monoliths at various
stages of leaching indicated that the acid attack starts at the grain boundaries
of the cordierite crystals. Scanning electron micrographs in Fig. 6 show that
the general shape of the crystals is not altered by leaching, indicating that the
leaching process is topotaxial. However, prolonged leaching produces silica
gel deposits which eventually obscure grain boundaries.
Discussion
The study shows that the therma? expansion of cordierite monoliths can
be dramatically lowered by acid treatment, and that the resulting weight loss
is due to selective removal of alumina and magnesia from the cordierite
crystallites.
Figure 2 shows that the expansion goes through a minimum with weight
loss. The reasons for the very low coefficient of expansion observed in such
monoliths on leaching are not completely understood. However, it is thought
that the low values may be partly due to formation of a silica-rich phase which
is lower in expansion than the cordierite phase. The finding that the expansion
vs
decreases to values below that of amorphous silica (0.25 x
0.55 x 10-6/oC) was unexpected. This can be explained by the fact that
leaching leads to the formation of microcracks and voids which provide room
for the expansion of residual amorphous and crystalline phases. The fact that
the thermal expansions measured in these materials reach a minimum and then
increase with prolonged leaching could be accounted for by the observed
redeposition of silica gel in the microcracked or porous regions of the structure and formation of trace amounts of cristobalite on subsequent thermal
treatments.
Figure 3 shows that the thermal expansion can be used as an indicator
of thermal shock resistance of the monoliths. The expansion in such materials
is comprised of the expansion of each individual structural component which,
according to X-ray diffraction studies, consist chiefly of amorphous silica and
cordierite. Since the cordierite crystallites are only about 1 to 2 pm in size,
it is conjectured that the stresses resulting on heating are relieved by the porous
silica-rich phase that is formed at the grain boundaries of the cordierite phase,
and any voids and/or microcracks that may form on leaching. Possible reasons
why leaching improves thermal shock resistance of monoliths are that it: (1)
introduces microcracks that do not propogate catastrophically on shocking,
(2) produces a low expansion silica-rich phase which, being microporous, has
a lower modulus of elasticity than the other phases in the body, (3) increases
porosity, and (4) reduces the amount of crystalline phase, thereby allowing
the latter to move about more freely on heating or cooling.
43
Figure 4 and Table VIII leave no doubt that acid attack of the cordierite
crystallites leads to formation of a microporous silica-rich phase. The fact that
the surface area of totally leached cordierite can be 400 m2/g suggests that
the pores in the leached body are extremely small and most likely less than
5 nm in diameter.
Expansion measurements and length measurements of leached and
unleached monoliths indicated no significant changes in these parameters on
prolonged firing, e.g., 500 h at 800C. This leads one to conclude that selective leaching does not impair the long-term stability of cordierite monoliths.
Conclusions
The thermal expansion of extruded cordierite bodies in substantially
lowered by acid treatment. The resulting bodies have markedly greater thermal
shock resistance than the untreated bodies. The hot acid solutions selectively
remove alumina and magnesia from the cordierite crystallites, leaving a
microporous silica phase. Complete leaching results in porous bodies having
a surface area comparable to that of a microporous silica gel. The acid attack,
which starts at the grain boundaries of the cordierite crystallites, reduces the
mechanical strength of the bodies. This loss is minimal since the leach time
required to obtain superior thermal shock resistance is short. The selectively
leached bodies do not degrade on prolonged exposure to elevated temperatures.
Acknowledgment
The writer is indebted to Dr. D.E. Campbell for analystical measurements,
D.L. Millhollen and Dr. W.A. Plummer for expansion measurements, E.H.
Fontana for porosimeter measurements, A.M. Chirino for thermal shock
testing, R.F. Heitzenrater for preparing the micrographs and Dr. R.C. Doman
for his interest in this study.
References
IF.Singer, Concerning New Stoneware Bodies. I Composition, Ber. Dtsch. Keram. Ges.,
10 [6] 269-70 (1929).
2W.M.Cohn, I1 Concerning New Stoneware Bodies, Ber. Dtsch. Keram. Ges., 10 [6]
271-84 (1929); 111 Expansion Behavior Between 20 and 1200C, ibid., 11, 62-70 (1930).
3R.F. Geller and H. Insley, Thermal Expansion of Some Silicates of Elements in Group
11 of the Periodic System, J. Res. Nat. Bur. Stand. 9 (1) 17-24 (1932).
R.S. Lamar, Development of Cordierite Bodies with Sierralite, A New Ceramic Material,
J. Am. Ceram. Soc., 32 [2] 65-71 (1949).
5E.Z.Basta and M.K.A. Said, A Contribution to the Synthesis of Ceramic Cordierite
Bodies, Trans. Brit. Ceram. SOC., 12 (21 69-75 (1973).
6E. Gugel, H. Vogel, and 0. Osterreid, Investigations on the Use of Barium OxideContaining Ceramic Bodies for Chemical Stoneware, Ber. Dtsch. Keram. Ges. 41 191 520-26
(1 964).
7I.M. Lachman, R.D. Bagley, and R.M. Lewis, Thermal Expansion of Extruded Cordierite
Ceramics, Am. Cerum. SOC.Bull. 60 [2] 202-5 (1981).
8R.D. Bagley, Extrusion Method for Forming Thin-Walled Honeycomb Structures, U.S.
Patent No. 3 790 654, February 5, 1974.
9I.M. Lachman and R.M. Lewis, Anisotropic Cordierite Materials, US. Patent No.
3 885 977, May 27, 1975.
*Digisorb 2500, Micromeritics Instrument Corp., Norcross, GA.
44
Table I.
Composition
SO,
MgO
51.4
49.4
44.5
41.9
36.4
34.8
35.9
48.6
48.7
*55.4
13.8
14.7
6.9
9.4
8.2
B
C
D
E
Note: All extruded ceramic cordierite monoliths had a wall porosity of 35 to 40%. Monolith C
and D contained appreciable mullite phase.
0.5
1
2
3
4
6
7.75
15.5
23
-24
.
Weight loss in Yo
A
B
-
Leachant
2.59
2.17 4.90
3.29 10.0
15.3
5.31 20.2
8.34 29.5
35.0
44.9
23.1
45.9
Composition B
Time (h)
Not Leached
0.5
1
0
2.59
4.16
9.78
14.37
19.2
29.6
34.3
2
3
4
6
7.75
Q X 106
(1/"C)
1.14
0.72
0.69
0.45
0.29
0.24
0.34
0.79
Note: All expansion measurements were made parallel to the direction of extrusion of the
monolith.
45
Not leached
A
B
C
D
E
2.45
1.37
3.24
2.40
2.63
Partially leached
2.05
0.70
2.99
3.23
2.18
(6 h, 7.28%)
(lh, 4.39%)
(21h, 8.22%)
(6h, 15.2%)
(6h, 10.9%)
Note: The leaching times is 1.5N HNO, and accompanying weight losses are given in
parentheses.
Partially leached
A
A
E
E
Yes
No
Yes
No
1075
825
1100
850
Note: Specimens of composition A were oval, 16.8 c m x 8.6 c m x 9.5-cm high (6.6 in. x 3.4
in.x3.75-in. high), and E were round, 11.8-cm diax7.6-cm (4.6 in. diax3-in. high).
Table VI.
Ceramic
Weight loss on
leaching, 0711
Axial
Radial
Diagonal
0
4.4
11.2
18.7
20.34
16.04
13.38
4.75
4.79
3.27
2.37
1.65
0.49
0.31
0.23
0.15
Note: Each numerical value represents the average for three 2.5-cm (1-in.) cube specimens.
Load applied parallel, perpendicular, and diagonal to the square channels.
Table VII.
Leaching in
1.5N HNO,
Thermal treatment
Not leached
I h
Completely
leached
l h
l h
l h
Major phase
Minor phase
Cordierite
Spinel
Cordierite
Spinel
Amorphous silica
Aluminum
and spinel
titanate
500 h @ 800C
Cordierite
Spinel
100 h @ 1000C
Cordierite
Spinel
4 h @ 1200C
Cordierite
Spinel and some
cristobalite
46
Table VIII.
SiO,
A1203
MgO
49.2
36.0
14.5
0.31
0.49
0.006
0.14
0.074
0.11
TiO,
Li,O
Na,O
KZO
CaO
91.63
*6.03
*1.14
0.20
0.55
<0.001
0.01
0.003
0.03
*These oxides were present in the form of spinel and aluminum titanate.
50r
HOURS
47
10
I
20
WEIGHT LOSS, %
I
30
I loo
600
500
0
LY
l\
2I
3I
48
I
30
49
70
I
60
50
40
30
I
30
02 e
20
10
I
70
I
60
50
40
02 8
I
20
10
50
51
Zircon Processing
K. K. CHEANC
Science University of Malaysia
Minden, Penang, Malaysia
Zircon (ZrSiOJ, a highly refractory mineral, is found in relatively great abundances
in the alluvium of the Kinta Valley,the largest tin-mining area in the world. Most of
the zircon isfound associated with cassiterite, ilmenite,monazite,xenotime,shuwrite,
mtile, garnet, and quartz obtained as a by-product of the tin-mining operations. These
"impure" mineral dumps are of no economical significance unless they can be separated
into their indiuidual phJSica1components.A powsheet is presented to show the processes
required to produce a fairly high grade (S297%) zircon concentrate which conforms
to market specifcations and hence, can contribute to the nation's development and
wealth. A combination of sewral processing techniques including classijication, gravity
stream-flowing,high tension, and magnetic methods are considered to be more q&ient
in obtaining a high quality product. Thisflowsheet is not only applicable to the Kinta
Valley area, but also to other regions in Malaysia and Southeast Asia.
Introduction
A lthough the Kinta Tinfields (Fig. 1) in peninsular Malaysia is well-known
as the largest tin-producing area in the world, relatively little is known about
the heavy accessory minerals which are obtained as a by-product of the tinmining operations there. Besides cassiterite, obtained chiefly from dredging
operation and gravel-pump mining' large quantities of heavy alluvial
minerals including ilmenite, zircon, monazite, xenotime, and struverite are also
processed and marketed (see Table I). In particular, zircon (ZrSiO,) a highly
refractory mineral is widely distributed throughout the alluvium of the Kinta
Valley and is next in abundance only to ilmenite.
The zircon concentrates obtained as a by-product of mining operations
are usually not of exportable grade and may contain significant amounts of
other minerals. As such, the problem facing most mineral processing engineers
is the upgrading of zircon concentrates to marketable grades (that is, containing
>95% zircon). The aim of our study was to design a practical method of
physically upgrading cassiterite by-product, rich in zircon, to export specification. In particular, we were given the task of designing a flowsheet for the
processing of a 100-ton zircon dump that had been purchased from various
dredging companies operating in the vicinity of the Kinta Valley and which
had been stockpiled until market conditions were right. This flowsheet would
also look into ways of reducing unnecessary and excessive processing steps
(which will only result in an increase in time, labor as well as fuel or energy),
and to identify other problems that may arise during operations and effective
ways of tackling these problems. Such a study would be useful not only to
the mining industries in Malaysia and Southeast Asia, but to research organizations in these countries as well. The results of this study would be extremely
useful in decision-making relating to mineral policies of the individual countries
as well as in monitoring future trends in mining technology in these countries.
52
Method
A Frantz Isodynamic separator was used to obtain a complete
mineralogical analysis on a representative sample of the zircon ore according
to the procedures outlined by Flinter3 and Santokh Singh and Teoh., The
results show that 10% ilmenite, 13% monazite, 1.2% cassiterite, 64% zircon
and 12% quartz were present. Most of these minerals can be readily distinguished from one another by their physical properties as viewed under the
binocular microscope.
Ilmenite (FeTiO,) is metallic black in color, pseudohexagonal in external
morphology, and is fairly magnetic. Monazite (Ce,La,Y,Th)PO,, is yellowish
to reddish brown in color, is resinous in luster and fluoresces dull green under
short-wave ultraviolet light. Cassiterite (SnO,) is brownish in color, has
adamantine luster and, on reaction with dilute hydrochloric acid in a zinc dish,
gives a coating of white metallic tin. Zircon (ZrSiO,) is characteristically
prismatic, sometimes terminated by pyramids, is pinkish to whitish in color,
and is generally smaller but more uniform in size than other minerals. Quartz
(SiOJ is usually devoid of crystal shapes, is whitish in color and has a large
range in sizes.
As ilmenite and monazite are fairly magnetic, they can be removed using
a magnetic separator. Cassiterite, being a conductor, can be separated from
zircon and quartz, which are not conductors, by electrical methods. Finally
quartz (S.G. = 2.65) can be removed from zircon (S.G. = 4.6) by gravity
processes. With these principles in mind, together with the continuous
mineralogical feedback from each step, processing of the zircon dump was
initiated. These studies must be coupled with the known capacities of the
various industrial machinery used (Table 11) in order to avoid any bottlenecks.
Bottlenecks will occur at stages where the amount of feed exceeds the total
capacity of the machines available. The capacities of the various machinery
used is estimated for normal Malaysian working conditions and from the
writers experience.
Results
A flowsheet for the processing of the zircon concentrate accumulated as
a by-product of dredging operations and gravel-pump mining in the Kinta
Valley is shown in Fig. 2. The initial zircon concentrate in the head-feed is
already upgraded to approximately 64% zircon with other associated byproducts being monazite (13%),ilmenite (lo%), and cassiterite (1.2%). Quartz
gangue constitutes 12%. The main purpose of this flowsheet is to upgrade
the zircon to above 95% purity (exportable grade) as well as to recover the
cassiterite, monazite, and ilmenite that are present in considerable quantities.
The capacities of the various industrial machines used in the processing of
the zircon concentrate are shown in Table 11. In some processing plants, the
Hoffman tables may be used instead of the lanchutes which are more dependent on human labor.
As the in-coming material is already fairly wet, concentration using wet
gravity methods are used in the preliminary stages. In particular, careful
classification using the Willoughby classifier is deemed essential in any gravity
concentration process utilizing streamflowing. As can be seen in Fig. 2, the
overflow is enriched in zircon, whereas the underflow contains less zircon,
but more cassiterite, monazite, and relatively larger-grained quartz (> 2 mm).
The processes involving the treatment of the overflow material are essentially
53
the same as that of the underflow material which is shown in Fig. 2 and, as
such, is not repeated.
The minerals from the underflow is sent to the lanchute (included, coffinlike sluice) for gravity concentration. Tables are not used because of their lower
capacities compared with lanchutes. The finer and heavier (higher specific
gravity) material accumulates in the concentrate (30To), whereas the lighter
and larger particles are washed down the inclined sluice as tailings (25%) which
are pumped out t o a stockpile dump. Minerals that are intermediate in properties are collected in the middlings (45%).
Both the concentrate and middlings are then dried and sent to the hightension separators where minerals that are electrical conductors are separated
from minerals that are non-conductors. For the concentrate, after the first
pass through the high tension separators, the conductor fraction (40%) comprise cassiterite (13%) and ilmenite (23%). However, because of the rapid rate
of throughput of the minerals, blocking or clouding effects do occur, and
because of the momentum of the minerals, monazite (13070), zircon (43%),
and quartz (7vo) are invariably thrown into the conductor fraction as well.
The conductor fraction is immediately sent for cassiterite recovery in view of
its high concentration (13%).
The non-conductors fraction consist essentially of zircon (67070), monazite
(32Oro), minor ilmenite (20/0), and even some cassiterite (0.8%). This necessitates
a second pass of the non-conductors fraction through another set of high tension separators. More ilmenite (9070) and cassiterite (4Vo) are removed. The
remaining fraction is not upgraded very much (69% zircon with 30% monazite)
because of the small amount of material (10%) removed.
As monazite is moderately magnetic compared with zircon, the non-conductor fraction is next passed through a Maclean-type magnetic separator
where after two passes, most of the zircon is upgraded to approximately 88%
purity although some monazite (12%) and cassiterite (0.4%) still remain. A
final pass of the products through an induced roll-lift magnetic separator
resulted in a concentrate consisting of 97% zircon.
In this flowsheet, unnecessary excessive processing steps which would
result in increased energy, time and labor are minimized by strict mineralogical
control. However, machinery breakdowns and wear-and-tear is anticipated
in view of the large tonnage of material processed. Security is another important
factor in ensuring that the upgraded material is safely stored and transported
from the storage area to the shipping depot.
Conclusion
A combination of technological principles including classification, gravity
streamflowing, high tension and magnetic methods resulted in the zircon dump
being upgraded from 64% to > 95% zircon in purity. This flowsheet can thus
be used for the processing of all zircon-rich by-products of tin-mining operations in the Kinta Valley as well as in other parts of Malaysia and Southeast
Asia.
In view of the eventual dwindling of mineral resources in Malaysia, the
nations alluvial reserves must be effectively developed to meet the country's
future demands for metallic (tin, tantalum, titanium, tungsten) as well as nonmetallic materials such as zircon, rare-earth phosphates, and even silica sand.
It is clear that the domestic mineral processing industry must and can improve
technology and productivity to survive in the competitive world. But the
CA
improvement can only come through a joint effort by the miners, mineral
engineers, as well as government and private agencies and research
organizations.
Acknowledgments
I wish to thank the management and staff of Beh Minerals Sdn. Bhd.
for their cooperation and support during this study. Thanks are also due Dr.
H. Hussin, Director of the Mines Research Dept., Ipoh, Malaysia for reviewing
the manuscript.
References
IH. Hussin and K. C. Chin, Design Considerations Related to Energy Consumption and
Costs of Material Transport and Beneficiation in Malaysian Gravel Pump Mines, Seatrod Centre
Tech. Publ. No. 3, 59-70 (1983).
ZAbdullah Hasbi bin Haji Hassan, Malaysia as a Source of Tantalum, Seatrud Bull., V
.--
4D. Santokh Singh and L. H. Teoh, Applied Mineralogy in Relation to Alluvial Tin Ore
Beneficiation, Seatrud Centre Tech. Publ. No. 3, 1-10 (1983).
Table I. Yearly Production in Metric Tons of Tin, Zircon and other Mineral
By-products from Peninsular Malaysia (Ref. 1)
Minerals
Cassiterite
Ilmenite
Zircon
Monazite
Xenotime
Struverite
1979
1980
1981
1982
63 995
199 819
1271
542
61 404
189 121
552
347
91 1
75 1
59 938
172 757
1307
300
80
395
52 342
103 937
2116
546
71
90
Willo&hby classifier
Hoffman tables
Lanchute
Rotary driers
Chinese driers
Carpco high-tension separator
Maclean magnetic separator
Induced roll-lift magnetic
Separator
Bagging
2.04
0.54-0.68
1.02- 1.36
1.63
0.34-0.54
0.27
0.68
0.37
0.68
55
56
2no P..
16.L
I'..
Fig. 2. Flowsheet with mineral analyses for the processing of a Malaysian zircon
concentrate.
TASTUOKAWAKAMI
Kawasaki Refractories Corp.
183 Mitsuishi Bizen, Okayama, Japan
During the period in which the torpedo car only had a role as the transportation vessel
of hot metal, high-alumina and fireclay series bricks were generally being applied for
the working linings of torpedo cars. Of late, along with extensivedemands on the more
efectiw techniquesfor refining the hot metal, the hot metal pretreatments have been
camed out inside the torpedo cars. Wedescribe the improvements, up to now and in
thefuture, of the bricb used in the torpedo car which are, and will be su$ciently resistant
to the flux to be injected into the torpedo cars for the hot metal pretreatments and
the hot metal stimng.
Introduction
T orpedo cars were used in the past as containers for transporting hot metal
produced in the blast furnace to the steelmaking plant. In recent years,
however, as a result of progress in efficient refining techniques in the steelmaking plant and requirements for high-grade steel production, techniques for
pretreatment for hot metal in the torpedo car, including desulphurization,
dephosphorization, and desiliconization, have been developed and incorporated
in the manufacturing process. The Mizushima Works of Kawasaki Steel Corp.
commenced desulphurization treatment in the torpedo car in 1976. At the time
of the introduction of this pretreatment, high alumina-type
(Al,O,-Si0,-based) bricks were used as lining refractories, but unburnt
Al,O,-SiC-C bricks were developed in 1979 and put to a use test. Since the
test results proved that these bricks had excellent resistance to slag corrosion
and spalling, they are now used for lining in all torpedo cars. However, the
price of the Al,O,-SiC-C brick is higher than that of the conventional
Al,O,-SiO, brick, and if higher grade raw material is used to improve the
quality of the brick, the price will become still higher.
Therefore, the authors have used mainly natural raw materials of moderate
price, made improvements in raw materials, and developed bricks with excellent
corrsion resistance. The authors examined the wear mechanism of this type
of brick to discover the foundation for material improvement and the guiding
principle for selection of appropriate raw materials. The results of these efforts
are reported below.
58
Sample Refractories
The Al,O,-Sic-C bricks are unburnt refractories in which alumina-type
grains of 3 mm or below in size, Sic grains of 1 mm or below in size, and
flake graphite are molded into brick shapes, using phenol resin as a binder.
Roles of the ingredients in the Al,03-Sic-C brick are as f01lows.~~~
(1) Alumina (Al,O,) is highly resistant to soda ash and mill scale-type
slag, and is one refractory material having high wear resistance to
stirring flow. However, alumina alone is inferior in spalling resistance.
(2) Graphite (C) is effective in preventing slag penetration and improving the spalling resistance which is the disadvantage of alumina.
(3) Silicon carbide (Sic) is effective as an antioxidant of carbon, as shown
in the reaction of 2C O2= 2C0, Sic + 2CO = SiO, + 3C, but inferior in slag resistance.
Bricks, in which, from among the above components, the types of rawmaterial alumina and graphite blending ratios were altered, were produced
on a trial basis and tested. Alumina raw materials included three kinds of
natural alumina, i.e., andalusite (X), calcined alumina shale (Y), and deadburnt alumina shale (Z), and a kind of synthetic alumina (SA). Samples A
and B (conventional brick), and C, and D through I consist of combinations
of raw materials X-Y, Y-Z and Z-SA, respectively. Physical properties of the
samples are shown in Table I.
After testing, wear areas at the center cross-sections of sample bricks were
measured and indicated in indices with wearing area of sample A as 100. The
relation between SiO, content in the brick and the wear index and that
between carbon content in the brick and the wear index are shown in Figs.
3 and 4, respectively. Point A in Fig. 4 shows a SiO, content of 22% and is
a reference point which is indicated for comparison purposes.
Wear of the brick shows a strong correlation with the SiO, content of
the brick. As the S O , content increases, the wear also increases. The relation between graphite content and the wear shows, within the scope of the
present test, that as graphite content increases, the wear decreases.
Upon inspection of bricks after their use in torpedo cars, it was found
that bricks A, B, and C developed cracks at locations 30 to 60 mm from their
hot faces, but bricks H and I developed no cracks.
As typical examples, cut surfaces of used bricks C and I are shown in
Figs. 6 and 7, respectively.
Microstructures obtained by microscopic observation of used bricks C
and I are shown in Figs. 8 and 10, respectively. EPMA characteristic X-ray
images of circled portions in Figs. 8 and 10 are shown in Figs. 9 and 11,
respectively.
Graphite remains even at a location 1 mm from the hot face. Both the
aggregate and matrix of brick C are eroded, as shown in Figs. 8 and 9, and
the brick is beginning to decompose as a result of slag erosion. On the other
hand, in brick I, with less SiO, content, the aggregate protrudes from the
matrix, as shown in EPMA Fig. 11. No decomposition of grains is observed,
and slag penetration is minimal. Specifically, the reaction between aggregate
and slag is very slight in test brick I. In contrast, the aggregate in brick C has
been eroded by slag from the hot-face side and is beginning to decompose.
To examine the slag penetration distanc, an EPMA line analysis has been made
of inside from the hot face of brick C. The results are shown in Fig. 12. The
penetration distance of slag components can be judged from the existence of
Ca ingredients.
60
Since Ca is not observed at the back face of the A1,0, grain which is
located at 3 to 4.8 mm from the hot face, it is considered that the slag penetration distance at the matrix is about 3 mm. Graphite exists even in the vicinity
of the hot face, but Sic is nor observed on the hot face. The Sic grain exists
from about 1 to 2 mm inwarJ lo the hot face. The state of Sic existence near
the hot face of brick C is shown in Fig. 13. The Sic grain which exists at a
location 2 mm from the hot face has degenerated, as if its circumference were
oxidized, as shown in Fig. 13(C).
Physical Properties of Used Bricks
Lining bricks C and I were sampled from the torpedo car after 195 heats.
The relation between the distance from the hot face and physical properties
of the bricks was investigated. Apparent porosity is shown in Fig. 14; bending strength in Fig. 15; changes in permanent linear change in Fig. 16.
In brick C, which developed cracks, strength is great at a location 80 mm
from the hot face and apparent porosity becomes smaller, andd the difference
in physical properties between the hot face side and the shell is great. By
contrast, brick I where no cracking was observed shows only slight changes
in physical properties at various distances from the hot face.
Examination has been made into the causes of crack generation in torpedo
car bricks and into resulting peeling-off and wear to determine whether these
phenomena are attributable to thermal spalling or other causes.
Regarding the relation between the material characteristic parameters and
the thermal shock damage resistance factor of porous material like refractories
which inherently have many micro-cracks, Hasselmans proposes the following formula:
R = Er/S*(1-u)
(5)
where, E = Youngs modulus
(kg .f /cm2)
S = Fracture strength
(kg .f /cm2)
r = Fracture surface energy
(erg/cm2)
v = Poisson ratio
(-1
On the other hand, the crack stability parameter when stabilized propagation of semi-static fracturing or cracking occurs is shown by the following
f~rmula:~
Rst = [ ~ ( ~ - u ~ ) / E o . ~ * ] ~
(6)
62
with an SiO, content of 7 to lo%, while giving attention to the mineral composition of SiO, contained.
Conclusion
A laboratory test was conducted of the corrosion resistance of various
types of Al,O,-Sic-C bricks containing different types of A1,0, raw
materials. As a result, the following have become clear:
(1) Al,O,-Sic-C bricks using raw materials containing much SiO,
develop severe damage.
(2) At a SiO, content of 10% or above, peeling-off wear occurs.
(3) In the AI,O,-Sic-C brick, the contribution to damage by thermal
spalling is minimal.
(4)Up to a carbon content of 15070, the higher the carbon content, the
less the wear of the brick.
( 5 ) Sic does not exist within a depth of 1 mm from the hot face.
(6) Carbon exists up to the hot face of the brick.
(7) An Al,O,-Sic-C brick with a 15% carbon, a maximum 5% Sic,
and a maximum 3% SiO, (preferably as small as possible) is
presumed to be the optimal brick.
References
64
Table I.
Item
Item
Wear rate
(mm / heat)
0.35
0.35
0.24
0.15
0.18
0.13
Before
desulfurization
After
desulfurization
Adhered slag
Table IV.
C/S
Softening Melting
point
point
("C)
("C)
40.4
3.6
53.1
0.4
1.32
1240
1305
21.9
36.1
2.4
6.5
51.0
53.8
18.8
2.0
2.33
1.49
1380
>1600
Brick Characteristics
Conventional
brick
B
Item
8.6
9.3
2.86
2.86
5.4
5.9
119
123
26
31
6.88
5.89
1.1
1.4
80.6
89.0
0.24
0.18
6.3
2.92
6.5
97
29
5.71
1.8
68.9
0.13
800 -
750
-100
Ln
c
Y
700650600-
00
-60
-s
-N
0:
40
20
.
:
Period [year)
M e l t -down
Desiliconizer
( 1 unit)
1.5 -
f
c
v
(1 u n i t )
Slag o f f
t-
Dephosphorizer
Desulphurizer
(1 / 2 u n i t )
;
354.5
-<
0
0
Slag o f f
Dephospho!izer
Desulphurizer(l/2 u n i t )
Stag off
\Aiurnina crucible
Induction coil
Fig. 2.
120
100-
80-
6040-
20-
.-
,.
E+m,
/*8
SiO,
content ( % )
66
M r k i n g face
1 rnm
( a ) SIC located 2 rnrn away from working face
c_i
0. lmm
0.05mm
O---.--U
-Brlck C
100
200
300
71
100
200
300
0)
IT
S
0
.-c
A
~
Q)
c
0.6 -
0.40.2 0-
a -0.2
(mm)
72
5102
CawAlrDp
I-
v
m
c
.-
C I S = 2.3
1400 -
Liquid
Y
0
.K
,300->
C/S=1.3
I
13
a,
0.6 -
0.5-
0.4-
EJwoF/S'(
0~
R"", c m )
; 0.62 0.5 -
-$
a,
t.
0.4 -
0.30.20.1 -
/ / /A/
f.
a,
L
0.5
0.4
0.3 0.2
0.1' 1-.1
2<D
1
Si02
content ( % I
74
Introduction
F or hot metal desiliconization and dephosphorization, there are two methods:
one uses solid iron oxide, and the other uses oxygen gas to oxidize and remove
silicon or phosphorous. To prevent the decrease of hot metal temperature and
for metallurgical reasons, the latter method is recognized as superior to the
former. The injection station is shown schematically in Fig. 1.
For injection methods, there are the top-blowing method and the fulldip method. With the full-dip method, the reaction efficiency is better but
the operating conditions of the injection lance are more severe. Therefore,
it is desired to develop a refractory material that can withstand such conditions.
Figure 2 shows a lance whose bottom 500 mm has fallen off due to cracking during its second heat. Major causes of the wear of a lance refractory are:
(1) erosion around gas outlet nozzles, (2) falling off of castable lining due to
cracking, and (3) erosion at the slag line. These causes are illustrated in Fig. 3.
The erosion around gas outlet nozzle governs the lance life and is assumed
to be attributable to the pulsating back attack of injected gas bubbles. Next,
we are going to verify this assumption by the water-model experiment.
Figure 4 shows the apparatus for the water model experiment. You can
see a water tank, a lance, and at the uppermost, a powder feeder. The water
tank material, was transparent acryl plate so that its interior could be observed.
Taking into consideration a 100 ton hot metal ladle, the tank size was set to
a scale of two-fifths of the actual size. A two-hole type lance was used; air
was used as the injection gas.
The injection conditions were determined by the modified Froud number.
75
eg
e,
=
=
76
Figure lO(A) shows the wear profile obtained with the immersion depth
of 500 mm and modified Froud number of 2.8. This condition was the greatest
in the degree of wear; the area around the outlet was steeply gouged. Figure
10(B) shows the case for the second greatest in the degree of wear; the area
above the outlet was locally gouged.
Figure ll(C) shows the case for the third greatest in the degree of wear;
the area above the outlet was locally gouged as in the preceding slide. Figure
ll(D) shows the case where the wear is rather slight.
Figure 12(E) shows the case with powder addition. As seen from Fig. l2(&
and 1 2 0 , the degree of wear was slight.
Lets consider the results (Fig. 13). Referring to the simulation of the actual
furnace by the water-model experiment, the wear profile of the outlet area
in the water model experiment was in good agreement with that in the actual
furnace. The crack of the lance in the actual furnace was considered attributable
to lance vibration. The influence of lance vibration was also clarified. Next,
concerning the influence of the gas flow rate, it was found that the erosion
due to the pulsating back attack of injected gas bubbles decreases even with
a modified Froud number over 30. As the velocity of the jet stream reaches
sound velocity, this decrease is considered ascribable to the effect of such highvelocity injection which causes jetting.
It was also found that adding powder reduces the erosion due to the
pulsating back attack of injected gas bubbles. With the addition of powder,
the outlet gas density becomes higher and the modified Froud number also
becomes greater. Also, it is considered that the barrier effect of the powder
energy reduced erosion (Fig. 14).
Next, let us consider the influence of thermal spalling. The wear of the
injection lance cannot be explained only by the previously-mentioned
phenomenon of pulsating back attack of injected gas bubbles and of lance
vibration. That the lance repeatedly suffers the influences of abrupt immersion in high-temperature molten iron bath and air cooling cannot be neglected.
Therefore, the castable lance was tested for spalling.
Figure 15 illustrates the test apparatus used. The test was conducted in
the following way: a sample was immersed in 1500C hot metal for 15 min
and then cooled outside the furnace for 15 min, and this cycle was repeated
10 times.
The typical quality of castable used for lances is shown in Table 111.
Material A contains 92% Alumina and material B 55% Alumina.
Figure 16 shows the appearance at the lst, 5th and 10th cycles. In the
first cycle cracks initiated during cooling for both materials. With material
B, the cracks then progressed gradually. But with material A, such progress
was not observed.
Conclusions
(1) The wear of gas outlet area is attributable to the erosion due to the
pulsating back attack of injected gas bubbles.
(2) The crack of the lance in the actual furnace is attributable to thermal
spalling and lance vibration.
(3) The erosion due to the pulsating back attack of injected gas bubbles
decreases with a modified Froud number Fr > 30.
(4)Adding even a small amount of powder considerably decreases the
erosion due to the pulsating back attack of injected gas bubbles.
77
Table I.
SDecifications
1 mmMax. 40 kg/min
Max. 60 Nm3/Hr
5 kg/cm3
VG: 0.63 m3. P: 9.9 kg/cmZ
Injection conditions
Flow rate
(Nm/h/hole)
1
2
3
4
5
6
7
8
*9
Solidlgas ratio
(kn/k.d
6
8
16
24
6
8
16
24
25
250
500
0.4
0.7
2.7
5.6
3.1
4.4
21.7
27.5
33.0
0.2
0.3
1.4
2.8
1.6
2.2
10.9
13.7
16.5
750
0.1
0.2
0.9
1.9
1.o
1.5
7.2
9.2
11.0
Added water
A1203
MgO
SiO,
CaO
92.19
4.73
0.16
2.23
9
54.94
5.6
(070)
78
39.63
1.40
10
7~8.5
Introduction
S ilicon carbide-class refractories have now been in use throughout the world
in a variety of applications in the blast furnace. This class of refractories
is particularly resistant to chemical, physical, and thermal shock attack in the
severe blast furnace environments, allowing longer and more efficient campaigns. Samples from several furnaces have now been obtained and examined
to determine the chemical and microstructural changes that have taken place.
Three furnaces were examined for this study and represent a variety of
applications. Furnace A is a larger North American, plate-cooled furnace with
water on the shell. Drill cores were obtained 52 mo into the campaign which
saw 10.3 tonne (1 1.4 million ton). These cores were taken from the fifth and
twelfth rows of plate coolers in the lower stack area. Furnace B is a smaller
North American furnace with Shannon one-pipe staves. Whole brick
samples were removed from the bosh, mantle and stack after the production
of 3 million tonne (3.3 million ton). Furnace C is a foreign furnace where the
silicon carbide was used as stave inserts in a four-pipe, stave-cooled system.
These inserts wre in service for eight yr. All three of these furnaces used silicon
nitride-bonded silicon carbide brick.
Background
Table I shows that about one-half of the worids blast furnaces are using
or testing silicon carbide refractories, with many installations of 225 to 765
net tonne (250 to 850 net ton).
Proper blast furnace cooling is more important than refractory selection.
When proper attention is paid to cooling, silicon carbide refractories can be
designed for cooling to improve both furnace life and fuel efficiency.
Worldwide, silicon carbide is being used or installed in over 90 lower and
middle stacks. Table I1 illustrates the various distribution of cooling schemes
utilizing silicon carbide refractories. Of these furnaces, 29 are stave cooled,
with silicon carbide lining thicknesses of 300 to 457 mm (12-16 in.). Of the
furnaces, 63 use copper plate coolers penetrating and supporting the masonry
79
walls; in 33 of these, vertical cooler plate spacing is less than 300 to 400 mm
(less than 12 to 16 in.). Location of silicon carbide here varies from safety
linings at water-cooled shells to full plate-cooler protection, with or without
insulation at the shell. One furnace has a spray-cooled stack, and three use
a combination of staves and plates.
Table I11 indicates the total net tonnage of silicon carbide used around
the world, differentiated by bond types. Silicon-nitride bonded silicon carbide refractories are by far the most commonly used material in the blast furnace as the primary lining. A study of the performance of these refractories
was therefore necessitated.
In furnace A, a safety lining concept was used with silicon carbide applied
against a water-cooled shell faced by fireclay on the hot face. This concept
is illustrated in Figs. 1 and 2. This situation has been used in furnaces in
Germany, South Africa, Spain, and the United States.
In the first 52 mo of furnace A, 10.3 million tonne (11.4 million ton)
of iron were produced. The fireclay eroded relatively rapidly to expose much
of the cooler plates to burden (Fig. 3). The rate of erosion noted with silicon
carbide, however, is lower, tending toward equilibrium. At the 1982 Aachen,
Germany Blast Furnace Refractory Conference, Bauer et al. indicated that
an exposed plate cooler had a heat flow approximately 14 times greater than
that of an insulated or protected plate cooler.
In the other North American furnace, B, a ring of silicon nitride-bonded
silicon carbide was used at the mantle area. After 3 .O million tonne (3.3 million
ton) of production, the 60% alumina refractories above and carbon refractories below were found to be completely gone. Figure 4 shows the location
of the five whole brick samples that were removed for examination. The black
line touching the hot faces of bricks 3 and 4 depicts the resulting minimal wear
condition of the silicon carbide. Brick 5 located in the bosh can be seen to
have worn back more than the others.
Silicon carbide stave inserts were cast into the second and third stack stave
rings and used in furnace C for 8 yr. Although the carbon ram material was
gone in the fourth stack stave ring, the inserts which were exposed to burden
from most of the campaign showed minimal wear. Figure 5 illustrates the condition of the stave inserts after removal.
Observations
The samples as received show that they are in quite good condition. The
cores from furnace A were solid and display only some signs of alkali penetration at the hot face. There was a noticeable darkening of each core near the
hot face. Each of the cores intersected a joint between bricks which may have
eventually influenced the chemical analysis to some degree. Each core displayed
evidence of core loss due to grinding or incomplete recovery. Core 12E had
no exposed hot face for this reason.
The bricks from furnace B were somewhat darkened in color. Upon cutting for sampling purposes, the silicon carbide grog appeared lighter in color
than the bond. The opposite is true for an unused brick. All three bricks showed
a black zone at the hot face. In the mantle and stack samples this zone was
less than 25-mm (1-in.) thick. The bosh brick displayed a zone nearly 50-mm
(2411.) thick. These brick remained well bonded and resisted efforts to dislodge
fragments. The mantle and stack bricks retained the original 33 cm (13 in.)
whereas the sample from the bosh had 18 cm (7 in.) remaining.
80
The stave inserts from furnace C were in very good condition, exhibiting
almost no wear or signs of chemical attack. The hot-face surface had a yellowwhite powdery coating which was later analyzed by X-ray diffraction and found
to be zinc oxide.
Method of Analysis
Samples for this study were analyzed using several methods. Petrographic
samples were taken at selected intervals to study any changes in the microstructural features. These samples were also studied by the scanning electron
microscope for chemical microanalysis in the case of the bricks from furnace
B and the stave inserts from furnace C. Chemistry data for total carbon, free
carbon, and total oxygen were obtained by inorganic analysis.* Silicon carbide content was calculated after subtracting free carbon from total carbon
for each sample. Silica values were calculated from total oxygen after adjusting
for oxygen contained in silicon oxynitride and potassium oxide. Silicon nitride,
silicon oxynitride, and silicon metal were measured by quantitative X-ray
diffraction (QXRD). The method has been described in detail by K. R.
Selkregg.* The remaining elements were analyzed by X-ray fluorescence.
Considering the variety of methods of analysis and the resulting accumulations of errors, the chemistries listed in the tables have yielded quite satisfactory results.
Results
The analyses for the remaining elements do not show any particular trends.
Sulfur, aluminum, iron, titanium, and calcium are found in background levels
and do not show any significant changes. Zinc analyses, however, reveal that
there has been a slight influx of this metal at the hot face. Because zinc
vaporizes and condenses at 907"C, it would be possible to define an isotherm
at a region of maximum deposition. These samples unfortunately do not give
us that information, as maximum deposition is located at the hot face.
In polished section, all cores appear quite similar in microstructure from
hot face to cold face. Figure 6 illustrates the glass formation at the hot face
found in core 5D.Although the position of the hot face edge is just above
the field of view, silicon nitride is present this close to the edge. This suggests
retention of strength in the brick and that mechanical wear is an important
factor in loss of material from this brick. It is uncertain whether the cracking
that is seen in the right hand portion of Fig. 6 is due to these mechanical stresses
or to thermal stress. Figure 7 illustrates a densely bonded area several mm
away from the hot face in core 12A. The relationship of the various phases
can be better seen. Glassy areas can be seen closely associated with several
of the silicon carbide grog. Pitting that is apparently crystallographically controlled within the silicon carbide grains can be observed and is typically due
to oxidation. Smaller grains are more susceptible to this reaction which can
be more easily seen in Fig. 8. Some oxidation of the silicon nitride can also
be detected. Deposition of free carbon in the open porosity is more common
in the hot face samples and can best be seen in Fig. 7.
The microstructures of the samples back from the hot face show various
degrees of glass formation and bond densities. Figures 8-10 serve to illustrate
these variations. Sample 12B-2 (Fig. 8), approximately 7.6 cm (3 in.) from
the hot face, illustrates a very densely bonded zone. Some signs of oxidation
on silicon carbide grains are visible as parallel pits. Little glass can be detected
in the area. Figure 9 from core 12E displays a mixture of bond and some glass
formation. Figure 10 illustrates a pocket of high glass content in core 5D
approximately 13 cm (5 in.) from the hot face. These variations are probably
due to local original fluctuations in density or porosity in the bricks as well
as proximity of the sample to a joint between bricks.
At the cold face, all cores showed some oxidation in the immediate area
of the cold face. The environment apparently is more oxidizing in the area
closest to the furnace shell. The packing material may exert some influence
in this zone, but this would be an area of movement for water and other vapors.
This small zone will not ultimately alter the performance characteristics of
the refractory lining. Figure 1 1 illustrates a well-bonded area at the cold lface
with some oxidized silicon carbide and altered bond at the left-hand side of
the photomicrograph.
the oxidation of the fine silicon carbide grog and subsequent redeposition of
carbon, and (2) the possible influx of carbon monoxide and subsequent reduction reaction to carbon.
The chemistry data for the remaining elements can be found in Table IX.
Potassium levels showed some expected penetration and deposition with a concentration of 2.5% found at the hot face. Other elements of interest are not
found to vary significantly and are at the expected background levels. Two
noteworthy exceptions are sulfur and zinc, but the levels are not very high.
Magnesium was not detected in these samples.
In polished section, the silicon nitride bond quality remains good even
in the vicinity of the hot face. Only at the exposed edge of the hot face is no
silicon nitride found. Just inside from this edge, bond appears and displays
some connective qualities. Adhesion of the bond to the silicon carbide grog
can still be observed. Some of the porosity has been filled with glass. Minor
amounts of amorphous carbon can also be found scattered throughout the
porosity. These alterations become less evident further into the brick, although
small amounts of glass are still evident.
Spectrochemical analyses by SEM show that much of the glass at the hot
face is silica with few impurities. Analyses 1 and 2 in Table XI1 represent areas
of glass in which chlorine was found. The analyses were not calculated in terms
of oxides, but rather weight percent for each element. Analyses 3 and 4 represent glass analyses from an area approximately 2 cm (?A in.) from the hot face.
Brick No. 3 from the Mantle: This brick was located in course 12 in the
mantle. It showed virtually no loss due to wear. Table X contains the calculated
silicon carbide and silica values for this sample, as well as the free carbon
distribution. The samples represent 2.5-cm (1-in.) increments from hot face
(No. 1) to cold face (No. 13). Free carbon data indicates that it was deposited
quite heavily within the first 7.6 cm (3 in.) of the hot face but decreases to
background levels through the rest of the brick. Silicon carbide and silica follow
the same trend as indicated by brick No. 5. The data for silicon nitride,
however, shows that very little of the bond phase has been lost. Calculated
silica values support this observation that oxidation has occurred to a limited
extent as they are only approximately twice that found in an unused brick.
Chemistry data for the remaining elements are in normal levels except
for potassium, sulfur, and zinc. Penetration by potassium vapors was quite
limited in this case and almost confined t o the hot face area. Minor amounts
of sulfur and zinc are concentrated 7.6 to 12.7 cm (3 to 5 in.) from the hot face.
In polished section, little alteration of the bond can be detected and a
well-developed bond that exhibits excellent connective qualities is displayed.
Minor oxidation features are visible on some of the silicon carbide grains.
Brick No. 4 from the Stack: This brick was retrieved from row 20 in the
stack. As with brick No. 3, this sample does not show any physical loss of
material. An examination of the chemistry data given in Table XI shows a
somewhat different pattern of variations in silicon carbide, silica, free carbon, and bond contents. It is curious that silicon carbide contents are the lowest
at both the hot face and cold face, with a corresponding increase of silica and
free carbon. This may indicate that there may be a slight tendency toward
oxidizing conditions along the furnace shell. It is possible that this brick was
located near a break in the water cooling system and had been subject to oxidation by steam. Overall silica values again are only twice that which would be
found in an unused brick.
83
was only 10% as high as that noted with 400-500 mm (16 to 20 in.) vertical
plate cooler spacing. This suggests benefits from the combination of silicon
carbide and intensified plate-cooler concentration.
In an early 1974 Japanese trial, silicon carbide fully covered the cooler
plates. Since 1979, this concept has been applied in 16 additional plate-cooled
furnaces in Belgium, Brazil, Canada, Germany, Portugal, Spain, Sweden,
Taiwan, and South Africa. This is illustrated by Fig. 12. With water-cooled
shells, a high conductivity ram was used between shell and silicon carbide;
with air cooled shell, insulating fill was used.
The latest concept with air-cooled shells locates silicon carbide at the platecooler nose, with fireclay brick and/or insulating fill between silicon carbide
and the steel shell (Fig. 13). Three-dimensional finite element analyses assure
that the silicon carbide/fireclay interface is kept well below 600C (1 100F),
the temperature at which fireclay would be subject to alkali vapor attack. This
idea, nicknamed the sandwich concept, saves money (less silicon carbide)
and coke (less heat flux in walls). This concept has been applied in 9 platecooled furnaces in Belgium, Brazil, Germany, Italy, Mexico, Sweden, and the
United States.
Second, the oxidation resistance of these samples was shown to be quite
good, as a high degree of preservation of the silicon nitride bond was found.
Oxidation seems to be most prevalent at the hot face and decreases toward
the cold face. Almost all samples show a small zone of local oxidation at the
immediate cold face, indicating some local effects of fluids present along the
furnace shell. Oxidation appears to affect the finer-grained bond and silicon
carbide as these particles have a higher surface area.
Carbon deposition is common to most samples and found to be most
prevalent to the first few cm within the hot face. The most likely source of
this is the redeposition of carbon coming from the oxidation of silicon carbide. Among other elements of interest, zinc is found as a minor component
in the chemistry, but does not appear to have any detrimental effects.
Finally, thermal cracking was not evident in the original samples as
received out of service. In polished samples, only small cracks in individual
silicon carbide grains were observed. No large cracks were at any time found
in the brick or the core samples.
The retention of silicon nitride bond demonstrates that abrasion by
descending burden of the alkali and/or oxidation altered surfaces was the dominant mechanism of wear in these blast furnaces.
References
85
00
o\
Hearth
diameter:
Number of furnaces/
SIC installations
VO Sic usageldiameter
49%
44 vo
3/2
4/ 1
15/8
53%
o/o
16/9
26/ 15
512
9/2
3/ 1
59/29
26/ 15
21/11
3/1
15/4
6/0
71/31
4/2
4/3
30-33 ft
9-10 m
23-30 ft
1-9 m
16-23 ft
5-7 m
53%
616
22/ 11
18/8
2/ L
5/2
53/28
33-39 ft
10-12 rn
Area
Table I.
69 Yo
2/ 1
5/5
25/16
1/1
2/ 1
35/24
39-48 ft
12-15 m
54/33
78/45
51/27
30/ 10
20/5
233/120
Total
61 Yo
58%
53%
33%
25
yo
52%
070 Fce.
with Sic
Bosh
Mantle
Belly
28
6
8
23
29
14
(12)
( 2)
24
2
68
29
3
63
26
NA
NA
NA
(22)
( 4)
37
Lower and
middle stack
(33)
(22)
( 8)
56
96
Table 111. Usage of Silicon Carbide Blast Furnace Refractories by Bond Type,
Tonne
Number of
Droducers
Bond tvDe
Silicon nitride
(Si3N.l)
Beta-silicon carbide
@-Sic)
Silicon oxynitride
(Si,ON,)
SIALON
(Si, - xA1xO,N, "j
~
World-wide
Outside Japan
tonne
Vo furnaces tonne
Yo furnaces
11
16 857 60.6
92
16 213 80.0
88
10
10 219 36.7
57
3 325 16.4
27
6
2
450
1.9
13
477
2.6
12
248
0.9
248
1.3
------
87
12A
0-25
5 1-76
102-127
152-178
203-229
12B
0-25
5 1-76
102-127
152-178
12E
0-25
51-76
102-127
152-178
203-229
5D
0-25
51-76
102-127
152-178
Table V.
AlphaSi,N,
BetaSi,N,
11.7
10.1
10.0
2.3
10.0
3.4
1.9
2.0
13.6
1.8
10.2
15.3
17.5
17.7
3.1
4.1
Si,ON,
Si metal
Cristobalite
0.3
3.5
0.2
3 .O
5.1
0.2
4.5
5.4
9.2
15.5
15.4
13.0
14.4
17.1
3.6
2.7
2.4
3.6
7.4
13.6
9.5
16.7
4.9
4.1
7.3
5.7
trace
2.2
Distance from
hot face (mm)
S i c (c)
Free carbon
SiO, (c)
Si3N,
Si,ON,
K2O
so3
A1203
Fe203
Ti02
CaO
ZnO
Si metal
Total
(c)-Calculated
0-25
5 1-76
64.90
1.51
10.29
15.1
75.88
1.22
3.59
12.0
3.5
0.33
0.05
0.33
0.86
0.13
0.22
0.005
6.95
0.05
0.39
0.78
0.04
0.33
0.363
0.3
101.oo
102- 127
152-178
203-229
78.82
0.87
4.07
12.00
65.73
1.34
8.18
15.9
3.0
5.21
0.05
0.26
0.78
0.03
0.22
0.017
75.34
1.19
4.17
11.8
5.1
0.22
0.05
0.31
0.68
0.09
0.27
0.004
100.72
99.17
0.23
0.05
0.26
0.77
0.03
0.30
0.005
0.2
97.35
98.12
88
Table VI.
Distance from
hot face (mm)
S i c (c)
Free carbon
SiO, (c)
Si,N,
Si,ON,
K2O
A1203
Fez03
TiO,
CaO
ZnO
Si metal
Total
Distance from
hot face (mm)
Sic
Free carbon
SiO, (c)
Si3N,
Si20N,
K@
so3
A1Z03
Fe203
TiO,
CaO
ZnO
Total
5 1-76
67.53
2.30
6.83
13.3
67.44
1.51
4.52
19.4
5.31
0.10
0.38
0.79
0.04
0.30
0.032
so3
Table VII.
0-25
96.91
102-127
72.86
0.86
2.50
22.0
3.77
0.06
0.28
0.87
0.04
0.39
0.028
0.2
98.51
0.09
0.05
0.26
0.85
0.03
0.47
0.0059
99.98
152-178
72.11
0.80
2.61
23.10
0.05
0.06
0.41
0.73
0.04
0.37
0.0049
100.29
5 1-76
102-127
152-178
203-229
69.64
1.27
3.37
24.70
74.31
1.08
3.14
19.00
76.92
0.70
3.38
15.70
76.58
0.74
3.30
16.80
73.54
0.80
3.34
20.70
1.37
0.05
0.55
0.78
0.04
0.29
0.007
100.70
0.16
0.05
0.90
0.68
0.05
0.3 1
0.003
99.68
0.05
0.03
0.65
0.57
0.04
0.32
0.003
98.36
0.05
0.04
0.68
0.84
0.04
0.42
0.005
98.50
0.03
0.06
0.55
0.60
0.04
0.20
0.003
99.86
89
Chemistrv of Core 5D
Table VIII.
Distance from
hot face (mm)
0-25
S i c (c)
Free carbon
SiO, (c)
Si3N4
%,ON,
K2O
so3
Fez03
TiO,
CaO
ZnO
Total
Table IX.
A1Z03
TiO,
CaO
K2O
so3
ZnO
Total
102-127
152-178
64.73
2.29
13.06
13.30
72.51
I .47
4.17
17.70
5.26
0.05
0.29
0.85
0.12
0.23
0.026
100.22
1.30
0.13
0.40
0.78
0.05
0.53
0.014
99.05
68.97
1.91
6.74
16.8
2.2
2.00
0.04
0.24
0.88
0.05
0.24
0.007
100.08
71.04
1.21
2.14
22.4
2s
76
127
178
69.14
5.14
11.17
6.6
70.19
4.24
10.17
9.2
72.69
3.07
6.40
11.2
72.73
2.39
6.44
12.5
0.25
0.37
0.04
0.20
2.51
0.08
0.006
95.51
0.31
0.38
0.04
0.25
0.52
0.11
0.02
95.43
0.27
0.36
0.04
0.23
0.31
0.12
0.02
94.71
0.26
0.37
0.04
0.22
0.40
0.12
0.04
95.57
0.17
0.03
0.24
0.84
0.04
0.35
0.004
98.46
Distance from
hot face (mm)
Sic
Free carbon
SiO,
Si3N4
Si,ON,
Si metal
S 1-76
90
Table X.
Distance from
hot face (mm)
Sic
Free carbon
SiO,
Si3N,
Si,ON,
Si metal
AM33
Fe203
TiO,
CaO
K20
so3
ZnO
Total
Table XI.
Sic
Free carbon
SiO,
Si3N,
Si20N,
Si metal
AW,
Fe203
TiO,
CaO
K2O
ZnO
MgO
Total
76
127
178
229
279
330
69.21
3.31
4.24
17.3
0.7
71.63
1.76
3.59
14.1
1.8
73.66
1.14
2.47
16.4
3.6
74.55
0.57
4.71
13.9
3.8
75.11
0.53
1.77
16.8
3.8
74.18
0.46
2.48
16.1
3.3
74.01
0.47
3.12
15.9
0.48
0.42
0.05
0.16
0.32
0.11
0.02
96.32
0.42
0.35
0.05
0.18
0.14
0.18
0.12
94.32
0.51
0.34
0.05
0.19
0.11
0.15
0.08
98.70
0.94
0.42
0.07
0.19
0.11
0.06
0.01
99.33
0.50
0.34
0.05
0.21
0.08
0.05
0.01
99.45
0.87
0.35
0.07
0.18
0.06
0.05
0.01
98.11
0.99
0.35
0.07
0.18
0.14
0.09
0.02
95.34
Distance from
hot face (mm)
so,
25
25
76
127
178
229
279
330
68.00
1.57
4.24
19.7
70.67
1.00
3.22
20.4
70.27
0.92
4.71
18.2
71.66
0.91
2.58
19.7
72.08
0.87
2.27
21.3
72.86
0.89
2.55
19.5
69.56
1.96
3.09
20.3
0.61
0.51
0.06
0.28
0.34
0.30
0.29
0.3
1.32
0.51
0.17
0.32
0.40
0.31
0.26
0.3
0.67
0.54
0.06
0.36
0.29
0.20
0.08
0.47
0.56
0.09
0.39
0.32
0.20
0.09
0.59
0.54
0.06
0.21
0.30
0.14
0.02
0.95
0.60
0.08
0.22
0.41
0.26
0.01
97.68
97.69
98.25
98.69
97.66
97.44
0.5
0.84
0.48
0.06
0.24
0.94
0.55
0.58
0.19
97.86
91
Table XII. SEM Spectrochemical Analysis in Hot Face Area from Brick
No. 5, Furnace B
Na
A1
Si
S
c1
K
Ca
Ti
Fe
(1)
(2)
1.3
9.4
68.6
2.2
3.1
4.8
1.9
1.O
7.6
n.d.
(3)
Na,O
A1203
SiO,
K2O
7.3
85.3
0.6
0.6
1.o
0.3
4.8
(4)
0.8
1.7
83.7
13.8
0.8
1.5
83 .O
14.8
n.d.
14.2
3.2
11.8
5.4
11.0
6.1
12.4
8.7
12.4
5.7
13.5
6.1
6.1
15.9
Trace
Trace
Trace
Trace
Trace
Trace
Trace
Table XIV. SEM Spectrochemical Analysis in Hot Face Area of Stave Insert
from Furnace C
(2)
(1)
Na20
MgO
A1,0,
SiO,
K2O
FeO
13.6
9.9
3.0
69.0
2.6
1.7
Na
Mg
A1
Si
c1
Fe
Zn
Mn
(3)
Trace
.68
22.2
50.7
0.6
19.7
Trace
92
(4)
(5)
Trace
13.9
27.1
1.5
14.3
20.0
11.8
3.4
11.0
45.2
2.5
41.3
0.3
1.7
46.2
51.8
t
12
3 I2111111
93
94
95
96
97
t
I
390
99
THOMAS
R. HOLMES
Refractories Division, Sohio Engineered Matls. Co.
End Crows Mill Rd. West, Keasbey, NJ 08832
Recent developments in the understanding of the wear mechanisms of blast furnace
refractories, and in laboratory testing methods, have been applied to the improvement
of the resistance to alkali attack of silicon nitride-bonded silicon carbide refractories.
Further work has led to the development of a Sic refractory bonded with a system
consisting predominantly of a sialon phase, exhibiting enhanced physical properties
and exceptional resistance to alkali attack and to the combined eflects of oxidation
and alkali aggression.
Introduction
S ilicon carbide was invented by the founder of The Carborundum Company
in the late 1800s and, after being widely used in the manufacture of abrasives,
entered the refractories industry in the period between the world wars. Those
early S i c refractory materials, bonded by clay, silica, and silicates, exhibited
attractive properties such as excellent resistance to abrasion and thermal shock,
and high thermal conductivity, which led to their extensive application in
nonferrous metallurgy, incinerators, burners, muffles, and kiln furniture for
the ceramic and abrasive industries. When nitride bonding was developed by
us in the late 1950s, Si,N,-bonded S i c refractories appeared in the market as
a premium product offering higher mechanical strength at elevated
temperatures and improved chemical stability. Nitride bonding, moreover,
eventually opened the road for the introduction of S i c refractories in the blast
furnace, if we discount the clay-bonded S i c wear plates that had been in use
in the throat for some time. In 1971 it was first used as stave inserts in a Port
Kembla, Australia, blast furnace, and the same year it was also installed in
the tuyere-zone lining of an American furnace.
The decade of the 70s saw Si,N,-bonded S i c refractories expanding their
area of application in the blast furnace towards the bosh, belly/mantle, and
lower stack areas, i.e., the most critical zones of the furnace. The first tests
took place sequentially in the lower stack (Muroran, Japan, 1974), in the bosh
(Sparrows Point, Maryland, 1976), and in the belly (Dunkerque, France, 1977).
The reasons for this expansion are the superior combination of desirable
properties (especially high-alkali and oxidation resistance, high thermal
conductivity, high strength, good thermal shock and abrasion resistance at
100
elevated temperatures) offered by these products. The trend towards increasingly severe service conditions in the blast furnace, and the modern
developments in blast furnace cooling technology, design and operational
procedures required improved refractories.
Meanwhile, new Sic refractories bonded with alternative bond systems
@-Sic, silicon oxynitride, and oxide phases in the Si0,-A1,03 system) were
developed and applied to the lining of the blast furnace. Their composition,
manufacture, and properties have been described in a number of
The result is that, although the world number of blast furnaces has diminished
drastically during the last five yr, the number of furnaces with Sic installations has actually grown from 30% in 1980to 50% in mid-1985, and this figure
reaches 69% in the class of large furnaces with hearth diameter above 12 m
(Table I). Table XI shows present areas of application in world blast furnaces,
and Table 111 summarizes the usage of Sic blast furnace refractories by bond
type. About 60% of the installed tonnage is of the Si,N,-bond class; another
40% is shared between the self-bonded (j3-Sic-bonded) products and the
Sic bonded with phases in the SO,-Al,O, system (this latter class has practically no share of the market outside Japan), and 2% belongs to Sic bonded
by silicon oxynitride, Si,ON,.
Finally, a new class of Sic refractories,bonded by sialon, has appeared
recently in the market6, exhibiting improved resistance to chemical corrosion
by the blast furnace atmosphere, in particular by alkali and oxidizing species.
Materials in this class have been installed in five blast furnaces to date, and
some years will still have to elapse before performance data become available;
only then will it be confirmed whether sialon-bonded Sic refractories can be
considered as the next-generation lining for the critical areas of the blast furnace
wall.
It is the purpose of this paper to outline the research work carried out
on the improvement of the alkali resistance of blast furnace Sic refractories,
and to discuss the composition and properties of a new sialon-bonded Sic
refractory wth exceptional resistance to alkali and the combined effects of alkali
and oxidation attack.
Alkali Attack Mechanisms
The primary objective of the research program was to elucidate the factors
affecting the alkali attack of SIC refractories in blast furnace environments,
and to apply this information to the improvement of the alkali resistance of
the product. A review of the literature showed that much information is
available on the recirculation and concentration of alkalis (especially potassium)
in the blast furnace atmosphere, and that the attack of alkalis on fireclay,
high-alumina, and carbodgraphite refractories is well documented. The
mechanisms of attack on these materials have been reviewed elsewhere*and
will only be summarized here. With refractories of the Si0,-Al,O, system, the
reaction appears to proceed via a vapor-phase mechanism; the reaction
products are, depending on the composition of the refractory, kaliophilite
(SiOJCAl), leucite (Si,O,KAl), and beta-alumina (K,O. 11A1203),formed
from the alumina or mullite grain and the silicate matrix. These products exhibit
higher specific volumes and higher coefficients of thermal expansion than the
original brick, and the refractory lining, subjected to cyclic temperature variations, fails through a combination of thermal and thermo-mechanical stresses.
With carbon and semi-graphite refractories, the attack mechanisms are not
101
103
Oxidation Test
A high resistance to oxidation attack by CO,, SiO, and H,O, inherent
to the traditional oxide refractories, is an important requisite in Sic blast
furnace refractories, second only to alkali resistance in the opinion of many
blast furnace operators. For laboratory evaluation, a steam test such as ASTM
C 863 is preferred because steam hydrolizes the protective surface silica film
formed on oxidation and allows the attack to proceed further into the sample,
thus giving a better discrimination. Table V lists the volume expansion and
cristobalite contents of different Sic refractories exposed to steam at 1100C
for either 375 or 500 h. It should be noted that cristobalite is only one of the
oxidation products; the major product seems to be silica or silicate glass. It
is seen that, as a class, Si,N,-bonded Sic refractories are more resistant to
steam oxidation than those bonded with P-SiC; individual differences exist
between products within the same bond class. The range of response to the
oxidation test is quite wide in the Sic refractories bonded with phases in the
Si0,-Al,O, system, and this is a reflection of the widely different bond
systems which are grouped together within this particular class.
Oxidation and Alkali Sequential Tests
In an attempt to study on the same test piece the combined effects of
oxidation and alkali attack, several workers have been conducting experiments
in which previously oxidized test pieces are subjected to alkali attack, or alternatively, previously alkali-attacked samples are subjected to an oxidation test.
The procedure adopted in this work follows the first approach: 150 x 25 x 25
mm test bars are oxidized in steam at 1100C for times ranging between 325
and 500 h, the oxidized samples being then subjected to the molten alkali test
described above. Table VI shows typical results for a number of Sic refractories in the Si3N, and /3-SiC bond systems. The Si,N,-bonded products
exhibited a much lower weight loss than the self-bonded Sic refractories, even
if the oxidizing period for the former was generally 500 h rather than the 325
h used for the latter. Residual MOR values are of limited significance because
of the distorted geometry of the specimens after the attack.
This sequential test is considered too severe to discriminate effectively
between individual products within the same bond class, but it does show a
clear distinction between the Sic-bonded refractories, which are practically
destroyed in the test, and the Si,N,-bonded products, which typically show
weight losses between 15 and 40%.
Research on Alkali Resistance Improvement
a blast furnace refractory. As shown in the figure, the response of the material
to the alkali test exhibited a wide scatter, and there seemed to exist an almost
linear relationship between the amount of as-fired surface present in the test
bars and the weight loss under the alkali test. Therefore, a research program
was initiated by mid-1981 with the dual purpose of improving the overall alkali
resistance of the product and, at the same time, decreasing the wide variations of response to the test both between and within bricks.
X-ray examination of the nitride-bonded material revealed that the two
crystalline phases of silicon nitride coexisted in proportions which differed
markedly from the fired surface to the interior of the brick. Silicon oxynitride
(Si,ON,) also appeared frequently as a relatively minor constituent of the
bond system. However, a correlation could not be established experimentally
between the molten alkali resistance and the relative proportions of these three
bond components (a-Si,N,, /3-Si,N4, and Si,ON,), at least in the composition
range normally seen in the product. Oxygen analysis revealed that the oxygen
content in the bulk of the brick was typically in the 0.8- 1.O% range, but rose
steeply in the vicinity of the fired surface. It was then speculated that this excess
oxygen, probably present as silica or silicate films surrounding the Sic grog
grains, would be selectively attacked by the alkali and would therefore be
responsible for the low alkali resistance of test bars containing a large amount
of as-fired surface. These observations led to improvements in the processing
of the refractory tending to a better control of the presence of oxygen in the
product. As a result, it was possible to achieve a better uniformity in the
response to the molten alkali test between outside and inside test bars,
and to reduce the alkali weight loss to a consistent 4-5% level (product 2 in
Fig. 6).
The properties of the original (product 1) and improved (product,2) refractories are listed in Table VIII. Apart from the increased resistance to molten
alkali attack, all other properties of the improved material were maintained
at their original levels, but it was observed that the improvement in alkali
resistance was accompanied by a decrease in the resistance to steam oxidation. The sequential oxidation/alkali test, however, demonstrated that the
overall corrosion resistance of the refractory to the combined effects of oxidation and alkali attack had been clearly improved. The thermal shock resistance
of the original and improved refractories was measured at the Teeside
Laboratories of British Steel Corp., via the ribbon test method. The retention
of Youngs modulus after the test was 99.49% for product 1, and 99.42%
for product 2, each figure being the average of six determination^.'^
This improved refractory became commercially available in 1981, and 3780
tome (4200 tons) have been installed or on order to date in 26 blast furnaces
in North America, Europe, and Australia.
that the alkali-attacked test bars still exhibit a strength in the 48 MPa (7000
psi) region as the original sample. Resistance to steam oxidation was maintained at the same levels as in the predecessor Si3N4-bondedSic refractory
(product 2).
Analysis of the final product by X-ray diffractometry (forward reflection area, using Ni-filtered Cu K, radiation) revealed diffraction peaks for
a-Sic, a-Si3N4,and /3-Si3N4.Judging from the diffractometry data, the bond
had the two nitrides of silicon as the sole components, with a (weight) a:P
ratio of 20:80. No silicon oxynitride or silica were detected. At the optical
microscope (Fig. 7), two regions of different reflectivity could be detected in
the bond phase; EDAX analysis showed that these two regions differed also
in elemental composition, one of them (accounting for about 70% of the bond
system) containing amounts of aluminum and oxygen that would identify it
as a sialon composition in the /3' -sialon range. The z-value of the sialon phase
has been studied by measuring the 28 shift of a representative X-ray diffraction peak, using the latest data available from the University of Newcastle
(U.K.) for the expansion of the unit cell dimensions, and has been found to
lie in the 0.5-0.7 range with the error in individual measurements estimated
as +0.05. Examination of fractured surfaces at the SEM (Figs. 8 and 9)
revealed a dense, massive bond structure, excellent adherence between the bond
and the a-Sic grog grains, and the type of intragranular fracture normally
associated with a high strength.
The excellent resistance to alkali attack of the product was confirmed by
an independent laboratory using hot MOR measurement of alkali-impregnated
samples. In this procedure, test bars cut from sample bricks are vacuumimpregnated with a 4 molar K2C03solution, dried, weighed and soaked at
the test temperature for 12 h, after which load is applied and the hot MOR
measured. These results are compared with the hot MOR values for the asreceived material.
Results are presented in Figs. 10 and 11 for the sialon-bonded refractory
(product 3) and its predecessor the Si,N4-bonded Sic refractory (product 2).
The hot strength of the alkali-impregnated bars of product 2 decreased gradually for temperatures above 400"C, which was described as typical for the
majority of Sic refractories, and attained a maximum loss (about 50%) at
1OOO"C. Product 3, by contrast, maintained its original strenght up to 1200"C,
which is about the maximum temperature expected at the hot face of the blast
furnace lining. l4 These data demonstrate dramatically the superiority of the
sialon bond over the Si,N, bond in resistance to chemical attack by alkali.
The resistance to steam oxidation of the sialon-bonded product remains
the same as for product 2. The response to the combined effects of oxidation
and alkali, however, has been noticeably improved.
Thermal diffusivity measurements were made by the laser flash technique
at the Virginia Polytechnic Institute: results are shown in Fig. 12 together with
data for the Si,N4-bonded refractory (product 2) for comparison purposes.
Thermal conductivity values shown in Table IX for product 3 were calculated
from these thermal diffusivity data, and have also been confirmed by an independent laboratory, in the room temperature-700C range, via the hot wire
method.14
Molten iron penetration tests were made at the Teesside Laboratories of
British Steel Corporation, England, on samples of the sialon-bonded refractory and their two predecessor Si,N4-bonded materials. The test involved
107
closed cylindrical crucibles (75 mm high and 25 mm diameter, internal dimensions) made of the refractory materials, which were charged with iron through
a 12-mm diameter opening in the lid. Test conditions were 1500C and reducing
atmosphere; after the test, the crucible was sectioned and examined by X-ray
fluorescence to measure the depth of iron penetration. Test results were
described as negligible penetration in all cases.15
Product 3 was commercially available in 1984, and 140 tonnes (155 tons)
have been installed to date for trials in four blast furnaces in North America,
Europe, and Australia.
Conclusions
Table IX shows typical properties for product 3 together with the
characterization carried out in our laboratories of three leading competitive
Sic refractories for blast furnace use.
Product P is a Sic refractory that has appeared recently in the European
market and which is also described as sialon-bonded. The fact that two independent manufacturers have developed almost simultaneously two different
versions of Sic refractories bonded with sialon shows the interest existing in
the industry towards alternative bond systems. The product has good physical
properties and oxidation resistance; the relatively low levels of resistance to
alkali attack (as evidenced by the strength loss after attack), and to oxidation/alkali attack, may be a reflection of a different manufacturing route
leading to incomplete sialon bonding. Product H is a leading self-bonded Sic
refractory that exhibits moderate physical properties and excellent resistance
to molten alkali attack; although the MOR degradation under alkali is slight,
the residual MOR is low because of the low original strength. As most selfbonded products, its resistance to steam oxidation is poor; the material is
practically destroyed in the oxidation/alkali test. Product S is a leading
Si,N,-bonded Sic refractory with excellent density and cold MOR, moderate
resistance to alkali attack, and poor steam oxidation resistance.
In conclusion, a sialon-bonded Sic refractory material has been developed
with excellent resistance to the attack by alkali and to the combined effects
of oxidation and alkali attack. Ongoing trials in blast furnace situations will
confirm whether the performance of the material in service responds to the
expectations raised by the results of laboratory tests.
Acknowledgments
The authors are indebted to J . Van Laar, Hoogovens IJmuiden, The
Netherlands, for his permission to present the results shown in Figs. 10 and
11 and to quote from his thermal conductivity work, and to M.O. Warman,
British Steel Corporation, U.K., for his permission to quote his ribbon test
and molten iron penetration test results.
Among our colleagues at SOH10 Engineered Materials, Refractories Division, especial thanks are due to Kevin R. Selkregg and Donald K. Henry who
have provided the analytical, X-ray diffraction, optical microscopy, and SEM
microscopy data, and to John A. Bonar and Roy W. Brown, who reviewed
the manuscript and contributed very valuable data, criticisms, and suggestions.
References
R.W . Brown, Silicon Carbide Refractories in Blast Furnace Linings, Paper presented
at the ILAFA-ALAFAR Congress on Refractories, Lima, Peru (1980).
2D. Campos-Loriz, and R. W. Brown, Silicon Carbide Refractories in the Blast Furnace,
108
Paper delivered to the 1st Ibero-American Congress of Ceramics, Glass, and Refractories,
Torremolinos, Spain (1982).
3J. W. Kaufman, D. Campos-Loriz, K. R. Selkregg, and T. R. Holmes, Performance
Characteristics of Silicon Carbide Refractories in Blast Furnaces, Infercerum (1983), Special
Issue, 48.
R. W. Brown, and J. A. Bonar, Special Refractories for the 198Os, Ind. Miner. (Supplement), April 1983.
5R. W. Brown, Silicon Carbide Blast Furnace Refractories, Iron Steelmaker, May 1983.
65. M. Bauer, R. D. Schmidt-Whitley, D. Dumas, B. Du Mesnildot, and J. P. Kiehl, New
Solutions for Problem Areas of Blast Furnace Linings, Intercerum (1983), Special Issue, 25.
7D. Campos-Loriz, Chemical Corrosion Testing of Sic Refractories for Blast Furnace
Use, Paper delivered to the 86th Annual Meeting of the American Ceramic Society, Pittsburgh,
PA. (1984).
ED. Campos-Loriz, K. R. Selkregg, and Y. Tagami, Alkali Attack Mechanisms on Blast
Furnace Refractories, Tuikubutsu Overseas, 2, 1 (1982).
9R. H. Herron, and C. R. Beechan, Effect of Surface Alteration of Refractory Linings
and Process Variables on Corrosion Kinetics in Ironmaking and Steelmaking Furnaces. Paper
presented to the American Ceramic Society, Washington, D.C., May 5, 1981.
lop. H. Havranek,: Alkali Attack on Blast Furnace Refractories, Trans. J. Brit. Cerum.
SOC.77 [3] 92 (1978).
1.
Shimada, Y. Koyama, T. Hayashi, and M. Shibuno, A Few Problems in Blast
Furnace Lining Behavior, SIPRE Working Group IV: Blast Furnace Refracotires. SIPRE and
ATS, p. 14 (1977).
l*K. Hiragushi, K. Mizutani, and T. Nagai, A New Approach to Blast Furnace Stack
Linings, Iron Steel Eng., 47 June 1978.
l3R. H. Herron, Bethlehem Steel Corporation, private communication (1981).
145. Van Laar, Hoogovens IJmuiden, private communication (1984).
I5M. 0. Warman, British Steel Corporation, Teesside Laboratories, U.K., private communication (1985).
Table I.
North America
Europe
Japan and
Far East
Africa/India/
Australia
South America
No. fces/SiC
installations
Yo Sic usage/
diameter
Hearth diameter:
16-23
23-30
5-7
7-9
30-33
9-10
33-39
10-12
39-48
12-15
Total
Yo Fces
with
Si c
4/2
4/3
28/15
21/11
17/10
26/15
7/7
22/10
2/1
5/5
58/35
78/44
60
56
0/0
3/1
5/2
18/8
25/16
51/27
53
3/2
4/1
15/4
4/0
9/1
2/0
2/1
4/0
2/1
1/1
3019
16/2
30
13
15/8
71/31
59/28
53/26
53
44
47
49
109
35/24 233/117
69
50
Table 11. Area of Usage of Sic Refractories in Blast Furnaces by Hearth Diameter
ft
m
Hearth diameter:
16-23
23-30
5-7
7-9
Tuyere band
Bosh
Belly
Mantle
Lower and
middle stack
Stave inserts
Stockline
30-33
9-10
33-40
10-12
40-49
12-15
Total
2
2
2
4
17
14
6
13
13
20
15
6
6
13
15
9
7
15
14
4
45
64
53
36
8
1
1
16
1
2
18
1
28
4
3
21
2
1
91
9
7
Table 111. Usage of Silicon Carbide Blast Furnace Refractories by Bond Type
(Net Tons)
World-Wide
Bond Type
No. of
producers
Si,N,
P-SiC
Si0,-Al,O,
System
Si,ON,
Sialon
Tons
To
9
7
16845
5690
57.9
19.5
many
6
2
5750
550
275
29110
19.8
1.9
0.9
100.0
~~
Outside japan
Fces
91
35
Tons
Vo
16300
3720
78.1
17.8
20
40
0.2
13
530
2.6
275 _ 1.3
~ 5_ _
164* 20965 100.0
Fces
85
25
2
12
5
129*
*Furnaces, not orders. Some multiple trials and obsolete furnaces included in these numbers.
Table IV.
Si,N,-bonded S i c
A
B
D
E
F
0-Sic-bonded S i c
G
H
- 13
-4
- 24
- 21
- 10
+1
+ 0.5
+ 0.8
I
*Bars too damaged for MOR measurement.
110
Change in
MOR (070)
30
- 20
(*)
(*I
-
30
20
10
- 40
Volume expansion
(To)
Cristobalite
(weight %)
0.9 - 2.6
0.8
0.5
1.6
0.1
1.o
7.1
5.2
5.O
5.6
1.4
5.5
16.9
58.0
3.5*-59.0
3.2 -10.6
Disintegrated
14.9
21.4
8.3*-19.4
9.1
83.7
0.9
2.0
12.6
5.7
5.3
Silicon nitride:
A
B
C
D*
F
G
Beta-silicon carbide:
E
H
I
J*
K
Silica and alumina-silica:
L
M
N
*Test duration: 375 h.
Weight
change (070)
Change in
MOR (To)
- 15
- 40
- 30
(**I
(**I
- 64
(**I
40
70
(**)
111
2.66
13.5
7100
- 0.04
Table VIII.
Product 2
Bond phase
Si,N,
Si,N,
Product 3
sialon/
Si,N,
2.63
16
20
5500
6100
2.65
16
20
5500
6100
2.70
14
31
6800
6900
4.7
17
4.7
17
5.1
23
- 6 to -20
-26 to -50
- 20
-4
+ 0.7
2.5
2.5
- 45
- 25
-4
unaffected
unaffected
unaffected
Table IX.
Product 3
sialon/
Si,N,
Product P
Si,N,/
sialon
Product H
Product S
p-Sic
SiP,
2.70
14
6800
6900
2.70
14
5473
4380
2.59
16
4875
5016
2.73
14
8088
5493
41
20
17
11
+ 0.7
- 1.5
0.5
4743
-3
3520
- 36
2.5
4.8
2.5
3.9
12.2
6.8
17.2
7.9
-4
4600
- 14
3085
- 50
6800
0
112
2.3
5519
- 31
33
Fig. 1. Loading the test bars in the molten alkali test tray.
113
Measure
20C
168"FI
GranularK&OI
Weight
Test
Betore
Test
927C
11700F
Liquid
K&OI
During
Test
20oc
168OFI
5opc1-j
1122OFI
TestTimes
and Temperatures
Water Wash
24 hrs.
65OC 1149OF1
Measure
for
Weight
Loss -MOR
H-L
A- I
Fig. 4. Cross sections of test bars of two different Si,N,-bonded Sic refractories after the molten alkali test.
114
10
12
14
Fig. 6. Molten alkali weight loss of Si,N,-bonded Sic refractoriesas a function of amount of fired surface in the test bars.
115
116
Fig. 9. SEM photograph of the sialon-bonded Sic refractory (product 3 ) . (bar = 100 pm.)
As-received Material
80
30
2oj
10
200
400
600
800
1000
1200
1400
Temperature ("C)
117
9080 -
200
800
600
400
1200
loo0
1400
Temperature ("C)
0
0.25
'
I-
Product 2
'T-
200
400
600
800
1000
-L
I
1200
1400
Temperature ("C)
Fig. 12. Thermal diffusivity vs temperature curves for Si,N,-bonded (product 2) and sialon-bonded (product 3) Sic refractories.
118
Introduction
F igure 1 shows the production of bricks for the BOF in our company. Before
1976, bricks for the BOF were mostly burned magnesia-dolomite bricks.
However in 1977, magnesia-carbon bricks were first used for the BOF. Since
then, the production of the magnesia-carbon bricks has rapidly increased. The
reason is that magnesia-carbon bricks have excellent thermal spalling resistance
and high resistance to basic slag, compared with other kinds of bricks.
At present, the production ratio of magnesia-carbon brick in our company
amounts to about 70% of the total production for the BOF. This figure will
be used as a criterion for estimating the total production of magnesia-carbon
bricks for the BOF in Japan.
the brick. In this figure, you can see that aluminum carbide is depicted as white
and ring-shaped grain at the edge of graphite flakes. Aluminum carbide seems
to enhance the binding effect between the mineral component of the brick,
thereby increasing the brick strength. Furthermore, since the affinity of
aluminum or aluminum carbide with oxygen is stronger than that of carbon,
it reacts more easily with oxygen or iron oxide in the slag and plays the role
of decreasing the rate of carbon oxidation in the brick.
Figure 4 shows the relationship between the amount of aluminum added
and the hot modulus of rupture, together with the relation of resistance to
oxidation. The graphite content in the brick is 20%. The horizontal axis
represents the amount of aluminum added. The hot modulus of rupture
increases with the increase of the amount of aluminum. The resistance to oxidation is evaluated by measuring decarbonized layer of the test piece, 50 by 50
by 50 mm after two h at 1400C in an electric furnace. The resistance to
oxidation also increases with the increase of aluminum added.
Figure 5 shows hot modulus of rupture and resistance to oxidation of
magnesia-carbon brick with magnesium added together with aluminum. The
amount of aluminum added is constant. Magnesium is added in a form of
aluminum and magnesium alloy. The hot modulus of rupture increases clearly
with increasing amount of magnesium. The reason is that the oxygen partial
pressure in the brick decreases with the addition of magnesium, which makes
aluminum carbide form easily. The resistance to oxidation also clearly increases
with an increasing amount of magnesium.
Figure 6 indicates the modulus of rupture at each temperature when
aluminum is added to the magnesia-carbon brick, or when aluminum and
magnesium alloy is added. The amount of aluminum added is constant. In
either case the graphite content in the brick is 20%. The alloy-added brick
clearly shows an increasing tendency of strength above 600C. This reason
is that the addition of magnesium enhances the effect of aluminum addition,
and the melting point of alloy is lower than aluminum.
We have confirmed the effect of these Fetals by the experiment with a
high frequency induction furnace capable of melting 500 kg iron. In the
furnace, as is shown in Fig. 7, 18 specimens can be set. Each specimen is
300-mm long, and 50-mm thick. After 100 kg of steel is heated to 1650"C,
6 kg of slag is added. The slag is changed every two h. The test is performed
for ten h total. This method is a comparative static corrosion test. A dynamic
corrosion test has been conducted along with the static test.
Figure 8 shows the dynamic corrosion test. Three supported specimens
at the angle of 120, evenly spaced, are immersed into molten slag and metal.
Each specimen is rotated at the speed of 180 rpm. This dynamic corrosion
test is conducted for two h.
Figure 9 shows the properties of the bricks used in this test and the test
results. Brick A is without any metal added. Brick B is with aluminum, and
brick C is with alloy. The test results are indicated by the indices. The wearing
rate of brick A is 100, under either static or dynamic testing condition. Under
the static testing condition the wearing index of brick C is the smallest. The
reason is that the carbon oxidation rate by iron oxide in the slag is decreased
with the addition of alloy. On the other hand, under the dynamic testing condition, brick C brings about a far better result than brick A. The dissolution
of brick into slag under the dynamic condition is called erosion. The resistance
to erosion of magnesia-carbon bricks is improved by adding metal which
120
A has decreased the wearing rate in both areas, thus resulted in a longer life
of this BOF.
Magnesia-Dolomite-Carbon Brick for BOF
In Japan, a few BOFs use the improved magnesia-dolomite-carbon bricks
at their bath and bottom areas.
Figure 13 shows the test results of the resistance to corrosion of magnesiacarbon and magnesia-dolomite-carbon bricks. The calcium oxide content of
magnesia-carbon brick is 1Yo. The calcium oxide content is controlled by the
partial exchanging of magnesia with dolomite. The graphite content in these
bricks is 20%.
The solid line indicates the index of wearing rate when slag A is used.
With slag A, the increase of calcium oxide content brings about the increase
of wearing index. This tendency is attributed to the high contents of iron oxide
in slag. The presence of calcium oxide in brick worsens the corrosion resistance
of brick against iron oxide containing slags. On the contrary, the dashed line
indicates the wearing index when slag B is used, and the increase of calcium
oxide content brings about the decrease of wearing index. This tendency is
attributed to the low content of iron oxide in slag.
This graph shows that magnesia-dolomite-carbon bricks can be more
resistant to BOF slags with lower iron oxide contents, when compared with
the corrosion resistance of magnesia-carbon bricks. Generally speaking, the
iron oxide content of BOF slags is high. However, with regard to slags flowing
down to the bottom area in a molten bath, the iron oxide in slags can be reduced
with carbon or silicon in molten metal, resulting in comparatively lower iron
oxide contents in slags. Therefore the bricks used in the bath and bottom areas
are influenced little by iron oxide in slags. The slag in bath and bottom has
a mild corrosive action to magnesia-dolomite-carbon bricks.
Figure 14 shows the wearing rate of magnesia-dolomite-carbon bricks
which are used at the bath and bottom areas of a 150-ton BOF. The calcium
oxide content in magnesia-dolomite-carbon bricks is 14%. This type of brick
has made it possible to decrease the wearing rate by 20 to 30%, compared
with conventional magnesia-carbon bricks.
The appearance of the hot face of magnesia-dolomite-carbon brick and
magnesia-carbon brick used in a campaign is shown in Fig. 15. As for
magnesia-carbon brick on the left, the partial oxidation has occurred near the
hot face because the reacting layer with slag has disappeared. On the other
hand, the hot face of magnesia-dolomite-carbon brick on the right, is protected
by the reacting layer with slag. Therefore, in case of magnesia-dolomite-carbon
bricks, there is no tendency to oxidize.
Regarding the mechanism of slag adherence on BOF linings, a schematic
diagram of the microtexture is shown in Fig. 16. With magnesia-dolomitecarbon bricks containing a proper amount of dolomite, slag reacts preferentially
with dolomite to increase the melting point, forming a highly refractory layer
on the hot face of the brick linings. The formation of this reacting layer is
effective to inhibiting the oxidation and the magnesia-carbon reaction within
bricks, thereby bringing about the decrease of slag corrosion rate.
Conclusions
As a result of the investigation and experiments, we have made successful
progress in the carbon-bearing refractories for the BOF which are summarized
as follows:
122
20,000
0 10.000
Brick A
Brick B
Alloy
Improved type
High purity type
Aluminum
Conventional type
Conventional type
0.3fi0.4
0.6-0.7
0.4-0.5
0.7-0.8
v
Y
5.000 -
123
140
120
110
.-L
ga
100
2.75
2.80 2.82
2.85
Bulk Density
2.90
Fig. 2. Influence of bulk density to HMOR and wearing rate of MgOC brick.
G : Graphite
M :Magnesia
A-C : Aluminum Carbide
124
Amount of Al Added
Large
..................................................................................
i Resistance / to Oxidation-Thickness
of
Layer(mm)i
.........................................Decarbonized
..
._.
.....................................
Fig. 4. Influence of Aladditionon hot MOR and
resistance to oxidation of MgO-Cbrick.
-1.0
180-
-0.8
," 160 u
0
0
0 140 -
0.6
- 0.4
120 -
0.2
80 -
.-0
CTJ
4.4
Q1
0
S
5
100 c.
I
4-
z
cri
T-
-0
CTJ
3
a
v)
125
320
0
0
0
0
0
0
0 Specimen
0 Monolithic
0 Induction
@ Slag
6)Steel
Refractories
Coil
(6kg)
(100kg)
Test Condition
Temperature : 1650'C
Time : 10 hours
Slag : C / S = 3.0,
Total Fe = 10%
........................ ................................... ..
126
0
0
0
0
0
0
0
0
0
0
0
Test Condition
l\l
Gr4J:ite
Ontent
Metallic
Additive
Wearing Index
20
40
60
80
100
~~
127
100 - 0
x 90
a,
-a
S 80
.E
(J,
a,
70
60
O\
O x 0
50 I
Magnesia
128
100
70
.E
L
OJ
130 -
120 -
--
110100
90 80 7060 50 -
(
,I
<
--.n--
yo
I
140 -
-n=-,o
Slag
129
Fig. 14. Comparison of wear rate of MgO-C brick and MgO-dolomiteC brick in bath and bottom area.
MgO-C Brick
Mg0-Dolomite-C Brick
S :Slag
D :Dolomite
M :Magnesia
P :Pore
Production using continuous casting of steel has markedly increased in Japan. In this
process. many improments in iundish-coating rejmctories have been made. This pper
describes the current properties and deposition method of tundish surface coating
refactories.
Introduction
Figure 4 shows the relation between fiber amount added and permeability
on the explosive spalling resistance. The system in Fig. 5 was utilized for
measuring the permeability, and the explosive spalling resistance has been tested
with the equipment indicated in Fig. 6.
The fiber amount added has a close relationship to the explosive spalling
resistance. An increase of fiber improves the explosive spalling resistance. The
appropriate amount, however, must be determined when also considering the
erosion resistance. Figure 7 shows the relation between fiber amount and
erosion resistance. Too much fiber added greatly lowers the erosion resistance
as shown in Fig. 7. Therefore, the fiber amount added must be determined
after consideration of a balance between the explosive spalling resistance and
the erosion resistance.
As mentioned above, fiber-added type magnesia-base coatings have taken
root. Recently, however, L-Coatings and gunning methods are being investigated because of resources and labor saving. In the next sections, these two
techniques are explained.
L-Coatings'
Requirements for TD coatings:
(1) At TD preheat-drying, there must be no explosive spalling due to
steam volatilization.
(2) At TD preheat-drying, there must be no thermal bulging and peeling.
(3) Less penetration and erosion by slag and molten steel.
(4) Less fusing with TD parent refractories.
L-Coatings have been investigated for satisfying the conditions above, reducing
unit consumption, preventing fusion with TD parent refractories, and maintaining the molten steel temperature. For the prevention of explosive spalling, a
porous material is required for smooth steam volatilization. On the other hand,
a material is required whose penetration of slag and molten steel is small.
Various means for achieving lightweight and heat insulation have been
investigated. As shown in Table I, adding an air entraining (AE) agent to the
conventional magnesia-base coatings was tried. The best feature of L-Coatings
is that, by adding an AE agent, air is entrained into the material during mixing
to cause foaming and realize a decrease in weight. Thus, it is critical to keep
an appropriate mixing time and an proper amount of AE agent as indicated
in Figs. 8 and 9, respectively.
Air Foam Produced
The air foam produced at the time of mixing by adding an AE agent is
made to remove water in the gaps between refractory particles. Therefore,
the particle size distribution of coatings has a large effect upon the diameter
of the pore produced. Figures 10-12 show a section of each of the coatings:
Fig. 10 is of a conventional type and Figs. 10 and 11 are of a light-weight
type. The particle size of light-weight type A in Fig. 9 is coarse and the pore
produced is large in diameter. On the contrary, the air foam of the light-weight
type B in Fig. 10 is small in diameter. Grain size distributions are shown in
Table 11. As for the distribution of pore diameter, the light-weight type B,
as shown in Fig. 13, has a much greater pore volume of 100 p or below.
132
Thus, steam-explosive spalling easily occurs. Here, the material used must be
of good permeability.
Thermal Bulging: When a dense substance is installed, it is hard to absorb
the thermal expansion, and this is apt to be a cause of bulging. Moreover,
the lamination formed will be a cause of peeling. Then, a cushion material
which can absorb the thermal expansion should be added, and the particle
size distribution should be small in order to prevent the formation of
lamination.
Maximum Particle Size and Rebound Loss: In the gunning mixes, maximum particle size is one of the critical factors having direct effects on rebound
loss (Fig. 17). For this case, the smaller, the better. Presently, a size of 2 mm
or below is normally used. Where the rebound loss is great, a lamination is
easily formed on the gunning substance installed, and it may cause trouble
at the time of preheat-drying of the TD.
Particle Size Distribution, Permeability and Explosive Spalling Resistance:
Figure 18 shows the relation between the amount of fine particles ( - 200 mesh),
permeability and explosive spalling resistance. As the fine particle amount
increases, the permeability is decreased. The explosive spalling resistance is
indicated in Fig. 18. Drying was executed with the system as shown in Fig.
19. As a result, we saw that an increase in the amount of fine particles is not
conducive to the explosive spalling resistance.
Conclusion
In conclusion, the light-weight and heat insulation of TD coating refractories, it was clarified that the problem of increase of penetration of the molten
steel and slag, with the realization of effect of porosity, could be solved by
adjusting the pore size. As mentioned so far, the quality of material has been
investigated from various aspects to meet the user's requirements for reducing unit consumption. The need to improve the work environment and labor
saving has spurred the development of new installation techniques such as
gunning. Ftq he future, it will be essential that the imptovement and development of ma a1 quality can be achieved only after considering the installation
method.
References
134
Table I.
L-coatings
MgO
Insulating
board
83
83
75
1.9
3.5
3.5
8.5
8.5
8.4
Mineral fiber Mineral fiber Mineral fiber
(070)
A1,0,
Composition SiO,
Additives
Bulk density (g/cm3)
Advantages Apparent porosity (To)
after drying Thermal conductivity
at 110C
(kcal/m.hr"C)
AE agent
1.65
47
1.55
2.20
35
0.5
1.20
0.6
Fig. 8
Conventional
type
Fig. 9
Light-weight
tyue A
Fig. 10
Light-weight
twe B
35
35
50
-0.074 m m "-7)
-s
90-
86.2
80-
UI
8 60-
60.4
31.2
1970
80
75
83 (Year)
CC
Fig.
x 100
ratios.
135
(A)
Material
Erosmn -ms,stant ~ m o r o v e m ~ n t
Decrease
inclusion
(B)
Installation method
ot GX-metalllc
10
Slag basicity
(CaO/Si02)
0.95
Molten metal
Ordinary
Steel
~~~,",~&
1570-16OO'C
136
- 9I"
Z 8.
n
\
7.
6-
--6 5 ..--------3
1-
0
0
4
2 3.
E 2 a
'I
0:Sound
.:Explosion
'I
I
Compressor
137
"
-1
30mm coating
::___rji_
Ln
E 3
2 2
!2 1
c
gg
0-
w 01
'
Fiber increasing
Erosion test condition
138
139
140
Type A
T.P.~
.KO. I O - ~ccig
= 40 */.
m
U
-P O
0.01
2>f Lo5
>
30.
3
01
10
Particle S i t e : Fine
::[
0
0.1
100
Liqht
.iqht -weiqht
-we 4qht Twe B
T.P.V -194
:194 10 -I c c l g
en1 Porosity
= 40 */.
0.1
1
0.01
Pore Diameter ( M )
Fig. 13. Effect of the particle size on pore size distribution (T.P.V. = total pore volume).
141
142
W e t Type Gunning
D r y T y p e Gunning
01
0 :Sound
Oogo
10
OL'
:Explosion
1;
20
25
30
3s
143
Gunninq
Orvinq
k n i n g nozzle
Gunned
material
144
SHICEO
MATSUURA
CAT Division, Toshiba Corp.
Shinjuku, Toyko 160, Japan
The use of industrial X-ray computerized tomography in the evaluation of refractories
was examined. The scanner enables nondestructive detection of defects as small as
several hundred pn. The X-ray absorption values can be processed so as to display
the distribution in density as an image or to represent it in numerical values. Specific
results are giwn for examination of a submerged nozzle and a tundish nozzle for steel
casting.
Introduction
A n X-ray Computed Tomography (X-ray CT Scanner or CAT-SCAN) was
announced in 1973,' and since then improvements of image quality and
higher operation speed have been made.2 From its beginning in the medical
field, improvements of the equipment have now led to industrial application^.^-^
For nondestructive inspection of refractories, ultrasonic wavesS and X-rays
have been used and, among these methods, the most popular is the X-ray
fluoroscopic m e t h ~ d In
. ~ this method, however, X-rays are applied to threedimensional objects and two-dimensional images are formed on photographic
films or fluorescent display plates by the volume of X-rays that have passed
through the objects. The resulting image is one representing the condition of
objects throughout their entire thickness in the direction of X-rays passing through
the objects, and accordingly, it is difficult to interpret the shades of image to
exactly judge their three-dimensional structure. Also, since the limit for this
method in detecting hidden structural defects is roughly 2% of their thickness
and since defects are generally small in size, the larger the thickness of the objects,
the lower the detectability of defects.
The inspection method using ultrasonic waves is also popular in the refractory industry. Since refractories contain aggregates comprising large grains up
to several mm, however, scattering of waves due to existence of large grain surfaces and pores takes place, and it is difficult to detect small defects as cracks
using ultrasonic waves. Therefore the method is not suitable for this purpose
but for detection of defects in large sizes, such as laminations. In the refractory
industry, therefore, ultrasonic waves are used as a method rather for quality control purposes by measuring sonic transmission speed of the material, than for
detection of hidden defects.
145
Outline of CT Scanner
In Japan, work for the development of CT scanner started in 1980, and
it was in 1983 that the No. 1 middie-energy industrial scanner was
produced.O Successively thereafter, a high-energy X-ray CT scanner was
developed in 1984. This is in use mainly for analysis of the inner structure
of steel products. CT scanning systems developed and used to date are classified
into four generations, and the scan method of each generation is shown in
Fig. 1. The middle-energy CT scanner (third generation) is a high speed CT
scanner for general use, pulsing 140 kV X-rays and have a Xe detector with
512 channels. The X-ray tube and the detector are stationary, and the object
rotates. A part of X-rays are absorbed by the object and X-rays that pass
through it reach the detector. Analog signals from the detector are converted
to digital signals and are sent t o the central processor. Hundreds of thousands
of data are obtained per scan of section.
Reconstruction of the image is carried out using the data thus obtained
and a tomogram is produced. Time required for scanning and interpreting
is 15 s. A hole of 300pm in diameter and slit of 20pm graduations can be found.
Materials such as ceramics, light metals, plastics, and wood permit X-rays
to pass through with comparative ease, so by vitue of the said pulse voltage
(140 kV), the scanner presents excellent images.
The high-energy CT scanner is a trial unit CT scanner of continuous (nonpulsating) X-ray type (420 kV) and, when classified by the data collection
method, it is a first generation scanner. Translation and rotation are carried
out by movement of the specimen table. The system is up-graded so as to enable
arbitrary selection of sampling pitch and number of data to be collected. Two
high precision tungsten collimeters remove scattered X-rays, and a BGO scintillator detects non-scattered X-rays efficiently. It is confirmed that by precisely
collimating projected beams, the system can be given a high resolving power
in no way interior to high density X-ray films. The unit was test produced
in order to study its potential as a CT scanner, and we used it for analysis
of zirconia-containing refractories and used submerged nozzles.
From the tomogram produced as distribution of X-ray absorption coefficients, CT values are obtained by conversion and are used as data for image
reconstruction.
CT value=- CI - P
K
(1)
PS
submerged nozzles-are correlated with the refractory material and the adhering material, the used submerged nozzle of Fig. 7 was cut at a position corresponding to the position where X-rays were applied, and a large area analysis
by the EPMA method (Mapping) was carried out. The results from this analysis
were compared to the results obtained using the CT method.
Figure 8(A) shows the tomogram and (B) the cut surface at the corresponding position. Since a diamond cutter was used for the cutting, the metal
in the adhering material was melted and spread by the cutter so that the metallic
part in the image presents a somewhat larger area.
Figure 8 (B) shows the appearance of the cut surface of the sample buried
in a plastic material for polishing. In (C) and (D), images obtained by mapping applying the large area analysis method to see the condition of Fe and
A1 are shown. The white luminous spots in (A)represent the metal in the adhering material. In the qualitative analysis of the adhering material, which had
been carried out preliminarily, elements of A1, Fe, Ca, and Si were detected
and, in Fig. 8., Fe exists in clods as seen in the tomogram (Fig 8. (A).)On
the other hand, grains of A1 fill the gaps between the Fe clods. From these
analysis results, it is understood that the sticking material comprises of, in
the order of X-ray CT value from high to low, Fe, Al, and Si or Ca. Elements
other than Fe exist in the form of oxides. Accordingly, in the histogram shown
in Fig. 4 (D),the element which showed the highest CT value (higher than
the peak of the value for the refractory material) was Fe metal. The area
between the refractory material and the Fe metal is filled with adhering oxide
materials, mainly of Al. The area where the CT value is lower than that of
refractory material and higher than that of air is considered to represent oxides
of Si or Ca which are low in CT value.
148
360 kV
3.5mA
1.Omm
0.5mm
0.5mm
200
wall as well as the condition of adhesion of the two layers at their bordering
faces.
The tomogram shows that the outer layer which is high in the density
and whitish in the color is high in the X-ray absorption value (CT value) and
the inner layer which is low in the density and darkish in the color is low in
the same.
In Fig. 17, a profile and a histogram are shown as examples of image
processing by the CT scanner; (A) shows the profile. The CT value is high
at the area near the nozzle outside surface and low toward the inside surface.
It presents sharp peaks at the part of nozzle bore wall where metal adheres.
Figure 17(B) shows an example of the histogram processing of the area sectioned by the white line. Roughly, the CT values distribute forming three peaks.
It is considered that the lowest peak (the peak centering on -250) corresponds
to the part where air is involved, and the other two peaks are the peaks which
correspond to the two kinds of substances. The values of the vertical axis are
scaled to one-fourth, and are used this time only as indices. Exact determination of CT values of individual substances remains a problem to be solved
in the future.
area in which the quality of the nozzle material differs from that of the nozzle
material as the result of the use.
Figure 19 shows examples of processing CT values obtained from the
tomogram into a profile and a histogram. As was in the case previously, the
CT values along the vertical axis are scaled to one-fourth to be usable as indices.
The profile, Fig. 19(A), shows that the CT value curve is high along the outside nozzle surface and is low along the side around the nozzle bore, forming
a flatness as a whole at the center where the nozzle bore is filled with metal.
This decrease in CT values at the nozzle center is considered to be the result
of the densification of the nozzle material and the beam hardening explained
above.
The histogram (Fig. 19(B)) has three peaks and the lowest peak corresponds mainly to the air in the area sectioned by the white line. The two
high peaks are formed by the nozzle material and the metal.
After taking the tomogram, the nozzle was cut at the same position, and
samples taken from the cut surface were measured for their physical properties and also for their pore size distribution by means of the pressured mercury intrusion method. The samples were taken so as to represent the hotface zone; the penetration zone, and the original brick material zone of the
used nozzle. The physical properties were as shown in Fig. 20.
The values in Fig. 20 show that, compared to the original brick zone,
the densification strongly progressed in the hot face zone, followed by the
penetration zone. Figure 21 shows the results of the measurement for pore
size distribution by means of the pressured mercury intrusion method.
Compared to the original brick part, the hot-face zone and the penetration zone are less permeable to the intrusion of mercury, and the hot-face zone
is the zone most dense with the least open pores. This result corresponds to
the results of the measurement for physical properties shown in Fig. 20.
The darkened part in the tomogram is considered to correspond to the
part where the density has become high due to filling of pores with foreign
materials that have penetrated into the structure of the nozzle material.
The quantitative analysis was carried out with the sample nozzle covering the distance from the hot face to the original brick part, using EPMA.
The results are shown in Fig. 22. In the area up to about 20-mm deep from
the hot face, a glassy phase of intrusion materials was observed. The analysis
was carried out with small areas of the matrix.
From the results obtained through this analysis, every substance such as
ZrO,, SO,, MnO, A1,0,, CaO, Fe,O, and TiO, was plotted for the distribution of concentrations in a range up to 50-mm deep from the hot face.
In the area up to 14-mm deep from the hot face, the glassy phase was
formed in the matrix, and the analysis was carried out with these glassy phases.
At positions deeper than 14mm from the hot face, the analysis was carried
out with the matrix.
These results show that SiO, was the largest in volume among the
substances penetrated into the nozzle, followed by others in the order of MnO,
A1203,CaO, and TiO,. As for Fe203,its penetration is concentrated at the
position about 14mm from the hot face. It is found that the dark part centering on the nozzle bore, as is found in the tomogram, almost corresponds to
the part where the material structure has become dense because of penetration of the above-mentioned foreign materials.
152
Conclusions
In order to detect hidden defects and to numerically examine the inner
structure of objects without destroying them, X-ray CT scanners have been
developed for industrial use. A middle energy scanner (X-ray tube: 140 kV)
was used for analysis of refractories for continuous steel casting, centering
on submerged nozzles, and a study was carried out for a further application
of the scanners. As the result, their suitability as the equipment for a
nondestructive scanner for detection of defects was confirmed, and also their
usefulness, when CT values are obtained for numerical evaluation of structural conditions of objects, has become apparent.
Also, zirconia refractories (the powder-line part of a submerged nozzle
and a tundish nozzle) after the use were reclaimed and analyzed using a highenergy X-ray CT scanner. As a result, it was found that a X-ray CT scanner
with a X-ray tube voltage of maximum 420 kV can be successfully used for
analysis of zirconia refractories. From the results obtained through the analysis
this time, the following conclusions can be reached concerning application of
an industrial CT scanner to refractory products:
(1) The scanner enables detection of defects in a size as small as several
hundred pm or less without destroying the object. This capacity makes the
CT scanner useful for detection of defects or for confirmation of secure bonding of refractories, such as alumina, silica, alumina-graphite, zirconia, and
metal-ceramic composite refractories.
(2) CT values (X-ray absorption values) can be processed so as to display
the distribution in the density as an image or to represent it in numerical values.
Therefore, it can be used successfully for observation of inner structural conditions of double or composite structures consisting of parts which are different in specific density, and for analysis of degeneration or damage produced
in used products, and so on.
(3) The scanner may also be successfully used for measurement of hidden shapes and dimensions of complicated ceramic products which are expected
to be developed in the future, in particular for engineering ceramics.
Recently, in compliance with the improvement of steel quality, conditions
for use of refractories have become more severe, requiring refractories more
superior in quality, longer in life, and more reliable in performance. Under
such a situation, we believe that timely realization of CT scanners as those
we report will greatly help advancement of the technology for refractories,
offering new information for evaluation of properties, and for study on the
mechanism of damaging them, including corrosion, cracking, nozzle-bore
clogging, etc. Further, since data obtained through the CT method can be
recorded and stores, it will be used increasingly for research and development
of new ceramic materials, and also for product quality control purposes.
References
153
Table I.
Substance
Air
Water
Carbon
Concrete
Aluminum
Alumina
Steel
Zirconia
Lead
: 100 keV
: Value of air
: - 1000
Value of water :
0
Mass absorption
X-ray absorption
coefficient
coefficient
U
0.155
0.171
0.153
0.169
0.169
0.162
0.370
0.750
5.46
0.279 x
0.171 x 1 =0.171
0.153 x 2.2 = 0.337
0.169 x 2.3 = 0.389
0.169 x 2.69 = 0.455
0.162 x 3.97 = 0.645
0.370 x 7.86 = 2.908
0.750x 5.90=4.422
5.46x 11.34= 61.916
154
CT value
- 1000
0
97 1
1 275
1 661
2 772
16 006
24 860
361 082
Object material
Maximum thickness
Size and weight
of object
Scanning time
Slicing thickness
X-ray rating
Detector
Image reconstruction
matrix
Pixel size mm
320 x 320
0.10.10.47
0.75
From - 1000 to 8000
For zooming
CT value
Functions
0.10.94
90
10
27.6
2.53
1580
1900
1896
80
20
24.1
2.44
1512
1772
1788
155
70
30
21.2
2.41
1480
1704
1708
60
40
16.1
2.39
1473
1672
1644
50
50
15.3
2.31
1361
1518
1524
Table IV.
Scanning method
X-ray tube
Detector
Scanning area
Beam size
Table V.
Chemical composition
(WtYO)
Apparent porosity (Yo)
Bulk density (g/cm3)
A1,0,
C
SiO,
ZrO,
51.8
31.4
15.8
18.9
2.29
DSample
D!
I
(a)1 st generation
Powder line
25.0
68.2
19.3
3.18
O X - r a y tuba QDetector
D
(b)Znd generation
(c)3rd generation
156
(d)4th generation
X-ra
contmller
Hi& v o l ~
generator 2
i
I
1 1
--
L-
--
Detector
Fig. 3.
Display
controller
Computer
cabinet
Console
157
158
159
Fig. 9. Analysis of oxidized layers (CT values and band display) (A) CT value
profile, (B) band display of CT value (800-1200oxidized part).
160
161
1920
1880
1840
1800
1760
1720
0-
1640 1600 -
1660
-f
Fired 1406)
D-
'\
--
Or8811body ( 4 W t
Fired (1306)
C.Bulk density (Fired)
Condition: 120kv. 2OOmA
Siic8:
lOmm
Area:
667 (406)
6683(13W)
0-
'?
- 2.60
1560-
- 2.50
1400 -
- 2.40
1820
1480
'f
Q
1440
2!
m
-*2.30
1380.
Ail03
90
80
70
60
50
C
wtn
10
20
30
40
50
Composition
A Apparent porosity
0
1600
Bulk density
>
>
2 - 25 - 2 . 4 0 '5
-24
,0
28
1500
1400
=
1
600
-2.30
121
.2.20
700
800
900
-23
500
1000
20
-2.10
162
Colllrneters
Rotationltranslation
mechanlsrn
163
Fig. 17. CT value profile and histogram of used submerged nozzle (A) profile,
(B) histogram.
Fig. 18. Tomogram of used zirconia tundish nozzle taken with high-energy
CT scanner and cut surface (A) slice position, (B) tomogram, and (C) cut
surface.
164
Fig. 19. CT value profile and histogram of used zirconia tundish nozzle (A)
profile, (B) histogram.
H o t face
zone
Penetration
zone
Original
brick zone
B u l k density
4-
o m
>-.
0.04
.rl
0-
0.03
C
4
0.02
f
;
0.01
Original brick
zone
Ti
/Hot
rl
100
10
-Penetration zone
face zone
I.
0.1
...
..
I.
0.01
..I
Pore s i z e (pm)
165
Hot
Reacted
0
Distance from hot face(mm)
166
CHARLES
A. SCHACHT
ladles, seueral obseroations were made on refmctoy lining behavior unique to cylindrical
refactoy-lined vessels. The investigations were directed to brick/mortar joint-type
linings subjected to transient temperatures and the resultant expansion loads. Observations were made on both the structural behavior of the refactoy linings and on a
failure mechanism. These obseruations are identified to assist investigators in the interpretation of analytical and field study data, and to assist in the design of refractory
lining systems.
Introduction
L adle vessels continue to play a major role in iron and steelmaking practices.
Continuing changes in secondary steelmaking and substantial growth of continuous casting, has had a significant influence on how teeming ladles are used.
The most current metallurgical practices imposed on ladles, such as arc heating,
inductive stirring, argon stirring, preheating, etc., have resulted in ladles being
subjected to increased physical, chemical and thermal abuse. As a result, the
industry is more concerned about the structural integrity of the ladle shell.
In order to design or maintain the ladle shell, the behavior of the refractory
lining must be better understood. With the new clean steel environments, the
ladle working lining usually consists of a high-alumina or a basic refractory
working lining, and is considerably stronger than the previously used fireclay
lining. The significant shell stresses resulting from the thermal expansion of
the strong linings have been identified in previous studies.' This paper
presents additional observations on the complex structural behavior of the
refractory linings of ladles. These observations also can apply to other
refractory-lined cylindrical vessels, such as torpedo cars, BOFs, blast furnaces,
stoves, and rotary kilns.
The Dimensionality of Lining Expansion Forces
One interesting behavior of the cylindrical refractory lining (Figs. 1 and
2) is the dimensionality of the lining thermal expansion stresses. The lining
compressive stresses are a function of the increase in the average lining
temperature, relative to the average shell temperature, through-thickness
temperature gradient, and dimensionality of the restraint applied to the lining.
The range in dimensional behavior of refractory linings can be demonstrated
by comparing the restraint and resultant thermal stresses in a two-dimensional
plate and in a one-dimensional bar. Thermal stresses in a restrained plate
167
S = EaAT
where:
S = Thermal stress
E = Modulus of elasticity
a = Coefficient of linear expansion
AT= Uniform temperature increase from ambient
u = Poissons ratio
With identical temperature differences in the bar and plate, the plate stresses
will be greater than the bar by the factor (u = 0.2 for refractory brick):
1
~
1-24
1
1-0.2
--
= 1.25
(3)
For refractory linings, such as used in ladles and other cylindrical lined shells,
the axial restraint can be altered. Since linings have circumferential and axial
joints, they have the unique feature of being able to transition from onedimensional to two dimensional-thermal stress behavior. With full axial
restraint, the circumferential stresses are at the higher two-dimensional value.
By reducing the axial restraint, the circumferential stress can be reduced to
the one-dimensional value. Through prudent design of the lining axial restraint,
circumferential stresses can be reduced up to approximately 25%.
When incorporating axial restraint into a lining design, it is important
to maintain closed circumferential joints when cycling from hot-to-cold conditions. If open joints occur, hot metal or gas penetration can cause severe
problems. Ideally, to maintain tight circumferential joints, the amount of axial
restraint should be sufficient to develop several thousand psi without causing
appreciable increases in the circumferential stresses. In ladles, the axial restraint
of the lining can be reduced by altering the top retaining ring stiffness or by
using compressible packing materials between the retaining ring and the lining.
Cyclic Response of Lining
Analytical research1 on teeming ladles, lined with high-alumina brick
refractory, has identified that significant residual tensile stress (strain) is
developed during the first few cycles of operation on the hot-face side of the
alumina working lining. This residual tensile stress (evaluated analytically) is
caused by inelastic flow at the working lining hot face during the initial preheat
and teeming events. As the lining cools to ambient temperature, the residual
tensile stress increases in magnitude. Figure 4 describes the variation of
analytically evaluated circumferential residual stress in the working lining at
ambient temperature. Additional tensile stress exists during the early stages
of cooling, resulting primarily from the cooling transient temperature gradient
at the hot face side of the working lining. This residual stress reflects the degree
168
lining. The analytical and field results also imply that methods used to evaluate
thermal shock resistance of refractory brick are not realistic if the stress states
due to thermal restraint are not included in the evaluation.
Lining Wear
When brick working lining deterioration is concentrated in the region of
the hot-face joints, it is referred to as cobbling.
As shown in Fig. 13, the stress distribution of the restraining force, during
the initial stage of heat-up, is concentrated at the hot-face side of the joints.
This joint pinching action is also described in Figs. 5 and 6 . The interior of
the brick (away from the joints) has lower compressive stresses and lower stress
gradients. The hot-face compressive stresses will increase as the transient heatup rates increase. The concentrated restraining force at the joints results from
the inability of the joints to develop tensile stress. The severe pinching action
occurs with more rapid transient heat-up, such as with the application of hot
metal. At the joints, the working lining expansion forces become more pronounced for tight linings which have no expansion allowance. Therefore,
cobbling action appears to be a combination of excessive distortions and
deleterious chemical attacks at the hot face side of the joints.
Slabbing or spalling is another form of lining wear in which transverse
cracks develop parallel to, and at a short distance from, the hot face. The
cracked layer gradually works loose resulting in a significant loss of working
lining thickness. Some investigators have attributed this form of lining wear
to rapid thermal transient stresses,* while others have shown that knuckle
loads (concentrated loads) within the joints are the primary cause.3 As shown
in Fig. 6 , the knuckle loads are present during preheat of the lining and during hot-metal hold time. The knuckle loads result from the inability of the
hotter portion of the lining to sustain the expansion force. As the hot face
increases in temperature, the hot-face lining region relaxes due to inelastic flow
causing a joint knuckle load, as shown in Fig. 6 . The knuckle load will become
more pronounced when the lining hot face is suddenly allowed to cool. The
result of the knuckle load is a tensile stress (analogous to the split-ring tensile
test) normal to the knuckle load, as shown in Fig. 14. If the lining knuckle
load has sufficient magnitude, the resulting tensile stress will exceed the tensile strength of the lining material to cause a slabbing-type failure. However,
this tensile failure may not be instantaneous. Sustained knuckle loads can
develop sustained tensile stress which would result in a similar crack due to
short-term tensile creep failure. It is important to note that this form of failure
will occur with gradual heat-up transients.
The analytical results of a finite element study on knuckle loads show
that the magnitude of tensile stress, in a typical brick shape, caused by the
knuckle load agrees favorably with the equation4 (for unit thickness):
sx=
2P
(4)
nD
where:
Sx= Tensile stress normal to direction of knuckle load
P=
Knuckle load
3.1416
D = Diameter of disc specimen (width of brick between knuckle loads)
IT=
170
Equation 4 is used for calculating the tensile strength in a disc specimen subjected to knuckle loads. The results of this analysis show that knuckle loads,
on both circular and rectangular brick shapes, develop similar tensile stress.
As shown in Fig. 15, tensile stress decreases drastically when the knuckle
loads are near the hot face of the brick. Therefore, this form of spalling or
slabbing will not occur until the knuckle loads shift away from the hot face
where sufficient tensile stress to cause failure is developed. As the distance
between the brick joints increases (distance between knuckle loads), the tensile
stresses are decreased inversely proportional to this distance. Therefore, short
brick (distance measured parallel to hot face, D),with the same magnitude
of knuckle load as long brick, have a higher tendency to spall.
The investigations on lining wear imply that lining restraint, hot face
inelastic flow and joint behavior impose a significant stress state within the
lining. Therefore, these stredstrain states must be included when evaluating
transient stresses and thermal shock conditions.
General Response of Refractory Lined Shells
The stredstrain vs time behavior of cylindrical refractory-lined shell
structures, subjected to heat-up, appears to have a characteristic response.
The response has been observed (shell strain-gage measurements) not only in
teeming ladles but also in blast furnace stove domes, large cylindrical furnaces,
and in coal gasification vessels with relatively thick castable linings.
Figure 16 describes the results of strain-gage measurementsSof a cylindrical furnace circumferential shell stress. The internal furnace gas temperature
was recorded and is shown to increase almost linearly from ambient to approximately 950C (1700F) in approximately 4% d. The outside shell surface
reached a maximum temperature of approximately 205C (320F) in nearly
the same time period. The furnace wall consisted of a 11.4-cm (4% in.) fireclay
working lining and a 11.4-cm (4%-in.) insulating brick against the shell. The
circumferential shell stresses peak at the end of the fourth d during heat-up.
The measured shell stress continues to increase at two of the strain-gage locations beyond the fourth d, but at a considerably reduced rate. Within the fifth
d, the shell stress begins to rapidly decay before reaching maximum heat-up
temperatures. By the end of the sixth d, the decay of shell stress has transitioned to a much slower rate. Similar type responses have been recorded in
other refractory lined cylindrical vessel^.^^^ The response of the ladle shell has
also shown a similar trend (Figs. 10 and 11) in which the circumferential shell
stress peaks before the maximum lining temperatures are obtained.
Previous research' has shown that inelastic flow at the refractory lining
hot face region is one of the primary reasons for the initial decay of the shell
stress. As the lining continues to heat-up, the threshold temperature is reached
at the hot face in which the strength of the refractory begins to rapidly decrease.
As lining temperatures increase, this decay in lining strength and increased
inelastic flow will progress to cause further reduction in measured shell stresses.
As steady-state temperatures are reached, the strength or force exerted by the
lining stabilizes and secondary or long-term creep of the lining causes a more
gradual decrease in the shell stress. In the case of thicker refractory linings
and faster heat-up rates, steady-state lining and shell temperatures will take
longer to stabilize.
The shape of the shell stredtime plot is related to various regimes of
lining behavior. As shown in Fig. 17, the general shape of the plot can be
171
Regime A
Regime A represents the initial response of the lining hot-face region
reflecting localized densification of mortar joints. In the case of castable linings,
this regime reflects the closure of shrinkage cracks.
Regime B
In regime B, the lining continues to increase in temperature. The thermal
expansion forces are directly proportional to the increase in lining temperatures.
A significant portion of the lining is at temperatures in which the lining refractory behaves elastically.
Regime C
Regime C marks the threshold of inelastic flow at the hot-face side of
the working lining. The lining is continuing to increase in temperature and
a significant thickness of the hot-face material exceeds the threshold
temperature. In this regime, the amount of inelastic flow begins to absorb the
expansion of the working lining. However, the growth of the expansion force
exceeds the inelastic flow rates in the working lining.
Regime D
In regime D, the higher lining temperatures result in increasing inelastic
flow on the hot face of the working lining. Here the working lining expansion
is completely offset by inelastic flow of the hot face material. The working
lining expansion force also shifts to the cooler portions of the working lining
to result in an effectively lower expansion force and reduced inelastic flow.
For faster temperature ramps, the shell temperature will continue to increase
the steady-state temperatures to result in decreasing shell restraint and lower
shell stress.
Regime E
In regime E, the lining and shell are at steady-state temperatures. Since
the expansion force is centered in the cooler regions of the working lining,
insignificant inelastic flow occurs. In fact, the inelastic decay is so insignificant that small changes in operating temperature and pressure may mask this
lining relaxation.
Ferrostatic Loads on Cylindrical Lined Shells
Cylindrical refractory lined shells such as teeming ladles are exposed to
primarily two types of loading. They are: (1) the thermal expansion load
developed by the refractory lining, and (2) the ferrostatic load imposed by
the molten metal. Teeming ladles are exposed to ferrostatic loads and lining
thermal expansion loads simultaneously with preheating.
Previous research' has shown that significant thermal expansion stresses
are developed in the lining during the preheating and teeming events. With
the high thermal expansion stresses in the lining, the lining has circumferential strength to carry a portion of the ferrostatic pressure. Assuming a molten
metal (temperature of 1554C (2830F) ) with a depth of approximately 3m
(10 ft), a ferrostatic radial pressure of 0.24 MPa (34 psi, Fig. 1) is developed.
The effect of the two loadings is described by the results of a nonlinear elastic
172
analysis of the lower ladle wall, as shown in Fig. 18. The material properties
of the refractory lining and shell of the ladle wall are described in Table I.
The circumferential shell tensile stress, if only the shell at 166C (330F)
is assumed to resist the ferrostatic load, is:
p r = (0.24) (2362)
s= (5)
t
38.1
= 14.26 MPa (2070 psi)
where:
p = Ferrostatic pressure
r = Shell radius
t = Shell thickness
The analysis shows that the ferrostatic pressure develops a small shell stress
compared to the lining expansion stress. Second, the analysis indicates that
the shell carries approximately 60% of the ferrostatic pressure load. Similar
results would occur in the axial direction of the ladle wall. This behavior would
also occur in other refractory-lined cylindrical vessels, such as blast furnaces,
stoves and torpedo cars.
It should be noted that the expanded lining does not have to be air tight.
That is, the pressure can be applied to the shell with the refractory lining still
sharing the pressure load.
AC
Ar
-= 2 n
(7)
173
where:
AC
Ar
= Differential
= Differential
circumferential motion
radial motion
Therefore, approximately six radial joints (2n) are equivalent to one circumferential joint. Most linings will have about two or three circumferential
joints. This implies twelve to eighteen working lining radial mortar joints would
be equivalent to the two or three circumferential mortar joints. This relationship assumes that the radial and circumferential joints are equal in thickness.
Most working linings are made of semi-universal brick with an average length
of about 200 mm (8 in.). Typically, there are about 75 radial joints (number
of semi-universal brick) around the circumference of a ladle working lining.
The effectiveness of radial joints is about six times greater than circumferential joints, based solely on geometry as shown by the following calculation:
Radial Joints
- -75
-S6
Effective Radial Joints
13
(circumferential joint)
In considering both mortar joint stresses and geometry, the working lining
radial mortar joints play the major role in relieving a portion of the thermal
expansion force. Using typical semi-universal brick, the radial mortar joints
are estimated to be two orders of magnitude greater in effectiveness than the
circumferential joints in relieving the working lining expansion force.
Conclusions
The observations on the complex thermomechanical behavior of refractory
linings provide an improved understanding of the refractory-lined cylindrical
vessel and the stress-related lining deterioration. As a result, improved shell
design is brought about. These observations may be applicable to the structural response of a wide variety of cylindrical refractory lined vessels, such
as torpedo cars, BOFs, blast furnaces and stoves.
References
C . A. Schacht and E. V. Aborotin, Structural Behavior of Teeming Ladles Lined with
High Alumina Refractories, American Iron and Steel Engineers, Annual Convention, September
1983.
J. H. Ainsworth, Calculation of Safe Heat-Up Rates For Steel Plant Furnace Linings,
Am. Ceram. SOC. Bull., 58 [7] (1979).
G. M. Thompson and W. Davies, Stress and Strain in Furnace Life, Trans. Br. Ceram.
SOC., 68 (1969).
4Ameri~an
Society of Testing Materials (ASTM) 1969 Book of ASTM Standards, Part 10,
ASTM Designation C496-69.
T . A. Schacht, Ludington Plant No. 13 Band Stress on No. 1 Calciner, Harbison-Walker
Memorandum, August 21, 1967.
6P. J. Pike, 0. Buyukozturk, J. J . Connor, Thermo-Mechanical Analysis of Refractory
Concrete Lined Coal Gasification Vessels, Dept. of Civil Engineering, Massachusetts Institute
of Technology, U.S. Department of Energy Report, No. R80-2, Order No. 659, January 1980.
Battelle Summary Report, Project No. 41-241, Thermophysical Properties of Refractory
Brick and Mortar, (For American Iron and Steel Institute), March 1, 1978, Battelle Columbus
Laboratories, Columbus, Ohio.
T . A. Schacht, The Effects of Mortar Joints on the Thermomechanical Behavior of
Refractory Lining Systems in Cylindrical Vessels, Association of Iron and Steel Engineers, Spring
Conference, Birmingham, Alabama, 1985.
174
Table I.
Type of brick
High Alumina
(70% Alumina)
Fireclay
Insulating
Youngs
modulus,
Coefficient
of expansion
in. /in. /OF
7.0 x lo6
3.0~
0.20
8.Ox 106
6.5 x 106
4.0 x 10-6
4.0~
0.20
0.20
vsi
Poissons
ratio
Note
The Youngs modulus of this table was evaluated by the sonic method.
Steel shell is A285 Grade C with following properties:
Youngs Modulus = 29 x lo6 psi; coefficient of expansion = 6.7 x 1 0 - 6
in. /in. / O F ;
Poissons Ratio = 0.30
Conversion Factor: 1 psi = 6.89 kPa; (OF-32) x 5 / 9 = C
158 DIA TOP I S .
P STIFFENER RING
TRUNNION BLOCK
TRUNNION BLOCK
175
15-2
/'I
HIGH-ALUMINA
BRICK
INSULATING BRICK
FIRECLAY BRICK
PLATE
S = EaAT
BAR
Fig. 3.
176
COLD
FACE
HOT
FACE
15r
DATA
COLD
FACE
-HOT
FACE
10
11
12
TIME.hourr
177
--
3f.3
x
z
m
U . . AL
0
(?
p g
g 5
0
50
100
MPa
2 Hr PREHEAT
lk$?
0
50
150
100
50
100
MPa
HOT METAL HOLD
MPa
4 H r PREHEAT
LINING
HOT
WORKING LINING
JOINT CRACK
179
*
COOL
PREHEAT
&TEEM
120r
*Ot
TEEM
--
i
2
4
TIME ,
10'
12
hrs
ANALYSIS RESULTS OF
INITIAL
WITH
PREHEAT AND
TIME, hrs
180
TEEM
SHELL
TYPICAL COMPRESSIVE
STRESS CONTOURS
(UNITS ARBITRARY)
RESTRAINING FORCE
FROM ADJACENT BRICK
181
QUARTER EVALUATED
*ARBITRARY UNITS
s x = 1.57'
Sx (-1
STRESS CONTOURS
sy
444 = 2.82
sx = 1.57
Sy
STRESS CONTOURS
(THEORETICAL RATIO = 3
182
I -
I 1
FACE
D1 <D2 <D3
X-DISTANCE
(L
FURNACE
a
E
200-
ad
gg
E5J
SI:
sG oy
c
.
15010050I
GAS
#-
,
\
183
'
,-\
-I
v)
*TIME
__
% OF FERROSTATIC PRESSURE
-xloo=
TAKEN BY SHELL
5 ,E
60%
;$
i
111 MPa
102 MPa
123 MPa
126 MPa
LINING EXPANSION
184
The industry trend toward the use of high alumina and dolomite refractories in steel
ladles coupled with longer holding times, has prompted the inwstigationof incorporating
insulation into the refractory lining. Benefits of insulating steel ladles are: reduction
in steel temperature loss ouer extended time, protection for the ladle shell, increased
refractory life,reduced scrap and skulling, and enhanced or minimizedpreheating. One
type of insulation is discussed that combines high strength, low thermal conductivity
and nominal thickness. Its success in reducing temperature loss in iron ladles led to
its use as steel ladle insulation. Case histories are discussed in addition to installation
techniques and perceived benefits of the insulating board. Ladle shell protection,
increased refractoy life, and enhanced ladle preheat are emphasized more than
reduction in steel temperature loss.
Introduction
T he refractory linings of most steel teeming ladles have been upgraded from
bloating fireclay to high-alumina or basic refractories to accommodate
higher tap temperatures and longer holding times, and to meet more stringent
metallurgical requirements. In addition to having greater heat capacity, these
refractories have significantly higher thermal conductivity as compared to
bloating fireclay brick. The 70% alumina brick have a thermal conductivity
that is roughly 50% higher than bloating fireclay, as shown in Fig. 1, while
dolomite brick are three times more conductive at low mean temperatures and
twice as conductive at higher mean temperatures as compared to conventional
fireclay refractories. Extended holding times due to ladle metallurgy, continuous casting, or process delay coupled with greater heat conduction through
the ladle lining can result in substantial steel temperature loss. A further
consequence of increased heat loss and higher tap temperature is that ladle
shell temperatures are in some cases exceeding 260C (500OF).
Insulating steel ladles has been investigated in the industry primarily as
a means of reducing heat loss through high-alumina or basic linings, thereby
maintaining steel temperature and reducing shell temperatures. Various types
of insulating materials have been evaluated, including insulating firebrick and
refractory fiber boards and paper. The effect of locating the insulation between
the working and safety lining, as opposed to against the shell, has also been
addressed. A board insulation that has been used successfully as back-up
insulation in rotary kilns and iron torpedo cars, has recently been used for
a similar purpose in steel teeming ladles. This paper will describe the application of this board in steel teeming ladles and the results of data collected to
determine its effectiveness. A number of benefits that were identified will also
be discussed.
185
Installation Procedure
The board is produced in 1.2 x 2.4-m (4 x 8-ft) sheets from which strips
are cut, typically 10-15 cm (4-6 in.) in width and 0.6-1.2 m (24-48 in.) in length.
Key-shaped strips are also supplied to accommodate the taper of the ladle.
Installation is accomplished by adhering the strips to the ladle shell with an
air-set mortar. A thin coating of mortar can be applied directly to the shell
and the strips then tapped into place with a masonry hammer. The strips can
be cut or broken over rivets and shell distortions so that there are no gaps
behind the insulation lining. The safety lining can be installed concurrently
with the boards or after the insulation lining has been completed. The ladle
bottom can also be insulated by laying the boards between the monolithic
bottom and the safety lining.
Case Studies
In November 1983, Aliquippa Works of LTV Steel Corporation insulated
the first 180-tonne (200-ton) steel ladle with 1.3 cm (one-half in.) of the high
strength board insulation. The refractory lining, as illustrated in Fig. 5 , consisted of a 15-23 cm (6-9 in.) 70% alumina working lining, a 6.4-cm (2%-in.)
bloating fireclay safety lining and a 15-cm (6-in.) basic slag line. The safety
lining has more recently been upgraded to a high-duty fireclay brick to
accommodate longer contact times resulting from trimming in the ladle.
Mechanical ladle covers and artificial slag cover are placed on virtually all heats
to the six-strand continuous caster.
Shell temperatures of the insulated and uninsulated ladles were measured
with a contact thermometer prior to tap at the BOF and as the ladle was emptied
at the continuous caster tundish. The contact thermometer was placed approximately 15 cm (6 in.) below the trunnion line. Shell temperatures were recorded
for seven of the first twelve heats on the insulated ladle and for nine heats
of newly lined uninsulated ladles. Only heats for the continuous caster were
monitored.
The shell temperatures that were measured just after the insulated ladle
was opened and prior to the time it was emptied at the caster are listed in Table
IV. The shell temperatures ranged from 93"-155"C (200-310F) for the
insulated ladle at the beginning of the cast and the average increase in shell
temperature was 8.7"C (15.7"F). The casting time, or time elapsed between
the two measurements, averaged 124.1 min. Similar data is shown in Table
V for the uninsulated ladle heats. Shell temperatures of the uninsulated ladles
range from 180C (355F) to 210C (410F) at the beginning of the cast and
the average increase in shell temperature was 13.3"C (23.9"F). The average
shell temperatures, shell temperature change and casting time are summarized
in Table VI. A comparison of the average shell temperatures indicates that
the insulation reduced the shell temperature by 62.4"C (1 12.4"F) at the beginning of the cast and by 67C (120.6"F) at the end of the cast.
A routine practice at Aliquippa Works is to measure and record shell
temperature prior to removal from the preheat station for each ladle. A comparison of these recorded shell temperatures of insulated and uninsulated ladles
revealed an average shell temperature of 170C (338F) vs 225C (437F) for
the insulated and uninsulated ladles, respectively (see Table VII). A total of
251 insulated ladle heats and 149 uninsulated ladle heats were averaged in that
comparison.
187
insulation, minimizes severe temperature changes in the working lining. A consequence of reduced thermal shock was an increase of 10% in working lining
life of the 70% alumina-lined ladles. An even greater benefit would be expected
for the more thermal shock sensitive basic linings.
Improved preheating efficiency is a potential benefit of insulating teeming ladles since the mean temperature of the working lining and safety lining
is increased and more heat is retained in the refractory linings after the ladle
is emptied. The desired hot-face temperature and stable gradient through the
lining can therefore be reached more rapidly, resulting in energy savings at
the preheater. Higher preheat temperatures could be attained if the preheater
output is unchanged which would contribute to a reduction in initial tap
temperature loss.
An effect on steel temperature may be difficult to identify, but on the
basis of an average shell temperature drop of 56C (100F) and a reduced
increase in shell temperature with time, a positive effect must exist. The use
of insulation in combination with mechanical ladle covers will produce significant results in terms of minimizing steel temperature loss that could be used
to alter hot metal requirements or tap temperature. At the very least, the insulation can provide a safety factor, relative to steel temperature, for instances
when the heat is held in the ladle for an excessive period of time or if a cold
heat is tapped.
The calcium silicate board insulation combines high compressive strength
and low thermal conductivity with nominal thickness. In comparison to insulating firebrick, additional ladle capacity is obtained with equivalent insulating
value. Installation time of the board insulation is less and there are at least
58% fewer joints as compared to a brick lining. Placement of the board insulation against the shell assures that it will remain intact for at least as long as
the safety lining so that the cost of the insulation is amortized more quickly.
WPa)
(psi)
3.4
13.8
27.6
41.3
55.1
68.9
500
2000
4000
6000
8000
lo000
1.2
4.8
11.0
17.4
23.8
29.6
6.0
10.8
17.4
24.0
30.4
34.3
0
1.4
2.4
7.6
13.8
18.6
189
1.8
3.8
9.4
15.4
20.8
24.8
8.9
15.4
24.1
32.6
41.0
45.6
3.6
9.2
16.0
24.4
31.2
36.0
(MW
(Psi)
21.2
40.4
5% deformation
10% deformation
3080
5870
Length
Thickness
Average
538
649
N/A
0.4
1.9
1.1
1.4
0.77
Temperature ("C)
760
N/A
3.5
1.6
87 1
982
3.7
12.1
6.8
3.6
13.6
6.9
Insulated
Ladle
2
3
5
6
8
11
12
-
93
149
160
160
107
138
154
107
157
168
163
124
143
160
Average
6.7
137.3
146.0
14
8
8
3
17
5
6
8.7
At (min)
122
148
146
130
114
104
105
124.1
Uninsulated
Ladle
5
6
6
7
7
7
8
8
9
-
Average
7.0
Shell Temperature
Ladle
Ladle
Open
Emptied
410
385
415
415
360
355
400
410
375
391.7
I 90
420
405
425
460
370
365
470
420
405
415.6
(OF)
AT
(OF)
10
20
10
45
10
10
70
10
30
23.8
At (Min)
125
117
103
144
102
110
117
104
125
116.3
Heats on
ladle
At ( M i d
Insulated Ladle
Average
6.7
137.5
146.0
8.5
124.1
Uninsulated Ladle
-4verage
7.0
199.6
213.0
13.4
116.3
Uninsulated Ladles
25 1
170
149
225
24.0
22.0
g 20.0
2
si 18.0
'r
2
'r
.-
5.-
16.0
14.0
12.0
?
il 10.0
.-
-s2
i!
8.0
6.0
Bloating
Fireclay
4.0
2.0
0
400
600
800
1,000
1,200
1,400
1,600
1,800
2,000
Mean Temperature ( O F )
191
1
.
High-Strength
24 pcl Ceramic
Fiber Board
Cakunn-Sllrate
Insulation Board
400
600
800
l,m
1im
1,m
1,800
1,;m
Mean Temperature ( O F )
192
6I
Fig. 7.
ladle.
194
S0.h Alumina/lnsulalion
InsulalWShdl
5 6
9 10 11 12 13 14 15 j 6 17 18 19 20 21 22 23 24
limp
fHmln\
195
Introduction
F inite-element analysis is being used more frequently to model industrial
furnaces, both thermally and mechanically. Modeling is being used both
for initial design and for product selection in currently operating equipment.
The success of this modeling hinges upon the quality of the data being used.
Our early attempts at finite-element analysis modeling of stresses in a
rotary kiln met with difficulties because of inadequate data. Since high
temperature Youngs modulus and Poissons ratio data were not available,
we had to use mom temperature values and assume that they remained constant
at higher temperatures. Due to the lack of creep data, we had to let the material
remain perfectly elastic at operating temperatures and settle for a steady-state
solution. Available expansion coefficients for castable had been determined
only on predried blocks, so the initial shrinkage had to be estimated. As a
result, compressive stresses of over 41 MPa (6000 psi) were calculated for a
castable whose cold crushing strenght was about 21 MPa (3000 psi). Since this
castable had not crushed out in service, the need for more thorough or at-temperature input data was evident. We have therefore improved our ability to
determine engineering property data as a function of temperature.
Thermal Conductivity
The ASTM calorimeter method has long been used for the measurement
of the thermal conductivity of refractories. We have switched to a hot wire
method for several reasons: smaller sample size, less labor, increased speed,
wider test temperature range, excellent reproducibility, and no thermal
gradient . I
Figure 1 shows a typical test sample. An electric current is passed through
a thin wire embedded in the sample and heat is conducted away from the wire
depending on the thermal conductivity of the refractory. The K-factor can
be calculated from a precise measurement of the rate of temperature change
of the hot wire during the test and a precise measurement of the power input
196
through the hot wire. The temperature increase is determined from the change
in resistance of the hot wire over a 15-cm (6-in.) span.
An integrated data acquisition system (Fig. 2) is used to provide automation, speed of data acquisition, and precise voltage readings. The computer
is programmed to automatically set up a complete test schedule for up to four
different test samples. When current is applied to the hot wire, voltage and
current measurements are made twice each s for about ten min. These
measurements are averaged to give 64 data points evenly spaced on a In (time)
plot (Fig. 3) and the most statistically significant linear portion of this curve
is determined and the slope through that portion of the data is calculated.
This slope is then used to calculate the K-factor.
The final plot (Fig. 4) shows the 99% confidence limits of the mean of
five tests at each temperature. The best fit of regressions from 2nd to 9th order
is plotted together with a listing of average data points, the chosen regression
equation, and K-values at 38C (100F) increments calculated from the regression equation. Field tests have shown hot-wire K-values to correspond with
measured heat flow values.
Thermal Dilation
Measurement of the thermal expansion of refractories under load is a
standard ASTM test (C832). Our single-position dilatometers consist of a vertical tube furnace containing a lower ram that is connected to a pneumatic
cylinder and a,load cell plus a stationary upper ram through which passes a
differential extensometer leading to a capacitive displacement transducer. A
3.8-cm (1.5-in.) square by 11.4-cm (4.5-in.) long specimen is heated at a
selected linear rate of advance with or without load. The furnace is capable
of reaching 1650C. One furnace is also equipped for a flowing gas atmosphere
for testing of pitch or resin-bonded products.
Because of the heavy usage of this type of equipment we have also constructed a six-station dilatometer for particular use in generating creep data
(Fig. 5 ) . The furnace is designed for 1500C operation with up to 158 kg (350
lb) of applied load at each station. Linear change at each test station is
measured using capacitive displacement transducers. A data logger had been
used to collect time, temperature, and transducer output on magnetic tape
prior to computer analysis and plotting. We are currently working on the hardware and software needed to perform this data collection using a personal
computer so that the progress of a test can be monitored continuously rather
than only after the test is completed.
A typical thermal dilation curve can be seen in Fig. 6. Since the 172 kPa
(25 psi) load has a negligible effect between room temperature and 1000C,
this curve can be used to determine both the linear thermal expansion coefficient (RT-1000C) and the thermal dilation under load. The six-station
dilatometer can be used to run a series of samples at various loads at several
temperatures in order to generate an equation representing the creep of a
product as a function of temperature and pressure:
D = eatbpce- Q / R T
(1)
where D = Deformation, Yo
t = Time, h
p =Pressure, Pa
T = Temperature, K
197
Figure 7 displays a series of curves that was generated for this purpose.
Another form of creep test, particularly used with refractories for blast furnace
stoves, is the measurement of creep deformation during the 20-50 h period
of the creep test soak.
Heat Capacity
Heat capacity can be measured using a drop calorimeter such as that shown
in Fig. 8. A'2.5-cm (1-in.) cube of material is polished on one face so that
it can be held in the furnace by pulling a vacuum through an alumina tube.
After the sample has come to thermal equilibrium (up to 145OoC),the vacuum
is released and the sample drops into the calorimeter. This vacuum method
replaces the conventional platinum wire loop suspension system and not only
eliminates the error from the heat capacity of the platinum wire, but also
eliminates the cost of platinum wire. By running tests at several temperatures,
heat capacity can be determined as a function of temperature.
We have devised a simple method of calculating heat capacity as a function
of temperature based on partial molal enthalpy in the MgO-Cr,O, and
Al,O,-SiO, systems. The enthalpy vs temperature of several pure refractory
materials was measured and found to compare well with literature data. Using
these results, a computer program was devised to consider a refractory as a
mixture of the pure materials that make up its chemistry and to generate constants for the following equations for enthalpy and heat capacity.
AH=A + B(
O K )
- Cln
(K)
(2)
C, = B - C(K)
(3)
The program will list the equations and then print values for enthalpy
and heat capacity at selected temperatures. Table I lists a comparison of
calculated vs measured heat capacity for a series of refractory materials.
Because of the close match, we can eliminate the time and cost of operating
the calorimeter for refractories within the MgO-Cr,O, and Al,O,-SiO,
systems.
Elastic Properties
The greatest deterrent to accurate mechanical modeling is the absence of
high temperature elastic property data. Others are using modified modulus
of rupture or resonant frequency methods for obtaining modulus of elasticity
at elevated temperatures. Measurement of both axial and diametral strain,
however, yields both modulus of elasticity and Poisson's ratio.
Our high temperature material test system* (Figs. 9-10) simultaneously
measures axial and diametral strain while under compressive loading up to
1650C. It is capable of handling both plastic and brittle materials with
precision and is flexible enough to do stress relaxation studies.
Core-drilled cylinders 5-cm (2-in.) in diameter and 11.4-cm (4.5-in.) long
(Fig. 11) are soaked for a minimum of two h at temperature before testing.
Data obtained from the continuous measurement of axial stress, axial strain
(EJ, and diametral strain (Ed) are used to plot stresdstrain curves and to
compute the modulus of elasticity and Poisson's ratio. They can also be used
to derive values for yield strength (a,) and ultimate strength (omax)as shown
198
Conclusions
In conclusion, engineering property data can now be generated for refractory materials as a function of temperature and, in some instances, pressure.
These data should enable the finite-element analysis modeler to do a better
job of thermally and mechanically modeling a refractory lining.
References
G. R. Angell, Thermal Conductivity of Refractories by an Automated Hot Wire Technique, presented at the 1980 Pacific Coast Regional Meeting of the American Ceramic Society.
*W. R. Alder and J. S. Masaryk, Compressive Stress Strain Measurement of Refractories
at Elevated Temperature, presented at the 1984 Annual Meeting of the American Ceramic Society.
Table I.
199
1.20
1.21
1.21
1.37
l.40
1.45
1.24
1.24
1.20
1.23
1.23
1.38
1.37
1.40
1.23
1.22
1.21
1.26
72
2000
2400
2550
2700
Modulus of
elasticity
(GPa) x lo6 psi
Poissons
ratio
I .4
3.3
2.8
1.2
0.14
0.12
0.31
0.4*
0.72*
0.41
200
Fig. 2.
201
DATA PCINT
c5
TEMPERRTUPC
74.38
i13.476
MIRE LENGTH
WIRE DIRMETER
BRSE CURRENT
5.524561 ~n (14.755S6B C m )
0.014672 I n C 0.037265 cm>
4.25 a m p e r e s
T I M
K-VALUE
0.16246
06/09;80
13x00~01
c~~
c 26.32 ~ e g0)
(t,.P25 51)
***&
t0,02
E 0.656554
8.16240
3.03 0.657775
0 : 0 4 0.658085
0 8 0 5 0.658158
0.06 0.6sa2za
0107 0.658272
0.08 0.6582%
On09 0.658321
0 ~ 1 00.658346
0 ~ 1 10.658362
5112 0.658378
Cs13 0.658390
0814 0.658400
0115 0.658409
0 8 1 6 0.658422
On17 0.658426
Or18
.-
8.16233
4.658437
Om19 0.656445
On20 0.658456
OtZl 0.658457
0122 0.658465
0123 0.658467
0125 0.658475
0127 0.658481
0124 0.658493
0.31
0.658SOl
0.33 0.659513
0 I 36 U .858523
0.39 0,658530
0.42 0.658538
0.46
0.658552
C.161850
4.056565
G.162138
tLlnr
-V3LLL-'
0 . 5 0 0.658563
0 : 5 4 1 658574
C.58 3 . C 5 8 5 3 0
i a C 3 ,- F5R 31
49 625
91.2w
0 162221 113.002
0.162244 119.042
0.162255 1 2 0 . 4 2 5
5.162263 12C.110
0 . ~ 6 2 2 6 9iizt.537
0.162274 118.323
0.162278 117.847
0.162262 117.120
4.556540
1.056710
? .056i85
4.056800
4.056830
4.456830
4.056855
4.0569i0
o.is:zas
4.05691 0
q . 056O15
4.056((50
4.056860
P os6ei5
4.056835
4.056820
4.856800
4.056785
4.056750
4.056755
4.056728
4.056635
4 . G58680
0.162317
0.162320
?.lW32
8.162
C.16I
0 1 - 335
4.056GS3
4.056613
4.056570
4.055533
95.350
94.9.58
4.056435
4.056483
91.435
68.291
94.683
3 24 0.656330
3141 0.659859
3.59 3.658876
4 . 1 0 6.658516
4 :39 0.8989"8
5:02 0.658986
202
093
066
018
OGO
36363
028
927
895
4.9!
4.3:
4.0:
4.0:
i56
131
835
f:;:
4.0:
553
4.3:
5EG
520
412
478
1.3' a 4 4
*.S!
"12
4.0:
4.0!
'1.152355
!.162357
;.162361
0.162365
0.162389
0.162573
2 0 ~o
750
707
575
855
625
4.P.
:.a!
267
4.2:
4.0:
4. 'I:
4.0:
4.6:
4.3:
9r25 0.65347Fi
0.16221
360
?33
316
243
4 .0:
8 r 0 3 0.5553i5
G z Z 2 C 658392
419
4.9:
4.0:
q.0:
5 . 2 7 0.659031
5 . 5 3 0.659077
6 . 2 2 O.ES9127
5 r 5 3 0.659130
7 - 2 6 0.6531)2+9
0.16227
Fig. 3.
4.::
4.c:
1i6.378
0.182289 115.E58
0.162293 115.,89
0.162296 114.296
0.162299 113.180
1.16t301 112.030
0.162303 110.698
G.16233E 159.41
0.182308 157.8
0.16/
106..854
A
1.162310
0.162314
4.056895
4.056865
i.08 ;:658$5?
fi
13
e.c!
4DG
.isma
0.1623WP
0.162356
3.i62391
0.12?97
0.1'32402
3 162407
0.:62413
).162G20
~.162+2
G.lE2133
3.1G24?0
O.iG2449
0.152'57
J.162466
3.16247G
0.162467
0.162498
0.:62512
2.162SZG
c.162541
C.ii2597
'1.16iS7i
0.1hZ59E
3.ih26:B
MTAmxws
TOP K-VWE
68
2944
naB
19.12
17.74
1174
481
947
1388
185
2306
23.07
22.88
2841
hscDoING
TDP K - V A L E
0 a
2
8
im 2864
288 27.24
388
400
ma?
788
888
22.83
588
808
am
leee
iim
1288
1388
1400
1588
lea0
I.j
1788
1888
1em
a
0
4
24.16
a44
2232
21.88
21.53
21.21
28.63
2888
a
4
4
a
2
8
19.85
19.78
19.42
19.13
z~se iasi
zim i a e
ZLBB lam
2300
2400
4.0
2588
2888
nee
am
ZBBB
3888
TEWERATUIE
17.8%
17.25
1888
1&33
15.65
15.37
14.88
14.43
(D.gR
203
inn
206
207
50
Urnax
I
I
1
I
OG
Ea
Straln(0XH)l)
208
Improved Analytical Procedures and Material Properties for Predicting the Thermomechanical Behavior
of Refractory Linings of Teeming Ladles
CHARLES
A. SCHACHT
Schacht Consulting Services
12 Holland Rd., Pittsburgh, PA 15235
The new clean steel procedures currently being developed in the steelmaking mills require
the use of stiff refractory working linings in ladles, such as high-alumina and basic
brick. Appropriate expansion allowance is required to avoid excessice thermal expansion
stresses in the working lining and the ladle shell. Optimum expansion allowance
minimizes hot metal runout, maintains the ladle shell integrity, and avoids premature
deterioration of the working lining. F3.esented are material properik.sof refract0 y linings,
and analytical procedures which predict ladle wall stresses that comparefavorablywith
Jield strain-gage data. Included are analytical comparisons of static stress/strain r&act o y property data with sonic or resonant elastic modulus data.
Introduction
T eeming ladle vessels continue to play a more significant role in steelmaking
plants. This has resulted primarily from the incorporation of clean-steel
processes throughout major portions of the steel industry requiring the use
of stiffer refractory linings. These linings typically consist of alumina or basic
refractory, replacing the softer fire clays. In addition, alloying, desulfurization, and many other steelmaking processes, including inductive and argon
stirring, arc heating, vacuuming, and decarburization are being done within
the ladle. In fact, some areas of the steelmaking community identify the ladle
as a ladle furnace.
Recent research on teeming ladles with high-alumina working linings
has expressed concern over the structural integrity of the ladle shell as a result
of the larger expansion loads imposed on the shell by the stronger linings. The
impact of stiffer linings on the strength and life of the ladle shell is of primary
concern throughout the steelmaking industry. However, this previous research
has also shown that appropriate refractory material properties are required
in order to develop accurate and dependable analytical predictions. This study
compares updated analytical results with previous field test data. These
revised analytical predictions were made because of recent developments in
refractory material tests which provide improved refractory structural material
proper tie^.^,^
209
Method of Analysis
The analysis of a typical section of the ladle wall (Fig. 1) was performed
using the finite element model6 shown in Fig. 2. Appropriate boundary
conditions were applied to the model planes of symmetry (Fig. 3), simulating
the non-tension behavior of the brick joints. Interface6 elements were
included at the X-Z and X-Y boundary planes which allow only compressive
loads to exist on these lining boundaries. The model represents a typical radial
plag section of the ladle wall and evaluates the composite nodinear behavior
of the ladle wall resulting from thermal expansion loads generated by the heated
lining. Three-dimensional solid linear strain elements6were used for the lining
and ladle shell.
Details of the thermal and other details of the ladle study were originally
described in Ref. 1.
Lining Structural Behavior
The most significant thermal expansion forces were developed during the
preheating of the lining as shown by the resultant equilibrating circumferential tensile stresses of the shell (Fig. 4). The previous elastidcreep analysis
and tests' show that high-alumina working lining develops the complete
expansion load with the highest circumferential compressive stresses starting
on the inside hot face (Fig. 5). However, in order to make the previous
analytical results compare favorably with test results, the material coefficients
of thermal expansion had to be adjusted to approximately 30% of the published
values. The initial analysis also included the creep response of the high-alumina
working lining, but the amount of accumulated creep, eve with the initially
high compressive stresses, was inadequate. The material creep data used did
not allow the necessary relaxation to provide agreement with test
measurements. As a result, the adequacy of the compressive creep data
(developed at laboratory compressive stresses of 193 kPa (28 psi) was
questionable since the lining stresses were considerably higher (average compressive stresses of 34.5 MPa (5000 psi)). In addition, the elastic modulus
(dynamic modulus) used, was developed using the resonance method in which
the imposed stresses, on the dynamically excited specimen, are exceedingly
small. At the time in which this study was conducted, other types of elastic
modulus data was not available and the knowledge of other testing methods
for the elastic modulus was not known. Another source of possible relaxation
was the mortar joints. However, the amount of relaxation per joint needed
to provide agreement with test results, when the dynamic elastic modulus is
used, would have been completely unrealistic. The adjusted coefficients of
expansion provide analytical results in which agreement with test results is
readily apparent.
Updated Analytical Procedures
A revised analysis was conducted using material property data developed
with a highly realistic test environmenL2 Typical static stredstrain data is
described in Fig. 6. The curves are developed for a realistic range of temperature
and compressive stresses. The elastic modulus (static modulus) was calculated
using a 13.8 MPa (2000 psi) compressive stress and the corresponding strain.
Table I3 provides a comparison of the elastic modulus (dynamic modulus)
used for the 70% alumina brick (manufacturer A) in the ladle study1 and the
elastic modulus (static modulus) for two similar 70% alumina brick materials
210
The improved agreement of the computer analytical shell stress with the
strain edge shell stress is shown in Fig. 14. Two aspects of the analytically
computed shell stress curve require additional attention.
Conclusion
The results of this revised analysis are very encouraging and provide
considerable confidence in the use of appropriate analytical methods in
predicting the behavior of refractory structures. The following conclusions
are made as a result of this study.
(1) The temperature-dependent static stredstrain material property test
procedure is currently the most comprehensive method of defining
refractory material behavior for structural analysis methods.
(2) The elastic/plastic method of analysis, coupled with static
211
stress/strain material property data, provides greatly improved predictions for the thermomechanical behavior of refractory structures.
The analytical procedures and the use of improved material properties
as described are applicable to other similar refractory-lined vessels
and furnaces.
A realistic densification of about 30% in the mortar joints is needed
to make the revised elastic/plastic analysis agree with test results.
Elastic/plastic analysis of homogeneous refractory materials such as
castables should provide close agreement with measured test data.
References
Manufacture A
dynamic modulus
(lW) MPa
Manufacture B*
static modulus
Type 1
(1W)MPa
20
800
1100
1200
1300
4.8
4.8
4.8
4.8
4.8
3.17
3.10
1.10
0.28
2.14
2.62
1.52
0.19
Type 2
Elastic
mod u1us
*lW MPa
Plastic
modulus
*1W MPa
Yield
stress
MPa
Poissons
ratio
20
800
1100
1200
1300*
1650*
2.41
2.41
1.45
1.03
0.34
0.0007
1.93
1.38
0.80
0.08
0.01
0.00003
48.3
48.3
14.5
7.8
3.45
3.45
0.07
0.09
0.17
0.14
0.14
0.14
212
'
7 0 PERCENT ALUMINA
BRICK
FIRECLAY BRICK
LAD!,
SHELL
INSULATING BRICK
SMELL
RADIAL PLANES
OF SYMMETRY
Xr
SAFETY
dz =UNIT HEIGHT
rde=UNIT WIDTH
NOTE: CROSSHATCHED REGION REPRESENTS QUARTER SECTlON OF
U N I T RADIAL LADLE WALL SEGMENT USED I N MODEL
213
.,
VERTICAL RADIAL
PLANES OF
SYMMETRY
CIRCUMFERENTIAL JOINT IN
L*g+xr
Y
HORIZONTAL RADIAL
WORKING
BACKUP LINING
PLANES OF
SY MM ETR Y
TEST RESULTS OF
SECOND LINING
ANALYTICAL
10
TIME, Hours
Fig. 4.
214
12
14
16
COLD
FACE
FACE
COLD
STRESS @ 1 0 HR
STRESS @ 4 0 HR
PREHEAT
TEEMING
C-
1 kii = 8 89 MP.
STRESS t
3 7 0 HR
STRESS B 7 68 HR
-COOLING+
--
STRESS @ 90 HR STRESS f3 12 0 HR
COOLDOWN
failure
I
I
I
I
ELASTIC MODULUS=E.
=- Sa
ea
YIELD STRESS= Sy
I
I
I
lea
!=Y
2
STRAIN
215
10'
MANUFACTURER
(dynamic data )
6-
5MANUFACTURER B
(static data )
4-
32-
----
type I /
-/--
\type
10
10
12
1200
STRAIN
5
x lo3
216
ELASTIC
SOLUTION
STATIC STRESS/STRAIN
AT HOT FACE
2
STRAIN
4
x
103
STRAIN
217
lo3
RESPONSE
"1 50r
40
In
STRAIN
x 1z3
STRAIN
218
lo3
: 8-
'$-*OL
PREHEAT
----ANALYTICAL
!y);EATL(
RESULTS
TEST RESULTS
COLDFACEOF
WORKING LINING
TEEM
K
3
w
n
5I-
1012
TIME , Hours
320
280.
TIME
Hours
219
1 4 '6
Introduction
M agnesium chromite refractory brick is a candidate for use as hot face linings
in slagging coal gasifiers. Laboratory studies' in which cylindrical
specimens are rotated in high temperature coal slags indicate that refractories
with high chromia content are very resistant to wear by coal slags. However,
refractories obtained from a pilot plant after several hundred h service were
deeply penetrated by slag and contained intergranular cracks parallel to the
hot face, suggesting that creep cracking can be a major cause of failure.' In
the present study the compressive strength and creep behavior of a commercial magnesium chromite refractory are characterized at high temperatures.
This will provide a basis to compare the creep behavior of the refractory when
it is impregnated with slag in future studies.
Test Material
Based on a manufacturer's report,2 the magnesium chromite refractory
material which was used in the present work consisted of 20 wt% MgO and
80 wt% Cr,O,. The Cr,O, was slightly in excess over the compound
MgCr,O,. The refractory was single phase, having the cubic structure of the
spinel group. Fused-grain aggregates of magnesium chromite, some of which
were as large as 3 mm across, had been sintered in a porous bonding matrix
of much smaller grains of the same material. Bulk density measurements
indicated a porosity of 14 t o 16% based upon the theoretical crystal density
of 4.414 g/cm3 at 25C.
220
CrzO,
(S)
4-
3
2
(1)
222
-..-
yIuocIc
u L 1 l s l a l l y , L l 1 G G A ~ C III I I C I I L ~ were termmatea wnen tne
specimens sustained from 0.01 to 0.02 creep strain.
Creep measurements were conducted on 9 specimens. The stress and
temperature applied to a given specimen were kept constant during a test. In
the collection of tests the stress ranged from 1.4 to 5.6 MPa and the temperature
ranged from 1300 to 1600C. The duration of the creep tests varied from about
3 to 170 h. Figure 4 shows a typical experiment of creep strain vs time. Absolute
Absolute values of strain were used to facilitate an analysis. Note that no
steady-state creep rate was attained.
oLI ai1i.
& = Ct"
in which (C) and (m) are coefficients that were evaluated by a least squares
fit of Eq. 2 for each experiment. An example of such a fit is the line in Fig. 4.
No systematic trend of the time exponent (m) was apparent either as a
function of the applied stress or as a function of temperature. Figures 5 and
6 show (m) as the slope of log, (E)versus log, (t)for various stresses applied
to specimens kept at constant temperature, and for various temperatures
applied to specimens held at constant stress, respectively. In these figures the
slopes are roughly parallel. The mean value of (m)for 9 experiments was 0.74
with kO.16 standard deviation of an individual measurement. If any creep
strain that might have occurred during the period of temperature equilibration of a specimen under the preload were included, a lower value of (m)and
perhaps a better precision would have resulted.
Differentiation of Eq. 2 and substitution of the strain equivalent of time
gives
dE/& = mCl/mE(l- I / m )
(3)
which shows a strain-hardening effect for (m)< 1. Thus, the creep rate (dddt)
decreases continually as the strain (E)increases, exemplifying primary creep.
The parameter (C) is a function of the applied stress (u) and the absolute
temperature (T).
Using customary stress and temperature functions,' the creep strain rate
can be represented as follows:
dddt = A
E(I-I/~)
a"
exp ( - Q / R n
(4)
where ( A )is a material constant, (n)is the stress exponent, (Q) is the activation energy, and ( R )is the molar gas constant. Strain rates were calculated
from Eq. 3, using values of strain generated in increments between 0.002 and
0.02. At constant strain ( E ) and the mean value of the time exponent (m),
the
coefficients A , n, and Q were evaluated by a least squares fit of the log, of
Eq. 4 to the strain rates at their respective stresses and temperatures. Although
the resulting values of the coefficients of Eq. 4 had a slight systematic trend
over the generated range of strain, they could be considered constant within
the precision of measurements. Table I shows the values of these coefficients.
Figures 7 and 8 show the stress exponent (n) and the activation energy (Q)
as slopes of log, (dddt) vs log, (0) and vs 1/T, respectively.
223
Summary
The compressive strength of a magnesium chromite refractory was
measured at temperatures up to 1600C. The strength decreased with increasing temperature above 1200C.
The creep behavior of the magnesium chromite refractory was measured
as a function of compressive stress in the range from 1.4 to 5.6 MPa and as
a function of temperature in the range from 1300 to 1600C. The strain rate
of this refractory was represented by a strain-hardening model.
The stress exponent and the activation energy for the creep of the
magnesium chromite refractory were evaluated from the strain rate data at
constant strain.
Acknowledgment
Funding was provided by the U.S. Department of Energy, Fossil Materials
Program, Oak Ridge National Laboratory, Oak Ridge, TN. Helpful discussions with Sheldon Wiederhorn, who suggested the work be undertaken, and
with Robert Polvani are gratefully acknowledged.
References
224
S i c rod a t t a c h e d
with bellows t o
crosshead
with bellows to
load cell
6000
z
6
4
4000
2000
0.1
0.2
0.3
0.4
0.5
DISPLACEMENT, rnm
225
125
=I-
100
I-
0
2
W
I-
75 -
v)
w
2
v)
v)
50
25
0:
2
0
Fig. 3. Compressive strength of magnesium chromite refractory specimens in nitrogen as a function of temperature.
0.010
0.008
za
a
c
v)
0.006
5
W
0.004
0.002
TIME, hours
226
-z
-3
-4
4
K
I-
fn
-5
W
W
-6
21
-7
227
-6
W
I-
<
=
I
-8
3
I-
-9
0
-
log, (STRESS. M P d
-6
-7
-8
lOOOlT
228
Introduction
C orrosion is one of the major causes for the high cost of materials for flue gas
cleaning systems in industrial, municipal, cogeneration, and refuse incineration facilities. Corrosion-resistant linings in stacks and ducts serving powergenerating facilities using fossil fuels are an important issue in FGD systems
and have become critical components with respect to materials problems and
failure consequences. Acid corrosion in FGD systems was a minor problem
until the use of lower grade fuels and the addition of scrubbers and heat
recovery units reduced exit gas temperatures. Inorganic corrosion-resistant
linings have been successfully used in a wide range of corrosive environments
for more than 30 yr. There exists room for improvement in many appiications, including power plant ducts and chimneys. The industry is actively
working to bring about these improvements and this paper discusses an
improved design concept to optimize the performance of corrosion resistant
monolithic linings through the use of dual-component systems.
Background
Brick and monolithic dual-lining systems have been used in other areas
of FGD systems with both success and failure. Many of these applications
have required erosion resistance as a primary consideration, with corrosion
resistance being provided by an organic back-up component. Quench and
venturi areas are specific parts of the system. Brick and mortar is the best
method of construction for erosion resistance and has given the longest service
life of available acid-resistant construction materials. Although many stacks
and ducts have been unlined, corrosion-resistant linings have included acidresistant brick and mortar, calcium aluminate cement, portland cement, gunited
monolithic silicates, organics, and plastics. A corrosion-resistant lining is
needed to prevent the reactive condensates from reaching the steel or concrete
shell. The nature of the protection mechanism is complex and depends upon
the type of lining system chosen and the method of application. With the
addition of scrubbers and other pollution or process control equipment, flue
229
gases are subject to a wider range of temperatures. An important consideration toward the poor performance of many materials is that all of the
parameters and conditions of the flue gas during normal operating and excursion periods are not completely identified. These include temperature distribution, gas velocities, pH levels, condensation analysis, etc. The acidic environment generated from the scrubber operations can become even more severe
during bypass conditions when temperatures are higher and other corrosive
species are introduced from the unscrubbed flue gas. The cumulative effect
on materials of continuing upset conditions during operation is also not
understood.
The outlet duct can be exposed to saturated flue gas at around 52C
(125"F), reheat flue gas, hot flue gas (near) 149"-252C (300" to 450'F) or
combinations of these conditions. Major materials corrosion problems being
addressed in the literature' are occurring in outlet ducts and stacks. Reduction of corrosion mechanisms is enhanced by improvements in several areas.
These include:
(1) Providing physical protection of the surface.
(2) Preventing concentration cells.
(3) Reducing current flow between areas of differing potential.
(4) Lower surface temperatures.
( 5 ) Preventing water and electrolyte from reaching the surface.
(6) Reducing thermomechanical stresses.
The majority of stacks in the power industry consist of an outer shell of concrete with an independent brick or metal interior flue, with an annular air space
between the flue and the outer shell. It is the interior surface of the flue which
must be protected from corrosive flue gas conditions. Independent selfsupporting acid brick linings have shown good performance and can withstand
hot acidic environments. However, they have a certain amount of permeability
and acid can penetrate both the brick and mortar materials and eventually
reach the substrate since corrosion-resistant masonry is not an impermeable
barrier in itself. This can be overcome by pressurizing the annular air space.
A common practice with brick and mortar lining construction in the chemical
industry is the application of a flexible and compressible membrane directly
to the substrate and then to install the brick lining directly over the membrane.
The brick lining provides protection from physical abuse and lessens the severity
of attack. The impervious membrane protects the shell of the tank from attack
if the corrosive media penetrates the brick lining.
Ducts and stacks are commonly protected with inorganic monolithic linings to withstand extreme temperature fluctuations. Protective corrosiveresistant linings over carbon steel and concrete have been an accepted method.
Monolithic linings can be cast in place or applied by guniting directly against
the shell. Careful consideration should be given to the physical attachment
of monolithic linings, as well as temperature and chemical resistance. These
linings are installed on studs, anchors, and wire mesh to hold them against
the shell. A limitation of inorganic concretes is the weight that these linings
contribute to steel flues designed originally for organic linings. However, they
have been used successfully in a number of power plants. As long as the
monolithic lining maintains its physical integrity and remains in intimate contact with the steel shell, corrosion at the interface will be minimal. If the lining
is broken or cracked by accident, improper installation, or as a consequence
of operational stresses and strains, the anchoring system will hold the lining
230
in place; however, oxygen, water and corrosive media can cause localized or
progressive corrosion.
Discussion
Recently a trend has emerged where dual-component lining systems are
being recommended and installed in FGD ducts and stacks similar to applications in the chemical process industry. Figure 1 illustrates the design of a typical
membrane/monolithic system in the chemical industry. There are numerous
reasons for this new construction process. Condensation occurs not only on
the face of the acid-resistant lining, but can penetrate and condense at the
shell. While the concrete linings offer the proper chemical resistance, they have
the characteristic of being inherently inelastic or brittle. Monolithic linings
may tend to crack and absorb flue gas condensate over time; therefore, it is
advantageous to have a back-up membrane. The coefficient of thermal expansion of the monolithic lining will not match that of the substrate. Therefore,
a flexible membrane will help accommodate stresses due to these differences
as well as other mechanically induced stresses. Evidence compiled by EPR11r2
indicates that lining problems may be more a consequence of temperature fluctuations or other unusual conditions that affect the lining life. For many
applications, the monolithic should not be bonded to the substrate and a
membrane can act as a bonding barrier. Figure 2 illustrates the design of a
monolithic/membrane dual-lining system.
The concept of placing an impervious membrane between the substrate
and inorganic linings which are not totally impervious has become a recommended practice. Some corrosion-resistant gunite manufacturers have installation specifications for use with membranes. Organic linings or coatings have
been in stacks and ducts, but usually will deteriorate under flue gas conditions of bypass temperatures of 149" to 260C (300" to 500F) or with high
sulfur fuels. There are many types of stack and duct lining materials; however,
because of unpredicted environmental conditions within a stack or system,
it may be difficult to select the best candidate material. Stacks that are not
designed for the actual conditions, or those with more than one flue inside
the shell, warrant giving consideration to this dual-lining concept.
Membranes include asphaltics, resins, and synthetic elastomers. The membrane selected should be resistant to the maximum acid concentrations and
temperatures expected. Failure of organic linings can occur by disbonding,
swelling, blistering, abrasion, and high temperature. Protection of an organic
membrane with an inorganic barrier will minimize mechanical abrasion and
thermal exposure as well as limit the volume of corrosive media that reaches
it. An organic membrane compensates for some of the shortcomings of
inorganic linings such as cracking or spalling as a consequence of mechanical
stresses from shrinkage, insufficient thermal expansion allowances, the
anchoring system, vibration, and thermal or mechanical stresses. In order to
provide an effective barrier, organic linings are applied much thicker than
typical coatings. Often they contain fillers to act as reinforcement and to
decreases permeability. Fillers are also incorporated to give wear resistance
to abrasive conditions. However, membranes protected by inorganic linings
can be applied thinner, do not require as much filler, and consequently will
cost less.
The installation procedure for a dual-lining system is principally the same
as if each component were being applied separately. These procedures are
23 1
established for both organic coatings and inorganic monolithic linings. The
condition of the working area and preparation of the surface follow standard
practices used throughout the i n d ~ s t r yAnchors
.~
can be installed on the steel
or in concrete substrates prior to application of the organic membrane. Techniques should be used and care taken to completely coat all anchor surfaces.
Figure 3 shows guniting of an inorganic lining over an asphaltic urethane
applied to a steel substrates. Figure 4 shows a 183 m (600 ft) steel liner protected
with 50 mm (2 in.) of inorganic lining over a membrane. Monolithic/membrane
dual-lining systems exist in South America and Europe and are under construction in the United States.
Conclusions
Programs are being set up to identify and develop better lining materials
and installation techniques more applicable to operating conditions. This will
be accomplished by efforts to more accurately identify, characterize, and
predict the environmental conditions within a specific stack. Observations of
existing dual-lining systems, along with new and improved materials, has
encouraged the use of inorganic monolithics over organic membranes. This
is in one way of optimizing a longer lasting approach to this critical corrosion
area.
References
H. S. Rosenberg, et. al., Construction Materials For Wet Scrubbers: Update, Vols. 1
and 2, EPRI Report CS-3350, July 1984.
D. C. Agarwal, FGD Scrubbers: Technology Nobody Wanted, Pollution Eng., 34-8,
June 1984.
ASTM Technical Publication 837, Manual of Protective Linings for Flue Gas Desulfurization Systems, 1983.
232
Permanently flexible
elastomerlc expansion
a+.,
iur
eL,
,
% -,
g2&! &
9@-
:*Q,
joint
Fig. 1. Design of chemical-resistant membrane/monolithic system which provides double protection in the form of
a flexible base lining and a rigid surface layer. The flexible
corrosion-resistantmembrane is applied in direct contact with
either steel or concrete substrates. It is then covered by a
monolithic which provides protection over a wide pH range
as well as against temperatures to refractory levels.
STEEL SHELL
MEMBRANE
LONGHORN OR V-TYPE
xiMINIMUM FROM SUBSTRATE
I
MINIMUM-OVER STUDS
t
\
STUDS
#
Fig. 2. Design of dual-component membrane/
monolithic corrosion-resistantsystem.
233
234
235
Industries
SUBRATA
BANERJEE
Introduction
T he performance of the refractory linings in oil refineries has become increasingly important as the technology of oil processing moved towards higher
temperatures for improved operating efficiency. Transfer lines, cyclones and
associated areas around them are most critical in the performance and durability of a refinery process. The failure of one or two cyclones inside the unit
may cause reduced efficiency, but the failure of a transfer line will cause shutdown of the whole process. Thus, most attention has been given to transfer
lines.
Earlier practice was to use a single-component, erosion-resistant material
on hexmesh with outside insulation. With increasing temperature of the refining
process, the metal pipes started to deteriorate by warping and cracking. The
next phase was a two-component lining with erosion-resistant material in hexmesh, supported by studs from the shell, and insulating castable back-up. The
failure of the stud support and consequent warping of the hexmesh exposed
the insulating lining to high erosion and consequent shut-down of the unit.
The later designs used placement of a single-component lining with appropriate
anchors by pneumatic gunning.'
It has only been seven or eight yr since refractories, have been regularly
installed by vibration casting, although some installations go as far back as
15 yr. The specific advantages of vibration casting over pneumatic gunning
have been explained by Staten.2
Vibration casting helps the refractory lining to be stronger through more
tightly knit intergrannular bonding which produces more uniformity with
smaller and fewer shrinkage cracks than with comparable material placed by
pneumatic gunning.
Application of vibration-cast refractories is becoming popular in the
overhead lines of CO ducts, stacks, oil preheaters, and H,-gas transfer lines.
Vibration-cast linings have also been tried in cyclones but the designs of the
236
Transfer Lines
Since the performance of the refractories in the transfer lines is very critical
for the life of a refining unit, vibration-cast refractories have been most successful. The refractories in the transfer lines need to have high erosion resistance
as well as low thermal conductivity. These are vibracast either at the job site,
or at the contractors place, in sections up to 12 m (40 ft). The normal lining
thickness is about 10 cm (4 in.) A typical composition with the specific
properties as vibration cast, pour cast and pneumatic gunning is given in
Table I.
A compromise has to be made between the need for low thermal conductivity and low erosion loss. At present, the refractory materials with high
performance records seem to range between 2160-2240 kg/m3 (135-140
lb/ft.3), which have thermal conductivity in the range 1.2-1.3 (W/m. k) of
8.5-9.0 Btu in./h ft OF.
The refractories mentioned in Table I are based on low moisture
technology; the open porosity is lower than that of conventional castables and
hence they will be less susceptible to coke penetration.
Overhead Lines
Overhead lines are usually much larger in diameter than transfer lines.
The CO ducts and stacks need to have fairly good abrasion resistance (in case
of malfunction of the slide valve in the reactor unit) as well as low thermal
conductivity. Pneumatic gunning of a medium-weight refractory has been
traditionally used. A lot of refineries are using a medium-weight vibration
castable in these lines. Typical compositions for the vibration cast and pour
cast, as well as gunning application, are given in Table 11. Again, since these
mixes are based on low moisture technology and yield lower porosity, they
will be less susceptible to gas permeation.
237
Cyclones
Since cyclones suffer the most erosion from the catalyst flow, the
refractory linings should be the most obvious choice of vibration casting.
Unfortunately, the design of the cyclones make it very inconvenient for
vibration-cast application. A properly designed cyclone suitable for vibration
cast application could eliminate the long and laborious process of installing
the refractory in the hexmesh. Instead, the vibration cast refractory could be
applied with V or steerhorn anchors. Three low moisture, vibrationcast refractories are given in Table 111. The exceptionally high compressive
strength and low erosion loss with provide longer carefree performance of the
refractory lining.
Reactor, Regenerator, and Gasifier Vessel Linings
These vessels are usually of large diameters. The normal practice is to
apply the lightweight refractory by pneumatic gunning, which is associated
with its normal drawback of possible lamination, striation, and nonuniformity. All these could be eliminated by vibration casting of lightweight castables.
This will provide uniformity of the lining and better strength properties at lower
bulk densities, especially with the use of low moisture castable. Table IV shows
compositions of the vibration cast, pour cast, and gunned refractories for these
applications.
Burner Blocks For CO Boilers
Vibration casting of low moisture castables for the burner blocks for the
CO boilers is one of the most convenient and effective applications. These
provide extremely strong, uniform, and high refractoriness along with the
resistance to CO and H2 atmosphere. Table V shows properties of the
material applied in burner blocks.
Sulfur Recovery or Burning Units
The problems associated with sulfur recovery, or burning units, are
permeation of sulfur oxides through the refractories attacking the metal shell,
slagging of the refractory, and consequent cracking and spalling of the lining.
Low moisture castables applied by vibration casting can eliminate these
problems. The chemistry of these castables with extremely low lime content
will render minimal slagging action. The very low porosity, extremely high
strength, and refractoriness will help protect the lining from gas permeation
and maintain the integrity. Table VI shows an ideal composition for this
application.
Conclusion
With the advent of low moisture technology, the vibration cast process
is going to provide the most optimum performance and longer life of the refractory linings in petrochem industries. The transfer lines are now using vibrationcast refractories. This new technology in other areas such as overhead lines
(CO duct and stacks), reactor, regenerator, and gasifier lines is coming more
into use. Burner blocks, sulfur recovery, and burning units are also ovbious
choices for vibration-cast refractories.
238
Acknowledgment
The author acknowledges with thanks the help in gathering information
regarding application and uses from M. S. Crowley of AMOCO Research Lab
and Ed Linck from Turnaround Maintenance.
References
IM. S. Crowley, Design Better Vessel Lining, Hydrocarbon Processing, 127-30, Dec.
1979.
*W. T. Staten, Vibration Cast Refractory Linings for FCCU Catalyst Transfer Lines,
Presented at the NPRA meeting, Paper #MC-85-4, Feb. 1985.
3s. Banerjee, et al., Low Moisture Castables-Properties and Applications, Proc. Intl.
Symposium Monolithic Refr., Am. Ceram. SOC.,1985.
SiO,
Fe203
TiO,
CaO
Alkalies
Yo Water for placement
Bulk density, kg/m3 (lb/ft3)
@ 104C (220F)
@ 815C (1500F)
CCS, MPa (psi)
@ 815C (1500F)
Linear change, Yo
@ 815C (1500F)
Erosion loss, cm3
44
50
1.2
1.4
2.8
0.4
44
50
1.2
1.4
2.8
0.4
7.0
7.5
2208 (138)
2160 (135)
2112 (132)
2064 (129)
Pneumatic
gunning
52
38
0.6
1.2
7.6
0.2
2112 (132)
2048 (128)
7.5
239
- 0.22
10.0
-0.11
14.0
SiO,
Fe20,
TiO,
CaO
A1kalies
070 Water for placement
Bulk density, kg/m3 (lb/ft3)
@ 104C (220F)
@ 815C (1500F)
CCS, MPa (psi)
@ 815C (1500F)
Linear change, Yo
@ 815C (1500F)
Erosion loss, cm3
53
41
1.2
0.3
3.0
0.5
53
41
1.2
0.3
3.0
0.5
7.0
8.0
1888 (118)
1856 (116)
1728 (108)
1696 (106)
44.8 (6500)
0.3
10.0
Pneumatic
eunnine
45
42
1.1
1.1
8.1
1.0
1792 (112)
1728 (108)
- 0.3
14.0
18.0
A1*03
SiO,
Fe203
TiO,
CaO
070 Water for placement
BuIk density, kg/m3 (lb/ft3)
104C (220F)
815C (1500F)
CCS, MPa (psi)
@ 815C (1500F)
Linear change, 070
@ 815C (1500F)
Erosion loss, cm3
@
@
57
39
0.2
1.8
1.o
91
7.5
1.2
1.o
4.5
4.5
4.0
2544 (159)
2528 (158)
2848 (178)
2848 (178)
3024 (189)
3024 (189)
62.0 (9000)
-
0.2
8.0
240
94
5
- 0.2
5.0
3.0
Table IV.
A1203
SiO,
FW,
Ti02
CaO
Alkalies
To Water for placement
Bulk density, kg/m3 (Ib/ft3)
@ 104C (220F)
@ 815C (1500F)
CCS, MPa (psi)
@ 815C (1500F)
Linear change, Yo
@ 815C (1500F)
54
37
1.8
0.8
4.8
1.2
54
37
1.8
0.8
4.8
1.2
17
22
1120 (70)
1056 (66)
54
37
1.8
0.8
5.0
1.2
1008 (63)
912 (57)
20.6 (3000)
- 0.3
Pneumatic
gunning
1280 (80)
1216 (76)
10.0 (1450)
- 0.4
13.8 (2000)
- 0.3
92
6.5
<0.1
<0.1
1.4
co.1
A1203
SiO,
Fe,O,
TiO,
CaO
A1kalies
To Water for placement
Bulk density, kg/m3 (Ib/ft3)
@ 104C (220F)
MOR, MPa (psi)
@ 104C (220F)
@ 955C (1750F)
@ 1372C (2500F)
@ 1593C (2900F)
CCS, MPa (psi)
@ 104"C.(22OoF)
@ 955C (1750F)
@ 1372C (2500F)
@ 1593C (2900F)
Linear change, To
@ 815C (1500F)
@ 1372C (2500F)
@ 1593C (2900F)
24 1
5.0
2880 (180)
17.2 (2500)
30.3 (4400)
31.3 (4550)
27.6 (4000)
117.1 (17000)
124.0 (18000)
130.9 (19000)
130.9 (19000)
-0.1
- 0.3
- 0.4
Table VI.
66
30
0.9
1.6
1.o
< 0.2
A1203
SiO,
Fe@,
TiO,
CaO
Alkalies
242
4.5
2608 (163)
7.7
11.3
12.7
11.9
16.2
28.9
28.6
32.7
(2350)
(4200)
(4150)
(4750)
41.3 (6000)
6.9 (1000)
69.6 (10100)
110.2 (16000)
- 0.3
-
0.3
+ 0.3
G . S. DHUPIA
and W. KRONERT
Institut fur Gesteinshuttenkunde der RWTH
Mauerstr. 5 , D-5100, Aachen, W. Germany
During the last few years there has been a rapid increase in the use of volatilized silica
as a raw material in a number of refactory products. Concretes based on microsilicablended high alumina cement were studied afrer drying andfiting. Microstructure of
the specimens was determined using scdnning electron microscopy and X-ray
microanalysis with phase analysis being camed out by X-ray difiaction. It is attempted
to correlate the difmences in microstructure to hot modulus of rupture data.
Introduction
During the past years a number of low cement castables with low-cement
content have been developed that exhibit properties similar or superior to
fired brick.1-3 Attempts are being made to further improve the properties of
low-cement castables through addition of fine reactive materials such as silica
and alumina. Silica fume, a by-product of ferrosilicon and silicon metal
production, is being increasingly used as the silica additive. The term
microsilica, first introduced by Elkem a/s is used here to denote this type of
material. The chemical and physical properties of the refractory-grade
microsilica available for this study are given in Table I, along with those for
the other raw materials. However, it is not always possible to predict the performance of different grades of microsilica from these data alone. Important
process variables such as charge composition, filtering procedures, etc., may
affect its suitability for various applications. The residual carbon content, free
carbon content and pH value are also important factors.
In the present investigation it was attempted to study more closely the
role played by microsilica as a substitute for cement in low cement castables.
Preliminary studies4 had indicated that the optimum composition was 14%
cement, 6% microsilica, and 80% aggregate when no other ingredients, such
as reactive alumina were added.
Experimental Procedure
All test materials were made from commercial high-alumina cement and
a refractory grade microsilica. Sintered alumina was used as the aggregate for
the refractory concrete. The chemical and physical data of the raw materials
are presented in Table I. Two test series are presented here: one with only
243
6% microsilica, and the other with equal amounts of microsilica and reactive
alumina. The compositions of the two series are given in Table 11.
All test specimens were vibration cast in molds. After curing at 40C for
24 h and subsequent drying at 110C for 24 h, the specimens measuring
25 x 25 x 150 mm were subjected to hot MOR tests between room temperature
and 1400C according to the German norm DIN 51048.Subsequent analytical
investigations were carried out with the help of XRD, SEM and standardless,
semi-quantitative X-ray microanalysis of polished sections. In addition, the
bulk density and open porosity of the specimens were determined as a function of temperature.
Results and Discussion
The phase changes occurring in the specimens were analyzed after hot
MOR tests at 40",400",800", 1200",and 1400C and are presented in Table
111. Apart from corundum and /%alumina resulting from the aggregate, the
results show the gradual development of high temperature C-A-phases. Early
work with neat cement pastes4 had shown that the addition of microsilica
leads to the formation of gehlenite hydrate, the presence of which can thus
be taken as evidence of reaction of microsilica with the cement. However,
detection of gehlenite hydrate in a refractory castable is not always simple,
due to the small amounts of microsilica added. Experiments with neat pastes
using the same raw materials as for castables I and I1 confirmed the formation of gehlenite hydrate. Heat treatment causes gehlenite hydrate to lose water
in ~ t a g e s .Above
~
210C the partially dehydrated gehlenite is completely
amorphous, crystallising above 990C.However, some of the hydroxyl groups
initially present in the hydrate may be retained in the amorphous dehydration
product up to 1000C.5Figure 1 shows a SEM fracture micrograph of a
hydrated neat cement paste. Apart from the plate-like C-A-H phases,
microsilica is incorporated in the fine-grained phase indicated as C-A-S in
the micrograph. Some unreacted microsilica is also evident.
The typical microstructure of a hydrated castable is shown in Fig. 2. As
evident in Fig. 3, this microstructure does not change appreciably at 400C.
Analysis of polished sections of specimens subjected to 400C show in Fig.
4 gray alumina grains, white CA (l), light gray CA, (3) and microsilica and
alumina fine meal in the dark grey areas (2)between the coarse grains. X-ray
microanalysis of all the various phases was quantified with the help of a standardless, semi-quantitative computer program (Figs. 5 (A)-(C)). The micrograph, Fig. 6, also at 40O0C, shows microsilica in its reacted form (Figs.
7(A)-(C)). However, the C-A-S ratios are not quite stochiometric, corresponding to GAS, due to the presence of some unreacted microsilica. The white
grains are pure C-A phases.
Even at 800C castable I appears only somewhat more sintered than at
400C (Fig. 8). However, castable I1 which contains 6% reactive alumina, is
evidentally at a much more advanced stage of sintering (Fig. 9). Pockets of
undispersed reactive alumina appear well crystallized (Fig. 10).
At 1200C,castable I achieves a stage of sintering (Figs. 11, 12) that is
equivalent to castable I1 at 800"C, which at this temperature presents a well
sintered appearance (Fig. 13) with considerably increased porosity. The pore
size distribution also shifts towards larger pore diameters. X-ray microanalysis
of castable I at 1200C (Fig. 14)shows a grain with CA as the light gray core
244
surrounded by CA, with anorthite being the phase in (3). CA however is not
evident in the XRD analysis at this temperature.
Fracture micrographs of both castables at 1400C show a well-sintered
microstructure with a large number of pores (Fig. 16). At this temperature
there has been a considerable amount of grain growth (Fig. 17). However,
this is more so for castable I than for castable I1 (Fig. 18). This sintered, porous
microstructure is also very evident in the micrograph of the polished section
(Fig. 19) where the white phase between the corundum grains is anorthite.
Hot MOR tests (Fig. 20) show generally higher strengths for castable I1
with 6% reactive alumina. However, both curves follow the same pattern. The
strength decreases with increasing temperature due to the dehydration
processes. Above 400C there is a gradual increase in strength due to formation of high-temperature C-A-phases and resulting sintering processes as
documented in the foregoing micrographs. Above 1200C both castables lose
strength very rapidly. It has been reported3 that the formation of a viscous
anorthite phase at high temperatures leads to strength deterioration. The
present microstructural investigation, however, also shows increased porosity,
with the pore size distribution shifting towards large pore diameters and large
increases in the corundum crystallite size at temperatures above 1200C (Fig.
21). These two factors by themselves would lead to a decrease in strength.
The hot MOR values are in good agreement with data presented earlier (Fig.
Z).It should be possible to reduce porosity through optimization of the grain
size distribution.
According to the phase diagram for the system CaO-Al,O,-SiO, (Fig.
23), corundum, mullite, and anorthite should form in both castables. When
the presence of small amounts of Na,O and Fe,O, are disregarded, the
mineral composition of castable I should be 85.5% corundum, 13% anorthite,
and 1.5% mullite. For castable I1 the mineral composition can be calculated
to be 84% corundum, 9% anorthite, and 7% mullite.
The results presented in Table I11 indicate that chemical equilibrium has
been established in castable I during firing at 1400C, but this is not the case
in castable 11. As seen from the table, only corundum and anorthite are found
in castable I by the X-ray diffraction analysis. This is not unexpected because
the mullite content must be very low. However, in castable 11, mullite should
be easily detectable, and the results therefore indicate that the SO, not
bonded in anorthite must be present in an amorphous phase. The presence
of CA, also indicate that equilibrium has not been reached during firing. In
a further investigation it would be desirable to change the composition in order
to facilitate the formation of mullite on the assumption that this would increase
the strength of the castables.
References
Kiehl et. al., U.S. patent 4 111 711, (1978).
Prost et al., U.S.patent 3 802 894, (1974).
1B. Clavaud, J. P. Kiehl, and R. D. Schmidt-Whitley, 15 Years of Low-Cement Castables
in Steelmaking, First Int. Conf. on Refractories, Tokyo Nov. 15-18 (1983).
4B. Monsen, A. Seltveit, B. Sandberg, and S. Bentsen, Effect of Microsilica on Physical
Properties and Mineralogical Composition of Refractory Concretes, Advances in Ceramics, 13
(1985).
245
Table I.
Oxide
SiO,
A1203
CaO
Fe203
MgO
K2O
Na,O
TiO,
MnzO,
so3
B. density
(g/cm?
BET surface
(m2/g)
App., porosity
(Yo)
Microsilica
wt%
98.00
0.21
0.10
0.08
0.12
0.31
0.08
0.01
0.01
0.17
2.25
22
Reactive
alumina
wt%
High-alumina
cement
wt%
High-alumina
aggregate
wt%
0.03
99.30
0.03
0.02
0.2
79.7
18.4
0.3
0.04
99.50
0.05
0.02
0.40
0.5
0.03
0.70
0.9
1.8-2.1
1.o
8-10
4
80
6
I1
Yo
78 '70
6 '70
6 Yo
10 070
0.24%
5.5 vo
070
14 Vo
0.25%
8.5 To
40C
400"c
800C
1200C
1400C
I1
Corundum, /3-Alumina,
C+W-i,, C2AH8, CA
Corundum, /3-Alumina,
CA, CA,, C,AS
Corundum, /3- Alumina,
CA, CA2, CizA7
Corundum, /3-Alumina,
CA,, CAS,, C2AS
Cristobalite
Corundum, CAS,
246
Corundum, /3-Alumina,
C2AH,, CA
Corundum, /?-Alumina,
CA2, CiZA7r CA
Corundum, /3-Alumina,
CA, CAI, C i A
Corundum, /3-Alumina,
CA,, CAS,
Corundum. CAS,. CA,
247
248
249
250
Fig. 6 .
25 1
252
254
255
256
257
258
" 1
40
w)o
800
Temperature I"C1
1600
12bo
.,1
10
400
EM)
1200
Temperature ["CI
1600
259
"----
--------
260
Introduction
D ue to environmental, operational, and economic considerations, blast
furnace casthouse refractories have undergone large changes in the past
five yr. During this time, the use of low-moisture castables in the casthouse
has seen a significant increase. Because low-moisture castables are a new
material and new variations are being developed, a need exists to determine
installation procedures and to predict service based on results of laboratory
testing.
The standard laboratory conditions used for sample preparation are
different than for field installation conditions because in the field, curing
temperatures and times cannot always be regulated. Therefore, laboratory
sample preparation conditions were varied to simulate the commonly occurring
field conditions. From these studies, it was possible to predict how new
materials would perform in the field and what curing procedures are required
for optimum properties when installing different low-moisture castables.
Material
Two low-moisture castables were selected for study. The properties of
the two mixes are shown in Table I. Mix A is an ultra-low cement castable
that has given acceptable service life in a wide range of installation conditions.
Mix A has been used for approximately 24 mo in conditions varying from
preformed shapes such as skimmer blocks, where an ideal installation is
possible, to hot patches where the base refractory is glowing bright red (above
816C (1500F) ). This material performed well in all installations; the hot
patch practice may have caused some loss in service life, but no severe loss
of life was ever encountered. Mix B is a second generation ultra-low cement
castable that has superior physical properties when tested under standard
laboratory conditions. This material was initially only used where good installation conditions existed.
Procedure
Bags from a single lot of each material were obtained to minimize
variables. The castables were tempered to a normal field vibration consistency
261
and vibration cast into ASTM gang molds. The material was then placed
through various curing and drying cycles. After drying, all samples were tested
for modulus of rupture and bulk density.
To study the effect of curing time on properties, molds were allowed to
cure at 21C (70F) for zero h, four h, eight h, 12 h, and 24 h prior to the
start of drying at 110C (230F); drying time was 24 h.
To study the effect of curing temperature on properties, one batch was
cast into a 110C (230F) mold and immediately placed in a 110C (230F)
dryer for 24 h, one batch was cast into a 232C (450F) mold and immediately
placed in a 232C (450F) dryer for 24 h, and one batch was cast into a room
temperature mold, placed in a cooler at 4C (40F) for one week and finally
dried at 110C (230F) for 24 h.
Samples for data sheet values are prepared by curing for 24 h at 21C
(70F) and drying for 24 h at 110C (230F). This sample preparation technique
has been proven to give consistent and good properties for data sheets.
Results
Figure 1 shows the modulus of rupture plotted against the curing time
for both mixes. The average and range bars are drawn for each data point.
With no curing time, Mix A develops only 44% of its maximum strength. With
four h curing, it reaches 85% of maximum strength. Mix A develops full
strength after 8 h. Mix B has 40% of maximum strength at zero h, 44% of
maximum strength at four h and also develops full strength after eight h.
Figure 2 is a plot of bulk density vs cure time for both mixes. Statistical
analysis reveals that for both mixes the zero h bulk densities are significantly
different from the other bulk densities. A linear regression of the remaining
four points for each mix shows the slope to be zero in both cases. Therefore,
except for zero cure time, the curing time is not affecting dried density.
Figures 1 and 2 show that:
(1) An eight h cure is required for development of maximum properties
in both mixes.
(2) When cured for less than eight h, both mixes lose a significant portion
of their dried strength, but their bulk densities are only slightly
affected.
(3) Mix B behaves similar to Mix A and, therefore, can be expected to
behave like Mix A under most installation conditions.
Figure 3 is a plot of the dried modulus of rupture vs curing temperature;
Mix A and B develop maximum strength at the 21C (70F) cure. At 4C
(40"F), Mix A develops 73% of its maximum strength. At 110C (230F) it
develops 44% of its maximum strength, and at 232C (450F) it develops 19%
of its 21C (70F) cured strength. Mix B behaves in almost identical manner. It
develops 84%,38% and 22% of the 21 "C (70F) cure strength at 4C (40"F),
110C (230F) and 232C (450"F), respectively. Figure 4 is a plot of bulk
density vs curing temperature for each mix. A significant difference is approximately 0.04 g/cc. This figure displays the significant drop in dehsity that
occurred at 110C (230F) and 232C (450F).
Figures 3 and 4 show that:
(1) The curing temperature has an effect on both strength and density.
Therefore, for maximum properties a curing temperature of less than
110C (230F) and greater than 4C (40F) is required.
(2) Mix B is similar to Mix A and can be expected to behave like Mix A.
262
Service life is a function of many properties, such as: slag resistance, hot
strength, and thermal shock resistance in addition to the physical properties
measured in this study. Our experience has shown that a materials ability to
withstand slag attack has the biggest influence on service life. Since erosion
due to slag attack is a chemical phenomenon strongly influenced by the surface
area open to attack, and the amount of surface area is related to bulk density,
we theorized that the bulk density has a stronger influence on slag resistance
than dried strength. To evaluate this theory, Mix C (which is similar to Mix
B) was cast at varying water contents. The effects of water content on slag
resistance, bulk density, and dried strength are illustrated in Fig. 5. The use
of additional water led to a reduction in bulk density and dried strength similar
to the reductions that were observed in the curing temperature and time study.
The effect of water content on slag resistance is slightly greater than the effect
on bulk density, but not nearly as drastic as the effect on dried strength.
Therefore, changes in bulk density are a more meaningful predictor of service
life deviations than are changes in dried strength.
The maximum density loss of approximately 5 % was due to curing
temperature variations. The curing time changes caused a maximum loss in
density of only 1.5%. These small changes should not significantly affect service
life. This point is supported by the fact that Mix A has been installed in very
hot, patching applications with only a slight penalty in service life. Therefore,
the substantial losses measured in dried strength are not critical to good field
performance.
As a result of this laboratory work, Mix B was tried in several shops that
had previously used Mix A. Under all installation conditions, including hot
patching, Mix B was found to be superior in service life to Mix A.
Conclusions
Curing temperatures had a significant effect on the properties of the lowmoisture castables tested. Extremes in temperature, either hot or cold, should
be avoided during castable installation; temperatures above the boiling point
of water caused a significant loss of dried properties in both mixes, while cool
conditions caused a slight loss of strength.
Curing times had a small effect on the properties of the low-moisture
castables tested. The two mixes evaluated in this work should be allowed to
cure for eight h prior to the start of dry out to achieve maximum physical
properties. However, cure time is not critical since a cure time of less than
eight h results in only a minor drop in strength.
Mix B can be expected to provide better service life than Mix A under
all installation conditions normally encountered. Mix B has better physical
properties when formed under ideal conditions and both mixes respond in a
similar manner to deviations from ideal forming conditions. Consequently,
Mix B will have better properties than Mix A regardless of installation
conditions.
Although the physical properties of a low-moisture castable installed in
the field can be significantly different than the physical properties of the same
material cast in the laboratory, low-moisture castables can be used in less than
ideal installation conditions with only a small loss in service life. Service life
was found to be more dependent on changes in bulk density than dried strength,
and the greatest change in bulk density due to the variations in curing times
or temperatures tested was only 5%. Further, low-moisture castables have been
263
successfully used in several blast furnace casthouses where less than ideal
installation conditions existed.
Table I.
Properties of Mixes
Mix B
Mix A
Water to cast
Porosity, 070
After drying at 110C (230F)
Bulk density, kg/m3 (pcf)
After drying at 110C (230F)
Modulus of rupture, MPa (psi)
After drying at 110C (230F)
At 1093C (2000F)
Rotary slag test
Relative ratio vs NARCARB XZR
Chemical Analysis
Al*O,
Sic+C
+
Q
4.3
16.0
9.2
2880 (180)
2976 (186)
4.8 (700)
4.0 (580)
1.8
11.3 (1644)
6.9 (1000)
0.95
68
22
68
22
I
I
I
I
750-
3
LL
v)
6.0
500-
n
0
2
250-
X
0
MIX A
MIX B
12
CURING TIME, HRS
264
24
3.00
0
\
0
cm 2.90-
>
k
v)
Y
-I
2.80-
2.70-
X
0
MIX A
MIX B
B
24
0
4
8
12
CURING TIME, HRS
v)
1000-
x MIX A
MIX B
Lrl
t-
750-
fx
v)
500-
3
-I
3
250I
230
CURING TEMPERATURE, O F
265
450
3.0C
0
2.9C
Icn
w 2.8C
0
_I
2.7C
2.6C
CURING TEMPERATURE, OF
40-
30-
'X
BULK DENSITY
SLAG RESISTANCE
x DRIED STRENGTH
20 10 I
?4 WATER ADDED
I
9
266
Everyone knows that it is time consuming and hard work to remove worn out
monolithic linings. With this in mind we developed a new anchoring system
which we called ANCHOREX (for which we have applied for world-wide
patents). The basic idea is to insulate the stainless steel anchor from surrounding
monolithic material by a conical preshaped refractory plug. Instead of welding
the stainless steel anchor to the shell you drill a hole in the shell and the metal
anchor is fastened from the outside with a nut. In case it is not possible or
allowed to drill holes through the shell, we work with inside welded nuts to
which the anchor is fastened (with the help of a threaded rod). The anchors
can be precast in any height up to 200 mm. They can also be applied with
insulation behind.
On the hot face side of the anchor there is an incast plastic plug in which
a see-through flexible plastic molding material is bolted to the anchor. This
gives you the advantage. of being able to follow the filling behind the mold
with full control. The anchors are placed with c/c 300-500 mm, depending
on the type of construction.
When the time comes to remove the old worn out lining you cut the nut
on the outside and with a compressed air hammer press the remaining anchor
to the inside. In this way you completely clean the whole construction from
anchors and the remaining castable can easily be removed.
Now you can place new anchors in the holes and you fasten them as earlier
described. No welding is needed. In the case where you have the nuts welded
on the inside of the shell you must screw out the anchor by using the remains
of the steel anchor. This can be done with a special tool. Apparently it is easier
to do partial repairs of a monolithic lining with this system, as you are able
to remove just the part of the lining which is most worn out by cleaning this
part from anchors.
Trials done in different places show that the installation time of castables
can be cut down with approximately 20% by using plastic molding material,
and the time for removing an old lining can be cut up to 50%.
Practical experience also shows that problem areas like in rotating construction where conventional anchored monolithics spa11 off because of flexure
can be solved with this system, as you have built in more flexibility right from
the start.
267
268
Introduction
Historically, E-type fiberglass has been difficult to contain in the glass melting
process without refractory contamination. Bonded chromic oxide refractories have traditionally been used in furnace construction to provide increased
corrosion resistance, thereby extending tank life. The main effort of this study
was directed toward improving performance over these traditional bonded
products, which can exhibit:
-A high degree of interconnected porosity, resulting in interior and surface corrosion and leading to accelerated wear.
- Sensitivity to thermal shock, requiring prolonged heat-up schedules
and close monitoring of temperature rise.
- Size and shape constraints that result in engineering design limitations.
A superior alternative to bonded refractories is fusion-cast refractories.
At present, there are three chromic oxide refractory products on the market.
This study concentated on making improvements to this class of fused-cast
products, using as a basis the investigation of stoning and corrosion
phenomena.
Experimentation
The study was restricted to the Cr203,MgO, and A1,0, system and was
concentrated on the high chromic oxide, low magnesia field.
The compositions studied can be broken down into three sets of
experiments:
-Those that evaluated the effects of changes in magnesia content. In
these trials, the alumina-to-chromia ratio was held constant and
magnesia was varied.
- Those that determined the effects of changes in the ratio of alumina
to chromia. The magnesia concentration was held constant at 1.5%
by weight.
- Those that evaluated high concentrations of chromia.
269
Discussion
The proportion of spinel phase is determined by the magnesia content.
It was found that 1.5% magnesia resulted in a highly recoverable product with
the highest corrosion resistance of any of the materials tested.
Figure 1 shows the microstructure of our Monofrax@E material. Its
primary phase is spinel, typical composition
Fe,,J
C I - , . ~03.%.
~)
The secondary phase in this micrograph is a mixed R203with a typical composition of (A10.25,Cr,,,,, Fe,,,,) 0,. The E material has between 60 and 75
vol% spinel phase and 20 vol% R203phase. Other minor phases present are
.
spinel phase in
glass and metal, which together total less than 6 ~ 0 1 % The
this material has both Mg+2and Fe+2occupying the A site of the spinel
crystal. This spinel phase has a slightly oxygen deficient structure.
Figure 2 is a micrograph of the new Monofrax B material in which the
primary phase is a mixed R203and the secondary phase a spinel. Unlike the
Monofrax E material, the B contains no detectable Fe203and therefore A
sites of this spinel are occupied only by Mg+2.The primary R,O, is approx. minor phases
imately 75 vol% while the spinel constitutes only 18-20 ~ 0 1 %The
in B are composed of a Ca0-A1,0,-Si02 glass and a chromium phase.
It became apparent that formation of a minor metal phase in chromiabearing, fused-cast refractories is inevitable. Technical literature states that,
when chromic oxide is heated at a low oxygen partial pressure, the Cr20,
molecule undergoes a reduction reaction.2 The reaction products are CrO,
gas, Cr liquid, and 1/2 02.Thermodynamic calculations made under the
direction of R. Tressler of Pennsylvania State University indicate that the
reduction of the chromic oxide to chrome metal and CrO, gas is the favored
direction for the r e a ~ t i o n The
. ~ direction of the reaction can be shifted to
favor formation of Cr,O, by high oxygen pressure in the reaction vessel.
Experimental work supports the theoretical model.
The reaction for metal phase formation is:
C r O3 -- - - --- -- - - >CrO,(g)+Cr(l)+ 1/2 02(g)
(1)
face. Comparative evaluations were run between the various compositions and
slip cast chromic oxide (Table 111).
Stoning potential was found to be a function of the specimen's thermal
history. Thermal upsets with rates on the order of several hundred degrees
per hour caused microcracking of the refractory, which eventually led to
disintegration by fragmentation as corrosion progressed. Some of these
fragments were of a size and composition that would ensure their survival as
they flowed through the textile fiberglass tank. Upon reaching the bushing,
they could interrupt a strand and cause a catastrophic collapse of all fiberization at the bushing. Therefore, a major finding of this study was that thermal
stress high enough to induce microcracking can in itself cause a stoning problem
and must be avoided.
Slip-cast refractory actually becomes saturated with the test glass. Corrosion occurs at both the glass contact surface and in the interior. This situation
promotes the release of chromic oxide grains and is the corrosion mechanism
for this material.
The corrosion mechanism for Monofrax E refractory is different from
that for non-fused cast products. The bulk of the fused-cast refractory is not
penetrated by the glass, and therefore reactions take place only at the surface.
Corrosion occurs by the spinel phase being taken into solution. This
phenomenon is shown in Fig. 4. When the spinel goes into solution, the R203
crystals are left behind and those crystals form a chrome-rich interface between
the bulk of the casting and the attacking glass. The glass adjacent to the casting
may contain small quantities of recrystallized R 2 0 3 that originate from the
decomposition of the refractory.
Figure 5 shows Monofrax B material and the glass-to-refractory interface. The B material undergoes corrosion similar to E. The spinel phase of
the casting is attacked first, exposing the R203crystals. The rate of attack of
B is slower than that of E due to B's lower level of spinel. The remaining
R 2 0 3 phase is then attacked by extracting the alumina and dissolving the
chromia rich crystal.
When the test glass contains significant quantities of MgO, the R,03 is
initially converted to a spinel phase. This intermediate spinel is then taken into
solution by the glass.
The thermal and physical properties of Monofrax B refractory are similar
to those of other chromic oxide materials. The thermal expansion of B is
8 . 0 ~ 1 0 -1/"K.
~
This expansion is equal to the slip-cast chromic oxide
l / " K . (Fig. 6).
material. E has a slightly higher expansion at 8 . 5 ~
The electrical resistivities of B, E, and slip-cast chromic oxide are shown
graphically in Fig. 7.
Summary
The expanded size and shape capability of Monofrax fused-cast chromic
oxide refractories provides design engineers with flexibility in furnace construction. This new product can be cast to 1.4 m (54 in.) in length. Also, intricate shapes such as channels can be fabricated. Thus, a multiple block construction can be replaced with a single piece.
In summary, this new Monofrax composition (Table IV summarizes
product data) offers a viable alternative refractory for textile fiberglass applications that provides superior corrosion resistance and expanded shape capability.
27 1
References
Composition
75%
20%
3%
< 2%
R23
Spinel
Glass
Metal
(A10.52cr1 . d 0 3
Mg(A10.~7cr~,~~)03.~7
CaO -A1203-Si02
Cr
A1203
MgO
Fe20,
Others
Ti
82.2%
13.7%
1.5%
tr.
2.6%
79.7%
4.7%
8.1%
6.1%
1.4%
Slip-cast
chrome
247
438
318
504
250
305
Structure
O-
272
213
Cr 0
WMonofrax E
~ M o n o f r a xB
274
..... ,
1.1
1.0 0.9 c
0
C
c
8
0.80.7
0.60.50.4 -
0.3-
o.o+
I
2
I
4
10
I
12
I
14
... Monofrax E
.--Monofrax B
215
.~
2.8 2.6
2.4
0.0; I I I ) I
0.56
0.61
0.66
0.71
I , I
0.76
0.81
0 I6
Temperature (1000/Deg. K)
...Monofrax E
--Monofrax B
-Slip
Cast Chrome
276
DE LA
GARZA,and J. C. DAVILA
Refractarios Mexicanos, S. A.
Box 16, Ramos Arizpe, 25900, Coahuila, Mexico
Laboratory tests showed that apartfrom the brick quality, the raw meal composition
plays an important role on the lining life of cement rotary kilns. This paper reports
the results obtained in these tests and their correlation with actual experience in the
field. It was found that some compositionsfavor the coating formation to increase the
lining life.
Introduction
1t is common practice to use magnesia-chrome brick at the burning zone of
cement rotary kilns. The main characteristics which influence the adherence
of a protective coating on these bricks are:
- Chrome ore content in the brick,
- Mineralogic structure of the brick,
- Porosity, and
- Thermal conductivity.
The influence of these characteristics on coating adherence depends on the
chemical-mineralogicalcomposition of the raw meals being burned. Since the
calcination of a raw meal is a complex phenomena, a practical way to select
a suitable refractory for the burning zone of a cement rotary kiln is to make
laboratory tests on coating adherence and silicate penetration. The tests are
carried out with the available brands of brick and the raw meals of interest.
The development of such tests and their correlation with the actual
behavior of the bricks on the field, was used to determine the influence of
raw meal composition on coating adherence and formation. The present works
reports the results of such tests when various compositions of raw meals were
tried on a magnesia-chrome brick.
Experimental Procedure
The tests are carried out by two methods: (1) static and (2) dynamic.
Static Method
This method is based on the static contact between the raw meal and the
refractory material. The procedure is as follows:
(1) Samples of refractory material are used, 10 x 10 x 7.5 cm, having a
cylindrical hole 4.5-cm deep and 5-cm diameter.
(2) The cylindrical hole is filled with the raw meal and the setting is fired
at 1450C, for 4 h.
(3) After firing, the adherence of the clinker (calcined material) on the
refractory is determined under the following criteria:
277
Type of Adherence
(A) Null
(B) Moderate
(C) Strong
Description
The pellet of clinker is removed by inverting the sample upside down.
The pellet of clinker is removed by slightly
hitting.
The pellet of clinker and the refractory are
welded together.
Dynamic Method
The dynamic method consists in calcining the raw meal in a laboratory
scale rotary kiln, lined with the refractory material under test. The laboratory
rotary kiln has the following characteristics
= 46 cm
length
diameter = 11.5 cm
rPm
= 3.5
fuel used = mixture of natural gas and oxygen.
The procedure is as follows:
(1) The laboratory rotary kiln is lined with 6.4-cm. thick splits of the
material under test. The temperature is increased to 1450C.
(2) The raw meal is fed at a rate of 2 kg/h, and this is continued for 4 h.
(3) After the test, the coating thickness is measured. The silicate penetration and the microstructure modification of the refractory are
evaluated by optical and electron microscopy.
Material Used
The properties of the magnesia-chrome brick used are presented in Table
I. The chemical composition of the various raw meals and their physical
characteristics are presented in Table 11.
Results
Static Test
The static tests show that as the modulus of alumina decreases (MA in
Table 11) the adherence between the clinker and the refractory becomes
stronger, as shown in Fig. 1. This can be explained as the viscosity of the liquid
formed during calcination is lower as the modulus of alumina decreases. A
low viscosity makes it easier for the liquid to wet the brick and so increases
the penetration and stabilization of the coating. It was also found that the
limiting factor for a low modulus of alumina is an excessive penetration of
silicates. This penetration, though necessary for the stabilization of the coating,
if excessive, increases the susceptibility to thermal shock.
Dynamic Test
The dynamic tests show the effects of the raw meal composition on the
thickness of the coating formed. The thickness of the coating depends on the
amount of liquid formed during calcination. A parameter referred to as
Solidification Gradient (SG) is closely related to the coating thickness. This
parameter is defined as:
SG = 070 of liquids at 1450C - 70liquids at 1338C
where:
278
(1)
279
3.O
36
46
21 1
18
> 1700
Chemical Composition
CaO
SiO,
1.4
0.8
5.2
5.8
9.5
77.3
A1203
Fez03
0
MgO
MgO
K2O
Na20
so3
MA = A1203/Fe,03
Liquids at 1338C
Liquids at 1450C
SG
67.90
22.10
4.17
3.46
1.12
0.54
0.21
0.20
1.21
16.11
20.30
4.19
67.51
20.77
5.58
4.11
1.18
0.40
0.23
0.09
1.36
24.28
25.99
1.71
67.12
20.03
6.00
3.75
0.85
0.60
0.30
0.15
1.60
22.80
26.44
3.64
66.54
20.47
6.50
3.25
1.30
0.54
0.35
0.05
2.00
19.76
26.81
7.05
67.27
21.31
6.50
2.32
0.95
0.38
0.20
0.10
2.80
14.11
24.72
10.61
67.98
20.60
6.50
1.81
1.oo
0.50
0.40
0.21
3.59
11.oo
23.57
12.57
280
2.0
3.0 ,
1 .0
MODULUS OF R L U M I N A , M R = A I z03/Fe203
10
SOLIDIFICRTION GRRDIENT,(SG),(%)
12
28 1
14
SOLIDIFICRTION
GRRDIENT,(SG),f%)
0
N
(rnrnl
Temperature
Liquids
Liquids
a t- - -145OoC
- -- .
at
133BoC
T
E
E
R
R
500
400
OF
5
300
30;
(%I
200
20
10
(OCI
0
nwis
10
282
283
The cement industry has since long recognized many factors affecting the lining life
of rotary kilns. However, as the rotary kilns increase in diameter, the combined
mechanical and thermal stresses make it necessary to develop bricks with better elasticity. This paper reports on a magnesia-chrome brick developed recently by paying
attention to its modulus of elasticity. Laboratory tests, such as for thermal shock
resistance, coatingformation, refractorinessunder load, and mechanical properties are
also reported. Experiences in the field are examined.
Introduction
C ement manufacture implies to calcine a mixture of materials, referred to as
raw meal inside a rotary kiln. The calcined material, called clinker, milled
with additives constitutes the cement. To protect the cement rotary kiln from
the high temperatures required in the process (1450C) and also to reduce the
energy consumption, the kiln is lined with refractory brick. The lining is
exposed to various factors which affect its life.
in particular involve:
- Factors related to the raw meals being fed in, i.e., composition, homogenity, reactivity, rate of feeding, coating adherence, etc.
- Factors related to the combustion process, i.e., type of fuel, operating
temperature, kiln atmosphere, shape of flame, etc.
- Factors related to mechanical forces exerted on the lining such as those
caused by: deformation and deflection of the kiln shell, restrained thermal expansion, thermal shock, abrasion, etc.
The relative importance of these factors in determining the lining life is
difficult to establish, and more so as they have different influences at various
zones and times within the kiln. However, some general tendencies are known,
some that help to design a suitable refractory for each zone. For example,
at the burning zone, where the temperature is the highest direct-bonded
magnesia-chrome brick is used.
The mechanical and thermal conditions to which the brick is subjected
have become more stringent in larger kilns with higher thermal ratings. These
conditions make peel spalling an important mechanism of lining wear. To
reduce or indeed prevent peel spalling, a different approach for brick design
was proposed. The aim of the present work was to develop a direct-bonded
magnesia-chrome brick, having a conveniently low modulus of elasticity. This
paper reports on such development and examines experiences of its use in
cement rotary kilns. A comparison is made with a brick of similar type having
a high modulus of elasticity.
284
Theoretical Background
One of the major weaknesses of refractories is their poor thermal shock
resistance. Rapid heating up or cooling down of brittle materials, as refractories, is known to cause cracks and if repeated leads to fracture. To explain
such behavior two theories have been developed: (1) the thermoelastic theory
and (2) the crack propagation theory.
The thermoelastic theory4 assumes that once a crack is formed under a
thermal gradient, its propagation is unavoidable. This means that crack initiation must be avoided to prevent thermal fracture. This assumption is based
on the Griffith theory5 which states that lack of plastic flow in brittle
materials causes stresses to concentrate at crack tips, resulting in unavoidable
crack propagation. Inglis6 showed that the stress concentration factor, SCF,
at a crack tip is given by:
SCF= 2
d T
[EA
. a e(
- CL
p )]
tensile strength,
modulus of elasticity,
thermal conductivity,
thermal expansion coefficient,
heat capacity per unit volume.
From the CIR index, it is seen that to have a high resistance to crack initiation under a thermal gradient, a brittle material must have a high fracturestrain (ratio of tensile strength to modulus of elasticity), high thermal diffusivity
and low thermal expansion.
The crack propagation theory on the other hand, ignores crack initiation but instead considers that crack propagation is the important factor in
controlling thermal fracture. This means that crack propagation must be
avoided to prevent thermal fracture.
Crack propagation under a thermal gradient is only possible if the thermoelastic energy available at the crack tip is always higher than the energy required
to create a new surface as propagation proceeds. Thus, when the thermoelastic
energy available is less than required to propagate the crack across the entire
cross-section of the specimen, thermal fracture will not occur. The crack propagation theory concludes that a crack propagation resistance index, CPR, for
brittle materials can be defined as:
where St
E
K
=
=
=
a
=
e.Cp =
286
are also indicated in Fig. 1 . The crack on brick B, parallel to the hot face,
was analysed on a scanning electron microscope and an electron probe
microanalyser. Figure 2 shows a chrome ore grain surrounded by magnesia
grains. It is clear that the adherence between the magnesia grains and the
chrome ore has deteriorated due to the differential thermal expansion of the
two phase^.^ Figure 3 shows intercrystalline cracking among magnesia
crystals.
Experience in the Field
The new brick, A, was installed at the burning zone of cement rotary kilns,
the same as for brand B. The service life achieved with these brick by different customers in various kiln diameters, is presented in Table 111. These
lives are compared with average lives achieved with other brands, which in
most cases are of foreign sources. Figure 4 shows the good results obtained
with brick A. On the contrary, Fig. 5 shows the poor results obtained with
brick B.
Discussion
Although many factors influence the service life of refractories at the burning zone of cement rotary kilns, it is believed that enough evidence exists to
state that in the field, brick A has performed better than brick B. Post-mortem
evaluation and test of coating adherence showed that a similar coating is
achieved with both bricks. In spite of that, brick B was prone to peel spalling.
It is known that silicate penetration has an important role in modifying
the mechanical and thermal properties of the brick hot face and so influences
the peel spalling susceptibility.1 However, it is felt that this influence would
have equal effect on both brick A and B, since they have the same apparent
porosity and the same silicate phase present, mainly dicalcium silicate."
On the other hand, a property which differs substantially comparing both
brick is fracture-strain. This property strongly influences the thermal shock
resistance of refractories. Table I1 shows that the fracture-strain for brick A
is twice that for brick B. The thermal cycles to induce thermal fracture on
brick A is about six to seven times that for brick B. Moreover, Brick B when
subjected to a severe thermal gradient developed massive cracking parallel to
the hot face (peel spalling) just as predicted by Kienow's mode1.I2 Also the
location of this crack coincides just too well with the calculated value by
Ainsworth and Herron13 for a magnesia-chrome brick with a fracture-strain
this value being so close to the value of brick B. Even more,
of 1.38 x
the high refractoriness under load and the low creep determined in both brick
indicate that for these brick, temperatures between 800" and 1450C at the
hot face would not suffice to induce pyroplasticity for the relieving of
mechanical and thermal stresses.
With regard to the cracks developed perpendicular to the hot face, they
are the result of the severe cooling-down experienced by the hot face when
the air-blowing continued.
Conclusion
In accordance with the thermoelastic theory, a direct-bonded magnesiachrome brick with a high value of fracture-strain performs well at the burning zone of cement rotary kilns. A low modulus of elasticity is an important
factor to avoid crack initiation under thermal and mechanical stresses. On
287
References
G. Routschka and A. Majdic, Refractories for the Cement Industry-A Review, ZKG,
[9] 475-85 (1983).
2H.M. Sylla and H.O. Gardeik, Present State of Refractories Technology in the Cement
Industry, ZKG, [l] 1-8 (1984)
3H. Xeller, Evolution of Burning Technology in the Cement Industry and Requirements
Applicable to the Refractory Lining, ZKG, [I] 9-17 (1984).
4W.D. Kingery, Factors Affecting Thermal Stress Resistance of Ceramic Materials, J.
Am. Ceram. SOC., 38 [l] 3-15 (1955).
5A.A. Griffith, Phenomena of Rupture and Flow in Solids, Phil. Trans. Roy. SOC.
(London), 221 A [4] 163-68 (1920).
6C.E. Inglis, Stress in a Plate Due to the Presence of Cracks and Sharp Corners, Trans.
Inst. Naval Architects (London), 55 219 (1913).
7D.P.H. Hasselman, Elastic Energy at Fracture and Surface Energy as Design Criteria for
Thermal Shock, J. Am. Ceram. Soc., 46 [ l l ] 535-40 (1963).
8B. Oberfeuer and M. Koltermann, Untersuchung und Beurteilung von Tonerdesilikatsteinen mit mehr als 50% A120, fur den Einsatz in der Eisenhuttenindustrie, Radex Rundschau,
3 [lo] 747-57 (1976).
9W.F. Ford and J. White, Mechanical Properties of Basic Refractories at High
Temperatures, Trans. Brit. Ceram. Soc., 56 [6] 309-30 (1957).
loM. Kunnecke, H. Naefe, M. Naziri, Die magnesitische Sinterzonenauskleidung unter
veranderter Beanspruchung, p. 10 in Vortragsband des XXVI Internationalen FeuerfestKolloquium in Aachen 1983.
E.M. Levin, C.R. Robbins and H.F. McMurdie, Phase Diagrams for Ceramists,
Published by Am. Ceram. SOC.(1964).
I2V.S. Kienow, Crack Formation in Fired Converter Bricks, Ber. Dt. Keram. Ges., 47
[7] 426-30 (1970).
J.H. Ainsworth and R.H. Herron, Thermal Stress Crack Initiation and Propagation in
Refractories, Ninth Annual Symposium on Refractories, Am. Ceram. SOC.,April 6, 1973.
*Edward Orton, Jr., Ceramic Foundation, Columbus, OH.
Table I.
CaO
Si02
Fe203
A1203
Cr203
MgO
CaO/SiO,
Brick A
Brick B
1.4
2.0
1.o
4.0
2.8
6.8
83.4
2.0
0.8
5.8
5.2
9.5
77.3
1.75
288
Brick A
Brick B
57.7
9.0
32.6
8.16
2.8
23.7
64
28
1.25
2
("C) > 1700
3.04
15.9
3 . 4 10-4
~
11
4
1.36
2
> 1700
2.93
16.4
1.5 x 10-4
1
2
2
3
4
5
6
7
Kiln diameter
Brick A
(d)
Brick B
(d)
Other Brands
5.03
5.2
4.8
4.8
4.11
3.66
5.2
4.4
158
171
135
147
365
123
17
158
90
42
150
180
90
120
130
(m)
30
60
Id)
Fig. 1. Cracking developed in bricks A and B by subjecting them to a severe thermal gradient.
289
Fig. 3 . Scanning electron micrograph showing intercrystalline cracking in magnesia grains (bar = 100 pm) .
290
Other
Brick A
CUSTOMERS
0
4 00
Brick B
DRYS
350
300
250
2 00
150
100
50
0
CUSTOMERS
29 1
*Work supported by the U.S. Dept. of Energy, Advanced Research and Technology Development Fossil Energy Materials Program.
292
Intevep, S.A.
Caracas, Venezuela
sulfur. sodium, and vanadium in most gasifiers. The correlation of desired physical
properties and service conditions is reviewed and suggestions are oJered on lining
designs. Analysis of refactory from slagged area showed degradation and cracking
due to a combination of chemical and thermochemical d e c k . Major alkali and sulfur
penetration was observed along with some euidence of vanadium penetration. The use
of a less permeable refactory reduced corrosion attack and improved thermochemical
performance.
Introduction
D espite their low cost, refractories are essential for the satisfactory operation
(2) During the dry out the temperature was raised to 120C (250F) at
a rate of 28C/h (50F/h) and held for 12 h.
(3) The temperature was raised from 120C (250F) to 205C (400F)
at a rate of 28C/h (50F/h) and held for 12 h.
(4) From 205C (400F) to 510C (950F) at a rate of 28C/h (50F/h)
and held for 8 h.
( 5 ) From 510C (950F) to the operating conditions of the vessel at a
rate of 11OoC/h (200F/h).
References
J.A. Bonar, Fuel Ash Corrosion, Hydrocarbon Proc., 51 [8], 76, August 1972.
2Coal Research and Development, Ind. Heating, 73-81, November, 1974.
R.E. Dial, Refractories for Coal Gasification and Liquifaction Processes, Znd. Heating,
53-60, November, 1974.
4M.S. Crowley and R.C. Johnson, Guidelines for Installing and Drying Refractory Concrete Linings in Petroleum and PetrochemicalUnits, Am. Ceram. SOC.Bull., 51 [3], 226-30 (1972).
T . R . Venable Jr., Right Refractory Concrete is Key to Good Linings, Oil Gas J.,
143-47, October, 1977.
6Some Effects of Attack on Refractories by the Oxides of Sodium, Sulfur, and
Vanadium, Trans. Br. Ceram. SOC.,69 [5], 205-10, May, 1970.
7Conversion to Fuel Oils and their Influence on Refractories, Ind. Heating, 29-32,
January, 1978.
8W.T. Bakker, Refractory Applications in Coal Gasifiers, NACE, March, 1979.
9R.W. Brown and K.H. Sandmeyer, Sodium Vanadates Effect on Superstructure Refractories, Glass Ind., 16, November, 1978.
I0M.S. Crowley, Design Better Vessel Linings, Hydrocarbon Proc., 127-30, December,
1979.
J.R. Wilson, Understanding and Preventing Fuel Ash Corrosion, NACE, March, 1976.
I2J.A. Bonar, Choosing Refractories for Fuel Ash Corrosion Resistance, NACE, March,
1976.
296
297
7FLEXICOKER GAS
DILUTE PHASE
NO GASIFICATION
REACTIONS
3 PHASES
BUBBLE PHASE
( GAS 1
BUBBLE CLOUD PHASE
(TRANSITION )
STEAM GASIFICATION
BOUDOUA RD
WATER GAS SHIFT
HYDROLYSIS
EMULSION PHASE
(FLUIDIZED BED OF SOLIDS)
BURNING
AIR
LAMINATED
AREA
REFRACTORY
STAINLESS
STEEL FIBERS
298
19-1176
9- 338
NWALSIO~
NEPHELINE
(Nk.K)ALSI04
SYN
IIEPHELINE SVN
299
Fig. 7.
slag.
300
Introduction
M ineral processing techniques being investigated by the Bureau of Mines and
others, such as processing at elevated temperatures, leaching with acids
and bases, chloride leaching, and dissolution in fused salt baths, require the
use of construction materials that have good corrosion resistance. Industrial
equipment designers, fabricators, and material suppliers frequently base recommendations upon experience, and suppliers advise that materials be tested in
an environment simulating the actual conditions of the industrial process. In
general, they can say only that their material passed ASTM C279' or C9802
specifications that deal with boiling (193C) 78 wt% H,SO,.
Information available in the literature generally deals with corrosion of
glass by aqueous solutions of acids and bases.3 Corrosion data on other
ceramic products are scarce and are based primarily upon supplier information or on selected situations where weight loss of a sample was monitored.
This report presents the results of tests conducted by the Bureau of Mines4-'
to determine the corrosion resistance of eight commercially available ceramic
materials (two red shale, two fireclay, a carbon, a silica, a silicon carbide,
and a high-alumina brick) exposed for 110 d to different temperature and acid
concentrations of HCI, HNO,, and H,SO,.
Test Equipment and Procedures
Chemical and physical properties of the ceramic materials tested are listed
in Table I. Bulk density and apparent porosity (Yo) were determined for each
test specimen before exposure, using ASTM test C20-80.* The main chemical
difference in the red shale and fireclay bricks is in their alkali, alkaline earth,
and iron oxide contents. Red shale A and fieclay B have high apparent porosity
and low bulk density compared to red shale B and fireclay A.
The selected ceramic materials were exposed to various acid conditions'
in the test apparatus shown in Fig. 1, which operates at temperatures up to
250C. Heat was supplied to a 12-L spherical Pyrex reaction vessel by heating
mantles. The temperature was controlled by means of a variable power source
301
Weight Changes
Statistically significant weight changes occurring in the ceramic materials
tested are listed in Table 111. Exposure of samples to HC1 for 110 d generally
resulted in increased weight loss with increased temperature at 20 wt% HCl
or with increased acid concentration (from 20 to 30 wt% HCl). The carbon
brick was an exception as it showed a weight gain with either an increase in
temperature or acid concentration. Weight losses were low in all cases for the
302
Sic and silica brick, about 0.25% for the Sic brick and 0.40% for the silica
brick.
Exposing the materials to HN03 generally resulted in a statistically
significant weight loss that increased with increasing temperature (from 50"
to 90C) or decreasing acid concentration (from 60 to 40 wt% HNO,).
Nitrous fumes developed when carbon and Sic bricks were exposed to
HNO,, and these materials were not evaluated.
Weight loss for the ceramic materials in H,SO, increased with an
increase in temperature. Weight losses for red shale B, Sic, silica, carbon,
and high-alumina materials were low in all acid concentrations evaluated,
ranging from 0.63 to 0.02 wt%.
The red shale and fireclay bricks with the highest porosity had the most
weight loss in all HCl, HNO,, or H,SO, conditions tested.
Strength Changes
Statistically significant strength decreases were not observed for most of
the samples exposed to the different acid environments. Only the high-alumina
brick exposed to 40 and 60 wt% HNO, at 90C showed a large statistically
significant strengtlh decrease of about 186 MPa (27 000 psi) from an original
value of 404 MPs (58 500 psi).
Chemical Composition Changes
The concentration of ions leached from the ceramic materials into solution during the 100 d of acid exposures tended to follow a second order
parabolic equation, in its general form listed as
y = a, + a g + c r ~ ~ ,
where
and
(1)
followed by fireclay brick B (2.63 wtVo). Again, the more porous materials
(red shale A and fireclay B) exhibited higher amounts of total ions leached
at all of the five HNO, test conditions compared to the denser types (red
shale B and fireclay A). The 40 wt% HNO, environment was generally more
severe than the 60 wt% HNO, at the same temperature. The silica brick had
the lowest total ion weight loss, with less than 0.07 wt% removed for all samples
exposed to HNO,.
The behavior of ceramic materials with respect to total ions leached when
exposed to H,SO, for 110 d is shown in Fig. 6. The red shale and fireclay
samples with the highest porosity again recorded the highest amounts of total
ions leached. Increasing temperature from 50" to 90C in 10 wt% H,SO,
increased the quantity of total ions removed. In red shale B and fireclay A
samples, 30 wt% acid was the most severe condition tested, while in the high
porosity red shale A and fireclay B samples, 50 wt% acid was the most severe.
The largest total ion removal in H,SO, occurred in red shale A at 90C in
50 wt% H,SO, (6.31 wt%). The Sic, silica, carbon, and high-alumina bricks
generally had less than about 0.3 wt% of total ions removed and showed a
maximum loss in 10 wt% H,SO,.
Dimensional Changes
To date, tests on volume expansion have been completed for the two red
shale and fireclay samples exposed to 20 wt% HC1 and to deionized water
environments at 90C. Statistically significant linear changes based on Ta pin
measurements occurred with all the samples except red shale brick B in the
water environment and for all samples in the acid environment as shown in
Table IV. Red shale brick A had the largest expansion of any samples, ranging
from 0.035% in deionized water to 0.115% in 20 wt% HCl. Red shale brick
A and fireclay brick B, the two samples with the largest linear expansion in
water and acid, are also those samples with the highest porosity. In all cases,
expansion occurring in HC1 was greater than that observed in a water environment under similar conditions of temperature and pressure.
Dilatometric runs were made on autoclaved samples as well as samples
exposed to an ambient pressure and are shown in Tables IV and V. A curve
for a red shale sample exposed to ambient pressure in 20 wt% HC1 at 90C
is shown in Fig. 7 and is typical of other dilatometric curves obtained. Heating
the sample to 700C removed the volume expansion, and subsequent cooling
returned the sample to its original, or preexposed, length. Therefore, the
difference shown as A in Fig. 7 associated with the dilatometer heating is
equivalent to the expansion produced by autoclaving. The data indicate that
under autoclave conditions the expansions associated with the HCI are generally
larger than expansions associated with water. The same relationship holds for
the samples exposed to acid and to water for 30 d at atmospheric pressure
as well as for the data obtained from the Ta pin measurements. Also, the
exposure of samples of a particular brick to higher autoclaving pressures
resulted in higher expansions. The expansions associated with autoclaving at
the lower top pressures, 0.5 and 1.5 MPa (80 and 220 psig), coincide better
with expansion data obtained from the Ta pin measurements than do those
at 4 MPa (580 psig). These results indicate that the dilatometric measurement
of samples after autoclaving in acid environments could be a valid accelerated
test to determine the possible expansion effects of various acids on different
ceramic materials.
304
Conclusions
Results of a study of the effects of HCI, HNO,, and H,SO, at 50" to
90C and acid concentrations from 10 to 90wt% on two red shale, two fireclay,
a carbon, a silica, a Sic, and a high-alumina material after 110 d of exposure
indicated the following:
(1) Statistically significant changes in cold crushing strength, weight, and
volume were generally small or not detected, except for a high-alumina
(85 wt% Al,O,) material, which had nearly a 50% drop in strength
after exposure to 40 and 60 wt% HNO, at 90C.
(2) The rate at which ions were leached from the samples at any given
temperature and acid concentration tended to follow a parabolic shape
during the 110-d exposure period.
(3) In general, the Fe and A1 ions had the highest ion removal rates, while
Ca, Mg, Na, K, and Ti ion removal was minor. The silicon ion was
generally not leached from any samples, indicating that the siliceous
bond or silicate mineral phases were not affected; this may explain
why physical property changes were small or not observed.
(4) Increasing temperature generally increased ion leach rates and sample
weight loss values. The total ion weight loss of the red shale and
fireclay samples was directly related to their initial apparent porosity.
( 5 ) The material with the best corrosion resistance to HCl was carbon,
with a maximum of 0.004 wt% total ions removed, followed by the
Sic, silica, and fireclay A materials. Red shale A (3.75 wt%) and
fireclay B (3.14 wtvo) had the most material removed.
(6) The material with the best corrosion resistance to HNO, was silica,
with a maximum of 0.063 wt% total ions removed, followed by red
shale B and fireclay A. Carbon and Sic materials developed NO,
gases.
(7) The materials with the best corrosion resistance to H,SO, were the
high-alumina brick (85 wt% Al,O,) and carbon, with a maximum of
0.076 and 0.087 wt% total ions removed respectively, followed by
the silica and Sic materials. Red shale A and fireclay B had the most
total ions removed, with over 4.25 wt% removed from each.
(8) Red shale and fireclay samples exposed to 20 wt% HCl at 90C for
30 d showed linear expansions ranging from 0.02 to 0.12%. The red
shale and fireclay brick with the lowest apparent porosity had the
lowest expansions.
(9) Expansion data from direct measurement of samples exposed from
30-d periods or from dilatometric measurements of autoclaved
samples exposed for 2 h were comparable. This suggests the use of
an accelerated autoclave procedure for determining volume expansion effects on ceramic materials in acid environments.
References
'American Society for Testing and Materials. Standard Specifications for Chemical-Resistant
Masonry Units. C279-79 in 1984 Annual Book of ASTM Standards: Section 4, Construction;
Vol. 4.05, Chemical-Resistant Materials; Vitrified Clay, Concrete, Fiber-Cement Products; Mortars,
Masonry. Philadelphia, PA, 1984, pp. 170-2.
'American Society for Testing and Materials. Standard Specifications for Industrial Chimney
Lining Brick. C-980-82 in 1984Annual Book of ASTM Standards: Section 4, Construction; Vol.
4.05, Chemical-Resistant Materials; Vitrified Clay, Concrete, Fiber-Cement Products; Mortars,
Masonry. Philadelphia, PA, 1984, pp. 743-5.
3T. A. Clancy, High-Temperature Corrosion Resistance of Ceramic Materials. BuMines IC
8843, 1981, 31 pp.
305
4J. P. Bennett, Corrosion Resistance of Ceramic Materials to Hydrochloric Acid (20 WtVo
at 50C). BuMines RI 8650, 1982, 11 pp.
sCorrosion Resistance of Ceramic Materials to Hydrochloric Acid. BuMines RI 8807, 1983,
14 PP.
Torrosion Resistance of Selected Ceramic Materials to Nitric Acid. BuMines RI 8851, 1984,
12 PP.
'5. P. Bennett and T. A. Clancy, Volume Expansion of Acidproof Brick Exposed to 20
Wt% HCl at 90C. BuMines RI 8962, 1985, 7 pp.
*AmericanSociety for Testing and Materials. Standard Test Methods for Apparent Porosity,
Water Absorption, Apparent Specific Gravity, and Bulk Density of Burned Refractory Brick and
Shapes by Boiling Water. C20-80a in 1981 Annual Book of ASTM Standards: Part 17, Refractories, Glass, Ceramic Materials; Carbon and Graphite Products. Philadelphia, PA, 1981, pp. 6-8.
91. Miller and J. E. Freund, Probability and Statistics for Engineers. Prentice-Hall, 1965,
432 pp.
306
NA = Not analyzed
Red shale
B
A
Sic
Silica
Carbon
High
alumina
68.6
9.6
98.4
0.27
8.5
22.9
0.76
0.51
0.10
85.6
1.9
0.37
0.12
0.047
0.3 1
1.5
0.046
0.049
0.0037
0.07
1.4
<0.05
0.11
0.0020
0.12
0.56
0.035
0.056
0.0083
3.1
0.27
0.017
0.53
0.013
0.2
096
0.22
0.12
0.01
1.1
NA
NA
NA
NA
0.77
NA
NA
NA 96.3
NA
NA
NA
NA
1.2
NA
NA
NA
87.9
NA
NA
11.06
10.89
11.91
10.3
0.54
2.26
2.64
1.90
1.61
3.70
9700
14 400
4100
8000
58 500
Fireclay
59.4
64.6
63.3
20.6
20.7
31.7
2.0
6.4
5.9
3.0
3.6
4.6
1.7
1.6
1.6
0.35
0.99
1.3
0.27
0.58
0.57
0.03
0.05
0.39
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
NA
5.66
10.86
3.26
2.38
2.39
2.56
18 800
20 300
9800
Propertv
Table I.
ribmo
mm-mo
-4-0
9999
3991 99991
0
a
3
+I +I +I +I
P-wmo
TI +I tl +I +I
mwwbm
03- I
I I I *
01 I I
I * * * *
????
* I *
Q1N9?09
I
*I
* * *
a<<<<
z z z z z gsss
m-wm
+I +I +I tl
wt-mm
ommo
FI +I +I +I
OmN-
o
+ *+ + i
01 I
1'911
I * * *
N N m b
mr-mmb
9999
+I +I +I +I
00-b
?N?S
01 I I
I * * *
99999
tl ti t l +I +I
omwwm
YqN-1
01 I
*I
I
* * * *
C-U44
i l +I +I +I
zzzzz
mbmm
NNYC'!
"-gsss
ti +I ti +I
m-P-S?"?
01 I
I * * *
mbmu
9999
TI +I tl +I
P-00-
ZSYN
01 I I
I * *
I l l
I * * *
+I ti ti +I tmtvr-wo
909911
- m l l y
I I * *
* *
+I +I tl +I
I I I I
* * * *
mmddm
b-mm
99999
9111
tl +I +I +I
5;qg
ScaFj
41 * *
OI *I Y y
I I
* *
-wm-
1911
0
+I +I ti +I
0 m m m
19??
O + l
I * * *
TI +I tl +I
nmm-
tl +I t l ti ti
""ZS,-
%
++
+****
t l tl +I +I
wmwm
ZC'!Sl
I l l
I * * *
wm-0
2-91
-
tl +I tl +I
ow--
rib'wm
?1?1
* * * *
I * * *
NO--
I I I I
0000
N N N m
"$k'
0000
mP-mP-
308
0-mm
I l l 1
Ta pin
Dilatometerl
Water
Red shale:
A
0.035 f0.009*
-.003+ .011
0.035
.000
.018k .009*
.033? .014*
.026
.039
Fireclay:
A
20 Wt% HCl
Red shale:
A
B
0.060
.019
A
B
.049+ .021*
.073f .036*
.031
.056
Fireclay:
80 psi
220 psi
580 psi
0.045'
.om
0.047
.013
0.077
.Ooo
.024
.031
.019
.048
.027
.lo3
Water
Red shale:
A
B
Fireclay:
A
B
20 Wt% HCl
Red shale:
A
B
0.048
.044
0.053
.040
0.161
.054
A
B
.025
.058
.023
.083
.134
.167
Fireclay:
309
Condenrer
-Saluiion
Solutlon
12-L
Heating
inlet
outlet
flark
mantle
eat solution
Bore
heoiinp
mantle
GlOsS
beadr
3 10
2.(
c
0
3 I.!
-=
--- =
Fa
IZZZ
CO,
g
Lr
I-
KEY
A1
K,
Ma.
Na. Si, Ti
I.(
z
0
.!
25
75
50
100
125
DAYS
Fig. 3. Ions leached vs time -40wt % HN03,90C, red shale brick A.
..
31 1
20
UI
PCI
nci
30 -t VI n a
KEY
0 . 4 0 w t pct HN03
1 . 6 0 wt pct HN03
Fig. 5. Total ions leached from ceramic samples in llOd of HNO, exposure.
3 12
60 L
KEY
A = Amount
of shrinkage
after cco! down
50
E,
40-
(3
30
gz
20
10
0 -
-10
100
200
300
313
400
500
600
700
Introduction
H igh temperature creep is one of the important engineering properties of practical significance for estimating service reliability of refractory materials.
This paper is a summarized review of our investigations on phase composition, microstructure, and creep behavior of different grades of high-alumina
materials based on diaspore-kaolinite (DK) type bauxites which occur in abundance in China.
Conventional torsion and compression creep tests have been conducted,
using both rising temperature (constant stress) and increasing stress (constant
temperature) techniques. Phase composition and microstructure are studied
by HF-treatment chemical method, optical microscopy, XRD and SEM.
Specimens with controlled composition, uniform structure and low porosity
are prepared by fine grinding and thorough blending of bauxites of predetermined chemical composition, isostatic pressing and firing at optimum
temperatures. Table I shows the chemical composition and physical
properties of the materials investigated.
Creep Behavior
The curves obtained in creep tests of the materials follow the general
pattern established by earlier ~ o r k . Figure
~ - ~ 1 shows schematically typical
creep curves at different temperatures by the torsion method. They may be
classified into three stages viz: (1) the elastic stage at low temperatures where
there is no creep; (2) plastic flow range at medium temperatures, where
creep comes into play, exhibiting a transient creep period during which
deformation rate decreases, followed by a steady-state creep period when
deformation rate remains constant; (3) viscous flow period at higher temperatures which also exhibits two creep periods-transient and steady-state;
however, the first period is shorter and the deformation rate at both stages
is noticeably enhanced. Correspondingly, there are two transition temperatures:
314
(1) Tp, signifying the change from elasticity to incipient plasticity, and (2) Tv,
indicating the beginning of prominent viscous flow.
Figure 2 shows the variations of Tp and Tv with A120, content. Figure
3 illustrates the relationship between total deformation and AI,O, content by
both torsion tests (1200C) and compression tests (1400"C).5 These results
clearly indicate that at about 70% A1,0,, which corresponds to maximum
mullite content in the sintered materials, there is an inflexion point where Tp
and Tv are highest and deformation is at its lowest. It may be concluded that
from the viewpoint of creep resistance, the order of merit is grade I1 > grade
I > grade 111. This is in agreement with the conclusion reached in our study
on modulus of rigidity and modulus of rupture.'
log
E,
= lo@
+ mlog t
(1)
317
References:
1G.C. Sun and X.C. Zhong, J. Chin. Silicate Soc., 12, [ 3 ] 355 (1984).
zC.0. Hulse and J.A. Pask, J. Am. Ceram. Soc., 49 161 312 (1966).
3P.J. Dixon, Stubbs and B. Wilshire, Trans. J. Br. Ceram. SOC.,80 180 (1981).
4X.C. Zhong, Thermomechanical Properties of Basic Refractories, The Publishing
House of Metallurgical Industry, Beijing, 1959.
5G.C. Sun and X.C. Zhong, Unpublished Work, L.I.R.R.,* 1984.
6K.Y. Wang, M.So. Thesis, L.I.R.R.,* 1985.
7J.X. Wang and X.C. Zhong, J. Chin. Silicate SOC.,10 [ 3 ] 289 (1982).
8X.C. Zhong, G.C. Sun and R.S. Yin, Microstructure and Properties of Ceramics
Materials, Eds. T.S. Yen and J.A. Pask, pp. 254-61, Science Press, Beijing, 1984.
9C.Y. Li, Unpublished Work, L.I.R.R., 1984.
1J.X. Wang and X.C. Zhong, J. Chin. Silicate SOC.,12 [ l ] 75 (1984).
I1R.S. Yin, Unpublished Work, L.I.R.R., 1984.
*L.I. R .R .-Luo yang Insti tute of Refractories Research.
Al,O,%
SiO,%
Fe,O,%
TiO,%
K,O%
AI,O,/SiO,
1-1
1-2
11-5
11-6
111-9
86.20
82.40
72.20
69.80
54.10
7.60
11.55
22.0
25.70
40.50
1.76
1.52
1.78
1.71
1.72
4.02
3.64
2.64
2.44
3.00
0.14
0.13
0.15
0.12
0.14
11.34
7.13
3.28
2.72
1.34
(To)
2.5
0.8
1.5
2.4
0.5
7.7
6.2
6.3
6.4
6.4
SiO,%
TiO,%
Fe,O,%
99
<0.5
92-96
1.4-4
1-1.5
<1
0.5-3.4
66-68
67-67.5
27-28
27-28
2.2-3.5
2.3-3.4
1.8-2.7
2.1-2.7
318
Table 111. Variation of Tp, Tv and Total Deformation with K,O Content
of Grade I1 Sintered Bauxite (Al,O,/SiO, = 2.88) (Torsion Creep Test, 11.25
Kg-cm Torque 23 h)
K,O%
I1 6
11-6-0.5K
11-6-1.OK
11-6-1.5K
I1 6-2.OK
I1 6-3.OK
Tp ("C)
Tv ("C)
0.1
0.6
1.2
1.8
lo00
lo00
800
600
1220
1220
1200
1200
0.2
0.4
0.4
0.6
2.2
3.2
600
400
1130
800
1.3
29.0
0.4
1.2
0.4
1.7
n.d.
3.6
1.6
3.O
(1150"C)
1.8
12.9
Very Large
Table IV. Variation of Steady-State Creep Rate (EJ with MgO Content at
1100-1300C for Grade I Sintered Bauxite (A1,03/Si02 = 6.4) (Torsion Tests.
Torque 11.25 Kg-cm)
No. 5
No. 6
Temp. ("C)
Creep rate (E,)x lo-, rad./h
18.9
30.4
1.2
1.o
1100
0.4
175
598
14.3
59
1200
6.2
Very High
403
362
1300
181
2.9
8.7
43.3
No. 2
3.8
No. 1
0.1
Code
MgO %
No. 3
No. 4
22.1
13.4
30.9
38.8
A$,
No. 1
2
3
4
48
39
14
44
40
33
6
No. 1
2
3
4
5
MA
M,S
(070)
M,A,S,
M,A,S,
Glass
amount
(Too)
6.63
13
7.86
45
6.69
42
46
10.12
81
8
Little 9.78
76
18
6
Trace
Crystal-to-Crystal Contact
Good direct bonding, mainly between corundum grains.
Some direct bonding, corundum and spinel not well developed.
Fairly good direct bonding, mainly between spinel crystals.
No Direct Bonding. Spinel crystals surrounded by glass and
sapphir ine.
No Direct Bonding. Spinel crystals surrounded by glass.
Good Direct Bonding.
A-Corundum, A3S,-Mullite, MA-Spinel, M,S-Forsterite
M-Periclase, M,A,S,-Sapphirine,
M,A,S,-Cordierite
319
320
Fig. 3. Variation of angular strain and deformation with A1203 content in sintered bauxite.
0.8
'
0.7
0.6
0.j
4 0.4
+
x 0.3
0.7
'
loo0
1100
1200
ooo
w
w
.oc
32 1
lo4,
r / o ~
1srG (-1
322
- 5
323
Application of Refractories: A collection of papers presented at the 87th Annual Meeting, Refractories Division. No. 1-2.
46th Annual Conference on Glass Problems: A collection of papers presented. This conference always focuses on production operations. These meetings
annually attract more than 500 glass technologists who participate in the program on factory-related problems and solutions. Sponsored by the Departments of Ceramic Engineering at the Ohio State University and the University
of Illinois at Urbana-Champaign. No. 3-4.
47th Porcelain Enamel Institute Technical Forum: A collection of papers
presented. These meetings feature outstanding down-to-earth coverage of developments in the porcelain enamel field. The Porcelain Enamel Institute has
sponsored this important annual program on plant practices and problems.
NO. 5-6.
(OVER)
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