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Application of Refractories

A Collection of Papers Presented at the


87th Annual Meeting
of the Refractories Division

Charles R. Beechan
Program Chairman
May 5-9, 1985

Cincinnati Convention Center


Cincinnati. OH

ISSN 0196-6219

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Vol. 7 , NO. 1-2, pp. 1-323, 1986
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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 ......................................

H. R. Crick, H. Golczynski, and G. G. Vining

Identifying and Controlling Sampling and Testing


Errorsin SPC ............................................
P. N. Sheldon and R. A. Landy

14

Effects of Oxidation-Reduction Reactions in


Magnesia-Graphite Composites ..............................

27

Selective Leaching of Extruded Cordierite Honeycomb


Structures ................................................

40

.........................................

52

................................

58

Water Model Experiment of the Refractory-Lined Lance to


Inject Oxygen into a Molten Iron Bath ........................

75

Analysis of Silicon Carbide Refractories after Service


in Blast Furnaces .........................................

79

Development and Properties of Silicon Carbide Refractories


for Blast Furnace U s e . . ...................................

100

Yu-Lian Lin and Charles E. Semler

Thomas H. Elmer

Zircon Processing
K. K. Cheang

Refractories for Torpedo Cars

Saburo Miyagawa, Makoto Yokoi, Akira Mastuo, Tadashi Morimoto,


and Tastuo Kawakami

K. Kurata

Donald K. Henry and Roy W. Brown

D. Campos-Loriz and Thomas R. Holmes

Progress on Carbon-Bearing Refractories for the BOF . . . . . . . . . . . 119


Yoichi Naruse, Keisuke Hiragushi, Sukekazu Kiwaki, and Ichiro Takita

Recent Technological Trends of Surface Coating Refractories


for CC Tundish Liners .....................................

131

Nondestructive Testing of Refractories Using Industrial


X-ray Computed Tomography ...............................

145

Observations on the Thermomechanical Behavior of Refractory


Linings of Cylindrical-Type Shells ............................

167

K. Watanabe, S. Fujisaki, and T. Takeshige

Yoshiro Aiba, Kazuo Oki, Kazumi Arakawa, and Shigeo Matsuura

Charles A. Schacht

.....................

185

Measurement of Properties for Use with Finite Element


Analysis Modeling ........................................

196

Improved Analytical Procedures and Material Properties for


Predicting the Thermomechanical Behavior of Refractory
Linings of Teeming Ladles. .................................

209

Compressive Strength and Creep Behavior of a Magnesium


Chromite Refractory .......................................

220

Optimizing Corrosion-Resistant Monolithic Performance


through the Use of Dual Lining Systems.. ....................

229

High Strength Insulation for Steel Ladles


Valeria E. McCallen

M. A. Stett

Charles A. Schacht

Ralph F. Krause, Jr.

Curtis E. Zimmer

Application of Vibratory Castables in Petrochemical Industries.


Subrata Banerjee

. . . 236

Microstructural Aspects of Microsilica-Blended High


Alumina Castables .......................................

243

The Effects of Curing Temperature and Times on Low-Moisture


Trough Castables .........................................

261

............................

267

A. Seltveit, G. S. Dhupia, and W. Kronert

Robert A. Howe and John A. Kaniuk

ANCHOREX Anchoring System.


E. Olsen

New High Chrome Fused Cast Refractory for Use in

Contact with Highly Corrosive Glasses


T. A. Myles and F. Knee

.......................

Influence of Cement Raw Meal Composition on Lining Life


T. K. Das, R. de la Garza, and J. C. Davila

....... 277

Importance of the Modulus of Elasticity on Basic Refractory


Brick for Cement Rotary Kilns ..............................
R. de la Garza

269

284

Corrosion of Ceramic Refractories in Synthetic Coal Slags


Determined by the Rotating-Cylinder Technique . . . . . . . . . . . . . . . . 292
Sherman Greenberg and Roger B. Poeppel

Monolithic Refractory Problems in a Gasifier . . . . . . . . . . . . . . . . . . 293


G. N. Zirczy

vi

Corrosion Resistance of Ceramic Materials To HCI,

........................................

301

Relationship of Creep Properties of Bauxite Refractories


with Microstructure .......................................

314

H N 0 3 , and H,SO,

James P. Bennett

Xiangchong Zhong, GengCheng Sun, and Rushan Yin

vii

Ceramic Engineering and Science Proceedings


Charles R. Beechan
The American Ceramic Society, Inc., 1986

The Deming System After One Year: One


Companys Experience
H. R. CRICK,H. GOLCZYNSKI,
and G. G. VINlNG
Faber-Castell Corp.
551 Spring Place Road, Lewisburg, TN 37091
Many companies have begun implementing the Deming system of statistical process
control. This paper presents the expetiences of one such company after mhg this system
for one y. It covers: (1) what exactly is the Deming system, (2) how it has helped,
and (3) what obstacles one can expect.

The Deming System


S tatistical Process Control, Statistical Quality Assurance, Statistical Quality
Control, call it whatever you wish, is sweeping American industry. Unfortunately, many people view these as purely statistical programs. Many look
at these programs as almost magical cures for their problems. These people
attend a SQA seminar. Upon their return they hire a statistician or an engineer
trained in statistics and then dump the entire mess into the new persons lap.
Commonly the underlying attitude is, Dont bother me with the details; just
go out and make it work.
The program just outlined misses the whole point of SQA. A well founded
SQA program involves a total philosophy of management, whose goal is to
help people work smarter, not harder. To this end, statistics happens to be
an important tool for making fundamental management decisions. Remember,
statistics is a tool for achieving a goal and not a goal in itself. Like all other
tools, statistics only has value to the extent we know how to use it. A welding
torch in my hands is not the same thing as a welding torch in the hands of
a master welder. Unless we learn to incorporate statistics into a total management system, then any SQA program, no matter how well developed, is doomed
to failure. Any initial gains such a program wrought will show themselves
illusory, soon to disappear.
Many fine programs for incorporating SQA into a total management
system have been developed. Actually, most of these programs simply express
the same thing in different ways. For just over a year now, we have been
implementing the program outlined by Deming. Please keep in mind that we
are still just implementing the program. We do not expect to have the total
program in place for many more months. Why are we taking so long? A well
developed SQA program represents such a radical departure from normal
management techniques that one must implement it gradually in order for
management fully to understand and to accept it. Deming comments that a
well managed company should expect to take five yr before seeing the fruits
of this approach. Many companies will require ten, while others never will.]
The heart of the Deming approach is the fourteen points. We have summarized these points by grouping them into four categories:
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(1) Management Principles,


(2) Training,
(3) Implementation Concepts, and
(4)Outside Suppliers.
The numbers to the left refer to Demings numbering system. Appendix A
offers a more detailed presentation of these fourteen points.
To understand the fourteen points, first we must understand that all processes, particularly manufacturing, are subject to various causes of variation.
In order to make products better and cheaper, we must isolate, attack, and
control these causes. We must help our people understand that their jobs
depend upon us eliminating as much variation as possible. We must train
ourselves in techniques that will help us achieve this goal. To do less is to place
the future of the company in jeopardy. The fourteen points simply represent
a systematic approach for management to attack its greatest enemy, process
variability. Those of you who remain skeptical should ask the American
automobile industry, who now realize that their survival depends upon the
constant attempt to eliminate process variation.
Traditionally, control charts have formed the foundation for SPC. How
do they function in this system? Initially, they serve as the basis for establishing
control over the process. The charts act like the lines on a highway, indicating
where we should go. If we go too far in either direction, we are sure to run
into trouble sooner or later. A person skilled in reading the chart can tell two
things from it: (1) what constitutes a problem (ie., an out of control situation),
and (2) approximately when the problem occurred. With this information, one
can more readily ascertain the cause of the problem, correct it, and take
measures to prevent its reoccurrence. As we said, one keeps the process on
the road. Eventually, one establishes a state of statistical control over the
process.
Once the process is in such a state, the chart then indicates how much
variation is inherent to the process as it now exists. At this point one can begin
to make significant comparisons of the processs performance relative to its
specifications. In some cases we discover that we have a well-controlled process
that consistently violates its specifications. Immediately, we realize that we
must either change the process or the specifications.
This situation points out a common problem, specifications that are
arbitrary and really without meaning. In some cases, people would reject
material that actually was fit for use. In other cases, people would grant waivers
for this material. If we commonly waiver such material, then we must ask
why the specification is set where it is? Particularly in such situations, the control charts offer us the opportunity to establish meaningful specifications and
to get our process to meet them.
Once we have verified the process specifications, we must attempt to
reduce the process variation to the point where the probability of violating
the specification is zero. In order to achieve this goal, we must understand
what composes the process. Figure 1 defines process in terms of five major
factors:
(1) Materials,
(2) Machines,
(3) Methods,
(4) People, and
( 5 ) Measurement.
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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

consistent. Whenever we tried to improve our quality level, our production


invariably fell behind. Orders then would come down to meet schedule and
to forget quality. Needless to say, we were caught in a vicious circle.
We knew that the machine cycle times were absolutely critical to consistent performance. Hence, the first goal of our SAQ program in this department was to get all of these cycle times within statistical control. From there
we could begin to make other changes as necessary to improve quality. Figure
6 illustrates our relative progress on a typical molding machine. Initially, the
machines cycle time averaged 33.2 s with an average range of 1.2 s. Obviously,
we experimented with several cycles before we reached what we considered
optimum. Now, the machines cycle averages 27.1 s with an average range
of .09 s. Since the machine is calibrated to f .1 s, we are actually controlling
this machine to as tight a cycle as we can with the machine calibrated as it is.
Not only are we getting more production from this department, we are
also getting more consistent production. The part we make today is extremely
similar to the part we made two weeks ago. We are now modifying our molds
to give parts that will yield better fits. In improving our quality, we have also
improved our productivity.
Overall, this program has led to two major areas of progress. We are getting our people: (1) to think not in terms of just making production, but in
terms of quality production, and (2) to communicate their problems to each
other and to management. As a result, our people are beginning to view
ourselves as part of a larger team.
Too often in the past, management placed too much emphasis on just
getting out production and not enough attention to the quality level of this
production. We called it our summer versus winter standards. Summer
is always our busiest season. In the past, no one cared what our summer quality
level was, only in meeting production schedules. Many times the parts from
one department would be so off specification as not to run in the next department. As a result, although the first department made its schedule, the second
could not. The next week would require the first department to make even
more parts to make up for the previous weeks poor performance in the second
department. As a result, the parts generally were worse than before. We were
caught in a vicious circle where we were running large amounts of gross production, with little, if any, gain in net production. Both quality and productivity
suffered.
Whenever we found ourselves in such situations, people seemed more
interested in shifting the blame to someone else than in discovering what needed
to be done to improve. Obviously, few problems were ever solved. No one
tried to communicate what the real problems were; rather, everyone tride to
shift the responsibility to someone else.
Certainly, we still place too much emphasis on numbers, and certainly,
we still try to shift the blame. We are all human and do not change completely
overnight. However, we do so to a lesser extent. Departments are beginning
to become aware of what the exact problems are rather than that some vague,
unknown problem exists. If the problem exists in a supplier, whether that supplier be another department within the company or an outside vendor, we
attempt to communicate the exact nature of the problem, why it is a problem,
and then work with the other group to improve the situation. In other words,
we try to determine the exact nature of the problem, to isolate its cause, and
then to correct it. We have found that this takes less effort in the long run.
5

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.

Appendix A: Discussion of the 14 Points2


1 . On Management Principles
i. Innovate and allocate resources to fulfill the long range needs of
the company and the customer rather than short term profitability.
For too long, American industry has taken for granted its own survival. We have failed to recognize that what we do today determines how
likely we will continue to do business in the future. Unless we commit
ourselves, not just in words and plans, but also in actions, to the long range
needs of our customers and ourselves, we will have no future as corporate
entities.
ii. Eliminate the old philosophy of accepting defective products.
We live in a society which accepts, as necessary, certain levels of defective products, poor workmanship, and poor service. We have stopped asking
how much these levels ultimately costs us. We do not even question why
they are necessary. When we accept a certain level of defectives as necessary,
we reduce, or even eliminate, our desire to improve. Only when we reject
this philosophy that defective production is a necessary part of manufacture, will we ever improve our quality levels.
iii. Reduce fear throughout the organization by encouraging open, twoway, non-punitive communications.
In many cases, people know, or have clues to, the sources of our major
quality problems, but they are afraid to communicate them to the proper
authorities. Why? In some cases, these people have reported other problems,
which management promptly ignored. In other cases, the people could do
nothing about the problem because they were afraid they may not make
their production quotas for that day. No matter what the reason, management is responsible for this fear, which must be eliminated for us to attack
our quality problems.
iv. Reduce waste by encouraging design, research and development,
and sales people to learn more about the problems of manufacturing.
Much waste occurs simply because these departments tend to view
themselves as rivals rather than members of the same team. Too often, each
department strives to optimize the product within its own predetermined
set of parameters rather than a mutually agreed upon set. Consequently,
the final product, from the prospective of both the manufacturer and the
customer, is far less than optimal. A little communication can save a lot
of trouble.
7

v. Make optimum use of the statistical knowledge and talent in your


company.
Statistics is an important tool for improving ones operation quickly
and efficiently. Many people, through formal and informal means, are well
trained in this area; yet, their talents go unused. Whenever, a company sets
out on an SQA program, such people are like buried treasure.
2. On Training
I. Institute more thorough, better job related training.
Too often, the only training an employee receives is how to operate
the machines. Once that person is capable of making the production quota,
he or she is considered completely trained. Often times, that person has
no idea what an acceptable part looks like; only how to make enough parts.
ii. Provide supervision with knowledge of statistical methods;
encourage use of these methods to identify which defects should
be investigated for solution.
Simple statistical methods provide supervision with powerful tools for
improving both quality and productivity. We must train all levels of supervision in these methods and encourage their use.
iii. Institute rudimentary statistical training on a broad scale.
Everyone in the company should know certain basic statistical concepts, which help each person perform a better job. Quality and productivity are everyones responsibility. Hence, everyone needs training in the
tools required to make improvements. Certainly, statistics is one of these
tools.
iv. Institute a vigorous program for retraining people in new skills to
keep up with changes in materials, methods, produce design, and
machinery.
Companies that are dedicated to the future are always changing. These
firms are constantly implementing new materials, new techniques, and new
equipment. Consequently, we must constantly retrain our people in these
new techniques as well as how to use the new materials and new equipment,
Unless our people thoroughly understand the changes, we cannot expect
to see the improvements necessary for survival.
3. On Implementation Concepts
i. Eliminate dependence on mass inspection for quality control;
instead, depend on process control through statistical techniques.
One cannot expect to inspect in quality. Such an effort is expensive,
inefficient, and misdirected. We must seek to make the product right the
first time. Statistical process control helps us to this goal.
ii. Use statistical techniques to identify the two sources of waste:
system (85%) and floor faults (15%). Strive constantly to reduce
this waste.
Statistical techniques indicate two sources of waste: (1) the level of waste
one should expect day in and day out, and (2) abnormal levels of waste
due to out of control situations. Once we know the source, we can begin
to make basic decisions on how to improve. One can never be satisfied with
any level of waste; hence, we must strive constantly to eliminate it.
iii. Eliminate the use of goals and slogans to encourage productivity
unless training and management support are also provided.

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

Managing the Quality Function


W. Edwards Deming, Quality, Productivity, and Competitive Position, MIT Center for
Advanced Engineering Study, 1982.
a presentation of the Deming approach to quality. A good outline of why American
industry needs SQA.
J. M. Juran, Quality Control Handbook, 3rd ed., McGran-Hill, 1974.
everything you ever wanted to know about quality and more. A good basic reference for
any quality program.
J. M. Juran and F. M. Gryna, Jr., Quality Planning and Analysis, McGraw-Hill, 1980.
a MBA level text on the total quality function. Basically, a summary of the Quality Control Handbook, with many cross-references. An excellent reference text.

Statistical Quality Control


D. H. Besterfield, Quality Control, Prentice-Hall, 1979.
fairly good text on approximately a sophomore level. Good overall treatment of the quality
function. Spends too much effort on acceptance sampling.
I. W. Burr, Statistical Quality Control Methods, Marcel Dekler, Inc., 1976.
a graduate level text that goes into theoretical details. Perhaps too mathematical for some.

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

Fig. 1. Composition of a process.

10

--_____-_---------I

DIRECTOR O F

Fig. 2. Faber-Castellquality/productivitysteeringcommittee.

Fig. 3. Manufacturing 1st level quality/productivitycommittee.


11

II
!-!

PEN & M4RKER


PACK SUPERVISOR

/_I

MKER
SUPERVISOR

Fig. 4.

I
!

i 1

L_/

TIPPING
SUPERVISOR

Manufacturing 2nd level quality/productivity committee

Fig. 5. Manufacturing 3rd level quality/


productivity committee.

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

Fig. 6. Evolution of control limits for a typical molding machine.

13

Ceramic Engineering and Science Proceedings


Charles R. Beechan
The American Ceramic Society, Inc., 1986

Identifying and Controlling Sampling and Testing


Errors in SPC
P. N. SHELDON
Allied Corporation
Buffalo, NY

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)

where K is permeability, in centidarcies; H is height of test piece, in cm; T


is the time of flow, in s.; A is the cross-sectional area of the test sample in
cm2; P is pressure under which air has passed through the test piece, in cm
of water; and Vis the volume of water, in mL, displaced as air is forced through
the sample.
Let us first examine the data in ways to observe general patterns. The
two measurements of the 100 cubes or samples from the plugs taken from
the various batches are shown in Fig. 4.As can be seen, the bulk of the data
(98.5%) fall between I000 and 3000 centidarcies. One value appears to be far
out of line at 4600; its mate is 1440. (The cube came from a batch where the
overall average is 1870 centidarcies and the specific plugs average is 1990.)
Plotting the differences between the two measurements produces a needle
plot format shown in Fig. 5 . Clearly the observation mentioned previously
is an outlier. We can also take these differences in Fig. 5 and plot them on
normal probability paper, and Fig. 6 is produced. Again, note that that specific
difference between two measurements is far from what we would have expected
from a random distribution of differences of duplicate measurements. The
outlier was then replaced by the value of the other measurement of the cube
for subsequent analysis of variance.
The data are now ready for more detailed analysis. Analysis of variance
of the permeability of the duplicate measurements made on the 100 cubes is
presented in Table I. In analyzing these data we shall suppose that in all cases
the formation of a nested class is obtained by sampling from a population
which is sufficiently large to be considered infinite.
Significance tests of the components of variance are made by forming
the appropriate variance ratio such as, for ox= 0
16

The F value for 16 and 80 degrees of freedom for = 0.05 is approximately


1.75; the null hypothesis is rejected; oxz, is not zero. The implication here is
that variations due to different positions within a plug are statistically significant, and care must be exercised not to make statements about one measurement from a batch. Variations from batch to batch are SO statisticdb Significant (0; =0) which we might have suspected, but variations between plugs are
not, and 0, = 0. Figure 7 shows measurements of each cube plotted as deviations from the average of each of the four batches.
The estimates of the components of variance are obtained by equating
the appropriate calculated value of the mean squares to them. The estimates
are tabulated in Table 11. About 37% of the total variation can be related
to differences between the duplicate measurements of permeability from one
plug; another 57% of the total variation can be attributed to differences
between position effects taken from a plug; and 5%, from different batches.
From this analysis one can quickly ascertain where the emphasis in sampling
belongs in this system.
The estimates of each component of variance can be used to form an equation for the total variance for a single permeability measurement from a
randomly selected cube taken from a randomly selected plug from a randomly
selected batch:
oyz=

02

+ oxz+ up (02= 0)

(5)

BY substituting the appropriate estimated components of variance


OT=

54 550 + 83 568 7 7 3 0 ~
145 848

(6)

The standard deviation of oT2= oT= 382 centidarc&.


The total Variance can be reduced most by taking n samples from a plug
and measuring its permeability k times. Mathematically, this will look like:
Obviously, there are many combinations of n and k. For example, with n = 4
and k=2:
+==

54 550
4x2

83 568
+-----4

0,=6819+20 892+7730
uT2= 188

+7730
(9)

(10)

We have effected almost a 75% reduction in variance, and a 50% reduction


in standard deviation, or actual measurement dimension. The optimum reduction in overall variance needs to be balanced by minimizing the cost of the
sampling patterns.
Before we leave this analysis, lets take a look at the estimate of the testing
or experimental error; a2= 54 550 and u = 233 with 100 degrees of freedom.
During the course of measuring the 100 cubes in duplicate, a previouslymeasured cube was analyzed 25 times; its 02=70 580 or 0=266 with 24

degrees of freedom. We thus have two independent estimates of the testing


error. To test whether these two independent variance estimates of the test
error are significantly different, we create a ratio of the two variances:

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

control. Similarly, the magnitude of the testing variation needs to be measured


before important decisions are needed. Having identified the variations, the
judicious control of sample location and number for measurement will go a
long way to helping you achieve efficient, high-quality statistical process
control.
*Error here is used synonymously with variability; that is, error is used in the statistical sense
and not as might commonly be thought of as a mistake.

Table I. Analysis of Variance of the Data Analyzed in a Completely Nested


Design
Source of Variation

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

069 622 690 02+2ux2+loo:+

500;

664 236 167 u2+20x2+10u1;2


4

122 218 789 u2+2ux2


972

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

*Pooled with plug effect.

19

Table 111. Analysis of Variance of the Data Analyzed as a Combination of


Crossed and Nested Factors
Source of Variation

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

622 690 u2+ loo:+

16

3 778 664

236 167 a2+ 100;

500;

4 441 837 1 110 459 02+20:+ 100,2+40u+*

12

2 487 234

64

10 574 051

100

5 454 972

207 269 o2+ 20:

+ 100,2

165 220 02+20,2


54 550 u2

199 28 604 827

PROCESS

SAMPLE
1 2

SAMPLE

1 2

SAMPLE

1 2

Fig. 1. Hypothetical example of a process involving batches comprisedof


distinct refractory pieces from which small samples were taken for testing.

20

LOT

LOT

LI

I 2 3 4 5

SAMPLE
ABCDE

1 1 1 1 1
f-l
MEASUREMENT

P P

Fig. 2. Experimental design of present paper.


7- F R O M

WATER SUPPLY

RUBBER MOLD

I(= l V x H l / ( T x A x P l xi888

Fig. 3. Schematic diagram of permeability apparatus.

21

4000

'GI

c>

3000

2000

1000

BATCH 1

A AMEASUREMENT 1

BATCH 2

BATCH 3

BATCH 4

0 OMEASUREMENT 2

Fig. 4.

Plot of all measurements for present experiment.

-.
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

Fig. 7. Measurementsof each cube plotted as deviationsfrom the average of each


of the four batches.

23

El
El
POSITION

POSITION

Fig. 8. Location of cubes (positions) within


a plug.

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

Fig. 9. Experimental design consideringpositions as


a main effect.

24

3500

3000 2500 -

2000

15001000 I

CUBE 1

CUBE 2

CUBE 3

CUBE I

CUBE 5

Fig. 10. Deviations of measurements from each cube position.

BATCHES X POSITION INTERACTION

2200

P-

--mI

fa

W
n

16001400-BATCH
x---xBATCH
1200- D-*BATCH
o.**...**BATCH

1000

2
3
4

Fig. 11. Permeabilityplotted by positions and batches.

25

2600 -

2400-

2
2

2200-

2000-

F
z
>-

PLUGS X POSITIONS INTERACTION


FOR BATCH I
PLUG 5
PLUG 4
PLUG 3

c-

1800-

16001400-

1200

POSITION NUMBER

Fig. 12. Permeability plotted by positions for all plugs of


batch 1.

26

Ceramic Engineering and Science Proceedings


Charles R. Beechan
The American Ceramic Society, Inc., 1986

Effects of Oxidation-Reduction Reactions in


Magnesia-Graphite Compositions
Yu-LIANLIN and CHARLES
E. SEMLER
Ohio State Univ. Dept. of Ceramic Eng.
2041 College Rd., Columbus, OH 43210
The microstructural eflects associated with oxidation-reduction reaction in seawater
magnesite-graphitecompositions have &en studied. Selected compositions of coarse,
intermediate, andfine particle size grading werefired at 1 6 0 0 O and 1650OC with various
hold times at temperature and controlled variation ofthefiringatmosphere. Evaluation
of the fired samples included percent oxidation, weight loss, dense zone, and
characterization ofthe MgO dense wne microstructure. The progressive sample bloating
that was observed for various materials and firing conditions are illustrated. The
mechanism{s)and rate of dense zone formation is discussed. The efect ofparticle size
and atmosphere wriation in controlling decarbonization is considered.

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

This reaction, if uncontrolled, results in magnesia volatilization, progressive


carbon burnout and degradation of the refractory properties. But the reaction of Mg(v) with oxygen (see below)
Mg(v) + %02
= MgO(s)

(2)

can result in the secondaryprecipitation/depositionof magnesia in regions


where the oxygen partial pressure is appropriate. The deposition of secondary
magnesia has been seen both as a crystalline buildup on the exterior of samples
and as a dense MgO layer in the hot-face region. The development of a dense
magnesia layer in a magnesia-carbon refractory can serve to restrict the ongoing
magnesia volatilization and carbon burnout (Eq. 1). Several of the previous
studies by various workers (see Literature Review) have indicated the beneficial,
protective effect of a secondary dense MgO zone formed around the exterior
(hot-face region) of magnesia-carbon refractories. Further, recent work12 has
shown that when the dense MgO zone development is intentionally promoted
in a magnesia-carbon refractory by the addition of Mg metal powder, the result
is beneficial by achieving decarbonation protection earlier in the refractorys
service life, with no associated bloating or cracking. But the fact that Mg metal
powder could initiate an explosion or fire in a plant setting is a significant
safety concern, whereby its widespread use in refractories, in untreated form,
is being questioned.
Ongoing research in this laboratory has focused on various aspects of
the dense MgO zone formation, and its relationship with decarbonation, in
different magnesia-carbon mixtures, both commercial and laboratory-made,
with or without Mg metal powder additions. This paper summarizes our recent
research to better characterize the physical and microstructural effects that
accompany the oxidation/reduction reactions in a controlled series of
laboratory-made magnesia-graphite compositions, containing no Mg metal
powder and fired at 1600C.

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

vacuum mounted in epoxy and polished for microscopic analysis (reflected


light). The microstructure of each fired sample was evaluated, including
measurement of the dense zone thickness in at least 50 different locations,
to obtain a representative value.
Because of the irregularity of the dense zone developed in the fired, coarsegrained samples, which increased the likelihood of error in the thickness
measurements, it was decided to use a normalizing factor to provide a more
uniform basis for comparing the integrity of the dense zone in each sample.
The factor used was called the Quality Index (Q.I.), and was calculated for
each sample as follows:
Quality Index = (n/N)X100
Where: n = the number of dense zone thickness measurements that wre
within &20% of the average thickness value.
N = the total number of dense zone thickness measurements.
The quality index values range from lower numbers for a dense zone of very
irregular thickness to a maximum value of 100 for a dense zone that has very
uniform thickness. An increase in the Quality Index numbers therefore
correlates with an improvement in the uniformity, and the general quality/
integrity, of the dense zone.
Experimental Results and Discussion
This study illustrates the progressive dense MgO zone development in a
controlled series of magnesia-graphite compositions. The main experimental
variables were sample particle sizing and firing time at 1600C. As a reminder,
the samples contained no metal powder additions and no binder of any type.
Photomicrographs showing the development history of the dense MgO zones
for the coarse (148 cm2/g), one intermediate (361 cm2/g), and the finegrained (469 cm2/g) sample compositions are presented in Figs. 2, 3, and 4;
in each figure the dense zone changes after 15, 30, 60, and 90 min at 1600C
are shown. In all cases it can be seen that the quality index of the dense zone
increases with increasing firing time and decreasing particle size of the batch
formulation. Visually it can be seen that the quality index provides at least
a relative measurement of the dense zone thickness uniformity and integrity;
that is, the dense zone irregularity decreases, and generally the microstructure
density (apparent) increases, as the quality index increases.
The relationship between the quality index and the sample particle sizing
is shown graphically in Fig. 5 ; specific particle surface area, which is calculated
assuming spherical particles, is used to provide an average particle sizing for
each sample formulation. The quality index is seen to vary directly with firing
time and inversely with sample particle size (average); i.e., the Q.I. increases
with increasing firing time and increases with decreasing particle size.
The dense zone microstructures shown in Figs. 2,3, and 4 show progressive
changes for the different samples with increasing firing time. In each case there
appears to be a decrease in the dense zone porosity, and an apparent increase
in crystal size, with increasing firing time. At this time, quantitative
measurements of the dense zone microstructure characteristics are not available,
but will be determined for later presentation.
The dense zone microstructure analysis showed that, in general, the
thickness, density, and uniformity are significantly affected by the batch
particle sizing and the reaction time. Clearly, the firing atmosphere also must

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

to document and explain the various interrelationships much more thoroughly.


It also appears that the dense zone phenomenon might be usable to achieve
practical benefits in other ceramic applications.
Despite the potential beneficial effects of the formation of a dense zone
of good quality, there is also at least one associated problem. Once a dense
zone of reasonable thickness and low porosity forms, the escape of gaseous
reactants will be restricted, resulting in progressive internal pressure buildup
which can lead to cracking and spalling. The effect of progressive pressure
buildup was observed in some samples in this study, as illustrated for the finegrained sample in Fig. 11. No effect is seen after 15 and 30 min firing at 160O0C,
but after 60 and 90 min there is sample cracking and deformation. The sample cracking and deformation was most prevalent in the finer-grained samples,
which indicates that it is likely associated with the progressively decreasing
porosity of the dense zone. This observation provides experimental support
for the previous statement that the dense zone porosity (and its permeability)
decreases with increasing firing time. The previous work in this laboratory12,
in which dense zone development in two commercial BOF refractories was
evaluated, did not show any evidence of material cracking or spalling in association with the dense zone formation. However, cracking, bloating, and spalling have been previously noted in some BOF refractorie~,'~
and thus must be
considered as a practical concern. A related feature observed in this study,
shown in Fig. 12, is the typical development of a porous depleted zone on
the inner, carbon-rich side of the dense zone. The development of this depleted
zone provides a porous, low strength region (parting plane) that seemingly
must ease the dense zone deformation, and eventual breaching, associated with
the internal pressure buildup. The complex ongoing reactions in these magnesiagraphite compositions therefore result in both beneficial and detrimental
effects. Additional study is needed to adequately establish our capability to
control the thickness, formation rate, and properties of the dense zone, if
optimum practical benefits are to be achieved in refractories for steelmaking
applications.

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

regions of a refractory, there are also detrimental features. It was observed


that dense zone development and densification can result in internal pressure
buildup in the body, due to trapping of the gaseous species formed, which
can result in cracking, bloating, and spalling. The associated sample deformation is seemingly eased by the existence of a porous depleted zone adjacent
to the dense zone. Through further research it will be possible to better control dense zone formation, which could permit improved realization of various
practical service benefits. Although this work is presented in the context of
commercial refractory applications, it is possible that the dense zone
phenomena may have use potential for other ceramic applications as well.

References

IT. Hayashi, Recent Development of Refractories Technology in Japan, pp. 5-33 in


Preprint of 1st Intl. Conf. on Refr., Tokyo, Japan, 1983.
2G. D. Pickering and J. D. Batchelor, Carbon-MgO Reactions in BOF Refractories, Am.
Ceram. Soc. BuII., 50 [7] 61 1-14 (1971);
3R. J. Leonard and R. H. Herron, Significance of Oxidation-Reduction Reactions Within
BOF Refractories, J. Am. Ceram. SOC., 55 [l] 1-6 (1972).
4B. Brezny and R. A. Landy, Microstructural and Chemical Changes of Pitch Impregnated Magnesite Brick Under Reducing Conditions, Trans. Br. Ceram. SOC., 71 [6] 63-70 (1972).
5s. Carniglia, Limitations on Internal Oxidation-Reduction Reactions in BOF Refractories, Am. Ceram. SOC. Bull,, 52 [2] 160-65 (1973).
6B. H. Baker, B. Brezny, and R. L. Shultz, The Role of Carbon in MgO Refractories,
Am. Ceram. SOC.Bull., 54 [7] 665-6 (1975).
7B. H. Baker, B. Brezny, and R. L. Shultz, The Role of Carbon in Steel Plant Refractories, Am. Ceram. SOC.Bull., 55 [7] 649-54 (1976).
US. M. Kim, P. S. Nicholson, and W. K. Lu, BOF Slag-Induced Formation and Destruction of Dense MgO Layers in Carbon-Containing Magnesites, Am. Ceram. Soc. Bull., 57 [7]
649-51 (1978).
9H. M. Mikami and J. R. Martinet, Carbon-Magnesia Bricks in Electric Arc Furnaces,
Refr. J., 25-32, 1980.
l o g . Jackson and R. Webster, Developments Continue in Magnesite-Carbon Refractories
for EAF and BOF Use, Iron & Steel Intl., 67-75, April, 1980.
A. Watanabe, H. Takahashi, T. Matsuki, and M. Takahashi, Effects of Metallic
Elements Addition on the Properties of Magnesia Carbon Bricks, pp. 125-34 in Preprint of
1st Intl. Conf. on Refr., Tokyo, Japan, 1983.
12R. Brezny and C. Semler, Oxidation and Diffusion in Selected Pitch-Bonded Magnesia
Refractories, J. Am. Ceram. SOC., 67 [7] 480-3 (1984).
13B. Brezny, Erosion Resistant Refractory, U.S. Patent Pending.
14M.Ikeda, Personal Communication, Nippon Steel Corp., Himeji, Japan, Nov. 1983.

*Harbison-Walker Refractories Co., Pittsburgh, PA.


Alfa Products, Danvers, MA.

Table I.

Particle Sizing of Sample Compositions

Raw Materials

Coarse

Sea water MgO (98 Grade)


- 65 + 100 mesh
- 100+200 mesh
- 200 + 325 mesh
-325 mesh
Graphite ( - 325 mesh)
Calculated surface area, cm2/g

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

SPECIFIC SURFACE AREA

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

FINE GRALN- - _ _ _ - -_- - - - INTER GRAIN I1


_ _ - -- _ - - - -

goo

iaoo

2700

3600

FIRING TIME (seconds)

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

FIRING TIME (seconds)

Fig. 8. Dense zone thickness squared vs finng time for the


four different size-gradedsample compositionsstudied. The
lines shown represent a least squares fit of the data and the
slope indicatesthe effectivediffusion coefficientof Mg (v).
A dual regime is seen, with the coarser samples having a
lower diffusion coefficientthan the finer samples.

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

Fig. 9. Decarbonized (oxidized)area vs firing time for the four


different size-graded sample compositions studied. The two
coarser samples showed up to 100%oxidized area, but the two
finer samples had less than 50%oxidized area. The initial oxidation rate was similar for all samples, but the finer samples more
quickly showed a marked slowing of the oxidation reaction.
OXIDATION 12
100.
90

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

QUALITY INDEX OF DENSE ZONE

90

100

Fig. 10. Decarbonized (oxidized)area vs the quality index for the


four differentsize-gradedsample compositionsstudied. It is clearly
seen that the higher quality index values correlate with lower carbon
loss, and vice-versa, so batch particle sizing is one factor that is
important for controlling the oxidation of carbon-containingrefractories. Other factors like temperature, firing time, and atmosphere,
likewise have an influentialrole.

38

Ceramic Engineering and Science Proceedings


Charles R. Beechan
The American Ceramic Society, Inc., 1986

Selective Leaching of Extruded Cordierite

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

Preparation and Testing of Specimens


The honeycomb cordierite structures used in this study were prepared by
the methods of Bagley,8 and Lachman and Lewis9 from raw materials such
as alumina, aluminum hydroxide, kaolin, silica, and talc. The extruded
monoliths had 200 channels/in.2 of cross-sectional area. The wall thickness
of the structures was about 0.25 mm. The oxide compositions of the specimens
discussed in this paper are given in Table I. All specimens were fired in an
electric furnace at = 1400C for 6 h.
40

The specimens for thermal shock tests consisted of cylindrical 11.8-cm


dia x 7.6-cm high (45/,-in. dia x 3-in. high) and oval 16.8 cm x 8.6 cm x
9.5-cm high (6.6 in x 3.75 in. high) monoliths. Smaller specimens ~ 2 . 5cm
(= 1 in. diameter and 3 in. length, were also used for property measurements.
All were leached in 1.5N HN03 solutions at 95C for times ranging from c 1
to 5 2 4 h. They were sequentially washed in 0.15N and distilled water for 15
min each at 95C.
The weight loss resulting on leaching was determined on specimens that
had been baked at 180C to remove mechanically held water.
The linear thermal expansion was measured on 5 cm-length specimens
in a recording dilatometer.
The surface area measurements were made with an apparatus* using
nitrogen as the adsorbent.
The thermal shock resistance of unleached and selectively leached
specimens was determined by two methods. One consisted of heating the
monoliths in an electric furnace for 15 min, cooling in room air, and then
reheating them at a temperature set 100C higher than before until the
monoliths crack. The other involved rapid heating of the monoliths by combustion products from a gas burner, the hot gas passing through the channels
of the monoliths. After reaching the desired temperature, the gas burner was
turned off and the monoliths were subjected to cooling air. The heating and
cooling cycle was repeated with periodic inspection of the monoliths until they
cracked.
Results

Loss in Weight on Leaching


The weight losses that result on leaching monoliths of composition A and
B are given in Table 11, and reproduced graphically in Fig. 1. Although both
monoliths are cordierite bodies, the former leaches considerably slower than
the latter. The difference in leaching rate is attributed to the presence of a
small amount of glassy phase in composition A, resulting from the manner
in which the raw ceramic batch was compounded.
Weight losses resulting from leaching other samples used in this study
are included in Table IV.
Thermal Expansion
The linear thermal expansion coefficients (25" -lOOOC) for samples of
composition B that had been leached in 1.5N HNO, for 0.5 to 7.75 h are
given in Table 111. Figure 2 shows the strong dependence of expansion on degree
of leaching, expressed here in terms of percent weight loss. The coefficient
of thermal expansion decreases from 1 . 1 4 10-6/oC
~
to as low as
0.25 x 10-6/oC (25"-1000"C) on leaching. The thermal expansion reaches a
minimum and then increases with prolonged leaching as shown by the curve
in Fig. 2.
A decrease in linear expansion on leaching was observed for a number
of other extruded ceramic cordierite compositions. This is illustrated in Table
IV. It includes data for some specimens that contained appreciable mullite
phase in addition to cordierite. These generally increase in expansion on
leaching as exemplified by composition D.

41

Thermal Shock Resistance


Figure 3 shows how the thermal shock resistance of various monoliths
is related to linear thermal expansion. Curve A is based on data obtained on
11.8 cm dia x 7.6 cm (4%in. dia x 3 in.) monoliths that had been selectively
leached prior to thermal shocking from furnace temperatures indicated to room
temperature. Monoliths which passed the 1200C test still had a nice ring when
struck with a clapper. The excellent thermal shock resistance exhibited by some
of the specimens, despite their high expansion, e.g., =2 to 3 x 10-6/oC, is
believed due to introduction of microcracks on leaching.
Curve B in Figure 3 is based on data for unleached companion samples.
Their thermal shock resistance falls off markedly with increasing expansion.
Thermal shock results obtained on cylindrical and oval monoliths that
had been subjected to the gas-fired test rig are given in Table V. The threshold
temperature shown in the table represents the temperature at which 50% of
the monoliths fail before reaching 150 cycles. The data leave no doubt that
selective leaching increases the thermal shock resistance of honeycomb
monoliths. However, such increase is accompanied by a decrease in strength,
as illustrated in Table VI. The leaching time required for composition B to
achieve a dramatic increase in thermal shock resistance is only about 1 h; the
resulting reduction in strength is about 20%.
Surface Area
The surface area of monoliths increases on leaching, as illustrated for
composition B in Fig. 4. Leahing of 200-mesh particles of cordierite glass
or recrystallized cordierite glass (24 h at 1000C) also results in a dramatic
increase in surface area, namely 207 and 21 1 m2/g, respectively. This leads
one to conclude that the silica-rich phase observed in such leached specimens
develops in identical manner during acid treatment of these two physically
different, but chemically identical, materials.
Figure 4 shows that the surfac: area can be increased to 414 m2/g.
However, firing at elevated temperatures results in substantial loss of surface
area, the values for composition B being 43 and 1.2 m2/g after 24 h at 1OOO"
or 1100"C, respectively.
Mercury porosimeter measurements indicated that the macroporosity of
the cordierite monoliths is slightly increased on leaching and that additional
pores, ranging from 60 to 100 nm (600 to < 100 A ) in pore diameter result
from acid treatment.
X-Ray Diffraction
X-ray diffraction studies show that totally leaclied cordierite monoliths
are no longer crystalline, but amorphous. Figure 5 shows that the leached product contains some spinel (MgA1,0,) and a trace of aluminum titanate
(A1203.Ti02).These two phases are present in the original ceramic monolith,
but the latter remains undetected until after an appreciable amount of cordierite
phase has been converted to an amorphous silica-rich phase.
Table VII summarized X-ray diffraction information obtained on partially
and completely leached monoliths of composition B. The partially leached
monoliths contain no critosbalite after prolonged firing at 800" or 1000C.
However, exposure to 1200C resulted in formation of cristobalite. Cristobalite
was absent in monoliths (that had been catalyzed) prior to thermal treatment
at 1000"C .
42

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.

Oxide Composition of Cordierite Monoliths

Composition

SO,

Content of oxide (wtVo)


A1203

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

*15% coarse A1,0, was used in preparing this body.

Note: All extruded ceramic cordierite monoliths had a wall porosity of 35 to 40%. Monolith C
and D contained appreciable mullite phase.

Table 11. Leaching Data for Composition A and B


Leaching time (h)

0.5
1
2
3
4
6
7.75
15.5

23
-24
.

Weight loss in Yo
A
B
-

Leachant

1.5 N HNO, @ 95C

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

Table 111. Linear Thermal Expansion Coefficients(25" -lOOOC) vs Leaching


Time in 1.5N HNO,
Monolith

Composition B

Time (h)

Weight loss (To)

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

Table IV. Linear Thermal Expansion Coefficients (25"-1000"C) of Various


Extruded Monoliths
ax106, 1/"C
Composition

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.

Table V. Thermal Shock Test Results


Monolith
composition

Partially leached

Threshold temperature ("C)

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

Crushing Strength of Partially Leached Cordierite Honeycomb


Average Strength, MPa

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.

X-Rav Diffraction Analvsis

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.

Chemical Analysis of Extruded Cordierite Monolith


Content of oxide (wt%)
Unleached
Leached

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

Fig. 1. Dependence of weight loss of


specimens from compositions A and B
(lower and upper curve, respectively) on
leach time in 1.5N HNO, a t 95OC.

47

10

I
20
WEIGHT LOSS, %

I
30

Fig. 2. Linear coefficient of expansion of


specimensfrom compositionB as a function of weight
loss resulting on leaching in 1.5N HNO, at 95OC.

I loo

600
500
0

LY
l\
2I

3I

EXPANSION COEFFICIENT, 10-6/T

Fig. 3. Thermal shock resistance of (A) partially leached and


(B) unleached monoliths as a function of their thermal expansion coefficients.

48

I
30

Fig. 4. Surface area of specimensfrom composition B as a function of time in 1.5N HNO,


at 95OC.

49

70

I
60

50

40

30

I
30

02 e

20

10

I
70

I
60

50

40
02 8

I
20

10

Fig. 5. X-ray diffractometertraces of totally leached (top)and


unleached (bottom)samples prepared from compositions B.

50

Fig. 6. Scanning electron micrographs of (A) partially leached and (B)unleached


specimens prepared from composition B .

51

Ceramic Engineering and Science Proceedings


Charles R. Beechan
The American Ceramic Society, Inc., 1986

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

.--

IV. 4. 9-18 119831.


--,
3B. H
. Flinter, The Magnetic Separation of Some Alluvial Minerals in Malaya, Am.
Mineral., 44, 738-51 (1959).
~

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

Table 11. Capacities of various Industrial Machines Used in the Processing


of Zircon Concentrates
Machine! f

Capacity*, metric tons/h

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

*Assuming optimum conditions of human supervision and production, 1 metric ton


= 2204.6 Ib.

55

Fig. 1. Active tin mining areas in Malaysia.

56

2no P..

16.L

I'..

Fig. 2. Flowsheet with mineral analyses for the processing of a Malaysian zircon
concentrate.

Ceramic Engineering and Science Proceedings


Charles R. Beechan
The American Ceramic Society, Inc., 1986

Refractories for Torpedo Cars


SABUROMIYAGAWA,
MAKOTOYOKOI,AKIRAMASTUO,and TADASHI
M oRIMoTo
Kawasaki Steel Corp.
1 Mizushima Kawasakidori
Kurashiki City Okayama, Japan 712

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

Changes in Service Life of Refractories for Torpedo Car


The Mizushima Works commenced desulphurization treatment of hot
metal in the torpedo car in 1976. More than 90% of hot metal is now treated
by this method. Refractories used at that time were A1,03Si02-based bricks
(A1203: 45%; SiO,: 5 % ) , and the desulphurization mainly consisted of
calcium carbide (CaC,). During the period 1978-1980, this calcium carbide
type desulphurizer was replaced by one consisting mainly of CaO. As a result,
the life of the torpedo car suddenly dropped, as shown in Fig. 1
Since the torpedo car life had dropped to 600 by the end of 1979, unburnt
AI,O,-SiC-C bricks were developed and put into use at the slag-line portion,
where damage was severe.
As a result, the life of the torpedo car returned to 680. Further in 1981,
all the lining refractories were changed to Al,03-SiC-C bricks, with a life of
about 700.
Upon investigating the used Al,03-SiC-C bricks of the initial development period, it was found that cracks appeared at locations 30 to 60 mm from
the hot faces of the bricks. With the aims of eliminating these cracks and
improving corrosion resistance, the authors attempted to improve brick quality.
Tests and Results

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.

Corrosion Resistance to Slag


Sample bricks were used to line a high-frequency induction furnace. Pig
iron was melted in the furnace and held at a prescribed temperature (15OO0C).
Then, a desiliconizer of the iron-oxide type and a dephosphorizer-desulphurizer
of the lime type-were aded to the hot metal, and the corrosion resistance of
the linings was compared. Test conditions and the schema of the test apparatus
are shown in Fig. 2.
59

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.

Wear Rate in Actual Use


Trial-made bricks were used in torpedo cars, and the relation between
the wear rate and the desulphurization treatment ratio was measured from
the residual thickness of used bricks.
The relation between the desulphurization treatment ratio and the wear
rate is shown in Fig. 5 . In general, when desulphurization treatment is performed, the brick wear increases because of the prolonged residence time of
hot metal and the effect of hot-metal stirring flow and erosion by the
desulphurizer. In the present test, the wear rate also increased as the
desulphurization treatment ratio increased.
From Fig. 5 , values of wear rates of samples were estimated when the
desulphurization treatment ratio was 85%. The results are shown in Table 11.
Wear rates of newly developed brick C, D, H, and I were lower than those
of conventional bricks.
Three kinds, E, F, and G from among the newly developed bricks are
currently undergoing use testing.

Observations of Cut Surfaces and Microstructures of Used Bricks

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.

Investigation on Torpedo Car Slag


Physical properties of torpedo car slag before and after desulphurization
and slag which adhered to used bricks are shown in Table 111.
Basicity of slag after desulphurization becomes 2.33, thereby raising the
melting point of slag.
Discussion of Relation between Wear of Brick and SiO, in Raw Material
The reaction between the slag for desulphurization and aggregate in the
brick, which has been obtained as a result of the microstructure observation
described previously, can be clearly explained by the equilibrium phase diagram
of the Ca0-Al20,-Si0, system.
The equilibrium phase diagram of the CaO-Al,O,-SiO, system is shown
in Fig. 17.
Basicity of torpedo car slag changes from 1.3 to 2.3; namely, this means
that basicity changes along the line PS connecting point P (c/s = 1.3) and
Q (c/s = 2.3) as shown in Fig. 17. On the other hand, SiO, content in
aggregate of the brick has a range from 0 to 20 percent. This means that the
changes occur from point R (SO, = 0%) to point S (SO, = 20%) along the
line RS.
The liquid-phase forming temperature at this time can be estimated as
shown in Fig. 18. From this Figure, it is considered that as SiOz content in
aggregate is increased, the liquid-phase forming temperature decreases; namely,
the higher the SiO, content, the greater will be the quantity of liquid-phase
formation, temperatures being equal. Aggregate is eroded by slag, thereby
separating and melting away the grain boundary, as shown in Fig. 9.
Therefore, graphite is added to prevent slag penetration. In the present
test, corrosion resistance of the brick also increases as the graphite amount
is increased, as shown in Fig. 4. Kitani et a1.2 maintain that the greatest
corrosion resistance is obtained when graphite content is 15%, and corrosion
resistance deteriorates at a percentage of graphite higher or lower than 15%.
The test by the authors5 has also indicated that 20% Sic + C is the optimal
61

level. This S i c is added as an antioxidant, in order to make graphite work


effectively at its optimal amount.
Yamaguchi et aL3s6explain this antioxidant mechanism of S i c by the
following reaction formulae:
(1)
2CW + O,(g) = 2CO(g)
SiC(s) + CO(g) = SiO(g) + 2C(s)
(2)
SiO(g) + CO(g) = SiO,(s) + C(s)
(3)
From formulae (2) and (3), the following reaction formula has been
derived by these researchers;
SiC(s) + 2CO(g) = SiO,(s) + 3C(s)
(4)
According to the above chemical formulae, C(s) is oxidized once, but the
generated CO(g) deposits C(s) by a reaction with SIC according to formula
(2). Simultaneously generated SiO(g) reacts further with CO(g) according to
formula (3) to deposit SiO,(s) and C(s). Formula (4) is derived from formulae
(2) and (3), and volume expansion of the solid phase due to the reaction in
formula (4) equals about 3.7 times and brings about compactness of the structure, thereby also suppressing carbon oxidation. Figure 13 shows how S i c is
oxidized and the surrounding material is changed into C(s) and SiO,(s).
Namely, S i c acts as a perfect antioxidant to a depth of 1 mm from the
hot face, and its existence can not be observed in the range within 1 mm from
the hot face, but C(s) exists even in the vicinity of the hot face. Thus, it is
considered that slag penetration is suppressed at a depth of about 3 mm from
the hot face.
The grains of SiO, which are generated by the reaction described in
formula (3) accumulate on the hot-face side, thereby lowering the resistance
as shown in Figs. 17 and 18.
Oishi et al. explain this point as follows: Deposit C which has been
generated by the reaction between S i c and CO compensates for the portion
of S i c consumed by oxidation and prevents the structure from deteriorating.
SO,, however, is formed simultaneously and produces low melting-point
substances from Al,03, CaO and CaF,; these substances cannot withstand the
strong stirring treatment.
Discussion of Peeling-off of AI,O,-Sic-C Bricks

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

where, Eo = Young's modulus when there


is no cracking
(kg.f/cm2)
(Y
= Thermal expansion coefficient
Kumagai et aLIO indicate that the thermal shock damage evaluation
method for magnesite-dolomite bricks using the panel AE method corresponds
well to the conditions at the time of actual use and also shows a good correlation with parameter Rst.
and Rst for
The relation of the wear rate to material parameters R
bricks B, C, H, and I which were used in torpedo cars was investigated.
Characteristic values of respective bricks are shown in Table IV. In this table,
Eo was assumed to be equal to the Young's modulus of each sample brick,
surface fracture energy was obtained by the WOF (Work of Fracture)
method," and the Poisson ratio was considered constant.
Results of the above investigation are shown in Figs. 19 and 20. No clear
relation is observed between the wear rate of the brick and R ' and Rst
of brick which developed cracking.
The above figures suggest that thermal spalling has no great effect on
wear in torpedo car bricks.
Next, examination was made of the possibility of causes other than thermal
spalling for crack generation. Characteristics of bricks which developed cracking are given below.
(1) Cracks occurred in bricks A, B, and C with SiO, content of 11Vo or
above.
(2) Cracks occurred in bricks for which natural A120, raw materials
(andalusite and calcined-A1203shale) were used.
As can be seen in Figs. 14 and 15, brick C showed great changes in physical
properties at a position about 70 to 80 mm from the hot face. In fact, it seems
that bricks containing much SiO, have developed sintering at the hot-face
side, promoting compactness of the structure. Cracks seem to have occurred
due to this difference in structure.

Wear Mode of AI,OJ-SiC-C Bricks


The relation between the wear rate and SiO, contents of bricks is shown
in Fig. 21.
As discussed previously, it is considered that the wear mechanism of the
Al,O,-SiC-C brick is the wear due to slag, when SiO, content is 10% or
below, and the wear due to slag and crack generation and peeling-off damage
due to changes in structure when SO, content is about 10%.
From the results of the present analysis of the wear mechanism of
Al,O,-Sic-C brick, and the results described in a previous report by the
author^,^ the indicated type of brick material has been found to be as
follows: When the SiO, content is minimized (3% or below), carbon content
is set to 15%, and Sic content is reduced to the minimum level (5% or below)
which is necessary for preventing carbon oxidation, such as Al,03-SiC-C
brick is presumed to be the best brick. Therefore, brick I, which contains less
SiO, and Sic than does brick H, is a better torpedo car brick.
From the technical point of view, it is desirable that SO, should be 3 %
or below, but the lower the SiO, content, the higher the price of the brick.
However, since lower SiO, content does not contribute proportionately
to the prolongation of life, it is necessary to make an appropriate use of bricks
63

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

loishi, S. Miyagawa, and T. Motomachi, Tuikubutsu, 33 617-23 (1981):.


*F. Kitani, T. Takahashi, M. Hanmyo, H. Ogura, S. Yoshino, and T. FujlWara, Tuikabufsu, 35 3-11 (1983).
3T. Takahashi, F. Kitani, Y. Miyashita, and A. Yamaguchi, Yogyo-Kyokuishi, 91 [4],
157-64 (1983).
4E.M. Levin, C.R. Robbins, and H.F. McMurdie, Phase Diagrams for Ceramists, The Am.
Cer. SOC.(1964), Fig. 630
5A. Matsuo, S. Miyagawa, M. Kuwayama, H. Toritani, T. Kawakami, K. Aratani, and S.
Hasegawa, Tuikubutsu, 36 717-22 (1984).
6A. Yamaguchi, Tuikubufsu, 35 617-22 (1984).
71. Oishi, T. Suzuki, and Y. Imaiida: Report No. 10 published by the 72nd Special Committee of Steel Making Refractories (1984).
8D.P.H. Hasselman, J. Am. Cerum. SOC., 46 [ll], 535 (1963).
9D.P.H. Hasselman, J. Am. Ceram. Soc., 52 [ l l ] , 600-04 (1969).
10M. Kumagai, R. Uchimura, and H . Kishidaka: Kawasaki Steel Tech. Report, 1, 132-42
(1979).
"J. Nakayama, J. Am. Cerum. Soc., 48 [ l l ] , 583-87 (1965).

64

Table I.

Characteristics of Al,O,-SiC-C Bricks


Sample Conventional
brick

Item

Newly developed brick

2.69 2.74 2.85 2.83 2.96 2.80 2.94 2.89 2.93


Bulk density (g/cm3)
Cold crushing
strength (kgf/cm2)
470 610 680 800 640 520 560 640 580
Al,O,
51 63 67 67 76 70 74 65 71
Chemical
8
SiO, 22 16 11
3
7
3
6
3
composition
8
7
9
Sic
5
5
5
9
5
10
(wtcr/o)
C
10 10 10 10 10 12 12 15 15
X
Main raw
Y
material
Z
SA
Wear rate index
100 72 67 58 40 50 30 40 22
Table 11. Wear Rates of Test Bricks
Sample

Item

Wear rate
(mm / heat)

0.35

0.35

0.24

0.15

0.18

0.13

Table 111. Slag Characteristics


30,

Before
desulfurization
After
desulfurization
Adhered slag
Table IV.

Chemical composition (070)


A1,0,
CaO
Fe,O,

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

Apparent porosity (Yo)


9.0
2.75
Bulk density (g/cm3)
5.9
Thermal expansion coefficient ( x
124
Modulus of rupture S (kgf/cm2)
Modulus of elasticity E ( x 104 kgf/crn2) 29
7.33
Fracture energy uwof( x 104 kfg/cm2)
1.4
EoWof/SZ
( a R ' ' ' ' , cm)
\/aWof/EaZ
( aRst, cm%)
86.1
0.35
Wear rate (mm/heat)
65

Newly developed brick


C
H
I

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)

Fig. 1. Changes in lining life and CaO/ (CaO + CaC,) .

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

Flow chart of wear test.

Fig. 2.

120

100-

80-

6040-

20-

.-

,.

E+m,

/*8

SiO,

content ( % )

Fig. 3 . Relation between SiO, content in brick


and wear index.

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

Lb) Enlarged photo of S i c (c) Enlarged photo of Sic


grain shown In phDtO (c)
grain shown in photo (bl

Fig. 13. Micrographs of used brick C


I

O---.--U

-Brlck C

100

200

300

Distance from working face (rnrn)

Fig. 14. Changes in apparent porosity of bricks


C and I after use in torpedo car.

71

100

200

300

Distance from working face (mm)

Fig. 15. Changes in bending strength of bricks C


and I after use in torpedo car.

0)

IT
S
0

.-c
A
~

Q)
c

0.6 -

0.40.2 0-

a -0.2

Distance from working face

(mm)

Fig. 16. Changes in permanent linear change of


bricks C and I after use in torpedo car.

72

5102

CawAlrDp

Fig. 17. CaO-AI,O,-SiO, equilibrium phase diagram.

I-

v
m

c
.-

C I S = 2.3

1400 -

Liquid

Y
0

.K

,300->

C/S=1.3
I

Si02 content in A1203 grain ( % I

Fig. 18. Relation between SiO, content in A1,0, grain


and liquid phase forming temperature.

13

a,

0.6 -

Region where cracking


is observed

0.5-

0.4-

EJwoF/S'(

0~

R"", c m )

Fig. 19. Relation between wear rate and


thermal shock damage resistance parameter of
AI,O,-Sic-C brick used in torpedo car.

; 0.62 0.5 -

Region where cracking i s


observed

-$

a,
t.

0.4 -

0.30.20.1 -

/ / /A/

Fig. 20. Relation between wear rate and


thermal stress cracking stability parameter of
Al,O,-SiC-C brick used in torpedo car.
0.6

f.
a,
L

0.5

0.4

0.3 0.2

0.1' 1-.1

2<D
1

Si02

content ( % I

Fig. 21. Relation between SiO, content and


wear rate of AI,O,-Sic-C brick used in torpedo
car.

74

Ceramic Engineering and Science Proceedings


Charles R. Beechan
The American Ceramic Society, Inc., 1986

Water Model Experiment of the Refractory-Lined


Lance to Inject Oxygen into a Molten Iron Bath
K. KURATA
Nippon Steel Corp.
Himeji, Japan
Recently the pretreatment. such as desiliconization or dephosphorization, of hot metal
from blastfurnaces has become more popular. As oxidizingagent, iron oxide or oxygen
gas is commonly used, but oxygen is sometimes preferred to avoid the temperature
decrease of hot metal and/or for metallurgical reasons. In such cases, lances are used
under extremely severe conditions, and refractory materials to meet such operating
conditions need to be developed. The authorsJirst investigated how used lances were
worn to estimate their wear mechanism and then made some water model experiments
to check the mechanism and to do some improvements. The major causes of the wear
were erosion around gas outlet nozzles andfalling oflof castable lining due to cracking. Theformer is found to be caused by pulsating back attack of injected gas bubbles
and to be reduced dramatically by injed'ng even a small amount of solid powder together
with oxygen. The latter is found to be caused by'lance vibration due to the said pulsation and thermal spalling.

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.

Figures for this paper were not available at press time.

75

eg

Outlet gas density (kg/Nm3)


Fluid density in apparatus (kg/Nm3)
V, = Outlet velocity (Nm/sec)
d = Outlet diameter (m)
L = Immersion depth of outlet (m)
g = Gravity acceleration (m/sec2)

e,

=
=

The specifications for powder feed by pumping are shown in Table I.


Alumina powder was used for injection because its particle size is easy to adjust.
The experimental conditions are shown in Table 11. Considering the actual
operational conditions, the depth of water in the water tank was fixed at 1000
mm, that is two-fifths of the actual depth. The numerical values in the table
represent the modified Froud number.
Experiment Nos. 1 to 4, were conducted without injecting powder.
Experiment No. 5 t o 8, were made under the same conditions as experiments
Nos. 1 to 4, but with the addition of powder. Experiment No. 9 was an additional test aimed at higher modified Froud number.
The figure on the left-hand side in Fig. 5 shows schematically an actual
lance lined with castable refractory. For the water model experiment, however,
we used lance pipes without castable lining as is shown on the right-hand side
of this figure to make the measurement and observations easier.
A schematic view of the experimental apparatus is shown in Fig. 6. Visual
observation and ITV recording were used for macroscopic observation.
Horizontal and vertical stresses of the lance pipe were measured at six points.
In a test in which powder was not injected, it was found that both the
influence of the pulsating back attack of injected gas bubbles and the vibration of the lance become greater with higher flow rate.
Next, I shall discuss the results of lance stress measurement referring to
the next two figures.
Figure 7 shows stress distributions in the lance with an air flow rate of
20 Nm3 / h/ hole, solid-gas ratio of 60(kg/,g) and immersion depth of 250
mm. The upper part of the ordinate represents the vertical stress and the lower
part the horizontal stress. The abscissa shows the measuring points. The dashed
lines show the measured data when only air was injected and the solid lines
show the measured data when powder was added.
From this figure, you can see that the stress level at the outlet is high and
that this is ascribable to the influence of the pulsating back attack of injected
gas bubbles. The stress level decreases when powder is injected.
Figure 8 shows the case for the immersion depth of 500 mm. Both the
horizontal and vertical stress level are higher than those in the previous figure.
Figure 9 shows the method of measuring erosion around an outlet of the
lance pipe due to the pulsating attack of injected gas bubbles. Shown at the
corner is the lance pipe. At the end of this lance pipe, a form of 100 mm wide
by 250 mm high was fixed with fasteners. This form was previously lined with
clay.
Next, six typical examples of the data of erosion of the lance refractory
due to the pulsating back attack of injected gas bubbles are shown in Figs.
10-12 in the order of decreasing order of wear.

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.

Specifications for Powder Feeder by Pumping


Items

SDecifications

1 mmMax. 40 kg/min
Max. 60 Nm3/Hr
5 kg/cm3
VG: 0.63 m3. P: 9.9 kg/cmZ

Particle size of powder


Capacity
Gas flow rate
Designed pressure
Tank
Table 11. ExDerimental Conditions

Modified Froud number


Immersion depth (mm)

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

*Additional experiment with a different lance.

Table 111. Quality of Castables


Chemical
composition
(VO)

Top size (mm)

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

Ceramic Engineering and Science Proceedings


Charles R. Beechan
The American Ceramic Society, Inc., 1986

Analysis of Silicon Carbide Refractories after Service


in Blast Furnaces
DONALDK. HENRYand ROYW. BROWN

Sohio Engineered Materials Co.


P.O. Box 339, Niagara Falls, NY 14302
Silicon carbide refractories haw been in use in 47% of the industrialized worlds blast
furnaces since the middle 19709. Applications haw ranged from the tuyere bowl to
the middle stack. Samplesfrom shutdownfumaces, as well as cores from operating
ones, have been obtuinedfrom a wrieiy of these install&*ons. The phqrpical and chemical
changes haw been studied to determine the effect of alkali attack and oxidation on
the overall performance of this class of refractories.

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

Furnace A Core Samples


The results of quantitative X-ray diffraction are listed in Table IV. Bond
contents range from 12.0% silicon nitride to a high of 24.7%. Only a small
amount of cristobalite was found at the cold face of core 12E. Cores 12B and
5D display the expected trend of increasing bond content from hot face to
cold face. The other cores do not show any particular trend of changing bond
content. Core 12E, in fact, shows an almost totally unaltered analysis by QXRD
when compared to what should be present in an unused silicon nitride-bonded
silicon carbide brick.
The chemistry data for each core are summarized in Tables V through
VIII. The analyses confirm alkali deposition in the hot face areas. Core 12E
does not show this because of the previously noted core loss of the hot face.
This particular core displays the least overall alkali penetration along the core
length. In fact, this may be because the core intersected less joint and
sampled more of the inside of the brick. Core 12B, which also sampled more
of the inside of the brick, displays this same fact in the samples 10 to 18 cm
(4 to 7 in.) and 15 to 18 cm (6 to 7 in.) from the hot face. This suggests that
alkali penetration is limited to the outer surfaces of the bricks along joint surfaces and at the hot face.
Oxidation appears to follow the same trend as alkali penetration. Again,
core 12E seems to show the least effect of oxidation as ewll as nearly identical
calculated values for silica throughout the core. The silica values appear to
be inversely proportional to the silicon carbide and silicon nitride contents,
that is, the higher the silica the lower the silicon carbide and silicon nitride
values. Free carbon seems to follow this same pattern. The free carbon has
resulted from either the oxidation of silicon carbide, or from deposition from
the decomposition of carbon monoxide. It is probable that both mechanisms
are at work.
81

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.

Furnace B Brick Samples


Tables IX-XI summarize the chemistry data that was obtained for these
samples. Each of the brick will be discussed separately below.
Brick No. 5 from the bosh: This brick shows the most well-defined trends
from hot face to cold face. Silicon carbide and bond contents increase from
hot face to cold face. A corresponding decrease of free carbon and silica also
occurs. It appears that some oxidation of both silicon carbide and bond has
occurred. Deposition of amorphous free carbon is common and is the obvious
cause of darkening of the bricks. The source for the free carbon include: (1)
82

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

The chemistries listed in Table XI show nearly identical results to those


of the other bricks. Elements of interest include increased potassium and sulfur
at the hot face. Zinc is also found in greater quantities decreasing from the
hot face, indicating cooler temperatures prevailing in the furnace at this point
to allow this metal to condense. Curiously, magnesium was found in an
anomalously high concentration at the hot face. It was not detected in any
other sample in this study.
In polished section, no alteration of microstructure was detected. A typical
fine-grained, web-like bond that adheres well to the silicon carbide grog was
found. Such a bond structure is favorable indicating retention of the physical
strength characteristics of the brick.

Furnace C Stave Inserts


These samples were studied by QXRD and spectrochemical analysis by
SEM. The results are listed respectively in Tables XI11 and XIV.
The QXRD values indicate that the bond constituents remain in excellent
condition. Sample 7 is actually an internal sample that displays the usual trend
of an increase of beta-silicon nitride in the interiors of most brick.
Petrographic analysis of the hot face reveals that at the immediate hot
face the silicon nitride had reacted to form a glass containing several different
phases. The composition of these various phases is given in Table XIV.
The glass phase listed in column one contains a variety of elements. One
crystalline phase within this glass is a magnesium silicate. Other spot analyses
in the hot face areas gave the results in columns 2 and 3. Column 4 represents
another analysis of a phase found on the immediate hot face. It appears to
be some type of a potassium aluminosilicate. Positive identification was not
obtained. The last analysis was of some crystals found away from the hot face.
These proved to be potassium chloride which also was confirmed by X-ray
diffraction.
These features lend support to the other data collected from furnaces A
and B. Zinc and sulfur were again found to be present in increased quantities,
as was the confirmation of the presence of potassium chloride. The overall
performance of these inserts, however, has not been affected, as changes in
the bond content and microstructure are minimal.
Discussion and Summary
The results of this study indicate good performance characteristics of
silicon nitride-bonded silicon carbide refractories in the blast furnace.
First, alkali penetration was found to be limited in most cases to the hot
face areas, with minimal effects at the furnace shell. In the case of the platecooled furnace A, a concentration of high alkali was found on the silicon carbide hot face with a 312-mm (12-in.) vertical plate cooler spacing. In 1981,
Herron and Beechan4made the observation that vapor/condensate attack can
occur within blast furnace walls at a distance of as much as 254-305 mm (10
to 12 in.) from the hot face. With minimal exceptions, such as furnace A,
most North American cooling-plate practice uses vertical spacing at 610 mm
and greater (24 in. and greater). Higuchi5 had also reported on as much as
9% alkali in blast furnace walls, 500 mm (20 in.) from the hot face with 500
mm (20 in.) vertical cooling plate spacing.
Hiragushi'j made the observation that, on furnaces using the same iron
ore, alkali absorption with vertical plate cooler spacing of 305 mm (12 in.)
84

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

lJ. M. Bauer, D . Dumas, J. P. Kiehl, and R. D. Schmidt-Whitley, New Solutions for


Problem Areas of Blast Furnace Linings, XXV Colloquium on Refractories, Aachen, Germany,
October, 1982.
2K. R. Selkregg, Quantitative Phase Analysis of the Bond Phase in Nitride-bonded S i c
Refractories, presented at the American Ceramic Society, Pittsburgh, PA, May 2, 1984.
3R. W. Brown, Silicon Carbide Blast Furnace Refractories, Iron Steelmaker, May 1983,
Updated tables I, 11, and 111.
4R. H. Herron and C. R. Beechan, Effect of Surface Alteration of Refractory Linings and
Process Variables on Corrosion Kinetics in Ironmaking and Steelmaking Furnaces, presented
at the American Ceramic Society, Washington, D.C., May, 1981.
M. Higuchi, Life of Large Blast Furnaces, Ironmaking Proceedings, 37, 492-505,
Chicago, (1978).
6K.Hiragushi, Personal communication, October 16, 1984.
*Leco Instrumentation, Leco Corp., St. Joseph, MI.

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

Industrialized World Blast Furnaces/Silicon Carbide Refractory

United States, Canada


Europe
Japan, Far East
Africa/Australia/India
Latin America

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

Table 11. Cooling of Blast Furnaces with Silicon Carbide Refractories


Staves
Staves and plates
Plate cooling (total)
Vertical spacing:
312-406 rnrn (12-16 in.)
406-624 mrn (16-24 in.)
Greater than 624 mm (24 in.)
Spray
Channel

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

------

27 774 100.0 167* 20 263 100.0 132*


*Furnaces, not orders; some multiple trials and obsolete furnaces included in these numbers.

87

Table IV. Quantitative X-Ray Diffraction Analysis of Bond Composition


Sample id
(distance
from hot
face (mm)

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

Chemistry of Core 12A

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

from LECO data.

88

Table VI.

Chemistry of Core 12B

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

Chemistry of Core 12E


0-25

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

Brick No. 5-Bosh

Distance from
hot face (mm)

Sic
Free carbon
SiO,
Si3N4
Si,ON,
Si metal

S 1-76

90

Table X.

Brick No. 3-Mantle

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

Brick No. 4-Stack

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.

Table XIII. Quantitative X-Ray Diffraction Analysis of Exposed Faces of


Stave Inserts from Furnace C
Alpha-Si,N,
Beta-Si3N,
Si20N,
Silicon

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

Fig. 1. Refractory, wall, cooler relationships.

Fig. 2. Masonry installation utilizing safety lining concept.

93

Fig. 3. Approximate wall condition of furnace A after 10.3


million tonne (11.4million ton.)

Fig. 4. Relative positions of bricks


retrieved from furnace B.

94

Fig. 5. Stave inserts and stave coolersafter removal from furnace C.

Fig. 6. Glass at hot face of core 5D, fumace A (h-siliconcarbide) (262X).

95

Fig. 7. Dense bond in hot face sample of core 12A,furnace


A (h-siliconcarbide) (262X).

Fig. 8. Dense nitride bond and oxidation pits on Sic,furnace


A (h-siliconcarbide, o-oxidation pits) (262X).

96

Fig. 9. Fine-grained nitride bond with glass, furnace A


(h-siliconcarbide) (262X).

Fig. 10. Local pocket of oxidation of bond, furnace A


(h-siliconcarbide) (262X).

97

t
I

390

Fig. 13. Typical silicon carbide cooler-plate nose protection,


with insulated, air-cooled shell.

99

Ceramic Engineering and Science Proceedings


Charles R. Beechan
The American Ceramic Society, Inc., 1986

Development and Properties of Silicon Carbide


Refractories for Blast Furnace Use
D. CAMPOS-LORIZ
Niagara Falls R&D Center, Sohio Engineered Matls. Co.
Box 832, Niagara Falls, NY 14302

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

fully understood. It is known that alkali compounds catalyze the oxidation


of carbon by CO,, and it has also been shown that potassium can form with
carbon intercalation compounds associated with important volumetric changes
(for instance, a 60% theoretical volume expansion for the formation of KC,).
It would appear that the two processes can occur simultaneously, but further
work would be needed to determine the exact mechanism.
The available literature does not abound in information on the alkali
attack mechanism on S i c refractories. In agreement with previous work by
Herron and B e e ~ h a n our
, ~ own investigation suggested the coexistence of two
mechanisms: (1) a liquid-phase attack by molten alkali salts (principally
carbonates) that takes place inside the lining at an isotherm suitable for the
condensation of the salt, and ( 2 ) a vapor-phase attack by potassium vapor
extending inwards from the refractory hot face. The relative severity of these
two mechanisms seems to depend on the nature of the bond phase. The liquidphase attack by molten alkali salts is certainly the major mechanism of alkali
aggression on S i c refractories bonded by silicon nitride, P-SiC, silicon oxynitride, and P' -sialon, but the contribution of the hot-face attack by potassium
vapor may increase considerably in S i c refractories whose bond system consists
of silica or silicates phases. This predominance of a liquid-phase attack
mechanism with S i c refractories means that the laboratory methods currently
used for the measurement of alkali resistance in conventional refractories
(fireclay, high alumina, carbon, and semi-graphite) may not be directly applicable to S i c products.

Chemical Corrosion Test Methods


Alkali Test Methods
Research aimed at the improvement of the alkali resistance of S i c refractories soon faces the problem of the lack of a reliable, widely agreed-upon
laboratory test method for the evaluation of the resistance to alkali attack of
these products. Not only is there a variety of methods, and their correlation
to the real-life behavior of the material in service is subject to much discussion, but all of them, in general, were developed for fireclay, high-alumina,
and carbodgraphite refractories, i.e., materials which are attacked by alkali
via a vapor-phase mechanism. In an attempt to categorize the many and widely
different test methods, the following classification may be useful: (1) Cuptype tests, ( 2 ) Liquid/vapor bar tests ( T c lOOO"C), and (3) Vapor bar tests
(T > 1000C).
Category 1 includes the test procedures in which a certain amount of alkali
(usually as the carbonate) is placed in a cavity drilled in a sample of the refractory material; the other two categories differ from the first one in that the
test samples are bars which are surrounded by the alkali. An attempt has been
made in categories 2 and 3 t o distinguish between those test methods in which
the attack takes place predominantly via the vapor phase, and those in which
both a liquid and a vapor phase are present. Havranek,Io quoting Japanese
workers, shows that the transition from the stability zones of K,CO, (I) and
K(v), in blast furnace conditions, occurs at some temperature between 927"
and 1127OC. The temperature of 1000C might well be taken as a frontier
between the test methods involving both vapor and liquid phases and those
in which the aggressive species is carried to the reaction sites predominantly
via a vapor phase.
102

ASTM Recommended Practice C 454,and the German test DIN 51069


are well-known examples of the cup-type tests. While useful in establishing
a ranking of alkali resistance with conventional blast furnace refractories, their
applicability to the more resistant Sic-based materials is very limited. The
same, with exceptions, is generally true for tests in category 3, many of which
have been developed in Japan during the decade of 1970 to overcome the shortcomings of the cup procedures, i.e., low reproducibility, subjectivism, and
difficult quantification of the results. The procedures described by Shimada
et al.," and Hiragushi et a1.,I2 are promising approaches which permit a
quantitative discrimination between different blast furnace refractory grades,
high-duty fireclay, mullite, high alumina, and silicon carbide materials.
However, their capability for effective discrimination between Sic refractories,
both between and within different bond classes, has not yet been established.
In view of the experimental observations reported in the preceding section, it would appear that the test methods capable of best discrimination
between different Sic refractories would be those which rely predominantly
on attack by molten alkali salts (category 2). The test procedure that our
laboratory eventually adopted was developed by Bethlehem Steel
Corporation13 and uses 1 5 0 x 2 5 ~ 2 5mm test bars which are placed on
stainless steel trays and embedded in powdered potassium carbonate (Fig. 1);
the trays are placed on a 50 mm layer of coke breeze inside a steel muffle,
and an additional 25 mm coke layer is spread over the potassium carbonate.
The covered muffle is placed in a furnace (Fig. 2) and subjected to two heating
cycles up to 927"C, with three-h soaks at temperature. After cooling, the bars
are removed, leached in warm flowing water for 24 h, and dried (Fig. 3). Weight
change and residual MOR (i.e., strength of the attacked bars) are reported.
This is a very useful, highly reproducible test for the determination of the
relative resistance of Sic refractories to molten alkali attack, and a very powerful tool not only in laboratory research but also for quality control purposes.
The aspect of the bars after the test (Fig. 4) shows the predominance of attack
in the zones of the sample that were submerged in the pool of molten alkali.
There is also evidence of a much more shallow potassium vapor attack at the
part of the specimen above the liquid surface (the partial pressure of K(v) at
bar), and in fact the prothe conditions of the test is estimated at 2 x
cedure has been used successfully with fireclay, high alumina, and carbodgraphite refractories. Figure 5 shows the aspect of test bars of different
Sic refractories after the test and demonstrates the discrimination obtainable
by the procedures. This test is finding increasing popularity among the blast
furnace refractory makers and users alike.
Table IV shows the response of different Sic refractories of the two major
bond classes (Si,N,, and P-Sic or self-bonded) to the molten alkali test.
Products bonded by Si,N, usually exhibit a weight loss which may range
between 4 and 30% according to the individual product, together with corresponding MOR losses. In refractories bonded by /3-Sic, a slight weight gain
is normally seen which, however, would not indicate that these refractories,
as a class, are inherently more resistant to alkali, since their MOR degradation can also be quite high. In other words, highly-resistant and poorly-resistant
Sic refractories can be found in both classes. The molten alkali test, therefore,
not only discriminates between these two major bond classes in terms of weight
change, but also distinguishes between individual products within the same
class in terms of both weight change and MOR loss.

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

Improved Sif14-Bonded S i c Refractory


As described previously, the application of the molten alkali test to
different brands of S i c refractories immediately revealed wide differences
among them (both between and within different bond classes) that had not
been detected by other alkali test procedures. It also became apparent that,
in many cases, the response to the molten alkali test depended on how the
test bars had been cut from a sample brick: external bars (i.e., bars containing original surfaces of the brick) tended to exhibit a heavier degree of
attack than internal bars (containing no original fired surfaces of the brick).
This is the situation represented in Fig. 6, where product 1 is the
Si,N,-bonded Sic product that we had been marketing for several years as
104

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.

Development of a /3SiC-Bonded S i c Refractory


In parallel to the improvement of the alkali resistance in Si,N4-bonded
Sic, another research line was started with the purpose of developing a Sic
refractory of the self-bonded type, i.e., bonded by a /3-SiC phase. The reason
was that the initial characterization of materials in the self-bonded class consistently showed small and generally positive weight changes in the alkali test,
and it was speculated at that time than perhaps self-bonded Sic refractories
were inherently more resistant to alkali attack than those bonded by silicon
nitride.
105

The self-bonded Sic refractories consist of large a-Sic grog grains


surrounded by a matrix of micro-crystalline /3-SiC. Also present as minor constituents are silicon oxynitride, silicon, and carbon. These refractories are
produced through a reaction bonding process with the B-SiC bond phase
formed in situ during firing. Firing is performed in a reducing atmosphere
maintained, in most cases, by the presence of coke packed around the
refractory.
Table VII shows the properties of the /3-Sic-bonded Sic refractory that
resulted from this development effort. Its properties are comparable to other
commercially available self-bonded products, with good physical properties
and the characteristically low alkali weight loss.
In the meantime, however, progress in the characterization of a wide range
of Sic refractories had evidenced that self-bonded products are not inherently
more alkali resistant than Si,N,-bonded refractories, and that they are
generally more susceptible to oxidation and to the combined effects of oxidation and alkali attack. These observations, together with data on in-service
performance, suggested that efforts leading to further improvements in blast
furnace Sic refractories should follow the nitride-bonding route rather than
the self-bonding approach. Research was then directed towards the development of modified silicon nitride (i.e., sialon) bonds.

Development of a Sialon-Bonded S i c Refractory


Assuming that the presence of oxygen as silica and/or silicate phases was
a major factor for the alkali attack of Si,N,-bonded Sic, it was obviously
desirable to limit the oxygen contamination of the raw materials to the lowest
possible le.;els, and to fire the product in an ideally oxygen-free atmosphere.
Both approaches are near to impracticable in an industrial situation such as
a refractories manufacturer. Both the Sic grog (especially the fine fraction)
and the Si metal powder are coated with oxide films whose removal prior to
mixing would be prohibitively expensive. The use of hydrogen-rich nitriding
atmospheres was expected to reduce the partial pressure of oxygen in the hightemperature firing zone, but at the cost of creating safety hazards. It was then
decided not to strive for the removal of oxygen contamination, but to combine this oxygen in a less deleterious form than silica and silicates.
The structures of /3-Si3N,can accommodate large amounts of oxygen in
nitrogen sites if the resulting charge imbalance is simultaneously neutralized
by the incorporation of a suitable cation in the silicon sites. Aluminum and
silicon have similar ionic radii; silicon substitution by aluminum and nitrogen
substitution by oxygen thus leads to a solid solution range in the Si-A1-0-N
system expressed by Si6-JlzOzN8-zwhere 0 < z < 4.2, the case z = 0 representing the pure /3-Si3N,. This solid solution has received the name of /3' -sialon,
alluding to the /3-Si3N, crystal structure which is maintained, with the corresponding expansion in the dimensions of the unit cell, up to the upper limit
of the range. By providing an aluminum source for the formation of the
/3 ' -sialon it would be expected to trap the unavoidable oxygen in a more stable
form which would exhibit a higher resistance to the attack by molten alkali
salts.
This approach has proved successful. As shown in Table VIII, the sialonbonded Sic refractory (product 3) exhibits consistently a small and generally
positive (typically 0.5%) weight change in the molten alkali test and, which
is most important, no appreciable strength degradation after the attack, so
106

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.

Industrialized World Blast Furnaces/SiC Refractorv


ft
m

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.

Results of Molten Alkali Test on S i c Refractories


Weight
change (070)

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

Table V. Steam Oxidation Resistance of S i c Refractories (ASTM C863,


1100"C, 500 h)
Bond Type

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.

Table VI. Sequential Oxidation + Alkali Test Results on SIC Refractories


(325-h steam oxidation followed by molten alkali test)
Si,N,-bonded Sic:
A
B*
F*
fi-Sic-bonded Sic:
G

Weight
change (070)

Change in
MOR (To)

- 15

- 40

- 30

(**I
(**I

- 64

(**I

40

70

(**)

*Steam oxidation period: 500 h.


**Bars too damaged for MOR measurement.

Table VII. Properties of P-Sic-Bonded Sic Refractory


Bulk density (g/cc)
Apparent porosity (To)
Modulus of rupture (psi)
Molten alkali resistance:
Weight change (To)

111

2.66
13.5
7100

- 0.04

Table VIII.

Development of Blast Furnace S i c Refractories


Product 1

Product 2

Bond phase

Si,N,

Si,N,

Product 3
sialon/
Si,N,

Bulk density (g/cc)


Apparent porosity (Yo)
Crushing strength (ksi)
Cold MOR (psi)
MOR at 1350C (psi)
Mean thermal expansion
20- 1400C (10-60C-')
MOE at 20C (lo6 psi)
Molten alkali resistance:
Weight change (To)
MOR change (To)
Steam oxidation resistance:
500-h volume expansion (Yo)
Oxidation / alkali test:
Weight change (Yo)
Resistance to CO attack:
100-h test

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.

ProDerties of Maior S i c Blast Furnace Refractories

Major bond phase

Bulk density (g/cc)


Apparent porosity (Yo)
Cold MOR (psi)
MOR at 1350C (psi)
Thermal conductivity (W/mC):
at 25C
at 800C
at 1200"C
Molten alkali resistance:
Weight change (070)
Residual MOR (psi)
MOR change (Yo)
Steam oxidation resistance:
500-h volume expansion (Yo)
weight increase (Yo)
Oxidation/alkali test:
Weight change (Yo)
Residual MOR (psi)

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.

Fig. 2. The loaded molten alkali test


muffle.

113

Sealed Test Furnace

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

Fig. 3. Schematic diagram of the molten alkali test.

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

Fig. 5. Bars of differentSicrefractoriesafter the molten alkali test.


-

10

12

14

Fired Surface (in*)

Fig. 6. Molten alkali weight loss of Si,N,-bonded Sic refractoriesas a function of amount of fired surface in the test bars.

115

Fig. 7. Optical micrograph of the sialon-bondedSicrefractory


(product 3). (bar = 50 pm.)

Fig. 8. SEM photograph of the sialon-bonded Sic refrac100 pm.)

tory (product 3 ) . (bar =

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)

Fig. 10. Hot MOR of as-received samples of Si,N,-bonded (product 2) and


sialon-bonded (product 3) Sic refractories.

117

After Alkali Impregnation

9080 -

200

800

600

400

1200

loo0

1400

Temperature ("C)

Fig. 11. Hot MOR of alkali-impregnatedspecimens of Si,N,-bonded (product 2)


and sialon-bonded (product 3) Sic refractories.

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

Ceramic Engineering and Science Proceedings


Charles R. Beechan
The American Ceramic Society, Inc., 1986

Progress on Carbon-Bearing Refractories for the


BOF
YOICHINARUSE,KEISUKEHIRAGUSHI,SUKEKAZUKIWAKI,and ICHIRO
TAKITA
Kurosaki Refractories Co., Ltd.
1- 1, Higashihama, Yawata-nishi, Kitakyushu 806, Japan
The wear of magnesia-carbon brick in the BOF is influenced by the brick texture, raw
matm'al, and the additives to depress carbon oxidation. Recently, the newly developed
magnesia-dolomite-carbonbrick has attained a satisfactoy petjormance in the linings
of molten steel bath area as well as bottom area of the BOF

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.

Progress on Carbon-Bearing Refractories for the BOF


As to magnesia-carbon bricks used in the BOF much progress has been
made recently.
Influence of Bulk Density of Magnesia-Carbon Brick
It is most impohant that magnesia-carbon bricks have high bulk density.
Figure 2 shows the comparative properties of experimental magnesia-carbon
bricks with various bulk densities. The graphite content in all of these bricks
is 20%. When the bulk density is lower than 2.82, the wearing rate tends to
increase rapidly.
The wearing rate is evaluated by a rotary slag test. The hot modulus of
rupture decreases in proportion with the decrease in bulk density. The result
of the test suggests that the higher the bulk density of the magnesia-carbon
brick, the lower the wearing rate becomes.
Effect of Metal Addition to Magnesia-Carbon Brick
The most common technique for the improvement of magnesia-carbon
bricks is the addition of metallic aluminum. Figure 3 is the microstructure of
the magnesia-carbon brick with aluminum fired at 1400C and at low oxygen
partial pressure. Aluminum reacts with carbon to form aluminum carbide in
119

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

strengthens the binding action of mineral components in the brick.


Recently, duplex blowing in BOF has become a common practice. The
fluidity of molten steel and slag is increased by the duplex blowing. Therefore,
the addition of metals, like aluminum and magnesium alloy, is definitely
necessary.

Improvement of Raw Material Used for Magnesia-Carbon Brick


We have studied raw materials for the improvement of magnesia-carbon
brick. Figure 10 shows the microstructure of two magnesia-carbon bricks which
have been used in the BOF. The magnesia-carbon brick that uses sintered
magnesia is on the left. You can see that slag penetrates into the boundaries
of crystals and a sintered periclase grain is going to float in the slag. On the
other hand, fused magnesia on the right, has been dissolved into slag as if
it has been torn from the surface. However, because of the large crystal size,
there is no penetration of slag into the boundaries. Therefore the wearing rate
is less.
Adoption of fused magnesia to magnesia-carbon bricks is effective in
increasing resistance to corrosion, but fused magnesia is too expensive.
Therefore, from an economical point of view, sintered magnesia must be
improved further. There are a few methods for improving sintered magnesia.
Figure 11 shows the relationship between periclase size and resistance to
corrosion of sintered magnesia. All of the brick have about 98% magnesia
content. For the magnesia-carbon bricks that use 20% graphite, there is a
definite correlation between the periclase size of magnesia clinker and the
wearing rate of brick. The clinker of larger periclase indicates good resistance
to corrosion. This is mainly because the increasing of periclase size reduces
the number of boundaries, and the floating rate into the slag becomes smaller.
As we have explained, the increasing of periclase size in sintered magnesia
clinker is one effective method to decrease the wearing rate of bricks. Graphite,
which is another raw material for magnesia-carbon brick, has a large influence
on the wearing rate. In graphite, there are impurities which are mainly
composed of silica.
Figure 12 shows the result of the resistance to corrosion of magnesiacarbon bricks using three different kinds of graphite. As several researchers
have already reported, the high purity of graphite improves the resistance to
corrosion. The reason is that the impurities in graphite worsens the quality
of magnesia.
Comparison between Improved Magnesia-Carbon Brick and Conventional
Brick
As we have explained so far, magnesia-carbon bricks have been improved
through the study of bulk density, metal addition, and raw materials. At
present, these improved bricks are used in almost all of the BOFs. Next Ill
give an example.
Brick A in Table I is characterized by aluminum and magnesium alloy
addition, improved sintered magnesia clinker, and high purity of graphite.
On the other hand, brick B in Table I is a conventional brick with only
aluminum added. A 150-ton BOF with brick B had suffered a large amount
of wear at the tapping side and the strike area. Brick B was replaced by brick
A on both of those areas. Brick A and B differed greatly in the wearing rate.
The improvement in brick B by brick A is clearly shown. The use of Brick
121

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

(1) Magnesia-carbon brick should have a bulk density as high as possible.


(2) The addition of metals gives significant effects, especially, aluminum,
and magnesium alloy,
(3) Increasing the periclase size of sintered magnesia clinker improves
the resistance to slag corrosion.
(4) To the area where corrosion resistance is required, high purity graphite
should be used.
( 5 ) In the bath and bottom area of the BOF, it is better to use magnesiadolomite-carbon brick than magnesia-carbon brick.
Table I. Comparison Between Improved MgO-C Brick and Conventional
Brick
Metallic additive
Type of MgO clinker
Type of graphite
Wearing rate (mm/heat)
Tapping side wall
Strike Area

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 -

Fig. 1. Production of brick for the BOF at


Kurosaki .

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

Fig. 3. Microstructure of MgO-C brick


with A1 fired at 1400OC.

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)

Fig. 5. Influence of Mg addition to hot MOR


and resistance to oxidation of MgO-C brick.

125

Fig. 6. Differencebetween A1-Mg alloy and


A1 on hot MOR of MgO-Cbrick.
50

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%
........................ ................................... ..

Fig. 7. Test condition of static corrosion by the induction furnace.

126

0
0
0

0
0
0

0
0

0
0
0

Test Condition

Specimen for Static Corrosion Test


Specimen Size :
Monolithic Refractories
250X45X45 (rnrn)
0 Induction Coil, @ Slag, @ Steel,
Time: 2hours
8 Specimens for Dynamic Corrosion
Revolution Rate: 180rprn
Test, 0 Specimens Holder

Fig. 8. Test condition of dynamic corrosion by the induction furnace.

l\l

Gr4J:ite
Ontent

Metallic
Additive

Wearing Index
20

40

60

80

100

~~

Dynamic Corrosion Test

Static Corrosion Test

Fig. 9. Properties of test brick and test results.

127

Fig. 10. Wear pattern of magnesia clinker used in MgO-Cbrick.

100 - 0

x 90
a,
-a
S 80

.E

(J,

a,

70

60

O\

Rotary Slag Test : 1700'C,


BOF Slag

O x 0

50 I

Periclase Size of Sintered Magnesia ( y )

Magnesia

11. Influence of periclase size of sintered magnesia to wear rate


of MgO-C brick.

128

100

70

Fig. 12. Effect of impurity of graphite on wear rate of MgOC brick.


I

.E
L
OJ

130 -

120 -

--

110100

90 80 7060 50 -

(
,I
<

--.n--

yo
I

140 -

-n=-,o

Slag

Rotary Slag Test : 17OO0C


Siag A : C / S =3.0,TFe = 10 %
Slag B : C / S = 1 . 5 , T F e = l %
I

Fig. 13. Relationship between CaO in the brick and resistance to


corrosion.

129

Wearing Rate (rnrn/heat)

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

Fig. 15. Appearance of MgO-C and MgO-dolomite-C


brick in bath (after use).

S :Slag
D :Dolomite
M :Magnesia
P :Pore

Fig. 16. Slag-adhering mechanism of


MgO-dolomite-C brick.
130

Ceramic Engineering and Science Proceedings


Charles R. Beechan
The American Ceramic Society, Inc., 1986

Recent Technological Trends of Surface Coating


Refractories for CC Tundish Liners
K. WATANABE,S. FUJISAKI,
and T. TAKESHIGE
Taiko Refractories Co., Ltd.,
Kitakyushu, Japan

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

S upported by the progress of continuous casting (CC) technology, the ratio of

steel produced by CC in Japan has markedly increased in recent years as


indicated in Fig. 1. In the same manner, the tundish (TD) coating refractories
and installation methods have been improved as shown in Fig. 2.
Since multi-CC production lines have increased and high quality steels
have been requested, magnesia-base material has been mainly used in refractories. Investigation of light-weight insulating coating refractories (Here after
called L-Coatings) has newly begun for the purpose of reducing unit
consumption.
The installation method has temporarily shifted to heat insulating boards
(IB), though the trowelling method has been employed in general, since the
IB method had the disadvantages of high cost and poor erosion resistance.
Recently, gunning has been tried in many cases in an attempt to improve the
working environment and to execute a labor saving.
In this paper, we describe a technical advance in materials, and furthermore, we explain a study of L-Coatings using trowelling and gunning.
Technical Advancement in TD Coating Refractories

Clay-base coatings were initially used in Japan. These materials, however,


have changed to a high alumina-base material due to the silicate non-metallic
-6
incl~sion.~
As shown in Fig. 3, erosion resistance increases in proportion to A1,0,
content. However, since the cost of high-purity alumina is high, material of
approximately 60% A1,0, has become popular from the viewpoint of
economy.
Due to a recent increasing demand for the production of clean steel, we
should improve alumina-base coatings. Both the reasonable price and high
erosion resistance of magnesite have been considered and examined for
aggregates. Using the above reasoning, magnesia-base material has found
practical application for coating refractories, and the fiber has been utilized
for improving the explosive spalling resistance.
131

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

Penetration Test by Molten Steel


Testing Method: Steel of 50 g is put into a crucible for the test having
a shape of OD: 0 7 0 x 70mm, 0 2 5 x 35mm, and melted at 1550C for two
h. Penetration of molten steel is then observed.
Results: Figures 14 and 15 show a section of the test piece after the crucible
test. Figure 14 is of light-weight type A whose particle size is coarse, and Fig.
15 is of light-weight type B whose particle size is fine. From the results of
this test, we realize that a minimization of the pores produced is effective for
the prevention of penetration of molten steel.
Study: In realizing a light weight as mentioned above, it is inevitable that
the structure of coating refractories becomes porous. The conventional
L-Coatings, therefore, have the disadvantage that there is the large penetration by molten steel or slag. For a realization of light weight in the future,
and in order to overcome this disadvantage, it is necessary to make the pores
finer. Especially when realizing in a light weight with an AE agent, it is essential
to select the optimal AE agent among the various agents in accordance with
the air foam to be produced.
TD Gunning Systems7.*
Gunning as an installation method for TD coating refractories has, in
recent years, been investigated for labor saving and improving work environments. The gunning method is roughly classified into two methods: wet and
dry. At present, these two methods are being investigated or tested for actual
application. An outline of these two methods is shown in Fig. 16.
In the wet gunning method, refractories mixed beforehand are fed by
squeeze pumping, and high-pressure air is blown into the nozzle. Then, the
gunning is made. On the other hand, in the dry gunning method, powder refractories are fed into the nozzle by a compressor and mixed with water. Then,
gunning is executed.
Since the wet gunning method has a process of preparatory,=pixing,the
texture of material after gunning is almost as uniform as th+,&ed in the
trowelling method. In this section, problems in the dry gunning%ethod and
refractories are described.
The dry gunning method has problems since dry mixes ranging from a
few mm to a few 1.1 in particle size are fed using compressed air and are gunned
after mixing with water at the tip of the nozzle. These problems are:
(1) Dry mixes are apt to segregate in the feeding tube,
( 2 ) Mixing with water in the nozzle is uneven, and
(3) Lamination is apt to form in the interface between gunning and the
parent material or on the inner surface of the gunning material in
parallel to the gunning surface.
In recent years, the gunning machine has been frequently improved and
the problems points (l), (2) and (3) have been mostly solved. Properties of
dry gun and troweling mixes are shown in Table 111.
TD Dry Gunning Refractories
TD dry gunning mixes, because of the problems mentioned above, have
to be developed by paying attention to the points discussed below.
Explosive Spalling: Since the refractories are gunned at high pressure,
the substance installed becomes dense easily and the steam is hard to volatilize.
133

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

IT. Taniguchi, Tuikubutsu, 34 [9] 511-16 (1982).


2T. Taniguchi, S. Fujisaki, ibid., 28 564-7 (1976).
X. Komamura, Iron & Steel, 67 [9] A133-Al36 (1981).
4M. Yamamura, ibid., 67 [9] A137-AI40 (1981).
ST.Kobayashi, ibid., 67 [9] A141-AI44 (1981).
&Y.Onishi, ibid., 67 [9] A145-Al48 (1981).
7% Kamata, Tuikubutsu, 35 [12] 687-92 (1983).
ST.Eguchi, ibid., 35 [12] 692-5 (1983).

134

Table I.

Comparison of L-Coatings with Conventional Ones


Conventional
type

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

Table 11. Grain Size Distribution in Each Coating Refractories


Materials
Item

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

Max. grain size (mm)


Grain size

90-

86.2

80-

UI

8 60-

60.4

31.2

1970

80

75

83 (Year)

Note: Ratio of continuous casting (7.)


Annual output of steel by

CC

Annudl output of total crude steel

Fig.

x 100

1. Trends in steel continuous casting

ratios.

135

(A)

Material

Clay basr cootings

Erosmn -ms,stant ~ m o r o v e m ~ n t

High alumina-base coalmgs


I

Decrease
inclusion

(B)

Installation method

ot GX-metalllc

lo Ihe problems on working


conditions and labor saving

Magnesia- base coatlngs


(fiber added )
Unil consumotion reduction
Light !nsulaling coatings
(L-coatings)

IS Heat Insulating Board 1

Fig. 2. (A) Technical advancement of materials fortundish coating refractories; (B)


Technical advancement of installation for tundish coating refractories.

10

All01 Content of AlzOl

- SiOz Coatings (Y.)

Erosion test condition

Slag basicity
(CaO/Si02)
0.95

Molten metal
Ordinary
Steel

~~~,",~&
1570-16OO'C

Fig. 3 . Erosion rate of AI,O,-SiO, base


coating refractories against AbO, content.

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

Fig. 5. Permeability test apparatus.

137

"

-1

30mm coating

Fig. 6 . Rapid heating test furnace

::___rji_

Ln

E 3
2 2

!2 1
c

gg

0-

w 01

'

Fiber increasing
Erosion test condition

Fig. 7. Fiber amount added vs erosion


resistance.

138

Mixing Time ( min)

Fig. 8. Relation between mixing time and


apparent porosity of tundish coating refractories containing air-entraining agent.

Amount of AE Agent Increasing

Fig. 9. Effect of the amount of airentraining agent on apparent porosity of


tundish coating refractories.

139

Fig. 10. Microstructure of conventional type coating (bar = 100 pm).

Fig. 11. Microshcture of light-weight


type A coating (bar = 100 pm) .

140

Fig. 12. Microstructureof light-weight


type B coating (bar = 100 pm).
Light -weight
-----

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

Fig. 14. Crucible test of lightweight type A coating.

Fig. 15. Crucible test of lightweight type B coating.

142

W e t Type Gunning

D r y T y p e Gunning

Fig. 16. Outline of wet and dry gunning methods.

01

Max. particle size (mm )

Fig. 17. Maximum particle size and


rebound loss.

0 :Sound

Oogo

10

OL'

:Explosion

1;

20

25

30

3s

Fine particle a m o u n t (-200mesh%)

Fig. 18. Relation between fine particle


amount, permeability, and explosive spalling resistance.

143

Gunninq

Orvinq

k n i n g nozzle
Gunned

material

Fig. 19. Explosive spalling test method.

144

Ceramic Engineering and Science Proceedings


Charles R. Beechan
The American Ceramic Society, Inc., 1986

Nondestructive Testing of Refractories Using


Industrial X-ray Computed Tomography
YOSHIRO

AIBA, OK1 KAZUO, and ARAKAWA


KAZUMI

Ceramic Division, Toshiba Ceramics Co., Ltd.

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

Contrary to this, the CT method can produce images sectioning them in


slices, which makes it possible to analyze the internal structure of threedimensional objects from multi-angles and in great detail. It thus enables quick
detection of hidden defects, their shapes and sizes, as well as fluctuations in density. Also, since X-rays that have passed through the object are sensed and
recorded as differences in the quantity of photons, it is possible to determine
with this method the differences in X-ray absorption values more exactly than
with conventional methods.
We experimented with the CT method for refractories using first a middleenergy CT scanner, and then a high-energy CT scanner. This paper presents
results obtained using industrial CT scanner on submerged nozzle and tundish
nozzle used in the continuous casting of steel.

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

Here, ps: X-ray absorption coefficient of reference material (normally,


water)
146

cc,: X-ray absorption coefficient of object material

K : Constant (normally 1000)


Generally, a CT value scale with -1000 for air and 0 for water is used.
Theoretical CT values of principal material at 100 KeV of effective X-ray
energy are shown in Table I.I2
Application of Middle-Energy CT Scanner to Refractories
The main specifications of middle-energy CT scanner are shown in Table
11, and a diagram of the system in Fig. 3 .

Inspection of Cracks and Slits of Used Submerged Nozzles


When zooming is performed, the resolving power of the middle-energy
CT scanner extends down to l00pm as shown in Table 11, so it is used for
detection of defects, observation of cracks or slits present inside refractory
products.
Figure 4(A) shows an example of detecting defects in an imitation specimen
of an alumina-graphite submerged nozzle, and (B) shows an example of cracks
in a reclaimed submerged nozzle of the same material used for casting Alkilled steel. Figure 5(A) shows a scanogram of a slit type submerged nozzle
and (B) shows a tomogram at the position indicated by the white line in (A).
The slit shown in Fig. 5 is for introducing gas into the nozzle bore to prevent the metal as well as inclusions from sticking to the nozzle bore surface.
It must be provided concentrically with the nozzle bore and exactness of its
position is very important for steel casting operation.
Analysis of Used Submerged Nozzle
Figure 6 shows another case of a reclaimed submerged nozzle used also
for casting Al-killed steel, with the measurement results of absorbed X-ray
values.12A scanogram is shown in (A). The white portion above the outlet
hole is the part made in a double structure, with the powder line layer containing zirconia as aggregate added to the base material layer. Inside the outlet
hole, a substance is deposited which is high in the X-ray absorption value.
This is assumed to be a mixture of metal and alumina-containing inclusion.
Figure 6 (B) shows the tomogram taken at the part indicated by the white line
shown in (A). The base material is in black, forming crescent shapes.
On the periphery and the outlet part of the nozzle, material adherence
is observed. This adhering material is about 15-mm thick, and its brightness
is high. Figure 6 (C) is the closeup image of the left-top part of the tomograph
in (B), and the profile of the CT values along the white line. The curve appearing at CT value around 2800 is for the base material of the nozzle. The adhering substance is thin on the outside nozzle surface, but is thick around the
nozzle outlet.
The CT values at this outlet part are high, ranging from 4000 to 6400,
and this means that a substance which is higher in CT value than the refractory material is sticking thereto. Figure 6 (0)
shows a histogram of CT values
obtained from the part boxed by white lines. From this, it is seen that the refractory material corresponds to a range of values centering on 2800, air to a range
around -1000 in the upper part, and as for the metal, to a range around the
peak of 6000 in the lower part.
In order to verify whether or not the CT value and the brightness observed
from the tomogram-these should represent internal conditions of the used
147

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.

Analysis of Oxidized Layer of Submerged Nozzle


Since the material of alumina-graphite nozzles contains graphite, it tends
to degenerate by oxidation during its use. Conventionally, the thickness of
the oxidized layer is measured by visual inspection after cutting the sample,
but it was difficult to determine the oxidized layer thickness because of the
ambiguity of the borderline between the oxidized part and the nonoxidized part.
Figure 9 shows an example of an analysis for the oxidized part. The
specimen in this figure was one heated at 1600C for 5 h using a gas furnace,
and oxidation occurred partially at parts where coating for prevention of oxidation was washed away. Figure 9(A) shows the tomogram and the profileprocessed CT values after zooming, and (B) the images obtained by banddisplaying. The parts appearing in black at the sample periphery are the parts
degenerated by oxidation, and from the profile in (A), it is judged that the
CT values of these parts are low.
By means of band-display, the oxidized parts and nonoxidized parts are
shown qualitatively, and this proves that the location and the extent of
degeneration of material can be easily found by the use of the scanner. The
band display processing can be used also for examination of density fluctuations of materials and for checking for contents of foreign materials.
Examination of Cracks Using Tomograms and Reformed Image
Reconstruction
A specimen made of unburned alumina-graphite material was heated
(holding at 1500C for 20 min), water-cooled, and cracks thus caused were

148

inspected. Images obtained are shown in Fig. lO.I3


The tomography was carried out adjusting the scanogram so as to
photograph 30 slices sequentially. The distance of 60mm between the position A and the position B is by a slicing thickness of 2mm (Fig. 10, left). The
tomogram at positions A and B (Fig. 10, right) show that cracks were starting
concentrically from the periphery and also we noted two heavy radial cracks.
In order to examine the development of these cracks in the vertical direction,
a further analysis was made by utilizing the function of reformed image
reconstruction for which the tomograms were grouped and processed (Fig. 11).
From the reformed image (vertical section image) of the outer surface
(the white lines show the cutting), it was found that the concentric cracks have
progressed vertically with irregularity, i.e., first, concentric cracks have
occurred through heavy thermal shock, which eventually caused cracks in the
direction of radius.
As seen from the examples of Figs. 10 and 11, grouping of images and
use of the reformed image reconstruction make it possible to carry out detailed
three dimensional analysis of the object.

Analysis of Refractories Using X-Ray Absorption Value (CT Value)'3


As explained in paragraph 2, the X-ray absorption value (CT value) of
energy part of an object can be calculated using the tomography method. By
using this function, internal conditions of refractories can be quantitatively
analyzed without destroying them.
Correlation between Alumina-Graphite Composition Ratio and CT- Value:
Burned and unburned alumina-graphite specimens were prepared changing
the ratio of the two ingredients, and their CT values were measured. Properties of the burned bodies, as well as CT values of the burned bodies (130mm,
40mm) and unburned bodies (40mm) are shown in Table 111.
The correlation between the CT value and the bulk density is shown in
Fig. 12. Both burned and unburned specimens of 40mm are similar in the CT
value, and their bulk densities as well as their CT values decrease in proportion to the decrease in alumina content. The specimens of 130mm (burned
bodies only) are low in CT value compared to the specimen of 40mm. This
is because X-ray transmission decreases due to beam hardening.
Accordingly, when comparing CT values based on tomograms, it is
important to prepare specimens of the same size and shape, to avoid influences
of such factors. As seen from the above, the CT value and the bulk density
of alumina-graphite material are correlated to the quantity of alumina contained in it.
Correlation of CT Value With Forming Pressure, Porosity and Bulk
Density: Alumina-graphite material of No. 3 in Table I11 (A1,0,: C = 70 :30)
was used to prepare specimens at different forming pressures. After firing,
they were measured for physical properties and CT values. The results are
shown in Fig. 13. We see there is a correlation between its CT value and its
forming pressure, bulk density, and apparent porosity.
Application of High-energy CT Scanner to Refractories
Among refractories for steel making, there are some which do not permit
X-rays to pass through effectively when a middle-energy CT scanner as one
149

we reported above is used. They are, for example, the zirconia-containing


refractory layer provided for submerged nozzles at the slag line, and tundish
nozzles made of zirconia. For these refractories, the scanner must have higher
power, and we use the high-energy CT scanner, which can generate X-rays
with energy as high as 420 kV, as reported in paragraph 2.
The method of data collecting of this scanner is that of the first generation. The translation and rotation movements are made by the sample table,
and the data sampling pitch as well as the number of data taking points can
be freely selected. Figure 14 is a diagram of the system, and Table IV shows
its main specifications.
Data are collected with the X-ray tube and the detector fixed to their positions and with the object placed on the table, by alternative rotation and
translation of the sample table while applying X-rays to the object. A part
of the X-ray radiated from the tube is absorbed by the object and the rest
of the radiation reaches the detector. The detector consists of a BGO (bismuthgermanium oxide) scintillator and a PMT (photomultiplier tube).
The X-ray data thus collected is called the projected data, which are
sent to a computer and the tomogram is reconstructed. This reconstructed
image (tomogram) is displayed on the CRT display, and at the same time stored
in a memory disk. The equipment is so made as that the sampling points can
be densified to a pitch of lOpm and the width of detector opening and the
thickness of X-ray slicing to an order of 10-pm graduations. These essentials
therefore can be set to values which enable obtaining necessary resolution
power. Also, both X-ray source and detector are provided with a collimeter.
Because of this, the image is not influenced by the scattering width of the Xray source so that high quality images can be obtained. Figure 15 shows an
example of measurement carried out with a test phantom which is a steel rod
of 50mm diameter having six holes of different diameters. Even the smallest
hole of 0.38mm diameter is clearly shown. The hole diameters of the test phantom are 2, 1.5, 1.0, 0.75, 0.5 and 0.38mm.

Tomography of the Powder Line Part of Submerged Nozzle


A submerged nozzle used for steel continuous casting (ladle: 250 t; kind
of steel: carbon steel) was reclaimed and its powder line part was analyzed.
The powder line part of the nozzle was made in a double-layer structure, Le.,
the outer peripheral part was made from zirconia and graphite, and the main
material part was made from alumina and graphite. Table V shows typical
properties of double-layer submerged nozzle before use. Tomography by the
high-energy CT scanner was carried out under the following conditions:
X-ray tube voltage:
X-ray tube current:
X-ray beam width:
Slicing thickness:
Sampling pitch:
Number of projections:

360 kV
3.5mA
1.Omm
0.5mm
0.5mm
200

Figure 16 shows a cross-sectional view of the double-structure submerged


nozzle, its slicing position for the scanning, and the tomogram obtained.
The tomogram clearly shows the differences in the density of material
between the outer layer (zirconia and graphite) and the inner layer (alumina
and graphite). It also clearly shows the metal which adheres to the nozzle bore
150

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.

Analysis of Used Zirconia Tundish Nozzle


A zirconia tundish nozzle, which was used with the tundish for 24 charges
(carbon steel from electric furnace, ladle capacity: 60 t) was reclaimed and
examined using the CT scanner for the condition of the inner structure after
the use.
The conditions for the scanning were as follows:
X-ray tube voltage:
370kV
X-ray tube current:
3.4mA
1.Omm
X-ray beam width:
Slicing thickness:
0.5mm
Sampling pitch:
0.5mm
Number of projections: 200
Figure 18 shows the slicing position, the tomogram and the cut surface
of the sample nozzle (it was cut at the same position as that for slicing). From
the tomogram, it appears that there are four cracks inside the nozzle which
have not progressed to the outside nozzle surface.
The cut surface shows four cracks which extend to the outside surface.
These cracks existed as hidden cracks but they developed to reach the outside
surface when the nozzle was cut by means of a diamond cutter.
The nozzle bore is blocked with metal. The tomogram shows this condition at the center of the image. It is whitish at the peripheral part and becomes
darkish toward the center. The darkened part of the tomogram image almost
corresponds to the blackened part appearing in the cut surface.
When the tomography is applied to an object which is cylindrical in the
shape and is uniform in material, there is a tendency that the CT value becomes
lower at the center of the object and the tomogram image becomes darker
at the image center. This effect is called beam hardening.I3 In the case of a
used nozzle, it is considered that when the layer around the bore becomes dense
by penetration of metal, the beam hardening will become more apparent. With
use of this beam hardening effect, it is possible to estimate the extent of the
151

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

G . N . Hounsfield, A Method of and Apparatus for Examination of a Body by Radiation


Such As X-Ray or Gamma Radiation, British patent; No. 1 283 915, London, 1972.
2Y. Yamagishi, Progress of X-ray CAT Scanner, Toshiba Rev., 38 [8], 686-90 (1983).
3R.P. Kruger and T.M. Cannon, The Application of Computed Tomography Boundary
Detection and Shaded Graphics Reconstruction to Industrial Inspection, Mater. Eva/., 36 [4]
75-80 (1978).
4R.P.Kruger, G.W. Wecksung, and R.A. Morris, Industrial Applications of Computed
Tomography at Los Alamos Scientific Laboratory, Optical Eng., 19 131, 273-82 (1980).
51. Taguchi, M. Kama, and S. Nakamura, Development of X-ray Computerized
Tomography for Iron and Steel and a New Analytical Method, Tetsu-to-Hugane, 70 151, s424
(1984).

153

61. Taguchi, Observation of Materials by X-ray Computerized Tomography, Bull. Japan


Inst. Metals., 22 [12], 1017-20 (1983).
K. Oki, K. Arakawa, M. Sugie, K. Kurihara, and Y. Aiba, Tomogram of Refractories
by Industrial X-ray CT Scanner, Tefsu-to-Hagane,70 [4], s166 (1984.)
8For Example: G . Ganelli and F. Monti, Ultrasonic Inspection of Slide Gate Valve Components, RefractoriesJ., 2, 11-12 (1981); R.O. Russell and G.D. Morrow, Sonic Velocity Quality
Control of Steel Plant Refractories, Am. Ceram. SOC.BUN., 63 [7], 911-914 (1984).
9For Example: H. Shibata, K. Hiragushi, H. Fukuoka, and K. Kanematsu, Some Studies
on Detection Methods for Inner Cracks of Casting Refractories, Taikabutsu., 32 [12], 696-702
(1980).

%. Nakamura, Y. Tanimoto and J. Fujii, Industrial CT Scanner, TOSCANER-3000,


Toshiba Rev., 38 [12] 1073-76 (1983).
1. Tanuchi. S. Nakamura, and 0. Tsuiii. High-Energy
-. X-Ray CT Scanner for Steel,
Toshiba Riv., 39 [12], 1083-86 (1984).
12Y. Aiba, K. Oki, S . Nakamura, and M. Fujii, Development of Industrial X-ray Computed Tomography and Its Application to Refractories, Tetsu-to-Hagane,71 [14], 1692-99 (1985).
l3Y. Aiba, K. Oki, K. Arakawa, M. Sugie, and T. Watanabe, Application of Industrial
X-ray Computed Tomography to Refractories, Taikabutsu Overseas., 5 [2], 18-28 (1985).
\ - - - - I -

Table I.

CT Values of Typical Substances


Effective energy
Assumption

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

Table 11. Specifications for Middle-Energy Industrial CT Scanner (Toscaner


3200)
Scanning method

By rotating of object (3rd generation scanner)

Object material
Maximum thickness
Size and weight
of object
Scanning time
Slicing thickness
X-ray rating
Detector
Image reconstruction
matrix

Plastics, rubber, wood, foods: max. 300 mm


Ceramics, refractories: 200 mm
Dimensions: max. 8300 mm x 600 mm (standard)
Weight: max. 100 kgllarge table (standard)
15 s/scan
0.5, 2.0, and 5.0 mm
140 kV, 300 mA, 2.0 ms pulse (standard)
High pressure Xe detector (512 channels)

Pixel size mm

Scanning field 150 mm6 240 mm8 300 mm0


For data
collection
0.3
0.6
0.6

320 x 320

0.10.10.47
0.75
From - 1000 to 8000

For zooming

CT value
Functions

0.10.94

Averaging, standard deviation.


Area calculation, and distance calculation

Table 111. Physical Properties of CT Values of Alumina-Graphite Samples


SDecimen

Chemical composition (wt%)


A1203
C
Apparent porosity
Bulk density g/cm3
CT Value
Burned, 130 mm8
Burned, 40 mme
Unburned, 40 mm6

90
10
27.6
2.53
1580

1900
1896

80
20
24.1
2.44
1512
1772
1788

(Forming pressure: 1000 kg/cm*, by isostatic press)

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.

Specification for High-Energy CT Scanner (Toscaner 4100)

Scanning method

1st generation scanner

X-ray tube
Detector
Scanning area
Beam size

Max. rating: voltage 420kV; current: 3mA


BGO+PMT, 1 channel
290 mmf3
Size variable from 10 to 1500 pm for both
Opening width and slice thickness

Matrix for image


reconstruction
Minimum pixel size
Minimum data pitch
Image processing

Table V.

Max. 1024 x 1024 (software adjustable)


10 pm
10 pm
Zooming; profiling; histgramming;
section-conversion, and others (image
processing can be made using middleenergy CT scanner.)

Properties of Double-Layer Submerged Nozzle before Use


Main body

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

Fig. 1. Data collection by CT scanner.

156

(d)4th generation

Tomogram of phantom with hole (hole size:


2.5, 2.0, 1.75, 1.50, 1.25, 1.0, 0.75, 0.60, 0.50,
0.30 mm).
Fig. 2.

X-ra
contmller

Hi& v o l ~
generator 2

i
I

1 1

--

L-

--

Detector

X-ray sealed room


'

Fig. 3.

Display
controller

Computer
cabinet

Console

Block diagram of middle-energy industrial CT scanner.

157

Fig. 4. Cracks in alumina-graphite submerged nozzle (A) crack found in


alumina-graphite imitation sample, (B) cracks found in a used submerged nozzle.

Fig. 5. Slit of alumina-graphite submerged nozzle (A) scanogram image of


slit-type submerged nozzle, (B) tomogram of slit-type submerged nozzle.

158

Fig. 6. Tomogram of used alumina-graphite


submerged nozzle and its processing (A) scanogram,
(B) tomogram, (C) profile, and (D)histogram.

Fig. 7. Tomogram and cut surface at the tomographed


position (A) tomogram, (B) cut surface.

159

Fig. 8. Tomogram, polished cut surface of


the sample and wide area mapping images
taken with computer aided microanalyzer
(JCMA-733, JEOL Ltd.) (A) tomogram, (B)
polished surface of the sample, (C) A1K image, and (D) AIK image. Acceleration
voltage, 15 kV,probe current, 0.1 FA, pixel
size, X = 100 pm, Y =80 pm, measuring
point, X=300, Y=460.

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

Fig. 10. Scanogram and tomogram of unburned alumina-graphite sample


after rapid heating (A) scanogram and slice position, (B) tomogram at position A, and (C) tomogram at position B.

Fig. 11. Reformed image from position A


to position B.

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

(Forming pressure: 1000kO/cm2)

Fig. 12. Correlation of composition of alumina-graphite


sample and CT value.
C T value

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

Forming pressure (kg/crn)


Specimen: 4 O @ x 4 0 h

Fig. 13. Correlation of forming pressure and CT value,


apparent porosity, and bulk density.

162

Colllrneters

Rotationltranslation
mechanlsrn

Fig. 14. Block diagram of high-energy CT scanner.

Fig. 15. Tomogram of steel test phantom


(X-ray, 420 kV,3 mA; detector, BGO PMT,
hole size 2.0, 1.5, 1.0, 0.75, 0.5, 0.38mm).

163

Fig. 16. Tomogram at the powder line submerged


nozzle, taken with high-energy CT scanner (A) position
where tomogram was taken, (B) tomogram at the powder
line.

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

Fig. 20. Physical properties of used tundish nozzle.

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)

Fig. 21. Pore size distribution of used tundish nozzle.

165

Hot

Reacted

Original brick zone

0
Distance from hot face(mm)

Fig. 22. Quantitative analysis of


used tundish nozzle by EPMA (acceleration voltage, 15 kV,probe current,
0.02 pA, probe diameter, 1 pm +I.

166

Ceramic Engineering and Science Proceedings


Charles R. Beechan
The American Ceramic Society, Inc., 1986

Observations on the Thermomechanical Behavior of

CHARLES
A. SCHACHT

Schacht Consulting Services


12 Holland Rd., Pittsburgh, PA 15235

As a result of recent thermomechanical inuestigatiue studies on iron and steelmaking

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

(midplane restrained in x, y, and z directions), with a uniform temperature


increase from ambient is expressed as (Fig. 3):

For the case of a restrained one-dimensional bar (beam axis restrained in x,


y and z, directions), with a uniform increase in temperature from ambient,
thermal stresses are calculated as:
(2)

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

of inelastic flow on the hot-face side caused by lining expansion restraint.


Figure 5 describes the compressive expansion stress in the lining during typical
ladle heating events. For preheat and hot metal hold times, compressive stress
at the ladle lining joints is shown in Fig. 6 . The higher compressive stress on
the hot-face side of the working lining, is a direct result of the temperature
gradient in the lining. At the hot-face side, the predominant inelastic flow
occurs at the higher temperatures during the later part of preheat and the initial
portion of the teeming event. The decrease in hot-face stress reflects the inelastic
flow of the material to accommodate the thermal expansion at higher
temperatures. The axial-stress components are considerably less since less
restraint is applied to the lining in the axial direction.
With the magnitude of residual tensile stress that is developed at cooldown,
vertical radial cracks would develop and dissipate the tensile stress. According to Fig. 4, the cracks would penetrate to a depth of less than 12 mm (% -in.)
from the hot face. Since the vertical radial joints cannot develop tensile stress,
the joints would open at ambient conditions. As shown in Figs. 7 and 8, the
vertical cracks would develop near the mid-length position where hot face
tensile stresses are at a maximum. Although cracks may develop from the combined cooldown thermal gradient and the residual tensile stresses, the residual
tensile stress (or residual tensile strain) would cause the cracks to remain open
in the ambient condition. As described schematically in Fig. 9, examination
of brick samples taken from the working lining showed open vertical radial
cracks at the mid-length position.
The residual tensile stress on the working lining hot face was confirmed
by comparing the initial preheat shell stredtime data with subsequent preheat
shell stredtime data for both the field measurements and analytical
evaluation.
For the field data, the initial preheat time was about 7 h and subsequent
preheat was about 6% h. In the field data, the initial and subsequent preheat,
with similar heat-up rates, showed the measured shell stressltime plots were
less steep during the early stages of subsequent preheat. Figure 10 shows
measured field data on the circumferential shell stress during initial and subsequent heat-up at the same gage location.
In the analytical evaluation of the subsequent preheat, a less steep shell
stresshime plot was also obtained (Fig. 11). The analytical results were
obtained by including in the model a radial hot face crack, as shown in Fig.
12. The analysis was made for the first 4 h of subsequent preheat. The analytical
radial crack had an opening in the cold condition proportioned to a width
of 0.0127 cm (0.005 in.) for a unit circumferential length.
In evaluating subsequent heat-ups, the residual tensile stress and cracks
would nullify the expansion of the hot face material, resulting in a flatter
stresdtime plot. During the later stages of subsequent preheat, the interior
lining temperatures become sufficiently high to develop expansion loads similar
to those of initial preheat. At various regions of the ladle shell, the difference
in shell stress response between initial heat-up and subsequent heat-up is
observed consistently throughout the field data. This response demonstrates
that significant residual tensile stress and crack development occur on the lining
hot-face side of the working lining.
Also, the residual tensile stress on the working lining hot face implies a
cooling thermal shock (rapid decreasing temperature change) would be considerably more severe than a heating thermal shock on a previously heated
169

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

categorized into five regimes of thermomechanical lining behavior.

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.

The Role of Mortar Joints


The radial mortar joints of the working lining provide the primary source
of initial relieving of the lining expansion forces. It is important to evaluate
the amount of relieving which takes place in the radial and circumferential
joints of both the working and safety linings.
Previous research* has shown that (Fig. 10) the new working lining
develops the greatest thermal expansion stresses in the lining and shell. As
shown in Fig. 5 and 6, the back-up lining does not develop appreciable circumferential expansion force and the radial joints separate. Therefore, the
back-up lining serves only to transfer the radial forces between the working
lining and the ladle shell. The relationship between the radial load and circumferential force is established by Eq. 5 . For a radial stress of about 2 MPa
(300 psi) which is developed by the expansion of the working lining, the corresponding circumferential stress is governed by the radius (r)to thickness (t)
ratio. The ratio between the circumferential and radial stresses is typically
about:
r r 20
t
Therefore, the working lining radial mortar joint is subjected to a circumferential compressive stress nearly twenty times greater than the radial compressive
stress on the circumferential joint.
Also it is necessary to consider the geometric aspects of mortar joints in
determining which mortar joints are principally responsible for relieving lining
expansion force. The relationship between the circumferential expansion and
the radial expansion is:
-

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.

Elastic Properties of Ladle Materials

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

Fig. 1. A 315 to 350 ton teeming ladle.

175

15-2

/'I

HIGH-ALUMINA
BRICK

INSULATING BRICK

FIRECLAY BRICK

Fig. 2. Typical materials of ladle wall

PLATE

S = EaAT

BAR

Fig. 3.

Dimensionality of thermal stress.

176

COLD
FACE

HOT
FACE

15r

DATA

Fig. 4. Residual stress distribution near working lining


hot face.

NOTE: CROSSHATCHED ZONE REPRESENTS


THE PORTION OF THE JOINT THAT I S
IN CIRCUMFERENTIAL COMPRESSION
AT THE INDICATED TIMES

COLD
FACE

-HOT

TYPICAL WALL SECTION

FACE

10

11

12

TIME.hourr

Fig. 5. Circumferential compressive stress zone in ladle lining.

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

Fig. 6. Circumferentialcompressive lining stress at various


times.

LINING

Fig. 7. Distribution of working lining


residual stress (S,) .
178

HOT

WORKING LINING
JOINT CRACK

Fig. 8. Typical cracks on working lining hot


face.

Fig. 9. Working lining brick sample.

179

*
COOL

PREHEAT

FIRST DAY EVENTS

FIFTH DAY EVENTS

&TEEM

120r

*Ot

TEEM

--

i
2

4
TIME ,

10'

12

hrs

Fig. 10. Circumferential shell stress/strain-gage measurements.

ANALYSIS RESULTS OF
INITIAL

WITH

PREHEAT AND

HOT FACE CRACKS

TIME, hrs

Fig. 11. Analysis of working lining hot-face cracks.

180

TEEM

SHELL

HOT FACE CRACK


WIDTH IN COLD
CONDITION PER 25mm
OF HOT FACE LENGTH

Fig. 12. Schematic of analytical hot-face


crack.

TYPICAL COMPRESSIVE
STRESS CONTOURS
(UNITS ARBITRARY)
RESTRAINING FORCE
FROM ADJACENT BRICK

Fig. 13. Stress dkhibution in working lining during


heat-up.

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

Fig. 14. Knuckle loads in brick joints.

182

I -

I 1

FACE

D1 <D2 <D3

FROM HOT FACE

X-DISTANCE

Fig. 15. Variation of knuckle load tensile


within brick.

(L

FURNACE

a
E

200-

ad

gg

E5J

SI:
sG oy

c
.

'FOUR STRAIN GAGES AT


90' SPACING AROUND SHELL
ADJACENT TO HEARTH

15010050I

GAS

#-

,
\

183

'

,-\

-I

v)

*TIME

__

Fig. 17. Time-dependentresponseof arefractoy-linedcylindricalvessel.

% OF FERROSTATIC PRESSURE
-xloo=
TAKEN BY SHELL

5 ,E

60%

;$
i

111 MPa

102 MPa

123 MPa

126 MPa

LINING EXPANSION PLUS


FERROSTATIC PRESSURE

LINING EXPANSION

Fig. 18. Elastic analysis of ladle wall

184

Ceramic Engineering and Science Proceedings


Charles R. Beechan
The American Ceramic Society, Inc., 1986

High Strength Insulation for Steel Ladles


VALERIE
E. MCCALLEN
Manville Corporation
P.O. Box 190, Zelienople, PA 16063

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

Physical and Thermal Properties of Insulation


The first requirement of an insulating material for consideration as ladle
insulation is that it have adequate compressive strength to withstand the forces
exerted by the refractory expansion and the ferrostatic head of the steel. The
combination of a 25-50070 higher density and a 1.O-2.0% linear expansion of
high-alumina and basic brick as compared to bloating fireclay, results in greater
stresses against the ladle shell. Although the insulating values of refractory
fiber boards and paper are very attractive, the compressible nature of these
products could lead to a loosening of the refractory lining. The actual insulating
value would also be negligible since the compression would eliminate most
of the porosity in the board or paper. A calcium silicate board is available,
however, that has a unique combination of low thermal conductivity and high
compressive strength. The nominal density of this board is 960 kg/m3 (60
lb/ft3) and even under an applied pressure of 69 MPa (10 000 psi), it will
maintain its structural integrity. The compressive properties of this material
are shown in Table I as permanent consolidation (PC) and deflection (DUL)
under load, which represents its inelastic and elastic behavior, respectively.
At a 13.8 MPa (2000 psi) applied pressure, the average typical PC is 1.4%
and DUL is 4.8%. After exposed to a soaking heat of 649C (1200F) for
24 h, the PC and DUL are 9.2% and 15.4%, respectively. The compressive
strength of the board insulation is also expressed in Table I1 as the pressure
required to produce a 5% and 10% deformation per ASTM C165.
Average typical shrinkage values of the board insulation after a 24-h soaking heat test are shown in Table 111. The average shrinkage after exposure
to a soaking heat of 649C (1200F) is 0.4% along the length and width and
1.9% through the thickness. Although a sharp increase in shrinkage is observed
for soaking heats above 760C (1400"F), such conditions in actual service
would be virtually impossible to exist.
A comparison of the thermal conductivity of the calcium silicate board
to refractory fiber board and two grades of insulating firebrick is illustrated
in Fig. 2. Since the thermal conductivity of the board is less than one-half
that of any insulating firebrick having at least a 3.5 MPa (500 psi) cold crushing
strength, a one-half inch thickness of the board will have approximately the
same insulating value as an insulating firebrick split. Inclusion of the 1.2-cm
(% -in.) of insulation in the refractory lining has little if any effect on the current
brick count and allows for increased ladle capacity as compared to the addition of an insulating firebrick lining. The board is available in thicknesses from
1.2-3.8 cm (%-1 %-in.), however a 1.2-cm (%-in.) or 1.9-cm (%-in.) thickness
provides ample insulation without increasing the mean temperature of the
refractory linings above recommended temperatures as well as maintaining
the mean temperature of the insulation lining below 649C (1200F).
A single test was conducted to determine the reaction of the insulating
board with molten steel in the event that leakage occurred through the safety
lining. A small ladle of steel was poured onto a 15.2-cm (6-in.) square sample
of the board at ambient temperature. After the metal had cooled, it was easily
removed from the surface of the board as shown in Figs. 3 and 4. Only minor
surface penetration (approximately I mm) had occurred and there was no
apparent themal shock damage to the board. Prolonged contact would certainly
have caused a more extensive reaction, but the test did demonstrate that the
board could contain hot metal for at least a short period of time.
186

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

The effect of ladle insulation on steel temperature was evaluated on the


basis of change in tundish temperature and various intermediate steel
temperature changes in the ladle. The rate of steel temperature loss was also
calculated for the following temperature and time intervals: final tap to
hoistway temperature, hoistway to final tundish temperature, and initial
tundish to final tundish temperature. Even after separating three mo of production data by grade of steel and number of heats on the ladle, no meaningful
conclusion or effect could be identified. The combination of other process
variables is most likely to have a more dominant effect on steel temperature
loss than insulation in the ladle. These variations include: ladle preheat time
and temperature actually achieved, tap temperature, degree of temperature
stratification in the ladle, amount of slag cover, and the temperature condition of the tundish. Even inaccuracies in temperature measurement itself could
mask an effect of steel temperature.
The wear pattern of the 70% alumina lining and basic slag line was
observed for several working linings and was found to exhibit normal wear.
A survey conducted after ten ladles were insulated and in service for at least
three mo showed that the average number of heats on the working linings of
insulated ladles before re-line was 10% greater than that of uninsulated ladles.
Extended working lining life is attributed primarily to the insulation which
reduces the temperature gradient through the working lining and deterioration from thermal shock.
The board insulation has also been used to insulate dolomite-lined teeming ladles. The Johnstown Plant of Bethlehem Steel Corporation applied 1.3
cm (%-in.) of the board insulation behind a 12.7-cm (5-in.) resin-bonded
dolomite working lining and a 6.4-cm (2% -in.) 60% alumina safety lining (Fig.
6). Thermocouples'were installed in the first insulated ladle 2.5 cm (1 in.) from
the hot face, at each lining interface and against the shell (Fig. 7). The thermocouples were located approximately one-third of the ladle height from the
bottom. Temperatures throughout the lining were recorded during the initial
preheat to 1093C (2000F). The temperature profile shown in Fig. 8 indicates
that the hot face of the working lining reached 1093C (2000F) in seven h,
and the temperature stabilized throughout the lining in approximately 14 h.
The maximum interface temperatures achieved during preheat were 899C
(1650F) between the dolomite and 60% alumina linings and 710C (1310F)
between the 60% alumina and insulation linings. The temperature drop across
the 1.3 cm (%-in.) of insulation was 427C (800"F), resulting in an interior
shell temperature of 266C (510F). It was not possible to obtain similar data
for an uninsulated dolomite-lined ladle, but it could be predicted that the shell
temperatures could well exceed 316C (600F) even if a more insulating safety
lining were used.
Conclusion
Insulation for steel ladles should be considered not only as an effective
means of reducing shell temperatures in high-alumina or basic-lined ladles,
but to prolong the life of these more costly linings. The importance of protecting the ladle shell has increased as higher conductivity linings are used and
as the contact time of steel in the ladle has increased. A nominal thickness
of a high strength board insulation placed against the shell has decreased the
shell temperature in 70% alumina-lined ladles by at least 56C (100F). The
decreased temperature gradient through the working lining effected by the
188

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.

Table I. Compressive Properties-(Average Typical Values 960 kg/m3 at


(60 Ib/ft3), 1.27-cm (?'iff
in. thickness)
pressure

WPa)

(psi)

3.4
13.8
27.6
41.3
55.1
68.9

500
2000
4000
6000
8000
lo000

Heat treated 24 h at temuerature


Oven dried
316C (600""F)
649C (1200'F)
149C (300F)
DUL
PC
DUL
PC
DUL*
PC'

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

*DUL = Deflection Under Load (Yo)


tPC = Permanent Consolidation ('70)

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

Table 11. Compressive Properties


Compressive strength

(MW

(Psi)

21.2
40.4

5% deformation
10% deformation

3080
5870

Table 111. Percent Shrinkage of Board Insulation at Various Soaking Heats


Dimension

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

Table IV. Recorded Shell Temperatures on Insulated Ladles for Continuous


Caster Heats
Heats on
ladle

Shell Temperature ("C)


Ladle
Ladle
open
emptied
AT ("C)

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

Table V. Recorded Shell Temperatures on Uninsulated Ladles for Continuous


Caster Heats
Heats On
Ladle

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

Table VI. Recorded Shell Temperatures on Insulated and Uninsulated Ladles


for Continuous Caster Heats
~

Shell temperature ("C)


Ladle
Ladle
ooen
emotied
AT ("C)

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

Table VII. Shell Temperature Comparison of Insulated vs Uninsulated Ladles


(Time Period Surveved: 3 Mo)
Insulated Ladles

Uninsulated Ladles

25 1
170

149
225

No. of Heats Surveyed


Average Shell temperature ("C)

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 )

Fig. 1. Thermal conductivity vs mean temperature for various working lining


refractories.

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 )

Fig. 2. Thermal conductivity comparison of various insulating refractories.

Fig. 3 . Molten steel contact on board insulation sample.

192

6I

Fig. 6. Schematic of 185-ton steel ladle,


Johnstown Plant, Bethlehem Steel Corp.

Fig. 7.
ladle.

Location of thermocouple wires in insulated

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\

Fig. 8. Temperature profile of insulated dolomite-lined ladle.

195

Ceramic Engineering and Science Proceedings


Charles R. Beechan
The American Ceramic Society, Inc., 1986

Measurement of Properties for Use with Finite


Element Analysis Modeling
M. A. STETT
National Refractories & Minerals Corp.
P.O. Box 877, Pleasanton, CA 94566
Early attempts atjhite-element analysis modeling ofstresses in a rotary kiln using room
temperature or etimated high temperature data yielded stresses in excess of product
strengths, yet the products in the model were being used successfully in practice.
Capabilities were therefore developed to measure at-temperature properties to be used
for thermal and mechanical jnite-element analysis modeling. These properties include
hot-wire thermal conductivity, thermal expansion, thermal dilation under load, creep,
speciJic heat, Youngs modulus, and Poissons ratio.

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

= Activation energy, kJ/mol


= 0.0083114 kJ/mol.K

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

in Fig. 12. Modulus of elasticity (secant modulus) is calculated by dividing


a stress value by the axial strain observed at this stress. Poissons ratio is
calculated by dividing diametral strain by axial strain, usually at 13.8 MPa
(2000 psi). Yield strength is the stress at which 0.2% axial strain occurs. Figure
13 shows stress-strain curves for a direct bonded 60% MgO brick as a function
of temperature. Note how the brick is more rigid at either 1093C (2000F)
or 1316C (2400F) than it is at room temperature. Table I1 shows the modulus
of elasticity and Poissons ratio for this 60% MgO brick that were derived
from Fig. 13. The assumption of a constant Poissons ratio that is used with
pulse velocity methods can be seen to be faulty. Neither resonance testing at
temperature nor room-temperature dynamic testing of reheated specimens
shows the drop in modulus of elasticity at elevated temperatures. Early applications of data generated by this method have shown improved accuracy over
the use of data generated by other methods.

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.

*MTS Systems Corp., Minneapolis, MN.

Table I.

Comr>arisonof Calculated vs Measured Heat CaDacitv at 1200C


Heat capacity, (J/g.K)
Calculated
Measured

60% MgO brick A


60% MgO brick B
60% MgO brick C
8% RC MgO-C
13% RC MgO-C
19% RC MgO-C
45% A1203castable
60% A1203castable
85% Al,03 castable
w/Cr,O,

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

Table 11. Compressive StresdStrain Data for a 60% MgO Brick


Test
temperature
C (OF)

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

*at 1500 psi

Fig. 1. Hot-wire thermal conductivity test sample


configuration.

200

Fig. 2.

Hot-wire thermal conductivity data acquisition system.

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

Hot-wire thermal conductivity summary printout

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

Fig. 4. Sample hot-wire thermal conductivity plot in English units.

Fig. 5. Six-station dilatometer.

203

Fig. 6. Thermal dilation plot.

inn

Fig. 7. Creep deformation plot.


204

Fig. 8. Drop calorimeter.

Fig. 9. High temperature material


test system furnace.
205

Fig. 10. High temperature material test


system control panel.

206

Fig. 11. High temperature material test


system sample configuration.

207

50

Urnax

I
I

1
I

OG

Ea

Straln(0XH)l)

Fig. 12. Typical stress-strain behavior of a monolithic


refractory.

Fig. 13. Stress-strain of 60% MgO brick.

208

Ceramic Engineering and Science Proceedings


Charles R. Beechan
The American Ceramic Society, Inc., 1986

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^.^,^

The need for an improved understanding of the thermomechanical


response of the refractory lining requires the use of more advanced analytical
tools such as an appropriate finite element computer program which
incorporates the behavior exhibited by refractory linings. Several of these
program capabilities necessary for the analysis of cylindrical refractory lined
shells have been previously identified.4,5

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

(Manufacturer B). A plot of this data (Fig. 7) provides a comparison. The


purpose of this study was not to diminish the usefulness of dynamic modulus
data. For the structural engineer, the static modulus provides a more realistic
property for structural analysis. However, for the refractory engineer, the
dynamic modulus assists in ranking the refractoriness of the material.
The material data of Type 2, Manufacturer B, was chosen for the revised
analysis since this 70% alumina brick was most similar in all aspects to the
manufacturer A 70% alumina brick used in the ladle tests and original analysis.
Stress/strain curves for the Type 2 materials are shown in Fig. 8.3
A revised elastic solution was first conducted using the temperaturedependent static modulus data for the Type 2 material described in Figs. 7
and 8. The results of this analysis showed shell stresses considerably higher
than the test results. Since the circumferential strain in the region of the hot
face is approximately 0.370, the analytical response of the material in the region
of the hot face is not according to the stress/strain material behavior shown
schematically in Fig. 9. The result is excessive thermal expansion stresses are
developed in the working lining and in the restraining shell. It should be noted
that this response is similar to the original analysis when a dynamic modulus
is used. When using the dynamic modulus, however, the thermal expansion
loads are even more severe since the dynamic modulus is developed with exceedingly small stresses resulting in a considerably steeper tangent and a considerably greater elastic modulus.
Since the elastic analysis using static modulus was inadequate, the analysis
method for the finite element model was converted to a nonlinear elastic/plastic
procedure. The material data was converted to bilinear stress/strain curves
as described in Figs. 10 through 12. The material properties for the 70% highalumina refractories are summarized in Table 11. The only condition applied
to the ladle was the thermal expansion of the lining. The temperature/time
curves for the working lining cold face and shell are described in Fig. 13.
The yield points and the two slopes of the bilinear curves were made based
on a best visual fit. That is, for the expected strain range, a balance of energy
(stresdstrain areas) above and below the test curve was preserved. Cyclic
stresdstrain data would provide considerable information on the nonlinear
material property data. This information was not available, however, since
only a one-cycle load was considered, the material data used appears
appropriate.
Results of Analysis

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

IC. A. Schacht and E. V. Abarotin, Structural Behavior of Teeming Ladles Exposed to


Clean-Steel Operations. Association of Iron and Steel Engineers Annual Convention, Pittsburgh,
PA, September, 1983.
2W. R. Alder, Stress/Strain Testing of Refractories, Kaiser Refractories Center for
Technology, Kaiser Aluminum and Chemical Corporation.
3M. A. Hartsock, Stress/Strain Data on Ladle Brick, Technical Memorandum, Kaiser
Refractories Center for Technology, Kaiser Aluminum and Chemical Corporation, July 6, 1983.
4C. A. Schacht and J. A. Hribar, An Elastic Analysis of a Refractory Spring Arch, Am.
Cerurn. SOC. Bull., 53 [7] (1974).
C. A. Schacht, Fundamental Considerations in the Structural Evaluation of RefractoryLined Cylindrical Shells, Iron Steel Eng., p. 45, June, 1982.
J. DeSalvo & J. A. Swanson, ANSYS Users Manual, Swanson Analysis Systems, Inc.,
Houston, PA.

Table I. Comparison of Dynamic Modulus and Static Modulus for 70%


Alumina Brick
Temperature
C

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

Values defined in Ref. 3.

Table 11. Material Data


Temperature
C

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

*Data extrapolated beyond the maximum test temperature of 1200C.

212

'

7 0 PERCENT ALUMINA
BRICK

FIRECLAY BRICK

LAD!,

SHELL

INSULATING BRICK

Fig. 1. Ladle wall lining.


TYPICAL 3 0 SOLID ELEMENT

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

Fig. 2. Radial slice model of ladle wall.

213

.,

TVPICAL THROUGH THICKNESS


INTERFACE ELEMENTS AT

VERTICAL RADIAL
PLANES OF
SYMMETRY

CIRCUMFERENTIAL JOINT IN

VERTICAL RADIAL PLANESOF


SYMMETRY WITH INTERFACE
ELEMENTS
HORIZONTAL RADIAL PLANES
OF SYMMETRY WITH
INTERFACE ELEMENTS

L*g+xr
Y

HORIZONTAL RADIAL

WORKING

BACKUP LINING

PLANES OF
SY MM ETR Y

Fig. 3 . Boundary conditions for model.

TEST RESULTS OF
SECOND LINING
ANALYTICAL

10

TIME, Hours
Fig. 4.

Shell wall stress vs time.

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

Fig. 5. Circumferential compressive stress gradients (ksi) through the lining at


various time intervals.

failure

I
I
I
I

ELASTIC MODULUS=E.

=- Sa

ea

YIELD STRESS= Sy

I
I

I
lea

!=Y

2
STRAIN

Fig. 6 . Stress/strain of refractory brick

215

10'

MANUFACTURER
(dynamic data )

6-

5MANUFACTURER B
(static data )

4-

32-

----

type I /
-/--

\type

10

10

12

1200

STRAIN

5
x lo3

Fig. 8. Stress/strain data for 70% alumina brick.

216

ELASTIC

SOLUTION (DYNAMIC MODULUS)

ELASTIC SOLUTION (STATIC MODULUS)


ELASTIC/PLASTIC

SOLUTION

STATIC STRESS/STRAIN
AT HOT FACE

2
STRAIN

4
x

103

Fig. 9. Impact of material property data on solution.

STRAIN

Fig. 10. Stress/strain at OOto 8OOOC.

217

lo3

RESPONSE

"1 50r

40

In

STRAIN

x 1z3

Fig. 11. Stress/strain at llOOC.

STRAIN

Fig. 12. Stress/strain at 120OOC.

218

lo3

: 8-

'$-*OL

PREHEAT

----ANALYTICAL

!y);EATL(

RESULTS
TEST RESULTS

COLDFACEOF
WORKING LINING

TEEM

K
3

w
n

5I-

1012
TIME , Hours

Fig. 13. Temperature-timeplots of ladle wall.

320

280.

TIME

Hours

Fig. 14. Shell wall stress vs time.

219

1 4 '6

Ceramic Engineering and Science Proceedings


Charles R. Beechan
The American Ceramic Society, Inc., 1986

Compressive Strength and Creep Behavior of a


Magnesium Chromite Refractory
RALPH F. KRAUSE, JR.

National Bureau of Standards


Gaithersburg, MD 20899
The compressiue strength of a magnesium chromite refactoy in nitrogen was measured
by rapidly loading specimens to failure at several temperatures up to 160OOC. Strength
retrogression was observed at temperatures above 120O0C. The creep behavior of the
refract0y in nitrogen was measured as a function of compressive stress in the range
from 1.4 to 5.6 MPa and as afunction of temperature in the rangefrom 1300 to 1600C.
A nitrogen atmosphere was used to suppress distillation of CrO, Generally, the
experiments were terminated when the specimens sustained from 0.01 to 0.02 creep
strain. The creep strain (E) at a given stress (a) and a given absolute temperature (T)
was represented by the followingfunction of time (t), E = C ,'"t where (C) depends on
stress and temperature. The time exponent (m) was evaluated as less than unity,
indicating a strain-hardening model, and was independent of stress and temperature
within the precision of measurements. The creep strain rate was represented by the
~ ) exp (- Q/RT), in which (R) is the molar gas conrelationship, (dE/dt) = A E ( ~ - ~ ' o"
stant. The material constant (A), the stress exponent (n), and the activation energy
(Q) were evaluated from a least squares J t of this relationship to the creep data at
constant strain.

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

The sample of refractory supplied2was a cross-sectional slice (9 mm x 62


mm x 102 mm) of a manufactured brick from current production. Test
specimens were diamond-sawed from the sample and diamond-ground with
a 50 pm finish to make bearing faces flat, parallel, and perpendicular to
adjacent sides. These specimens (nominally 8 mm x 9 mm x 18 mm high) were
used in compressive strength tests and in a series of creep tests described below.
Test Environment
During the high temperature tests, the refractory specimens were kept in
a nitrogen atmosphere to suppress oxidation and subsequent distillation of
chromia,

CrzO,

(S)

4-

3
2

-002 (g) =2Cr0, (g)

(1)

At 1600C the minimum vapor pressure of MgCr20, (s) occurs with an


oxygen partial pressure of about
atm., At higher oxygen pressures, the
partial pressure of CrO, (g) becomes predominant and increases with increasing oxygen pressure. When the partial pressure of oxygen is less than
atm, the partial pressure of Cr (g) becomes predominant and increases with
decreasing oxygen pressure. A flow at 500 mL/min of 99.99 vol% nitrogen
was maintained through a gas-tight furnace to keep decomposition of the
MgCr,O, specimen at a minimum. An alumina tube (100 mm x 28 mm inside
diam) surrounded the specimen in the center of the hot-zone of the furnace
and was supported on legs to clear both the furnace floor and ceiling by 25
mm. In this way the furnace interior was protected from exposure to any
chromium vapor species. The furnace interior remained uncontaminated while
gas circulated freely around the specimen, leaving a slight film of chromia
condensed inside the protection tube near its openings.
The gas-tight box furnace had a hot-zone cavity (150 mm cube) that was
radiantly heated by molybdenum disilicide resistive elements and could be
controlled to operate at a temperature as high as 1600C. Figure 1 shows a
test specimen as mounted between 99.8 wt% recrystallized A1,0, discs
(5 mm x 19 mm diam) to prevent contact between the specimen and silicon
carbide loading rods (19 mm diam). New discs were ground flat and parallel
for each test and were easily separated from the specimen and the loading rods
following a high temperature run. The loading rods protruded into the center
of the furnace cavity through upper and lower ports which were made in the
stainless steel shell and alumina fiber insulation of the furnace. The loading
rods were supported and aligned by set screws in socket fixtures that had gastight seals with the furnace. The upper fixture was attached to the underside
of a moveable crosshead in a frame and was surrounded by a bellows assembly
between the crosshead and the furnace top. The lower fixture was attached
to a load cell on the frame and was surrounded with a bellows assembly between
the load cell and the furnace bottom. Water from a controlled 24C constant
temperature bath circulated through these fixtures to avoid uncertain thermal
deformations, which would be especially troublesome in the creep
measurements discussed below, This circulating water also cooled the rubber
seals of the front door of the furnace and the radiation shields which were
placed above and below the furnace shell. The furnace was heated from
ambient to 1200C in about 20 min and thereafter about 20 K/rnin to attain
the test temperature. After reaching temperature, approximately another hour
22 1

was required for steady-state temperature equilibration. The temperature of


the furnace cavity was controlled within kO.5 K and was determined by a
calibrated Pt and 6% Rh vs Pt and 30% Rh thermocouple.
Compressive Strength Measurements
The furnace was established in the frame of a universal test loading
machine. The gear-driven crosshead of the machine was used at a constant
speed of 0.5 mm/min to apply uniaxial, compressive loading on a specimen
through a hemispherical block of silicon carbide. Loading was indicated by
a linear strain gauge type of load cell and was recorded on a constant-speed
chart. The load cell was calibrated at the full scale of the chart with a known
10 kg mass acting at the local 9.801 m.s-* acceleration of gravity. Calibration was performed with the furnace at the elevated temperature of a given
test to avoid any systematic error due to thermal changes in the spring action
of the bellows attached to the load cell. Alternative proportional chart scale
factors besides unity (2,5, 10,20, 50, and 100) allowed larger loads to be read
within k0.2Vo full scale.
Figure 2 shows two examples of typical loading versus displacement curves
for specimens of the magnesium chromite refractory. The dashed curve, which
represents a test at 1200"C, is similar to that obtained in a room temperature
test. In these tests, failure of the specimen occurred suddenly. The solid curve,
which represents a test at 1500"C, is similar to all tests conducted at
temperatures at 1300C and higher; broadening of the peak load is due to
specimen creep. Figure 2 indicates that the displacement, which was deduced
from the chart and crosshead speeds, corresponds to about 2% rupture strain
at the peak loads.
Figure 3 shows the results of duplicate tests on separate specimens at room
temperature in air and at 1200, 1300, 1400, 1500, and 1600C in nitrogen.
The compressive strength for a given specimen was calculated from the
observed peak load divided by its initial cross-sectional area. The compressive
strength of the magnesium chromite refractory appears to decrease at
temperatures above 1200C and at 1600C is about one-third of the room
temperature value.
Compressive Creep Measurements
Creep specimens of the refractory were mounted in the same apparatus
as that used for the compressive strength measurements. A preload of 50 N
was applied to a specimen prior to heating in order to maintain alignment.
Crosshead movement was controlled automatically by the test machine to
accommodate thermal expansion during heat up and to maintain the preload
within 10% variation. Temperature equilibration of the loading train at the
test temperature was indicated by a steady crosshead position. A linear voltage
displacement transducer, calibrated with gauge blocks, was used to monitor
the crosshead displacement resulting from the specimen deformation. The
transducer was sensitive to k 1 pm displacement which corresponds to about
k (5)
creep strain. A creep test was initiated by application of a test
load in the range from 100 to 400 N. The load was held constant within f0.5%
full scale chart throughout the test by automatic adjustment of the crosshead
position, using intermittently a crosshead speed of 0.8 mm/h. Variation in
stress due to specimen deformation during the test was assumed negligible.
Creep strain was measured as a function of time following the initial elastic

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.

Analysis of Creep Data


The compressive creep strain (E) of a given specimen under a constant
stress and at a constant temperature was found to be represented within 1%
by the following primary creep function4 of time (t)
(2)

& = 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

'W. T. Bakker, S. Greenberg, M. Trondt, and U. Gerhardus, Am. Ceram. SOC.Bull., 63


870-6 (1984).
2M. E. Washburn, private communications, The Norton Company, Worcester,
Massachusetts, March 9, 1984.
?T. Sata, T. Sasamoto, H. L. Lee, and E. Maeda, Rev. h i . Hautes Temp. Refract., 15
237-48 (1978).
45. D. Lubahn and R. P. Felgar, p. 157 in Plasticity and Creep of Metals, John Wiley and
Sons, Inc., New York, 1961.
SJ. T. Boyle and J. Spence, pp. 12-13 in Stress Analysis for Creep, Butterworths, London,
1983.

Table I. Values of the coefficients of Eq. 4 for the creep of magnesium


chromite refractory at 1'70 strain
0.74 k 0.16
m
n
2.26 f0.23
Q, kJ/mol
364 +. 29
log, A"
12.95 f 1.97
Number runs
9
Residual standard
deviation of
f0.28
log' (dddt)
Corresponds to stress in MPa and time in h. The uncertainties are the standard deviations
of the respective coefficients.

224

S i c rod a t t a c h e d
with bellows t o
crosshead

Sic rod attached

with bellows to

load cell

Fig. 1. Schematic of compressive loading of


specimen.
8000

6000

z
6
4

4000

2000

0.1

0.2

0.3

0.4

0.5

DISPLACEMENT, rnm

Fig. 2. Typical compressive loading tests conducted at constant


0.5mm/min displacement rate for magnesium chromite refractory specimens (8mm x 9 mm x 18 mrn high) in nitrogen at
120OOC (dash) and 150OOC (solid).

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

Fig. 4. Typical experiment for compressive creep of a


magnesium chromite refractory specimen in nitrogen, in this case
at 1400OCunder an applied stressof 2.25 MPa. The circles denote
observed values, and the line represents Eq. 2 fitted by a least
squares method.

226

-z

-3

-4

4
K
I-

fn

-5

W
W

-6

21

-7

Fig. 6. Time exponent (m) as the slope of log, of creep


strain vs log, of time at various temperatures of a
magnesium chromite refractory under applied stressof 3.5
MPa in nitrogen. The circles, hiangles, and squares denote
observed values for separate specimensat temperatures of
1400,1500, and 16OO0C,respectively.The lines represent
the log, of Eq. 2 fitted by a least squares method.

227

-6

W
I-

<

=
I

-8

3
I-

-9

0
-

log, (STRESS. M P d

Fig. 7. Stress exponent (n) as the slope of log, of stress


for a magnesium chromite refractory in nitrogen.The circles
are observed strain rates that were temperature corrected
to 15OO0C,using the fitted value (Q)in Eq. 4, and the line
represents the log, of Eq. 4 fitted by a least squares
method.
-5

-6

-7

-8

lOOOlT

Fig. 8. Activation energy (Q) as the slope ( - Q/R) of


log, of strain rate at 0.01 creep strain vs absolute reciprocal
temperature for a magnesium chromite refractory in
nitrogen. The circles are observed strain rates that were stress
correctedto 3.5MPa, using the fitted value (n)in Eq. 4, and
the line represents the log, of Eq. 4 fitted by a least squares
method.

228

Ceramic Engineering and Science Proceedings


Charles R. Beechan
The American Ceramic Society, Inc., 1986

Optimizing Corrosion-Resistant Monolithic


Performance through the Use of Dual Lining
Systems
CURTISE. ZIMMER
Sauereisen Cements Co.
160 Gamma Dr., Pittsburgh, PA 15238
A properly selected and designed combination of materials has evolved that ofers
excellent resistance to chemical, thermal, and physical abuse common to Jue-gas
systems. The concept of chemically resistant membranes top-coated with one or more
chemically resistant linings of inorganic silicate cements is now being recommended
for applications in ducts and stacks.

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

First line of defense


Chemicallmoisture-resistant
monolithic surfacing

Permanently flexible
elastomerlc expansion

a+.,

iur

eL,
,

% -,

g2&! &

9@-

Second line 01 defense


Flexible chemicallmolstureresistant membrane

:*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

Fig. 3. Gunite application of inorganic lining over


membrane-coated steel substrate in duct.

234

Fig. 4. Steel liner protected with membrane/monolithic system.

235

Ceramic Engineering and Science Proceedings


Charles R. Beechan
The American Ceramic Society, Inc., 1986

Application of Vibratory Castables in Petrochemical

Industries
SUBRATA
BANERJEE

Gunning Refractories, Inc.


P.O. Box 267, South Webster, OH 45682
In recent years, the use of vibration castables has been recognized by petrochemical
industriesfor giving better performance and easier installation. Primary uses have been
in the iransfer lines which have been the most critical problem areas because of increased
reaction temperatures. Overhead lines, reactor and regenerator vessels are now becoming popular for vibration casting. Cyclones are more obvious areas for application but
they need to be redesigned for installation practicality. An optimum balance between
performance and thermal conductivity is needed to obtain best results. The obvious
benefits of uniformity and superior properties of vibration castables are discussed.

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

cyclones need to be changed to facilitate vibration casting. Gasifiers, part of


the regenerator and reactor vessel, are potential areas for vibration casting.
The objective of this paper is to identify the specific advantages of vibration casting, particularly with the advent of low moisture technology, over
other methods of placement in most of the refractory applications in oil
refineries.
Specific Application
The exceptional properties of hydraulically bonded, vibration-cast refractories have been published el~ewhere.~
The material is mixed in a paddle-type mixer with the appropriate amount
of water. A collapsible form is placed inside the metal pipes made to provide
correct and uniform diameter of the lining. Air vibrators are attached both
on the outside of the metal pipe as well as in the inside of the forms (wherever
the diameter of the pipe permits). The wet mix is then placed in the space
between the form and the shell with the vibrators running in the specific areas.
Installations are carried out in batches depending on the size of the lining as
well as the available equipment of the contractor. After at least 24-h curing,
the forms are stripped and the lining is then inspected for cold joints, voids
or any other defects. They can be patched effectively if necessary. The drying
is then carried out at the manufacturers recommended schedule before shipping or installation in place.

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.

Table I. Transfer Line Refractory Materials


Cast installation
Vibration
Pour
A1203

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)

58.6 (8500) 48.2 (7000)37.9 (5500)


- 0.22

7.5

239

- 0.22

10.0

-0.11
14.0

Table 11. Overhead Line Refractory Materials


Cast installation
Vibration
Pour
A1203

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)

34.5 (5000) 27.6 (4000)


- 0.3

- 0.3

14.0

18.0

Table 111. Refractorv Materials for Cvclones


A

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
@
@

Cast installation with vibration


B
C

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

10.2 (16000)124.0 (18000)


- 0.3

- 0.2

5.0

3.0

Table IV.

Refractory Materials Regenerator, Reactor, and Gasifier Walls


Cast installation
Vibration
Pour

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

Table V. Refractorv Materials for Burner Blocks (CO Boiler)


~

Cast installation by vibration

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.

Refractory Materials for Sulfur Burning and Recovery Units


Cast installation by vibration

66
30
0.9
1.6
1.o
< 0.2

A1203

SiO,
Fe@,
TiO,
CaO
Alkalies

Vo Water for placement


Bulk density, kg/m3 (lb/ft3)
@ 104C (220F)
Porosity, Vo
@ 104C (220F)
@ 955C (1750F)
@ 1372C (2500F)
@ 1593C (2900F)
MOR, MPa (psi)
@ 104C (220F)
@ 955C (1750F)
@ 1372C (2500F)
@ 1593C (2900F)
CCS, MPa (psi)
@ 104C (220F)
@ 955C (1750F)
@ 1372C (2500F)
@ 1593C (2900F)
Linear change, Vo
@ 955C (1750F)
@ 1372C (2500F)
@ 1593C (2900F)

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

Ceramic Engineering and Science Proceedings


Charles R. Beechan
The American Ceramic Society, Inc., 1986

Microstructural Aspects of Microsilica-Blended High


Alumina Castables
A. SELTVEIT
SINTEF, Div. of Metallurgy
N-7034 Trondheim NTH, Norway

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).

5H.-J.Kuzel, Crystallographic Data and Thermal Decomposition of Synthetic Gehlenite


Hydrate, N . Jahrb. fur Mineralogie, Monatsheft, 319-30, (1976).

245

Table I.

Chemical Analysis and Physical Properties of the Raw Materials

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

Table 11. Composition of Castables I and I1


Alumina aggregate
Microsilica
Reactive alumina
High-alumina cement
Dispersing agent
Water

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

Table 111. Temperature-Dependent Changes in the Mineralogical Compositions of Castables I and I1


Temperature

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,

Fig. 1. SEM fracture micrograph of hydrated paste


at 4OoC (bar = 100 pm).

Fig. 2. Typical microstructure of a castable hydrated


at 4OoC (bar=4 pm).

247

Fig. 3. SEM fracture micrograph of castable at 4OOOC


(bar = 4 pm) .

Fig. 4. Polished section of castable I at 4OOOC


(bar = 40 pm).

248

Fig. 5(A-C). EDX microanalyses of points 1-3 in


Fig. 4.

249

Fig. 6 . Polished section of castable I at 4OOOC


(bar=20 pm).

250

Fig. 7(A-C). EDX microanalyses of points 1-3 in

Fig. 6 .

25 1

Fig. 8. SEM fracture micrograph of castable I at


800OC (bar = 4 pm).

Fig. 9. SEM fracture micrograph of castable I1 at


80OOC ( b a r = 4 pm).

252

Fig. 12. SEM fracture micrograph of castable I at


12OOOC (bar = 4 pm).

Fig. 13. SEM fracture micrograph of castable I1 at


1200C (bar = 4 pm).

254

Fig. 14. Polished section of castable I at 120OOC


(bar = 10 pm).

255

Fig. 15(A-C). EDX microanalyses of points 1-3in


Fig. 14.

256

Fig. 16. SEM fracture micrograph of castable I at


1400OC (bar = 40 pm) .

Fig. 17. SEM fracture micrograph of castable I at


14OOOC (bar = 4 pm) .

257

Fig. 18. SEM fracture micrograph of castable I1 at


140OOC (bar = 4 pm).

Fig. 19. Polished section micrograph of castable I at


14OOOC (bar = 100 pm).

258

hot modulus of rupture o f


concretes after firing for 12 h
I

" 1

40

w)o

800

Temperature I"C1

1600

12bo

Fig. 20. Hot modulus of rupture of castables I and


I1 after firing for 1 2 h.

.,1

10

400

EM)
1200
Temperature ["CI

1600

Fig. 21. Apparent porosity and bulk


density of castables I and I1 as a function of temperature.

259

"----

--------

Fig. 22. Cold and hot modulus of


rupture of concretes after firing for 12
h (A. Seltveit et a]., Advances in
Ceramics 13).

Fig. 23. Total composition of castables I and 11.

260

Ceramic Engineering and Science Proceedings


Charles R. Beechan
The American Ceramic Society, Inc., 1986

The Effects of Curing Temperature and Times on


Low-Moisture Trough Castables
ROBERTA. HOWEand JOHNA. KANIUK

North American Refractories Co.


3127 Research Dr., State College, PA 16801
The strengths and densities of huo low moisture trough castables were measured under
various laboratory environments representing conditions that fiequently occur in actual
practice. These results were then compared to properties measured during standard
laboratory preparation conditions and found to be signijcantly diferent

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

Fig. 1. The effect of curing time on strength.

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

Fig. 2. The effect of curing time on bulk density.

v)

1000-

x MIX A
MIX B

Lrl

t-

750-

fx

v)

500-

3
-I
3

250I

230

CURING TEMPERATURE, O F

Fig. 3 . The effect of curing temperature on slrength.

265

450

3.0C
0

2.9C

Icn

w 2.8C
0

_I

2.7C

2.6C
CURING TEMPERATURE, OF

Fig. 4. The effect of curing temperature on bulk density.

40-

30-

'X

BULK DENSITY
SLAG RESISTANCE

x DRIED STRENGTH

20 10 I

?4 WATER ADDED

I
9

Fig. 5. The effect of water content on strength, bulk


density, and slag resistance.

266

Ceramic Engineering and Science Proceedings


Charles R. Beechan
The American Ceramic Society, Inc., 1986

ANCHOREX Anchoring System


E. OLSEN
Hijganis AB
Box 501, S-263 01, Hbganis, Sweden
The wrecking of old refactory linings has always been a diflcult and time-comsuming
job. A new anchoring system has been developed which cuts down the removal to onehalf the time. A new molding system has also been developed, together with the
anchoring system, which saves a lot of valuable installation time.

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

Also in constructions where there are intermittent conditions there is an


advantage as the cracks seems to run right between two anchors and then
around the anchor, following the dry joint. This means that you can in a way
control the cooling cracks by the way you place the anchors.
The System has been in practical use for almost two yr, mainly in cement
works in the wear zones. There has been no sign that there should be less
lifetime expected with this system compared to a conventional monolithic
lining. On the opposite, it seems to give longer lifetime.
The system is also being used in steel industry as in ladle roof where the
lining has to be replaced every week. By cutting the nuts on the outside and
turning the roof upside down, the remaining lining will fall out from its own
weight.
The benefits with this system can be summarized:
(1) Removal of lining is considerably easy.
(2) Partial repairs can be made easily.
(3) Full control of the installation with plastic molding system.

268

Ceramic Engineering and Science Proceedings


Charles R. Beechan
The American Ceramic Society, Inc., 1986

New High Chrome Fused Cast Refractory for Use in


Contact with Highly Corrosive Glasses
T. A. MYLESand F. KNEE
Refractories Div., Sohio Engineered Materials Co.
P.O. Box 832, Niagara Falls, NY 14302
A new ceramic oxide-based,fused-cast refactoy has been dewloped which has an
improued corrosion resistance to E-type textilejlberglass. The new material has a
primary phase of Cr203and A1f13 with a minor MgO spinel phase. The high percentage of the of the Rf13 phase is responsiblefor the improment in corrm*onresistance
when compared to otherfused-cast products which have similar Cr203contents, but
haw higher concentrations of a spinel phase. Experimental results are presented
depicfing corrosion rates and mechanismfor chrome refractries in contact with E-type
fiberglass.

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)

Additional phases are necessary in this system. Efforts to eliminate either


the spinel phase or the glass phase resulted in severe cracking. It appears that
the presence of these phases retards formation of extremely large plate-like
crystals in the center of the casting and results in a dense, uniform structure.
The phase diagram, Fig. 3, shows the composition of Monofrax B material
and the other compositions evaluated. The relative volume percentages for
each of the phases present in B are shown in Table I. The chemistry shown
in Table I1 compares Monofrax B and Monofrax E materials. The absence
of Fe20, and the lower MgO content of the B material causes a corresponding reduction in spinel content.
The technique used to evaluate corrosion resistance and glass compatibility
of the various compositions was the Owens-Corning Fiberglas bushing test.
The parameters evaluated were corrosion resistance, petrographic changes, and
stoning rate. Specimens were suspended in contact with E-glass for two to
four weeks at 1600C, with fresh glass additions made twice daily. Rate of
specimen attack was calculated both at, and below the melt line. A count was
made of trapped refractory fragments or recrystallized material generated
during the test period, and the specimens were sectioned to determine
microscopically the type and extent of corrosion at the glass-refractory inter270

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

US. Patent No. 4 490 474, December 25, 1984.


2H. L. Lee, and Sata Toshiyuki, Yogyo-Kyokui-Shi.86 [l] (1978).
)Private correspondence with R. Tressler, Professor of Ceramic Engineering, Pennsylvania
State University.

Table I. Typical Phase Composition of B


Content

Composition

75%
20%
3%
< 2%

R23

Spinel
Glass
Metal

(A10.52cr1 . d 0 3
Mg(A10.~7cr~,~~)03.~7
CaO -A1203-Si02
Cr

Table 11. Comparative Chemistry of B and E


(3203

A1203
MgO
Fe20,
Others

Ti

82.2%
13.7%
1.5%
tr.
2.6%

79.7%
4.7%
8.1%
6.1%
1.4%

Table 111. Corrosion Test Results


Days to cut 1 in. at melt line
Days to cut 1 in. below melt line

Slip-cast
chrome

247
438

318
504

250
305

Product Data Summary


Primary R203
Secondary MgO .R,03 spinel
Chemistry ('Yo)
Cr20,
82.2
A1203
13.7
MgO
1.5
Other
2.6
Bulk density
290 lb/ft3
4.65 g/cm3
Thermal expansion
100 1400 "C
8 . 0 10-6/"C
~
Electrical resistivity
@1400"C
10.2R-cm
Table IV.

Structure

O-

272

Fig. 1. Microstructure of Monofrax E; phases identified are: R = R203,S =spinel, M = metal, G =


glass, and V =void.

Fig. 2. Microstructure of Monofrax B; phases identified are: R = R,O,, S =spinel, M = metal, G =


glass, and V = void.

213

Cr 0

WMonofrax E

~ M o n o f r a xB

ASlip Cast Chrome

Fig. 3. Experimental composition field.

Fig. 4. Microstructure of Mondrax E after bushing


test; phases identified are: R = R,O,, S =spinel,
M = metal, G =glass, V = void, and T = test glass.

274

Fig. 5. Microstructure of Monofrax B after bushing


test; phases identified are: R = R 2 0 3 , M = metal,
G =glass, V =void, and T =test glass.
1.2

..... ,

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

Temperature (Deg. C/100)

... Monofrax E

.--Monofrax B

-Slip Cast Chrome

Fig. 6. Therm(a1expansion of the three types of chromic oxide products.

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

Fig. 7. Electrical resistivity of the three types of chromic oxide products.

276

Ceramic Engineering and Science Proceedings


Charles R. Beechan
The American Ceramic Society, Inc., 1986

Influence of Cement Raw Meal Composition on Lining Life


T. K. DAS, R.

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)

Vo of liquids at 145OoC=3.0 (Yo A1203)+2.25 (Vo Fe203)


To of liquids at 1338C=6.8 (YOFe203)if MA 21.38
Vo liquids at 1338C = 8.21 (To A120,) - 5.24 (To Fe203)if MA c 1.38
The results obtained with these tests showed that as the solidification
gradient increased, the thickness of the coating increased (Fig. 2). This can
be explained as the larger the difference between the liquids at 1338 and
1450C the larger the amount of material solidified with a reduction in
temperature.
Some extreme cases are shown in Fig. 3. The raw meal B, with a low
modulus of alumina and a low solidification gradient makes the liquid silicates
penetrate the refractory excessively, making it more susceptible to thermomechanical stresses. The raw meals E and F, both with high modulus of alumina,
avoid the wetting of the brick. This together with a high solidification gradient,
makes a thick coating unstable, subjecting the lining to frequent thermal
shocks. The raw meals A, C and D, are the ones with better behavior, since
they have a proper modulus of alumina, coupled to a convenient solidification gradient.

Correlation with Behavior in the Field


The results obtained with these tests and the behavior in the field are in
good agreement. For example, during the analysis of the data of a rotary kiln
it was found that the variations in the raw meal composition were directly
reflected in the coating formation and so in the shell temperature (Fig. 4).
When there is a solidification gradient between 3 to 5, with a modulus
of alumina less than 2, the shell keeps cool, with a good coating formation.
When the solidication gradient is high (SG < 10) the coating formed is too thick
and easily detaches due to its weight, subjecting the brick to thermal shock.
When the solidification gradient is too low (SG> 1) the coating is thin,
and the temperature of the shell is high. Figure 5 shows an impregnated
microstructure with a clinker of low modulus of alumina and low solidification gradient.
Conclusions
Based on the experimental results and their correlation with expedriences
in the field, it is concluded that to adhere and form a proper coating, two
important factors are dependent on the raw meal composition:
- The adherence force between the coating and the brick, and
-The thickness of the coating.
For the first factor, the modulus of alumina, MA, is an indicative
parameter of the clinkers capacity to penetrate the brick. The lower the
modulus of alumina, the better the adherence of the coating to the brick. For
the second factor, the solidification gradient, defined as the difference between
the amounts of liquids present at 1450, and at 1338C, determines the
thickness of the coating. The larger the solidification gradient, the thicker the
coating formed.
Bibliography

Advanced in Cement Technology, Ed. S. N. Ghosh, Pergamon, 1981.


The Chemistry of Cements, Ed. H. F. W. Taylor, Academic Press, 1984.
ConsiderationsOn The Subject Cement And Refractory Lining Materials As Seen Through
The Eyes Of The Refractory Industry, Walter Zednicek, Radex No. 3/83.
Reaction Test For The MineralogicalCharacterizationOf The Contact Zone Coating And
Basic Refractory Lining In Rotary Kiln Burning Zone, A. Wiesler, W. Munchberg, and J. A.

279

Imlach. Translation ZKG No. 9/82.


Electron Probe Microanalytical Investigations On Portland Clinkers, I. Older and H.
Koster. Translation ZKG No. 1002.

Table I. Properties of Magnesia-Chrome Brick


Density (g/cm3)
Modulus of rupture (kg/cm2)
Hot modulus of rupture at 1260C (kg/cm2)
Cold crushing strength (kg/cm2)
Apparent porosity (Yo)
Refractoriness under load (DIN 51053) (C)

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

Table 11. Raw Meal Compositions and Their Characteristics


CaO
Si02
A1203
Fe203

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

Fig. 1. Relation of alumina modulus to adherence.

10

SOLIDIFICRTION GRRDIENT,(SG),(%)

12

Fig. 2. Relation of solidification gradient to coating thickness.

28 1

14

SOLIDIFICRTION
GRRDIENT,(SG),f%)

0
N
(rnrnl

Fig. 3. Relation of solidification gradient to coating thickness and liquid penetration.


She1 1

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

Fig. 4. Variation of shell temperature and the amount of liquidsformed at 1338'


and 145OOC over a period of 10 d of cement kiln operation.

282

Fig. 5. Mapping of calcium showing the penetration


of the ZCaO-Fe,O, phase into the brick (bar = 1OOpm).

283

Ceramic Engineering and Science Proceedings


Charles R. Beechan
The American Ceramic Society, Inc., 1986

Importance of the Modulus of Elasticity on Basic


Refractory Brick for Cement Rotary Kilns
R. DE LA GARZA
Refractarios Mexicanos, S.A.,
Box 16, Ramos Arizpe 25900,
Coahuila, Mexico.

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

where L = half the length of the crack,


r = radius of curvature at the crack tip.
This factor reaches values of 102 for micron-sized cracks with radius of curvature in the order of interatomic distances.
The thermoelastic theory concludes that the crack initiation resistance
index, CIR, for brittle materials can be defined as:
CIR

[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 =

where y = surface energy or work to fracture.


From the CPR index, it is seen that to have a high resistance to crack
propagation under a thermal gradient, a brittle material must have a low fracture strain and a high surface energy.
285

This apparent discrepancy between the two theories is easily resolved if


one considers that they apply at different times and conditions. The thermoelastic theory applies before the crack forms, while the crack propagation
theory applies after the crack has formed.
The present work was conceived in view of the thermoelastic theory. It
was thought that to increase the peel spalling resistance of a direct-bonded
magnesia-chrome brick, it was convenient to reduce the modulus of elasticity, while keeping at acceptable levels the tensile strength. The other two
parameters, thermal diffusivity and thermal expansion, were not taken into
account, as it is difficult to modify them substantially without incurring great
compositional changes.
Evaluation of Properties
The Young's elastic modulus at room temperature was measured by the
flexural resonance method, according to ASTM-C-885. Thermal shock
resistance was determined in accordance with DIN-51068 and the VDEh
method.* The latter method consists in heating samples (200 x 35 x 35 mm)
up to 1350"C, for 45 min and afterwards placing them on a water-cooled copper plate. In both cases, thermal cycling was continued until the specimens
fractured. Refractoriness under load and weep were determined in accordance
with DIN-5 1053. Tensile strength, crushing strength, bulk density and apparent
porosity were all determined in accordance with ASTM standards. Thermal
expansion up to 1500"C, was measured in an automatic dilatometer.*
New Brick
The new brick (A) was formulated using Mexican high-grade synthetic
magnesia and high purity chrome ore. Its modulus of elasticity was achieved
by systematically adjusting the granulometrics of the various components. The
chemical composition of the new brick is presented in Table I, along with the
composition of other brand (B).
These brick were fired at a peak temperature of 1750C, for 8 h, under
a reducing atmosphere. The average properties for each brand are listed in
Table 11.
5.71-4.92
One complete brick of A and one of B, both 22.86 x 1 5 . 2 4 ~
cm in dimensions, were subjected to a high thermal gradient by placing them,
side-by-side, fully plugging the door of a laboratory gas furnace. In both brick,
the face of 15.24 x 4.92 cm was placed inwards toward the furnace. Once the
bricks were in place, the temperature of the furnace was increased from room
temperature at a rate of 250"C/h. After keeping the furnace at 1480"C, for
4 h, the gas flow was interrupted and the air continued blowing until the
temperature inside the furnace decreased to 300C. The maximum temperature
of the cold face (15.24x5.71 cm) during the test was recorded as 460"C, for
brick A and 480C, for brick B.
Two effects resulted from this operation. The brick A developed a single
and small crack perpendicular to the hot face, as indicated in Fig. 1. On the
other hand, brick B developed two massive cracks, one parallel and the other
perpendicular to the hot face. The crack parallel to the hot face was visible
at both faces of 2 2 . 8 6 ~15.24 cm, but not at the lateral faces of
22.86x5.71-4.92 cm, and it extended almost the 15.24 cm of width. This
crack was located at 10.79 cm from the hot face. The crack perpendicular to
the hot face was like the one on brick A, although not as small. These cracks

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

the contrary, a direct-bonded magnesia-chrome brick with a low fracture-strain


exhibited a pronounced tendency to peel spalling, in spite of having a high
strength.

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.

Chemical ComDosition of Bricks A and B (wt%)

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

Table 11. Average Properties of Bricks A and B


Prooertv

Brick A

Elastic modulus (E) lo9 N/mZ)


Flexural strength (S,) (106 N/m2)
Crushing strength (CS) (106 N/mZ)
Thermal cycles to fracture
DIN
VDEh
Thermal expansion ("C-' x
Creep at 1500"C, 24 h, 20 N/cmz (Yo)
Refractoriness under load, 20 N/cmZ, T,,,
Bulk density (g/cm3)
Apparent porosity (Yo)
Fracture-strain (SJE)

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

Table 111. Service Life of Bricks A and B


Client

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. 2. Scanning electron micrograph showing the lack


of adherence between the central chrome grain and the
magnesia surrounding it (bar = 100 pm) .

Fig. 3 . Scanning electron micrograph showing intercrystalline cracking in magnesia grains (bar = 100 pm) .

290

Other

Brick A

CUSTOMERS

Fig. 4. Service life of brick A.


Other

0
4 00

Brick B

DRYS

350

300

250
2 00
150

100

50
0

CUSTOMERS

Fig. 5. Service life of brick B

29 1

Ceramic Engineering and Science Proceedings


Charles R. Beechan
The American Ceramic Society, Inc., 1986

Corrosion of Ceramic Refractories in Synthetic Coal


Slags Determined by the Rotating-Cylinder
Technique*
SHERMAN
GREENBERG
and ROGERB. POEPPEL

Materials Science and Technology Div.


Argonne National Lab, Argonne, IL 60439
Of the refractories tested to date, those containing over 75% Cr203 are the most
resistant to corrosion by coal slag at temperatures up to 160O0C. Free magnesia is
deleterious to performance; other factors, e.g., aggregate sue and bonding, are also
magnesia is so great that some medium-chromia
important. The deleterious effect ofrefractories (50-60% Cr203)can be superior in performance to refractories containing high percentages of Cr203along with some free magnesia. Porosity and iron concentration, per se, are not deleterious to corrosion perjhrmance. Corrosion rate increases
rapidly with an increase in temperature and slag flow rate, but slag viscosity is not
a prima y variable. The MgO/FeO ratio of the slag may be of importance in determining corrosion behavior and, fi so, the control ofthis ratio may provide a pmctical method
of corrosion inhibition. Laborato y corrosion data agree gualitatiwly with the limited
available plant experience.

*Work supported by the U.S. Dept. of Energy, Advanced Research and Technology Development Fossil Energy Materials Program.

292

Ceramic Engineering and Science Proceedings


Charles R. Beechan
The American Ceramic Society, Inc., 1986

Monolithic Refractory Problems in a Gasifier


G.N. ZIRCZY

Intevep, S.A.
Caracas, Venezuela

Refractory materials must withstand a variety of aggressiue agents, hydrogen, steam,

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

of a gasifier. Refractory materials must withstand a variety of aggressive agents


like hydrogen, steam, sulfur, vanadium and erosive particles. The presence of
high conductivity gases makes the design of the reactor lining critical to prevent
gas penetration and hot-spot formation at the shell due to thermo-mechanical
failures. The correlation of desired physical properties and service conditions is
reviewed and suggestions are offered on lining designs.
Designing with brittle materials is more complex than with ductile metals.
Therefore, refractory lining design is largely based on experience, instead of being
based engineering principles. Development of refractory technology and refactory product improvement is the result of the combined efforts of the refractories industry and the consumers.
Gasifiers must generally be considered a more severe operation for the following reasons:
- The impurity level in coke is higher than in most crudes and petrochemical feedstocks.
- Pressures and temperatures are generally higher.
- Process vessel size will be significantly larger, thus chance of local stress
concentration is enhanced.

Brief Description of the Flexicoker Process


The unit is designed to process 52.000 B/D of heavy fuel with high sulfur
and vanadium content, to produce naphtha, gasoline, flexigas, and coke (Fig.
1). The coke produced in the reactor flows through the heater to the gasifier
and is reacted with air and steam to produce flexigas. The gas formed is used
to heat the coke proceeding from the reactor.
The process conditions in the gasifier are shown in Table I and the refractories details are shown in Table 11. The lining cross-section is shown in Fig. 3.
293

Problems Related with the Existing Refractory Design


(1) A destructive chemical reaction occurred between the refractory
castable and impurities of the slag.
(2) Major alkali and sulfur penetration was observed with some evidence
of vanadium pentoxide deposition.
(3) Severely laminated in dense-bed region and fibers-corroded to a depth
of 5 cm ( 2 in.). It was observed that some cracks originated at the anchor tips
of the refractory, creating a plane of weakness in the lining. The bottom area
of the gasifier showed most severe damage and failure.
(4) Hot-spot formation developed in the outer carbon-steel shell and partial melting of the refractory lining in the bottom area of the gasifier was
observed.
( 5 ) The gasifier was in operation only for three mo before the hot-spot
formation occurred.
(6) There was no evidence of refractory degradation in the dilute phase.
Analysis of Refractories from Slagged Area
(1) X-ray Diffraction: Major predominant phases were nepheline, albite,
anorthite, sillimanite, and corundum (Fig. 4).
(2) Scanning electron microscope: The fracture surface showed evidence
of sodium, vanadium and sulfure penetration. The microstructure revealed
that a portion of the aggregate melted to a glassy phase (Fig. 5 ) . Also a reaction zone was observed with the stainless steel fibers; they were removed by
corrosion (Fig. 6 ) .
(3) Composition of the slag (Fig. 7):
Sodium
2.0 wt%
Vanadium
20.6 wt%
Nickel
4.3 wt%
Sulfur
1.1 wt%
Evaluation of the Problem
(1) The microstructure showed evidence of slag attack by vanadium pentoxide which caused severe fluxing in almost all cases. The vanadium pentoxide
slag reacted with the calcium aluminate matrix in an abrasive-like action,
resulting in exposure of the grog grains. The corrosive action of the slag was
severe enough to cause expansion and even cracking. The presence of sodium
reduced the viscosity of the liquid phase formed that facilitated the further
transport of vanadium pentoxide through the liquid phase to the calcium
aluminate interface. Green to gray-green reaction zones which were friable
also resulted from the slag attack.
(2) Sulfidation produced stable sulfates. Their presence can cause a
volume change and thus generate cracks in the refractory. These cracks will
lead to more surface area in the refractory to be exposed to the reacting species
and also offer faster transport paths for them into the refractory. Therefore,
the net result of sulfur formation is probably enhanced refractory degradation. Sulfur in heavy oils generally attacks the refractory and tends to cause
extensive deterioration in refractory insulation.
(3) The impurities present in the fuel penetrated the lining, reacting with
the refractory to form a new eutectic composition that melted. Whether the
change in structure is caused by vitrification or chemical attack, the altered
294

structure has a different coefficient of expansion. As a result, a high stress


is set up and caused cracks to develop parallel to the hot face of the lining.

Key Design Considerations


(1) Operating conditions and their interactions with the refractory.
(2) The stress in both the lining and structural support.
(3) Shrinkage effect of the refractory.
(4) Anchor selection, spacing, and pattern.
( 5 ) Selection of the refractory material.
Conclusions and Recommendations
(1) Sulfur and vanadium pentoxide were responsible for the degradation
of the semi-insulating refractory. Sulfur combines with vanadates present to
form corrosive, low melting compounds. The matrix of the castable was the
primary area of attack. The most degradation of the refractory was due to
high porosities, which resulted in more extensive penetration of the very low
viscosity vanadate melts and reactants to cause high corrosion rates.
(2) Corrosion of refractories generally takes place by a simple dissolution mechanism that is influenced by the physical and chemical properties of
the materials. Thus, the selection of a dense refractory concrete of the superduty type with mullite aggregates, lower porosity, minimum glass phase, and
low alkali content will minimize the chance of fuel-ash corrosion and spalling
of the lining.
(3) The application of the dense refractory 1872 kg/m3 (117 lb/ft3)
raised the shell temperature of the vessel from 115" to 172C (240" to 342F).
(4) The crack at the anchor tips is due to stress concentrations around
the tips; during heat-up the anchors expand about two times as much as the
surrounding refractory. This problem can be eliminated by coating the anchors
with an organic material which will soften and burn out.
( 5 ) Anchors of the type 310 SS were selected and spaced on centers about
two times the lining thickness. The size of the anchors covered 60 and 75%
of the way through the lining which helps to avoid a plane of weakness in
the lining.
Major Contributing Factors That Improved the Thermochemical Behavior of
Refractory Concrete Lining in the Gasifier
(1) The selection of a dense refractory concrete, manufactured under certain specifications required for the gasifier, such as lower porosity, minimum
glass phase, low alkali content, and with mullite grog appear to improve
materials properties requirements such as shrinkage, slag penetration, thermal
expansion, and thermal shock resistance.
(2) The application of a dense single-component refractory concrete lining
allows the single layer to expand and contract more freely.
(3) Coating on the anchors prevents anchor refractory interactions and
reduces the cracking effect on the refractory due to thermal expansion of the
anchors.
(4) Reduction of the anchor size appears to have a beneficial effect on
crack formation.
Curing, Drying and Heat-up Rates
(1) Curing was accomplished keeping the concrete moist for 24 h.
295

(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.

Table I. Process Conditions of the Gasifier


Temperature
900 -925 C
Pressure
234 kPa
Atmosphere
co
4.63 1 kg .mol/h (10.209 lb .mol/h)
co2
1.711 kg.mol/h (3.773 lb:mol/h)
H2
3.030 kg.mol/h (6.679 lb-mol/h)
H2S
109 kg.mol/h (241 Ib.mol/h)
N2
11.213 kg.mol/h (24.720 lb.mol/h)
H*O
1.607 kg.mol/ (3.542 lb-mol/h)
S
3.1%
v20,
580 ppm
Na
11 PPm
Linear reheat change at 1095 C (2000 O F )

296

Table 11. Existing Refractory Lining Materials and Application


Refractory semi-insulating castable:
50.5 wtolo
A1203
40.5 wt%
SiO,
Fe203
1.8 wt%
Na,O
1.o wtvo
CaO
5.0 wt%
Ti02
1.2 wt%
Cold crushing strength at 1095C (2000F) 8.3 MPa (1200 psi)
Linear reheat change 070 at 1095C (2000F) 0.2070
Thermal conductivity
0.40 W/m.K
(2.8 Btu-in./ft2.h-"F)
Mean temperature
815C (1500F)
Fiber reinforcement: type 446 SS
Anchors: V-type 26 Cr 1 Mo
Method of application: gunning

Fig. 1. Simplified flexicoker flow plan.

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

Fig. 2. Gasifier vessel model.

LAMINATED
AREA
REFRACTORY
STAINLESS
STEEL FIBERS

Fig. 3 . Lining cross-section

298

19-1176

9- 338

NWALSIO~

NEPHELINE

(Nk.K)ALSI04

SYN

IIEPHELINE SVN

Fig. 4. X-ray diffraction of the reaction zone.

Fig. 5. Scanning electron microscope of the fracture surface.

299

Fig. 6 . Scanning electron microscope of the reaction zone.

Fig. 7.
slag.

Scanning electron microscope analysis of the

300

Ceramic Engineering and Science Proceedings


Charles R. Beechan
The American Ceramic Society, Inc., 1986

Corrosion Resistance of Ceramic Materials To HCl,


HNO,, and H2S04
JAMESP. BENNETT

Tuscaloosa Research Center, Bureau of Mines


U.S. Dept. Interior, University, AL 35486
Eight commerical ceramic materials (two red shale, huo fireclay, a silica, a silicon carbide, a carbon, and a high-alumina brick) were exposed for 11O-d petiods in HCl,
HNO,,and H.$SO&Acid concentrations rangedfrom 10 to 90 wt% and temperatures
from 50' to WOC. Cold w h i n g sirength, volume expansion, and weight changes were
determined. The leaching ojAl, Ca, Fe, K , Mg, Na, Si, and Ti ions is also discussed.
An accelerated autoclave procedure for determining volume expansion is proposed.

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

and monitored in the reactor by a type K thermocouple. A peristaltic pump


was used to withdraw, add, or circulate liquid in the system. The system was
continuously agitated by a variable-speed stirrer, while a condenser refluxed
any vapor and maintained the system at atmospheric pressure. Thirty samples
of 2.5-cm diameter x 5-cm. high (1 in. diameter x 2 in. high) were placed on
a 0.95-cm (%-in.) Teflon fluorocarbon polymer platform and positioned
vertically so that half of the sample was immersed in the acid solution and
half of the sample was exposed to the atmosphere above the acid solution.
Grooves cut in the upper surface of the platform allowed liquid to circulate
under each test specimen. The platform was prevented from moving by
embedding the supporting legs in layers of 6-mm glass beads.
Weight, cold crushing strength, microstructural, and visual changes were
determined on each test sample after exposure. Atomic abosrption analysis
was used for monitoring Al, Ca, Fe, K, Mg, Na, Si, and Ti ions in the leach
solution. An acid-filled vessel containing no test samples was used to provide
a control solution for establishing background ion concentrations. The acid
conditions investigated for brick exposure of 110 d in HCl, HNO,, and
H,SO, are listed in Table 11.
Two different techniques have been used to calculate dimensional changes
on red shale A and B and fireclay A and B brick samples exposed to various
temperature and pressure conditions in deionized water and 20-wtYo -HC1
environments. In the first method, the distance between tantalum (Ta) pins
cemented to opposite ends of a 18 x 4.8 x 2.9-cm (7% x 1%x 1%-in.) sample,
cut from full-size production brick, was measured. Two Ta pins, 0.6-cm
(%-in.) long and 0.5-cm (x6-in.) diameter with one end rounded to a 0.5-cm
(&in.) diameter hemisphere, were attached opposite each other at the center
of both ends of the 18-cm (7%-in.) dimension of the sample using a chemicalresistant epoxy, as shown in Fig. 2. Sample length was measured with a
cm ( 1 . 0 ~
in.), at the start and end
micrometer, accurate to 2.5 x
of a 30-d exposure to 20 wt% HCl and to deionized water at 90C.
The second method, based on thermal expansion measurements, utilized
test samples 0.5 cm (3/16in.) in diameter that were cored from brick specimens
and cut to a final size of 1.3-cm (%-in.) long. The samples were cored in the
same direction as the 18-cm (7 % -in.) sample length used for Ta pin dimensional
measurements. After a 30-d exposure the samples were heated in a dilatometer
to 700C and sample length changes were measured. Autoclaved samples were
used additionally as an accelerated method of determining the amount of linear
expansion of cored samples. The samples were exposed to 20 wt% HCl and
to deionized water in an autoclave for 2-h periods at temperatures of 150",
200", and 250C and pressures of 0.5, 1.5 and 4 MPa (80,220, and 580 psig),
respectively.
Results and Discussion

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)

y = ion concentration in solution,


x = days,
a,, a,, a, = constants.

A plot of ions leached from red shale A samples exposed to 40 wt%


HNO, at 90C is given in Fig. 3 and is typical of leach curves. Generally, the
Fe and A1 ions have the highest removal rates, followed by Ca, Mg, Na, K,
and Ti. Except in a few instances, silicon was not leached, indicating that the
siliceous bond or silicate mineral phases were not affected; this may explain
why cold crushing changes were small or not observed except for the highalumina brick.
A comparison of the weight percent of total ions leached from the ceramic
materials exposed to HCl for 110 d is shown in Fig. 4. The general trend of
increasing weight loss with increasing temperature or acid concentration
observed with sample weight changes is also noted with total ions leached.
A maximum total ion weight loss of 3.75 wt% is noted for red shale A at 90C
and 20 wt% HCl. As mentioned previously, the red shale and fireclay brick
with the highest porosity had the highest rate of total ion removal, a trend
noted also in HNO, and H,SO,. Ion removal from carbon, silica, and Sic
materials ranged from 0.0005 to 0.13 wt%. The high-alumina brick recorded
a high of 1.13 wt% total ion loss at 90C and 20 wt% HCl, most of it as the
A1 ion.
Total ion weiglht losses in weight percent for the ceramic materials exposed
to HNO, are shown in Fig. 5 . The largest total ions leached for any sample
occurred with red shale brick A in 40 wt% HNO, at 90C (2.79 wt'%)
303

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

Chemical and Physical Properties of Commercial Ceramic Materials

Zhemicai composition, wt% :


SiO,
A1203
Fe203
K2O
TiO,
MgO
Na,O
CaO
BaO
Carbon
Sulfur
Sic
Apparent porosity 070
Bulk density g/cm3
Cold crushing strength psi

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

Table IV. Percent Linear Expansion of Acidproof Materials After 30 d


Exposures in 20 Wt% HCl and Deionized Water at 90C, Atmospheric
Pressure
Brick

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

0.115 If: 0.030*


.044k .011

0.060
.019

A
B

.049+ .021*
.073f .036*

.031
.056

Fireclay:

'Single data point.


*Statistically significant change at 95 To confidence level compared to untreated speciment
(Student's t-test).
NOTE-Plus-minus (+) values are at 95% confidence level.

Table V. Percent Linear Expansion of Acidproof Materials Exposured for


2 h to Autoclave Conditions
Brick

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:

'Single data points for a11 values.

309

Condenrer

-Saluiion
Solutlon

12-L
Heating

inlet
outlet

flark

mantle

diameter by 2-in SpeCimln


flon plotform ond r u p p o r i r

eat solution

Bore
heoiinp

mantle

GlOsS

beadr

Fig. 1. Construction detail of reaction vessel.

Fig. 2. Measurementof linear distancebetween Ta pins attached to brick


sample.

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.

Total ions leached from ceramic samples in llOd of H,SO,


exposure.
Fig. 6.

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

Ceramic Engineering and Science Proceedings


Charles R. Beechan
The American Ceramic Society, Inc., 1986

Relationship of Creep Properties of Bauxite


Refractories with Microstructure
XIANCCHONC
ZHONG,GENGCHENC
SUN,and RUSHANYIN
Institute of Refractories Research
Luoyang, China
The creep properties at elevated temperatures of different grades of bauxite refactories
with and without additions of K f l , MgO,etc., h a w been studied by torsion and

compression test methods and correlated with phase composition and


microstructure. The creep mechanism is discussed, based on analysis of
parameters such as transient creep deceleration exponent (m), creep activation energy (AH)and stress exponent (n). It is concluded that creep behauior
is mainly determined by microstructural characteristics and controlled by glass
efect and crystar effect.

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.'

Analysis of Creep Parameters

Deceleration Exponent (m)f o r Transient Creep


It is found from our experimental results that during the transient creep
period, the amount of strain (E,) fits well with the following empirical
formula (correlation coefficient = 0.95):
E~ = Btm, i.e.,

log

E,

= lo@

+ mlog t

(1)

where t = time, rn = deceleration exponent, B = initial strain at first unit time.


It is also found that the m value varies little with stress increase, but is
increased appreciably with use of temperature6 (Fig. 4). There is a transition
point showing abrupt change of slope for grade I and I1 materials at
1120"-1130C which may be associated with the temperature of initial liquid
formation as deduced from Al,O,-Si0,-impurity oxide ternary ~ysterns.~

Steady-State Creep Rate (EJ and Creep Activation Energy (AH)


In Fig. 5, log E, (strain rate) is plotted against 1/T (temperature); creep
activation energy values (AH) are also shown.8 For grade I and grade I11
materials, there is a distinct transition point showing an abrupt increase of
slope with corresponding increase of AH values, indicating that some noticeable
change in creep mechanism has occurred. This transition point is 1120"-1130C
for grade I and 1050C for grade 111, which is in accordance with the transition point of the rn-T curve (Fig. 4), as well as with the critical temperature
from plastic to viscous flow Tv (Fig. 2). However, for grade I1 material, no
transition point in log E, - 1/ T relationship is observed. These results suggest
that there are differences in creep mechanism for different grades of bauxite
refractories at different temperatures.
Stress Exponent (n)
Figure 6 shows the logarithmic relationship between steady-state creep
rate ( E ~ )and stress (o), with calculated stress exponent values (n) shown.5
Since the n values are all close to unity (grade I1 0.6-0.7, grade I 1.0-1.2, grade
I11 1.3-1.6), it may be deduced that creep mechanism is mainly diffusional
creep along grain boundaries in the direction of applied stress. The increase
of AH and n values above Tv may be attributed to the effect of liquid phase,
acting as a lubricant to facilitate crystal slip and as a medium for promoting
diffusion process.
315

Correlation with Microstructure


Based on our investigations, it has been postulated that the mechanical
behavior at elevated temperatures of bauxite refractories is determined largely
by microstructural characteristics, dependent on two principal factors: (1) the
amount and viscosity of the glassy matrix (glass effect), and (2) the extent and
mode of crystal-to-crystal contact (crystal
High glass content and
low viscosity would culminate in increased creep rate, whereas a high degree
of crystal-to-crystal bonding, especially in the mode of continuous interlocking network structure, would lead to lower creep rate. Above the temperature
of incipient plasticity (Tp), both glass effect and crystal effect would exert
their influences, but which is the controlling factor varies with different
materials at different temperatures according to their differences in phase
composition and microstructure.
The inferior creep resistance of grade I11 material may be interpreted in
terms of its high glass content (15-25%) and its lack of crystal-to-crystal bonding, since microstructurally it is essentially composed of small mullite crystals
embedded in a practically continuous glassy matrix. Hence the glass effect
is the dominant factors controlling creep process.
Now why is the creep resistance of grade I material inferior to that of
grade 11, in spite of its higher A1,0, content, low glass amount, and appreciable crystal-to-crystal contact? This may be explained as follows.
(1) The glass composition of grade I material is characterized by relatively high Al,O,/SiO, ratio and high impurities content, especially TiO,, as shown
in Fig. 7' which would result in considerably lower glass viscosity. The glass
viscosity at 1400C calculated for grade I material is only 4.3 Pa.s, which
is much lower than that of grade I1 141.3 Pa.s.
(2) The crystalline phase in grade I material is predominantly granular
corundum (60-70%) with appreciable crystal-to-crystal contact. Therefore,
the reinforcing effect of the crystal "fillers" interspersed in the glassy matrix
is quite prominent at the plastic flow stage (1000"-1120"C), but above Tv
(1 120"-1 120"C), the rapidly increased mobility of the glassy matrix would
gradually dissolve the crystd-to-crystal contact via grain boundaries, resulting
in noticeable enhancement of strain rate due to viscous flow.
On the other hand, the microstructure of grade I1 material is characterized
by abundance of well-developed mullite crystals ( 6 5 4 5 % ) exhibiting a high
degree of crystal-to-crystal bonding in the form of continuous interlocking
network, the glassy phase being mostly distributed in the interstices within
the network. Consequently, Tp and Tv are higher and the creep rate is much
lower. Even above the temperature of liquid formation (about 1130"C, see
Fig. 4), when the glass effect tends to exert more influence, the crystal effect
still retains its controlling role. That is why there is not transition point in
the log &-1/Tdiagram (Fig. 5) and the n value is lower (Fig. 6).
EPMA results show that there is noticeable difference in chemical composition of the core and the edge of corundun grains in grade I material, but
there is practically no change in case of mullite crystals in grade I1 materialg
(Table 11). This suggests that diffusion into corundum grains is much more
activated and slip along grain boundaries is expected to be more intensified.
Effect of Addition of Impurity Oxides
The dependence of creep properties of bauxite refractories on microstructural characteristics may further be verified by the results of our investiga316

tions on the effect of impurity oxide additions, as shown by the following


examples.

Effect of K,O Addition on Grade I f Material


It is found that for every 1% increase of K,O, glass content increases
7%, mullite content decreases 15-20% and corundum increases 8-13%.'O
Hence, with K,O addition, the interlocking network of mullite crystals typical
of grade I1 material is gradually disrupted with simultaneous increase in the
amount of glass rich in alkali. When the K,O content reaches 2-3%, only
remnants of irregular mullite crystals are observed. Such dramatic microstructural changes would lead to marked deterioration of high temperature creep
properties, as demonstrated in Table 111. With 0.5-3'70 K,O addition, not only
Tp and Tv are lowered, but also total deformation is considerably
increased. I '
Effect of MgO Addition on Grade I Material
Table IV shows the variation of steady-state creep rate (E,) of grade I
material (A1,0,/Si02 = 6.4) at 1100"-1300C with MgO content.6 There are
three stages of changes. With addition of up to 14% MgO, there is a marked
increase in deformation rate. Further increase of MgO content to 20-30% leads
to dramatic rise in deformation; the creep rate of No. 4 and No. 5 specimens
at 110Oo-1200"C is 30-100 times that of No. 1. However, when MgO content
reaches 38070, a dramatic drop in creep rate is observed. The creep rate of No.
6 specimen at 1100C is only slightly greater than that of No. 1, but at 1300C
it becomes much less.
The above changes in creep behavior may be closely related to the changes
in phase composition and microstructure6 summarized in Table V.
Within the 14% MgO range, corundum content is gradually reduced with
formation of spinel. Consequently, direct bonding between corundum grains
is gradually destroyed and replaced by direct bonding between smaller spinel
crystals. At the same time, glass amount and the impurities content in glass
composition has increased somewhat. Both effects would lead to degeneration of creep resistance. When the MgO content reaches 20-30070, besides
appreciable increase in glass amount, sapphirine and cordierite of low incongruent melting point are observed. Spinel crystals are enveloped by glass and
low melting crystallites and there is practically no crystal-to-crystal contact.
This would result in very serious deterioration of creep properties. But when
the MgO content approaches 40%, the main crystalline phases are all of high
melting point, and they exhibit a good degree of direct bonding. Therefore
the dramatic reduction in creep rate at this stage is observed.
Conclusions
The closer the A1,0, content approaches about 70%, the better is the
creep resistance of bauxite refractories at elevated temperatures. The order
of merit is grade I1 > grade 1 > grade 111.
The creep mechanism is mainly diffusional creep along grain boundaries.
Creep behavior is largely determined by microstructural characteristics and
controlled by glass effect (amount and viscosity of glassy matrix) and crystal
effect (extent and mode of crystal-to-crystal contact).
Addition of foreign oxides such as K,O, MgO, etc., may considerably
alter the creep properties because of changes in microstructure. It is envisaged

317

that it may be possible to monitor thermomechanical properties of these


materials by microstructure control.

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.

Table I. Chemical Composition and Physical Properties of Sintered Bauxite


Specimens
Grade

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

App. Por.True Por.


(To)

(To)

2.5
0.8
1.5
2.4
0.5

7.7
6.2
6.3
6.4
6.4

Table 11. Composition of Corundum and Mullite Crystal by EPMA


A1,0,%

Grade I material Corundum


grain Core
Edge
Grade I1 materia1 Mullite
crystal Core
Edge

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

Creep deformation (10-5 rad)


1OOO"C
1100C
1200C

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

Table V. Phase Composition and Microstructure of Grade I Sintered


Materials with MgO Additions
Crystalline phase
Code

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

Fig. 1. Schematic creep curves at different


temperatures.

*Fig. 2. Curves of transition


temperatures vs A1,0, content.

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

Fig. 4. Variation of transient creep


deceleration exponent (m) with
temperature (T).

32 1

AH: creep hetivation %erg

lo4,

r / o ~

Fig. 5 . Plot of log E, vs 1/T.

1srG (-1

Fig. 6. Plot of log i, vs log u (n=stress


exponent).

322

- 5

A120, C Q m t h Shtmed -it*

Fig. 7. Variation of AI20,/Si0, ratio and TiO,


content in glass composition with A1203content
in sintered bauxite.

323

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