Introduction

Out of the Fire

-.:t=he braided history of high heat manufacturing and refractory
technology begins with the discovery of fire. Nature provided the
first refractories, crucibles of rock where metals were softened and
shaped into primitive tools. More than five thousand years later, the
twin elements of our industrialized future continue to power human
progress. Today's refractories are themselves manufactured from
scores of raw materials, in hundreds of forms, to contain heat and
withstand the high temperature manufacturing conditions of nearly
every kind of metal, glass, chemical, mineral, or ceramic product.
INDUSTRIAL SYMBIOSIS
The evolution of refractories can be
traced for well over a century by
following the technological advances
of pyro-processing industries and the
ability of the refractory industry to
respond to or anticipate those
changes. In virtual lockstep, the two
industries have moved through time,
defined and stimulated by their
reciprocal achievements.
If any single event triggered the
birth of refractories as an industry, it
was the advent of the steel-producing
Bessemer Converter served by blast
furnaces capable of melting metal.
Companies appeared throughout
Europe, manufacturing firebrick to
construct the walls of blast furnaces,
kilns, crucibles and ladles. After the
American Independence, firebrick
companies surfaced in the United
States and took off as an industry,
ignited by the Industrial Revolution
and a manufacturing boom in ma-
chinery, glass and forged metals.
With the end of the Civil War,
the U.S. population pressed West,
consuming massive quantities of iron
tools, machinery, rails and locomo-
tives as it went. The steel industry
responded to the nation's increasing
appetite for its product with the
development of open hearth technol-
ogy - an advancement which far
outstripped the production capacities
of the Bessemer Converter and
increased firing temperatures to
unprecedented levels.
THE SEEDS OF SPECIALIZATION
Traditional firebrick could not take the
heat or the corrosive slags produced
through this new steelmaking process.
Up to this point, the capacity to retain
physical stability and chemical
identity at high temperatures suffi-
ciently qualified refractory material to
line the furnaces of industry. Indeed,
chemical and structural integrity
continue to be the fundamental
prerequisite of modem refractory
material. But the conditions of the
open hearth furnace launched the
search for refractory materials with
properties in addition to heat contain-
ment and tolerance of ever higher
temperatures.
Silica brick met those conditions,
having, along with a higher melting
point, similar conductivity, unique
reversible expansion and more
durability. Future refractories would
be required to withstand even more -
the thermal shock of rapid heating
and cooling, the enormous pressures of
furnace loadings, shattering vibration,
extremes of mechanical wear and the
corrosive attack of chemicals.
As both the steel and refractory
industries gained experience with open
hearth technology, the need for special-
ized refractory materials grew even
more apparent. Better than traditional
firebrick, silica brick still could not
stand up to the basic slag found on the
bottom and sides of the open hearth.
The steel industry needed a chemically
basic brick for application below the
slag line and refractory manufacturers
competed vigorously to find one.
Whereas efforts associated with
the development of silica brick concen-
trated on the purity of a single element,
basic refractories opened the door to a
multitude of raw material possibilities.
These included dolomite, chromite
and magnesite, alone or in various
combinations. Initially, dolomite
refractories were found to be most
suitable for open hearth technology.
But further improvements to magnesite
and magnesite-chrome combinations
over several decades shifted the
balance. Ultimately, magnesite and
magnesite-chrome surpassed dolomite
in the open hearth and became the
refractory of choice. As service condi-
tions continued to change in steelmak-
ing as well as copper smelting, glass
and other pyro-processing industries,
variations of magnesite basic bricks
were in more demand than ever.
Illustration depicts laborers loading a
blast furnace in post-Civil War period.
HARBISON-WALKER 1-1
Introduction
HEATED COMPETITION:
EXPANDING INDUSTRY
Two World Wars and a growing
automobile industry intensified U.S.
steelmaking, which led the world in
the production of iron and steel during
the first half of the 20th century. In
tum, the refractories industry achieved
even higher levels of productivity.
Refractory companies merged to
form great enterprises able to supply
American steelmakers who consumed
60% of their product.
The development of new and
better refractory products was espe-
cially prolific during that period.
Monolithic refractories first appeared
during World War I, in answer to
urgent requests from overseas. These
unshaped, unburned refractory
materials, applied dry or mixed with
water and installed by gunning,
ramming or brushing into place, met
the unforgiving demands of a military
timetable. Peacetime applications for
these lightweight, joint-free refractory
linings which could be easily installed
proved to beeven more abundant.
Super duty silica brick-noted for
higher refractoriness and longer
furnace life than its predecessor-
replaced traditional silica brick during
World War II. Following the war,
however, basic and high-alumina brick
became the preferred alternatives.
Refractories output peaked during
World War II and when the dust
cleared, the industry had come of age.
The post-war era brought a rising
demand for higher quality refracto-
ries-and not solely from steelmakers.
Increasingly competitive consumers
from a variety of industries required
refractories tailored to the specific
service conditions of their processes.
Refractory companies rose to the
challenge. Development of ever higher
quality basic bric.k the
steel industry. High-alumina bnck
proved superior for the manufacture
of non-ferrous metals and chemicals,
however-and post-war production
of that product increased steadily.
The next big leap in refractory
production came in the early.1950's
with an enormous technological
breakthrough in steelmaking, the Basic
Oxygen Process (BOP). While the
principle of forcing a of air .
through molten iron ongmated with
1-2 HARBISON-WALKER
In 1875, Samuel Harbison and Hay Walker acquired the Star Fire Brick Company.
the Bessemer Converter, the availabil-
ity of pure oxygen permitted refine-
ments that set remarkable new
productivity standards for steelmak-
ing. Steel producers constructe? .huge
furnaces with individual capacities of
50 to 300 tons and operating tempera-
tures in excess of 3000degrees
Fahrenheit. Refractory manufacturers
vied to develop products appropriate
to the new process, which is respon-
sible for the largest portion of
American steel produced today.
Decades later, the continuous
casting method of steelmaking further
fueled the demand for refractories of
specialized design to fit the conditions
of the caster.
Emerging high technology
industries created new and ultimately
massive markets for "specialized"
refractories-products based on
materials such as graphite, carbon,
silicon carbide, zircon, zirconia and
dolomite and fused silica.
In just over a century,
products had
advancing in tandem with contmuous
industrial development, providing
longer, more specialized service to
customers who, ironically, would con-
sume refractories in smaller quantities.
Those realities signalled the new status
quo-highly competitive conditions
which were to become more sharply
drawn as technological capabilities
accelerated in the years to come.
THE HISTORY OF
HARBISON-WALKER
The standards and practices that set
Harbison-Walker on a course to
industry leadership, and continue as
guiding principles of the company
today, were established by its founders
over a century ago.
A Star is Born
On March 7, 1865, Pittsburgher
J.K. Lemon opened the Star Fire.Brick
Company. Lemon joined a
of enterprising businessmen competmg
to supply the ceaseless demand of
post-Civil War America for refractory
brick. Lemon's company manufactured
the STAR brand silica brick and, like
virtually all of its industry counter-
parts, struggled to produce a consistent
product. Far from a
and knowing little about hISproduct or
the process he used to manufacture it,
Lemon's most visionary act came a
year later, when he hired Samuel
Pollock Harbison as a part time
bookkeeper. ..
Within four years, the mdustnous
bookkeeper had acquired sufficient
expertise in the business and enough
stock in the company to be named
General Manager of Star Fire Brick.
The birth of Harbison and Walker
. --....
occurred five years later in 1875,
when Harbison and major stockholder
Hay Walker acquired and named the
new firm after themselves.
Introduction
-:> Product Improvement
through Continuous Research
Like other successful entrepreneurs of
the 19th century, Harbison was
determined to master every aspect of
his industry, including raw materials,
mining, production, shipping and
marketing. His powerful drive to
understand the nature of different
clays, the chemistry of mixing and
burning and the essentials of brick-
making presaged what would later
become the largest research and devel-
opment capability in the industry.
Harbison's systematic investiga-
tion of clay chemistry and processing
set a rigorous research standard and
marked an early dedication to match-
ing the characteristics of raw materials
to the service conditions they must
endure. In 1877, with their partnership
barely two years old, Samuel Harbison
and Hay Walker officially committed
their company to a continuous
program of product improvement
through research. That year, chemist
George Hay was hired to lead and
~ expand the company's research
~ activity. Over the next decade, Hay
formalized data collection and record-
ing procedures, fastidiously entering
findings in a company "Test Book': A
variety of product improvements
followed, including the development
of the first chrome refractories in the
United States. In 1910, Harbison-
Walker established the company's first
formal research facility, the Hays
Laboratory.
Over the next 50 years, the Hays
Laboratory advanced refractory
technology and product quality on
multiple fronts. Laboratory chemists
and engineers developed prototypes
for VEGA super duty silica brick;
special and super duty fireclay brick;
magnesite and magnesite-chrome
products for a full range of industrial
furnaces; forsterite refractories for the
glass industry; tar containing OXILINE
products for basic oxygen furnaces;
and a comprehensive line of specialty
products including mortars, castables,
ramming mixes and plastic refractories.
During this period, Harbison-
?'--- Walker also achieved a major break-
through in magnesite refractories by
producing unfired magnesite brick.
The metal-case bonding technique that
opened the way for this advancement
had eluded commercial developers for
more than 20 years. Commercial
development of the metal-case
principle culminated in 1923 with
production of the first chemically
bonded magnesite brick. Sheathed in
steel, the new brick was patented by
Harbison-Walker and marketed
under the "Metalkase" trademark.
With requirements for laboratory
space and staff increasing, and
technological possibilities proliferat-
ing following World War II,
Harbison-Walker recognized the need
for additional research capacity. The
Garber Research Center, named for
then company president Earl Garber,
was constructed in 1958. The new
facility vastly enhanced the company's
ability to test products under simu-
lated service conditions as well as
conduct "postmortems" on samples
from actual service.
Uncompromising Quality Control
In his first years with Star Fire Brick
Company, Samuel Harbison acknowl-
edged the need to do better than
"chance work" in the production of
firebrick. His pursuit of the facts and
program of self-education in clay
chemistry are an industry legend. At
the turn of the century, Harbison and
Walker was methodically testing raw
materials to select those most quali-
fied for use in the manufacture of
blast furnace brick.
Those early attempts to control
for uniformity in the selection of raw
materials were forerunners of activi-
ties undertaken by the Quality
Control Department organized by
Harbison-Walker in 1950.Then and
now, the Department is responsible
for quality standards for every
Laboratory, Hays Works 1909.
Harbison-Walker brand, from mining
of raw materials through mix formu-
lation, in-process control and ship-
ment of finished refractories. Related
philosophically to company research
efforts and closely allied with manu-
facturing, the Quality Control Depart-
ment is distinct from both--eompar-
ing actual product characteristics with
stated specifications and submitting
its findings to the president for an
objective view.
Decisive Action
From its inception, the principals of
Harbison and Walker recognized the
benefits of swift and decisive action in
the face of opportunity. Building on
existing contacts within the steel
industry was an early and crucial case
in point. The Carnegie rolling mill had
purchased firebrick from STAR for
several years. In its first year as
Harbison and Walker, the ongoing
business relationship with Thomas
Carnegie helped the company land a
contract from Kloman, Carnegie and
Company to build the Lucy furnace,
the largest blast furnace ever designed.
The new partners viewed this as a
"breakthrough" opportunity for their
company and their prediction was
right on the mark.
The reputation of Harbison and
Walker refractories was forged in the
Lucy furnace whose superior perfor-
mance the two partners broadly
publicized. The company grew,
acquiring manufacturing capabilities
closer to sources of raw materials,
including the purchase of its first
plant outside of Pennsylvania.
The new silica brick plant located in
Kentucky would enable Harbison and
Walker to supply refractories able to
withstand the unprecedented tem-
perature conditions of the open
hearth.
The explosive growth of the
steel industry by the turn of the
century prompted an answering
expansion by Harbison and Walker.
A 10-company merger in 1902
created Harbison-Walker Refractories
Company, the largest of its kind in
the world, with 33 plants. By 1916,
the holdings of Harbison-Walker
Refractories Company included 38
plants in five states, making it capable
of supplying every major steel
producing area.
HARBISON-WALKER 1-3
Introduction
Coal firing periodic kilns, circa 1920.
The key to industry dominance was
not strictly a matter of company size,
however, but more one of company
structure. Vertically organized,
Harbison-Walker exerted complete
con trol over its production process,
from mining and processing of raw
materials through manufacturing,
transportation, and distribution.
New developments in high temper-
ature manufacturing created new
opportunities for Harbison-Walker.
With imported magnesite fast becoming
the raw material of choice for industrial
furnaces, and World War I putting the
squeeze on foreign supply, Harbison-
Walker sought to secure and control a
domestic source of the mineral. In 1916,
Harbison-Walker organized the North-
west Magnesite Company near
Chewelah, WA and acquired majority
ownership in 1927.
During World War II and the
decade that followed, Harbison-Walker
propelled itself into the future with a
massive program of modernization,
new construction and acquisition:
Northwest Magnesite was commis-
sioned to build and operate a sea-water
magnesite facility at Cape May,
New Jersey.
Harbison-Walker built 32 continuous
tunnel kilns for firing refractory brick
and systematically monitored and
recorded their operations to improve
product uniformity.
In 1945, the company purchased
Canadian Refractories Limited, makers
of Magnecon, an outstanding refractory
for cement rotary kilns.
During the 1950's, changing service
conditions called for denser, higher
purity magnesite. Harbison-Walker
positioned itself to meet the need by
1-4 HARBISON-WALKER
constructing a high quality magnesite
facility in Ludington, MI. This raw
material was key to the manufacture of
the NUCON line of direct bonded
magne-site-chrome brick, the OXILINE
family of pitch-bonded and pitch-
impregnated magnesite products, the
NULINE brand of magnesite carbon re-
fractories and other new and improved
refractory products.
Before the Basic Oxygen Process of
steelmaking reached American shores
in the early 1950's, representatives of
Harbison-Walker were observing it
with keen interest in Austria. Fascinated
by the productivity possibilities, com-
pany officials immediately authorized
product development efforts for oxygen
steelmaking. In 1954, Harbison-Walker
became the first American company
to produce refractories for the Basic
Oxygen Process.
Harbison-Walker realized another
opportunity in 1962with the discovery
of high purity alumina calcines in
Eufaula, AL. The presence of these raw
materials enabled the company to pro-
duce a line of high-alumina products at
their Fairfield and Bessemer, AL plants.
This improved high-alumina brick
represented significant improvement
over previously used alumina products
and was widely used by the iron and
steel industry in blast furnaces and
stoves, ladles and in minerals process-
ing rotary kilns.
StrengthinDiversity
The steady growth and accumulation
of financial resources that Harbison-
Walker enjoyed during its first century
enabled it to supply a comprehensive
line of refractories, backed by research
and development, that guaranteed the
quality of its product. The strength of
the company's operations also made it
an attractive takeover target. On Octo-
ber 27, 1967, Harbison-Walker was pur-
chased by Dresser Industries, Inc.,
an acquisition which supplied the
necessary diversity to buffer the com-
pany during periods of economic
adversity. A huge corporation employ-
ing over 16,000people, divisions
of Dresser Industries catered to a
broad spectrum of industries. Under
Dresser's direction, Harbison-Walker
accelerated its move into non-steel
related industries.
During the mid-1970's, when
energy and raw materials shortages
dimmed prospects for many compa-
nies, Harbison-Walker's broadened
capabili- ties kept it operating at peak
capacity. The company supplied
refractory prod-ucts and high purity
fused grains to the electronics,
chemical, fiberglass and foundry
industries. Harbison-Walker sold
improved high-alumina products to the
non-ferrous industry and resin bonded
magnesia-carbon brick for basic oxygen
converters and electric furnaces and
special magnesite refractory products. "'
As always, Harbison-Walker continuedr-cc,
to supply the steel industry, whose
demands during this period included
more sophisticated and specialized
refractories such as slide gates and
shroud tubes for steel pouring.
The recessionary spiral finally
snagged the steel industry in the 1980's,
causing a similar downturn in overall
refractories manufacturing. Harbison-
Walker weathered the period through
internal efficiencies and the key ability
to serve many additional markets.
Worldwide refractory technology
continued to change rapidly in the
1980's. As the company entered the
1990's, its dominance as the worldwide
leader in new technology refractory
products and service was heightened
with the receipt of The "E" Award,
which recognizes excellence in
exports and the introduction of new
generation magnesite-carbon, ultra
high-alumina brick and specialty
products.
Today, Harbison-Walker stands
ready to answer the industry's heat
containment questions, to offer
technical support, and to assist in the -r--, __
evaluation and implementation of
advanced refractory-related solutions
for its customers' high temperature
production problems.
CHAPTER 2
,-.
ClassesofRefractories
Basic Refractories CR-2
High-AluminaRefractories CR-7
FireclayRefractories CR-lO
,..
SilicaRefractories CR-12
SpecialPurposeRefractories CR-14
<

MortarMaterials CR-17
/"
MonolithicRefractories CR-19
""
,-.
HARBISON-WALKER CR
Classes of Re'fractories
The broad variety of pyroprocessing applications across
industry demands great diversity in the supply of refractory
materials. In fact, many of these materials have been devel-
oped specifically to meet the service conditions of a particu-
lar process. The characteristic properties of each refractory
class are a function both of their raw materials base and the
methods used to manufacture the refractory products.
Primarily, refractories are classified as basic, high-
alumina, silica, fireclay and insulating. There are also classes
of "special refractories" which include silicon carbide,
graphite, zircon, zirconia, fused cast and several others.
Most refractory materials are supplied as preformed shapes.
However, they also are manufactured in the form of special
purpose clays, bonding mortars, and monolithics, such as
hydraulic setting castables, plastic refractories, ramming
mixes and gunning mixes. A variety of processed refractory
grains and powders are also available for certain applica-
tions.
This chapter reviews primary refractory classifications,
their typical properties and most common applications, as
well as several specially designed refractories. Technical
data are also included.
HARBISON-WALKER CR-l
Basic Refractories
Overview
Basic refractories were so named because they exhibit resistance to corro-
sive reactions with chemically basic slags, dusts and fumes at elevated
temperatures. While this is still a useful definition, some classes of basic
refractories have been developed that exhibit excellent resistance to rather
acidic slags. Some types of direct bonded chrome-magnesite brick, such
as those used in primary copper applications, fall into this latter category.
Broadly speaking, basic refractories generally fall into one of five
compositional areas:
1. Products based on deadburned magnesite or magnesia.
2. Products based on deadburned magnesite or magnesia in combination
with chrome-containing materials such as chrome ore.
3. Deadburned magnesite or magnesia in combination with spineL
4. Deadburned magnesite or magnesia in combination with carbon.
5. Dolomitic products.
One of the more important types of magnesite brick are those that
have low boron oxide contents and dica1cium silicate bonds. These
chemical features give the brick excellent refractoriness, hot strength and
resistance to load at elevated temperatures. Another category of
magnesite brick contains a higher boron oxide content to improve
hydration resistance.
Chrome containing basic refractories continue to be an important
group of materials due to their excellent slag resistance, superior spalling
resistance, good hot strengths, and other features. Historically, silicates in
the groundmass or matrix formed the bond between the chrome ore and
periclase in the brick. However, the advent of high purity raw materials
in combination with high firing temperatures made it possible to produce
"direct bonded" brick, where a ceramic bond between the chrome ore
and periclase particles exists. These direct bonded brick
exhibit superior slag resistance and strengths at elevated temperatures.
Magnesite-spinel brick have increased in importance due to a desire
to replace chrome-containing refractories because of environmental
concerns. Brick made with spinel and magnesite have better spalling
resistance and lower coefficients of thermal expansion than brick made
solely with deadburned magnesite. These features minimize the chance
of the brick cracking during service.
Basic brick containing carbon include pitch impregnated burned
magnesite brick with carbon contents up to 2.5%, pitch bonded magnesite
brick containing about 5% carbon, and magnesite-carbon brick which
contain up to 30% carbon. Development of the more corrosion resistant
magnesite-carbon brick has resulted in decreased consumption of pitch
impregnated and pitch bonded magnesite brick. In addition, in many
instances the magnesite-carbon brick have replaced magnesite-chrome
brick in applications such as electric arc furnaces. It is anticipated that
magnesite-carbon brick will continue to grow in importance as new
products are developed and additional uses for these products are found.
Dolomitic products are an important class of refractories that are used
for example in rotary cement kilns, steel ladles and AGO's. Dolomite
brick offer a good balance between low cost and good refractoriness for
certain uses. They also offer good metallurgical characteristics for certain
"clean steel" applications.
CR-2 HARBISON-WALKER
RAW MATERIALS
The principal raw materials used in the
production of basic refractories are
dead-burned and fused magnesites,
dead-burned dolomite, chrome ore,
spinel and carbon. In recent years, the
trend has shifted to developing highly
engineered basic refractories. This has
resulted from attempts to address the
rapidly evolving needs of the metallur-
gical and mineral processing industries
that use basic refractories. One result of
this effort has been the development of
technology to address specific wear
mechanisms by employing special
additives in the refractory composition.
These additives generally constitute
less than 6% of the total mix, although
levels at 3% and below are probably
the most common.
Examples of these special additives
include zirconia, which is sometimes
used to improve the spalling resistance
of burned basic refractories. As carbon
has become an important constituent in
the formulation of composite magnes-
ite-carbon refractories, metallic addi-
tives, such as powdered aluminum,
magnesium or silicon have been used
to improve hot strength and oxidation
resistance. Small boron carbide (B
4
C)
additions also can improve the oxida-
tion resistance of certain magnesite-
carbon compositions. These composi-
tions are used in special applications
such as bottom blowing elements of
basic oxygen furnaces.
MAGNESITE BRICK
Brick made with dead-burned magne-
site are an important category of basic
refractories. Magnesite brick are
characterized by good resistance to
basic slags as well as low vulnerability
to attack by iron oxide and alkalies.
They are widely employed in
applications such as glass tank check-
ers, as subhearth brick for electric arc
furnaces, and sometimes as backup
linings in basic oxygen furnaces. They
are often impregnated with pitch in the
latter application. Magnesite composi-
tions are also widely used to control
the flow of liquid steel in continuous
casting systems, either as the slide gate
refractory or as a nozzle. ..........
Basic Refractories
Various grades of dead-burned
magnesite are available for the produc-
tion of magnesite brick. They range
from natural dead-burned materials,
with MgO contents of 90% or less, to
high-purity synthetic magnesites
containing 96% MgO or greater.
A large amount of work has been
done to produce highly refractory
magnesites. Since magnesia itself has
an extremely high melting point, i.e.,
5070F (2800C), the ultimate refractori-
ness of a magnesite brick is often
determined by the amount and type of
impurity within the grain. In practice,
the refractoriness of a dead-burned
magnesite is improved by lowering the
amount of impurities, adjusting the
chemistry of the impurities, or both.
There are many types of magnesite
refractories, both burned and chemi-
cally-bonded. For simplification, they
can be divided into two categories on
the basis of chemistry. The first
category consists of brick made with
low boron magnesites, generally less
than 0.02% boron oxide, that have
lirne-to-silica ratios of 2 to 1 or greater.
Often, the lime-to-silica ratio of these
brick is intentionally adjusted to a
molar ratio of 2 to 1 to create a
dicalcium silicate bond that gives the
brick high hot strength. Brick with
lirne-to-silica ratios greater than 2 to 1
are often of higher purity than the
dicalcium silicate-bonded brick. This
greater chemical purity makes them
more desirable for certain applications.
The second category of magnesite
brick generally has lime-to-silica ratios
between 0 and 1, on a molar basis.
These brick may contain relatively
high boron oxide contents (greater
than 0.1% BP3) in order to impart
good hydration resistance. Sometimes,
for economic reasons, these brick are
made with lower purity natural dead-
burned magnesites with magnesia
contents of 95% or less. At other times,
the brick are made with very pure
magnesites with MgO contents greater
than 98% for better refractoriness.
MAGNESITE-CHROME
AND CHROMEMAGNESITE BRICK
A major advance in the technology of
basic refractories occurred during the
early 1930's,when important discoveries
were made regarding combinations of
chrome ore and dead-burned magnesite.
Chrome ores are often represented
by the generic formula RO- Rz031
where the RO constituent consists of
MgOand FeO, and the Rz03constitu-
ent consists of AlzOy Fe
Z03
and Cr
Z03.
It should be recognized that most of the
iron content of raw chrome ores is
present as part of the RO constituent.
Chrome ores also contain siliceous
impurities as interstitial gangue
minerals. These are generally olivine,
orthopyroxene, calcic plagioclase,
chlorites, serpentine and talc.
If raw chrome ore were fired in the
absence of dead-burned magnesite, the
FeO that is present would oxidize
readily to Fe
Z03.
This would result in
an imbalance between the RO and
Rz03' as the RO decreases and the Rz03
increases. Two solid phases would
appear: (a) a spinel consisting mainly
of MgO- RP3 and (b) a solid solution
of the excess Rz03constituents (FeZO
y
Cr
Z03
and AlP3)' Frequently, the solid
solution is easily visible under the
microscope as needle-like inclusions.
When a chrome ore is heated with
added magnesia, as in a chrome-
magnesite or magnesite-chrome brick,
MgO enters the chrome spinel to
replace the FeO as it oxidizes to Fe
Z03.
The MgO also combines with the
newly formed Fe
Z03
to maintain the
spinel structure. The new spinel will
have essentially the formula
MgO-RP3'
The reaction of chrome ore with
dead-burned magnesite increases the
refractoriness of the spinel minerals,
since spinels formed by MgO with
CrZOy Al
Z03
and Fe
Z03
have higher
melting points than the corresponding
spinels formed by FeO. In addition, the
added magnesia also reacts with the
accessory silicate minerals of low
melting points present in the ground-
mass of the ore, and converts them to
the highly refractory mineral forsterite,
2MgO-SiO
z.
These reactions explain
why magnesite-ehrome and chrome-
.-
brick are used.in
sidewalls of electnc arc furnaces In foundnes.
magnesite refractories have better hot
strength and high temperature load
resistance than refractories made from
100% chrome ore.
Direct-Bonded
Magnesite-Chrome Brick
While the reactions between chrome
ore and magnesite outline the funda-
mental chemistry of magnesite-
chrome brick, a significant advance in
the quality of these products occurred
in the late 1950's and early 1960's with
the introduction of "direct-bonded"
brick. Prior to that time, most magne-
site-chrome brick were silicate-
bonded. Silicate-bonded brick have a
thin film of silicate minerals that
surrounds and bonds together the
magnesite and chrome ore particles.
The term direct-bonded describes the
direct attachment of the magnesia to
the chrome ore without any interven-
ing films of silicate. Direct-bonding
was made possible by combining high
purity chrome ores and magnesites,
and firing them at extremely high
temperatures. High strength at
elevated temperatures is one of the
single most important properties of
direct-bonded brick. They also have
better slag resistance and better
resistance to "peel spalling" than
silicate-bonded brick.
HARBISON-WALKER CR-3
Basic Re'fractories
Thisfeatureresultsintheavoidanceor
inhibitionofpeelspallingcausedby
temperaturecyclingandinfiltrationof
constituentsfrom theserviceenviron-
ment.Spinel additionsalsolower the
thermalexpansioncoefficientsof
magnesitecompositions.Thiscan
reducethermalstresses thatcould
contributetocracking incertain
environments.
Adesiretousechrome-freebasic
brickforenvironmentalreasonshas
increasedtheimportanceofmagne-
site-spinelbrick.Trivalentchromium
(Cr+
3
) presentinmagnesite-chrome
brickcanbeconvertedtothe
hexavalentstate(Cr+
6
) by reactionwith
alkalies,alkalineearthconstituents,
andothercompoundsthatare present
insomeserviceenvironments.These
factorshaveled tobroaduseof
magnesite-spinelbrickinrotary
cementkilns.Theyhaveexcellent
spallingresistance,goodthermal
expansioncharacteristicsandhave
been showntoprovideexcellent
serviceresultsinmanyrotarykilns.
CARBON-CONTAINING
BASIC BRICK
Theidea ofaddingcarbontoamagne-
siterefractoryoriginallystemmed
from theobservationthat carbonisnot
easilywettedbyslag.Thus, oneofthe
principalfunctionsofcarbonisto
preventliquidslagfrom enteringthe
brickandcausingdisruption.Until the
mid 1970'sbrickbasedoncarbonin
combinationwithmagnesitewere
mainlyusedinbasicoxygensteelmak-
ingfurnaces;butsincethat timethey
havebeen morebroadlyutilizedin
electricarcfurnacesandsteelladle
applications.
Carbon-containingbasicbrickcan
becategorizedasfollows:
1. Pitch-impregnated,burned
magnesitebrickcontaining
about2.5%carbon;
2. Pitch-bondedmagnesitebrick
containingabout5%carbon;
3. Magnesite-carbonbrickcontain-
ing8%to30%carbon(inthisclass,
carboncontentsrangingfrom 10%
to20%aremostcommon).
Whileallbrickinthese categories
containbothmagnesiteandcarbon,
theterm"magnesite-carbonbrick" as
typicallyusedintheUnitedStates
refers tobrickwithcarboncontents
greaterthan8%.
Pitch-impregnatedandpitch-
bondedmagnesitebrickcanbe
thoughtofasproductscontainingjust
enoughcarbontofilltheirpore
structures.Inmagnesite-carbonbrick,
however,thecarbonadditionistoo
large tobeconsideredmerelyapore
filler.Thesebrickareconsidered
compositerefractoriesinwhichthe
carbonphasehasamajor influenceon
brickproperties.
Carbon containing basic brick are used in BOF bottoms.
Burned Pitch-Impregnated
Magnesite Brick
One categoryofburnedpitch-impreg-
natedmagnesitebrickismadewitha
dicalciumsilicatebond.Dicalcium
silicatehasan extremelyhighmelting
pointofabout3870
0P
(2130C).Useof
thisbondincombinationwithtight
chemicalcontrolofotheroxidesgives
thesebrickexcellenthot strengthand
anabsenceoffluxesattemperatures
commonlyfoundinmetallurgical
processes.
Thecarbonderivedfrom the
impregnatingpitchwhenthebrickis
heatedinservicepreventsslag
constituentsfrom chemicallyaltering
thedicalciumsilicatebond,preserving
thehotstrengthandhighrefractori-
ness.Thecarbonalsopreventsthe
phenomenonofpeelspalling,where
thehot faceofabrickcracksandfalls
awayduetoslagpenetrationin
combinationwithtemperature
cycling.
Dicalciumsilicatebondedburned
magnesitebrick that havebeen
impregnatedwithpitchare usedina
numberofapplications.Inbasic
oxygenfurnaces,thistypeofbrickis
sometimesusedinchargepads,
whereitshighstrengthenablesitto
resistcrackinganddisruptioncaused
by theimpactofsteelscrapandliquid
metalbeingaddedtothefurnace.
Thesebrickarealsowidelyusedasa
tankliningmaterial,i.e.asabackup
lining behindthemainworkinglining
ofabasicoxygenfurnace. Theyare
alsousedinsubhearthsofelectricarc
furnaces.
Notallpitchimpregnatedburned
magnesitebrickaredicalciumsilicate
bonded,however.Oneimportant
classofbrick that deservesmention
hasalow limetosilicaration,below1,
andahighboronoxidecontent.These
chemicalfeaturescausethebrickto
haverelativelylow hot strength,but
atthesametime, resultinverygood
hydrationresistance. Thus,bricksuch
asthisare theproductsofchoice
whereitisjudgedthat thereis
potentialforhydrationtooccur.
HARBISON-WALKER CR-S
Basic Refractories
Pitch-Bonded Magnesite Brick
Pitch bonded magnesite brick are used
in various applications, but mainly in
basic oxygen furnaces and steel ladles.
These products have excellent thermal
shock resistance and high temperature
strength, and good slag resistance.
Pitch bonded magnesite brick were
the principal working lining materials
for basic oxygen furnaces for many
years. Although in severe service
environments they have been replaced
to a large extent by more erosion
resistant graphite-containing
magnesite-carbon brick, they continue
to play an important role in, for
example, lower wear areas of basic
oxygen furnaces.
Magnesite-Carbon Brick
The high carbon contents of magnesite-
carbon brick are generally achieved by
adding flake graphite. The high
oxidation resistance of flake graphite
contributes to the reduced erosion rates
of these brick. In addition, the flake
graphite results in very high thermal
conductivities compared to most
refractories. These high thermal
conductivities are a factor in the
excellent spalling resistance of
magnesite-carbon brick. By reducing
the temperature gradient through a
brick, the high thermal conductivities
reduces the thermal stresses within
the brick. High thermal conductivity
also results in faster cooling of a
magnesite-carbon brick between
heats and thus reduces potential for
oxidation.
In recent years, product develop-
ment efforts have been directed to-
wards producing magnesite-carbon
brick with good slag resistance and
high temperature stability. High tem-
perature stability refers to the ability
of the brick to resist internal
oxidation-reduction reactions that
can reduce hot strength and adversely
affect the physical integrity of the
brick at elevated temperatures
(i.e. the oxides in the brick are re-
duced by the carbon). A high degree
of slag resistance and good high
temperature stability have been
found to be advantageous in the
hotter and more corrosive service
environments.
The high temperature stability of
magnesite-carbon brick has been
achieved by utilization of high pu-
rity graphites and magnesites. Since
flake graphite is a natural, mined
material, there are impurities associ-
ated with it. These may be minerals
such as quartz, muscovites, pyrite,
iron oxides and feldspars. Although
much purification is accomplished
through flotation processes, most
flake graphites contain a limited
amount of these impurities. These
mineral impurities are often referred
to as graphite "ash". Some of the ash
constituents, especially the silica and
iron oxide, are easily reduced by car-
bon and thus will result in a loss of
carbon from the brick and a reduc-
tion in hot strength at elevated tem-
peratures. Magnesia can also be re-
duced by carbon at high tempera-
tures. For best high temperature sta-
bility, high purity magnesites are
used. Magnesites with very low bo-
ron oxide contents are especially de-
sirable.
The service environments in
which these carbon-containing basic
brick are used are very diverse due
to process changes in the steelmak-
ing industry and due to broader use
of the products. A great deal of work
has been done to develop special
additives to improve the perfor-
mance of carbon-containing brick in
these applications. These additives
include powdered metals such as
aluminum, magnesium and silicon.
One reason for adding these metals
is to improve oxidation resistance.
The metals consume oxygen that
would otherwise oxidize carbon.
The aluminum and silicon also cause
the pore structure of a magnesite-
carbon brick to become finer after
the brick is heated. It is believed that
the pores become finer due to
formation of aluminum carbide
(AI
4C)
and silicon carbide (SiC) by
reaction between the metals and the
carbon in the brick. The finer pores
result in decreased permeability of
the brick and inhibit oxidation by
making it more difficult for oxygen
to enter the brick structure.
Another reason for adding met-
als is to improve the hot strength of
magnesite-carbon brick. It has been
suggested that the improvement in
hot strength is due to the formation
of carbide "bridges" within the ma-
trix of the magnesite-carbon brick. m
Another way that metals may im-
prove hot strength is simply by
protecting the carbon bond in these
brick from oxidation.
Silicon has been employed as an
additive to inhibit the hydration of
aluminum carbide that is formed in
aluminum-containing magnesite-car-
bon brick. Aluminum carbide can
react with atmospheric humidity or
any other source of water to form an
expansive reaction product that can
disrupt the brick. This is illustrated
by the following equation:
Al
4C3
+ 12 Hp ---> CH
4
+ 4 Al(OH)3
This reaction represents a potential
problem for applications with inter-
mittent operations such as some steel
ladles or electric arc furnaces. Adding
silicon to an aluminum-containing
brick greatly extends the time before
which hydration will occur.
Boron-containing compounds such
as boron carbide (B
4C)
are used to
improve oxidation resistance in certain
critical applications such as tuyere
elements in bottom blown basic oxygen
furnaces. In addition, magnesite-carbon
brick are sometimes impregnated with
pitch in order to improve oxidation
resistance as well as to promote brick
to brick bonding in service.
DOLOMITE BRICK
Dolomite brick are available in burned
and carbon-bonded compositions. The
carbon-bonded varieties include both
pitch and resin-bonded versions. Some
of the carbon-bonded products contain
flake graphite and are somewhat
analogous to magnesite-carbon brick.
Dolomite brick are widely applied in
applications as diverse as argon-
oxygen decarburization vessels
(AOD's), rotary cement kilns and steel
ladles.
m A. Watanabe et.al., "Effects of Metallic
Elements Addition on the Properties of
Magnesia-Carbon Bricks", Preprint of The
First International Conference on Refractories,
Tokyo, Japan, Nov. 1984, pp. 125-134.
CR-6 HARBISON-WALKER
Basic Refractories
This feature results in the avoidance or
inhibition of peel spalling caused by
temperature cycling and infiltration of
constituents from the service environ-
ment. Spinel additions also lower the
thermal expansion coefficients of
magnesite compositions. This can
reduce thermal stresses that could
contribute to cracking in certain
environments.
A desire to use chrome-free basic
brick for environmental reasons has
increased the importance of magne-
site-spinel brick. Trivalent chromium
(Cr+
3
) present in magnesite-chrome
brick can be converted to the
hexavalent state (Cr+
6
) by reaction with
alkalies, alkaline earth constituents,
and other compounds that are present
in some service environments. These
factors have led to broad use of
magnesite-spinel brick in rotary
cement kilns. They have excellent
spalling resistance, good thermal
expansion characteristics and have
been shown to provide excellent
service results in many rotary kilns.
CARBON-CONTAINING
BASIC BRICK
The idea of adding carbon to a magne-
site refractory originally stemmed
from the observation that carbon is not
easily wetted by slag. Thus, one of the
principal functions of carbon is to
prevent liquid slag from entering the
brick and causing disruption. Until the
mid 1970's brick based on carbon in
combination with magnesite were
mainly used in basic oxygen steelmak-
ing furnaces; but since that time they
have been more broadly utilized in
electric arc furnaces and steel ladle
applications.
Carbon-containing basic brick can
be categorized as follows:
1. Pitch-impregnated, burned
magnesite brick containing
about 2.5%carbon;
2. Pitch-bonded magnesite brick
containing about 5% carbon;
3. Magnesite-carbon brick contain-
ing 8% to 30% carbon (in this class,
carbon contents ranging from 10%
to 20%are most common).
While all brick in these categories
contain both magnesite and carbon,
the term "magnesite-carbon brick" as
typically used in the United States
refers to brick with carbon contents
greater than 8%.
Pitch-impregnated and pitch-
bonded magnesite brick can be
thought of as products containing just
enough carbon to fill their pore
structures. In magnesite-carbon brick,
however, the carbon addition is too
large to be considered merely a pore
filler. These brick are considered
composite refractories in which the
carbon phase has a major influence on
brick properties.
Carbon containing basic brick are used in BOF bottoms.
Burned Pitch-Impregnated
Magnesite Brick
One category of burned pitch-impreg-
nated magnesite brick is made with a
dicalcium silicate bond. Dicalcium
silicate has an extremely high melting
point of about 3870
0P
(2130C). Use of
this bond in combination with tight
chemical control of other oxides gives
these brick excellent hot strength and
an absence of fluxes at temperatures
commonly found in metallurgical
processes.
The carbon derived from the
impregnating pitch when the brick is
heated in service prevents slag
constituents from chemically altering
the dicalcium silicate bond, preserving
the hot strength and high refractori-
ness. The carbon also prevents the
phenomenon of peel spalling, where
the hot face of a brick cracks and falls
away due to slag penetration in
combination with temperature
cycling.
Dicalcium silicate bonded burned
magnesite brick that have been
impregnated with pitch are used in a
number of applications. In basic
oxygen furnaces, this type of brick is
sometimes used in charge pads,
where its high strength enables it to
resist cracking and disruption caused
by the impact of steel scrap and liquid
metal being added to the furnace.
These brick are also widely used as a
tank lining material, i.e. as a backup
lining behind the main working lining
of a basic oxygen furnace. They are
also used in subhearths of electric arc
furnaces.
Not all pitch impregnated burned
magnesite brick are dicalcium silicate
bonded, however. One important
class of brick that deserves mention
has a low lime to silica ration, below 1,
and a high boron oxide content. These
chemical features cause the brick to
have relatively low hot strength, but
at the same time, result in very good
hydration resistance. Thus, brick such
as this are the products of choice
where it is judged that there is
potential for hydration to occur.
HARBISON-WALKER CR-5
High-Alumina Refractories
~ Overview
Thetermhigh-aluminabrickreferstorefractorybrickhaving
an alumina(Al
z03
) contentof47.5%or higher.This descriptive
titledistinguishesthemfrombrickmadepredominantlyofclay
orotheraluminosilicateswhichhavean aluminacontent
below47.5%.
High-aluminabrickareclassifiedby theiraluminacontent
accordingtothefollowingASTMconvention.The50%,60%,70%
and80%aluminaclassescontaintheirrespectivealuminacontents
withanallowablerangeofplusor minus2.5%fromtherespective
nominalvalues.The85%and90%aluminaclassesdifferin that
theirallowablerangeisplusorminus2.0%fromnominal.The
final class,99%alumina,hasaminimumaluminacontentrather
thanarange,andthisvalueis97%.
Thereareseveralotherspecialclassesofhigh-alumina
productsworthnoting:
Mullitebrick- predominantlycontainsthemineralphase
mullite(3Al
z03
.2SiO
z)
which,on aweightbasis,is
71.8% Al
z03
and28.2%sio,
Chemically-bondedbrick- usuallyphosphate-bondedbrick
inthe 75%to85%Al
z03
range.An aluminumorthophos-
phate(AIP0
4
) bondcanbeformedatrelativelylow
temperatures.
Alumina-chromebrick- typicallyformedfromveryhigh
purity,high-aluminamaterialsandchromicoxide(Cr
Z03
) .
Athightemperatures,aluminaandchromiaformasolid
solutionwhichishighlyrefractory.
Alumina-carbonbrick- high-aluminabrick(usuallybonded
by aresin)containingacarbonaceousingredientsuchas
graphite.
CHEMISTRY AND PHASE strictlyapplied.Forexample,a 70%
MINERALOGY aluminaproductmightcontaina
Foralumina-silicabrick,refractori-
ness isgenerallyafunctionof
aluminacontent.The refractoriness
combinationofabauxiteaggregate
ofabout90%alumina,withvarious
clay mineralscontainingless than
/_
of50%aluminabrickisgreaterthan
fireclay brickandprogressively
improvesasaluminacontentin-
creasesupto99+%.This relationship
isbestdescribedby the AIP3-SiOz
phasediagram.Theprimarymineral
phasespresentinfired high-alumina
brickaremulliteandcorundum
whichhavemeltingpointsof3362F
0850C)and3722F(2050C),
respectively.However,since phase
equilibriumisseldomreached,
particularlyin the fired refractory,
the Al
z
0
3-SiOz
diagramcannotbe
45%AIP3'Whenfired, the brick
couldcontainarangeofphases
whichincludescorundum(alu-
mina),mullite,free silicaandglass.
InadditiontoAIP3-SiOzcon-
tent,thepresenceofcertainimpuri-
ties iscriticalindeterminingrefrac-
toriness.Mostnaturallyoccurring
mineralscontainamountsofalkalies
(Na.O,KzO, andLi.O),ironoxide
(Fep3)andtitania(TiO
z
)' Alkalies
can be particularlyharmfulsince
theyultimatelyreact withsilica to
form alowmeltingglasswhenthe
brickarefired orreachhightem-
peratureinservice.BothFe
Z03
and
TiO
z
will reactwithAIP3andSiO
z
toformlowermeltingphases.
Therefore,withinanyclassofhigh-
aluminabrick,the rawmaterialsand
theirassociatedimpuritiesimpacton
the qualityofthe productandper-
formanceinservice.
Inadditiontothemelting
behaviorofbrick,severalother
propertiesareaffectedby composi-
tion.
Slag Resistance
High-aluminabrickareresistantto
acidslags,thatis,thosehighin
silica. Basiccomponentsinslag, such
asMgO, CaO, FeO,Fe
Z03
andMnO
z,
react withhigh-aluminabrick,
particularlybrickhighinsilica.As
Al
z
0
3
contentincreases,slagresis-
tancegenerallyimproves.
Creep or Load Resistance
This propertyismostaffectedby
meltingpointand,therefore,islikely
tobedirectlyrelatedtoAl
z
0
3
content.Impurities,suchasalkalies,
lime, etc.,haveasignificanteffecton
creepresistance.Mullitecrystal
developmentisalso particularly
effectivein providingload resis-
tance.
Density
Aluminahasaspecificgravityof
3.96andsilica,initsvariousforms,
rangesinspecificgravityfrom 2.26
to2.65.Inrefractoriesformulated
from bothaluminaandsilica,bulk
densityincreaseswithalumina
content.
Otherphysical,chemicaland
thermalpropertieswillbediscussed
withinthefollowingsections
concerninghigh-aluminabrick.
TYPES OF HIGH-ALUMINA BRICK
50% Alumina Class
Aspreviouslymentioned,abrick
classifiedasa50%aluminaproduct
hasan aluminacontentof47.5%to
52.5%.Chemically,suchbrickare
notgreatlydifferentfrom superduty
fireclaybrickwhichcancontainup
to 44%alumina.Brickwithinthe
50%aluminaclassareoftenup-
gradedversionsoffireclay brick
HARBISON-WALKER CR7
High-AluminaRe'fractories
with the addition of a high-alumina
aggregate. Compositions of this class
are designed primarily for ladles.
These 50% alumina class brick have
low porosity and expand upon
reheating to 2910
0p
(1600C) -
desirable features for ladle applica-
tions since they minimize joints
between brick, giving a near mono-
lithic lining at service temperature.
These brick are also characterized by
low thermal expansion and good
resistance to spalling. Many high-
temperature industries use them as
backup brick.
Fifty percent alumina products
based on high-purity bauxitic kaolin,
and other ingredients in the matrix,
provide exceptional load-bearing
ability, alkali resistance and low
porosity. These qualities make such
brick an excellent choice for carbon-
baking flues, glass-tank regenerator
rider arches, blast furnace stoves and
incinerators.
60% Alumina Class
The 60% alumina class is a large,
popular class of products. These
brick are used in blast furnaces, hot-
metal transfer cars, and ladles in the
steel industry, as well as incinerators
and rotary kilns. Brick in this class
are made from a variety of raw
materials.
Some are produced from
calcined bauxitic kaolin and high-
purity clay to provide low levels of
impurities. As a result of firing to
high temperature, these brick have
low porosity, excellent hot strength
and creep resistance, and good
volume stability at high tempera-
tures.
A major application for brick in
this class is in the checker settings of
blast furnace stoves, where load-
bearing ability or creep resistance is
critical to prevent slumping and
eventual blockage of the flues. The
brick are also widely used in other
applications, including incinerators
and rotary kilns. The tar-impreg-
nated version is used in hot-metal
transfer cars.
Severe loading often dictates
the use of andalusite in 60% alumina
products and a series of products
based on andalusite and calcined
bauxitic kaolin have been developed
to meet the most demanding specifi-
cations for blast furnace checkers.
These products contain about 60% to
64% alumina with variations in
constituent amounts of andalusite
and fine matrix materials. These
brick are burned to a high tempera-
ture to completely convert the
andalusite to mullite, reduce poros-
ity and maximize creep resistance.
70% Alumina Class
This is the most frequently used
high-alumina product class because
of its excellent and cost-effective
performance in multiple environ-
ments. Applications include steel-
industry vessels, e.g., ladles, hot-
metal transfer cars, etc., and various
other industrial areas, e.g., cement
and lime rotary kilns, petroleum
coke calciners, etc.
Most brick in this class are based
on calcined bauxite and fireclay.
Brick are usually fired to fairly low
temperatures to prevent excessive
expansion in burning which causes
problems in final brick sizing.
Expansion is caused by reaction of
the siliceous ingredients with
bauxite to form mullite. The brick
typically undergo large amounts of
secondary expansion when heated.
This is advantageous in reducing the
size of joints between brick and
providing a tight vessel structure,
e.g., a rotary kiln.
A higher cost and higher quality
alternative to producing a 70%
alumina brick is represented by
brands based on high-purity cal-
cined bauxitic kaolin. These brick
have superior high-temperature
strength and refractoriness and
significantly lower porosity than
typical products based on calcined
bauxite. Due to their more homoge-
neous structure, they show some-
what less expansion on reheating
than bauxite-based products.
Although originally developed
for electric furnace roofs, bauxitic-
kaolin-based alumina brick have
become multi-purpose products
with major applications in steel
ladles and many high-temperature
heat enclosures.
80% AluminaClass
These products are based primarily
on calcined bauxite with additions of
various amounts of other fine
aluminas and clay materials. They are
usually fired at relatively low tem-
peratures to maintain consistent brick
sizing. Most brick in this class have
about 20% porosity, good strength
and thermal shock resistance. Be-
cause they are relatively inexpensive,
perform well and are resistant to
most slag conditions present in steel
ladles, they are used extensively in
steel ladle applications.
90%and 99% AluminaClasses
These brick contain tabular alumina
as the base grain and may include
various fine materials such as cal-
cined alumina, clay, and fine silica.
As these brick generally have low
impurity levels, alumina and silica
typically make up 99% of the chemi-
cal composition. Usually, the only
mineral phases present are corundum
and mullite. Properties such as high
hot strength, creep and slag resis-
tance benefit from this purity level.
Ninety percent alumina brick
have served successfully in applica-
tions such as induction furnaces,
where they resist corrosion and
penetration by metal and slag, and in
constructions where heavy loads and
high temperatures prevail. This class
of brick can have excellent load-
bearing capability at temperatures
above 3200
0p
(1760C).
Other versions of 90% alumina
brick have been developed to opti-
mize certain properties. Some pro-
vide a further reduction in porosity,
giving longer campaign life in
horizontal channel induction fur-
naces. Other versions have excep-
tional thermal shock resistance, as
well as low porosity and high hot
strength. Some modified brick in this
class offer the best balance of proper-
ties for critical slide-gate application
in continuous casting.
Brands with alumina content of
over 99% are used in applications
where the high melting point, about
3700
0p
(2040 C), and the stability and
inertness of alumina are required.
CR-8 HARBISON-WALKER
High-AluminaRe'fractories
with the addition of a high-alumina
aggregate. Compositions of this class
are designed primarily for ladles.
These 50% alumina class brick have
low porosity and expand upon
reheating to 2910F (1600C) -
desirable features for ladle applica-
tions since they minimize joints
between brick, giving a near mono-
lithic lining at service temperature.
These brick are also characterized by
low thermal expansion and good
resistance to spalling. Many high-
temperature industries use them as
backup brick.
Fifty percent alumina products
based on high-purity bauxitic kaolin,
and other ingredients in the matrix,
provide exceptional load-bearing
ability, alkali resistance and low
porosity. These qualities make such
brick an excellent choice for carbon-
baking flues, glass-tank regenerator
rider arches, blast furnace stoves and
incinerators.
60%AluminaClass
The 60% alumina class is a large,
popular class of products. These
brick are used in blast furnaces, hot-
metal transfer cars, and ladles in the
steel industry, as well as incinerators
and rotary kilns. Brick in this class
are made from a variety of raw
materials.
Some are produced from
calcined bauxitic kaolin and high-
purity clay to provide low levels of
impurities. As a result of firing to
high temperature, these brick have
low porosity, excellent hot strength
and creep resistance, and good
volume stability at high tempera-
tures.
A major application for brick in
this class is in the checker settings of
blast furnace stoves, where load-
bearing ability or creep resistance is
critical to prevent slumping and
eventual blockage of the flues. The
brick are also widely used in other
applications, including incinerators
and rotary kilns. The tar-impreg-
nated version is used in hot-metal
transfer cars.
Severe loading often dictates
the use of andalusite in 60% alumina
products and a series of products
based on andalusite and calcined
bauxitic kaolin have been developed
to meet the most demanding specifi-
cations for blast furnace checkers.
These products contain about 60% to
64% alumina with variations in
constituent amounts of andalusite
and fine matrix materials. These
brick are burned to a high tempera-
ture to completely convert the
andalusite to mullite, reduce poros-
ity and maximize creep resistance.
70%AluminaClass
This is the most frequently used
high-alumina product class because
of its excellent and cost-effective
performance in multiple environ-
ments. Applications include steel-
industry vessels, e.g., ladles, hot-
metal transfer cars, etc., and various
other industrial areas, e.g., cement
and lime rotary kilns, petroleum
coke calciners, etc.
Most brick in this class are based
on calcined bauxite and fireclay.
Brick are usually fired to fairly low
temperatures to prevent excessive
expansion in burning which causes
problems in final brick sizing.
Expansion is caused by reaction of
the siliceous ingredients with
bauxite to form mullite. The brick
typically undergo large amounts of
secondary expansion when heated.
This is advantageous in reducing the
size of joints between brick and
providing a tight vessel structure,
e.g., a rotary kiln.
A higher cost and higher quality
alternative to producing a 70%
alumina brick is represented by
brands based on high-purity cal-
cined bauxitic kaolin. These brick
have superior high-temperature
strength and refractoriness and
significantly lower porosity than
typical products based on calcined
bauxite. Due to their more homoge-
neous structure, they show some-
what less expansion on reheating
than bauxite-based products.
Although originally developed
for electric furnace roofs, bauxitic-
kaolin-based alumina brick have
become multi-purpose products
with major applications in steel
ladles and many high-temperature
heat enclosures.
80%AluminaClass
These products are based primarily
on calcined bauxite with additions of
various amounts of other fine
aluminas and clay materials. They are
usually fired at relatively low tem-
peratures to maintain consistent brick
sizing. Most brick in this class have
about 20% porosity, good strength
and thermal shock resistance. Be-
cause they are relatively inexpensive,
perform well and are resistant to
most slag conditions present in steel
ladles, they are used extensively in
steel ladle applications.
90%and 99%AluminaClasses
These brick contain tabular alumina
as the base grain and may include
various fine materials such as cal-
cined alumina, clay, and fine silica.
As these brick generally have low
impurity levels, alumina and silica
typically make up 99% of the chemi-
cal composition. Usually, the only
mineral phases present are corundum
and mullite. Properties such as high
hot strength, creep and slag resis-
tance benefit from this purity level.
Ninety percent alumina brick
have served successfully in applica-
tions such as induction furnaces,
where they resist corrosion and
penetration by metal and slag, and in
constructions where heavy loads and
high temperatures prevail. This class
of brick can have excellent load-
bearing capability at temperatures
above 3200F (1760C).
Other versions of 90% alumina
brick have been developed to opti-
mize certain properties. Some pro-
vide a further reduction in porosity,
giving longer campaign life in
horizontal channel induction fur-
naces. Other versions have excep-
tional thermal shock resistance, as
well as low porosity and high hot
strength. Some modified brick in this
class offer the best balance of proper-
ties for critical slide-gate application
in continuous casting.
Brands with alumina content of
over 99% are used in applications
where the ~ melting point, about
3700F (2040 C), and the stability and
inertness of alumina are required.
-"
CR-8 HARBISON-WALKER
High-AluminaRefractories
ALUMINA-CHROME BRICK
Alumina-chrome brick consist of
combinations of the two oxides fired
to develop a solid-solution bond. A
wide range of products are available
depending upon Cr
2
0
3
content.
These include a 90% AI
2
0
3-10%
Cr.O, product based on high purity
sintered alumina and pure chromic
oxide. The solid-solution developed
in firing results in brick with excep-
tional cold strength, hot strength
and load-bearing ability. In addition,
the solid-solution bond between
alumina and chromic oxide is inert
to a wide variety of slags. This
premium product is used in slag
lines of induction furnaces, carbon-
black reactors, and other selected
areas where slag corrosion is a major
consideration.
Brick with higher Cr
2
0 , content
are also available. Based on a special
fused grain high in chromic oxide,
these products are selected for the
most extreme cases of high tempera-
ture and corrosiveness.
MULLITEBRICK
In brick of this special category, the
mineral phase mullite predominates.
The alumina content varies from
about 70% to 78% and the brick can
contain a major portion of either
sintered grain or fused mullite grain.
These brick are typically fired to
high temperature to maximize
mullite crystal development.
Their major application is in
glass-melting furnace superstruc-
tures which require high purity,
creep resistance and solubility in
glass.
PHOSPHATE-BONDEDBRICK
Phosphate-bonded brick can be
produced from a variety of high-
alumina calcines, but typically they
are made from bauxite. A P205
addition, such as phosphoric acid or
various forms of soluble phosphates,
reacts with available alumina in the
mix. After the pressing operation,
brick are cured at temperatures
between 600F and 1000F (320C
and 540C) which sets a chemical
bond of aluminum phosphate. They
may even be fired at higher tempera-
tures to develop a combination
chemical and ceramic bond. Phos-
phate-bonded brick are character-
ized by low porosity and permeabil-
ityand very high strength at inter-
mediate temperatures between
1500F (815C) and 2000F (1090C).
Phosphate-bonded brick are
widely used in the aluminum
industry because of their excellent
resistance to wetting and penetra-
tion by - and reaction with -
molten aluminum and its many
alloys. Other uses are in the mineral
processing industries, particularly in
applications such as nose rings and
discharge ends of rotary kilns where
excellent abrasion resistance is
required.
ALUMINA-CARBONBRICK
In this class, brick are bonded by
special thermosetting resins that
yield a carbonaceous bond upon
pyrolysis. A wide variety of compo-
sitions are possible based on the
various high-alumina aggregates
now available. Graphite is the most
common carbonaceous material,
although silicon carbide is used, as
well. These products are used in
applications where reducing condi-
tions prevail, such as during hot
metal transfer or in torpedo cars.
Alumina-chrome and 90% alumina brick
are used in zoned linings for
horizontal channel induction furnaces.
HARBISON-WALKER CR-9
Fireclay Refractories
Overview
Refractory fireclay consists essentially of hydrated aluminum sili-
cates with minor proportions of other minerals. As defined by the
American Society for Testing Materials (ASTM), there are five stan-
dard classes of fireclay brick: superduty, high-duty, medium-duty,
low-duty and semi-silica. These classes cover the range from ap-
proximately 18% to 44% alumina, and from about 50% to 80% silica.
A blend of clays is commonly used in the manufacture of high-
duty and superduty fireclay brick. Flint clays and high-grade kaolin
impart high refractoriness; calcined clays control the drying and
firing shrinkages; plastic clays facilitate forming and impart bonding
strength. The character and quality of the brick to be made deter-
mines the relative proportions of clays used in a blend.
Superduty fireclay brick have good strength and stability of
volume at high temperatures and an alumina content of 40% to 44%.
Some superduty brick have superior resistance to cracking or
spalling when subjected to rapid changes of temperature. There are
several possible modifications in the superduty fireclay class, includ-
ing brick fired at temperatures several hundred degrees higher than
the usual product. High firing enhances the high temperature
strength of the brick, stabilizes their volume and mineral composi-
tion, increases their resistance to fluxing, and renders them practi-
cally inert to disintegration by carbon deposition in atmospheres
containing carbon monoxide gas.
High-duty fireclay brick are used in large quantities and for a
wide range of applications. Because of their greater resistance to
thermal shock, high-duty fireclay brick can often be used with better
economy than medium-duty brick for the linings of furnaces oper-
ated at moderate temperatures over long periods of time but subject
to frequent shutdowns.
Medium-duty brick are appropriate in applications where they
are exposed to conditions of moderate severity. Medium-duty brick,
within their serviceable temperature ranges, can withstand abrasion
better than many brick of the high-duty class.
Low-duty fireclay brick find application as backing for brick with
higher refractoriness, and for other service where relatively moder-
ate temperatures prevail.
Semi-silica fireclay brick contain 18% to 25% alumina and 72%
to 80% silica, with a low content of alkalies and other impurities.
With notable resistance to shrinkage, they also have excellent
load-bearing strength and volume stability at relatively high
temperatures.
FIRECLAY MATERIALS
Refractory fire clays consist essen-
tially of hydrated aluminum silicates
with minor proportions of other
minerals. The general formula for
these aluminum silicates is
Alz0
3-2Si02-2H20,
corresponding to
39.5% alumina (Alz0
3
) , 46.5% silica
(Si0
2
) , and 14.0% water (H
20).
Kaolinite is the most common
member of this group. At high
temperatures, the combined water is
driven off, and the residue theoreti-
cally consists of 45.9% alumina and
54.1% silica. However, even the
purest clays contain small amounts
of other constituents, such as com-
pounds of iron, calcium, magnesium,
titanium, sodium, potassium, lithium,
and usually some free silica.
Of greatest importance as
refractories are flint and semi-flint
clays, plastic and semi-plastic clays,
and kaolins.
Flint clay, known also as "hard
clay", derives its name from its
extreme hardness. It is the principal
component of most superduty and
high-duty fireclay brick made in the
United States. Most flint clays break
with a conchoidal, or shell-like,
fracture. Their plasticities and drying
shrinkages, after they have been
ground and mixed with water, are
very low; their firing shrinkages are
moderate. The best clays of this type
are low in impurities and have a
Pyrometric Cone Equivalent (PCE)
of Cone 33 to 34-35. Deposits of flint
and semi-flint clays occur in rather
limited areas of Pennsylvania,
Maryland, Kentucky, Ohio,
Missouri, Colorado, and several
other states.
Plastic and semi-plastic refrac-
tory clays, often called "soft clays" or
"bond clays", vary considerably in
refractoriness, plasticity, and bond-
ing strength. Drying and firing
shrinkages are usually fairly high.
The PCE of clays of this type ranges
from Cone 29 to Cone 33, for the
most refractory varieties, and from
Cone 26 to Cone 29 for many clays of
high plasticity and excellent bonding
power. Substantial deposits of plastic
and semi-plastic refractory clays are
found in Pennsylvania, Ohio,
Kentucky, Missouri, Mississippi,
Alabama, and various other states.
CR-10 HARBISON-WALKER
-
Kaolins consist essentially of the
mineral kaolinite. They usually are
moderately plastic and have ex-
tremely high drying and firing
shrinkages. Siliceous kaolins shrink
less and bauxitic kaolins shrink more
than kaolins which consist almost
wholly of kaolinite. Refractory
kaolins generally have a PCE of Cone
33 to 35; less pure varieties with a
PCE of Cone 29 to 32 are common.
Among the largest deposits of
refractory kaolin are those which
occur in Georgia and Alabama.
Most commercial deposits of flint
and plastic refractory clay occur in
sedimentary strata in association
with coal beds. Usually, individual
occurrences are relatively small and
of irregular form. In the north-central
Ozark region of Missouri, bodies of
refractory clay occur in the form of
isolated sink-hole deposits. The
kaolin deposits of Georgia and
Alabama occur in the form of lens-
like bodies.
BRICK CLASSIFICATIONS
Superduty
The outstanding properties of
superduty fireclay brick are refracto-
riness, alumina content of 40% to
44%, strength, and volume stability at
high temperatures. Many superduty
brick have good resistance to crack-
ing or spalling when subjected to
rapid changes of temperature. Their
refractoriness, in terms of their PCE
values, may not be less than 33. In the
class of superduty fireclay refracto-
ries are several modifications,
including brick which are fired at
temperatures several hundred
degrees higher than the usual
product. The high firing temperature
enhances the high-temperature
strength of the brick, stabilizes their
volume and mineral composition,
increases their resistance to fluxing
and renders them practically inert to
disintegration by carbon deposition
in atmospheres containing carbon
monoxide gas.
High-Duty
The PCE value of high-duty
fireclay brick may not be less than
31
1/2,
and ordinarily varies from
31
1
h to 32
1
h -33.
Medium-Duty and Low-Duty
Fireclay brick of the medium-duty
class have PCE values of 29 to 31.
The PCE values of low-duty fireclay
brick cover the range from 15 to
27-29.
POURING-PIT REFRACTORIES
These include nozzles, sleeves,
stoppers, runner brick, and certain
other shapes required in transferring
molten steel from ladle to ingot
molds by bottom pouring. Sleeves
and most runner brick are of high-
duty quality. However, nozzles, and
sometimes runner brick, are made
from plastic clays uniquely suited
for these services but, for the most
part, having refractoriness values in
the lower ranges.
FIRECLAY BRICK MANUFACTURE
Most fireclay brick are made from
blends of two or more clays. Some
brick, especially those of the low-
duty class, are made of a single clay.
The mixes for superduty and high-
duty brick commonly contain raw
flint and bond clays, with or without
calcined clay. In making brick of
kaolin and various other clays, a
large proportion of the mix is
precalcined to control firing
shrinkage and stabilize the volume
and mineral composition of the
product.
In making fireclay brick, the
particles of ground clay must
include a range of graded sizes, each
in proper proportion. The clays are
typically ground in a "dry pan,"
which is a rotating, pan-shaped
grinding mill having slotted open-
ings in the bottom. The batches are
screened to the desired sizes and
thoroughly mixed with a small but
closely controlled amount of water.
The moistened batch is then fed to a
mechanically or hydraulically
operated press in which the brick are
formed under pressure.
In a modification of the power-
press process, certain physical
properties are enhanced by the
application of a high vacuum during
the forming of the brick. Brick made
in this way typically have a more
homogeneous texture and are harder,
stronger, less porous, and more dense
High-duty bottom pouring refractories are
used for ingot casting.
than those made without vacuum. As
a consequence, they are more resistant
to impregnation and corrosion by
slags and to penetration by gases.
The extrusion process is some-
times used for making special shapes.
In making extruded brick, clays are
ground in a dry pan, mixed wet or dry
in a mixer, brought to the proper
consistency in a pug mill, and ex-
truded through the die of an auger
machine in the form of a stiff column.
The air is removed from the clay
before extrusion by a de-airing system
within the auger machine chamber.
The column is cut into brick by means
of wires. The brick are then typically
re-pressed to give them sharp comers
and edges and smooth surfaces. Many
intricate special shapes are formed in
vertical piercing-and-forming presses,
in which blanks from the extrusion
machine are completely reshaped.
Brick formed by any of the
processes described above are dried in
tunnel or humidity driers. The
temperature of firing depends upon
the maturing temperatures of the
clays, and often upon the service for
which the brick are intended. In firing
the brick, several necessary ends are
accomplished: Free and combined
water are driven off; iron and sulfur
compounds and organic matter are
oxidized, and the gases formed are
eliminated; mineral transformations
and changes in volume are affected;
and finally, the particles of clay are
ceramically-bonded together into
mechanically strong brick.
HARBISON-WALKER CR-11
SilicaRefractories
Overview
Silica refractories are well adapted to high-temperature service
because of their high refractoriness, high mechanical strength and
rigidity at temperatures almost up to their melting points, as well
as their ability to resist the action of dusts, fumes, and acid slags.
The American Society for Testing Materials (ASTM) divides
silica brick into Type A and Type B based on the brick's flux fac-
tor. Flux factor is determined by adding the alumina content and
twice the total alkali content. The Type A class includes silica brick
with a flux factor of 0.50 or below; Type B includes all silica brick
with a flux factor above 0.50.
Both classes require that brick meet the following criteria: Al
z03
less than 1.5%; TiOzless than 0.20%; Fe
z03less
than 2.5%; CaO less
than 4.0%; and average modulus-of-rupture strengths not less
than 500 psi.
This system for classifying silica brick was preceded by a less
exact system which still is referenced today. Under the earlier
system, non-insulating silica brick were either of conventional or
superduty quality. Insulating silica brick were classified only as
superduty. Brick classified as superduty silica brick could not
contain more than a total of 0.5% alumina, titania, and alkalies.
MANUFACTUREOF SILICA EFFECTSOF ALUMINASAND
REFRACTORIES ALKALIES
The raw material used in the manu- After firing, silica brick contain a
facture of silica refractories consists small proportion of silicates in the
essentially of quartz in finely body that is otherwise crystalline
crystalline form having the proper silica. Upon being reheated to high
characteristics for conversion to the temperatures, these silicates melt
high-temperature crystal modifica- and form a small amount of liquid.
tions of silica. To assure the highest As the temperature rises, the liquid
commercial quality in the refractory increases because the silica also
product, the mineral must be washed melts, at first slowly and then more
to remove natural impurities. rapidly - especially above 2900
0P
After being formed, the brick (1600C). When relatively small
must be fired at a temperature high amounts of silicate liquid are
enough to convert the quartz into present, the solid crystalline portion
forms of silica that are stable at high of the brick forms a rigid skeleton,
temperatures. In the firing and with liquid merely present between
cooling process, refractories must the solid particles, and the brick as a
pass through several critical tem- whole retains its rigidity even under
perature ranges; consequently, it is load. When larger amounts of liquid
necessary to maintain a carefully develop at higher temperatures, the
planned time-temperature schedule bond weakens and the brick may
during the firing process. A proper lose its rigidity.
schedule assures the production of When silica brick contain the
strong, well-bonded brick which usual 2.0% to 3.5% of lime, the
attain their normal permanent percentage of liquid formed at high
expansion of 12% to 15% by volume. temperatures increases almost in
direct proportion to the total amount
of alumina, titania, and alkalies
present. The temperature of failure
under load decreases correspond-
ingly. Individually, these oxides and
alkalies vary appreciably in their
effects on temperature of failure, but
their total concentration is the
significant factor. When the sum of
alumina, titania, and alkalies is less
than 0.50%, the temperature of
failure under a load of 25 pounds
per square inch is 50
0
p (28C) to 90
0P
(50C) higher, than for brick contain-
ing a total of 1.0% of these oxides.
For this reason, brick classified as
superduty must contain no more
than a total of 0.50% alumina,
titania, and alkalies.
CHARACTERISTICPROPERTIES
Among the important properties of
silica brick are their relatively high
melting temperatures, i.e., approxi-
mately 3080
0P
(1695C) to 3110
0P
(1710C); their ability to withstand
pressure of 25 to 50 pounds per
square inch at temperatures within
50
0
p (28C) to 100
0
p (56C) of their
ultimate melting points; high
resistance to acid slags; constancy of
volume at temperatures above
1200
0
p (650C); and virtual freedom
from thermal spalling above 1200
0
p
(650C). At high temperatures, the
thermal conductivity of most silica
brick is somewhat higher than that
of fireclay brick.
At temperatures below 1200
0
p
(650C), silica brick have less resis-
tance to thermal shock. They are
readily attacked by basic slags and
iron oxide at high temperatures in a
reducing atmosphere.
CR-12 HARBISON-WALKER
Silica Refractories
- / SILICA BRICK PRODUCTS
Certain superduty silica brick have
been developed to meet the demand
for a silica refractory that would
permit higher furnace temperatures,
give longer life, and reduce main-
tenance costs. These brick contain no
more than 0.35% alumina plus
alkalies and titania. Superduty silica
brick are used with excellent results
in the superstructures of glass-tank
furnaces.
For many years, conventional
quality silica brick have been re-
garded as the standard. The proper-
ties responsible for the excellent
service record of this brick are
rigidity under load at high tempera-
tures, high resistance to spalling
above 1200F (650C), high mechani-
cal strength, resistance to abrasion,
resistance to corrosion by acid slags
and uniformity of size. Improved
versions of conventional quality
silica brick are available having
better resistance to high-temperature
thermal shock.
A lightweight silica brick with
a bulk density of 65-70 pounds per
cubic foot (1041 to 1121 kg/m
3
) is
suitable for use up to 3000F
(1650C). At a mean temperature of
1200F (650C), its insulating value is
excellent. Lightweight silica brick are
used largely for the insulation of
silica brick constructions, especially
the crowns of glass-tanks. They are
also ideal for the construction of
tunnel kiln crowns, and their proper-
ties are conducive to arches having a
wide span.
Superduty silica brick are used in
glass-tank crown construction.
HARBISON-WALKER CR-13
Special Purpose Refractories
Overview
Materials that surpass commonly used refractories in one or
more of their essential properties are often required for indus-
trial purposes. Carbon and graphite, silicon carbide, zircon,
zirconia, fused cast, fused silica and insulating brick are some of
the refractories with extraordinary properties for special applications.
CARBON AND GRAPHITE
This type of refractory is essentially
composed of the element carbon. Its
use is limited to applications which
are either strongly reducing or where
the oxygen content of the atmosphere
at a given operating temperature is
low enough to prevent appreciable
combustion of carbon. Starting mate-
rials for the production of carbon re-
fractories are typically the amorphous
carbons, e.g., metallurgical coke,
petroleum coke, heat treated coal tar
pitches and the like.
Naturally occurring flake graph-
ite or artificial graphites are some-
times blended with amorphous
carbons to achieve a desired thermal
conductivity. These materials are
combined with high carbon yielding
resins or pitch and formed into blocks
and slabs. Such shapes are well suited
to places where high heat transfer is
required, such as areas using water-
cooled panels. Historically, carbon
blocks have been used to line the
hearth and bosh of blast furnaces.
Carbon blocks have also been used to
line the hearth and sidewalls of alu-
minum reduction pots. Electrodes
and anodes used in numerous indus-
trial applications also are typically
made from carbon.
Carbon is a desirable element for
refractory use because it is not wetted
by most molten metals and slags; it
has excellent thermal shock resis-
tance; and its strength increases when
it becomes heated. Because of its sus-
ceptibility to oxidation, however, this
refractory should be used under re-
ducing conditions; or efforts should
be made to minimize reaction with
gaseous oxygen by adding oxidation
inhibitors to the shape, such as boron
carbide, fine metals (AI, Si, Mg), or by
coating the shape with a protective
glaze. Metal-melting crucibles made
of clay-graphite have been used for a
considerable number of years as have
CR-14 HARBISON-WALKER
clay-graphite shapes, such as stopper
rods and sleeves. Clay-graphite shapes
have been replaced, for the most part,
by alumina-graphite shapes which
provide longer service life.
SII_ICON CARBIDE
Silicon carbide, a major component in
this special refractory class, is pro-
duced by reacting silica sand and
coke at temperatures above 3600F
(2000C). The center of the reacted
mass is the area having the highest
purity, with the purity level decreas-
ing towards the outer zones of the
mass. By selectively cropping a sili-
con carbide ingot, a producer can sell
various grades of silicon carbide
grains ranging from 90% SiC content
to 98% SiC. Silicon carbide by itself is
extremely inert. Under normal atmo-
spheric conditions, it will not self-
bond, even at highly elevated
temperatures. Various schemes have
been developed to bond silicon car-
bide using clay, silica, metallic pow-
ders, and molten silicon.
Clay bonded SiC refractories are
made by adding crude clay to silicon
carbide grain and firing the shape to
sufficient temperature to vitrify the
clay and produce a glassy bond.
These shapes are used with success in
hot, abrasion-prone applications with
temperatures under 2600F (1427C).
Their usefulness is limited by the re-
fractoriness of the clay bond.
Higher strength bonds can be
achieved by bonding silicon carbide
with a nitride phase or by self-
bonding silicon carbide grains with
secondary in situ formed silicon car-
bide. Nitride bonds are typically
formed by adding fine silicon powder
to SiC, forming a shape and heating
the shape in a nitrogen atmosphere
to above 2200F (1205C). Gaseous
nitrogen reacts with the dispersed
silicon phase and forms silicon ni-
tride crystals which readily bond to
the surface of the silicon carbide
aggregate. To produce a silicon
oxynitride bond, an oxygen source
(typically silica) is added to the start-
ing materials. To form a sialon bond,
alumina is typically added to the
starting mixture. The various nitride
phases all possess non-wetting prop-
erties, relatively low thermal expan-
sion, and high strength. The
selection of an appropriate nitride
bond is dependent upon the degree
of oxidation in the service environ-
ment. Generally, the sialon bond
possesses the highest degree of oxi-
dation resistance. Nitride-bonded
SiC-Shapes are typically used in alu-
minum melting and refining appli-
cations, as well as in the bosh and
lower inwall of blast furnaces.
Self-bonded SiC refractories are
made by first forming a shape using
conventional ceramic binders and
then firing the shape at very high
temperatures 3622F - 4082F
(2000C - 2250C) in an atmosphere
of silicon vapors. Fine carbon placed
in the starting materials reacts with
the silicon vapors to form a silicon
carbide secondary phase. Such
shapes have a "recrystallized"
appearance and are readily distin-
guishable. Self-bonded SiC is
typically used in heating elements
and structural supports.
ZIRCON
Zircon is a silicate of zirconium
having a composition of about 67%
zirconia and 33% silica. Zircon re-
fractories are made by blending
beneficiated zircon sands, milled
zircon sands and a plasticizer or
temporary binder, forming a desired
shape, and firing to an elevated tem-
perature. The firing temperature of
zircon is limited to temperatures be-
neath 2732F- 3OO0F (1500 - 165OC),
because within this temperature
range zircon dissociates. The actual
temperature at which zircon dissoci-
ates into zirconia and silica is influ-
enced by mineralizers, such as
alkalies and fluorides. Brick consist-
ing essentially of zircon are typically
made by a forming process called
impact pressing, originally devel-
oped by Harbison-Walker. This pro-
cess uses a rapid series of air
hammer impacts to compress the
Special PurposeRefractories
- ,- mix into simple shapes, such as rect-
angles. Other, more intricate shapes
are made by air ramming or vibra-
tion casting. The main advantages of
zircon refractories are their relative
chemical inertness against acidic
slags and their good thermal shock
resistance. Zircon shapes are typi-
cally used to pave glass-tank bot-
toms and port floors.
ZIRCONIA
Zirconia (ZrO ) is usually obtained
z
through a chemical process involv-
ing zircon or by fusing zircon with
coke in an electric furnace. Zirconia
has held promise as an ideal refrac-
tory material for many decades. It
has long been known to have excel-
lent chemical inertness. It has an ex-
tremely high melting point of 4856F
(2680C). Widespread use of zirconia
has been limited, however, because
of two major drawbacks - its high
cost and its tendency to change crys-
tal form upon heating.
Zirconia can occur in three
polymorphs -monoclinic, tetrago-
nal, and cubic. The typical room
temperature phase is monoclinic
which is stable to about 2120F -
2174F0160
0
e -1190C) upon heat-
ing. Heating through the mono-
clinic-tetragonal transition causes a
volume contraction; cooling through
the transition causes a volume ex-
pansion. The phase change transi-
tion through cooling is instantaneous
and results in spontaneous failure of
the zirconia crystal. This failure is
expressed in the cracking and/ or
disintegration of the refractory
shape.
The fundamental cracking prob-
lem can be overcome using either of
two contrasting approaches. One is
to mill monoclinic zirconia to a fine
size (less than one micron) and dis-
perse it within a refractory body so
that destructive micro-cracking is
avoided. In fact, the dispersed phase
works as a stress absorber as energy
is absorbed by zirconia to convert
from one phase to another. In this
way, the dispersed phase is said to
- produce a "toughening" effect.
The other approach is to stabi-
lize the cubic structure with lime,
magnesia or yttria by heating zirco-
nia with one of these oxides within
the temperature range 2750F -
3100F 0500
0
e -1700C). The cubic
form of zirconia has a uniform ther-
mal expansion, whereas thermal ex-
pansion of the other polymorphs
reflect volume changes which occur
upon heating. A disadvantage of sta-
bilized zirconia is its tendency to
thermally age. That is, the stabilizer
tends to migrate out of the structure
when the material is exposed to long
term temperatures within the
1472F- 2552F (800
0
e -1400C)
range.
Due to its high cost, zirconia re-
fractories are only used in critical ap-
plications, such as metering nozzles
used in continuous casting and in-
serts in the bore area of slide gates.
In these applications, control of the
bore diameter during casting is vital.
Some zirconia is used to make cru-
cibles for refining special alloys
where purity of the molten metal is
of concern. The main use of zirconia
in the refractories industry, how-
ever, is as an additive to increase the
thermal shock or slag resistance of
the refractory.
FUSED SILICAREFRACTORIES
Fused silica is produced by electri-
cally heating quartzite (SiO
z
) with a
purity of at least 98% silica in a fu-
sion furnace. In this process, the
crystalline nature of the silica is
transformed into an amorphous
structure by rapid quenching from a
molten condition. Because of the ex-
tremely low thermal expansion of
fused (amorphous) silica, this mate-
rial has excellent thermal shock re-
sistance. Fused silica also has
excellent corrosion resistance in
acidic media, such as strong acids.
Fused silica powders are used in the
electronics industry as resin extend-
ers due to their excellent electrical
insulating property. Fused silica
filled resins are used to encapsulate
electronic components to protect
them from the environment.
Fused silica grains are classified
into various sizes and formulated
into a slip mix for casting into plas-
ter molds. Using this technique,
many intricate, complex shapes can
be made. These shapes are used as
coke oven doors, shroud tubes,
glass-tank refractories, nonferrous
troughs and spouts, and as linings
for chemical reactors. Fused silica
shapes can be used in constant tem-
peratures up to 3000F 0650C) and
cyclical temperatures up to 2000F
0094C). Beyond about 2000F
0094C), amorphous silica devitri-
fies into cristobalite which under-
goes a volume expansion when
heated, displaying a significantly
higher thermal expansion than fused
silica. Because of these properties,
devitrified fused silica is not consid-
ered volume or thermally stable
when heated to elevated tempera-
tures.
FUSED CASTREFRACTORIES
As the name implies, this classifica-
tion of refractories is formed by
melting refractory compounds in a
fusion furnace and casting the liquid
melt into a simple shape, such as a
block. Special attention must be paid
to the cooling rate of the melt to pre-
vent cracking of the shape and local-
ized defects, such as shrinkage
cavities.
The advantage of using fused
cast refractories to contain molten
metal or slag is their lack of intercon-
nected porosity - a feature inherent
to sintered refractories. The absence
of open porosity enables this type of
refractory to resist corrosion and in-
filtration of corrosive agents. The
main disadvantage of fused cast re-
fractories is their great sensitivity to
thermal fluctuations. The sudden
temperature changes which occur in
many applications are simply too
rapid to prevent cracking or shatter-
ing of fused cast refractories.
Fused cast refractories are typi-
cally sold in the following composi-
tions: alumina, alumina-zirconia-
silica, alumina-silica, magnesite-
chrome, zircon and spinel.
Of these, fused cast alumina is
the predominant type. Its primary
usage is in glass melting furnaces,
especially in zones where it is im-
portant to maintain glass purity.
Most of the alumina-zirconia-silica
fused cas t shapes are used to line
less sensitive areas of glass-tanks.
Fused cast alumina-silica (mullite)
has found use as skid rails in slab
heating furnaces because of its
extreme hardness at operating tem-
HARBISON-WALKER CR-15
Special Purpose Re'fractories
peratures. Fused cast magnesite-
chrome refractories are generally
composed of 50%-60% dead-burned
magnesite and 40%-50% chrome ore.
They offer excellent resistance to
fluid corrosive basic slags; however,
their relatively high cost and the de-
velopment of suitable alternative re-
fractories at lower cost has limited
their widespread usage.
Fused cast zircon is used as a
backup brick in fiberglass melters.
Fused cast magnesium aluminate
spinel is used to line magnesium
electrolysis cells.
INSULATING BRICK
Insulating brick are made from a va-
riety of oxides, most commonly fire-
clay or silica. The desirable features
of these brick are their light weight
and low thermal conductivity, which
usually results from a high degree of
porosity. The high porosity of the
brick is created during manufactur-
ing by adding a fine organic material
to the mix, such as sawdust. During
firing, the organic addition bums
out, creating internal porosity. An-
other way to accomplish high poros-
ity involves the addition of a
foaming agent to slip. Using this ap-
proach, insulating brick can be cast
instead of dry pressed. Additions of
lightweight aggregates like diato-
mite, haydite, etc., is another ap-
proach. Because of their high
porosity, insulating brick inherently
have lower thermal conductivity and
lower heat capacity than other re-
fractory materials. For a more de-
tailed discussion of this topic, please
see Chapter 3, "Thermal Conductiv-
ity", p. PR-lO.
AS1M classifies fireclay and
high-alumina insulating refractories
in the following sequence: 16,20,23,
26, 28, 30 and 33. These numbers
multiplied by 100 represent the
nominal service temperature in de-
grees Fahrenheit to which the refrac-
tory can be exposed in service.
Products numbered from 16 to 26
are made from a fireclay base and
products numbered from 28 to 33
are made from a high-alumina base.
Typically, insulating refractories are
used as backup materials, but they
can also be used as working linings
CR-16 HARBISON-WALKER
of furnaces where abrasion and wear
by aggressive slag and molten metal
are not a concern. Where they can be
used, insulating materials offer sev-
eral distinct advantages:
1. Savings in fuel cost due to de-
creased heat losses through the
furnace lining and less heat loss
to the refractory.
2. Faster heat-up of the lining due
to the insulating effect and lower
heat capacity of the insulating
refractory.
3. Thinner furnace wall construc-
tion to obtain a desired thermal
profile.
4. Less furnace weight due to the
lower weight of the insulating
refractory.
A variety of insulating brick pro-
vide a range of thermal efficiencies
and strengths. By composition and
property characteristics, lightweight
insulating silica brick are similar to
Fused silica shapes are used in coke oven repairs
and for shrouds in continuous casting.
conventional silica brick with the x ~
ception of density and porosity.
They have a maximum service limit
of 3000F (1650C) and are used in
the crowns of glass furnaces and
tunnel kilns. Insulating brick based
on fireclay aggregate are also avail-
able with a combination of high
strength and low thermal conductiv-
ity. These brick offer a maximum
service limit in the range of 2100F -
2300F (1150C - 1261C). They are
primarily used in rotary cement
kilns and glass-tanks.
For even higher temperature ap-
plications, lightweight, insulating
90% alumina brick are also made.
These brick possess high strength,
good spalling resistance and low
permeability. Typical use is in con-
trolled atmosphere and heat-treating
furnaces, billet reheating furnaces,
ore pelletizing and ferroalloy fur-
naces, forging furnaces, and incin-
erators.
Mortar Materials
Overview
Masonry built of refractory brick consists of many relatively
small units laid together to conform to a prescribed plan or
design. The strength of the masonry depends upon the strength
of the individual brick, the manner in which they are laid to-
gether and the nature of the mortar material used in the joints.
The purpose of the mortar is to fill the joints and bond the indi-
vidual brick together. It should protect the joints from attack by
slag and other fluxes and provide resistance to infiltration by
cold air and to the outward flow of gases.
Mortar material should be selected as carefully as the brick
with which it is to be used. Users of refractories recognize that
poorly made joints, or joints filled with improper material, may
greatly shorten the life of a refractory structure.
MORTAR CLASSES
Refractory mortar materials are
divided into two classes:
1. Heat-setting mortars
2. Air-setting mortars
Most heat-setting mortars
require relatively high temperatures
~ develop a ceramic set, in contrast
vith air-setting mortars which take a
rigid set merely upon drying.
Phosphate-bonded mortars develop
a chemical bond at lower tempera-
tures. Temperatures in excess of
700F (370C) are necessary to
permit formation of more stable
phosphate bonds which are less
susceptible to rehydration in high
moisture conditions. Included in
each of these groups are materials
of various compositions for use in
specific applications.
Mortar materials and their
methods of preparation have been
developed for particular combina-
tions of properties each bonding
mortar should possess. Among the
factors included are workability,
plasticity, water retention, fineness
of grind, drying and firing shrink-
ages, chemical composition, refracto-
riness, cold and hot bonding
strengths, vitrification temperature,
and resistance to chemical attack.
The conditions which a bonding
mortar must meet in service are
~ ften extremely exacting and require
... carefully adjusted balance of
properties. For economy and conve-
nience in laying, a mortar should
have good working properties when
mixed to either dipping or troweling
consistency. With excellent work-
ability and water retention over a
range of consistencies, a mortar can
be used for dipped or trowelled
joints, as a surface coating for walls,
or for patching. The mortar should
not shrink excessively upon drying
or heating, nor should it overfire
and become vesicular at the maxi-
mum service temperature. The
thermal expansion of the mortar
should be approximately the same
as that of the brick with which it is
used; otherwise, temperature
changes will affect the bond between
brick and mortar and cause surface
coatings to crack or peel. If strong
joints are needed, the mortar mate-
rial must be affected sufficiently by
the heat to develop a strong ceramic
bond. However, the refractoriness of
the mortar must be high enough to
resist melting or flowing from joints
at high temperatures.
In some cases, there must be
adequate chemical reaction between
brick and mortar to develop a strong
bond between them, but in no case
should the chemical reaction be
sufficient to damage the brick. In
many types of service, it is essential
that joint material be highly resistant
to chemical attack by the furnace
charge, slag, dust, volatized fluxes or
gases; and for certain uses it is
important that the mortar material
should not discolor nor otherwise
contaminate the material being
processed in the furnace. Mortars
which do not develop a strong bond
are often desirable for use in laying
brick walls which are alternately
subjected to soaking heat and
cooling cycles.
TYPES OF MORTARS
Fireclay Mortars
Air-setting mortars containing a
mixture of high fired, fireclay and
high-alumina calcines and smooth
working plastic clays are recom-
mended for use in laying high-
alumina brick in the 50% to 70%
range, as well as insulating brick.
Mortars of this kind meet ASTM
specification C 178-47 superduty
class mortar and are available in a
wet or dry form.
Other air-setting mortars are
available with high refractoriness,
excellent intermediate temperature
strength and smooth working
properties. These are particularly
suited for laying blast furnace brick.
High-Alumina Mortars
Heat-setting mortars with very high
refractoriness, volume stability, and
resistance to attack by molten metal
or slag are used in laying high-
alumina and superduty fireclay
brick in various applications,
especially those where resistance to
ferrous slags is required. These
mortars can be dipped or trowelled.
High-alumina air-setting mor-
tars are used in applications up to
3200F (1760C). They have high
refractoriness and excellent resis-
tance to attack by corrosive slags.
Phosphate-bonded mortars with
high refractoriness and exceptionally
smooth working properties are used
for laying high-alumina brick in a
variety of applications, including
steel ladles and nonferrous environ-
ments.
Heat-setting mortars based on
high purity tabular alumina calcines
are available for use up to 3400F
(1871C). These mortars have
HARBISON-WALKER CR-17
Mortar Materials
exceptional stability and load-
bearing ability at high temperatures
and are highly resistant to corrosion
by volatile alkalies and slags in all
types of furnaces. They are typically
used for laying brick in the 90%
alumina class.
Phosphate-bonded alumina-
chrome mortars generate high bond
strengths and show excellent
resistance to corrosion by ferrous
and nonferrous metals. Mortars of
this kind are recommended for use
when laying alumina-chrome brick,
brush coating over refractory walls,
or other applications where strong
bonded joints and resistance to slag
or metal penetration are desired.
Basic Mortars
Dry, air-setting mortars with a
chrome ore base have excellent
resistance to a wide range of corro-
sive slags and fumes in chemical
applications. They are used for
laying basic brick of all types, but
can be used as a neutral layer
between basic and acid brick.
Mortar brands are also available
which contain high quantities of
penetration and corrosion inhibitors.
These materials have exceptionally
high resistance to corrosive slags
and are used for laying all types of
basic brick, as well as some high-
alumina compositions where slag
attack and corrosion are especially
damaging.
Mortars based on high purity
magnesite are also available and
often used for refractories with high
MgO content. These are usually dry,
and may be used with other types of
basic brick.
Trowelling mortar on high-alumina brick.
Dipping-consistency mortar is used for tight joints
in furnace construction.
CR-18 HARBISON-WALKER
Monolithic Refractories
Overview
Monolithic or monolith-forming refractories are special mixes or
blends of dry granular or cohesive plastic materials used to form
linings. They represent a wide range of mineral
compositions and vary greatly in their physical and chemical
properties. Some are relatively low in refractoriness, while others
approach high purity brick compositions in their ability to with-
stand severe environments.
ADVANTAGES OF
MONOLITHIC REFRACTORIES
Monolithic refractories are used to
advantage over brick construction
in various types of furnaces. Their
use promotes quick installation,
avoiding delays for the manufacture
of special brick shapes. Using
monolithics frequently eliminates
difficult bricklaying tasks, which
may be accompanied by weakness
in construction. They are of major
importance in the maintenance of
furnaces because substantial repairs
can be made with a minimum loss
- of time and, in some cases, even
.uring operations. Under certain
conditions, monolithic linings of the
same chemical composition as
firebrick provide better insulation,
lower permeability, and improved
resistance to the spalling effects of
thermal shock.
Monolithic refractories are
packaged in suitable containers for
convenience in handling and ship-
ping. With little or no preparation,
they can be applied to form mono-
lithic or joint-free furnace linings in
new construction, or to repair existing
refractory masonry.
TYPES OF MONOLITHIC
REFRACTORIES
Common usage divides monolithic
refractories into the following
groups:
Plastic Refractories
Ramming Mixes
Gunning Mixes
Cas tables
Plastic refractories are mixtures
r- .'"---f refractory aggregates and cohe-
.ve clays, prepared in stiff plastic
condition at the proper consistency
for use without further preparation.
They are generally rammed into
place with pneumatic hammers, but
may also be pounded into place with
a mallet.
Ramming mixes consist essen-
tially of ground refractory aggre-
gates, with a semi-plastic bonding
matrix which can be purchased
ready-to-use or prepared by adding
water in the mixer at the construc-
tion site. Ramming mixes are placed
with pneumatic hammers in 1-1
1
/z-
inch layers. They supply a denser,
stronger refractory body than
plastics, but need some sort of form
to restrain them when rammed.
Gunning mixes consist of
graded refractory aggregate and a
bonding compound, and may
contain plasticizing agents to
increase their stickiness when
pneumatically placed onto a furnace
wall. Typically, gunning mixes are
supplied dry. To use, they are
predamped in a batch mixer, then
continuously fed into a gun. Water is
added to the mix at the nozzle to
reach the proper consistency.
Castables consist of graded dry
refractory aggregates combined with
a suitable hydraulic-activated
bonding agent. Cas tables are fur-
nished dry and form a strong cold
set upon mixing with water. They
are usually poured or cast in much
the same manner as ordinary concrete,
but are sometimes vibrated, trowelled,
rammed, or tamped into place or
applied with air placement guns.
They form strong monolithic linings,
possessing combinations of proper-
ties that make them ideal for many
applications.
The discussion above suggests
the manner in which each class of
monolithic refractory is most com-
monly installed. However, not
infrequently, material of one group
may be installed by a technique
more common to another group.
Specially designed plastics are
sometimes gunned, as are many
castables and ramming mixes.
Gunning mixes are often cast or
trowelled. Typically, however, the
best properties are achieved when
monolithic materials are installed in
their intended manner.
When air-setting or hydraulic
activated monolithic refractories are
used, the entire thickness of a lining
becomes hard and strong at atmo-
spheric temperatures. The strength
can be somewhat lower through the
intermediate temperature range, but
increases at higher temperatures with
the development of a ceramic bond.
Heat-setting monolithic refracto-
ries have very low cold strength and
depend on relatively high tempera-
tures to develop a ceramic bond. In
the case of a furnace wall having the
usual temperature drop across its
thickness, the temperature in the
cooler part is usually not enough to
develop a ceramic bond. However,
with the use of a suitable insulating
material as backup, the temperature
of the lining can be high enough to
develop a ceramic bond throughout
its entire thickness.
When monolithic linings are
used as the primary furnace lining,
they are usually held in place with
either ceramic or high temperature
steel anchors. Each method of
anchoring has advantages, depend-
ing upon furnace conditions and
installation technique.
Castable linings are vibrated into place.
HARBISON-WALKER CR19
Monolithic Re'fractories
Plastic Refractories
Plastic refractories are used to form
refractory monolithic linings in
various kinds of furnaces, and are
especially adaptable for making
quick, economical emergency repairs.
They are easily rammed to any shape
or contour.
The high refractoriness, the range
of compositions, and the ease with
which they can be rammed into place
make plastics suitable for many
important applications. Typically,
these include boiler settings, linings
of heating furnaces, soaking pits,
forge furnaces, annealing ovens,
tilting spouts and iron runners,
cupolas and cupola troughs, burner
blocks, firing hoods, electric furnace
delta sections, and furnace door
linings. Plastic refractories are often
highly resistant to destructive
spalling and slagging influence of
furnace operation.
Plastics can include all the fire-
clay, clay-graphite, high-alumina,
high-alumina graphite, and chrome
types adapted for many different
operating conditions. They are
typically packaged in strong, easy-
to-handle, moisture-proof cartons.
Special gunning versions are also
available and are shipped in granu-
lated form in moisture resistant pallet
packages. These are prepared at the
proper consistency, ready-
to-use.
Types of Plastic Refractories
Heat-setting superduty fireclay
plastics form a solid monolithic
surface highly resistant to thermal
shock and many acid slags. They
have excellent workability and very
low shrinkage, making them the
ideal choice for reheat furnaces,
soaking pits, rotary kiln hoods,
incinerators, and other general
superduty plastic requirements.
Cold setting versions of superduty
fireclay plastics are available with
many of the same features.
Superduty heat setting plastics
with graphite exhibit excellent
resistance to wetting and corrosion
by molten metal and slags. This type
of composition is typically used in
ladles, troughs, and other foundry
iron applications.
CR-20 HARBISON-WALKER
Plastics in the 50% alumina class
typically serve as upgrades to super-
duty plastics. They are resistant to
spalling due to thermal shock and
many types of acid slags. Aluminum
furnace upper sidewalls, iron ladles,
troughs and reheat furnaces are
typical applications for 50% alumina
plastics.
Heat-setting 60% alumina class
plastics offers higher refractoriness
over superduty plastics, with
increased strength and volume
stability throughout their tempera-
ture range. Application areas include
soaking pits, reheat furnaces, cement
kiln coolers, aluminum furnace
upper sidewalls, ladles and various
foundry applications.
Air-setting high-alumina plastics
in the 80% alumina class are
primarily used where improved
refractoriness over 60% alumina
plastics is desired. They offer good
resistance to fluxing oxides and slags
up to their maximum service
temperature. Typical applications
include steelplant uses, electric
furnace roofs and reheat furnace
hearths.
Phosphate-bonded high-alumina
plastics ranging in alumina contents
from 70% to 90% are widely used in
many applications as primary lining
materials and for patching existing
refractory linings. These products
typically have high density and
strengths, combined with excellent
volume stability throughout their
temperature range. Plastics ranging
from 70% to 85% alumina content are
often used in applications where
reistance to slags and metal wash are
required. The excellent abrasion
resistance of 85% alumina plastics
make them suitable for use in high
abrasion conditions in petrochemical
applications. Additional uses include
both ferrous and nonferrous metal
applications, where slag and metal
penetration are wear mechanisms.
Plastics in the 90% alumina class are
based on high purity aluminas. These
products typically have high
strengths at high temperatures and
are often used in the foundry and
steelmaking process.
Phosphate-bonded alumina-
chrome plastics have very high
strength at high temperatures. These
compositions, based on high purity
alumina aggregates and chromic
oxide, form an alumina-chrome solid
solution bond at high temperatures
which has extremely good resistance
to high iron oxide slags of an acid to
neutral nature, and to attack by coal
slag. Applications include iron and
steel troughs, dams, impact areas,
spouts, tap holes, industrial incinera-
tors, boiler bottoms, and slagging
areas over tubes.
Application areas of plastics include completed cement kiln firing hood installation shown here.
Monolithic Re'fractories
Castables are typically mixed with water in paddle mixers.
Other phosphate-bonded
alumina-chrome plastics with lower
alumina contents have been develop-
ed for specific service conditions.
These include mullite based
alumina-chrome plastics which have
outstanding slag resistance to acid to
neutral slags. The presence of mullite
grain allows for earlier
making this type of plastic refractory
.deal for slagging applications be-
tween 2500F (1370C) and 2900F
(1593C). Applications include
foundry troughs, ladles, and induc-
tion furnaces, as well as delta
sections and steel troughs.
Silicon-carbide based phosphate-
bonded plastics with an aluminum
phosphate bond are also
These have high conductivity and
high abrasion resistance as well as .
non-wetting properties to many acid
slags and nonferrous metals.
pal applications include municipal
incinerators, fluid-beds, boiler tube
protection, and high abrasion o.r
wear areas in copper and alummum
applications.
There are also mixes made of
carbon-bonded plastics specially
designed for closing the blast
taphole. Since each blast furnace IS
different, special mixes have been
designed for individual furnaces,
taking into account the needs for
extrudability, slag erosion resistance,
strength, and setting characteristics.
i-.r'
Castable Refractories
Castables are generally referred to
as refractory concretes. They are
available in a wide variety of base
materials and typically consist of a
refractory aggregate, special purpose
additives and a cement binder. The
bonding systems used are often
to classify the types of castables mto
four categories: conventional,
cement, ultra-low-cement and lime-
free castables.
Conventional castables have a
cement-bonded matrix where,
typically, a calcium-aluminate type
of cement fills in the spaces between
aggregates. This kind of castable is
the most versatile for placement
purposes in that normally it can be
poured, vibrated, or .gunned
into place while mamtammg ItS
designed properties.
Low-cement castables are
materials with lime contents of
roughly between 1%-3%.
densities and strength are achieved
by careful particle packing and the
use of additives to reduce the water
needed to cast.
Ultra-low-cement castables
contain from .2%-.8% lime. Like low-
cement castables, they consist of sized
particles to achieve maximum
particle packing. Because of the low
cement content, these mixes are not
usually as strong in the low to
intermediate temperature range as
other types of castables; but they tend
to have higher hot strength and .
refractoriness compared to chemi-
cally similar mixes with conventional
or low-cement bonds.
Lime-free castables have been
developed with bonding systems
containing no cement. !hese
have desirable properties for use in
certain chemical applications and
where the highest possible hot
strength and high temperature load
resistance is required, such as
metallurgical operations and other
high temperature furnace
tions. Some of these matenals can
approach the properties of pressed
and fired brick.
Fireclay Castables
Mixtures of high fired fireclay with
a refractory cement binder are
designed to impart high initial
strength and maintain good interme-
diate temperature strength. At high
temperatures, a strong ceramic bond
forms, providing good strength
throughout their working temperature
range. These castables are .used
many applications, includmg boiler
furnace ash pits, piers, hoppers, .
annealing furnace tops, tunnel kiln
bottoms, flues, stacks, linings for cham
sections in rotary kilns, and sub-
bottoms of various types of furnaces.
Use of higher purity aggregates
and higher purity cements can
castables with additional refracton-
ness. Primary uses for these. casta?les
include rotary cement and kilns
in sections other than the burnmg
zone.
Other types of fireclay :astables
include high purity conventional types
developed for high strength and
abrasion resistance. These are excellent
all-purpose castables for applications
up to 2800F (1538C).
Castables can be installed using
gun-casting installation methods.
HARBISON-WALKER CR-21
Monolithic Refractories
In the petrochemical and mineral
processing industries, fireclay
castables designed for extreme
abrasion applications in the inter-
mediate temperature range, have
been developed. They have out-
standing intermediate strength and
abrasion resistance.
Low-cement fireclay castables are
used where high strength and refracto-
riness are needed. The lower lime
content and porosity compared to
conventional fireclay castables make
them ideal for many chemical applica-
tions.
High-Alumina Castables
High-alumina castables typically
consist of accurately sized high-
alumina aggregates with low iron
refractory cements. This mixture
provides good all-purpose castables
with service temperature limits of
3000F 0650C). They can be used in
trough covers, boilers, low wear
foundry ladles, small tundish backup
linings, and blast furnace hearth
maintenance.
Upgraded high-alumina
conventional castables based on low
alkali, high purity alumina-silica
aggregate and super purity cements
offer better high temperature
strengths and more total refractoriness
than castables made from lower
purity cements. These products have
a wide range of uses up to 3100F
0705C).
High purity alumina-bonded
conventional castables with super
high purity cement typically have
extremely high refractoriness and
chemical resistance up to 3300F
0816C). These types are extremely
low in silica content, making them
quite effective where silica could
react with furnace constituents. This
form of castable is used in many
severe abrasion and chemically
corrosive applications.
Low-cement high-alumina
castables with excellent intermediate
to high temperature properties are
another alternative in this category.
When properly vibrated into place,
they provide high density, strength,
and excellent abrasion resistance. The
lower lime content provides good
chemical resistance to furnace
CR-22 HARBISON-WALKER
atmospheres that can attack lime.
Alumina cantents of 60% to 70% are
typical of many low-cement castables
and are used for applications up to
3100F 0705C), such as kiln floors,
doors, cartops, cement kiln coolers,
and precast shapes.
High-alumina castables also
include 85% alumina low-cement
castables for use up to 3200F
0760C). They are chemically similar
to 85% phos-bonded plastics, but
can develop greater intermediate
strengths. Their uses include taconite
furnace linings, rotary kiln lifters, car
decks, and cooler curbs.
Low cement castables based on
high purity aluminas with alumina
contents frm 90% to 98% are also
used. Because of their high purity
and very low silica content, they
have outstanding hot strength at
elevated temperatures and are
excellent for metal contact areas.
Their uses include RH degasser
snorkels, copper and brass induction
furnaces and carbon black reactor
combustion chambers.
Ultra-low-cement castables in the
70% alumina category exhibit
excellent high temperature strength
and thermal shock resistance. These
are excellent for foundry ladles,
tundish dams and weirs, and ladle
covers.
Bauxite-based, 85% alumina
ultra-low-cement castables offer
excellent hot strength and thermal
shock resistance. At steelmaking
temperatures, their high refractori-
ness makes these castables ideal for
ladle splash pads, tundish impact
pads, steel foundry ladles, and
electric furnace delta sections.
Silica Castables
Silica-based castables include those
made with vitreous silica as the raw
material with extremely low thermal
expansion, giving them excellent
resistance to cracking under repeated
thermal cycling to 2000F 0093C).
Their maximum service temperature
is 2400F 0316C) under continuous
service conditions. Primary
applications are coke oven doors,
zinc induction furnaces, glass
forming dies, and aluminum transfer
ladles.
Other silica-based castables
include high strength castables
containing a fortified matrix and
silica aggregate. This type of
composition has substantially lower
density and thermal conductivity
than fireclay extra strength castables
with comparable strengths and
abrasion resistance. This combina-
tion of properties allows it to be
used as a single component lining
where a dense castable with a
lightweight castable backup would
otherwise be used. With excellent
thermal shock resistance up to
1800F (982C), the principal uses
include petroleum industry applica-
tions where fine catalyst abrasion is
a problem, ash hoppers in power
plants, and flash calciners in alu-
mina processing plants.
Ultra-low-cement silica based
castables with chemistry, refractori-
ness, density, and porosity equiva-
lent to high quality fired silica brick
are also produced. These are used in
extreme applications such as coke
oven repair, glass-tanks, hot patch-
ing of glass-tank crowns and burner
blocks, and as precast shapes for
severe acid applications.
Basic Refractory Castables
This class of castables includes
chrome ore base products with
hydraulic cement binders. These
compositions have outstanding
strength and abrasion resistance and
resist chemical attack and thermal
spalling. Typical uses include reheat
furnace hearths, aluminum furnaces
below metal line, recovery boiler
bottoms and other chemical recovery
furnaces in the paper mills, and
other areas requiring a chemically
neutral monolith.
Basic castables also come in the
form of chrome-magnesite mixes
with chemical air-setting bonds.
They can be cast, rammed, or
gunned and have many uses around
electric furnaces and open hearths.
Other high strength, air-setting
magnesite castables have bonding
systems which can give them .-.,
extremely high hot strength. Typical -:>
applications include BOF taphole .
sleeves.
Monolithic Refractories
Gunning mixes are used for maintenance of many industrial furnace linings.
Refractory Gunning Mixes
In some industrial furnaces, turn-
around time and installation costs
are the major factors when choosing a
refractory lining. In other cases,
repairs need to be made with little or
no downtime. In both circumstances,
pneumatic conveying of material, or
gunning, is often the method of
choice. Dense, homogeneous mono-
lithic linings can be gunned without
the use of forms and with a marked
savings in time.
Gun mixes include siliceous,
fireclay, high-alumina, dead-burned
magnesite, and chrome types. Many
castables, ramming mixes, and
specially designed plastics can also be
applied successfully with pneumatic
guns. Acid gun mixes are nor-mally
predamped and fed through a
continuous dual chamber or rotary
gun. Magnesite and hot gun mixes
are not predamped and are placed in
a batch pressure gun. Gun mixes
should wet up well, have as wide a
water range as possible, and provide
excellent coverage in a variety of
applications.
Fireclay Gunning Mixes
Fireclay gunning mixes include
multi-purpose hard-fired fireclay and
standard calcium-aluminate cement
compositions especially formulated
for easy installation and low re-
bounds. These mixes are used in
boilers, incinerators, process heaters,
stacks, breechings, and a variety of
other medium service areas.
There are also fireclay gunning
mixes with high-purity calcium-
aluminate bonding systems, de-
signed for more severe service
conditions experienced in incinera-
tors, iron ore furnace pre-heat units,
wind boxes, fluid-bed catalytic
cracking process transfer lines,
risers, and slide valves. Other
versions are designed for high alkali
applications such as in cement kiln
preheaters; or to provide excellent
CO and load deformation resistance,
for use in blast furnace stack linings.
High-Alumina Gunning Mixes
These are high purity alumina mixes
which provide exceptional refracto-
riness, volume stability, and a
service temperature up to 3000F
0650C). Gun mixes which combine
high fired alumina aggregate with a
high strength, high purity calcium-
aluminate binder have excellent
strength and chemical purity which
allow them to withstand severe
environments with a maximum
service temperature of 3300F
0820C). Primary application areas
include ammonia reformers,
combustion chambers, and catalytic
or naphtha reformer cyclones.
There are also gunning mixes
developed specifically for hot
gunning maintenance. These are
based on high-alumina content
aggregates, providing a 3000F
0650C) service temperature limit.
They typically have good slag and
corrosion resistance.
Silica and Silicon Carbide
Gunning Mixes
A gun mix based on vitreous silica
and a special combination of cal-
cined fireclay and high purity
calcium-aluminate cement binder
gives excellent strength and abrasion
resistance coupled with outstanding
thermal shock resistance and low
thermal conductivity. The primary
application is in catcracker units for
the petroleum industry.
Silicon carbide-based gunning
mixes are designed for boiler and
waste-to-energy incinerators. They
are available in a variety of silicon
carbide levels and have either a high
purity calcium-aluminate cement or
a phosphate bond. The cement bond
has the advantage of forming a room
temperature set and a water in-
soluble bond at low temperatures.
The phosphate bond attaches itself
better to metal studs found in waste-
to-energy units, but takes higher
temperatures to form a strong,
insoluble bond.
Both ramming mixes and plastics are used in
finishing some brick constructions.
HARBISON-WALKER CR-23
Monolithic Refractories
Basic Refractory Gunning Mixes
A series of gun mixes are available
for hot electric furnace maintenance.
These range in magnesia content
from 60% to 95% and are available
with or without a phosphate bond.
Gunning mixes of this kind are
designed to provide an even feed in
a batch gun, wet up well, and stick
to a hot furnace wall.
Refractory Ramming Mixes
Refractory ramming mixes consist of
refractory aggregates and a semi-
plastic bonding phase. When
properly installed, ramming mixes
offer a way of placing a cementless
monolithic lining at high density
and relatively low porosity.
A well balanced selection of
ramming materials includes compo-
sitions with base materials of silica,
high-alumina, corundum, mullite,
dead-burned magnesite, chrome ore,
zircon, and others. These materials
are particularly suited for forming
dense monolithic hearths, linings of
induction furnaces, finishing in brick
construction, and numerous other
monolithic constructions. Ramming
mixes are typically supplied in both
wet and dry forms, depending on
the binder system.
High-Alumina Ramming Mixes
Alumina-silicon carbide ramming
mixes are designed for the copper
and brass industries. They are
particularly useful in the linings of
induction furnaces since they show
excellent resistance to copper
penetration.
High purity ramming mixes
based on mullite grain are also used
in electric furnace roofs, induction
furnaces, burner blocks, ports, and
similar applications.
Ramming mixtures of 80% plus
alumina content have excellent
resistance to shrinkage and thermal
spalling at high temperatures. These
mixes are typically for use in burner
rings, electric furnace roofs, and
ladle linings for ferrous and nonfer-
rous industries.
Other air-setting high-alumina
mixes employ stabilized, chemically
refined high purity aluminas. These
have excellent resistance to thermal
spalling at high temperatures and
remarkable volume stability up to
their temperature limit. Primary
application areas include induction
furnace linings, burner blocks, high
temperature kiln linings, and electric
furnace roofs.
Phosphate-bonded, alumina-
chrome ramming mixes can offer
exceptionally high purity. They
typically feature very high strength
at high temperatures and extremely
good resistance to acid to neutral
slags, including coal ash slags. They
are used in any working lining
where high iron oxide slags of an
acid to neutral nature are especially
corrosive.
Alumina-graphite ramming
mixes are designed for foundry
troughs and electric furnace spout
patching. Their combination of high-
alumina aggregate and slag inhibi-
tors gives them excellent slag
resistance to acid to slightly basic
slags.
Basic Refractory Ramming Mixes
Dry ramming mixes based on high
purity magnesite and a sintering aid
have been designed for electric
furnace bottoms. Magnesite ram-
ming mixtures of exceptional purity
and stability are used primarily as
lining materials for coreless-type
induction furnaces melting ferrous
alloys. Magnesite-chrome fused
grain ramming mixes exist which
provide exceptional density and
strength. The bond of this composi-
tion provides adequate strength at
low temperatures until direct-
bonding occurs at higher tempera-
tures. This kind of ramming mix
works well in degasser linings and
other extreme service conditions.
Basic refractory rarnrninq mixes are installed in the bottom working linings of
meiling furnaces In the ferrous and nonferrous industries.
CR-24 HARBISON-WALKER