CHAPTER 10

THE CERAMIC INDUSTRIES

The ceramic industries, also sometimes called the clay products or sili-.
cate industries, have as their finished materials a variety of articles tha~
are essentially silicates. These products may be classified as follows:
1. Whitewares-chinaware, earthenware, pottery, porcelain, stoneware, ane(
vitreous ware.
2. Heavy clay products-common brick, face brick, terra cotta, sewer pipe,
and drain tile.
3. Refractories-fire-clay brick, chromite, silica brick, basic bricks (magnesite
aed forsterite), alumina products, silicon carbide refractories, pure oxide refnic"
tories (alumina, magnesia, beryllia, stabilized zirconia, and thoria), and metl,\l-
bonded ceramics (oxides, nitrides, borides, and carbides).
4. Enamels and enameled metal.
5. Glass.

The first four of these will be presented later in this chapter; the glasf?
industry will be dealt with separately in Chap. 12. /
The making of pottery is one of the most interesting and ancient of
man's industries; the Chinese and the Egyptians engaged in the art over
6,000 years ago. Ceramics are an important hobby for American men an4
women. Museums contain, as a record of man's culture, the clay prod-
ucts produced throughout the ages, many of which have an artistic as
well as a utilitarian aspect. Although the essential manufacturing proc-
esses used in most of ~he ceramic industries have remained largely un:~
changed for a long time, since 1920 many significant new developments l
have taken place, such as pure oxide refractories, metal-bonded oxides,
carbides, nitrides, and:borides. .
Uses and Economid. The value of the pottery produced in the Unite,j
States from 1930 to ,1940 fluctuated between $40,000,000 and $112,;-
000,000 annually. The present position is around $150,000,000. Table]
shows certain statistics for the ceramic industry. Brick production varies
greatly with the general building program for the country. In 1925 the
production of commo~ brick reached 7.6 billions and in 1924 face brick

I See Ceramics, in Materials of Construction reviews, published annually in Ind.

Eng. Chem., for October, since 1944. .
173
 174 THE CERAMIC INDUSTRIES

TABLE 1. PRODUCTION AND SHIPMENTS OF CERAMICS, FOR THE

UNITED STATES: 1952"
(Money figures in thousands of dollars)

Shipments and
Production interplant transfers
Product quantity
Quantity Value

Clay brick and hollow tile:

Unglazed clay brick (common and face),
M brick .............................. . 5,881,748 5,635,249 154,566
Unglazed clay structural tile, ton .......... . 962,837 919,761 11 ,243
Hollow facing clay tile, M brick equivalents .. 413,479 389,376 22,104
Glazed and unglazed clay floor and wall tile
and accessories, M sq. ft ................. . 125,966 117,544 , 60,962
Drain tile, tons .......................... . 819,919 815,490 14,073
Clay sewer pipe, tons ........... , ........... . 1,646,110 1,544,80!) 58,943
Clay refractories ........................... . 161,934
Fire-clay brick, standard and special shapes,
except super-duty, M 9-in. equivalents .... 628,262 610,254 70,849
Super-duty fire-clay brick, standard and
special shapes, M 9-in. equivalents ....... . 96,495 93,428 -'16,951
High-alumina brick, standard and special
shapes, M 9-in. equivalents ............. . 22,251 21 Ji55 6,655
Insulating firebrick, M_9-in. equivalents .... . 60,343 60,127 11 ,510
Ladle brick, M 9-1n. equivalents ............ . 209,511 199:913 13,490
Hot-top refractories, M 9-in. equivalents ... . 49,148 48:892 5,042
Sleeves, nozzles, rupner brick, and tuyeres,
M 9-in. equivalents .................... . 55,085 54,231 7,789
Glass-house pots, tank blocks, upper struc-
ture, and floaters, tons .................. . 20,513 19,404 3,373
Vitreous and semivitreous plumbing fixtures:
Vitreous china ....., ...................... . n.a. n.a. 82,295
Glazed earthenware, concrete, and compo-
sition ................................. . n.a. n.a. 2,935
Nonclay refractories ........................ . 138,643
Silica brick, standard and special shapes,
M 9-in. equivalents .................... . 336,579 327,997 46,797
Magnesite and magnesite-chrome (magnesite
predominating) brick, standard and spe-
cial shapes, M 9-in. equivalents ...... -.... . 38,420 38,150 21,949
Chrome and chrome-magnesite (chrome pre-
! dominating), M 9-in. equivalents ........ . 48,708 48,187 23,658
I
Graphite and other carbon crucibles and re-
torts, tons ............ ,................ . 9,810 9,844 5,578
Other graphite and carbon refractories, tons .. 1,358 1,329 593
Other nonclay refractories, standard and special
shapes ........ , ....................... . 18,973
Silicon carbide ........................... . 7,761
Mullite and kyanite ...................... . 3,766
Fused alumina and bauxite ................ . 2,560
Zirconia, forsterite, fused magnesia, pyro-
phyllitei sillimanite, and other nonclay
shapes ................................ . 4,886

.. Annual Survey of Manufactures, 1952.

 BASIC HAW l\lA'l'EHI.\ Ll't 175
attained 2.5 billions. Rot.h have declined since those maxima. Ohio and
Pennsylvania are the chief IlHtllufacturing states for the eeramie indus-
tries with New .Jersey, West Virginia, California, and Missouri foi"lowin!!;
in sequence.
BASIC RAW MATERIALS

The three main raw materials used in making the common ceramic
products are (1) day, (2) feldspar, called spar in the industry, (3) sand,
called flint in the industry. Clays are more or less impure hydrated alu-
minum silicates that have resulted from the weathering of igneous roeks
in which feldspar was a noteworthy original mineral. The reaction may
be expressed,
K 2 0·Ab03·6Si0 2 + CO + 2H 0
2 2
Potash feldspar
~ K 2 C0 3 + AI 2 0 3·2SiO,·2H 20 + 4SiO~
Kaolinite Silica

There are a number of mineral species called clay minerals but the most
important are kaolinite, Ah(h2Si0 2 '2H 2 0; beidellite, AhQ3'3Si0 2 'H 20;
montmoriilonite, AI 2 ()a-4Si0 2 ·H 2 0; and hailoysite, AI 2 0:I ·2SiO,·3H 2 0.
From a ceramic viewpoint days are plastic and moldable when sufl1-
(:iently finely pulverized and wet, rigid whell dry, and vitreous when
fired at a suitably high temperature. Upon these propert.ies depend the
manufacturing procedures.
TABLE 2. BASIl' RA\\" :\lATERIALR FOR CERAMICS
/

Kaolinite Feldspar Quartz or flint

Formula ................ AI.0 3·2SiO.·2H.O K.O·AI.0 3 ·6SiO, SiO.

Plasticity ............... Plastic Nonplastic Nonplastic
Fusibility ............... Hefractorya Easily fusible binder Hefractorya
Meltlng point ........... 3245°F.; 1785°C. 21(}')°F.; 1150°C. 3110°F.; 1710°C.
Shrinkage on ):mrning .... Much shrinkage Fuses XO shrinkage

• Infusible at highest tcnlpcrature of coal fire (1400°C.)

,
Accompanying the clay ~inerals in the days of commerce' are varying
amounts of feldspar, qJartz, and other impurities such as oxides of iron.
In nearly all the clays u~ed in the ceramic industry, the basic clay mineral
is kaolinite, although bentonite l clays based on montmorillonite are used
to some extent where 'very high plasticity is desired. This property of
the plasticity2 or workability of clays is influenced most by the physical
1See PERRY, ap. cit., pp},1085-1091 for flotation,
2LEWIS, SQUIRES, andl BROUGHTON, "Industrial Chemistry of Colloidal and
Amorphous Materials," b~ntonite, pp. 241-248; plasticity, pp. 453-456, Tl1e Mac-
millan Company, New York, 1942.
176 THE CERAMIC INDlTSTRIES

condition of the clay and varies greatly among the different types of clay_
Clays are chosen for the particular properties desired and are frequently
blended to give the most favorable result. Clays vary so much in their
physical properties and in the impurities present, that it is frequently
necessary to upgrade them by the beneficiation procedure. Figure 1 shows
the steps! necessary for such a procedure wherein sand and mica are re-
moved. The steps in this flow sheet apply almost altogether to the phys-
ical changes or unit operations such as size separation by screening or
selective settling, filtration, and drying. However, the colloidal properties
are controlled by appropriate addition agents, such as sodium silicate and
alum_

I/O
/b. air t. Pressure tonk
Note: Quantities cannot be given sinc.e day recovery vories from 8 to 18 percent,d6pending On Gr-ude
cloy used. Plant snown h.... desi'3ned for JO tons per day output re'3arc:lless of c:r""'. ciD.y variations
FIG. 1. China clay beneficiation. (Courtesy of Harris Clay Company.)

There are three common types of feldspar: potash feldspar, K 20--

AhOa· 6Si02; soda feldspar, Na20·AbOa·6Si02; and lime feldspar CaO·-
Ah03' 6Si0 2, all of which are used in ceramic products to some extent.
The first is the most common. Feldspar is of great importance as a flux:-
ing constituent in ceramic formuias. It may exist in the clay as mined, or
it may be added as n~eded.
The third main ceramic constituent is'sand or flint. Its essential prop-
erties for the ceramic industries are summarized along with the similar
characteristics of clay and feldspar in Table 2. For the light-colored
ceramic products, sand with a low iron content should be chosen.
In addition to the three principal raw materials there is a wide variety
of other minerals, salts, and oxides that are used as fluxing agents and
special 'refractory ingredients. Some of the more common fluxing agents
are
1 SMITH, Deflocculation and Controlled Separation Improve Domestic China Clay,

Chem. & Met. Eng., 44, 594 (1937). .

 UNIT PROCESSES INCT.UDJNG FUNDAMENTAL CERAMIC CHEMISTRY 177
Borax, N a2B 40 7'lOH 20 Fluorspar, CaF 2
Boric acid, HaBOa Cryolite, NaaAIFs
Soda ash, N a2CO a Iron oxides
Sodium nitrate, NaNO a Antimony oxides
Pearl ash, K 2CO a Lead oxides

Some of the more common special refractory ingredients are

Alumina, AhOa Lime, CaO, and limestone, CaCO a
Olivine, (FeO, MgOhSi0 2 Zirconia, Zr02
Chromite, FeO'Cr20a Titania, Ti0 2
Aluminum silicates, AhOa·Si0 2 Hydrous magnesium silicates,
(cyanite, sillimanite, andalusite) e.g., talc, 3MgO·4Si0 2·H 20
Dumortieri te, Carborundum, SiC
8Al 20 a·B 20 a·6Si02·H 20 Mullite, 3AhOa·2Si02
Magnesite, MgCO a

UNIT PROCESSES INCLUDING FUNDAMENTAL CERAMIC CHEMISTRY

All ceramic products are made by combining various amounts qf the

foregoing raw materials, shaping, and heating to firing temperatures.
These temperatures may be as low as 700°C. for some overglazes ,or as
high as 1300 to 1400°C. for many vitrifications. Such temperatures pause
a number of reactions which are the chemical bases for the unit proc-
esses of
/

1. Dehydration or "chemical water smoking" at 150 to 650°C.

2. Calcination, e.g., of CaCOa at 600 to 900°C.
3. Oxidation of ferrous iron and organic matter at 350 to 900°C.
4. Silicate formation at 900°C and higher.

Some of the initial chemical changes are relatively simple, like the cal-
cination of CaCO a and the dehydrations and decompositions of kaolinite.
Other reactions, such as silicate formations, are quite complex and cllange
with the temperature and constituent. ratios as depicted by Figs. 2 and 4.
The phase-rule! studies as exemplified by Fig. 2 and also by Fig. 4
have been of revolutiona~y importance in interpreting-the empirical obser-
vations in the ceramic i~dustries and in making prediction~ for improve-
ments. For instance, the data of Fig. 2 on the A1 20 a-Si0 2 system have
led to the important dkvelopment of processes for mullite refractories
(see page 192). This diagram shows that any percentage of liquefaction
I
I BIRCH,Phase-equilibrium Data in the Manufacture of Refractories, J,. Am.
Ceram. Soc., 24, 271 (1941) ;jHALL and INSLEY, A Compilation of Phase Rule Diagrams
of Interest to the Ceramis~ and Silicate Technologist, J. Am. Ceram. Soc., 16, 455
(1933).
178 TIm CERAMIC INOURTRIF.S

can he obtained, depenrJent Oil 11 ilplillite temperature, except at the mono-

variant points. Thus, if the progressive melting be kept from going too
far by controlling the rise in temperature, sufficient solid skeletal material
will remain to hold the hot. mass together. This AhOa-Si0 2 diagram
shows that mullite is the only stable compound of alumina and silica at
high temperature.
Being primarily silicates, ceramic products are all more or less refrac-
tory, i.e., resistant to heat, and t4e degree of refractoriness of a given
product is determined by the relative quantities of refractory oxides and
fluxing oxides. The principal refractory oxides are Si0 2 , AhOa, CaO, and

2000 Liquid

Corundum
+ liquid
1810·
1800

3AI Z0,' 2 Si 0z + Liquid

Corundum
+3Al z03 '2SiO z
1545°

Cristobolite+ 3Al z O,'2SiO z

14000 20 40 60 80 100
SiO z Weight Per Cent aAIZOJ
FIG. 2. Phase diagram of the system alpha Al,O,-SiO,. Mullite has the formula
aA!,():.·2SiO,.

MgO, with Zr02, TiO z, Cr 20a, and BeO used less commonly. The prin-
cipal fluxing oxides ate NazO, K 2 0, B 2 0 a, and Sn02, with fluorides also
llsed as fluxes in certain compositions.
The essential ingredient of all ceramic products is clay (kaolinite, usu-
ally) and therefore the chemieal_ reactions which occur on heating clay
are quite important. The first effect of the heat is to drive off the water
of hydration which occurs at around 600 to 650°C. and which absorbs
much heat, leaving an amorphous mixture of !l-lumina and silica, as
shown by X-ray studies.
AI 20 a·2Si0 2 ·2H 20 --> Al 20 a + 28i0 2 + 2H 0 2

In fact a large proportion of the alumina can b,e extracted with hydr<h
chloric acid at this stage. As heating is continued, the amorphous alu-
mina cp.anges quite sharply at 940°C. to a crystalline form of alumina,
gamma alumina, with the evolution of considerable heat. At a slightly
higher temperature, beginning at about lOOO°C., the alumina and silica
combine to form mullite, 3AI 2 0 a·28i0 2 • At a still higher temperature, the
 WHITEWARES 179
rcmainiJJg silica is converted into crystalline cristobalite. Therefore the
fundamental over-all reaction in the heating of clay is as follows:
3(AhOa·2Si0 2 ·2H 2 0) ----> 3A1 2 0 a·2Si0 2 + 4Si0 + 6H zO
2
Kaolinite Mullite Cristobalite

The equilibrium state of Al zO a-Si0 2 mixtures as a function of temperature

is summarized in the phase equilibrium diagram of this system shown in
Fig. 2. The presence of fluxes tends to lower the tempera~ure of forma-
tion of mullite and of attainment of the equilibrium conditions reported
in the equilibrium diagram.
An actual ceramic body contains many more ingredients than clay it-
self. Hence the chemical reactions are more involved, and there Will be
other chemical species besides mullite and cristobalite present in the final
product. For example, various silicates and aluminates of calcium, mag-
nesium, and possibly the alkali metals might be present. However, the
alkali portion of feldspar and most of the fluxing agents become a part
of the glassy or vitreous phase of the ceramic body. All ceramic bodies
undergo a certain amount of vitrification or glass formation during heat-
ing and the degree of vitrification depends upon (1) the relative amounts
of refractory and fluxing oxides in the composition, (2) the temperature,
and (3) the time of heating. The vitreous phase imparts desirable prop-
erties to some ceramic bodies, e.g., acting as a bond and imparting trans-
lucency in chinaware. Even in refractories some vitrification is desirable
to act as a bond but extensive vitrification would destroy the refractory
property. Thus it is seen that any ceramic body is composed of a vitreous
matrix plus crystals, of which mullite and cristobalite are two of the
most important.
The degree of vitrification provides the basis for a useful classification
of ceramic products as follows:
1. 'Whitewares. Varying amounts of fluxes, heat at moderately high tempera-
tures, varying vitrification.
2. Heavy clay products. A:bundant fluxes, heat at low temperatures, little
vitrification.
3. Refractories. Little fluxes, heat at high temperatures, little vitrification.
4. Enamels. Very abun~ant fluxes, heat at moderate ~mperatures, complete
vitrification.
5. Glass. Moderate fluxes, heat at high temperatures, complete vitrification
(see Chap. 12). I
WHITEWARES

The whitewares incl~lde chinaware, earthenware, pottery, porcelain,

stoneware, and vitreou~ ware. These arc based on selected grades of clay
bonded together with :Varying amounts of fluxes and heated to a mod-
erately high temperature in a kiln (1200 to 1500°C.). Because 'of the dif-
180 THE CERAMIC INDUSTlUES

ferellt amounts and kinds of fluxes there is a corresponding variation ill

the degree of vitrification among the whitewares from earthenware to
vitrified china. These may be broadly defined as follows:
Earthenware' is "a porous nontranslucent ware with a soft glaze."
Earthenware is sometimes called semivitreoU8 dinnerware.
Chinaware' is "a commercially vitrified translucent ware with a medium glaze
which resists scratching to a greater or less degree."
Porcelain' is "a thoroughly vitrified, translucent ware with a hard glaze which
resists scratching to the maximum degree." This includes dinnerware but also
the exceedingly important insulation porcelain so essential in the electrical field.
Stoneware especially chemical stoneware 2 is closely related to porcelain. The
stoneware may be regarded as a crude porcelain, the raw materials being of poorer
grade and the manufacturing not so carefully carried out.
Pottery is usually a broad classification including earthenware, c~ina, and
porcelain.

Detailed presentations of the different kinds of whiteware should be

sought in the specialized books to which,ref~rence is given at end of this
chapter. To represent the typical manufacturing procedures in this group,
porcelain is chosen.
Manufacture of Porcelain. There are three lines of production: (1) the
wet process porcelain used for production of fine-grained highly glazed in-
sulators for high-voltage service, (2) the dry process porcelain employed
for rapid production of more open-textured low-voltage pieces, and (3) the
cast porcelain necessary for the making of pieces too large or too intricate
for the other two methods. These three processes are based on the same
raw materials, the differences in mar.ufacturing being largely in the dry-
ing and forming (shaping) steps. The wet process is illustrated 3 by Fig. 3.
This flow sheet may be broken down into the following sequences of unit
operations (Op.) and unit processes (Pr.): ' I

Tge raw materials of proper proportions and-properties to furnish porcelain of

desired quality are weighed from ()verhead hoppers into the weighing car (Op.).
The feldspar, clays, and flint are mixed with water in the blunger (clay-water
mixer) and then passed over a magnetic separator, screened, and stored (Op.).
Most of the water is removed (and wasted) in the filter press (Op.). All the
air is taken out in the pug mill assisted by vacuum and slicing knives. This
results in a denser and stronger porcelain (Op.).
The prepared elay is formed into blanks in a hydraulic press or by hot pressing
in suitable molds/(Op.).

'WATTS, The Selection of Dinnerware for the Home, Uhio Slale Univ. Eng. Expl.
Sta. Cire. 21, 3d cd., 1940; Classification of Ceramic Dinnerware, Bull. Ant. Ceram.
Soc., 16, 246-247 (1937).
• Pictured flow sheet, Chern. & Mel. Eng., 47, 637 (1940).
a Pictured flow sheet, Chern. «(; Mel. Eng., 46,421 (1939).
 MANUFACTURE OF PORCELAIN 181
The blanks are prp,1iminal'ily dried, trimmed, ami finally completely dried-
all under carefully controlled conditions (Op.).
A high surface luster is secured by glazing with selected materials COp.).
The vitrification of the body and the glaze is carried out in tunnel kilns with
exact controls of temperature and movement (Pr.).
The porcelain articles are protected by being placed in saggersl fitted one on
top of the other in the cars. This represents a one-fire process wherein body and
glaze are fired simultaneously. The porcelain pieces are rigidly tested electri-
cally and inspected before storage for sale (Op.).

Much tableware is manufactured by more complicated procedures than

illustrated by the somewhat related porcelain product. Some objects are
shaped by "throwing" on the potter's wheel by skilled hands working

FIG. 3. Porcelain manufacture by the wet process of Westinghouse.

the revolving plastic clay into the desired.form; some objects are "~ast"
from the clay slip in molds of absorbent plaster of Paris. After drying,
the latter are removed and further processed. Mass production of simple
round objects like cups, saucers, or plates, is carried out economically by
" jigging" where the plastic clay is pressed into or on a single revolving
imold, the potter often being aided in shaping the other surface and in
removing excess clay by a lever which he lowers over the mold, shaped in
the profile of the object desired. The mold is placed in the drying room.
The vitrification as shown in Fig. 3 tis by the one-fire process. Fre-
quently the two-fire method is used wherein the body is fired, cooled,
glazed, and fired again. I

Glazing is always important in whitewares; it is particularly so for

tableware. A glaze is a thin coating!of glass that is melted onto the sur-
face of the more or less porous ceramic ware. It contains ingredients of

1 S~ggers are made by mixing coarse g~anules obtained from grinding old saggers

with new clay and water in a pug mill and discharging the doughlike mass from an
extrusion machine in loaf form. These loaves are placed in a molding machine, where
box shape is imparted, and then fired. They may be used several times.
182 THE CERAMIC INDUSTRIES

two distinct types in different proportions: (l) refractory materials such

as feldspar, silica, and china clay and (2) fluxes such as soda, potash,
fluorspar, and borax. Different combinations of these materials and dif-
ferent temperatures at which they are fired give a wide rlJ,nge of texture
and quality. The glaze must bond with the ware, and its coefficient of
expansion must be sufficiently close to that of the ware to avoid defects
such as" crazing" and" shivering." The glaze may be put on by dipping,
spraying, pouring, or brushing. All of these methods need a great deal
of care. Decorations may be applied by carving, painting with a thick
paint, marbling (dabbing on paint), tracing with a glass tube, or combing.
For high-grade tableware, the decorations are by decalcomania paper
which is simply a mechanical means for manifold duplication of the same
design. However, such designs are "touched up" by an artist. For the
highest type of tableware much hand decorating is practiced. Decora-
tion of such ware may be "underglaze" or "overglaze."
Glost firing is the technical term for the firing of the glaze. Care should
be taken in packing the kiln or the saggers so that the ware does not
touch except for the three necessary underneath supports. As much space
as practical is allowed between the different pieces of the ",ares since the
glazes often bubble and rise before flattening. The temperature of the
glost kiln may be increased more rapidly than during the first firing, but
heating should not be hurried as strains would be set up. Large shapes
should be packed in the center of the kiln to avoid uneven heating and
should be fired more slowly than small ones. Earthenware should be
glazed between 1050 and 1l00°C.; stoneware between 1250 and 1300°C.

HEAVY CLAY PRODUCTS

Low-cost but very durable products, such as common brick, fac~

brick, terra cotta, sewer pipe, and drain tile, are frequently manufactured
from the cheapest of common clays with or without any glazing. The
clays used generally carry sufficient .impurities to provide the needed
fluxes for binding. When glazed, as in sewer pipe or drain tile, this may
tbe done by throwing salt' ("salt glaze") upon the Juln fire. The vola-
tilized salt reacts to form the fusible coating or glaze..
Manufacture of Buildu;.g Brick. One of the most important of clay
products is building brick, which comprises common and face brick. The
raw materials are clays from three groups: (1) red burning clay, (2) white
burning clay, (3) buff burning clay, usually a refractory. The require-
ments for a face-brick clay are freedom from warping, absence of soluble
salts, suffici~nt hardness when' burned at a moderate temperature, and
general uniformity in color upon burning. Requirements for common
brick are much less stringent. Red burning clay is most used for both
 MANUFACTURE OF BUILDING BRICK 183
common and face brick; however, the semirefractory buff-colored clay is
ill great demand because coloring matter may be added to vary the color
effects. Manganese, with white or buff burning clay, gives a very' attrac-
tive color.
Bricks are manufactured by one of three processes:! the soft-mud, the
stiff-mud, or the dry-press. The soft-mud procedure consists in molding
the clay mixture containing 20 to 30 per cent water in molds coated with
a thin layer of either sand or water to prevent sticking. The molded
brick is burned. Such bricks are of a uniform and excellent quality with
good edges. This soft-mud process is much employed for firebrick and is
the ancient method for making building bricks. In the now predominant
stiff-mttd procedure, the clay is just wet enough (12 to 15 per cent) to
stick together when worked. This clay is forced out through a die in a
screw or auger machine. An important new development, called deairing,
is the operation o~ the auger in a vacuum chamber (14 to 29 in. Hg).
Dcairing increases the workability, plasticity, and' strength of the un-
dried brick by reducing voids, for all but a few clays. The extruded clay
bar passes along a short belt conveyer onto a cutting table on which a
frame with a number of wires automatically cuts the bar into appropriate
lengths. These bricks (as well as those from the soft-mud process) may
be repressed to make face brick. This repressing not only ensures a more
uniform shape but overcomes the internal stresses set up by the extru-
sion in the screw. These molded bricks may be stacked 6 to 10 ft. high
without damage before being dried. In the dry-prcss procedure the water
content is from 4 to 7 per cent (usually the "as-is" condition) which
makes the clay relatively nonplastic. The brick unit here is molded at
pressures around 5 tons per sq. in. A typical dry press for brick manu-
facture costs about $30,000, uses 30 to 40 hp., and delivers a maximum
of 750 tons pressure.
The stiff-mud process is employed for the ~anufacture of pra;ctically
every clay product, including all types of brick, sewer pipe, drain tile,
hollow tile, fireproofing, and terra cotta. The clay in some cases can be
worked directly from It bank into the stiff-mud machine, but a more desir-
able product will result if the clay is ground and tempered before being
used. The greater percentage of clay ware is m~de by the stiff-mud
process.
Bricks are dried in. various ways: outdoors, in sheds, or in tunnel
driers. After drying, the bricks are fired in kilns of such type: as de-
scribed later in the chapter, to a temperature from 875 to somewhat
above 1000°C.
I,

1 KIRK and O'1'HMER, op. cit., Vol. 3, pp. 521-545. Competitive with these ceramic

bricks in certain areas are sand-lime hricks (see Chap. 11).

 184 THE CERAMIC INDUSTRIES

REFRACTORIES

Refractories' embrace those materials which are us~d to withstand the

effect of thermal, chemical, and physical effects that are met with in fur-
nace procedures. Refractories are sold in the form of firebrick, silica
brick, magnesite brick, chromite brick, magnesite-chromite brick, silicon
carbide refractories, zirconia refractories, aluminum silicate products, oli-
vine products, and others. The variety of refractories available is increas-
ing, thus making possible a better selection of a refractory for a particular
use. In making refractories the main .material is chosen to adapt itself
best to the thermal, chemical, and mechanical conditions to be met with.
The fluxes required to bind together the particles of the refractories are
kept at a minimum. Largely because of this there is but little vitrifica-
tion. The possibility of shaping articles made from bodies without clay
and even with no natural plasticity led to the manufacture of single-com-
ponent ceramics with superior qualities, e.g., pure oxide refractories.
These are monocrystalline and self-bonded as compared with the con-
ventional vitreous-bonded refractories.
Properties of Refractories. In determining the refractory best suited
for a definite operation it is necessary to consider the working tempera-
ture of the furnace where the refractory is needed, the rate of temperature
change, the load applied during heats, and the chemical re;;tctions that
are encountered. Generally, several types of refractories are required for
the construction of anyone furnace because usually no single refractory
can withstand all the different conditions that prevail in the various
parts of the furnaces. In order ~o guard against reaction between the
different kinds of bricks a separating cement or brick that has little tend-
ency to react with either of the adjacent refractories should be used.
Chemical Properties. The usual classification of commercial refractories
divides them into acid, basic, and neutral groups, although in many cases
a sharp distinction cannot be made. Silica bricks are decidedly acid, and
magnesite bricks are strongly basic; however, fire-clay bricks are gener-
ally placed in the neutral group though they may belong to either of
; these classes depending up,on the relative silica-~lumina content. Also, in
the alumina-silica series of refractories many types can, be made with
wide differences in their chemical reactions. It is usuaJly inadvisable to
employ an acid brick in contact with an alkaline product, or vice versa.
Neither chemical reactions nor physical properties are sole criteria of ac-
ceptable behavior; both should be considered. Chemical action may be
due to contact with slags, fuel ashes, and furnace gases as well as with
products sU9h as glass or steel, Among the gases that have a deleterious
1 NORTON, "Refractories," 3d ed., McGraw-Hill Book Company, Inc., New York,
1949. This volume is most essential for everyone working in this field particularly,
because of the hundreds of ulassified references to further details in the literature.
 PROPERTIES OF REFRACTORIER 18.5
effect are carhon monoxide, sulfur dioxide, natural gas, hydrogen, and
steam.
TABLE 3. FUSION TEMPERATURES OF REFRACTORIES·

Temperature, Temperature,
Material °C. OF.

Fire-clay brick ...................... . 1600-1750 2912-3182

Kaolinite, Al,03·2SiO.·2H.O .......... . 1785 3245
Silica brick ......................... . 1700 3090
Silica, SiO •.......................... 1710 3110
Bauxite brick ....................... . 1732-1850 3150--3362
High-alumina clay brick .............. . 1802-1880 3276-3416
Mullite, 3AI 2 0 3·2SiO •................. 1810 .3290
Sillimanite, AI.SiO •................... 1816 3300
Forsterite, 2MgO·Si0 2 • • • • • • ' • • • • • • • . . 18\)0 :3434
Chromite, FeO·Cr 203 ................ . 1770 3218
Chrome brick ....................... . 1\)5(}-2200 3542-3992
Alumina, AI.0 3..................... . 2050 3720
Spinel, MgO·Al.0 3................... . 21:\5 3875
Silicon carbide, SiC .................. . 27()0 4890
Magnesite brick ..................... . 2200 3992
Zirconia brick ....................... . 2200-27()() 3992-4892

4 NORTON, "Refractories," pp. 356-36l, 3d ed., McGraw-Hill Book Company, Inc.,

New York, 1949. For other data on refractory materials, see PERRY, op. cit., pp. 1538,
1549.

Porosity. The porosity is directly related to many ~ther physical prop-

erties of brick including resistance to chemical attaCK. The higher the
porosity of the brick the more easily it is penetrated by molten fiu?,es and
gases. For a given class of brick the one with lowest porosity has the
greatest strength, thermal conductivity, and heat capacity.
Fusion Point. Before use, the softening point of a refractory should
be determined. It is found by use of pyrometric cones of predet~rmined
softening points. Most commercial refractories soften gradually over a
wide range and do not haye sharp melting points because they are com-
posed of several different. minerals both amorphous and crystalline in
type. The pyrometric ~ones (once known as Seger coues) are small pyra-
mids made of mixtures of oxides and are useful for the approximate
measurement of temperatures by steps averaging about 36° from 1100 to
3700°F. These are cohsidered indispensable, not because of high-tem-
perature accuracy but because their temperature-timtl performance is
similar to that of thei materials being fired. The fusing points of these
pyrometric cones are I~vailable in the literature.' Typi~al fusion points
1 A.S.T.M. Designation: C24-42. Many other specifications for refractories and
refractory materials are given in the A.S.T.M. standards. See PERRY, op.cit., p. 1272.
186
of refractories, ooth for pure substances and for technical products, arc
given in Table 3.
Spalling. A fracturing or a flaking off of a refractory brick or block
due to uneven heat stresses or compression caused by heat is known as
spalling.' Refractories usually expand when heated. Bricks with the
highest expansion and least uniform rate are most susceptible to spalling
when subjected to rapid heating and cooling. When refractories are
heated for a great length of time at high temperatures, they may have a
permanent volume change, either expansion or contraction, which may
be caused by mineral inversion, softening, or overfiring. .
Strength. Cold strength usually has only slight bearing on strengths at
high temperatures. Although most of the applications place refractories
under compressive loads, in rare cases they may be subjected to tension
or shear alone. Resistance to abrasion or erosion is also very important
for many furnace constructions such as co-product coke-oven walls, and
linings of the discharge end of rotary cement kilns.
Resistance to Rapid Temperature Changes. Generally speaking, bricks
with the lowest thermal expansions and coarsest textures are most re-
sistant to rapid thermal change; less strain develops also. Bricks that
have been used for a long time are usually altered in their properties,
often being melt.ed to glassy slags on the outside surface' or even heing
more or less corroded away.
'l'hermal Conductivity. The densest and least porous bricks have the
highest thermal conductivity, owing to absence of air in voids. Though
heat conductivity is wanted in some furnace constructions, as in muffle
walls, it is not so desirable as some other properties of the refractories
such as resistance to firing conditions and is given minor consideration.
Insulation is desired in special refractories.
Heat Capacity. Furnace heat capacity depends upon the thermal con-
ductivity, the specific heat, and the specifici gravity of the refractory.
The low quantity of heat absorbed by lightweight brick works as an
advantage when furnaces are operated intermittently because the work- .
ing temperature of the furnace can be obtained in less time with less
fuel. Conversely, the dense alld heavy fire-day brick would be best f9r .
regenerator checkerwork, as in coke ovens, glass furnaces, and stoves for
blast furnaces. I

Manufacture of Refractories. The usual methods for manufacturing

refractories include these unit physical operations and unit chemical proc-
esses: (1) grinding and screening, (2) mixing, (3) pressing or molding and
repressing, (4) drying, and (5) burning or vitrification. Usually the most
important single property t~ produce in manufacture is high bulk den-
sity, which affects many of the other important properties such as
1 NORTON, op. cit, Chapter 15 is devoted entirely to spalling with many literature
references.
 MANUFACTURE OF REFRACTORIES

strength, volume stability, slag, and spalling resistance, as well as hea,t

capacity. On the other hand, for insulating refractories a porous stru<;-
ture is required, which means a low density.
Grinding. Obviously, one of the most important factors is the size of
the particles in the batch. It is known that a mixture in which the prQ-
portion of coarse and fine particles is about 55 to 45, with only few inter-
mediate particles, gives the densest mixtures. Careful screening, separa-
tion, and recycling are necessary for close control. This works very well
on highly crystalline materials but is difficult to obtain in mixes of high
plasticity.
Mixing. The real function of mixing is the distribution of the plastic
material so as to ClJat thoroughly the nonplastic constituents. This serves
the purpose of providing a lubricant during the molding operation and
permits the bonding of the mass with minimum voids.
M oiding. The great demand for refr!lctory bricks of greater density,
strength, volume, and uniformity has eventually resulted in the adoption
of the dry-press method of molding with mechanically operated presses
and the discarding of hand molding and extruding processes. T~e dry~
press method is particularly suited for batches that consist primarily of
nonplastic materials, In order to use high-pressure forming it is. neces-
sary to deair the bricks during pressing to aVQid laminations and crack-
ing when the pressure is released. There are four ways of deairing dry-
press bricks: (1) Decreasing the rate of pressure application and 'release
so that the air in the voids has opportunity to seep through the sides of
the brick and mold box. (2) Double pressing of the materials. In this
method the bricks are pressed and allowed to crack. Repressing then
closes the cracks. (3) Deairing by use of a gas, such as butane, which is
piped to the mold box to displace the air. When pressure is applied, the:
gas is absorbed by the clay or condensed. If a flammable gas is used, it
should be more carefully handled to reduce the fire hazard. (4) The use
of a vacuum applied through vents in the mold box (cf. vacuum pug mill
in Fig. 3). Large special shapes are not 'adapted to machine molding;
however, their manufacture has been improved by the use of tamping
with pneumatic tools to attain very high densities.
Drying. Drying is used to remove the moisture that was added before
molding to develop plasticity. It should be noted that the elimination
of water leaves voids and causes high shrinkages and internal strains.
For this reason the dry-press process (requiring only 4 to 7 per cent of
moisture, instead of 10 to 15 per cent in the stiff-mud method) has been
favored in the manufacture of practically all types of refractory materials.
In some cases drying is~omitted entirely and the small amount necessary
is accomplished during the heating stage of the firing cycle.
Burning. Burning may be carried out in the typical round down-draft
kilns or continuous tunnel kilns. Two important things take place dur-
 188 THE CERAMIC INDUSTRIES

ing burning: (1) the development of a permanent bond by a partial vitri-

fication of the mix and (2) the development of the stable mineral forms
for future service as shown in the phase diagrams of Figs. 2 and 4. The
changes that take place are the removal of the water of hydration and,
then, the calcination of carbonates and the oxidation of ferrous iron.
During these changes, the volume may shrink as much as 30 per cent,
and severe strains are set up in the refractory. This shrinkage may be
eliminated by the prestabilization of the materials used. There are com-
mercial refractories (see Fig. 4) in which the burning operation is entirely
eliminated because the raw materials are prestabilized, appropriately
sized, and pressed.
Varieties of Refractories. About 95 per cent of the refractories manu-
factured are nonbasic-with silica (acid) and fire-clay (neutral) brick
predominant. Although a refractory is usually thought of in terms of its
ability to withstand temperature, it is really only in exceptional cases
that heat is the sole agent that effects the final destruction which is usu-
ally caused by chemical action at that temperature; hence the need for
refractories of different chemical composition.
Fire-clay Brick. Fire clays are the most widely used of all the various
refractory materials since they are well suited for a variety of applica-
tions and may be obtained in quantity. Fire clays range in chemical com-
position from those with a large excess of free silica to those with a high-
alumina content. With material of such variation in quality, there is a
price spread from $50 to $75 per M for bricks made therefrom. The steel
industries are the largest consumers of refractories for the linings of blast
furnaces, stoves, open hearths, and other furnaces. Other industries hav-
ing use for these are foundries, limekilns, pottery kilns, cupolas, brass
and copper furnaces, continuous ceramic and metallurgical kilns, boilers,
gas-generating sets, and glass furnaces.
Silica Brick. Silica bricks contain about 95 to 96 per cent Si0 2 ;'nd
about 2 per cent of lime added during grinding to furnish the bond.
Silica bricks have a permanent expansion which occurs during firing and
/ which is caused by an allotropic transformation that takes place in the
crystalline silica. When reheated, silica brick:;; again expand about 1.5 per
cent, but the effect is rev~rsible, the bricks returning to size when cooled.
This fact should be considered in their installation. Silica bricks are manu-
factured in many standard sizes by power pressing. They have a very
homogeneous texture free from air pockets and molding defects and
possess a low porosity. These are highly desirable properties for the re-
sistance to slag penetration. 1he price is around $78 per M. .
Tile phy~ical strength of silica bricks when heated is much higher than
for those made from clay. Consequently they are suitable for arches in
large furnaces. I"urnaces using these must, however, be heated and cooled
gradually to lessen spaIling and cracking. Open-hearth furnaces have
 I
I
VARIETIES OF REFRACTORIES 18~

silica bricks in their main arch, side walls, port arches, and bulkheads)
but the newest installations here are the super-duty silica bricks and basiq
bricks. Because of their high thermal conductivity silica bricks have beell
utilized in co-product coke ovens and gas retorts. Other uses are in glass
furnaces, electric. furnaces, and copper-smelting reverbatory furnaces!
Superduty silica brick results from the greater chemical purity of th«:)
silica. The sum of the alumina, titania, and alkali impurities in the
super-duty brick does not exceed 0.5 per cent. Super-duty silica bricks
have higher refractoriness and lower permeability to gases than eonven;
tional silica bricks.
High-alumina Refractories. The present demand for these high-alumin~
refractories is largely caused by the improvements in the quality and by,
the growing demand for refractories that can witl\stand severe conditions
for which the older fire-clay and silica bricks were not suitable. High",
alumina bricks are really high-alumina clay bricks made from clays ricQ,
in bauxite and diaspore. The refractoriness and the temperature of in~'
cipient vitrification increase with the alumina content (see phase dia-
gram, Fig. 2). Another valuable property of high-alumina bricks is that
they are practically inert to carbon monoxide and are not disintegrated
by natural gas atm?spheres up to 1000°C. Alumina content ranges from
48 per cent upward. High percentages are classed among the superrefrae,
tories, and almost pure alumina (97 per cent) is considered among the'
recently developed special refractories termed "pure oxides." High-alu-
mina brick prices vary directly with the alumina content, with an averag~
value of $176 per M.
High-alumina bricks are employed in the cement ~ndustry and paper~
mill refractories. They have proved successful in boiler settings because
of the resistance to the chemical action of fuel ash which contains basic
oxides. They have proved economical for the linings of glass furnaces, oil"
fired furnaces, high-pressure oil stills, in the roofs of lead-softening fur'-
naces, crowns of silicate of soda furnaces, and in regenerator checkers of
blast furnaces.
Basi,; Refradories.! The important basic bricks are made from magne~
sia, chromite, and forsteri.te. To achieve the required strength and other
physical properties, t'\le basic bricks are usually power pressed and are
either chemically bonded or hard burned. The disadvantages of lack of
bond and volume stability in unburned basic or other bricks have been
overcome by three i~provements in manufacturing: (1) Interfitting of
grains has been devel~ped to a maximum by using only selected particl~
1 RocHOW and BRAsHAREs, Recent Developments in Refractories and Their Appli-
cations, Chem. Eng. Proqr., 44, 869 (1948); Dem,merle, et al., Manufacture of Basib
Refractory Brick, Ind. Eng. Chem., 40, 1762 (1948); Byrns, Integrated Basic Refrac,-
tories Operation in California, Chem. Eng., 57, (5), 153 (1950); 57 (5), 200, pictured
flow sheet.
190 THE CERAMIC INDUf;TRIES

sizes combined in the proper proportions to fill all the voids. (2) The
forming pressure has been increased to 10,000 lb. per sq. in. and deairing
equipment used to reduce the air voids between the grains. (3) The use
of a refractory chemical bond. The flow sheet for the manufacture of un-
burned refractories, as compared with the burned-brick process, is shown
in Fig. 4. The unburned bricks have a higher density and, therefore,
better slag-resisting properties than burned brick and an outstanding
resistance to spalling.
The magnesia refractories are made from domestic magnesites, or mag-
nesia extracted from brines (Chap. 11). Magnesia hricks do not stand
much load at elevated temperatures, but this difficulty has been over-
come by blending with chrome ores. Many blends are possible, ranging

*Selecteol grain sizes are screened out and recombined in definite proportions for
ma~imum ciensity. It has been found that a suitable proportion for many purposes
is 55 parts of coarse to 45 parts of fine particles, with elimination of intermediate sizes.
Unburned mfructories made by several manufacturers; process shown is that of
Generul Refrdctories CO.
FIG. 4. Flow chart for unburned refractories by Ritex process, compared with burncd-
hrick process. (Courtesy of General Refractories Company.)

from predominantly magnesia to predominantly chrome. In the nomen-

clature the predominant blend constituent is given first. There is a large
price variation because of the composition variation, but the average
value is about $350 per M which makes these bricks among the most
expensive.
Chemically bonded magnesite-chrome bricks l/-re frequently supported
with mild steel to hold the brickwork and minimize spalling loss. These
refractories are used in open-hearth _and electric-furnace walls, in the
burning zones of cement kilns, and in the roofs of various nonferrous
Ireverberatory furnaces. Hard-burned chrome~magnesite bricks have many
important physical properties because of their special composition, par-
ticle sizes, high forming pressure, and high firing temperature. They are
of particular interest in the basic open-hearth furnaces.
Forsterite (2MgO·Si0 2) is employed both as a bond and as a base for
high-temperature refractories. Where forsterite forms the base, the re-
fractories are generally made from olivine. This naturally occurring sili-
cate contain's 2(Mg,Fe)O'Si0 2 'and is characterized by its refractoriness.
In the manufacture of forsterite refractories, dead-burned magnesite is
usually added to convert some accessory minerals also to forsterite, whirh
is the most stable magnesium silicate at high temperatures, as shown by
 VARIETIES OF REFHACTORIES 19,
Fig. 5. For example, enstatite (or clinoenstatite of Fig. 5) occu~ring in
the rock olivine as mined, is converted to forsterite,
MgO·Si0 2 + MgO ----> 2MgO·Si0 2
Enstatite Magnesia Forsterite

1:iuch refractories have the advantages of a high melting point, no trans-

formations during heating, and unsurpassed volume stahility at high tem-
peratures. No calcining is necessary in their preparation. The most illl~
portant use of forsterite is in glass tank superstructures and checkers as
1900
Periclose + liquid B
1850·

1800
Liquid A \
, I
'(

,, Liquids A+ B
\
I

,,
U J \
Vl Periclase + Forsterite \
\
Q)
Q) 1700 1695°
I- F
0' Cristobali+e +liquid AI
I))
0

Cristobal ite +liquid B

1600
I Clin~enstatite + liquid B
1557" I
1543·

1500
0 'l0 40 60 80 100,

, MgO 2I-1g0-SiO Z SiO z

Weight Per Cent

FiG. 5. Phase diagram of the system MgO-Si0 2 • [From Hall and Insley, J. Am. Ceram.
Soc., 16, 493 (1933).] I

its high chemical resistance to the fluxes employed. and good strength a~
high temperatures allow enhanced tank output. These refractories alsq
find many other industrial applications such as in open-hearth end walt~
and copper-refining fJ.rnaces.
Silicon Carbide Refractories. These super-refractories are noted for the'ir
chemical resistance aJtd ability to withstand sudden temperature changes.
In their manufacture: the crude material from the silicon carbide furna~c
is ground and the ceramic bond is added. The latter may be finely di-
vided silicon carbide,' itself, or clay. The mixture is molded to shape aqd
 192 THE CERAMIC INDUSTRIES

the less than 10 per cent of bond vitrified. These bricks are extremely
refractory and possess a high thermal conductivity, low expansion, and
high resistance to abrasion and spalling. They are strong mechanically
and withstand loads in furnaces to temperatures as high as 1650°C. At
higher temperatures this strength is less. Such refractories are used chiefly
in muffles because of their thermal conductivity. Their ability to absorb
and release heat rapidly and their resistance to spalling under repeated
temperature changes make them desirable for recuperators. Refractories
of this type can be made thinner than those from fire clay.
Refractories from Crystalline Alumina or Aluminum Silicates.! Research
has revealed that mullite and corundum have high slag resistance and
remain in the crystalline state at temperatures of 1600°C. and higher
(see Fig. 2 for phase diagram). High-temperature kilns now furnish alu-
mina bricks that closely approach pure corundum in properties and mullite
bricks that are made from calcined Indian cyanite with the old clay bond
replaced by a mullite bond consisting of interlocking crystals. Such re-
fractories are finding many new applications, particularly where severe
slagging has been a problem.
Electrocast Refractories. Many kinds of bonded refractories are made
from electrically fused _mullite. These are manufactured by introducing
a mixture of diaspore'clays of high-alumina (to furnish 3AI 20 a,2Si0 2 ratio)
content into the top of an electric furnace. If necessary, these are ad-
justed to furnish the stable mullite ratio of 3AI 2 0 a·2Si0 2 • Molten alu-
minum silicate at 3400°F. is tapped from the furnace at intervals and
run into molds built from sand slabs. The molds containing these blo_gk_s:::::
are annealed from 6 to 10 days before the blocks are usable. The refrac-
tory obtained from this process has a vitreous, nonporous body which
shows a linear coefficient of expansion of about one-half that of good fire-
brick. The blocks cannot be cut or shaped but may be ground on Alundum
wheels; however, skill in casting has progressed rapidly and now many
sizes and intricate shapes are available. This electrocast mullite has only
0.5 per cent voids in contrast with the usual 17 to 29 per cent in fire-clay
/ blocks. Cast refractories are employed in gl~ss furnaces, as linings of hot
zones of rotary kilns, in modern boiler furnaces exposed to severe duty,
and in metallurgical equiJ?ment such as forgi~g furnaces., The refractories
have the advantages of long life and minimum wear, against which must
be balanced their greater initial cost. A newer and superior variety of
fused cast refractories with from 83 to 95 per cent alumina is available.
Here the interstitial glass content is greatly reduced, along with voids in-
duced during the usual castin~ process. 2
1 REMMEY, 'New Alumina-~ilica Refractories, Chem. Eng. Progr., 44, 943 (1948).
• GEIGER, el al., Applications of Super Refractories Made from Electric Furnace
Products, Chern. Bnyr. Progr., 44, 933 (1948).
 VARIETIES OF REFRACTOlUES 193
1
Pure Oxide Refractories. The refractories industry is constantly faced
with increased demands for products which will withstand higher tem-
peratures and more severe operating conditions. To meet these require-
ments, a group of special or pure oxide refractories has been developed.
The superior qualities are based mostly on freedom from fluxes. Refrac-
tory oxides of interest in order of increasing cost per unit volume include
alumina, magnesia, zirconia, beryllia, and thoria. All these have been de-
veloped commercially for light refractory wear, but only alumina, mag-
nesia, and zirconia have been used in heavy refractory products. These
last three have certain properties in common: (1) they have high purity
(a minimum of 97 per cent alumina, magnesia, or stabilized zirconia) and
(2) they are principally composed of electrically fused grain. Beryllia is,
not used commercially in heavy wear because of its high cost and volatil...
ization above 3000°F. in the presence of water vapor. Thoria has a num-
ber of disadvantages, particularly since its radioactivity places it under
the control of the Atomic Energy Commission.
The material that has the widest application of these pure oxide re"
fractories is sinter alumina. It is used successfully at temperatures up to
about 3400°F. Magnesia is a basic refractory and is easily reduced at
high temperatures. Its applications are limited to oxidizing atmospheres
at temperatures not much over 4000°F. Since pure zirconia undergoes a
crystalline change from monoclinic to tetragonal form at about 1800°F. ac-
companied by a drastic volume change on inversion, stabilization of the
crystal structure to the cubic which undergoes no inversion was neces-
sary. This is accomplished by adding certain metalliq"oxides (particularly
CaO and MgO). Processing temperatures in the range of 4600 to 4700°F.
are now commercial with available fused stabilized zirconia. Only pres-
ent large-scale use is as kiln furniture for the firing of barium titanate
resistors, but future large usage seems probable.
~nsulating Brick. Insulating bricks are of two types: (1) for backing of
refractory bricks and (2) in place of regular refractory bricks. Most
bricks used for backing are made from naturally porous diatomaceous
earth, while the second type, usually called lightweight refractories, are
similar in compositionl to heavy bricks and owe their insulating value to
the method of manufacturing. For instance, waste cork is ground and
sized; this is mixed with the fire clay, molded, and burned. In the kilh
the cork burns out leaving a highly porous and light brick. These light-
weight refractories ll{ay be used safely for temperatures of 2500 to
2900°F., while diatOlnac~ous-earth brick are not suitable above 2000°F.
under ordinary conditions.
I
I WHITTEMORE, Pure Oxide Heavy Refractories'; Chem. gnu. Progr., 44,872 (1948) j
BALDWIN, Zircon and Zirconia RefraetorieH, Chem. Eng. Proflr., 44, 875 (1948); ANON.,
Fused Stabilized Zireonit(, Chern. Eny., 58 (2), 199 (1951).
 196 THE CERAMIC INDUSTRIES

a nickel flash on the base metal is still necessary to promote optimum

1

adherence, the complete deoxidation of the metal prior to enameling has

eliminated surface defects such as reboiling which can often be traced to
the evolution of gas by the metal at temperatures necessary for maturing
the enamel coating.
Application of the Enamel. Enamel may be applied to the metal in a
number of different ways. Sheet-iron coats are generally applied by dip-
ping or slushing, since the ware is usually coated on all sides. Slushing
differs from draining in that the enamel slip is thicker and must be
shaken from the ware. It is convenient for small odd-shaped pieces. A
third method of application is spraying. Any of these three processes may
be employed wet or dry. Cast-iron treatment is very similar to that for
sheet iron, but slushing here consists of pouring the enamel slip over the
casting and allowing the excess to run off. The enamel is now air-dried,
and colors are brushed and stenciled on if wanted. The enamel is usually
applied in two coats for premium products.
Firing. All enamels should be fired on the ware to melt them into a
smooth, continuous, glassy layer. The requirements for successful firing
of a good enamel are (1) proper firing temperature 1400 to 1500°F., (2)
time 1 to 15 min., (3) proper support of the ware, (4) uniform heating
and cooling of the ware, and (5) an atmosphere free from dust. Heat is
provided in either intermittent-fired muffle furnaces or continuous-tunnel
furnaces. The product is taken from the furnace and given many tests
for its thermal, optical, physical, and chemical properties. Enamel coats
average about 0.0065 in. as compared with 0.026 in. a few years ago. T~e
ware is now ready for use. The special enamel- or glass-lined equipment
so extensively used in chemical plants is tested even by high-frequency
waves to exclude any defects which only this method will detect but
which in course of use would offer an avenue for acid penetration.

KILNS

The vitrification of ceramic products and the prior unit processes of

/dehydration, oxidation, and calcination are carried out in kilns that may
be operated in a periodic or continuous manner. Ml!ffie kilns are also
employed. Usually all the'newer installations are continuous-tunnel kilns
which have many advantages over the batch kilns, such as lower labor
costs, greater thermal efficiency, shorter processing time cycle, and better
operating control. Coal and oil are the most important fuels for firing,
but gas and electricity are used in some cases. The choice of the kiln
and fuel 2 is ~argely a question of economics and product quality.
I

1 HARMAN and KING, Applications of Nickel Compounds in Ceramics, Ind. Eng.

Chern., 44, 1015 (1952).
• NORTON, op. cit., pp. 242, 244, and 252, tabulates fuel consumption for periodic,
tunnel, and chamber kilns.
 PERIODIC KILNS

Continuous Kilns. The most important kilns are the continuous-car

tunnel kilns used for the firing of brick, tile, porcelain, tablewll:re, an<;l
refractories. There are two general types of such kilns: the direct-fired
type where the combustion gases burn directly into the wares and the
indirect (muffle) type where the products of combustion are not allowed
to contact the wares. The wares are loaded directly onto open cars or
enclosed in saggers which keep the wares clean. The cars pass through the
tunnel counterflow to the combustion gases from the high-fire zorie.
The continuous chamber kiln consists of a series of connected chambers.
The heat from one chamber is passed to another countercurrent to the
ware. Because the chambers are burned in succession, the operation :is
continuous. There is always one chamber cooling, another being fired,
and another being heated by the waste heat of the two other chambers.
This type of kiln is used to burn brick and tile.
Periodic Kilns. Downdraft kilns, which are round or rectangular shaped,
are used in burning face brick, sewer pipe, stoneware, tile, and common
brick. In them the heat is raised from room temperature to the finishing
temperature for each burning operation. The kiln is "set" (filled with
wares to be burned) ; the heating is started and the temperature raised at
a definite rate until the firing temperature is reached. The downdraft kiin
is so named because the products of combustion go down in passing over
the ware set in the kiln. The gases leaving the furnace go up inside the
walls to the crown of the kiln and are pulled through the ware by means
of a system of flues connected to an outside stack.
The updraft kiln has been most commonly used in 1)urning pottery ware
but is rapidly being replaced by tunnel kilns. It is similar to the down-
draft type except for the movement of the gases. It gives better heat con~
trol than does the downdraft type. Common bricks are burned in scove
kilns, which are really vatiations on the updraft type. The kiln itself is
built from the green brick with the outside walls daubed or "scoved"
with clay. The clamp kiln is a variation on the preceding in which the
side walls are permanent. After burning, the kiln is completely dismantled.

I SELECTED REFERENCES
Norton, F. H., "Refractories," 3d ed., McGraw-Hill Book Company, Inc., New
York, 1949. Standard book.
Norton, F. H., "Elemerits of Ceramics," Addison-Wesley Publishing Company,
Cambridge, Mass., Hl52. Introductory book. .
Ries, H., "Clays, Their Occurrence, Properties and Uses," John Wiley & Sons, Inc.;
New York, 1908. . I
Searle, A. B., "An Encyclopedia of the Ceramic Industries," 3 vols., Ernest Benn,
Ltd., London, 1930. '
- - , "Chemistry and, Physics of Clays and Other Ceramic Materials," 2d ed.;
Ernest Benn, Ltd., IJondon, 1933.
McNamara, E. P., "CeramicS'," 3 vols., Pennsylvania State College, State College,
1945.
198 THE CERAMIC INDUSTRIES

Newcomb, R., Jr., "Ceramic Whitewares," Pitman Publishing Corporation, New

York,1947.
Anon., "Refractories," General Refractories Company, Philadelphia, 1949.
Andrews, A. I., "Enamels," The Twin City Ptg. Co., Champaign, Ill., 1935.
Ladoo, R. B., and W. M. Myers, "Nonmetallic Minerals," 2d ed., McGraw-Hill
Book Company, Inc., New York, 1951.
Kirk, R. E., and D. F. Othmer, "Encyclopedia of Chemical Technology," Interscience
Encyclopedia, Inc., New York, 1947-1956.
Bulletins and Journals of the American Ceramic Society, Columbus, Ohio.