o

UNITED STATES ATOMIC ENERGY COMMISSION

ORNL-1354

CRUCIBLE HANDBOOK
A Compilation of Data on Crucibles Used for
Calcining, Sintering, Melting, and Casting

By
M. A. Schwartz
G. D. White
C. E. Curtis

April 17, 1953

[Site Issuance Date]

Oak Ridge National Laboratory

Oak Ridge, Tennessee

Technical I n f o r m a t i o n Service, Oak Ridge, Tennessee

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<?<,**" ^ ' «*>?4^ J>£^
 r . 4

Subject Category, METALLURGY AND CERAMICS.

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 CRUCIBLE H A N D B O O K

M. A. Schwartz G. D. White
C. E. Curtis

INTRODUCTION

Personnel in the atomic energy program are con- the ORNL Ceramic group felt that a valuable con-
fronted at times with an immediate need for infor- tribution could be made by compiling information
mation concerning the properties of commercially from both published and unpublished sources in a
available nonmetallic crucibles. Some of the infor- form that would enable the casual worker to ascer-
mation is unavailable to the casual worker, and tain readily the type of crucible best suited to his
the published portion is widely scattered through- needs and to find a source of supply on the market
out the literature. for each type. In addition, forming methods are
presented to aid those who may wish to fabricate
Since nonmetallic crucibles are usually ceramic, their own crucibles.

FABRICATION OF CERAMIC CRUCIBLES

Ceramic raw materials are obtained mostly as than to the making of crucibles, although extruded
powders or grains from which crucibles are pro- rods are sometimes cut into sections and machined
duced generally by a forming procedure at room into crucibles in the moist, dry, or fired state. The
temperature followed by a high-temperature treat- need for a special steel die for each different
ment to produce strength. Principal forming methods shape makes this process rather inflexible. A
requiring this procedure are jiggering, extruding, plastic mixture is desirable, and some degree of
ramming, dry-pressing, and slip-casting. Another plasticity can be given to nonplastic materials by
procedure combines forming and heating in one fine grinding, by deairing, and by adding plasti-
operation and is called "hot-pressing." cizers and lubricants. The extruded product usually
has medium-to-high porosity and rather uniform
JIGGERING texture.
Jiggering is an adaptation of the potter's-wheel
method of forming and consists in forcing the moist RAMMING
ceramic composition against the inside of a ro- Ramming is a method in which a moistened com-
tating mold by means of a stationary jigger tool. position is tamped by hand or with an air hammer
The mold is usually made of plaster of paris, between the wall of a mold and a core. The mold
although steel or wooden molds are employed in and core may be made of plaster, wood, or steel;
some cases. Jiggering is useful in forming circular steel is preferable since coarse grains in the
products in which a high degree of uniformity in ceramic mixture tend to embed themselves in softer
structure and low porosity are not essential. It mold materials and make removal of the crucible
permits the use of coarse-grained raw materials, difficult. Ramming is particularly adapted to the
which, in some cases, add to the resistance of the forming of tubes or crucibles of round or irregular
crucible to cracking during rapid temperature shapes and for compositions of low plasticity and
changes. A certain degree of plasticity in the coarse grain sizing. Binders such as starch or
composition is desirable, and the process lends resins from paper wastes (such as Goulac) are
itself more readily to the forming of ware con- usually added to give dry strength to the crucible.
taining plastic clay than to ware containing only Coarse grain sizing generally increases the re-
nonplastic ceramic materials. sistance of the fired crucible to rapid temperature
changes; consequently, ramming is probably the
EXTRUDING method best suited for forming heat- and shock-
Extruding consists in forcing a column of the resistant crucibles of nonplastic materials. How-
moistened material through a die. It is especially ever, it requires a separate mold for each shape
adapted to the production of rods and tubes, rather and therefore is rather inflexible. Also, uniform

1
 t-j^r'

A".TV-
d e n s i t y and low porosity cannot be expected in requires a mold of the proper shape and character
r a m m e d crucibles because of the nature of the and a properly deflocculated slip.
procedure and the compositions used.
Mold

DRY-PRESSING The proper method of mold making is described

in books on pottery making and in literature avail-
Dry-pressing is a procedure in which a powdered able from the manufacturers of plaster of paris
mixture of the desired composition is dampened (Table 1). Figure 1 shows the properties obtained
with a suitable liquid and formed in a mold, usually by various plaster-water mixtures.
of steel, under mechanical or hydraulic pressure.
This method is suitable for forming compositions Deflocculation
of low-to-medium plasticity and fine-to-medium A fundamental requirement for good slip-casting
grain sizing. It would be used more often for
behavior is a proper degree of deflocculation, a
producing high-temperature crucibles, except that
term that denotes a rather stable suspension of
a carefully machined and therefore costly steel
solid particles in a liquid medium. Deflocculation
mold for each size and shape is required. Uniform
is frequently accompanied by a slowing down of
density is difficult to attain by dry-pressing, since
the rate of absorption of the liquid by the mold
a higher density is produced nearer the moving
and by a thinning (lowered viscosity) of the slip.
portions of the mold. Furthermore, lamination
These effects favor easier casting by prolonging
cracks from entrapped air are often encountered.
the casting time (which is rather short in the case
of most nonplastic materials) and by permitting
SLIP-CASTING efficient draining of the excess slip from the mold
Slip-casting is probably the most readily adapta- to form smooth inner surfaces in the case piece.
ble method for the casual forming of nonplastic Deflocculation is attained by the presence (usu-
crucibles. This method of fabrication depends ally in fractions of a per cent) of a soluble, ion-
upon the ability of plaster of paris molds to extract izable dispersing agent that may be either a base,
the liquid from a suspension, leaving the solid an acid, or a salt. Dispersing action is ascribed
particles as a coating on the mold. The general to the adsorption upon the surfaces of the solid
procedure consists in pouring a slip of about the particles of a layer of oriented molecules of the
consistency of gravy into the plaster mold, which electrolyte to form a charged sheath. The solid
immediately begins to absorb water and to build up particles being thus similarily charged repel each
a coating of the solid particles. As soon as the other, and any tendency toward coalescing and
coating has attained the desired thickness, the settling is inhibited. In addition, the charged
remaining slip is poured from the mold, leaving the surfaces attract a layer of liquid about each
center hollow. A solid casting can be made by particle, which provides lubrication and free
continually adding the slip as the water is absorbed flowing of the suspension.
until the entire cavity in the mold is filled with the Characteristics of a well-deflocculated sus-
dewatered composition, if the original slip was in pension are a slow settling rate, low viscosity,
the proper state of deflocculation, the casting will slow rate of absorption of liquid from the slip
shrink away from the mold in a short time and can by the mold, good green strength, high density,
then be removed. To be successful, slip-costing minimum shrinkage and less cracking of the piece

TABLE 1. SUPPLIERS OF PLASTER OF PARIS

B. F. D r a k e n f e l d , I n c . , 45-47 Park P l a c e , New York 7, N. Y .

C e r t a i n - T e e d P r o d u c t s C o . , 120 South La Salle Street, C h i c a g o , I I I .

Harrop Ceramic S e r v i c e , I n c . , Pearl Street at Gay, Columbus 15, Ohio

N a t i o n a l Gypsum C o . , B u f f a l o , N. Y ,

T h e 0 . Hommel C o . , P i t t s b u r g h 3 0 , P a .

U n i t e d States Gypsum C o . , 300 West Adams Street, C h i c a g o 6, I I I .

2
 /%$%:

DWG 17781

— 60 75 1 40

68.3 — 55 300 46

62 4 — 50 650 54 5

g
<r
57 UJ (300 . . — 62
45
5
s

2100

— 40

44 3300 —
— 35

40 45 50 55 60 65 70
30
PLASTER OF PARIS (wt % )

F i g . 1. Effect of Varying Plaster of Paris—Water Mixtures on Properties of the Mold.

in drying, and less tendency of the piece to leave no deleterious substance in the crucible.
stick to the mold. Underdeflocculation or over- Their unfavorable characteristics are: (1) a long
deflocculation usually have the opposite effects. period of soaking the nonmetallic material in the
Adsorption of the dispersing agent by the solid acid is usually required; (2) the smooth surfaces
phase is a surface phenomenon, and proper de- of the plaster mold are attacked by the acid, which
flocculation requires that the proportion of surface makes them rough and unusable after three or four
to volume of the solid shall be extremely high. castings; and (3) the acid fumes are rather un-
Plastic clays usually break down readily to fine pleasant to work w i t h .
particles that are plate-shaped and thus are easily Basic deflocculants have not been so widely
deflocculated. In the case of nonplastic materials, used in the casting of nonmetallic substances,
the particles are normally not plate-shaped, and although they have these advantages over the
fine sizing must be obtained by milling. An acids: (1) their deflocculating effect takes place
average particle size of 3 to 5 /x is usually suf- almost immediately without prolonged soaking;
ficient for good deflocculation; finer sizing may (2) they do not attack gypsum molds; and (3) they
be desirable in certain cases but is usually at- are not unpleasant to work with in most cases.
tained at the risk of undue contamination from the Disadvantages of basic deflocculants are: (1) a
milling apparatus. rather critical range of concentrations for good
The principal acidic deflocculating agents are deflocculation, and (2) the possibility of con-
the common inorganic acids, which have these tributing to the fired ware a nonvolatile element
valuable properties: (1) they are effective over such as sodium or potassium that may be dele-
a rather wide range of concentration compared terious, although only 0 . 1 % of dry weight or less
with basic deflocculants in general, and (2) they is normally present. The basic deflocculants most
volatilize during the firing of the refractory and used are the hydroxides, carbonates, phosphates,

3
 >'/

silicates, and organic salts of sodium, potassium, to permit it to sinter. Very dense and accurately
and ammonia. Sometimes mixtures of these are shaped products can be produced by this pro-
recommended. cedure; it is especially suited to induction heating
The choice of a deflocculant for a given casting and to the production of shapes from carbides,
application depends, in part, upon the nature of nitrides, sulfides, and other easily oxidizable
the solid material. Thus, sodium carbonate, which materials, as well as to oxides.
is effective in the case of clay slips, w i l l seldom The maximum size of test piece obtainable is
deflocculate nonplastic materials. Tetrasodium limited to about 4 in. in diameter and the maximum
pyrophosphate is effective when used with zircon pressure to 3000 to 4000 psi; the limitation is due
but is less so with zirconia. Alumina is usually to the low strength of the graphite molds employed.
deflocculated with acid, although tetrasodium pyro- Graphite is used because it is practically the
phosphate has been used successfully with alu- only mold material that is abundant and stable at
mina, also. the high temperatures required (1400 to 2200°C),
A water suspension is sometimes inadvisable, and it has an advantage in being electrically con-
as in the casting of CaO crucibles, in which case ductive so that the mold can act as susceptor in
other liquids such as absolute alcohol, kerosene, induction heating or as resistor. Unfavorable
or carbon tetrachloride may be used. However, properties are a short mold life of 1 to 3 cycles
most dispersing agents are not ionized in these and a tendency to reduce oxides and to form
liquids, and choice of an effective deflocculant carbides.
is somewhat of a problem.
Hot-pressing equipment is costly by reason of
the expensive, electrical apparatus required; the
HOT-PRESSING hot-pressing procedure is therefore limited to work
Hot-pressing consists in compressing a ceramic with expensive raw materials and to those that
material while it is at a temperature high enough cannot be fabricated by other methods.

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COMPOSITION OF CRUCIBLES USED FOR MELTING METALS

METAL CRUCIBLE MATERIALS REMARKS REFERENCES METAL CRUCIBLE MATERIALS REMARKS REFERENCES METAL CRUCIBLE MATERIALS REMARKS REFERENCES

A l k a l i metals Refractory s u l f i d e s * 1 Iron Magnesium oxide For extremely pure iron, 1 , 10, 1 1 , 12 Steel Magnesium oxide Basic steels are melted in 9
5 m g l e crystal MgO Beryllium oxide beryllio or thoria is best Silica magnesia, ond acidic steels
Aluminum oxide are melted in s i l i c a
A l k a l i n e earth Zircon
m.tols Refractory sulfides 1 Fire clay Thorium Cer.um sulfide The metal sticks to the sulfide 6 , 10
Thorium oxide Thorium sulfide
Z.rcon There is least contamination 1,2 Refractory sulfides T i t a n i u m nitride
Zirconio with zircon
Lead 5, 13 Zirconium nitride
C l a y graphite Chromite
Refractory sulfides Magnesium oxide Tin Magnesium oxide 1
F i r . c l a y (dense) Ftre clay (dense)
C . n u m sulfide
Beryllium Beryllium oxide Melting must be conducted in a 3 Magnesium Steel plate coated with The steel plate should be 6, 9, 14 Thorium sulfide
vacuum sand-blasted before spraying F i r e clay
Refractory sulfides Heat-cost mixture of Ond heat-treated after
10 to 60% Z r 0 2 spraying Titanium Cerium sulfide Titanium sticks to the sulfide 1 , « , 18. 19
Bismuth Cerium sulfide 1 7 to 25% MgO crucibles. There is slight
Thorium sulfide 30 to 80% A l 3 0 3 Barium sulfide attack of the thoria, melting
Cor.um sulfide Thorium sulfide i s accomplished in either a
Boron Boron nitride 4 Thorium sulfide vacuum or an argon
atmosphere
Brass Magnesium oxide Charcoal or fluxing material on 5 Manganese Alum.numox.de The metal should be pure. 7
Graphite surface of melt helps to Magnesium oxide since a manganese-rich alloy Uranium Magnesium oxide 6, 10
Clay-graphite reduce oxidation Thorium oxide w , l l p,ck up . . l , c . Calcium oxide
High-grade fire clay Cerium sulfide
N.ckel Zircon For melting pure n i c k e l , 15, 16 Titanium nitride
C M urn T i t a n i u m nitride Cerium sulfide crucibles resist Magnesium oxide Zirconium mtr.de
1, a
Zirconium nitride attack better if the porosity Mullit. vacuum is best Thor.um oxide
Cerium sulfide is from 10 to 1 5 % " F i r e clay (dense) Thorium sulfide
Banum sulfide Graphite
Platinum Thorium oxide Also for platinum-rich alloys 9, 17 Nickel
Zirconium oxide
Chromium Aluminum oxide 7
Magnesium oxide Vanadium Beryllium oxide T h e s e materials were calcu-
Zircon Magnesium oxide lated to be suitable for
Copper Silica 5, 8 Calcium oxide containing molten vanadium
Magnesium oxide Rare-earth
Algmmum oxide Refractory sulfides 1 T i t a n i u m nitride
Clay-graphite

Zinc 1
Rhodium Zirconium oxide 9
Gold Magnesium oxide 9 F l i n t fire clay

Aluminum oxide Cerium sulfide

Silicon S.l.ca 7
Thorium sulfide
Clay-graphtte
Hahdo m . t a l . Refractory sulfides 1 Silver Graphite 9
Magnesium oxide Zirconium Z.rcon.umox.de 10
Iridium Thorium oxide 9 Aluminum oxide Thorium oxide

• T h e refractory Sulfides include BaS, CeS, T h S , C e 3 S 4 , C e 2 S 3 , T h j S j , T h ^ , and T h S j .

' P o r o s i t y is defined as the volume of i i r space expressed as percentage of the total volume of the pie

en
 / .- > J . 5/
REFERENCES 9. Metals Handbook, American Society for
M e t a l s , C l e v e l a n d , 1948.
1. E . D. Eastman, L . Brewer, L . A . Bromley,
10. H. K. Richardson, " S m a l l C a s t Thorium
P. W. G i l i e s , and N. L . L o f g r e n , " P r e p a r a t i o n and
Oxide Crucibles, J . Am. Ceram. Soc. 18, 65
T e s t s of Refractory Sulfide C r u c i b l e s , " J. Am.
(1935).
Ceram. Soc. 34, 128 (1951); see also A E C D - 2 2 4 2
( A u g . 25, 1948) and reference 6 . 1 1 . D. Turner, " S p e c i a l Refractories for M e t a l -
2 . R. W. Knauft, " Z i r c o n Refractories for A l u - lurgical Research, Trans. Faraday Soc. 2 7 , 112
minum M e l t i n g F u r n a c e s , " Metals and Alloys 18, (1931).
1326 (1943). 12. J . G. Thompson and H. E. C l e a v e s , " P r e p a -
3. A . R. Kaufmann and E. Gordon, " V a c u u m ration of H i g h - P u r i t y I r o n , " RP1226, J. Research
Melting and C a s t i n g of B e r y l l i u m , " Metal Progress Natl. Bur. Standards 23, 163 (1939).
52, 387 (1947). 13. E. R. T h e w s , " T h e S u i t a b i l i t y of V a r i o u s
4 . G. R. F i n l a y and G. F e t t e r l y , " B o r o n N i - Refractory Materials for Lead Refining F u r n a c e s , "
t r i d e — An Unusual R e f r a c t o r y , " J. Am. Ceram. Feuerfest7, 84 (1931).
Soc. 3 1 , 141 (1952). 14. T . E. F i e l d , Heat-Cast Refractory for Mag-
5. F. A . Harvey, ' R e f r a c t o r i e s , " Handbook of nesium Melting Furnaces, U. S. P a t . 2,416,472
Nonferrous Metallurgy, D. M. L i d d e l l ( E d i t o r - i n - ( F e b . 25, 1947).
C h i e f ) , M c G r a w - H i l l , New York, 1945. 15. A . U. Seybolt, " A P r a c t i c a l Furnace for
6 . L . Brewer, L . A . Bromley, P. W. G i l l e s , and Vacuum M e l t i n g , " Metal Progress 50, 1102 (1946).
N. L. L o f g r e n , The Preparation and Tests of Re- 16. L . Jordan and W. H. Swanger, " P r e p a r a t i o n
fractory Sulfide Crucibles, A E C D - 2 2 5 3 (Sept. 7, of Pure N i c k e l , " RP257, J. Research Natl. Bur.
1948). Standards 5, 1291 (1930).
7. M. L . V . Gayler, " T h e Preparation and 17. W. J . B a l d w i n , " Z i r c o n and Z i r c o n i a Re-
Properties of C h e m i c a l l y Pure M e t a l s , " Metallwirt- f r a c t o r i e s , " Chem. Eng. Progress 44, 875 (1948).
scbaft 9, 677 (1930); see a l s o C. A. 24, 5595 18. P. H. Brace, ' R e a c t i o n s of Molten T i t a n i u m
(1930). w i t h Certain Refractory O x i d e s , " J. Electrochem.
8. S. H. B o o t h , " U s e of Refractories in M e l t i n g Soc. 94, 170 (1948).
Copper and Copper A l l o y s in an Ajax-Wyatt In- 19. P. H. Brace, W. J . Hurford, and T . H. Gray,
duction F u r n a c e , " Bull. Am. Ceram. Soc. 19, 171 "Preparation and Properties of Titanium-Base
(1940). A l l o y s , " Ind. Eng. Chem. 4 2 , 227 (1950).

ALUMINA CRUCIBLES

TYPES to 3425°F (1885°C), and a porosity ranging from

35 to 5 0 % . * * C r u c i b l e s are a v a i l a b l e from 1/£_ i n .
Clay-bonded high by 1 / , i n . top diameter to 6 i n . high by 4 i n .
When neutral chemical c o n d i t i o n s are required top diameter.
i n the m e l t i n g of m e t a l s , alumina c r u c i b l e s are
u s u a l l y u s e d . A c i d i t y is increased and r e f r a c t o r i -
Recrystallized Alumina
ness decreased as the proportion of fused alumina
is decreased by a d d i t i o n s of p l a s t i c - b o n d c l a y . A 99+% pure alumina powder is formed into
Clay-bonded alumina c r u c i b l e s in standard sizes c r u c i b l e s that are heated under c o n d i t i o n s that
(see T a b l e 2) are e s p e c i a l l y suited for t h e m e l t i n g produce a growth of i n t e r l o c k i n g corundum c r y s -
of steel and ferrous a l l o y s in high-frequency i n - tals. A nearly impervious structure ( w i t h 0 . 2 ± %
duction furnaces, since they have good thermal porosity) is obtained that has e x c e l l e n t r e s i s t a n c e
shock q u a l i t i e s . to both a c i d and basic attack and is p r a c t i c a l l y
Fused alumina-bonded c r u c i b l e s that have a inert under varying furnace c o n d i t i o n s .
s i l i c a content of 7 to 1 1 % , such as N o r t o n ' s * R e c r y s t a l l i z e d alumina c r u c i b l e s are suggested
" A l u n d u m " brand, have a pyrometric cone e q u i v a - for use in high-frequency and vacuum melting of
lent ranging from C / 3 7 to C / 4 0 , 3 3 1 0 ° F (1820°C) pure metals, including i r o n , chromium, manganese,

* * P o r o s i t y is defined as the v o l u m e of air space ex-

*See " L i s t of Manufacturers." p r e s s e d as percentage of the t o t a l volume of the p i e c e .

6
 ji&
TABLE 2. STANDARD SIZES OF INDUCTION FURNACE CRUCIBLES OF
CLAY-BONDED ALUMINA, MAGNESIA, AND SILICA

OUTSIDE TOP OUTSIDE BOTTOM

HEIGHT CAPACITY
NUMBER DIAMETER DIAMETER
(in.) (in. )
(in.) (in.)

3-P \
A A 2.1

3-P 1 A ^% 5.9

3-P 2 A A 10.0

3-L* A A 30.0

3-P 4
A 3 20.0

5-L 6 A 50.0

10 A A A 52.0

12-L 7 A 73.0

17-L 8 A 87.0

30-L
A A A 162.0

170-L
A 7 242.0

171 n A 248.0

172-L n 7 296.0

173 n A 347.0

304 5 1.5
\
305 5/3 /
0
4 i 2.5

306 5/5 /
3
8 i3/ 3.2
"16
307 6 l3/ 4.4

308 8 2 13.0

309 8 A 23.0

310 A 3 39.0

311 10 4 77.0

312 10 5 135.0

313 n% 6 240.0

410-L 10^ >% A 160

509 12^ *% A 528

* " L " denotes l i p .

 TABLE 2 (continued)

OUTSIDE TOP OUTSIDE BOTTOM CAPACITY

HEIGHT
NUMBER DIAMETER DIAMETER
(in.) (m. )
(in.) (in.)

510 14^ 9 700

512-L 16 9 775

513 133/£ A 9 625

10 \ 920
515 ™\
529 16% 12>4 11% 1,360

H-529 18% 12> 4 11% 1,480

532 14 12> 4 1,028

"3/16

545 18% A 1,945

564 19^ 15> 4 14 2,600

H-564 23 isV4 14 2,800

572 20^ 16 \ 14 2,476

576-L 22 16 2,700

580-L 26 19 4,420

601 22 \ 20 17 4,008

602 22>8 20 5,570

701 34 25 22 11.250

702 49 34 32,820

703 32 23 \ 8,280

boron, and germanium; melting special g l a s s e s s u c c e s s f u l l y . An a l u m i n a - l i n e d m i l l w i t h alumina

requiring a s i l i c a - f r e e c r u c i b l e ; fusing inorganic b a l l s is preferable if contamination is to be
charges high in a l k a l i e s , f l u o r i d e s , or other h a l - a v o i d e d . Iron b a l l s in an iron m i l l have been u s e d ;
i d e s ; and producing f l u o r e s c e n t powders such as the iron contamination i s subsequently removed
phosphates and s i l i c i d e s of z i n c , magnesium, or by means of a magnetic separator, after w h i c h it
beryllium. i s leached by a c i d . T h u s , 1 kg of Alundum N o . 38
C r u c i b l e s are a v a i l a b l e in standard s i z e s in was m i l l e d dry for 32 hr in an iron m i l l of 1-gal
three main shapes: A-shape, c y l i n d r i c a l , and c a p a c i t y that contained 10 kg o f iron b a l l s . T w o
c o n i c a l (see T a b l e 3 ) . l i t e r s of water was added to the powder, and t h i s
suspension was passed 25 times through a mag-
F A B R I C A T I O N OF A L U M I N A C R U C I B L E S
n e t i c separator. Then 200 ml of concentrated HCI
Slip-Casting was added, and the s l i p was stirred for 8 hours.
Raw Materials. Alundum N o . 38 ( - 2 2 0 mesh) or A f t e r f i l t e r i n g and w a s h i n g , the suspension was
any other good grade of fused powdered alumina brought to the proper pH according to T a b l e 4 by
is s a t i s f a c t o r y in s l i p - c a s t i n g . adding HCI or tetramethylammonium hydroxide and
Grinding. When the alumina is coarser than 3 to the proper s p e c i f i c g r a v i t y by siphoning off a
to 5 fi, it w i l l probably need m i l l i n g to be cast portion of the supernatant water.

8
 /j*r^
Casting. The usual casting technique is used Drying. Small crucibles should be air-dried over-
(cf. "Fabrication of Ceramic C r u c i b l e s , " this night; large crucibles should be dried slowly in a
report). dryer.
Firing. Crucibles should be fired at 1750 to
TABLE 3. STOCK SIZES OF CYLINDRICAL 1800°C for 5 hr, either in an induction furnace or
RECRYSTALLIZED ALUMINA CRUCIBLES* an oxypropane k i l n .
Properties. Slip-cast alumina crucibles have a
DIAMETER HEIGHT CAPACITY total shrinkage of 15%, with apparent porosities
(in.) (in.) (cc) of 1 to 3%.

X 1 5 Dry-Pressing
The procedure outlined for dry-pressing beryl lia
\ A. 10
may be followed (cf. "Fabrication of Beryl lia
1
A. 20 C r u c i b l e s , " this report).

Ai At 20 Manufacturers*

A 2 /
z/2
1
50 Clay-bonded, Fused Alumina Crucibles. Bart ley
(3), Dixon (12), Electro (10), Massilon (14), Mullite
A6 A 65 (16), Norton (19), Remmey (20).
Recrystallized Alumina. Laboratory Equipment
A A 95
(13), Morganite (15), Remmey ( 2 0 ) .

A 3/9 /
J
16
100
References
i17/ 3
J
15
/ 100
1
'32
'16 W. E. Hauth, Jr., " S l i p Casting of Aluminum
2 / 1
175
O x i d e , " J. Am. Ceram. Soc. 32, 394 (1949).
A6 H . M. L e e , Alumina, NEPA-1262 (June 27, 1950).
25/
A* 250

* S e e " L i s t of Manufacturers" for complete names and

*See 13 and 15, " L i s t of Manufacturers." addresses.

TABLE 4. RELATIONSHIP OF pH AND SPECIFIC GRAVITY TO CASTING PROPERTIES

OF ALUMINA SUSPENSIONS

DRAIN-CAST PROPERTIES SOLID-CAST PROPERTIES

Rapid Medium Slow

Rapid Cast Slow Cast
Release Release Release

High Density

pH 2.95 5.30 to 12.4 4 . 4 0 to 12.0 2.95 to 12.4

Specific gravity 3.0 2.8 2.8 3.0

Low Density

PH 6.05 to 10.4 6.05 to 10.75 4.6

Specific gravity 2.8 to 2.6 2.8 to 2.6 2.6

 £ BERYLLIUM OXIDE CRUCIBLES

TYPES paraffin is 5 to 10% of the weight of the beryllia.

After the CCL has been thoroughly evaporated,
Beryllia the batch is pelletized by forcing it through a
Beryl lia is one of the most stable refractory 14-mesh screen.
materials and is used for making crucibles that Pressing. The beryllia containing the u i f W
are employed particularly in the melting of pure is pressed at 30,000 to 40,000 psi. During the
metals and alloys. It can be used at temperatures pressing of the resin-iubricated material, the die
close to its melting point, which is over 4530°F is uniformly heated to 150 to 155°C. When this
(2500°C); it is especially adaptable for use in heating is not uniform, the pressed material sticks
high-frequency heating. It is claimed to be some- to the die on removal.
what volatile in the presence of water vapor at Firing. The crucibles are fired to 1950°C by
temperatures above 3270°F (1800°C). Beryllia induction-heating in air. A recrystallization ap-
has excellent thermal shock properties and high pears to take place that causes the ware heated
thermal conductivity and can be fabricated into to 1950°C to be much more resistant to attack
crucibles that have almost no porosity. at higher temperatures than that heated only to
Beryllia crucibles may be used in either oxi- 1900GC or less.
dizing, reducing, or neutral atmospheres, but they Properties. Crucibles with a total shrinkage of
react readily with such oxides as magnesia, calcia, 14.5 to 16.5% and densities of about 2.7 are ob-
alumina, and silica to form less refractory com- tained by this procedure.
pounds.
Beryllium oxide powder is considered to be a Slip-Casting
toxic material, and specific precautions must be Raw Materials. A refractory-grade, —325 mesh
t jken in its use. beryllia is preferable for the preparation of cruci-
Table 5 lists the standard-size crucibles avail- bles. When a commercial c.p. grade or low-fired
able on the market. material is used, it must be calcined to above
1500°C before milling.
FABRICATION OF BERYLLIA CRUCIBLES Grinding. When the refractory-grade material is
used, the milling is merely to prevent lump for-
Dry-Pressing mation; about 2 hr is sufficient. However, the
Raw Materials. Refractory-grade, finely divided calcined material is too coarse to pass a 325-mesh
beryllia is required for dry-pressing. When the screen, and it must be ground in a steel-ball mill
material is c.p. grade or low-fired material, it until it can pass such a screen. About 25 hr of
can be calcined to above 1500°C to make it ac- grinding, either wet or dry, is usually required to
ceptable. reduce the calcined material to the necessary
Grinding. The beryllia is ball-milled to pass a particle size.
200-mesh screen, with 14% by weight of phenol- Preparation of Slip. The metal picked up during
formaldehyde resin and 1% of hexamethylene- the grinding operation can be removed with a 10%
tetramine added to accelerate curing and act as a solution of HCI in two or three teachings, or until
lubricant. (Resinox 615, available from Monsanto the supernatant liquid no longer shows the iron
Chemicals Co., and Bakelite BR-2428 are equiva- color. The acid is then washed out with distilled
lent resins.) A typical mill charge is: 700 g of water; two or three washings are usually sufficient.
beryllia, 104 g of powdered resin, 9.8 g of hexa- On the final wash, the pH should be adjusted to
methylenetetramine, and 4000 g of 1.5-in. Porox between 4.5 and 5.0, the slip should be allowed
balls. After grinding, 21% water that contains a to settle, and the supernatant liquid decanted until
small amount of wetting agent is added and mixed the specific gravity is about 2.0.
in by hand; this is followed by granulation through Casting. The usual drain-casting technique is
a 14-mesh screen. The batch is then dried at employed, and care is taken that no air is en-
60° C. trapped when the slip is being poured into the
Paraffin also makes an effective binder and plaster mold.
lubricant. It is added by means of a 20% solution Drying. The green pieces are air-dried overnight.
in CCL to the dry-ground beryllia and worked in Firing. The crucibles are fired to 1800°C in
by hand. Enough solution is added so that the either an oxypropane kiln or an induction furnace.

10
 /i^jl
TABLE 5. STOCK SIZES OF BERYLLIA CRUCIBLES*

OUTSIDE INSIDE OUTSIDE INSIDE

NUMBER DIAMETER DIAMETER HEIGHT HEIGHT
(in.) (in.) (in.) (in.)

X-1A
'*
1 A A
X-1B A A A A
X-2A A A A A
X-8A
A A 3 % A
X-8B
A A 5 A
X-12A A* 2 A 4

X-13A 2 A 6 5
a
13
/
'16

X-14A 2 A 7
'%
X-17A
A. 2 / 3
A A
X-28A
A 2 A A
X-33A 3/3 /
J
8 A 6
^16
X-39A >% A. 8 A
X-44A
A A 4
4
' 8/
3
4

X-47A 215/
* '16
29/ 10 A
X-49A Z/7/
J
8
3^
J /
16
5
3
15
/
T6 A
X-89A 4 3
^16
9
A
X-130A 5 A»° A 10 \ A
X-157A 5/3 /
3
8 A A A
X-250A 7 6 12 ii

X-405A 7% A 12 n
X-425A
A 6% to 7 12
»4
X-590A
A A »x 10^

X-670A
A 7%to7,/2 16 \s\
X-1000A 10 9 16 15

X-1500A u\ 10% 19J£ 18^

X-2000A 12 11 23 22

X-2700A u\ \i\ 21 20

•Brush (4).
 Properties. B e r y l l i a c r u c i b l e s prepared by t h i s C a s t i n g , " RP1236, J. Research Natl. Bur. Stand-
method can be expected to have a total shrinkage ards 2 3 , 319 (1939).
of 14% and an apparent porosity of about 1%.
G e n e r a l l y they are w h i t e , hard, and emit a b e l l - l i k e J . L . Utter, Slip-Casting of Non-Plastic Re-
tone when s t r u c k . fractory Materials, CT-3371.

Manufacturers
A . R. Kaufmann and E. Gordon, " V a c u u m Meh-ing
Beryllia Crucibles. Brush (4), Massilon (14), and C a s t i n g of B e r y l l i u m , " Metal Progress 5 2 , 387
Norton (19). (1947).

References
H. B. B a r l e t t , Note on the Preparation of Small
J . G. Thompson and M. W. M a l l e t t , " P r e p a r a t i o n Dense Beryllia Crucibles, AECD-2170 ( J u l y 28,
of Crucibles from Special Refractories by Slip 1948).

GRAPHITE CRUCIBLES

TYPES that c o n s i s t s of p l a s t i c fire c l a y , s i l i c a , s i l i c o n

carbide, and feldspar. The f l a k e graphite imparts
Carbon-bonded
e x c e p t i o n a l r e s i s t a n c e to stresses from temperature
Graphite c r u c i b l e s are not often o b t a i n a b l e in and mechanical handling, increases the thermal
the carbon-bonded form, but they can be r e a d i l y c o n d u c t i v i t y of the body, and contributes to the
machined from graphite stock or electrodes that resistance to molten metals. The graphite is pro-
are pure carbon. As an example of the electrode- t e d e d from oxidation in f i r i n g and in use by a
forming process, a mixture of coke flour and p i t c h s i l i c a t e glaze that is formed on the outside surface
or tar to serve as a binder is extruded or molded of the c r u c i b l e as it is f i r e d . In this operation, a
into form and is then baked in gas- or o i l - f i r e d temperature of 1200°C and a reducing atmosphere
furnaces at 1500 to 2 0 0 0 ° F . A t t h i s stage, the are employed. These c r u c i b l e s are a v a i l a b l e in
c r u c i b l e s are designated as " c a r b o n " e l e c t r o d e s . various shapes and c a p a c i t i e s ranging from a few
G r a p h i t i z a t i o n is accomplished by d i r e c t - r e s i s t a n c e ounces to several hundred pounds of molten metal
furnace heating to 4 0 0 0 ° F for severol days, w h i c h (see T a b l e 6).
is f o l l o w e d by slow c o o l i n g . The two furnace The f o l l o w i n g l i m i t a t i o n s in the use of c l a y -
operations require a t o t a l of 12 to 16 weeks for bonded graphite c r u c i b l e s should be observed:
completion. (1) In o x i d i z i n g furnace atmospheres the graphite
Outstanding among the properties of graphite tends to burn out, p a r t i c u l a r l y on the unglazed
electrode stock are its high p u r i t y , high heat edges, w h i c h results in c r u c i b l e f a i l u r e . (2) The
c o n d u c t i v i t y , a b i l i t y to w i t h s t a n d r a p i d heating graphite imparts a certain degree of e l e c t r i c a l
and c o o l i n g w i t h o u t s h a t t e r i n g , e l e c t r i c a l conduc- conductance. (3) The clay bond is rather soft and
t i v i t y , and inertness to most molten m a t e r i a l s . The porous and is attacked by strong a l k a l i e s and
electrode material normally has 29 t o 30% porosity fluorides. (4) The clay bond tends to rehydrate
and a d e n s i t y of 1.5 to 1.7 (true d e n s i t y of graphite and crumble in the presence of moisture. (5)
is 2.21 to 2.25). T h e c h i e f defects are the a f f i n i t y Carbon and s i l i c a t e s may be contributed to the
of carbon for oxygen and the tendency to reduce charge. (6) Maximum temperature is l i m i t e d to
o x i d e s and form c a r b i d e s , the tendency of carbon 1200°C.
to enter molten materials to form either mechanical
mixtures or s o l i d s o l u t i o n s , and the low r e s i s t a n c e FABRICATION OF GRAPHITE CRUCIBLES
of the material to erosion and a b r a s i o n . Graphite
Dry-Pressing
begins to o x i d i z e at about 5 0 0 ° C .
Powdered graphite, lampblack, or charcoal is
Clay-bonded
mixed w i t h powdered coal-tar p i t c h in the pro-
Clay-bonded graphite crucibles are formed by portion of 3 parts of carbon to 1 part of p i t c h , and
jiggering a composition of about 40% by w e i g h t of the mixture is blended w i t h gum tragacanth and
Madagascar f l a k e graphite w i t h a bonding mixture water to form a thick paste. Other binders that

12
 TABLE 6. STANDARD SIZES OF GRAPHITE AND SILICON CARBIDE CRUCIBLES
/sty
HEIGHT TOP BILGE BOTTOM APPROXIMATE CAPACITY*
NUMBER
(in.) (in.) (in.) (in.) (lb of water)

2 15,
0000
* '16 A 2%
A 0.25

1
A A A A 0.50

2
A A *X A 0.75

3
A A A 3 1.0

4
A A As A 1.50

6
A A A A 2.25

8
A A A A 3.0

10
A. A* A6 <X 4.8

12
A A A A6 5.6

14
A <X A* A 6.4
is
* /
16
A 6 ;
u
A A 7.2
13
18 7X /5 / 71 1 5 /
9
y /
16 16 '16 >X 8.6

7 1 17/
20 10
*16 16
8%
A 10

25
"X 83/
16 A A 12

30 n\ A Ae >X 14

35 12 9
A A 16

40 12^
A 10%
A6 18

45 13
^6 A "X ?X 21

io%
50 13%
"'< A 24
13
60 147/
16
io /16
" '16 As 28

70
'Ae nV4 12 /3
*X 32
11
80 15%
" %
12
,z /
'16 A 36

90
'A6 12
\ 13%
As 40

100 «% 12% 13%

A 44

125 17% 13 14l/ 50

16 "%6
150 18% 13%
A 10% 60

175 19 J, 14%
'As 11% 70

200 20 15 16% 80
"\
*1 lb of water = 0.96 pt or 27.7 in. . Dimensions are outside measurements.
Note: Tilting furnace crucibles are furnished with a long lip.

13
 / ."':
TABLE 6 (continued)

HEIGHT TOP BILGE BOTTOM APPROXIMATE CAPACITY*

NUMBER
(in.) (in.) (in.) (in.) (lb of water)

225 20% 15%

"X 12^
'16
90

11
250 21% 16 17^" 12
u / 100
"'16 '16
275 22 16?/ 17 13 / 13 110
16 " '16
300 22%
'A 18% 13% 120
11
400 24^ 19 / 160
'As |y
'16 'As
*1 lb of water = 0.96 pt or 27.7 in. . Dimensions are outside measurements.
Note: T i l t i n g furnace crucibles are furnished with a long l i p .

soften and become adhesive at 100 to 3 0 0 ° C such Clay-Bonded Graphite Crucibles. American
as coal tar, asphalt, or rosin may be used. Cruci- Crucible (1), Bartley (3), Dixon (12), Massilon
bles are pressed from the paste and these are (14), National Crucible (18), Vesuvius (24).
heated at red heat in a reducing atmosphere,
whereupon the binder is fused, the volatiles are
driven off, and the pitch is coked. References

Manufacturers
H. A . Wilhelm and P. S. Gerald, Carbon Cruci-
Graphite Electrode Stock. National Carbon (17). bles, U. S. Pat. 2,521,495 (September 1950).

MAGNESIA CRUCIBLES

TYPES F A B R I C A T I O N OF MAGNESIA C R U C I B L E S

Clay-bonded Dry-Pressing of Fine-grained Magnesia

Magnesia crucibles are suggested for use where Raw Materials. Fused magnesia from General
basic conditions exist, such as in the induction- Electric Co., c.p. grade, heavy-calcined magnesia
melting of steels. The magnesia content may supplied by Mallinckrodt Chemical Works, and
range from 83 to 97% and the porosity from 15 to White Seal Periclase, - 2 0 0 mesh, from the Vitre-
20%. Manufacturers specify that crucibles of lower frax Corp. are suitable materials for dry-pressing.
magnesia content may be used up to 3 6 3 0 ° F When a crucible with a silica content of less than
( 2 0 0 0 ° C ) , whereas those of higher magnesia con- 2% is desired, the G-E product is " d i l u t e d " with
tent, containing electrically fused magnesia, may the c.p. grade material and calcined to 1300°C; a
be used up to 4 5 3 0 ° F ( 2 5 0 0 ° C ) , depending upon 1:1 mixture lowers the silica content sufficiently
their application. However, magnesia is sensitive and also makes a satisfactory working body.
to any type of reducing conditions and requires a
strong oxidizing atmosphere above 3090°F (1700°C) Grinding. It is not necessary for the —200 mesh
to minimize its tendency to volatilize, which is magnesia to be ground. The 1:1 mixture of fused
considerable in a vacuum at temperatures above and c.p. material is ground for 15 hr in a mill with
2000°C. Standard-size crucibles suitable for in- Porox balls and 95% ethyl alcohol. The silica
duction-furnace use are listed in T a b l e 2 . pickup in this operation is about 1 % .

14
 /Sty
Preparation {or Pressing. After grinding, the -48 +65 35 ± 3
material is dried during constant stirring at 105 to -65 +100 10 ±3
1 1 0 ° C . It is important that all alcohol be evapo-
rated. The material is forced through a 65-mesh The two increments are mixed dry in a Simpson
screen after it is dried. Either Carbowax 4000 or mixer; then 5% by weight of distilled water is
paraffin can be used as a binder. added and mixed with the increments for not more
Carbowax is added in an aqueous solution (1 g than 5 minutes. The batch is pelletized by forcing
of wax for each 2 ml of solution) until the batch it through a 10-mesh screen and is then bottled.
K contains 12% by weight of Carbowax. The material The damp material should not set unpressed for
is dried at less than 8 0 ° C to granulating con- more than 48 hours.
* sistency and then forced through a 14-mesh screen. Pressing. The magnesia is pressed in a steel
After further drying at less than 8 0 ° C to drive die at 10,000 psi.
off the remaining water, the material is allowed Drying. The crucibles are air-dried overnight or
to cool for pressing. for 16 hr; this is followed by 24 hr of drying at
The paraffin is added in a C C L solution. Suf- 90° C .
ficient solution is added to the magnesia to form Firing. The magnesia crucibles are fired to
a paste containing paraffin to the extent of 5 to 1750°C either by induction or in a gas kiln.
10% of the weight of magnesia. The C C L is fully
evaporated and the material is forced through a Slip-Casting
14-mesh screen.
Raw Materials. Fused magnesia supplied by
Pressing. The Carbowax-lubricated batches are General Electric C o . is suitable for casting cruci-
pressed at 30,000 to 50,000 psi in steel dies bles. When a crucible with a silica content lower
heated to 30 to 4 0 ° C with jacket heaters. The
than 2% is desired, the fused product is mixed in
paraffin-lubricated material is pressed cold at the
equal parts with a calcined (1500°C) c.p. grade
same pressures.
magnesia. (Mallinckrodt Chemical Works product
Drying. The crucibles containing Carbowax are
has a silica content of less than 0.30%.) Shrink-
heated in porous saggers (made from insulating
ages vary from 7 to 15% according to the firing
brick) to 500 or 600°C in 25 hours. The pieces
temperature. Apparent porosities of from 0.5 to
containing paraffin can be fired directly if the
8.5% may be expected.
temperature is raised slowly up to 6 0 0 ° C (200
Grinding. The magnesia is ground dry or with
deg/hr).
absolute alcohol for 34 hr in a steel-ball m i l l .
Firing. The crucibles are fired at 1750 to
Preparation of Slip. When excess alcohol is
1800°C from 30 min to 1 hour.
used in grinding, the slip should be adjusted to
a specific gravity of 2.2 or 2 . 3 . Dry-ground mag-
Dry-Pressing of Grain-sized Magnesia Crucibles nesia should be blunged with alcohol and adjusted
Raw Materials. Magnesia supplied by General to the same specific gravity.
Electric Co. or Norton Co. is used to fabricate Casting. The crucibles are cast in plaster molds
grain-sized crucibles. The Norton product should in the usual drain-casting manner. The slip and
be - 2 0 +100 mesh. green crucibles should be protected from the air
Grinding. Equal amounts of General Electric and as much as possible to prevent scumming.
Norton products are ball-milled in naphtha for 24 Drying. The crucibles are dried in a desiccator
hours. A 2000-g batch of the magnesia mix re- overnight.
quires /7 gal of balls and % gal of naphtha in a Firing. The crucibles should be fired at 1850
1-gal m i l l . Ninety-eight per cent of the ground to 2 0 5 0 ° C by induction heating with a 30-min soak.
material should be less than 200 mesh.
Preparation for Pressing. The grain-sized body Manufacturers
is made up of 63% coarse material and 37% fines. Magnesia Crucibles. American Crucible (1),
- ,.» About 98% of the coarse fraction should be held Bartley (3), Dixon (12), Electro (10), Massilon
on a 100-mesh screen and should have the fol- (14), Norton (19).
lowing grain-size distribution:

Screen Interval Per Cent References

- 2 8 +35 15 ± 8 H . B. Barlett, Tfie Preparation of Small Dense
-35 +48 40 ± 5 Crucibles of Magnesia, CT-3372.

15
 /
f .
NITRIDE CRUCIBLES

N i t r i d e c r u c i b l e s are not a v a i l a b l e commercially w o u l d be: the same as for T i N , except that only
at present. They are fabricated most r e a d i l y by a l c o h o l is used as a grinding medium and the
dry- or h o t - p r e s s i n g . A n y of the refractory n i t r i d e s charge is increased to 600 grams.
may be used in the f a b r i c a t i o n of c r u c i b l e s . The Preparation for Pressing. A f t e r g r i n d i n g , the
ones most s u i t a b l e for the purpose, l i s t e d w i t h batch is mixed w i t h a s o l u t i o n of Carbowax com-
their m e l t i n g p o i n t s , are: B e _ N - , 2 1 9 7 ° C ; ScN, pound 4000 in hot benzene. The Carbowax should
2 6 5 0 ° C ; T i N , 2950 ± 5 0 ° C ; Z r N , 2980 + 5 0 ° C ; be from 6 to 10% of the w e i g h t of the n i t r i d e used.
H f N , 3 3 0 0 ° C ; V N , 2 1 0 0 ° C ; T a N , 3 1 0 0 ° C ; and U N , The slurry is stirred and ground in a mortar u n t i l
2500° C . a l l the benzene has evaporated; after t h a t , the
material is p e l l e t i z e d by forcing it through a 14-
FABRICATION OF NITRIDE CRUCIBLES mesh screen.
Pressing. T h e p e l l e t i z e d material is pressed
Dry-Pressing
in a steel die at 15,000 to 20,000 p s i . C r u c i b l e s
Raw Materials. The dry-pressing technique de- can also be pressed h y d r o s t a t i c a l l y w i t h o u t the
scribed here is s p e c i f i c a l l y adaptable for f a b r i - use of a binder.
c a t i n g Z r N and T i N , but it can be used w i t h the Drying. The crucibles are held at 2 5 0 ° C for
other n i t r i d e s that are s u f f i c i e n t l y s t a b l e to stand several hours to remove the Carbowax.
the grinding and f i r i n g . Firing. The c r u c i b l e s are fired in an induction
Grinding. The n i t r i d e s are ground w i t h steel furnace w i t h a tungsten heating element in an
b a l l s in a rubber-lined m i l l for 75 to 90 hr so that ammonia atmosphere, Z r N at 2050°C for 30 min
95% of the p a r t i c l e s achieve a grain s i z e less and T i N at 1600°C for 30 minutes.
than 8 m i c r o n s . A sample m i l l charge for T i N in
a 1-qt m i l l would be: 400 g of coarse n i t r i d e (—20 References
mesh), 1.6 kg of a l l o y steel b a l l s v a r y i n g in d i - G. R. F i n l a y and G. F e t t e r l y , " B o r o n N i t r i d e —
ameter from /. to / . i n . , and either 200 g of a l c o h o l A n Unusual R e f r a c t o r y , " J. Am. Ceram. Soc. 3 1 ,
or 250 g of water; a charge for Z r N in a 1-qt m i l l 141 (1952).

ALUMINUM SILICATE CRUCIBLES

TYPES may contaminate the melt with silica and with

iron from the c l a y .
Fire Clay
Fire-clay c r u c i b l e s are used e x t e n s i v e l y in
F i r e - c l a y c r u c i b l e s are prepared from a mixture
mining for fire assay work and for melting non-
o f c a r e f u l l y s e l e c t e d raw and c a l c i n e d f i r e c l a y s ,
ferrous metals, enamels, c h e m i c a l s , and g l a s s e s .
die-pressed or jiggered in steel or plaster of paris
T a b l e 7 l i s t s the standard sizes commercially
molds, and f i r e d to about pyrometric cone 12.
a v a i l a b l e . They are a l s o a v a i l a b l e w i t h or w i t h o u t
T h e i r range of chemical analyses is as f o l l o w s :
pouring l i p s and in a form w i t h a triangular cross
Si0 2 50.0 to 69.0% section.

Al203 25.0 to 45.0%

Sillimanite or Mullite
Fe203 1.0 to 2.0%
S i l l i m a n i t e or m u l l i t e c r u c i b l e s are u s u a l l y used
CaO 0.1 to 0.40%
when a more refractory aluminum s i l i c a t e than
MgO 0.10 to 0.5% f i r e c l a y is r e q u i r e d . They are suggested for use
TiO_ and alkalies (Na-O and K_0) . . . about 1% each in induction furnaces for melting glass and m e t a l s .
These c r u c i b l e s contain m u l l i t e , 3 A L 0 3 - 2 S i O » ,
These c r u c i b l e s are inexpensive and are useful as p r i n c i p a l ingredient, together w i t h excess
to a maximum temperature of 2 7 5 0 ° F ( 1 5 1 0 ° C ) . silica. The material is often clay-bonded and in
T h e i r porosity ranges from 15 to 25%. In use, they most cases suggested for safe use up to 3 1 0 0 ° F

16
 TABLE 7. STANDARD SIZES OF FIRE-CLAY CRUCIBLES
/sA^
JOSEPH DIXON CRUCIBLE CO. (12) THE DENVER FIRE CLAY CO. (9)

Size Height (in.) Top Diameter (in.) Height (in.) Top Diameter (in.)

A
A A
B 3
A
C
A A
D 4
A 4
A
E
A' A
F 5 3 5
A
G
A 3/5 /
J
8 A A
H
A 4
A 3

1 6 4

J
A A A A
K
A 5
A A
L
A A 8
A
M
A A
N
A A A A
0 10 7 7
9/ 7
"'fe-
P 10%
A ll
A
Q 12
A 12% 9

S 14%
A
(1700°C). Two typical chemical compositions are Pyrometric cone
as follows: equivalent C/38(3335°F) C/38to39

Taylor Taylor A list of standard sizes is shown in Table 2 .

Sillimanite Sillimanite, Two types of mullite crucibles are produced by
(%) Fortified (%) the Richard C . Remmey Sons C o . : crystalline
mullite, a low-fired ( 2 7 8 6 ° F , 1530°C) material
Al 2 0 3 61.20 68.72
that has a comparatively high percentage of mullite
Si02 35.35 28.48 crystals and a firing range of 3 3 9 0 ° F ( 1 8 6 5 ° C ) ;
and recrystallized mullite, a high-fired ( 3 2 0 0 ° F ,
F
«2°3 0.84 0.70
1760°C) material, of nearly 100% crystalline struc-
Ti02 1.96 1.40 ture that has less than 0.5% porosity, an alumina
CaO 0.11 0.15 content of over 70%, and a firing range of 3 4 2 5 ° F
MgO ( 1 8 8 5 ° C ) (see Table 8 ) .
0.05 0.08
Chemical porcelain, such as that produced by
Alkalies 0.48 0.46 the Coors Porcelain C o . , is essentially a mullite
Porosity (%) 20.0 to 22.5 20.0 to 23.0 body that may or may not be glazed. Its limit of

17
 1
TABLE 8. STOCK SIZES OF SILLIMANITE-MULLITE CRUCIBLES

MANUFACTURERS INSIDE DIAMETER WALL THICKNESS* HEIGHT

NUMBER (in.) (in.) (in.)

With Pouring Lip

CS-2 (6)
3*8 X 8

CS-3 (6) 2%
X A
CS-5 (6) 2%
\s A
CS-7 (6) 6% (bilge)
% A
4 (bottom)

CS-8 (6) 5
X A
3
CS-8A (6) 5 / n%
'8
01 (20) 1% (top)
V 3
% (bottom)

1 (20) 2% (top)
V 3% to 4
1,£ (bottom)

2 (20) 3(top)
V A
2% (bottom)

4(20) 4% (top) 5

'16
/ * A
3 (bottom)

10 (20) 5% (top) 3 / it
'8 A
3% (bottom)
7
11 (20) 6% (top) / *
'16 10
4 / (bottom)

12 (20) 10%, (top)

V 12

8% (bottom)

SI (20)
A V 3%

S3 (20)
A V A
S6(20) A V A
S8 (20) 3
V A
Without Pouring Lip

CS-6 (6) 5% (top)

X A
4 (bottom)

2099A (9) X \s A
*Wall thickness for recrystallized mullite is 25 to 50% less than that shown above for crystalline mullite.

18
use unglazed is 2550°F (1400°C), and glazed is bles range from 0.75 to 250 cc (glazed) and from
2280°F (1250°C). The capacities of these cruci- 15 to 1900 cc (unglazed).

SILICA CRUCIBLES

TYPES Vitreous Silica

Clay-bonded Vitreous silica crucibles consist of 99 to 100%

pure silica fused into a glass. They have a low
Clay-bonded silica crucibles contain about 95 thermal expansion, are resistant to heat shock, are
to 98% silica in the form of quartzite and have strongly resistant to acid slags, and may be used
porosities ranging from 20 to 30%. The possibility for continuous operation up to 2012°F (1100°C) or
of silica, alumina, or iron contamination from the for short periods up to 2460°F (1350°C). They
crucible should not be overlooked. are readily attacked by basic materials and fluo-
These clay-bonded crucibles are suggested for rides and may contribute silica to molten metals.
use where acid conditions exist, such as in the Water absorption is less than 1%.
melting of steels, ferrous metals, and siliceous Vitreous silica is obtainable in either opaque
glasses. They are particularly suited for induction or transparent form; the opaque form is glazed or
heating, with a useful temperature range up to unglazed in standard sizes (see Table 9).
2800°F (1540°C), depending on the application.
Vycor Glass
High-Silica Vycor crucibles are made from a soft glass that
separates into two phases, one high in silica and
Imported Hessian sand crucibles are used prima- the other high in borates. The borates are leached
rily for the melting of precious metals. They are out and the resulting siliceous framework is
produced either with a circular cross section shrunk into a homogenous structure by heating.
(ranging in size from 3% in. in height by 2/2 in. Normally, 2.9% of B 2 0 3 and 0.4% of A l 2 0 3 are
in diameter to 11 in. in height by 7% in. in di- present. Vycor crucibles are less expensive than
ameter) or with a triangular cross section (ranging fused silica and have the same advantages and
from iL i n . in height by 1 % in. in diameter to 4 in. disadvantages.
in height by 3 in. in diameter).
Manufacturers
Another material used for precious-metal melting
is produced by the Western Gold and Platinum Clay-bonded Silica Crucibles. Dixon (12),
Works under the trade-mark "Wesgo." Its compo- Massilon (14).
sition is not given in the company's literature, Fire Clay and High-Silica Crucibles. American
but according to its physical properties, it is Cuttlefish (2), Denver (9), Dixon (12), Massilon
probably a siliceous material. Its recommended (14), Western (25).
continuous service temperature is 2190°F(1200°C), Sillimanite or Mullite Crucibles. Bartley (3),
and it can be used for short intervals up to 2640°F Taylor (6), Coors (7), Denver (9), Electro (10),
(1450°C). This material is produced in a large Massilon (14), Mullite (16), Remmey (20).
variety of shapes ranging in size up to 6 in. in Vitreous Silica Crucibles. Thermal (22).
height by 2 A in. in inside diameter. Vycor Silica Crucibles. Corning (8).

42
 T A B L E 9. STOCK SIZES OF VITREOUS SILICA CRUCIBLES (22)

TOP OUTSIDE OUTSIDE INSIDE INSIDE

CAPACITY
NUMBER DIAMETER HEIGHT DIAMETER HEIGHT
(cc)
(in.) (in.) (in.) (in.)

Crucibles with L i p

3
A A 350
4 4
A 500
6
A A 925
7 5
A 1,500
14
A A 1,875
16
A A 2,500
30
A 10% 5,000
60 10% 12% 8,000
62 12 12% 10,000
70 12 20 21,500

Pots

16 21% 12 gal
19 21% 17 gal
19 23 18 gal
19 28% 24 gal
25% 37% 50 gal

Cylindrical Crucibles

3
A 525
4
A 1,000

A A 1,500

A A 2,500

SILICON CARBIDE CRUCIBLES

S i l i c o n carbide (SiC) is produced by a process c r y s t a l s are an iridescent blue or green from

d i s c o v e r e d by A c h e s o n , in w h i c h a mixture of coke, carbon, iron, or other i m p u r i t i e s that are present
sand, and sawdust is heated by e l e c t r i c a l re- in small amounts on the surfaces. C r u c i b l e s made
s i s t a n c e to 3 0 0 0 ° C . T h e f l a t , s i x - s i d e d s i l i c o n from s i l i c o n carbide may be used in a m i l d l y r e -
carbide c r y s t a l s that are formed in a crumbly mass ducing atmosphere up to 1500°C. They are strong
i n s i d e the furnace are, i n d i v i d u a l l y , nearly as hard and possess high heat c o n d u c t i v i t y and good re-
as diamonds and are s t a b l e t o about 1800°C. Pure s i s t a n c e to thermal s t r e s s e s . A l s o , they are rather
silicon carbide is w h i t e , but, o r d i n a r i l y , the heavy and may contribute carbon, s i l i c a , sodium,

20
or boron to the melt. Dissociation of silicon carbide that is obtained by dipping the ware in a borax
takes place with volatilization of the silica be- solution and reheating to fuse the borax.
tween 1600 and 1800°C. Silicon carbide crucibles
are available in a variety of shapes and in sizes Silicon-bonded
varying from a few ounces to several hundred pounds Silicon-bonded silicon carbide crucibles are
of capacity (see Table 6). produced by oxidation of powdered silicon metal
that is intimately mixed with the silicon carbide
before the jiggering operation. The silicon oxidizes
TYPES in firing to form a silica bond that does not need
protection from oxidation.
Carbon-bonded
Silicon carbide crystals are not readily bonded Manufacturers
together to form ware; hence, bonding materials Pure (Recrystallized). Carborundum (5), Electro
such as carbon, clay, or silica are commonly used. (10), Norton (19). (A special order will probably
Carbon-bonded silicon carbide crucibles are made be required.)
from a plastic mixture of silicon carbide, pitch, Carbon-bonded Crucibles. American Crucible (1),
and tar, which is jiggered in a steel mold of the Electro (10), Dixon (12), Ross-Tacony (21).
desired shape, buried in sand, and fired to develop Silica-bonded Crucibles. Ross-Tacony (21).
the carbon bond. This carbon bond is protected Silicon Carbide Grain. Carborundum (5), Electro
from oxidation in use by an additional borax bond (10), Exolon (11), Norton (19).

SULFIDE CRUCIBLES

Barium sulfide, cerium sulfide ("cerium brass"), passed through with the fan operating. A steel-ball
Ce,S4— Ce,S 3 ("cerium black"), thorium sulfide mill is placed inside the dry box.
("thorium s i l v e r " ) , and ThjSg—Th 4 S. ("thorium Sulfide crushed to 4 mesh in air (since oxidation
brown" and "thorium black ) are used to make is negligible in this operation) is screened in the
refractory sulfide crucibles. Large cerium-black inert atmosphere to remove air. It is then charged
crucibles are sensitive to thermal shock, the sensi- into the steel-ball mill that is kept in the dry box
tivity being greater at the Ce 2 S 3 end of the solid- during the screening operation. After the ball mill
solution series. Small crucibles (1 by 1 /^ in.) show is sealed, it is removed from the dry box and
no signs of damage from thermal shock. rotated for several hours. The sulfide should be
emptied from the mill while it is in the dry box,
since a slight oxidation occurs when the sulfide
FABRICATION OF SULFIDE CRUCIBLES
is removed in air.
Dry-Pressing Another method of grinding sulfides without the
Raw Materials. Cerium black can be made by use of a dry box is to cover the material in the
mixing correct proportions of CeS and Ce 2 S 3 . The mill with a solution of 2% cetyl alcohol in ether.
resulting crucibles show no traces of the CeS After the grinding and emptying processes are
phase by x-ray analysis. Thorium brown and completed, the ether is allowed to evaporate into
thorium black are prepared by blending and pressing the air during constant stirring of the mix. The
ThS and ThS 2 . cetyl alcohol thus remains as a coating on the
Grinding. Although sulfides do not react with sulfide grains. The sulfides should be ground to
air below 200°C, enough heat is developed in pass 325 mesh for pressing.
grinding to oxidize them so that they must be Preparation for Pressing. The sulfides that are
ground in an inert atmosphere. This grinding is ground in a gas atmosphere are mixed with 5%
accomplished by the use of a dry box. The box is naphthalene by volume and made into a slurry with
first subjected to a partial vacuum and soap and ether. After the ether has evaporated completely,
water are used to test the most likely places for the batch is pelletized through a 14-mesh screen.
leaks. A volume of propane equal to 1% times the The sulfides that are milled with cetyl alcohol
volume of the dry box is passed through without and ether are pelletized through a 14-mesh screen
the aid of the fan; then 5 times the volume is after all the ether has been evaporated.

21
 Pressing. Pressures of 50,000 to 100,000 psi t e r i n g temperature should be 1900 to 2000°C.
are used in pressing in a steel d i e . A p p r e c i a b l e amounts of T h 2 S _ l i m i t the s i n t e r i n g
Drying. The binders can be d r i v e n off by heating temperature to a maximum of 1900°C. Free thorium
in a vacuum at 100°C. lowers the sintering temperature; but its presence
Firing. T h e c r u c i b l e s are sintered by induction should be a v o i d e d , s i n c e it makes the c r u c i b l e less
heating for 10 to 30 min in a vacuum (10~ to r e s i s t a n t to a t t a c k i n g m e t a l s .
10 mm Hg) at a temperature appropriate to the T h , S - — T h . S , c r u c i b l e s should be sintered at
s u l f i d e . The c r u c i b l e s are p l a c e d on molybdenum 1700 to 1800°C. The presence of oxygen does not
during f i r i n g . lower the s i n t e r i n g range.
Barium s u l f i d e should be f i r e d at 1400 to 1600°C. Rough surfaces are caused by s i n t e r i n g at a
Below 1400°C, the product is powdery; above temperature at which the s u l f i d e has a high vapor
1600°C, the s u l f i d e v a p o r i z e s . pressure. Some defects are caused by the presence
Cerium s u l f i d e is fired at 1800 t o 1900°C, de- of oxygen, which reacts w i t h the s u l f i d e s . Re-
pending on its p u r i t y . If both C e , S 4 and C e 2 0 _ S c r y s t a l l i z a t i o n or d i s c o l o r a t i o n is caused by im-
are present in amounts up to 10% combined, the purities in the vacuum l i n e . A pure inert gas should
s i n t e r i n g temperature w i l l be lowered considerably be used to break the f i r i n g vacuum below 4 0 0 ° C .
(1600 to 1700°C) and p o r o s i t i e s of less than 5%
w i l l be attained because of the e u t e c t i c between References
the two compounds. However, the presence of For procedure in synthesis of s u l f i d e s , see
either compound alone has l i t t l e e f f e c t on the E. D. Eastman, L . Brewer, L . A . Bromley, P. W.
s i n t e r i n g temperature. Gilles, and N. L . L o f g r e n , " P r e p a r a t i o n and
Oxygen-free cerium-black materials sinter to low Properties of Refractory Cerium S u l f i d e s , " J. Am.
porosities at 1700 to 1900°C; the lowest s i n t e r i n g Chem. Soc. 72, 2248 (1950); and " P r e p a r a t i o n and
temperature is for C e S , . , w i t h a r i s e to 1900°C in Properties of the Sulfides of T h o r i u m and U r a n i u m , "
the case of C e S , 3 3 . With increasing amounts of J. Am. Chem. Soc. 72, 4019 (1950). See a l s o ,
oxygen present, the s i n t e r i n g temperature drops to L . Brewer, L . A . Bromley, P. W. G i l l e s , and
as low as 1600°C. N. L. L o f g r e n , The Preparation and Properties of
The s i n t e r i n g temperature of thorium s u l f i d e is Refractory Sulfides, AECD-2242 ( A u g . 25, 1948);
not much affected by the presence of i m p u r i t i e s . AECD-2253 (Sept. 7, 1948); and J. Am. Ceram.
When a low-porosity c r u c i b l e is d e s i r e d , the s i n - Soc. 34, 128 (1951).

THORIA CRUCIBLES

Thoria has the highest melting point of any of F A B R I C A T I O N OF T H O R I A C R U C I B L E S

the a v a i l a b l e pure o x i d e s - a b o v e 5 4 3 0 ° F (3000°C).
It is stable in both o x i d i z i n g and neutral atmos- Dry-Pressing
pheres, and in carbonaceous atmospheres up to
Raw Materials. T h o r i a supplied by L i n d s a y
3 9 9 0 ° F (2200°C). With thoria in contact w i t h
Chemical Co. is used in making the c r u c i b l e s .
carbon, formation of the carbide has been observed
The z i r c o n i a f l u x material can be obtained from
at 4 0 0 0 ° F (2250°C). T h o r i a has a low vapor
Foote Mineral Co. under the trade-mark " Z i r c o n a l b a . "
pressure at high temperatures, w h i c h makes it
desirable for vacuum work; however, il has a high Grinding. A batch made up of 98% thoria and
d e n s i t y of 9.6 and a high s e n s i t i v i t y to thermal 2% z i r c o n i a (2 to 5% can be used) is ground for
shock. Thoria c r u c i b l e s are reported to be re- 10 hr in a 1-gal porcelain m i l l loaded w i t h 1-in.
s i s t a n t to chemical a t t a c k by a c i d i c and e s p e c i a l l y Porox b a l l s . A t y p i c a l m i l l batch c o n s i s t s of
by basic f u s i o n s and can be used for the f u s i o n of 1680 g of t h o r i a , 34.3 g of z i r c o n i a , 4000 g of
metals of high melting p o i n t s . Porox b a l l s , and 1450 g of water. A f t e r g r i n d i n g ,
A l i s t of standard-size crucibles is given in the material should have a p a r t i c l e s i z e finer than
T a b l e 10. a b o u t 10 m i c r o n s .

22
 TABLE 10. STOCK SIZES OF THORIA CRUCIBLES (13)
/ 3&
TOP OUTSIDE DIAMETER BOTTOM OUTSIDE DIAMETER HEIGHT CAPACITY
NUMBER
(in.) (in.) (in.) (cc)

T158 20
Al Al Al
T160
A \ A 19

T162
A X As 28

T164 2 1
•"32/ l11 3 /
'16
29/ 70
2
T166 %
-32 '9'32
/ l12 5 '32
/ 7

T168
A A 27/
•^'16
50

Preparation for Pressing. After the m i l l e d batch Preparation of Slip. T h e dry-ground thoria is
is d r i e d , i t is passed through a 65-mesh screen by agitated w i t h d i l u t e HCI (10 ml of H C I per 100 ml
means of a Ro-Tap. A solution of Carbowax com- of w a t e r ) , permitted to s e t t l e , and the supernatant
pound 4000 in water (0.2 g of wax per m i l l i l i t e r of a c i d s o l u t i o n is decanted. Three c y c l e s of leaching
solution) is added to the dry batch and worked in should remove the contaminating iron. The de-
by hand u n t i l 6% by w e i g h t is incorporated. T h e canted acid solution should be tested for d i s s o l v e d
batch is partly dried at 8 0 ° C ; t h i s is f o l l o w e d by t h o r i a . The leached s l i p is not washed w i t h water;
p e l l e t i z i n g through a 14-mesh s c r e e n . The material it should be adjusted to a pH of 3.75 or above and
is then dried in shallow trays at 60 to 8 0 ° C . to a s p e c i f i c gravity of 2.0 to 2.5.
Pressing. T h e material is pressed in a steel die Casting. T h e s l i p is c a s t i n plaster molds in
at 20,000 to 30,000 p s i . When less Carbowax the usual manner.
binder is used, the die must be heated s l i g h t l y to Drying. The c r u c i b l e s should be air-dried over-
a c h i e v e the same d e n s i t y as w i t h the 6% binder. n i g h t . The dry ware i s q u i t e f r a g i l e .
Drying. The Carbowax binder is burned out by Firing. F i r i n g of the c r u c i b l e s should require
placing the c r u c i b l e s in small saggers (hollowed- not less than 30 min to reach 1675°C.
out i n s u l a t i n g brick) and heating t o 5 0 0 ° C in not Properties. Shrinkages of 10 to 15% may be
less than 8 hours. C r a c k i n g sometimes occurs as expected. T h o r i a c r u c i b l e s are q u i t e s u s c e p t i b l e
a r e s u l t of the raw t h o r i a . to rupture from mechanical or thermal shock.
Firing. T h e c r u c i b l e s are f i r e d at a rate of
Manufacturers
8 . 5 ° C / m i n to 1800°C and soaked for 30 minutes.
A small oxypropane k i l n or an induction furnace T h o r i a c r u c i b l e s are not now a v a i l a b l e as a stock
can be used for f i r i n g . item from Laboratory Equipment (13) or Morganite
Properties. C r u c i b l e s prepared by t h i s method (15), but some sizes may be a v a i l a b l e .
have d e n s i t i e s ranging from 9.55 to 9.70 and are
References
p r a c t i c a l l y nonporous. They are tan in color and
have a pearly luster. 0 . J . Whittemore, J r . , Trie Preparation of Small
Dense Thoria Crucibles, AECD-2187 ( J u l y 28,
Slip-Casting 1948).
J . G. Thompson and M. W. M a l l e t t , " P r e p a r a t i o n
Raw Materials. Thoria ( - 3 0 0 mesh, code No. 112) of C r u c i b l e s from Special Refractories by Slip
supplied by the L i n d s a y Chemical C o . is suitable C a s t i n g , " RP1236, J. Research Natl. Bur. Standards
for c a s t i n g . 2 3 , 319 (1939).
Grinding. The dry material as received is ground H. K. Richardson, " S m a l l C a s t Thorium Oxide
for 4 hr in a s t e e l - b a l l m i l l . C r u c i b l e s , " J . A m . Ceram. Soc. 18, 65 (1935).

23
 /£l ZIRCON AND ZIRCONIA CRUCIBLES

TYPES This behavior may shatter the ware unless the

the firing procedure is carefully controlled. Severity
Zircon of the volume change is reduced by additions of
Zircon (ZrSiO.) is obtained principally from the 5 to 8% of CaO that has the property of forming
beach sands of India, Florida, and Australia by cubic solid solutions with the zirconia at 1500 to
washing and flotation operations; it can be pur- 1800°C, Zirconia that has been partly changed to
chased either in the naturally occurring grain size the cubic form is termed " s t a b i l i z e d . " Its proper-
("granular," 100 to 200 mesh) or in milled form. ties are similar to those of electrically fused
The tetragonal zircon crystals are stable in the zirconia, except that the CaO addition imparts
range from room temperature to 1500°C, have a resistance to rapid temperature changes, lowers the
rather low coefficient of thermal expansion (approxi- fusion point by perhaps 100 to 200°C, lowers the
mately 4 x 10 i n . / i n . / ° C ) , and a medium thermal temperature of sagging under load to 2050 to
conductivity, all of which contribute to thermal 2100°C, and may be detrimental when in contact
shock resistance. with certain melts.
Zircon crucibles are made in standard sizes Most of the available zirconia ware is made from
(see Table 11) mainly by the slip-casting method. " s t a b i l i z e d " material and is formed by slip-casting,
Mixtures of 10 to 50% granular and 50 to 90% milled although the larger sizes are sometimes made by
material are self-bonded when fired at 1450 to ramming the moistened powder into a mold. Slip-
1500°C. Porosities up to 5 to 10% are common. cast crucibles have from 0.7 to 5% porosity, where-
These crucibles can be used at 1700°C, although as the rammed type have porosities of perhaps 20%.
the silicate tends to dissociate at this temperature Standard sizes available are given in Tables 12
and may eventually cause disruption of the ware. and 13.
Zircon is notable in being unwetted by molten
aluminum, and it withstands molten platinum, FABRICATION OF ZIRCON AND
platinum-rhodium alloys, copper, copper alloys, ZIRCONIA CRUCIBLES
some enamel frits, and all acid slags. It is also
reported to resist the action of metaphosphates, Slip-Casting with Acid Deflocculant
sodium chloride, sodium sulfate, zinc chloride, and Raw Materials. Electrically fused, —325 mesh
potassium chloride at temperatures several hundred zirconia, with beryl I ia as a fluxing material and
degrees above the various melting points. However, with an acid deflocculant, is sometimes used for
zircon crucibles are not recommended for melting the casting of crucibles. The zirconia is supplied
strongly basic materials. by the National Lead Corp. and the beryl I ia flux
material by the Brush Beryllium Co.; the refractory
Zircon ia grade is preferable.
Zirconia is produced from the mineral baddeleyite Grinding. A batch of 99% dry zirconia and 1%
(mainly Z r 0 2 plus zircon) or from zircon in an beryl I ia is mixed by grinding in a steel-ball mill
electric arc furnace operation. Electrically fused for about 4 hours.
zirconia does not hydrate readily, has a high melt- Preparation of Slip. Upon removal from the mill,
ing point of 2700°C, and withstands loads of 25 psi the contaminated mix is leached with a dilute HNO,
to 2100°C. It is stable chemically in contact with bath (10 ml of HN0 3 per 100 ml of water). To
acidic or metal fusions and has been used for prevent lumping, the acid is first prepared and the
containers for melting fused silica. It is not easily powdered zirconia is added. The batch is shaken
reduced except that it may form a carbide when in well and then allowed to settle; the supernatant
contact with carbon at 1800 to 1900°C in an inert liquid is removed with an aspirator. This process
atmosphere and at 1500°C in a vacuum. Zirconia is repeated until the acid solution is no longer
is a conductor of electricity above 1600°C and discolored; usually about three washings are re-
should not be used in contact with resistance quired. The acid is removed from the slip by wash-
windings at these temperatures. ing two or three times with water. For best casting
The chief defect of electrically fused zirconia is properties, the slip should have a pH of 0.5 to 1.5
a reversible crystal change at approximately 1100°C and a specific gravity of 2.8 to 3.2.
from the monoclinic to the tetragonal form, which is Casting. The casting is done in plaster molds by
accompanied by a considerable volume change. the usual drain method.

24
 TABLE 11. STOCK SIZES OF ZIRCON CRUCIBLES

NUMBER AND OUTSIDE DIAMETER HEIGHT WALL THICKNESS CAPACITY

MANUFACTURER (in.) (in.) (in.) (cc)

15 (23)
A A \< 35

17(23)
A A X 75

23(23)
A A X 125

25(23) 2\ A X 200

27(23) 2%
A X 275

28(23)
A A X 325

33(23)
A A \ 400

35(23)
A A X 550

37 (23)
A A X 700

40(23) 4 4
X 600

45 (23)
A A % 1300

56(23)
A A % 2300

58 (23)
A A \ 2300
3
60 (23) 6 10 / 3000

65 (23)
A A % 3600

MC (13)
A A6 \e
MC (13)
A 3/3 /
J
16 %t
MC (13)
A6 3
%
MC (13)
A* Al ^2
MC (13)
A 4
\
MC (13)
A A %2
CZ-1 (6) 2
A \
CZ-3 (6)
A A X
CZ-4 (6)
A A X
CZ-5 (6)
A A %.
CZ-5 (6)
A A %6
CZ-6 (6)
A 8
%
CZ-7 (6) 7% (bilge)
A %
5 ^ (bottom)

25
/
TABLE 12. STOCK SIZES OF ZIRCONIA CRUCIBLES (UNSTABILIZED) (23)

OUTSIDE DIAMETER HEIGHT WALL THICKNESS CAPACITY

NUMBER
(in.) (in.) (in.) (ce)

5
\. X \. 1

7 X A. \ 5

10 1 A \. 45

13
A A \. 165

14
A A \.
130

15
A A \e 25

16
A A X 65

17
A 4 X 85

20 2
A X 130

21 2 8 250
\.
23
A A X 125

27 2\ 4 210
%6
28
A A %. 375

Drying. The crucibles should be air-dried over- to be used in a given case are determined by trial
night. and error. As the optimum deflocculation is ap-
Firing. The crucibles should be fired to 1800°C proached from neutrality, the mixture usually be-
by induction or in an oxypropane or oxyacetylene comes notably resistant to stirring with a glass
furnace. Slow firing and care in handling dry ware rod, but it flows readily under gravity. At the
are necessary to prevent cracking. optimum point for good casting, the slip is easily
stirred and flows smoothly from a glass rod.
Slip-Casting with Basic Deflocculant Underdefloccuiation of the slip is indicated by a
rapid casting rate (5 to 15 sec), thick w a l l s , easy
Raw Materials. Stabilized zirconia is obtainable
release from the mold, weakness of the dried ware,
in both coarse and milled forms. Since the fine
and rapid settling out of the zirconia from the slip,
material must be depended upon for the defloccula-
the settled portion being rather soft and easily
tion of the slip, it is essential that its average
returned to suspension. Overdeflocculation is
particle size be from 3 to 5 microns. If it is de-
usually attended by a slower casting rate (30 to
sirable to produce a less dense ware than that
45 sec), thin w a l l s , strong ware, and rather slow
obtained with fine-grained stabilized zirconia,
settling of the zirconia, which forms a dense mass
from 10 to 40% of coarse-grained (80 to 100 mesh)
that can be restored to suspension with difficulty.
material can be stirred into the deflocculated fine
Properties between these extremes should be
material without disturbing the deflocculation
sought.
appreciably.
Casting. Zirconia usually has a rapid casting
Preparation of Slip. When basic deflocculation rate if dry molds are used. Sufficient wall thick-
is to be used, the zirconia must be freed of any ness is often obtained by pouring the slip into the
acid ions by calcination at red heat. The powder mold and out again in 15 to 30 seconds. Three to
is then dampened by adding 10 to 15 ml of distilled four pieces can be cast in a mold before drying of
water to 100 g of zirconia. From 1 to 5 ml of a the mold is necessary. A wet mold is likely to
2% solution of tetrasodium pyrophosphate in water cause sticking and to require undue jarring to
is then stirred into this mix. Proper proportions release the ware.

26
 TABLE 13. STOCK SIZES OF ZIRCONIA CRUCIBLES (STABILIZED) (23)
/ss%
OUTSIDE DIAMETER HEIGHT WALL THICKNESS CAPACITY
NUMBER
(in.) (in.) (in.) (cc)

50-5
X X \t 0.70

50-2 2 2.35
\ \.
i 75-1
X 1
hi 3.2

3
75-4 4 / 12.9
% "32
100-1 1 1
X 6.0

100-6 1 6
X 38.0

125-2
A 2
X 22.0

125-6
A 6
X 68.0

150-2
A 2
X 34.0

150-8 A 8
X 142.0

175-2 A 2
\ 38.0

175-8
A 8 3

'16
/ 169.0
3
200-2 2 2 / 55.0
'l6
3
200-8 . 2 8 / 237.0
'16
3
225-2
A 2 / 73.0

225-8 A 8
3
'16
/ 317.0
3
250-2
A 2
'16
/ 94.0

250-8 A 8
*.
407.0

275-2
A 2
Is 102.0

275-8
A 8
i 543.0

300-2 3 2
X 126.0

300-10 3 10
X 704.0

Firing. Stabilized zirconia is usually made rather Zirconia Crucibles. Norton (19), Titanium (23).
dense (5 to 10% porosity) by firing to 1730°C in
12 hr and by holding the temperature for 1 hr, References
allowing the ware to cool with the kiln. Gas firing J. G. Thompson and M. W. Mallett, "Preparation
is usually employed. of Qucibles from Special Refractories by Slip
Casting," RP1236, J. Research Natl. Bur. Standards
Manufacturers 23, 319 (1939).
, Zircon Crucibles. Bartley (3), Taylor (6), Elec- R. W. Knauft, "Zircon Refractories for Aluminum
/'trq* (10), Laboratory Equipment (13), Massilon Melting Furnaces," Metals and Alloys 18, 1326
(14), Remmey (20), Titanium (23). (1943).
W. J. Baldwin, "Zircon and Zirconia Refracto-
^Zirconium oxide lining in silicon carbide crucible. ries," Chem. Eng. Progress 44, 875 (1948).
/

27
' / LIST OF MANUFACTURERS

(1). American Crucible Co., North Haven, Conn.

(2). American Cuttlefish Bone and Crucible Co., 75 Cliff Street, New York 38, N. Y . *
(3). Bartley Crucible and Abrasive Corp., 15 Muirhead Avenue, Trenton 3, N . J . «

(4). Brush Beryllium Co., 4301 Perkins Avenue, Cleveland 3, Ohio. _

(5). Carborundum C o . , Niagara F a l l s , N. Y . •> <
(6). The Charles Taylor Sons Co., Cincinnati, Ohio.
(7). Coors Porcelain Co., Golden, Colo.
(8). Corning Glass Works, Corning, N. Y .
(9). The Denver Fire Clay Co., Denver 17, Colo.
(10). Electro Refractories and Abrasive Corp., 334 Delaware Avenue, Buffalo 2, N. Y .
(11). Exolon Co., Tonawanda, N. Y .
(12). Joseph Dixon Crucible Co. Jersey City 3, N. J .
(13). Laboratory Equipment Corp., St. Joseph, Mich.
(14). Massilon Refractories C o . , Massilon, Ohio.
(15). Morganite, Inc., 3302 48th Avenue, Long Island City 1, N. Y .
(16). Mullite Corp., Shelton, Conn.
(17). National Carbon Co., 30 East 42nd Street, New York 17, N. Y.
(18). National Crucible Co., Mermain Lane and Queen Streets, Philadelphia 18, Pa.
(19). Norton Co., Worcester 6, Mass.
(20). Richard C . Remmey Sons Co., Headley Street and Delaware River, Philadelphia 37, Pa.

(21). Ross-Tacony Crucible Co., Tacony, Philadelphia 35, Pa.

(22). Thermal Syndicate, L t d . , 12 East 46th Street, New York 17, N. Y .

(23). Titanium Alloy Manufacturing Division, National Lead Corp., I l l Broadway, New York 6, N. Y .

(24). Vesuvius Crucible Co., Swissvale, Pittsburgh 18, Pa.

(25). Western Gold and Platinum Works, 589 Bryant Street, San Francisco, Calif.

28