United States Patent Office 2,942,991

Patented June 28, i960

2
will tend to become unhomogeneous as the particles settle
out, and the composition of the slurry used in a series of
2,942,991 moulds will vary. The tendency for a slurry of finely
SL-CASTING PROCESS divided refractory material and silica sol to deposit refrac
tory material on standing can be reduced or eliminated
Eric Smith, Springfield, Mass, or to Monsanto by the incorporation of a suitable organic stabilizing agent
Chemicals Limited, London, England, a British com and appropriate adjustment of the pH. The stabilizing
pany agents in some way enable the kind of association which
No Drawing. Filed Oct. 19, 1956, Ser. No. 616,942 is referred to above to occur, thus altering the nature of
O the surface properties of the particles of refractory ma
Claims priority, application Great Britain Oct. 28, 1955 terial and enabling them to remain in suspension.
10 Claims. (C. 106-44) The process of slip-casting of the present invention is
therefore one in which there is used an aqueous slurry
comprising a finely-divided refractory material, a silica
This invention relates to slip casting processes for the s sol and a minor proportion of an organic stabilizing agent,
manufacture of refractory articles. the pH value of the slurry being such that it remains
The slip-casting process is a well-known method for homogeneous on standing.
making shaped refractory articles and can be described Silica sols which are suitable for use in the composi
briefly as follows. A non-settling aqueous slurry of a tions of the invention include those which have been ob
finely-divided refractory material and a bonding agent is tained by the ion-exchange process from sodium silicate,
poured into a dry porous mould, which is usually made or by the so-called autoclave process employing a silica
of plaster. The mould soaks up and absorbs water from gel, such as the silica sols described in British Patents
the slurry, building up on its surface a coating of the par 607,696; 645,703; 649,897; 654,850 and 662,423. The
ticles of refractory material mixed with bonding agent concentration of silica in the silica sol used is preferably
from which water has been withdrawn, and thus forming 25 from 10% to 30% by weight and about 15% is partic
a layer of solid material of even thickness conforming to ularly suitable. The silica sols sold under the registered
the surface of the mould. When sufficient time has trademark "Syton,' such as those known as "Syton C,"
elapsed since pouring to give the desired thickness of “Syton W-20, and "Syton 2X,” which contain 15%, 15%
coating on the mould surface, the excess-slurry is poured and 30% by weight of silica respectively, are particularly
off and the coating (or "casting') is allowed to dry. The suitable, and the 30% sol can, if required, be diluted with
so water
dry casting is removed from the mould (this is easy as to provide a 15% sol for direct use.
the casting shrinks slightly during drying), and is then The powdered refractory material used will, of course,
fired to give it strength, which is usually provided by some not be one which is sufficiently acidic or basic to cause the
chemical interaction between the particles of refractory silica sol to gel rapidly. Suitable refractory materials are
material and the bonding agent. - .. . . . r alumina, Carborundum, chromite, silica itself and sili
In such slip-casting processes ceramic clays are widely cates such as zirconium silicate and sillimanite. The par
used as the bonding agents for the refractory particles, ticle size of the finely-divided refractory material is prefer
and the initial slurry thus contains a fine dispersion of clay ably such that it will pass through a British Standard sieve
as well as refractory material. Clays, however, suffer of 200 mesh to the inch.
from the disadvantages that they need careful prepara Suitable organic stabilizing agents are non-ionic and
tion before use and they contain sodium or other metallic cationic surface-active agents, and gelatin. Gelatin may
residues which impair the refractory properties of the be used in the form of a commercial product, such as
castings. animal glue. .
It has now been discovered that instead of clays, silica Suitable. non-ionic surface-active agents are condensa
sols can be used as the bonding agent in these slip-casting tion products of an alkylene oxide (for example ethylene
processes provided that the slurry of refractory material oxide) with an organic Substance containing a large non
and colloidal silica is appropriately stabilized and its pH polar group and an active hydrogen atom, for instance
adjusted so that the slurry remains homogeneous on stand ethylene oxide condensates of long-chain fatty alcohols
ing. Moreover, the silica in colloidal solution appears to (such as the product sold under the name "Lubrol W'),
associate itself in some unknown way with the particles of the condensation products of ethylene oxide with alkyl
SO phenols, for instance an octylcresol (such as "Lissapol
refractory material in the slurry and when such a slurry N'), and the condensation products of ethylene oxide with
is employed in slip-casting a high proportion of the silica long-chain alkyl mercaptains, for example a dodecyl mer
remains in the coating which provides the casting and is
thus available for bonding the refractory material, in captan. Another non-ionic surface-active agent which
stead of being absorbed into the porous mould with the can be used is a polyethylene glycol fatty acid ester such
55 as that sold under the name "Nonex 99.” Examples of
water as would have been expected. This discovery en
ables the production by slip-casting processes of shaped cationic surface-active agents, which can be used are the
refractory articles, in which the bonding agent is Substan quaternary ammonium salts such as the cetylpyridinium
tially pure silica. bromide sold under the name "Fixanol C,' and cetyltri
It is not practicable to employ slurries consisting simply methylammonium bromide.
O The stability of the slurry containing the refractory ma
of aqueous silica sol and finely-divided refractory mate terial, silica sol and stabilizing agent is greatly influenced
rial, for there is a tendency for the refractory particles by its pH, and where necessary the pH must be suitably
suspended in the silica sol to settle out on standing and in adjusted, by the addition of acid, for instance, after the
fact the association referred to above does not occur. If ingredients of the slurry have been mixed. The most
such a slurry is used in slip-casting, there is a tendency for 5 suitable pH for stability varies unpredictably with the
the refractory particles to fall out of suspension and thus particular production batch of silica sol used but it can
provide coatings which are thicker at the bottom of the easily be found by simple testing. Usually with a non
mould than those accumulating at places higher up on the ionic Surface-acting agent the pH which is suitable will be
mould wall solely due to the absorbing action of the mould
on the alkaline side of neutrality, but it may be found
pores. Moreover, where a reservoir of slurry is main ro that comparatively low pH values are acceptable when
tained for pouring into the individual moulds, the slurry the proportion of non-ionic surface-active agent present
 2,942,991
3. 4.
is small. Where gelatin is used as the stabilizing agent, then suitable to place the mould containing the casting in
the pH value is desirably less than 7. a drying oven maintained at a temperature below 100
The proportions of silica sol to powdered refractory C., and conveniently between 50° C. and 80° C. After
material and any added water used will depend in any drying for a suitable period the shrunk casting is re
given instance on the thickness or "viscosity” of the slurry moved from the mould, and can then be fired and treated
desired. The most suitable amount of stabilizing agent by other processes to give the finished article desired.
employed in any particular slurry will depend to some. The mould is then repeatedly re-used.
extent on the nature of the stabilizing agent as well as The invention is illustrated by the following examples.
on the other materials present, but in general up to 1% Example I
of stabilizing agent is sufficient and it is unnecessary or O
undesirable to add as much as 4% or 5% or more. Comminuted zirconium silicate passing a 200 mesh
Where a non-ionic surface-active agent is employed, from British Standard sieve (3.5 kg.; the material used was that
0.05% to 1% by weight of surface-active agent is usually sold under the name. “Zircosil D') was added in portions
sufficient, and where a cationic surface-active agent is with vigorous stirring to a mixture of Syton C (1200 cc.;
used even small quantities are suitable. Where gelatin 5 Syton C is a silica sol prepared by the so-called autoclave
is used as stabilizing agent, an amount corresponding to process and containing 15% by weight of SiO2) and 30
about 0.04% by weight of the slurry is usually sufficient, cc. of an aqueous solution containing 50% by weight of
though more can be added if desired. a non-ionic Surface-active agent sold under the name
The viscosity of a slurry used in the process of the 'Lissapol N' (a condensation product of ethylene oxide
invention is not critical and can be within a wide vis 20 and octylcresol): 10 cc. of 1%, hydrochloric acid were
cosity range. It should, however, not be too low, as the then added and stirring continued for a few minutes. The
casting obtained then shrinks little on drying and con pH of the slurry: thus prepared was 8.4. Its “viscosity"
sequently release from the mould is not easy. On the is indicated by the time taken for 50 cc. of the slurry at
other hand if the viscosity of the slurry used is very a temperature of 20 C. to flow. from a pipette held ver
high, cracks tend to appear in the casting, either while 25 tically, which was 85 seconds, while the time taken for an
the casing is being formed in the mould or when it is equal volume of water to flow from the pipette under
dried. If the viscosity of the slurry is gauged by meas identical conditions, was found to be 30 seconds.
uring the time taken for a given volume to flow through The slurry was poured into a dry plaster mould, al
a standard pipette and comparing it with the time taken lowed to stand for 5 minutes, and the excess slurry was
for water to do the same, then as a general guide, where 30 then poured off. . The mould containing the casting was
the flow time for water is 30 seconds, a very satisfactory then air dried at room temperature for two hours and
flow time for a slurry suitable for use in the process of placed in an oven at 80° C. overnight. The casting,
the invention is from 70 to 60 seconds. which was in the form of a basin of wail thickness 346
In some instances where non-ionic surface-active inch, was easily removed from the mould and successfully
agents are used as the stabilizing agents, it may be found 35 fired to 900 C. to give a refractory article of satisfactory
that the viscosity of the slurry produced increases strength and surface finish.
markedly on standing, although the silica sol does not
gel. This behaviour appears to depend to a consider Example 2
able extent on the pH of the slurry. It is possible to re A slurry of fused alumina (175 g., passing a 200 mesh
duce any tendency of the slurry to thicken or increase-in 40 British Standard sieve), Syton C (80 cc.), the non-ionic
viscosity on standing, or even reduce to the desired ex surface-active agent “Lissapol N” (0.75 cc.) and 1%.
tent the viscosity of a slurry which is already thickened, hydrochloric acid (6.3 cc.) was prepared in a manner
by incorporating in addition to the non-ionic surface similar to that described in - Example 1. This slurry
active agent an anionic surface-active agent, for instance was poured into a bone. dry plaster mould at room tem
an alkylary, sulphonate (for example sodium dodecyl 4. 3 perature and allowed to stand for 10 minutes. The
benzene sulphonate), a salt of an alkyl hydrogen Sulphate excess slurry was then poured off and the mould and
(for example sodium lauryl Sulphate, sodium cetyl sul casting were air dried at room temperature and after
phate or one of the commercial detergents-sold under the wards placed in an oven at 65° C. overnight. The cast
names "Teepot" and "Iranopol”), and an alkyl sulpho ing, of 4-inch thickness, was easily removed from the
succinate (for example: sodium dioctyl sulphosuccinate or mould and fired to 900 C., giving a refractory article
the substance sold under the name “Alcopol O'). Of the having a good surface finish and satisfactory strength.
anionic surface-active agents which may be used to re
duce the thickening of a slurry in which a non-ionic stir Example: 3
face-active agent is present there is usually necessary only A slurry of comminuted zirconium silicate passing a
a small amount in proportion to the non-ionic substance. 55 200 mesh British Standard sieve (175 g) was added
Thickening of a slurry which has already occurred can with stirring to Syton C (60 cc.) in which was incorpo
generally be reduced by increasing the pH of the slurry rated 0.6 g. of an aqueous solution containing 10%
by careful addition of an alkali, for example ammonia. by weight of cetylpyridinium bromide (Fixanol C).
Slurries prepared using gelatin as stabilizing agent show The slurry had a flow time (see Example 1) of 51
a tendency to be more viscous with decreasing pH, and GO Seconds.
their viscosity can be controlled by adjustment of pH. The slurry was poured into a plaster mould, allowed
The viscosity of any slurry can of course also be read to stand for 5 minutes, and the excess slurry then poured
justed by the incorporation of additional quantities of one off. The mould and casting were air dried at room tem
or more of its ingredients. perature for 2 hours, and then overnight at 98 C.
In carrying out the slip-casting process, the time for Removal of the easting from the mould, and firing to
which the slurry needs to stand in the mould before ex 900 C., gave a satisfactory refractory article.
cess slurry is poured off is not only dependent on the
thickness of the casting required and the absorbing char Example 4.
acteristics of the mould, but also on the viscosity of the Gelatin (0.1 g) was dissolved with gentle warming in
slurry. In practice the period between pouring in the Syton C (60 cc.; pH 9.7) and to the solution thus ob
slurry and pouring off excess is usually between 2 and 10 tained comminuted zirconium silicate (175. g., passing a
minutes. 200 mesh British Standard sieve) was added in portions
After the slurry has been poured off it is preferable With vigorous mechanical stirring. When addition of the
to allow the mould containing the casting to stand for a . zirconium silicate had been completed, sufficient dilute
few hours at room temperature in the open, and it is hydrochloric acid was added slowly and with stirring to
 8,942,991
5
produce a slurry of pH 5.5. It was found that this could
6
product of ethylene oxide with an organic substance
be used successfully in a process of slip-casting similar containing a large non-polar group and an active hydro
to those described in the above examples. gen atom, the said organic substance being selected .
What is claimed is: from the group consisting of long-chain fatty alcohols,
1. A slip-casting process, in which the slurry used to alkylphenols, long-chain alkyl mercaptans, and fatty
form the wet casting on the porous mould is an aqueous acids, the weight ratio of silica to the finely divided
slurry consisting essentially of a finely-divided refractory refractory material being from 9 to 12 parts by weight
material, a silica sol whose silica content is in the range of silica for each 175 parts by weight of the refractory
of from 10% to 30% by weight, and a stabilizing amount material.
up to 1% by weight of an organic stabilizing agent se O 7. The slip-casting process of claim 6 wherein the
lected from the group consisting of a non-ionic surface non-ionic surface-active agent is the condensation prod
active agent and a cationic surface-active agent, said uct of ethylene oxide with an alkyl phenol.
slurry having a pH such that the slurry remains homo 8. In a slip-casting process wherein an aqueous slurry
geneous on standing, said refractory material being com of a finely-divided refractory material and a bonding
posed of particles which pass through a 200 mesh British 5 agent is used to form a wet casting on a porous mould,
Standard sieve and being selected from the group con the casting is dried and separated from the mould and
sisting of alumina, Carborundum, chromite, silica, zir fired to give it strength, the improvement which comprises
conium silicate and sillimanite, said cationic surface using an aqueous slurry consisting essentially of a finely
active agent being selected from the group consisting of divided refractory material, a silica sol whose silica
quaternary ammonium salt surface-active agents and 20 content is in the range of from 10% to 30% by weight,
gelatin, the weight ratio of silica to the finely divided and from 0.05 to 1% by weight of the slurry of a
refractory material being from 9 to 12 parts by weight non-ionic Surface-active agent, said slurry having a pH
of silica for each 175 parts by weight of the refractory Such that it remains homogeneous on standing, said re
material. fractory material being composed of particles which pass
2. A slip-casting process, in which the slurry used to 25 through a 200 mesh British Standard sieve and being
form the wet casting on the porous mould is an aqueous Selected from the group consisting of alumina, Carbo
slurry consisting essentially of a finely-divided refractory rundum, chromite, silica, Zirconium silicate and silliman
material, a silica sol whose silica content is in the range ite, the Weight ratio of silica to the finely divided refrac
of from 10% to 30% by weight, from 0.05 to 1% by tory material being from 9 to 12 parts by weight of
weight of a non-ionic surface-active agent, an anionic 30 silica for each 175 parts by weight of the refractory
surface-active agent, said slurry having a pH such that material.
the slurry remains homogeneous on standing, said refrac 9. The slip-casting process of claim 8 wherein the
tory material being composed of particles which pass non-ionic Surface-active agent is the condensation prod
through a 200 mesh British Standard sieve and being uct of ethylene oxide with an organic substance con
selected from the group consisting of alumina, Carbo 35 taining a large non-polar group and an active hydrogen
rundum, chromite, silica, zirconium silicate and sili atom, the said organic substance being selected from
manite, the weight ratio of silica to the finely divided the group consisting of long-chain fatty alcohols, alkyl
refractory material being from 9 to 12 parts by weight phenols, long-chain alkyl mercaptains, and fatty acids.
of silica for each 175 parts by weight of the refractory 10. The slip-casting process of claim 9 wherein the
material. , . 40 non-ionic surface-active agent is the condensation prod
3. The slip-casting process of claim 2 wherein the uct of ethylene oxide with an alkyl phenol.
anionic surface-active agent is an alkyl aryl sulfonate.
4. The slip-casting process of claim 1 wherein the re References Cited in the file of this patent
fractory material is zirconium silicate and wherein the UNITED STATES PATENTS
organic stabilizing agent is a non-ionic surface-active 45 1,364,875 Fulton ---------------- Jan. 11, 1921
agent.
5. The slip-casting process of claim 1 wherein the or 2,288,661 Wadman ---------------- July 7, 1942
ganic stabilizing agent is cetyl pyridinium bromide. 2623.809 Myers ---------------- Dec. 30, 1952
6. A slip-casting process, in which the slurry used to 2,701,902 Strachan -------------- Feb. 15, 1955
2,799,658
form the wet casting on the porous mould is an aqueous 50 2,888,354 Nickerson -------------- July 16, 1957
slurry consisting essentially of a finely-divided refractory Smith et al. ------------ May 26, 1959
material, a silica sol whose silica content is in the FOREIGN PATENTS
range of from 10% to 30% by weight, and from 0.05 594,671 Great Britain ----------- Nov. 17, 1947
to 1% by weight of the slurry of a non-ionic surface
active agent, said slurry having a pH such that the slurry 55 OTHER REFERENCES
remains homogeneous on standing, said refractory ma "Atlas Spans and Atlas Tweens,” December 1943, pub.
terial being composed of particles which pass through by Atlas Powder Co., p. 17.
a 200 mesh British Standard sieve and being selected "Ceramics-A Symposium," pub. 1953 by British Ce
from the group consisting of alumina, Carborundum, ramic Soc., Stoke-on-Trent, England (pages 551-556).
chromite, silica, zirconium silicate and sillimanite, said 80 Serial No. 426,244, Passelecq (A.P.C.), published
non-ionic surface-active agent being the condensation June 1, 1943.