U.S. patent number 3,561,494 [Application Number 04/710,316] was granted by the patent office on 1971-02-09 for castable silicate compositions, casting methods and articles produced thereby.
Invention is credited to Robert J. Hackett.
United States Patent |
3,561,494 |
Hackett |
February 9, 1971 |
**Please see images for:
( Certificate of Correction ) ** |
CASTABLE SILICATE COMPOSITIONS, CASTING METHODS AND ARTICLES
PRODUCED THEREBY
Abstract
Castable compositions including soluble or colloidal silicates
as binding agent. The composition is cast as an aqueous slurry in a
mold coated with a reagent for precipitating the silicate, to
prevent penetration of silicates into the mold surface. A
lightweight, expandable, refractory tube having excellent
resistance to thermal shock is produced.
Inventors: |
Hackett; Robert J. (Brookfield,
CT) |
Family
ID: |
24853518 |
Appl.
No.: |
04/710,316 |
Filed: |
March 4, 1968 |
Current U.S.
Class: |
138/177; 138/145;
501/80; 138/140; 264/30 |
Current CPC
Class: |
F16L
9/14 (20130101); F16L 9/10 (20130101) |
Current International
Class: |
F16L
9/10 (20060101); F16L 9/14 (20060101); F16L
9/00 (20060101); F16l 009/10 () |
Field of
Search: |
;264/66 (For/ purposes/
of/ restriction/ only)/ ;138/177 (For/ purposes/ of/ restriction/
only)/ ;106/40 (For/ purposes/ of/ restriction/ only)/
;138/140,141,143,145,177,149 (Cursory)/ ;106/(Perlite digest)/ |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Ross; Herbert F.
Claims
I claim:
1. An article of manufacture, comprising:
A. a metal tube; and
B. a foamed ceramic body surrounding and bonded to said tube, said
ceramic body essentially comprising:
1. 40--67.5 percent mullite;
2. 5--15 percent Si0.sub.2;
3. 3--5 percent Na.sub.20;
4. 0--10 percent perlite; and
5. 0--10 percent clay;
said ceramic body having an outer peripheral layer comprising a
blend of said ceramic body and an insoluble silicate salt, said
insoluble silicate salt resulting from the reaction of calcium
stearate and the aqueous silicate of said body to form a
substantially nonporous insoluble layer.
2. An article of manufacture as defined in claim 1, wherein said
nonporous, insoluble layer comprises polysilicic acid.
3. An article of manufacture as defined in claim 1, wherein said
nonporous, insoluble layer comprises a copper salt.
4. An article of manufacture as defined in claim 3, wherein said
silicate salt comprises calcium silicate.
5. An article of manufacture as defined in sinc 1, wherein said
nonporous, insoluble layer comprises a zinc salt.
6. The article defined in claim 1, wherein said ceramic body is
cellular in structure.
7. The article defined in claim 6, wherein said ceramic body
contains about 10 to 15 percent entrained gas, by volume.
8. An article of manufacture, comprising:
A. a metal tube; and
B. a foamed ceramic body surrounding and bonded to said tube, said
ceramic body consisting essentially of about:
1. 67.5 percent mullite;
2. 14.7 percent Si0.sub.2;
3. 4.2 percent Na.sub.20;
4. 7.1 percent perlite; and
5. 6.5 percent clay;
said ceramic body having an outer peripheral layer comprising a
blend of said ceramic body and an insoluble silicate salt, said
insoluble silicate salt resulting from the reaction of calcium
stearate and the aqueous silicate of said body to form a
substantially nonporous insoluble layer.
Description
The present invention relates to castable silicate compositions and
methods. As a particular aspect of the invention, a refractory,
expendable, lightweight tube is produced.
Refractory tubes are used for a number of purposes, such as for
withdrawing molding metal for analysis, for determining
temperatures of molten substances, for injecting gases into molten
metals, etc. Since such tubes are normally used only once or a few
times before being discarded, they must be inexpensive.
Particularly, in applications where the tube will be plunged into
molten metals, it must withstand great thermal shock.
Known prior art tubes for these applications include a steel tube
covered with layers of paper. The paper, although destroyed in use,
protects the steel tube for a limited period of time. Another known
prior art construction has the steel tube coated with asbestos
fibers admixed with fibers such as cotton. Each of these known
prior tubes are somewhat hazardous to use, and have a service life
of only a few seconds.
According to one major aspect of the present invention, the steel
tube is protected by a foamed ceramic composition including
refractory materials bonded together with silicate. The resulting
tube withstands high temperatures much better than known prior art
tubes, and has a greater service life under severe conditions.
Other major aspects of the invention include particular refractory
compositions, methods of formulating these refractory compositions
and methods of casing silicate-containing compositions
generally.
Accordingly, a primary object of the invention is to provide
methods of casing silicate-containing compositions.
A further object is to provide such methods which are particularly
suited for use with porous molds which are to be separated from the
cast article.
A further primary object is to provide inexpensive refractory
castable compositions.
A further object is to provide compositions of the above character
which can be formed to produce lightweight, insulating, refractory
ceramic structures.
A further primary object of the invention is to provide a metal
tube coated with compositions of the above character.
Other objects of the invention will in part be obvious and will in
part appear hereinafter.
The invention accordingly comprises the several steps and the
relation of one or more said steps with respect to each of the
others, the compositions possessing the characteristics,
properties, and the relation of constituents which will be
exemplified in the compositions hereinafter described, and the
articles which possess the relation of elements, all as exemplified
in the detailed disclosure hereinafter set forth, and the scope of
the invention will be indicated in the claims.
For a more complete understanding of the nature and objects of the
invention, reference should be had to the following detailed
description taken in connecting with the accompanying drawing, in
which:
FIG. 1 is a perspective view, partly broken away, of a ceramic
coated metal tube produced according to one aspect of the
invention;
FIG. 2 is an action view, partly in section, showing the metal tube
being assembled into a nozzle for applying the castable
compositions to the exterior of the tube;
FIG. 3 is a side elevation view, partly broken away of a paper
mold;
FIG. 4 is an end view of the mold shown in FIG. 3;
FIG. 5 is a sectional view of the assembled tube and mold on the
nozzle, just prior to injection of the castable composition;
and
FIG. 6 is an action view similar to FIG. 5, showing an intermediate
stage in the injection of the composition into the space bounded by
the tube and mold.
THE CASTING OPERATION
The composition and process according to the invention are
disclosed in the context of producing the tube illustrated in FIG.
1, which includes tube 20 surrounded by a cylindrical ceramic
casting 22 bonded to tube 20. As will be disclosed, casting 22 is
refractory, lightweight and inexpensive. FIGS. 2--6 illustrate
suitable apparatus for producing the FIG. 1 product.
Referring to FIG. 2, nozzle 24 includes inner and outer coaxial
cylindrical walls 26 and 28 spaced apart by ribs 30 to define an
annular passage 32. A plug 34 is inserted in the left end of the
tube 20, which is then telescopically inserted into cylinder 26
until the right end of tube 20 is flush with the right end of
cylinder 26 (FIG. 5). The dimensions of cylinder 26 are selected
for easy sliding reception of tube 20. Since in this application it
is intended that casting 22 adhere to tube 20, the surface of tube
20 is preferably etched or otherwise thoroughly cleaned prior to
insertion in cylinder 26.
As illustrated in FIG. 3, mold 35 includes cylinder 36, formed for
example of kraft paper, and a cup-shaped mold end piece or cap 38
secured as by staples 40 at the right end of cylinder 36. The
central bottom portion of cap 38 is slit to provide tabs 42
extending radially inward from a distance approximately equal to
the radius of tube 20. The interior surface of cylinder 36 and the
cap 38 are coated with a release coat of a character to be
described. The dimensions of cylinder 28 are selected so that
coated cylinder 36 can telescope thereon, as shown in FIG. 5. When
the mold 35 has been installed on cylinder 28, tapered pin 44 is
inserted through the center of cap 38. This wedges tabs 42 into
contact with the inner surface of tube 20 and seals mold 35 to tube
20. Mold 35 and tube 20 thus define an annular volume for receiving
the castable composition in the form of slurry 46 which is injected
through passage 32 by conventional pumping means (not shown).
Tube 20 and mold 35 are pushed to the right as a unit as their
enclosed annular volume is filled by slurry 46. When the enclosed
volume is filled with slurry 46 and tube 20 and mold 35 are removed
from nozzle 24, the left or open end is preferably closed with a
further release-coated cap 38 and tapered pin 44, so that both ends
are identical and tube 20 is centered within cylinder 36. For this
purpose, cylinder 36 is preferably slightly longer than tube 20, to
accommodate end caps 38. The slurry should substantially completely
fill the mold when both end caps 38 are installed. After this
slurry 46 in the resulting intermediate product has been cured or
set, pins 44 and mold 35 are removed, to produce the final product
shown in FIG. 1.
THE SLURRY COMPOSITION
The preferred specific composition for refractory casing 22 is as
follows: ##SPC1##
The mullite is an inexpensive refractory substance, and can be
replaced by other refractory substances depending upon the desired
end use.
The preferred aqueous silicate in the above composition is
available from Philadelphia Quartz Company as their product S-35,
and contains 6.75 percent by weight Na.sub.20, 25.3 percent
Si0.sub.2 and 67.95 percent water. This results in approximately
440 ounces of "silicate solids" combined with 936 ounces of water.
In terms of weight percent of the total slurry composition, the
silicate expressed as Si0.sub.2 (348 ounces) constitutes some 10.5
percent of the slurry, or about 14.7 percent of the cured
casting.
The perlite is a lightweight refractory extender, and contributes
to ease of foaming of the slurry.
The clay in the composition adds to the strength of the casting and
reduces the viscosity of the slurry. It is also believed to reduce
the size of the foam bubbles.
The free water is added to this particular composition for two
reasons. When using the particular aqueous silicate as specified
above, the resulting slurry is rather difficult to pump. Addition
of this small amount of further water makes the slurry conveniently
pumpable. If substantially more water were added, the final casting
22 would tend to crack upon curing. The other purpose of the free
water is to facilitate blending the surface active agent into the
slurry. The preferred surface active agent is an anionic surfactant
commercially available as Santomerse No. 1 from Monsanto Company,
and is believed to be essentially dodecyl benzene sulfonate. A
number of other surface active agents are commercially available
and would be suitable. The principal function of the surface active
agent is to stabilize the foam produced when the slurry is stirred
so as to entrain air.
Operative ranges for the above ingredients are generally as
follows: ##SPC2##
COMPOUNDING THE SLURRY
The several ingredients are preferably combined as follows. The
aqueous silicate, clay and mullite are thoroughly mixed with
approximately 17 ounces of the free water and then let stand for 2
or 3 days. The perlite is then blended in. The surface active agent
is then dissolved in the remainder of the free water (which may be
warmed) and added to the mixture. The mixture is then stirred so as
to entrain air and produce a foamed slurry stabilized by the
surface active agent. Stirring is discontinued when the mixture has
expanded to about 110 percent to 115 percent of its original
volume. The foamed slurry is then ready for extrusion through
nozzle 24.
It should be understood that the specific aqueous silicate
composition indicated above can be replaced by other aqueous
silicates containing different amounts of alkaline oxide (either
sodium or potassium oxide), and different amounts of total solids
in water. In such cases it may be necessary to add differing
amounts of free water, or perhaps no free water, or to make other
adjustments in the composition. The term aqueous silicate as used
in the specification and claims is intended to include silicates
present either as colloidal dispersions or in true solution.
The indicated range of foamed expansion is significant in that a
less expanded slurry would be difficult to pump while one expanded
to a considerably greater degree would tend to crack upon curing.
The foamed structure contributes to the insulating qualities of the
casting, improves its thermal shock resistance and makes it
lightweight and less expensive.
SETTING THE SLURRY
The slurry 46 in the intermediate product is preferably cured by
drying between 180.degree. and 210.degree. F. for a period of time
depending on the radial thickness of the slurry, and then gradually
raising the temperature to about 400.degree.--500.degree. F., to
set the silicate. When the radial thickness of the slurry is
substantially 0.22 inch, the following schedule has been found to
give excellent results.
Temperature, .degree. F. Time
180-- 210 5--61/2 hours
212-- 225 15 minutes
300 15 minutes
400 30 minutes
450 10 minutes
470 10 minutes
500 5 minutes
Of these heating periods, the first is considered to be highly
desirable with the above formulation, and the second heating period
is also of considerable importance. If the temperature is too low
during the first period, the foamed slurry tends to collapse and
settle while if the temperature is too high, the ceramic tends to
blister and crack. The ceramic 22 cured in accordance with the
above schedule can be plunged directly into molten steel without
cracking.
Assuming that all the water is removed during the curing, the
casting using the above specific slurry composition will have the
following approximate empirical composition:
Ingredient Weight Percent
mullite 67.5
Si0.sub.2 14.7
Na.sub.2O 4.2
perlite 7.1
clay 6.5
Total 100.0
separation of casting from mold
according to another major aspect of the invention, means are
provided for preventing an aqueous silicate from sticking to a
surface, such as to mold 35, particularly when the mold is porous.
It has been discovered that such sticking can be prevented by
coating the surface with a setting agent, which is defined as a
substance which chemically reacts quickly with aqueous silicate to
form an insoluble material. The insoluble material is believed to
form a film or layer which prevents penetration of the unreacted
aqueous silicate to the surface being protected. The insoluble
material can be, for example, polysilicic acid (formed when the
setting agent is more acidic than silicic acid, e.g., sulfuric or
acetic acid), or insoluble silicate salts (formed when the setting
agent donates cations forming insoluble silicate salts, e.g.,
copper, zinc or calcium silicate). Selection of a particular
setting agent for a given application is within the scope of one
skilled in the art.
The presently preferred setting agent is calcium stearate, which is
commercially available in the form of a wettable powder. When using
this wettable calcium stearate powder as the setting agent for
coating the interior surfaces of mold 35, it is preferably sprayed
as an aqueous slurry and dried so as to leave a film approximately
0.015 to 0.030 inch thick on the interior mold surfaces. A
considerably thicker coating might prevent proper escape of water
vapor through the mold walls during the curing of the slurry, while
considerably thinner coatings would not provide an effective
barrier.
The calcium stearate apparently reacts substantially
instantaneously with the aqueous silicate to form a layer of
insoluble calcium silicate. This in turn prevents penetration of
the aqueous silicate to the mold, so that the mold can be readily
stripped from casting 22.
It should be understood that the use of a setting agent to prevent
adhesion of silicate-containing compositions to surfaces (such as
molds) is not restricted to production of the article shown in FIG.
1 or to the specific compositions herein disclosed, but is of
general application.
From the above disclosure and the accompanying drawing it may be
seen that there is provided a method using setting agents for
casting silicate-containing compositions, which method is
particularly useful when the mold is to be separated from the cast
article. The setting agents may be applied to the mold surface as
thin coatings, permitting ready release of the mold. The preferred
castable compositions disclosed herein are well suited for exposure
to extremely high temperatures, and are inexpensive. When foamed as
above disclosed, the resulting castings are lightweight and provide
substantial insulating properties. The disclosed metal tube coated
with foamed refractory ceramic is rugged and inexpensive, and can
withstand sudden immersion into molten steel.
While the objects of the invention are efficiently achieved by the
preferred forms of the invention described in the foregoing
specification, the invention also includes changes and variations
falling within and between the definitions of the following
claims.
* * * * *