U.S. patent number 3,647,488 [Application Number 04/873,790] was granted by the patent office on 1972-03-07 for dental prosthesis model base composition containing calcium fluoride.
This patent grant is currently assigned to Ceramco, Inc.. Invention is credited to Kristin Brigham, Ronald C. Vickery.
United States Patent |
3,647,488 |
Brigham , et al. |
March 7, 1972 |
DENTAL PROSTHESIS MODEL BASE COMPOSITION CONTAINING CALCIUM
FLUORIDE
Abstract
A composition and method for preparing model bases in the
manufacture of dental prostheses, in which the model base is made
of a castable-refractory composition that is stable at high
temperatures and is compatible with commercially available dental
porcelains and gold alloys, as well as with the implaced dies and
dowels. The catable-refractory composition of the invention is made
by a dry blend consisting essentially of 40-50 weight percent of a
refractory oxide, 6-8 percent by weight of an alkali phosphate, and
42-47 percent by weight of an alkaline-earth fluoride, and then
mixing that dry blend with a colloidal silica sol of 40 weight
percent content, using a ratio of 4 to 5 parts of blend to 1 part
of sol.
Inventors: |
Brigham; Kristin (New York,
NY), Vickery; Ronald C. (Northport, NY) |
Assignee: |
Ceramco, Inc. (Long Island
City, NY)
|
Family
ID: |
25362318 |
Appl.
No.: |
04/873,790 |
Filed: |
November 4, 1969 |
Current U.S.
Class: |
106/35; 106/690;
264/16; 501/111; 501/118; 501/122; 264/621 |
Current CPC
Class: |
A61K
6/90 (20200101); A61K 6/807 (20200101); A61K
6/864 (20200101); A61K 6/78 (20200101); C04B
28/24 (20130101); C04B 28/24 (20130101); A61C
9/002 (20130101); C04B 35/03 (20130101); A61K
6/871 (20200101); C04B 40/02 (20130101); C04B
14/30 (20130101); C04B 22/16 (20130101); C04B
22/12 (20130101); C04B 22/06 (20130101); C04B
14/303 (20130101) |
Current International
Class: |
C04B
28/00 (20060101); C04B 28/24 (20060101); A61C
9/00 (20060101); C04B 35/03 (20060101); A61k
005/00 (); C04b 035/04 (); C04b 035/66 () |
Field of
Search: |
;264/16,17,18,19,63
;106/35,85,58,62,38.3 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Frome; Julius
Assistant Examiner: Miller; John H.
Claims
We claim as our invention:
1. A castable-refractory composition consisting essentially of a
mixture of (a) 4 to 5 parts of dry blend consisting essentially of
about 43 weight percent of magnesia, about 10 weight percent of
alumina, about 7 weight percent of ammonium dihydrogen phosphate,
about 38 weight percent of calcium fluoride, and (b) 1 part of
colloidal silica sol of about 40 weight percent solids content,
which composition has good as-fired dimensional stability as
evidenced by an as-fired dimension change of no more than 0.2
percent, and a good coefficient of thermal expansion of about
13.0.times.10.sup.-.sup.6 in./in./.degree. C. and higher.
2. The composition of claim 1 wherein the dry blend also consists
of up to about 1 weight percent of a metal oxide as colorant.
3. In the making of dental prostheses by a method including the
casting of dies of castable-refractory material capable of
maintaining its physical integrity when solidified and then heated
to 2,000.degree. F, the positioning in said castable-refractory
material while in its fluid state of dowels, the subsequent
solidification of said castable-refractory material, and the
casting about said dies and dowels of a model base composition to
form a structure, the steps of preparing a model base of
castable-refractory composition consisting essentially of a mixture
of (a) 4 to 5 parts of a dry blend consisting essentially of about
43 weight percent of magnesia, about 10 weight percent of alumina,
about 7 weight percent of ammonium dihydrogen phosphate, about 38
weight percent of calcium fluoride, and (b) 1 part of a colloidal
silica sol of about 40 weight percent solids content, casting said
model base composition about said dowels and dies, permitting said
model base composition to solidify, heating said structure to a
temperature of ranging from about 1,800.degree. F. to 1,850.degree.
F., and cooling to room temperature.
4. The method of claim 3 wherein the dry blend also consists of up
to about 1 weight percent of a metal oxide as colorant.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to castable-refractory compositions that
exhibit excellent dimensional stability after being fired at
temperatures as high as about 2,000.degree. F., together with a
high coefficient of thermal expansion, on the order of 12 or more
microinches per inch per .degree. C., and other properties suiting
them for use in the manufacture of dental prostheses. It relates
further to methods of making dental prostheses wherein such a
castable-refractory composition is used as a model base.
2. Description of the Prior Art
Until recently, the construction of porcelain jacket crowns for
dental prostheses has required the use of a fabricated metal
substrate or matrix. The technician, having received from a dentist
an impression of teeth in wax, rubber or the like, poured into it
dental stone comprising unfireable gypsum-type materials to provide
a model of a tooth. He then constructed on the model a platinum
foil matrix comprising a thimble-shaped cone having a thickness of
about 0.001 to 0.002 inch. The porcelain is fabricated on this cone
and the whole assembly gingerly removed from the stone die and
fired. After firing, the platinum matrix is painstakingly removed
from the internal surface of the jacket before cementation in the
mouth. This procedure, besides being tedious, provides for an
inaccurate fit--the thickness of the platinum foil insuring that
the jacket is oversize. Also, the forces necessary to remove the
porcelain and platinum from the die before firing will derange the
weak, unfired structure.
Similarly, when porcelain is being applied and fired to a cast gold
structure, unless the metal span is adequately supported, and
geometrically restricted, warpage and sagging of the total
structure can and do occur on heating.
Many of the aforesaid difficulties are eliminated if the porcelain
restoration is constructed directly on a fireable stone model or
die. However, until recently, materials which were employed for
making models or dies could not be used for direct construction of
porcelain jacket crowns and the like since the material used for
the die or model was unable to withstand the thermal treatment
necessary to glaze the porcelain without loss of its physical
integrity. Furthermore, the coefficients of thermal expansion of
such materials were such that any porcelain surmounting the dies
would crack on firing and cooling.
Recently, refractory die compositions have been devised upon which
dental prostheses can be directly fabricated and fired. These
include, as essential constituents, magnesium oxide and ammonium
dihydrogen phosphate, with or without additions of aluminum oxide
and a soda-lime silicate glass. With this type of composition, all
of the intermediate and expensive steps between the initial model
and the formation of the metal substrate or matrix are eliminated,
and the porcelain restoration can be constructed directly on the
stone model or die material.
In forming a porcelain jacket crown, inlay or the like, a thickness
of the tooth structure is first removed by a dentist. Thereafter, a
wax, rubber or similar impression is made of the tooth so prepared.
In this process, the impression of more than a single tooth is
formed. That is, a reproduction of a group of teeth is formed in
the wax impression; and, thereafter, a model of the entire group is
cast. While the model of an entire group of teeth possibly can be
used directly as a base for the fabrication of porcelain jackets on
individual teeth, problems of bulk usually require that individual
tooth dies be extractable from a gross model. This is accomplished
by inserting a brass or other metal pin or dowel into the
surrounding material before it sets, then pouring further stone to
provide a "model base." The individual tooth die with the dowel
attached is then cut away from the gross model, where upon the
dentist can use the cutaway die as a basis for the metal matrix on
which the porcelain is constructed, without interference from
adjacent tooth dies.
When the material used to form the model or die is of the ceramic
type containing magnesium oxide and ammonium dihydrogen phosphate,
it is not satisfactory to use for the above-mentioned "model base,"
which is cast around the dowels, etc., the same material that is
used to form the above-mentioned die or model. The model base is,
of necessity, a piece of material considerably more massive than
any of the small, individual tooth dies. Moreover, the die material
has a high specific heat and a low coefficient of thermal
conductivity, as well as a low coefficient of thermal expansion. If
an attempt were made to fire in an oven, at temperatures up to
about 1,800.degree. F., an assemblage of dies and dowels resting in
a model base, with the model base being made of the same material
as the dies, cracking or misalignment would develop. The small,
individual tooth dies would rapidly be heated to a temperature
approaching that of the furnace, whereas the more massive "model
base" piece would reach only a substantially lower temperature,
such as about 1,000.degree. F. at the most. Accordingly, it has
hitherto been necessary, in firing the castable-refractory die
pieces that are used in the making of dental prostheses to remove
the die pieces from the model base employed and place them into the
furnace individually. This is undesirable, not only from the
standpoint of the labor required in the removal of the die pieces
from the model base before firing and the replacement of them in
the model base after firing, but also from the standpoint that the
pieces involved are deprived of support during the firing
operation, increasing the chances of warpage or misalignment.
It has not been obvious to those skilled in the art how to produce
a castable-refractory composition that possesses the desired, high
coefficient of thermal expansion that is required for the making of
relatively massive model base pieces for use in the manufacture of
dental prostheses and, at the same time, is sufficiently cohesive
and also resistant to the development of components in the
refractory composition that would, upon repeated firing, cause
rupture of the model base in view of the thermally induced stresses
that occur in it in the course of such repeated firing. Indeed,
those skilled in the art have, for the most part, looked away from
the development of refractory compositions exhibiting a high
coefficient of linear expansion, for the very reason that the more
a refractory composition expands, the more likely it is to spall or
crack or otherwise fail when subjected to rapid heating or
cooling.
SUMMARY OF THE INVENTION
As an overall object, the present invention seeks to provide a
model base for ceramic dies used for dental prostheses having a
coefficient of expansion which accommodates fireable ceramic dies
such that the dies and the model base can be fired together.
More specifically, an object of the invention is to provide a model
base composition of the type described usable with ceramic tooth
dies containing as essential constituents, magnesium oxide and
ammonium dihydrogen phosphate, added as a mixture to a colloidal
silica solution, the mixture containing as possible additives
aluminum oxide and a soda-lime silicate glass.
In accordance with the invention, a dry blend is formed comprising
a mixture of 47 to 50 percent by weight of at least one refractory
oxide selected from the group consisting of magnesia, alumina and
zirconia, 6 to 8 percent by weight of an alkali phosphate and 42 to
47 percent by weight of an alkaline-earth fluoride. Four to five
portions by weight of this dry blend is then mixed with one portion
by weight of a colloidal silica sol of about 40 weight percent
solids content. It is possible, although not necessary, to add up
to about 1 percent by weight of a metal oxide to the dry blend
prior to mixing with the colloidal silica sol for the purpose of
coloring the model base material.
The resulting composition has good as-fired dimensional stability
as evidenced by an as-fired dimension change of 0 to +0.2 percent,
and good thermal expansion characteristics as evidenced by a
coefficient of thermal expansion of about 13.0.times.
10.sup.-.sup.6 in./in./.degree. C. and higher.
The above and other objects and features of the invention will
become apparent from the following detailed description taken in
connection with the accompanying drawings which form a part of this
specification, and in which:
FIG. 1 is a perspective view of a ceramic die with a group of
teeth, showing the manner in which the die is supported on a model
base;
FIG. 2 is a cross-sectional view of a rubber or wax mold impression
from which the model of FIG. 1 is formed;
FIG. 3 illustrates the first step in the formation of the model of
FIG. 1 by pouring a fireable refractory material into the mold of
FIG. 2 and inserting a dowel therein; and
FIG. 4 illustrates the final step in the formation of the model of
FIG. 1, comprising pouring the refractory material of the invention
over the previously formed refractory material and dowel to form a
model base.
With reference now to the drawings and particularly to FIG. 1, a
stone model of a group of teeth is shown. It will be assumed that
the two items identified by the numerals 10 and 12 are models of
teeth which have been previously ground to remove a portion of the
surface thereof preparatory to the formation of a porcelain
prosthetic restoration. Models 10 and 12 as well as the remainder
of the teeth in the bridge model are formed from a
castable-refractory composition, hereinafter described in detail,
to form an upper portion 14 of the overall model. This upper
portion 14, it will be noted, conforms to the teeth of the bridge
as well as the gum portion which supports these teeth. Beneath the
upper portion 14 is a lower model base portion 16 which is formed
from the material of the present invention.
Projecting through the base portion 16, the upper portion 14, and
into the two teeth models 10 and 12 are dowels 18 and 20. It is
often necessary to remove from the model of the complete group, the
individual tooth dies 10 and 12; and it is for this reason that the
dowels 18 and 20 are included. To remove an individual die such as
die 10, for example, saw cuts 22 and 24 are formed in the upper
portion 14 and base 16 on either side of the die. Thereafter, as
illustrated by the die 12, the dowel is pushed upwardly whereupon
the area 26 beneath the die breaks away from the remainder of the
overall bridge model, thereby producing an individual tooth die.
Thereafter, this die may be utilized as a base upon which a
porcelain jacket crown, inlay, restoration or the like is
formed.
With reference now to FIG. 2, the initial step in forming a model
of FIG. 1 comprises forcing a wad or mass of soft pliable material
such as rubber or wax over the teeth which have been previously
ground to form the mold 28 of FIG. 2. The thus formed mold has a
plurality of teeth cavities therein, one of said cavities being
indicated in FIG. 2 by the reference numeral 30.
After the mold 28 of FIG. 2 is formed, a castable-refractory
composition is poured into the mold (FIG. 3) to the level indicated
by the reference numeral 32. As will be understood, this forms the
upper portion 14 of the complete model shown in FIG. 1. The
castable-refractory material 34 comprises a dry blend of magnesium
oxide and ammonium dihydrogen phosphate, the dry blend being mixed
with a colloidal silica sol of about 40 weight percent solids.
Added to the dry blend of magnesium oxide and ammonium dihydrogen
phosphate, depending upon the required firing temperature and other
factors, are possibly a soda-lime silica glass and aluminum
oxide.
The dry blend, when mixed with the colloidal silica sol, forms a
thixotropic slurry which is poured directly into the mold cavity 30
up to the level 32. After the refractory composition and colloidal
silica sol are thus cast into the impression, it is allowed to
remain therein for a time sufficient to enable the cast material to
set to a hard mass. However, before the hard mass is formed, a
dowel 36 is inserted therein above the impressions 10 and 12, for
example, shown in FIG. 1.
After the refractory material 34 has thus hardened with the dowel
36 inserted therein, the refractory material of the present
invention is poured over the previously formed refractory material
up to the level 40. This, of course, forms the lower model base
portion 16 of FIG. 1.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The castable-refractory composition of the present invention is
made by first forming a dry blend of refractory oxide, alkali
phosphate, and alkaline-earth fluoride, and then mixing the dry
blend, in the ratio of 4 to 5 parts of dry blend to 1 part of a
colloidal silica sol of about 40 weight percent solids content.
This yields a castable-refractory composition that sets in about 30
minutes at room temperature, is capable of withstanding firing in a
furnace at temperatures up to about 2,000.degree. F. without
cracking (even upon repeated refiring), and exhibiting at the same
time a high coefficient of thermal expansion, greater than
13.0.times.10.sup.-.sup.6 in./in./.degree. C. or greater, and
preferably about 20.times.10.sup.-.sup.6 in./in./.degree. C, such
as to suit the composition for use as a model base in the
manufacture of dental prostheses.
The refractory oxide used in the making of the above-indicated
castable-refractory composition is one selected from the group
consisting of magnesia, alumina and zirconia. Other refractory
oxides might be used as well, but it is advisable to avoid the use
of lime, since this tends to form with the silica of the silica sol
the compound calcium orthosilicate, which tends to undergo a phase
transformation upon repeated refirings, becoming brittle and
causing spalling or other forms of failure. Indeed, it is rather
not to be expected that the particular compositions disclosed
herein as constituting embodiments of the present invention would
(in spite of their containing ingredients permitting the formation
of the calcium orthosilicate in substantial amounts, such as over 3
percent) perform so satisfactorily in respect to the avoidance of
the development of cracking upon repeated refiring.
Although, as indicated above, satisfactory results may be obtained
with the use of various refractory oxides as indicated above, we
find that we prefer to use a composition wherein the magnesia
amounts to 38.0 to 39.0 percent by weight of the dry blend, the
magnesia being in the form of a finely divided periclase, and the
remainder of the refractory oxide is made up with 9.0 to 10.0
percent of alumina, preferably a finely divided alumina in tabular
form. Using this particular combination of magnesia and alumina
gives good values for strength and hardness, and at the same time,
dimensional accuracy and a high coefficient of thermal expansion
are obtained.
The alkali phosphate may be any of a great variety of materials,
among which may be mentioned the various phosphates of sodium,
potassium, and other members of the alkali-metal group, as well as
the phosphates of the ammonium radical. We have obtained
satisfactory results, working with ammonium dihydrogen phosphate,
NH.sub.4 H.sub.2 PO.sub.4. This is used in the dry blend to the
extent of 6 to 8 percent by weight.
The dry blend also contains a substantial proportion of an
alkaline-earth fluoride, such as calcium difluoride (fluorspar).
This is also used in finely divided form to the extent of 42 to 47
percent by weight.
The dry blend preferably also contains a small addition, up to
about 1 percent by weight, of an oxide that imparts to it a color
distinguishing it from the die material. We have obtained
satisfactory results by using 0.6 percent by weight of ferric
oxide, which is preferably used in the form of a finely divided
powder. This imparts a pink tone to the unfired composition, and
although the intensity of the color is somewhat diminished upon
firing, the addition of ferric oxide imparts a distinctive color
difference between the die composition and the model base
composition in the fired state. Those skilled in the art will
readily perceive how other oxides, such as nickel oxide or cobalt
oxide, might be substituted for the ferric oxide.
The ingredients indicated above as comprising the dry blend are
thoroughly mixed with one another, and then the dry blend so made
is mixed, in a ratio of 4 to 5 parts by weight of dry blend to 1
part of liquid, with a colloidal silica sol of 40 weight percent
silicon dioxide solids content, such as that sold under the name
"Ludox" by E. I. DuPont de Nemours & Company. Those skilled in
the art will readily perceive how other commercial silica sols in
about the same composition may be substituted.
This yields a castable-refractory composition that will remain
workable for about 5 to 7 minutes and will set to hardness within
20 to 30 minutes. The castable-refractory composition is used, at
least initially, in substantially the same manner as any of the
model base compositions known in the prior art, e.g., plaster of
Paris or the like. That is to say, in the making of dental
prostheses, the various steps up to the pouring of the model base
over the dies and dowels assembled in the impression are exactly
the same as before. Also the same as before is the step of allowing
the model base composition to harden.
At this point, however, the practice changes somewhat. The model
base compositions hitherto known have not been capable of
withstanding furnace temperatures of 1,800.degree. F. or the like.
It has hitherto been necessary, before firing the porcelain on the
dies, to remove the dies and their dowels from the model before
placing them into the furnace. This has meant that it has been
necessary to expend not only the time and labor for such removal of
the dies from the model base and the replacement of the dies
therein after they have been fired, but also to suffer the
disadvantage of the increased likelihood of warpage during the
firing operation that is caused by having the dies present
unsupported in the furnace. Moreover, the number of firings that
may need to be done is not necessarily limited to one. If, for
example, there are a few places found, after the first firing
operation, in which the porcelain is somewhat too thin, it is
customary to paint additional porcelain over them and refire. This
implies that the above-indicated tedious steps and dangers of
warpage are doubled, and all this is avoided when there is
provided, as in accordance with the present invention, a model base
composition that will withstand furnace heat up to 1,800.degree. F.
and at the same time exhibit the necessary other
characteristics.
The invention described is illustrated by the following specific
example:
EXAMPLE I
There is prepared and used a model base composition in accordance
with the invention. To be somewhat more precise, there is first
prepared a dry blend consisting essentially of 38.4 parts by weight
of magnesia, 9.6 parts of alumina, 6.4 parts of ammonium dihydrogen
phosphate, 44.5 parts of fluorspar and 0.6 part of ferric oxide.
This dry blend is then mixed with silica sol of 40 weight percent
solids content in the proportion of 20 grams of dry blend per 4
cubic centimeters of silica sol.
The resultant mixture is poured over dies and greased dowels
established in a dental impression, and the mixture is then
permitted to harden, forming a model base for the above-mentioned
dies and dowels. The entire assemblage--dies, dowels, and model
base--was then suitably baked to produce the desired end product--a
model base surmounted by doweled dies appropriately positioned with
respect to the desired positions of the individual original teeth
in the mouth of the patient being worked upon. Further
characteristics of the model base compositions so produced are
indicated below:
Hardness - 50 Modulus of Rupture - 562 p.s.i. Dimensional Accuracy
(as-fired) - +0.2% Coefficient of thermal expansion
20.69.times.10.sup.-.sup.6 in./in./.degree.C. for the range of
0.degree. to 300.degree. C., and 28.0.times.10.sup.-.sup.6
in./in./.degree.C. above 300.degree. C.
as indicative of the difficulties encountered, or likely to be
encountered, by a person of ordinary skill in the art, attempting
to reproduce the applicants' invention with the use of compositions
somewhat similar in chemical content, there are presented the
following data in the table below and the results obtained with
such compositions:
---------------------------------------------------------------------------
TABLE
Content in Weight Percent Total refrac- Sample MgO Al.sub.2 O.sub.3
tory oxide NH.sub.4 H.sub.2 PO.sub.4 CaF.s ub. 2
__________________________________________________________________________
P-B 43.01 6.45 49.46 7.68 42.86 P-A 41.45 8.29 49.74 7.40 42.86 J-D
38.62 9.65 48.27 6.90 44.83 J-E 39.30 9.82 49.12 7.02 43.86 J-B
41.48 10.37 51.85 7.41 40.74 J 43.08 10.77 53.85 7.69 38.46 Y 38.62
11.03 49.65 5.52 44.83 V 38.57 11.43 50.00 7.14 42.86 W 37.14 12.86
50.00 7.14 42.86 Percent, modulus of coeff. of No. firings ave.
rupture, expansion until onset shrinkage p.s.i. .times.10.sup.6 per
of crack- Sample Set Fired .degree.C. ing
__________________________________________________________________________
J-D 0.87 -- 455 16.0 4 V -- -- 526 15.2 4 W 0.68 -- 433 7.2 4 J-E
1.10 0.54 520 12.05 4 P-A -- -- -- 11.1 -- P-B -- -- 150 11.5 --
J-B 0.865 0.13 414 -- 2 J 0.794 -- 274 13 6 Y -- -- -- 10.7 --
__________________________________________________________________________
the data presented above may be interpreted as follows. The
composition of sample J-D is substantially the same as that of
example I given above and the reported properties, though somewhat
poorer, are nevertheless a substantial improvement over those of
any castable-refractory composition known prior to the present
invention as respects the particular properties useful for model
base purposes. The sample V is another nonpreferred embodiment of
the invention. The sample W exhibits an undesirably low coefficient
of thermal expansion, and this may due in part to its relatively
high alumina content. The alumina content should not, in most
instances, exceed 12 percent, and there are data to indicate that
even in a range of 8 to 12 percent, increasing the alumina content
lowers the observed coefficient of thermal expansion. In this
regard, the results of sample V are not typical. The results of
sample J-E are disappointing; although within the chemical
composition limits specified above, it gives an unsatisfactory
as-fired shrinkage and a borderline or unsatisfactory coefficient
of thermal expansion. Similarly, samples P-A and P-B are too low in
coefficient of thermal expansion to find use as model base
compositions. Sample J-B is too high in refractory oxide content
and too low in fluorspar content, and it withstood only two firings
(without die) before developing cracking. On the other hand, sample
J, which is similarly high in refractory oxide and low in
fluorspar, withstood six firings before it developed in cracking
but its performance was poor in modulus of rupture and was
borderline in coefficient of thermal expansion. Sample Y, low in
ammonium dihydrogen phosphate, gave an unsatisfactory coefficient
of thermal expansion.
From the foregoing data, it can be seen that substantially
different results can be obtained as a result of seemingly slight
alterations in the chemical composition of the castable-refractory
composition. The compositions that are useful for the making of
model bases lie within the ranges indicated above, but observation
of those ranges is not, of itself, enough to ensure that a
satisfactory combination of properties will be obtained. Indeed,
the data now available appear rather contradictory of one another
concerning the effects of changing the amounts used on the various
ingredients. We have established, however, in the example, that a
combination of properties can be achieved that will be useful for
model base purposes, and that (from the data available), those
skilled in the art may well devise others that have compositions
within the relatively narrow ranges indicated above that will serve
as well, if not better. We, accordingly, lay claim to the invention
as it is defined in the appended claims.
* * * * *