U.S. patent number 3,727,299 [Application Number 05/147,222] was granted by the patent office on 1973-04-17 for method for making a dental appliance.
This patent grant is currently assigned to Fried Krupp Gesellschaft mit beschrankter Haftung. Invention is credited to Alfred Hoffmann, Erich Surbach.
United States Patent |
3,727,299 |
Hoffmann , et al. |
April 17, 1973 |
METHOD FOR MAKING A DENTAL APPLIANCE
Abstract
An alloy consisting essentially of 8 to 16 weight-percent
chromium, 5 to 15 weight-percent nickel, 1 to 10 weight-percent
titanium, remainder cobalt, as a material that can be bonded to
ceramic masses by burning, whereby an integrally assembled
alloy-porcelain dental applicance is formed for making
non-removable dental prostheses.
Inventors: |
Hoffmann; Alfred (Erkrath,
DT), Surbach; Erich (Essen, DT) |
Assignee: |
Fried Krupp Gesellschaft mit
beschrankter Haftung (Essen, DT)
|
Family
ID: |
22520718 |
Appl.
No.: |
05/147,222 |
Filed: |
May 26, 1971 |
Current U.S.
Class: |
228/121;
228/262.1; 228/123.1 |
Current CPC
Class: |
A61C
13/0003 (20130101); A61K 6/84 (20200101) |
Current International
Class: |
A61K
6/02 (20060101); A61C 13/00 (20060101); A61K
6/04 (20060101); B23k 031/02 () |
Field of
Search: |
;75/170,171
;29/472.7,504,472.9,160.6,473.1 |
References Cited
[Referenced By]
U.S. Patent Documents
Other References
Cochardt, A., "Development of a Ferromagnetic Cobalt--Base High
Temperature Alloy", ASM Transactions, Vol. 52, preprint No. 119,
pp. 1 and Table 1a of appendix, 75-170..
|
Primary Examiner: Overholser; J. Spencer
Assistant Examiner: Shore; Ronald J.
Claims
We claim:
1. The method of using an alloy consisting essentially of 8 to 16
weight-percent chromium, 5 to 15 weight-percent nickel, 1 to 10
weight-percent titanium, remainder cobalt, comprising placing such
an alloy in contact with several layers of ceramic masses as parts
of a dental appliance, and heating the contacting alloy and masses
for causing their bonding to one another, whereby an integrally
assembled alloy-porcelain dental appliance is formed.
2. The method as claimed in claim 1, wherein said alloy contains up
to 3 weight-percent molybdenum, up to 2 weight-percent tungsten, up
to 1 weight-percent manganese, and up to 0.1 weight-percent
carbon.
3. The method of using an alloy consisting essentially of 8 to 16
weight-percent chromium, 5 to 15 weight-percent nickel, 1 to 10
weight-percent titanium, up to 3 weight-percent molybdenum, up to 2
weight-percent tungsten, up to 1 weight-percent manganese, up to
0.1 weight-percent carbon, remainder cobalt, comprising bonding a
body of such an alloy to ceramic masses by burning for making
non-removable dental prostheses.
Description
BACKGROUND OF THE INVENTION
The present invention relates to a method of using a
cobalt-chromium-nickel-titanium alloy for high-temperature bonding
to porcelain for dental purposes.
An alloy with 5 to 15 weight-percent chromium, 5 to 15
weight-percent nickel, 4 to 10 weight-percent titanium, contents of
carbon, silicon, manganese, aluminum, and iron up to 1
weight-percent, contents of molybdenum up to 3 weight-percent,
remainder cobalt, may be used as a material for tooth prostheses
and general surgical implants. This alloy is especially suitable
for these purposes, because it possesses good resistance to
corrosion and excellent receptivity by the human body, in addition
to having better mechanical properties (especially elongation and
tensile strength) than the alloys previously used for such
purposes.
The present invention concerns the new use of a certain alloy as a
material to be bonded by heating to porcelain to make dental
appliances, such as crowns and bridges. The joining of metal alloys
with ceramic masses by high-temperature bonding to make such
appliances places a number of special requirements on the metal
alloy. Among the alloy properties of importance are the permanence
of color, the ability to form a strong bond with a ceramic mass,
and a certain and not overly difficult procedure for working the
alloy.
The strength of the bond between the alloy and the ceramic mass is
determined essentially by the oxides formed on the surface of the
alloy. These surface oxides must not react so strongly with the
ceramic mass that a discoloration of the ceramic mass occurs.
Generally, noble metal alloys are relatively less desirable for
high-temperature bonding to ceramic masses, since as compared with
other metals they have relatively high density and smaller values
for their mechanical properties. Therefore, nickel-based alloys
have been developed to serve as material to which ceramic masses
can be bonded, Some of these alloys contain, along with about 60 to
70 weight-percent nickel, about 15 to 20 weight-percent chromium,
about 1 to 5 weight-percent of each of the elements silicon,
molybdenum, manganese, and aluminum, and about 0.5 to 1
weight-percent beryllium. These alloys require, however,
considerable safety measures when being made or worked, because of
their beryllium content.
Other alloys which have been used for bonding to ceramics contain
about 60 weight-percent nickel, about 15 to 16 weight-percent of
each of the elements chromium and molybdenum, and about 0.5 to 5
weight-percent of each of the elements silicon, tungsten,
manganese, vanadium, iron, and cobalt.
SUMMARY OF THE INVENTION
An object of the present invention, therefore, is to add to the
group of alloys which can be used for the bonding of porcelain for
dental purposes an alloy which has been discovered to be especially
suited for such purposes, meeting in excellent manner the
requirements as above given and possessing outstanding mechanical
properties.
This as well as other objects which will become apparent in the
discussion that follows are achieved, according to the present
invention, by using an alloy consisting essentially of 8 to 15
weight-percent chromium, 5 to 15 weight-percent nickel, 1 to 10
weight-percent titanium, 0 to 3 weight-percent molybdenum, 0 to 2
weight-percent tungsten, 0 to 1 weight-percent manganese, 0 to 0.1
weight-percent carbon, remainder cobalt, as a cast material which
is provided in several operations with ceramic masses which are
deposited by burning for bonding to the said metal body and to each
of the successive ceramic layers, whereby the last deposited
ceramic porcelain mass with glazing is shaped by burning to form
artificial teeth so that the metal body in conjunction with the
deposited ceramic masses can be used as a non-removable dental
prosthesis. During the burning of the first deposited ceramic
layer, the so-called basic mass, oxides are formed on the metal
body surface which produce an excellent bond between metal and
ceramic mass.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
It is permissible for the alloy used in the present invention to
contain the impurities which are commonly present in the raw
materials used for its manufacture. Examples of such impurities are
silicon and aluminum, each to be present in the alloy preferably at
substantially less than 1 weight-percent.
The alloy for use in the present invention surpasses the previously
used alloys in terms of mechanical properties and additionally
forms bonding surface oxides more easily because of its titanium
content.
In preparing the alloy for practice of the present invention, the
alloy may be melted in vacuum induction furnaces using either a
vacuum of 10.sup.-.sup.3 to 5 mm Hg or a protective gas atmosphere
(for example, argon) at a pressure of about 1 to 300 mm Hg. Casting
of the alloy is usually done in burned ceramic molds such as used
for small, fine-detail castings.
Conventional casting processes can be used with the alloy in the
present invention, since the melting point of the alloy is about
1,350.degree. C. It can be formed in ceramic molds using the
techniques of centrifuge casting. The alloy may be melted using an
oxygen-acetylene flame adjusted neutrally (that is neither
oxidizing nor reducing).
Test specimens for determining the mechanical properties of the
alloy used in the present invention are produced using a centrifuge
casting method. The cast specimens are turned to final size and
polished. They have a diameter of 2.1 to 2.6 mm and a gage length
of 25 mm. This corresponds closely to the directives of British
Standard 3366:1961 entitled "Specification for Dental Cobalt
Chromium Casting Alloy." The strain rate used in obtaining 0.2
percent yield strength data is about 10.sup.-.sup.4
sec.sup.-.sup.1.
In order to test the compatibility of the alloy used in the present
invention with the bodies of animals and, in particular, humans,
corrosion and electrochemical measurements were carried out.
The corrosion measurements were carried out both in artificial
saliva and in an aqueous solution containing 1 percent lactic acid
and 0.25 percent NaCl. The solution was held at 40.degree. C. The
test specimens were left in such solution for more than one year.
Even for such a long test time, the alloy gave the extremely small
corrosion velocities of 0.01 mm/year or less. Such velocities are
below the accuracy of measurement of usual equipment.
The artificial saliva was an aqueous solution containing the
following additions per liter;
0.95 grams K.sub.2 HPO.sub.4 0.23 grams NaCl 0.16 grams CaCl.sub.2
0.55 grams KCl 0.22 grams KSCN 0.13 grams (NH.sub.2).sub.2 CO 0.77
grams NaHCO.sub.3
current-time curves were recorded in artificial saliva in the
electrochemical measurements. Potentials of +100 and +150 mV as
measured against a saturated calomel electrode were used. These
potentials can arise should the alloys of the present invention
come in contact with gold in the mouth of an individual. In these
experiments, the alloys gave current densities of 10.sup.-.sup.4 to
10.sup.-.sup.5 milli-amperes per square centimeter. Such values are
hardly measurable using conventional equipment. In no case in these
experiments was evidence of corrosion found.
In addition to the above experiments, the alloy of the present
invention has been in the mouths of humans now for more than 3
years. Neither evidence of corrosion nor any type of disturbance or
effect on the persons involved has been noted.
Further illustrative of the present invention are the following
examples:
EXAMPLE I
An alloy usable in the present invention has the following
composition: 13.6 weight-percent Cr, 7.9 weight-percent Ni, 0.045
weight-percent C, 8.5 weight-percent Ti, remainder Co. And, it has
the following mechanical properties: a 0.2 percent yield strength
of 75.7 kiloponds/mm.sup.2, a tensile strength of 116.0
kiloponds/mm.sup.2, and an elongation of 12.4 percent.
The test specimens used for determining the mechanical properties
of this alloy were manufactured in the following manner:
At first, cobalt, chromium and nickel mixed in proportions to
obtain the desired composition of the alloy were melted in a vacuum
induction furnace using a vacuum of 10.sup.-.sup.1 to
10.sup.-.sup.3 mm Hg. After complete degassing of the metal bath,
commercially pure titanium melted in a vacuum arc furnace was added
to the liquid alloy in the quantity required to obtain the desired
composition. After complete solution of the titanium in the metal
bath, the liquid alloy was cast at a temperature of about
1,430.degree. C into a burned ceramic mold placed in a vacuum
induction furnace. This burned ceramic mold had been manufactured
in the conventional manner by the lost wax process. The cast alloy
which after solidification was available in cylindrical or
rectangular parallelopiped form was blasted with steel shot and
subsequently cut up into pieces weighing between 15 and 30 grams.
For making the test specimens, these metal pieces were melted using
an oxygen-acetylene flame adjusted neutrally, whereupon the liquid
metal was cast centrifugally into burned ceramic molds also made by
the lost wax process. Before casting, these molds were preheated to
about 950.degree. C and the casting temperature was again about
1,430.degree. C. The solidified as-cast specimens had a diameter of
2.8 mm. When turned and polished, the test specimen had a diameter
of 2.4 to 2.5 mm and a gage length of 25 mm. The mechanical
properties as above given represent the average values obtained
from measurements on four different test specimens.
EXAMPLE II
An alloy B usable in the present invention was prepared having the
following composition: 11.9 weight-percent Cr, 9.0 weight-percent
Ni, 0.53 weight-percent Mo, 0.003 weight-percent C, 8.2
weight-percent Ti, remainder Co.
EXAMPLE III
An alloy C usable in the present invention was prepared having the
following composition: 12.1 weight-percent Cr, 9.1 weight-percent
Ni, 1.3 weight-percent Mo, 0.008 weight-percent C, 8.2
weight-percent Ti, remainder Co.
EXAMPLE IV
An alloy D usable in the present invention was prepared having the
following composition: 9.8 weight-percent Cr, 11.9 weight-percent
Ni, 0.040 weight-percent C, 8.1 weight-percent Ti, remainder
Co.
EXAMPLE V
An alloy E usable in the present invention was prepared having the
following composition: 12.0 weight-percent Cr, 7.8 weight-percent
Ni, 0.53 weight-percent Mo, 0.030 weight-percent C, 8.4
weight-percent Ti, remainder Co.
EXAMPLES VI TO X
Alloys F to J usable in the present invention were prepared having
the following compositions in weight-percent: ##SPC1##
The alloys of Examples II to X exhibited the following
properties:
Alloy 0.2% yield strength tensile strength elongation in
kiloponds/mm.sup.2 in kiloponds/mm.sup.2 in % B 77.5 113.5 11.4 C
81.5 112.2 10.0 D 72.0 108.0 10.0 E 70.8 107.0 12.2 F 79.5 108.4
10.3 G 58.5 92.0 13.6 H 61.8 111.8 14.5 I 67.7 92.3 14.0 J 76.7
104.7 10.1
EXAMPLE XI
An alloy K was prepared having the following composition: 12.0
weight-percent chromium, 9.0 weight-percent nickel, 8.1
weight-percent titanium, 1.0 weight-percent molybdenum, 0.011
weight-percent carbon, remainder cobalt. This alloy had the
following mechanical properties:
0.2% yield strength 79.5 kiloponds/mm.sup.2 tensile strength 116.4
kiloponds/mm.sup.2 elongation 11.5% Brinell hardness 357
kiloponds/mm.sup.2
This alloy was provided in several operations with ceramic masses
which were deposited and bonded to the metal body and to each of
the successive ceramic layers by burning, whereby the last
deposited ceramic porcelain mass with glazing was shaped by burning
to form artificial teeth so that the metal body in conjunction with
the deposited ceramic masses could be used as a non-removable
dental prostheses. It was found that all requirements as above
given were met in outstanding manner. Additionally advantageous is
that the average linear coefficient of thermal expansion for this
alloy between room temperature and 600.degree. to 900.degree. C
amounts to (15.4 to 16.4) .times. 10.sup.-.sup.6 .degree.
C.sup.-.sup.1 and consequently adequately matches that of fired
porcelain, which lies from about (14 to 15) .times. 10.sup.-.sup.6
.degree. C.sup.-.sup.1.
The alloys for use in the present invention have been found to be
suited for making alloy-to-porcelain bonded dental appliances from
the ceramic masses presently available on the dental supplies
market. The making of the bonded appliances can proceed according
to the instructions provided by the manufacturers of the ceramic
and porcelain masses.
The mentioned ceramic masses are produced and delivered for example
by the firms VITA-Zahnfabrik H. Rauter KG, Saeckingen (BRD) and
IVOCLAR AG, Schaan (Liechtenstein). The burning takes place mainly
with temperatures between 650.degree. and 1,000.degree. C.
The terms "0.2 percent yield strength," "tensile strength," and
"elongation" are used as defined on pages 4 and 5 of "Elements of
Materials Science" by Lawrence H. Van Vlack, 2nd edition, 1964,
Addison-Wesley Publishing Co.
The Brinell hardness was calculated with the formula as set forth
on page 94 of the "Metals Handbook," American Society for Metals,
1948, where the test load was 187.5 kiloponds and the ball has a
diameter equal to 2.5 millimeters.
It will be understood that the above description of the present
invention is susceptible to various modifications, changes and
adaptations, and the same are intended to be comprehended within
the meaning and range of equivalents of the appended claims.
* * * * *