U.S. patent number 3,901,693 [Application Number 05/378,360] was granted by the patent office on 1975-08-26 for method of preparing dental restorative material.
This patent grant is currently assigned to Dentsply Research & Development Corporation. Invention is credited to Donald Timothy Wolf.
United States Patent |
3,901,693 |
Wolf |
August 26, 1975 |
Method of preparing dental restorative material
Abstract
Dental amalgam material and method of making the same in which a
silver alloy particle is formed and coated with gold. Upon the
addition of mercury, the gold coating retards the formation of the
silver alloy-mercury amalgam, thus extending working time.
Inventors: |
Wolf; Donald Timothy (Milford,
DE) |
Assignee: |
Dentsply Research & Development
Corporation (Milford, DE)
|
Family
ID: |
23492832 |
Appl.
No.: |
05/378,360 |
Filed: |
July 11, 1973 |
Current U.S.
Class: |
420/527; 428/672;
148/400; 428/673 |
Current CPC
Class: |
C22C
7/00 (20130101); A61K 6/847 (20200101); Y10T
428/12889 (20150115); Y10T 428/12896 (20150115) |
Current International
Class: |
C22C
7/00 (20060101); A61K 6/02 (20060101); A61K
6/05 (20060101); C22c 007/00 () |
Field of
Search: |
;29/192CP,199,192R
;117/1M ;106/35 ;75/169,173 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Rutledge; L. Dewayne
Assistant Examiner: Crutchfield; O. F.
Claims
I claim:
1. A method of making a dental amalgam comprising the steps of:
a. providing a plurality of silver-tin alloy spheres;
b. coating the individual silver-tin alloy spheres completely with
gold; and
c. triturating the gold coated silver-tin alloy spheres with
mercury to form an amalgam.
2. The invention of claim 1 wherein the particles comprise up to
30% by weight of particles between about 30 microns to about 60
microns; between 40 to 70% by weight of particles between about 10
microns to about 44 microns; and between 30 to 60% by weight of
particles of less than about 10-15 microns.
3. The invention of claim 1 wherein the silver-tin alloy spheres
also contain a small amount of one or more of the following:
copper, zinc, mercury.
4. The invention of claim 1 wherein mercury is added to comprise
about 30 to about 50% of the amalgam.
5. The invention of claim 1 wherein mercury is added to comprise
about 38 to about 44% of the amalgam.
6. The invention of claim 1 wherein the silver-tin alloy spheres
are coated with from about 0.05 to about 3% gold.
7. The invention of claim 1 wherein the spherical cores are under
approximately 60 microns in size.
8. A method for preparing dental restorative material having a
controlled working time prior to set comprising the steps of:
a. forming a test group of alloy spheres;
b. sub-dividing the test group;
c. coating each sub-divided test group with a different thickness
of gold;
d. applying an amalgamating substance to the spheres of each test
group;
e. measuring the working time elapsed from the application of the
amalgamating material to the penetration thereof through the gold
coatings of the spheres and until the alloys of the spheres set in
each test group;
f. forming a working group of alloy spheres;
g. applying to said working group of spheres a gold coating having
a thickness corresponding to the aforesaid test group most
approximating the desired working time, prior to final setting of
the coated spheres by application of an amalgamating material
thereto.
9. The invention of claim 8 wherein the amalgamating material is
mercury.
10. A method for making dental restorations comprising the steps
of:
a. manufacturing spherical particles having spherical inner alloy
cores individually covered with substantially uniform gold
coatings, said particles having a capacity to snap set after a
period of working time upon trituration with mercury, said working
time being variable in accordance with the length of
trituration;
b. determining the working time required to complete the
restoration; and
c. triturating mercury and the coated particles for a preselected
length of time to produce the required working time.
Description
BACKGROUND OF THE INVENTION
This invention relates to dental amalgams and methods for the
production thereof.
The prior art is replete with various suggestions for providing
dental amalgams, and includes various possibilities as to
compositions and modes of manufacture.
In searching for improved combinations, a number of formulations
have been proposed. As noted in U.S. Pat. No. 1,574,714, the
so-called "amalgam" or "silver" dental fillings are usually made of
an alloy of silver and tin often containing small percentages of
copper and zinc which is mixed with mercury to form the amalgam.
That patent, for example, discloses an alloy formula comprising 67
parts silver, 27 parts tin, 5 parts copper and 1 part zinc, and
suggests the addition of elements from the fifth, sixth or seventh
group of the periodic system, such as chromium, vanadium,
manganese, tungsten, molybdenum and tantalum, to increase
hardness.
Other prior art patents suggest alternative amalgam combinations
comprising, in addition to silver and tin, elements such as gold,
nickel and palladium. See, e.g., U.S. Pat. Nos. 2,460,595; 249,880,
109,173; 1,215,678; 1,022,596 and 485,280. Many of these patents
discuss the use of gold, which is also discussed in "Research and
Development" magazine, August, 1971 (P.6) and "Dental Industry
News," November, 1971.
It has also been suggested that the mechanical properties of
conventional alloy materials can be materially affected by
processing techniques. For example, see U.S. Pat. No. 3,305,356,
which discusses the preparation of spheroidal alloy particles
through an atomizing process and the use of various cooling
methods.
Notwithstanding all of the various formulations and processes
discussed in the prior art, including the literature mentioned
above, the dental amalgams presently in use are subject to certain
drawbacks in that none ideally meets all of the characteristics
desirable for such materials. This, however, is not particularly
surprising since the ideal material must possess a wide range of
attributes, such as excellent corrosion resistance, durability and
hardness, high tensile strength, shear resistance and compressive
strength, proper working time, flow rate and expansivity for dental
purposes, resistance to crushing and the like.
BRIEF SUMMARY OF THE INVENTION
The broad object of the present invention is the production of a
dental amalgam material possessing the foregoing desired attributes
to a degree which surpasses that of prior art formulations.
Essentially, it has been discovered that an improved dental amalgam
can be formed by initially making spherical silver alloy particles
of more or less conventional composition by any of the known
particle-forming techniques. Then, in a sharp departure from the
prior art, the particles are plated or coated with gold.
Subsequently, when the coated particles are mixed with mercury, the
gold layer controls the rate of penetration of the mercury into the
silver-tin core, providing for longer work time, punctuated by a
quick-setting mechanism as the mercury-gold layer provides a
vehicle for rapid diffusion of mercury into the core accelerating
the amalgamation of the silver-tin alloy.
The mechanism obtained, using the alloy of this invention, permits
the use of alloy materials in the core capable of developing higher
strength in the set amalgam. For example, unannealed alloys impart
better properties to the set amalgam restorations than annealed
alloys but are generally not professionally acceptable because the
work time of the amalgam is too short for proper placement of the
restoration. Therefore, the amalgams prepared with unannealed
gold-plated alloy possess significantly greater strength, corrosion
resistance and hardness (among other desirable qualities) in
comparison with prior art materials.
Thus, it is the object and purpose of this invention to provide an
improved dental amalgam and method for making the same. This object
and purpose, and others attendant thereto, will be more fully
understood by reference to the following detailed specification and
claims,
DETAILED DESCRIPTION
Following prior art procedures and formulations, there are almost
inevitably formed several phases of the mercury-silver alloy
amalgam upon trituration. These appear to be a first phase of
silver-mercury composition, e.g., Ag.sub.2 Hg.sub.3, and a second
phase of tin-mercury, e.g., Sn.sub.7 Hg.sub.8. The second phase is
highly undesirable because, among other reasons, it corrodes easily
and is weak.
While it is thus necessary to reduce or eliminate the second
(tin-mercury) phase, this cannot be accomplished by removal of the
tin, since this element prevents undue size change as the amalgam
sets.
It has been discovered that the troublesome mercury-tin phase can
be virtually eliminated without the necessity of disposing with the
use of tin. Broadly, this is accomplished through the preparation
of a silver alloy, comprising at least about 65% silver, and not
more than about 29% tin, with minor proportions of copper (e.g.,
6%) and zinc (e.g., 2%), and forming the same into particles by one
of several known methods, such as by lathe cutting to produce
irregular shapes, or by spraying, to produce spheres and coating
the alloy with a thin layer of gold, i.e., no more than 3% by
weight of the alloy.
Initially, the uncoated alloy particles are separated into
fractions according to size. For example, three fractions may be
selected: fines (below 10-15 microns), medium (about 10-15 microns
to about 30-44 microns) and coarse (about 30 microns to about 50-60
microns). Good results have been achieved by annealing the fine
fraction at high temperatures (e.g., 250.degree.C to 400.degree.C)
for more than one hour until the alloy is lightly annealed.
It should be noted that the amount of annealing which may be used
with the present invention is substantially less than that employed
in conventional technology relating to the preparation of silver
alloys. In the conventional process, the substantial annealing is
required to slow down the amalgamation of the mercury and silver,
but results in a weakening of the amalgam. In particular, the
annealing conventionally used reduces compression strength, thereby
making the filling susceptible to cracking.
Thus, the present invention provides a means for extending working
time, i.e., the period from mixing the mercury with the silver
particles until setting of the resulting amalgam, without loss of
strength. Moreover, for the first time, the setting time is
selectively controlled by the gold coating on particles of the
present invention in which the thickness of the coating varies,
thereby affecting the time required for the mercury to "penetrate"
the enteric gold coat to join with the silver alloy.
Indeed, with the novel gold coated particles of the present
invention, one can select the desired working time, at the end of
which there occurs a so-called "snap set." When the working time is
expressed graphically, it appears as a virtually horizontal line on
the hardness/time coordinates, followed by a sharply rising curve,
representing the snap setting. Such graphic depiction makes it even
clearer that the setting is a function of how long it takes the
mercury to penetrate through the gold coating to the silver alloy
particle. This selective setting and extensive working time is
something never before achieved in the art and of great value,
since conventional compositions afford very little latitude in
terms of time.
In more detail, the conventional alloy develops viscosity slowly
and, at some point between one and one-half to three minutes, the
material becomes unpackable. At some point between 4 to 8 minutes,
conventional alloys become carvable.
By contrast, the gold-plated alloy of the present invention has a
working time of (preferably) 2 to 3 minutes after which it snap
sets and can be carved almost immediately. The material is
susceptible to carving for about 3 minutes, according to the
preferred formulations, after which it becomes very hard. Such
initial high hardness is continued through the life of the
material.
As indicated, with the present invention, it may be desirable to
use different thicknesses of gold coating. More particularly, it
has been found advantageous to use a gold coat of from about 0.5 to
about 3% gold (expressing the weight of the gold as a percentage of
the total weight of the particle). The gold-plating or coating can
be applied by a number of known methods.
The gold plated alloy can also be treated, if desired, with from
0.05 to 3% mercury by plating or by vapor deposition. This mercury
coating improves the solution characteristics of the gold-plated
alloy and gives better mixes and lower mercury ratios.
Additionally, the judicious selection of particle sizes will also
improve the mechanical properties of the amalgam of the present
invention. Good results have been achieved with the following
mixtures of particles according to the following sizes:
Coarse 0-30% Medium 40-70% Fine 30-60%
After the particles are formed and gold-plated as hereinbefore
generally described, they are blended. Thereupon, the blend is
ready to form an amalgam. Thus, when the dentist has prepared the
tooth cavity, he mixes the gold-plated particles with mercury and
the amalgamation process begins at the rates heretofore described.
He may select working time by adjusting the particle blend, i.e.,
by using heavier or lighter gold coatings, the working time can be
controlled, or by varying the time of trituration which directly
modifies working time.
It is novel and of substantial commercial importance that a
superior amalgam can be formed using between 35 to 50% mercury.
Indeed, excellent results are obtained by using from about 38 to
44% mercury, and no known alloy will form a suitable amalgam with
so little mercury as that set forth in said range. This low mercury
ratio is significant advantage per se.
The invention can be further understood by reference to the
following examples which illustrate, but do not limit, the
concept.
EXAMPLE 1
A dental alloy prepared according to the American Dental
Association Specification No. 1 for alloy for dental amalgam with
June 1970 revision (see Guide to Dental Materials and Devices --
6th edition, American Dental Association publication, 211 East
Chicago Avenue, Chicago, Ill. 60611, pp 168-171), comprising a
minimum of 65% by weight silver, a maximum of 29% tin, a maximum of
6% copper, and a maximum of 2% by weight zinc, was obtained in
spherical form by spraying as described in U.S. Pat. No. 3,305,356.
The resultant alloy was sized by air classification in a Vortec
brand air classification apparatus to obtain two fractions, one
having particle sizes 15 microns and larger, and one having
particle sizes 15 microns and smaller. Typically, the larger
particle size fraction is sieved with a 325 mesh sieve to produce a
fraction having particle sizes from 15 microns to 44 microns. This
fraction and the smaller particle size fraction are blended into a
bimodel distribution in the ratio of up to about 60% by weight of
the larger particles and up to about 40% by weight of the smaller
particles.
The resulting alloy was plated with between 0.5% by weight gold and
3% by Weight to form a product having the ability to be amalgamated
with as little as 38 to 44% by weight of mercury and was able to be
carved for about 3 minutes after a 3 -minute work time with nearly
full strength being developed within approximately 30 minutes.
Likewise, the set amalgam exhibits superior corrosion resistance
due principally to the reduction in the amount of Gamma 2 formed
during the setting reaction.
Other proportions of alloy are, of course, possible to make for
optimum properties in a given application, while still employing
the novel teaching herein. Likewise, it is possible to coat various
alloys with other amalgamatable materials to achieve the advantages
of the present invention in the same or different applications,
using, for example, copper, palladium, platinum, indium, nichel,
cadmium and silver.
* * * * *