U.S. patent number 3,841,848 [Application Number 05/341,661] was granted by the patent office on 1974-10-15 for hard watch case comprising tin, t, and at least one of mn, al and v.
This patent grant is currently assigned to Kabushiki Kaisha Suwa Seikosha. Invention is credited to Masami Kasai, Motoki Kishida.
United States Patent |
3,841,848 |
Kasai , et al. |
October 15, 1974 |
HARD WATCH CASE COMPRISING TiN, T, AND AT LEAST ONE OF Mn, Al AND
V
Abstract
A watch case resistant to mechanical defacement and corrosion
having an external pressed and sintered component at least a part
of which comprises TiN with Ti in combination with at least one
material selected from the group consisting of Mn, Al, and V as
metallic binders.
Inventors: |
Kasai; Masami (Nagano,
JA), Kishida; Motoki (Nagano, JA) |
Assignee: |
Kabushiki Kaisha Suwa Seikosha
(Tokyo, JA)
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Family
ID: |
27277706 |
Appl.
No.: |
05/341,661 |
Filed: |
March 15, 1973 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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110959 |
Jan 29, 1971 |
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Foreign Application Priority Data
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Jan 30, 1970 [JA] |
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45-7675 |
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Current U.S.
Class: |
428/564; 368/280;
428/164; 428/660; 75/244; 419/13; 428/457; 428/927; 968/365 |
Current CPC
Class: |
G04B
37/22 (20130101); C04B 35/58014 (20130101); G04B
37/221 (20130101); Y10T 428/12806 (20150115); Y10S
428/927 (20130101); Y10T 428/12139 (20150115); Y10T
428/24545 (20150115); Y10T 428/31678 (20150401) |
Current International
Class: |
C04B
35/58 (20060101); G04B 37/00 (20060101); G04B
37/22 (20060101); C22c 001/04 (); G04b 037/00 ();
C22c 001/05 (); C22c 029/00 () |
Field of
Search: |
;29/182.5,182.3 ;75/205
;58/88R ;117/129 ;161/213 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Sebastian; Leland A.
Assistant Examiner: Schafer; R. E.
Attorney, Agent or Firm: Blum, Moscovitz, Friedman &
Kaplan
Parent Case Text
CROSS REFERENCE TO RELATED APPLICATION
This application is a continuation-in-part of our application Ser.
No. 110,959, filed: Jan. 29, 1971, now abandoned; the priority of
said application Ser. No. 110,959 is claimed, and a certified copy
of the Japanese application of which said Ser. No. 110,959, is
based, is in said application.
Claims
What is claimed is:
1. A watch case resistant to mechanical defacement and corrosion,
having an external pressed and sintered component comprising TiN,
Ti and at least one binder metal selected from the group consisting
of Mn, Al and V, the percentage by weight of TiN being from 50 to
95, of Mn being 0.5 to 10, of Al being 0.1 to 8 and of V being 0.1
to 10 with Ti constituting the remainder.
2. The watch case as defined in claim 1 wherein the percentages by
weight of TiN, Ti, and Mn are respectively 87, 11 and 2.
3. The watch case as defined in claim 1 wherein the percentages by
weight of TiN, Ti, Mn and Al are respectively 87, 11, 1 and 1.
4. The watch case as defined in claim 1 wherein the percentages by
weight of TiN, Ti, Al and V are respectively 75, 10, 5 and 10.
5. The watch case as defined in claim 1 wherein the percentages by
weight of TiN, Ti, Mn, Al and V are respectively 87, 9, 2, 1 and
1.
6. A watch case as defined in claim 1 having a stainless steel body
covered at least in part by said pressed and sintered
component.
7. A watch case as defined in claim 6 wherein said pressed and
sintered component engages said stainless steel body
mechanically.
8. A watch case as defined in claim 6 wherein said pressed and
sintered component is attached to said stainless steel body by
cement.
9. A watch case as defined in claim 6 wherein said pressed and
sintered component is a bezel.
10. A watch case as defined in claim 1 wherein said pressed and
sintered component comprises the entire watch case body.
Description
BACKGROUND OF THE INVENTION
In the mass production of conventional watch cases the materials
generally used are gold, gold alloy and stainless steel. All of
these materials have a low surface hardness (Vickers hardness, Hv,
200 maximum) so that they are easily scratched or abraded by
contact with hard metals or concrete and the original high polish
of the surface lasts for only a limited time. Also the range of
color available with these metals is either the yellow of the gold
or the gray of the stainless steel. In addition, gold and gold
alloys have high specific gravity as is shown in the Table I below
so that where the watch case is large, it can be annoying to the
wearer.
SUMMARY OF THE INVENTION
Hitherto, nitrides have been used only as refractory materials in
the form of bricks, boards and crucibles. Such materials are
extremely hard, heat and corrosion resistant; in the case of
silicon nitride the material has a beautiful light-green color.
Moreover, the range of colors can be extended by choice of various
binding metals. In addition to being harder than the conventional
metals now used, nitrides are available which are much lighter than
gold or gold alloys and substantially lighter than stainless steel
and some of the carbides which have been used for watch cases. The
weight of a watch case made of nitrides can then be substantially
lower than the weight of conventional cases, thereby decreasing the
burden to the wearer.
TABLE I ______________________________________ Characteristics of
Various Materials For a Watch Case
______________________________________ Specific Hardness Materials
Gravity (g/cc) (Knoop) Color ______________________________________
WC 15.8 1880 Black TiC 4.9 2460 Black Si.sub.3 N.sub.4 3.18 1800
Faint Green AlN 3.26 1225 Ash TiN 5.4 1770 Gold and White ZrN 7.3
1510 Black and White 18-8 Stainless Steel 7.9 200 Gray Au 19.3 50
Yellow ______________________________________
Of the above materials TiN is particularly suitable for use as the
principal constituent of a watch case composition, since it can be
varied in color by choice of suitable binder metals, and since
compositions containing TiN as herein disclosed have high hardness
and high tensile strength and can be sintered at convenient
temperatures.
In order to prepare a nitride watch case, a quantity of a metallic
powder to serve as a binder is added to powdered nitride, and the
mixture is pulverized and mixed in a wet condition in a ball mill
for about 100 hours. The powder is then dried in vacuo and
lubricants are added. The mixture is formed into a watch case at a
pressure 2 ton/cm.sup.2. It is given a preliminary sintering in a
vacuum furnace at a pressure of 1 .times. 10.sup.-.sup.1 to 7
.times. 10.sup.-.sup.2 mm Hg at a temperature of about 850.degree.
C. for about an hour. The watch case is given a final sintering in
a vacuum furnace at a pressure preferably of 7 .times.
10.sup.-.sup.2 to 9 .times. 10.sup.-.sup.2 mm Hg at a temperature
of 1,400.degree. to 1,540.degree. C. for an hour. The lower
pressure limit is, of course, not critical. The product is
sufficiently hard so that it can be polished only with a diamond
wheel.
Accordingly an object of the present invention is to provide a
watch case which is resistant to mechanical defacement and to
corrosion.
Another object of the invention to provide a watch case which is
lighter than conventional watch cases.
Still another object of the invention to provide a watch case with
a wide range of colors.
Yet another object of the invention to provide an attractive watch
case at reduced cost.
Still other objects and advantages of the invention will in part be
obvious and will in part be apparent from the specification.
The invention accordingly comprises the features of construction,
combinations of elements, and arrangement of parts which will be
exemplified in the constructions hereinafter set forth, and the
scope of the invention will be indicated in the claims.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a sectional view of a watch case the outer surface of
which is protected by a nitride layer;
FIG. 2 is a sectional view of a watch case in which the bezel is
made of a nitride in accordance with the present invention;
FIG. 3 is a sectional view of a watch case in which a peripheral
ring and a lug are made of a nitride composition in accordance with
the present invention; and
FIG. 4 is a sectional view of a watch case in which the entire case
body and cover are made of nitride in accordance with the present
invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
To prepare a watch case in accordance with the present invention,
binder metals including Ti and at least one of Mn, V and Al powders
having a particle diameter of 2-3 microns are added to powdered
TiN. The powders are pulverized and mixed wet in a ball mill with
hard balls for about 100 hours. They are then dried in vacuo and a
lubricant, preferably of the paraffin group, necessary for forming
is added. The powder is formed into a watch case at a pressure of 2
ton/cm.sup.2 and then given a preliminary sintering in a vacuum
furnace at a pressure of 1 .times. 10.sup.-.sup.1 to 7 .times.
10.sup.-.sup.2 mm Hg at a temperature of 850.degree. C. for an
hour. The watch case is given a final sintering in a vacuum furnace
at a pressure of 7 .times. 10.sup.-.sup.2 to 9 .times.
10.sup.-.sup.2 mm Hg at a temperature of 1,400.degree. to
1,540.degree. C. for an hour. In the process, allowance is made for
the fact that the watch case will contract during the final
sintering. The product is extremely hard and a diamond wheel is
used for the polishing. The resultant surface color varies from
that of white gold to that of 18K gold and the surface is lustrous,
resembling a jewel. The Vickers hardness is 1,020 to 1,132 and the
material cannot be scratched by a knife, a razor, or file or broken
glass. In addition, the material is not corroded either by
artificial perspiration or by sea water and consequently the
lustrous appearance is essentially permanent. Such a watch case is
much lighter than a conventional case made of stainless steel, gold
or a gold alloy and is also lighter than cases which are chiefly
composed of carbide and contain substantial quantities of heavy
metal binders such as nickel, cobalt or molybdenum.
Table II lists a number of compositions based on TiN as the
refractory constituent. In each case Ti, together with at least one
of Mn, Al and V is used as the binder. The TiN concentration can
vary from about 50 percent to about 95 percent by weight. Preferred
ranges for the binder metals are as follows:
Mn 0.5 to 10% Al 0.1 to 8% V 0.1 to 10% Ti -- Balance.
At TiN concentrations below about 50 percent, the hardness
decreases, while at concentrations above 95 percent the tensile
strength decreases. For Mn concentrations below 0.5 percent no
effect is noted, while at above 10 percent both the color and the
hardness are degraded. For Al and V, concentrations below 0.1
percent show no effect, while above about 8 percent for Al and 10
percent for V, color tone, luster and hardness are adversely
affected. Titanium in the examples of Table II is shown as lying
between 3 and 35 percent. Actually, titanium is used to bring the
total weight up to 100 percent after the concentrations of the
other constituents are selected.
In making the selection of a composition, the first consideration
is usually the color tone desired. Table II makes it possible to
choose a composition which will yield the desired properties.
Another consideration may be the sintering temperature. As would be
expected, the higher the TiN content, the higher the temperature
required for proper sintering. The tensile strength also correlates
directly with the TiN content.
TABLE II
__________________________________________________________________________
Sintering Tensile Temp Color Hardness Strength Example TiN Ti Mn Al
V .degree.C Tone Hv kg/mm.sup.2
__________________________________________________________________________
1 60 32 8 1450 white gold 1226 55 2 87 11 2 1520 18K gold 1150 70 3
85 10 5 1540 gold 1115 62 4 50 35 10 5 1500 silver yellow 1290 53 5
55 33 7 5 1400 silver yellow 1310 48 6 87 9 2 2 1520 light gold
1087 68 7 87 11 1 1 1520 18K gold 1132 72 8 86 9 3 2 1520 light
gold 1018 70 9 95 3 0.5 1.5 1520 white gold 1020 70 10 75 10 5 10
1500 white gold 1048 60 11 83.5 8 0.5 8 1530 gold 1090 58 12 87 9 2
1 1 1520 reddish gold 1058 70
__________________________________________________________________________
Note: The sintering time for all of the compositions listed is 1
hour, but, in general, the sintering time is not crucial.
In general, the higher the tensile strength, the lower the
hardness, which is surprising.
Where these titanium nitride compositions are to be used in
combination with stainless steel, the design must take account of
the fact that the compositions are extremely hard and show little
deformability. FIG. 1 shows a stainless steel watch case in which a
hard layer 1 of nitride is superimposed upon the stainless steel
case 2. The nitride layer 1 is attached to the stainless steel by
the cement.
FIG. 2 shows a stainless steel watch case in which the bezel 1
engages the stainless steel 2 at the snap-ring 3. Since the bezel
of nitride can not be substantially deformed, provision must be
made for the stainless steel snap-ring to deform. This provision is
made through the formation of the groove 4 in the stainless steel
body 2. The lug 5, here, is part of the stainless steel body.
In the watch case shown in FIG. 3, the outer case body 1 and the
lug 5 are both made of a nitride composition. The outer case body 1
is attached to the inner body 2 by means of cement inserted into
the grooves 3 and 4.
In the watch case shown in FIG. 4 the entire case body including
the back cover is made of the nitride composition. Such a watch
case is resistant to scratching on all of its surfaces.
It will thus be seen that the objects set forth above, among those
made apparent from the preceding description, are efficiently
attained and, since certain changes may be made in the above
constructions without departing from the spirit and scope of the
invention, it is intended that all matter contained in the above
description or shown in the accompanying drawings shall be
interpreted as illustrative and not in a limiting sense.
* * * * *