U.S. patent number 3,746,456 [Application Number 05/187,493] was granted by the patent office on 1973-07-17 for ball point pen writing ball composed of a cemented carbide composition.
This patent grant is currently assigned to The Parker Pen Company. Invention is credited to Franklin J. Hill.
United States Patent |
3,746,456 |
Hill |
July 17, 1973 |
**Please see images for:
( Certificate of Correction ) ** |
BALL POINT PEN WRITING BALL COMPOSED OF A CEMENTED CARBIDE
COMPOSITION
Abstract
Cemented carbide compositions and shaped bodies produced
therefrom containing tungsten carbide or titanium carbide and a
binder alloy containing cobalt and nickel, and, by weight, about 18
to 20 percent chromium, 0.1 to 1 percent platinum and 0 to 3
percent iron.
Inventors: |
Hill; Franklin J. (Janesville,
WI) |
Assignee: |
The Parker Pen Company
(Janesville, WI)
|
Family
ID: |
26883084 |
Appl.
No.: |
05/187,493 |
Filed: |
October 7, 1971 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
|
851038 |
Aug 18, 1969 |
3628291 |
|
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Current U.S.
Class: |
401/215; 75/241;
419/17; 428/546; 419/18; 428/923 |
Current CPC
Class: |
C22C
29/067 (20130101); B43K 1/082 (20130101); Y10S
428/923 (20130101); Y10T 428/12014 (20150115) |
Current International
Class: |
B43K
1/00 (20060101); B43K 1/08 (20060101); C22C
29/06 (20060101); B43k 007/00 () |
Field of
Search: |
;401/215 ;29/182.8
;75/204 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Quarforth; Carl D.
Assistant Examiner: Hunt; B. H.
Parent Case Text
This is a division of application Ser. No. 851,038, filed Aug. 18,
1969, now U.S. Pat. No. 3,628,291.
Claims
I claim:
1. In a pen having a writing ball which will rotate freely against
an inking magazine, the improvement comprising said writing ball
formed from a cemented carbide composition comprising from about 75
to 95 percent by weight of a carbide selected from the group
consisting of tungsten carbide and titanium carbide and from about
5 to 25 percent by weight of a binder alloy containing cobalt and
nickel and, by weight, about 18 to 20 percent chromium, 0.1 to 1
percent platinum and 0 to 3 percent iron.
2. The pen of claim 1 wherein the binder alloy contains, by weight,
about 30 to 60 cobalt and 20 to 50 percent nickel.
3. The pen of claim 1 wherein the binder alloy contains, by weight,
about 45 to 55 percent cobalt and 25 to 35 percent nickel.
4. A cemented carbide writing ball for a ball point pen, comprising
from about 75 to 95 percent by weight of a carbide selected from
the group consisting of tungsten carbide and titanium carbide and
from about 5 to 25 percent by weight of a binder alloy containing
cobalt and nickel and, by weight, about 18 to 20 percent chromium,
0.1 to 1 percent platinum and 0 to 3 percent iron.
5. The writing ball of claim 4 wherein the binder alloy contains,
by weight, about 30 to 60 percent cobalt and 20 to 50 percent
nickel.
6. The writing ball of claim 4 wherein the binder alloy contains,
by weight, about 45 to 55 percent cobalt and 25 to 35 percent
nickel.
Description
BACKGROUND OF THE INVENTION AND DESCRIPTION OF THE PRIOR ART
Cemented carbide compositions containing a hard metal carbide
bonded by a metal alloy binder are well known in the art. The hard
metal carbide is typically a tungsten or titanium carbide and the
metal alloy binder is typically an iron group metal. The hard metal
carbide is normally present in the cemented carbide composition in
at least major proportion by weight. Cemented carbide compositions
can be used where hard and wear resistant compositions are required
such as in cutting tools, turning tools, etc.
It has been suggested to supplement the normal iron group metal
alloy binder with small amounts of chromium. The addition of small
amounts of chromium or chromium carbide to a tungsten
carbide-cobalt system is said to improve the corrosion resistance
of the alloy but with an accompanying reduction in strength and
metallurgical soundness. Additionally, the corrosion resistance of
a tungsten carbide-nickel system to certain environments is said to
be increased by the addition of chromium carbide but with an
accompanying reduction in strength. To overcome these
disadvantages, it has been suggested in U.S. Pat. No. 3,215,510 to
employ compositions of tungsten carbide and about 10 to about 25
percent, but not more than 30 percent, by weight of binder of
chromium and nickel wherein the ratio by weight of chromium to the
combined weight of nickel and chromium ranges from about 0.015 to
about 0.15. This composition is said to give outstanding corrosion
resistance particularly to acids and alkalis .
DESCRIPTION OF THE INENTION
An object of the present invention is the provision of novel and
improved corrosion resistant cemented carbide compositions.
A further object of the present invention is the provision of
improved shaped bodies made from said cemented carbide
compositions.
Further objects and improvements of the present invention will be
apparent upon reading the undergoing specification and claims.
Novel corrosion resistant cemented carbide compositions and shaped
bodies produced therefrom are provided containing tungsten carbide
or titanium carbide and a binder alloy containing cobalt and nickel
and, by weight, about 18 to 20 percent chromium, 0.1 to 1 percent
platinum and 0 to 3 percent iron.
The cemented carbide compositions of the present invention are
produced by powder metallurgy techniques. Powder metallurgy
techniques are, in general, well known in the art and include
pressing a mixture of powders of the desired carbide and binder
metals and then sintering the pressed mixture of powders to form a
cemented composition. More particularly, a powder mixture of
tungsten carbide or titanium carbide and the metals cobalt, nickel,
chromium, platinum and iron is prepared and screened to obtain
proper size particles. The powders may be mixed, for example, in a
ball mill wherein the powders are suspended in a suitable liquid
such as benzene. The milled powder is then dried, mixed with a
suitable binder-lubricant and pressed or compacted. The pressed
mixture is preferably presintered and then given a final sinter at
conventional temperatures and preferably in vacuo. The final
sintering is generally carried out under reduced pressure. It is
conventional to form cemented carbide compositions by milling
together the carbide and binder alloy metals as elemental powders.
It has been found, however, that cobalt and nickel coated carbide
powders with chromium, platinum and iron added as elemental powders
may be milled together with equally good results.
The finally sintered cemented carbide compositions can be shaped by
conventional technique as by grinding. Small diameter spherical
shapes have been found to have excellent properties for use as
writing points which will rotate freely against an inking magazine
in a pen. Pens of this nature are conventionally referred to as
ball-point pens. "Pen" as used in this context, however, is
intended to refer to any instrument which can be used to apply ink
or other fluid or viscous material to a receptive surface.
The cemented carbide compositions of the present invention possess
outstanding corrosion resistance properties, particularly to
aqueous ink and ferric chloride solutions. Additionally, shaped
cemented carbide compositions of the present invention possess
crush strengths comparable to conventional cobalt or nickel bound
carbides. The above properties, therefore, make the cemented
carbide compositions of the present invention particularly
advantageous for use as writing points in ball-point pens as
described above.
The cemented carbide compositions of the present invention
preferably contain about 75 to 95 percent by weight of tungsten
carbide or titanium carbide and about 5 to 25 percent or, more
preferably, about 3 to 15 percent by weight of binder alloy. The
binder alloy compositions according to the present invention
usually contain, by weight, about 30 to 60 percent cobalt, 20 to 50
percent nickel, 18 to 20 percent chromium, 0.1 to 1 percent
platinum and 0 to 3 percent iron. The preferred binder alloy
compositions contain, by weight, about 45 to 55 percent cobalt, 25
to 35 percent nickel, 18 to 20 percent chromium, 0.5 to 1 percent
platinum and 0 percent iron.
In order to compare the properties of the novel cemented carbide
compositions of the present invention with the properties of prior
art cemented carbide compositions, binder alloy compositions were
prepared as shown in table 1. Table 1 lists the composition of
binder alloys A through E in parts by weight of metal
components.
TABLE 1
Binder Alloy Co Ni Cr Pt A 40 40 20 B 40 40 19 1 C 50 30 19 1 D 30
50 19 1 E 60 20 19 1
a comparison of the properties of tungsten carbide-cobalt and
tungsten carbide-nickel cemented compositions with cemented
compositions formed from tungsten carbide and binder alloys A
through E from Table 1 is shown in Table 2. Corrosion data is given
for aqueous ink and aqueous ferric chloride solutions.
TABLE 2
Profilometer Reading, Microinches Cemented Carbide Composition, %
of Binder alloy After 1 After 1 year year By Weight Initial in ink
in 25 %FeCl.sub. 3 at 140.degree.F at 100.degree.F WC+10% Co 0.75
1.50 Attached, >20 WC+10% Ni 0.75 1.50 Attacked, >20 WC+10%
Alloy A 0.40 1.00 WC+10% Alloy B 1.50 2.00 Attacked, >20 WC+10%
Alloy C 1.50 1.50 Etched, 9 WC+10% Alloy D 1.00 2.00 Attacked,
>20 WC+10% Alloy E 1.50 1.50 Attacked, >20
A writing ball for a ball-point pen was prepared by grinding
tungsten carbide and titanium carbide compositions cemented with
nickel and cobalt binders and by grinding tungsten carbide and
titanium carbide compositions cemented with Alloy C binder from
Table 1 to compare the crush strength and microhardness properties
of these compositions when formed into shaped bodies. The results
of this test are set forth in Table 3.
TABLE 3
Crush Micro- Cemented carbide composition Strength hardness % of
binder alloy by weight (lbs.) (DPH) WC + 9 wt. % Ni 200 1510 WC +
10 wt. % Co 177 1450 WC + 10 wt. % Alloy C 173 1680 TiC + 20 wt. %
Ni 128 1608 TiC + 20 wt. % Co 157 1626 TiC + 20 wt. % Alloy C 136
1680
the following non-limitative examples illustrate the invention:
EXAMPLE 1
Cobalt and nickel coated tungsten carbide powders, tungsten carbide
powders and elemental chromium and platinum powders were prepared
and screened to minus 325 mesh. The total charge of powders was as
follows:
Carbide Binder Alloy 30.55 g. Co (9%) Coated WC 27.80 g. 2.75 g.
18.33 g. Ni (9%) Coated WC 16.68 g. 1.65 g. 5.02 g. WC 5.02 g. 1.04
g. Cr 1.04 g. 0.06 g. Pt 0.06 g. 55.00 g. 49.50 g. 5.50 g.
The powders were ball milled for 92 hours under benzene in a steel
mill with steel balls. The milled powder was dried, mixed with
Carbowax 1000 (a water-soluble lubricant available from Union
Carbide Corp.) as a binder-lubricant and compacted in a steel die
at 20 tons/sq. in. pressure. Cylindrical pieces of 1/4 inch dia.
.times. 1/2 inch in length were packed in a graphite-alundum
mixture and presintered by heating slowly to 1850.degree.F in a
dissociated ammonia atmosphere. The pieces were then given a final
sintering in vacuo at 2550.degree. for one hour under 100-200
microns pressure. A flat may be ground on the side of selected
presintered pieces prior to final sintering if profilometer
measurements or other corrosion tests are contemplated.
EXAMPLE 2
Titanium carbide, cobalt, nickel, chromium and platinum powders
were prepared and screened. The total charge of powders and
corresponding particle size were as follows:
40 g. TiC 5 microns 5 g. Co 1.5 microns 3 g Ni 7-13 microns 1.9 g.
Cr -325 mesh 0.1 g. Pt -325 mesh 50.0 g.
The powders were ball milled for 96 hours under benzene in a steel
mill with steel balls. The milled powder was dried, mixed with a
resin binder-lubricant and formed into 0.060 inch diameter spheres.
The green spheres were packed in a graphite-alundum mixture and
presintered by heating slowly to 1850.degree.F in a dissociated
ammonia atmosphere. Final sintering of the spheres was carried out
in vacuo at 2650.degree.F for 1/2 hour under 500 microns pressure.
The spheres had shrunk to approximately 0.047 inch diameter and
were then ground into 0.043 inch diameter balls for use as writing
points in pens. The material of Example 1 was also processed in
like manner into balls for use as writing points in pens.
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