U.S. patent number 3,615,901 [Application Number 04/881,265] was granted by the patent office on 1971-10-26 for method of making a plastically shapeable cathode material.
Invention is credited to Gustav K. Medicus.
United States Patent |
3,615,901 |
Medicus |
October 26, 1971 |
METHOD OF MAKING A PLASTICALLY SHAPEABLE CATHODE MATERIAL
Abstract
A plastically shapeable cathode material is prepared by
depositing on a nickel substrate a layer of a mixture of nickel or
nickel oxide powder and barium, strontium and calcium carbonates;
sintering in a neutral or reducing atmosphere the nickel substrate
with deposited layer; compressing the sintered material; cold
rolling the sintered and compressed material; annealing the
resulting cold-rolled material; and repeating the latter two steps
until the nickel substrate with deposited layer has a desired
thickness.
Inventors: |
Medicus; Gustav K. (Dayton,
OH) |
Family
ID: |
25378112 |
Appl.
No.: |
04/881,265 |
Filed: |
December 1, 1969 |
Current U.S.
Class: |
419/8; 419/10;
419/28; 75/247; 419/19; 445/50 |
Current CPC
Class: |
H01J
9/042 (20130101); B22F 7/04 (20130101) |
Current International
Class: |
H01J
9/04 (20060101); B22F 7/02 (20060101); B22F
7/04 (20060101); C22f 001/10 (); B44d 001/18 ();
H01j 063/02 () |
Field of
Search: |
;148/11.5R,126,31.5
;29/25.11,182.5,420.5 ;117/223 ;75/206,208 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Rutledge; L. Dewayne
Assistant Examiner: Stallard; W. W.
Claims
I claim:
1. A process for preparing a plastically shapeable cathode material
which comprises depositing on a surface a layer of a mixture of
nickel powder or nickel oxide powder and at least two carbonates
selected from the group consisting of barium, strontium and calcium
carbonates; sintering said layer in a reducing or neutral
atmosphere, thereby decomposing said carbonates and reducing said
nickel oxide powder; compressing said sintered layer, thereby
causing said nickel powder and said reduced compounds to adhere and
form a unitary mass; cold rolling said sintered and compressed
layer; and annealing said cold-rolled layer in a reducing or
neutral atmosphere.
2. A process according to claim 1 in which said surface is a sheet
of nickel; said sheet with said layer deposited thereon is sintered
in a reducing or neutral atmosphere; said sintered sheet with
adhering layer is compressed; said sintered and compressed nickel
sheet with said layer bonded thereto is cold rolled; and said
cold-rolled nickel sheet and bonded layer are annealed in a
reducing or neutral atmosphere.
3. A process according to claim 2 in which said mixture consists
essentially of nickel powder or nickel oxide powder, barium
carbonate, strontium carbonate and calcium carbonate, said
carbonates constituting 20 to 65 weight percent of said mixture
with the remainder being nickel or nickel oxide; said nickel sheet
has a thickness in the range of 0.25 to 5 mm.; and the ratio of the
thickness of said layer to the thickness of said sheet is in the
range of 10:1 to 1:10.
4. A process according to claim 2 in which said mixture consists
essentially of nickel powder or nickel oxide powder, barium
carbonate, strontium carbonate and barium carbonate, said nickel or
nickel oxide constituting from 70 to 80 weight percent of said
mixture, the remainder being carbonates.
5. A process according to claim 2 in which said layer is formed by
sieving nickel powder or nickel oxide powder onto said sheet and
then sieving onto said nickel powder or nickel oxide powder a
mixture of nickel powder or nickel oxide powder and said
carbonates.
6. A process according to claim 3 in which said sintering and said
annealing are conducted in a hydrogen atmosphere.
7. A process according to claim 6 in which said sheet with
deposited layer is sintered at a temperature in the range of
900.degree. to 1300.degree. C. for a time to reduce substantially
all of said carbonates; a pressure between about 5,000 and 20,000
p.s.i.a. is applied to said sintered sheet with adhering layer;
said sintered and compressed sheet with bonded layer is cold rolled
in one direction until said sheet can no longer be worked; and said
cold-rolled nickel sheet with bonded layer is annealed at a
temperature in the range of 500.degree. to 800.degree. C.
Description
This invention is concerned with a process for preparing a
plastically shapeable cathode material. In one aspect it relates to
a cathode material prepared by the aforementioned process.
As shown in the prior art, thermionic cathodes can be made by
compressing and sintering a mixture of nickel powder with barium,
strontium and calcium carbonates. The resulting product either has
the desired form, or it is shaped by machining, e.g., by turning,
drilling, milling, or the like. Such cathodes have excellent
properties with respect to poisoning, exposibility to the
atmosphere, and resistance to cathode sputtering as well as related
effects. The cathode material of the present invention is an
improvement over the prior art material in that it provides many
additional advantages.
It is an object of this invention to provide an improved cathode
material.
Another object of the invention is to provide a shapeable cathode
material which can be worked by any of the conventional
metalworking processes, such as shearing, punching, bending,
welding, shear forming or spinning, deep drawing, and the like.
A further object of the invention is to provide a cathode material
which has improved emission characteristics and a longer life than
the prior art cathodes.
Still another object of the invention is to provide a material
which is suitable for direct ohmic heating.
Other objects and advantages of the invention will become apparent
to those skilled in the art upon consideration of the accompanying
disclosure.
In a preferred embodiment, the present invention resides in a
cathode material that is prepared by depositing on a nickel
substrate an active layer of nickel powder or nickel oxide powder
and alkaline earth metal carbonates; sintering in a reducing or
neutral atmosphere the nickel substrate with deposited layer;
compressing the sintered material; cold rolling the sintered and
compressed material; annealing the cold-rolled material in a
reducing or neutral atmosphere; and repeating the latter two steps
until the nickel substrate with deposited layer has a desired
thickness.
A cathode formed by the process of this invention is superior in
many respects to the prior art cathodes. Since the cathode is
plastically deformable, it can be shaped by any conventional
metalworking process. As a result wastage of material is reduced to
a minimum while making it possible to fabricate a cathode of any
desired configuration. The cathode can be stored without
deterioration for extended periods in the atmosphere. The cathode
can be readily spotwelded, and it is suitable for direct ohmic
heating. Furthermore, the cathode often has better emission and
longer life than conventional cathodes.
The thickness of the nickel sheet material used as a substrate can
vary over a wide range. Generally, the thickness of the substrate
is in the approximate range of 0.25 to 5 mm. although it is to be
understood that a nickel sheet of any desired thickness can be used
in the practice of the present invention. For example, in large
production runs, it is advantageous to commence with a piece of
nickel having a thickness ranging from a few centimeters to 10 or
15 centimeters. A mixture of nickel or nickel oxide powder and
barium, strontium and/or calcium carbonate is deposited as by
sieving on the substrate as an active layer of substantially
uniform thickness. The alkaline earth metal carbonates generally
constitute about 20 to 65 weight percent of the mixture, the
remainder of the mixture being nickel or nickel oxide powder. The
mechanical properties of the layer can be varied over a wide range
by changing the amount of nickel or nickel oxide powder present in
the mixture. As to the amount of the alkaline earth metal
carbonates, each is usually present in an amount equal to zero to
75 weight percent of the total amount of carbonates, and at least
two of the carbonates are present. The ratio of the thickness of
the layer of nickel or nickel oxide powder and alkaline earth metal
carbonates to the thickness of the nickel sheet can be varied
within rather wide limits in order to adjust the malleability of
the cathode material for different degrees and kinds of plastic
deformation. It is also within the scope of the invention to adjust
the concentration of nickel powder in the layer mixture so that it
is higher at the substrate surface. In a preferred procedure nickel
or nickel oxide powder is first sieved onto the nickel substrate
followed by the deposition of the mixture of nickel or nickel oxide
powder and alkaline earth metal carbonates. By proceeding in this
manner, the deformation properties of the cathode material can be
improved. However, the ratio of layer thickness to substrate
thickness generally falls in the range of 10:1 to 1:10. To improve
adherence the surface of the substrate can be scarred or roughened
by chemical or electrochemical etching or by mechanical means prior
to depositing the layer thereon.
The nickel substrate with deposited layer of nickel or nickel oxide
powder and alkaline earth metal carbonates is then sintered. The
sintering step is carried out by heating the substrate and adhering
layer to a temperature below the melting point of nickel for a
period sufficient to reduce the alkaline earth metal carbonates to
oxygen-containing compounds and, when used, the nickel oxide powder
to nickel. The exact composition of the compounds obtained in the
sintering step is not known with certainty, but corresponding
alkaline earth metal oxides as well as alkaline earth metal
nickelates, e.g., calcium nickelate (Ca(Ni0.sub.4) ), are
apparently formed. This is accomplished by placing the substrate
and adhering layer in a furnace maintained at a temperature below
about 1,400.degree. C., e.g., at a temperature in the range of
900.degree. to 1,300.degree. C. In general, the higher the
temperature the shorter the time the material must remain in the
furnace, but in any event the time and temperature are adjusted so
as to obtain substantially complete reduction of the nickel oxide
and decomposition of the carbonates. Although the sintering is
preferably conducted in a reducing atmosphere, e.g., in the
presence of hydrogen, it is within the purview of the invention to
carry it out in a neutral atmosphere, such as argon or helium. It
is preferred to employ nickel oxide since a more homogeneous
mixture is thereby obtained. And when nickel oxide is used, it is
necessary to carry out the sintering in a reducing atmosphere. An
important purpose of the sintering step is to obtain uniform
adherence between the substrate and the active layer. In order to
ensure that this is accomplished, it may be desirable to apply a
slight pressure to the layer, e.g., by placing a weight on the
layer so as to exert 1 to 5 pounds per square inch pressure.
The sintered material, i.e., the nickel substrate with deposited
layer, is then compressed without delay at a high pressure. Any
suitable pressure inducing means can be employed although it is
preferred to use a hydraulic press. The pressure is usually in the
range of 5,000 to 20,000 pounds per square inch absolute (p.s.i.a.)
although higher and lower pressures can be used without departing
from the spirit or scope of the invention. It is not necessary to
subject the substrate with deposited layer to the pressure for an
extended period of time. It is usually sufficient merely to apply
the pressure and then immediately release the pressure in order to
cause nickel and alkaline earth metal compounds to adhere and form
a unitary mass bonded to the substrate.
In the preferred procedure, the sintering and compression steps are
carried out in that order. By proceeding in this manner, the layer
is in a porous state during sintering as compared to a compacted
state after the compression step. As a result gases formed during
sintering, such as carbon dioxide, are driven out of the porous
layer by the heat or are squeezed out of the layer upon being
compacted during the compression step. The possibility of gases
being entrapped in the layer is thereby reduced to a minimum as is
the chance of carbon deposits being formed during use of the
cathode material.
Immediately after the compression step, the nickel substrate with
adhering layer is removed from the hydraulic press and cold rolled.
The cold rolling is continued until such time as the material can
no longer be worked and annealing becomes necessary. The substrate
with bonded layer is then annealed by heating it to a temperature
in the range of 500.degree. to 800.degree. C. The annealing step is
conducted in a reducing or neutral atmosphere as is the sintering
step. The cold rolling and the annealing steps are thereafter
repeated, as necessary, to obtain a cathode material having a
desired thickness. It is also within the scope of the invention to
carry out the annealing step immediately after the compression step
after which the material is then cold rolled.
The cold-rolling step homogenizes and compacts the active layer of
nickel or nickel oxide powder and alkaline earth metal carbonates.
The rolling also gives the layer a unique grain structure which is
responsible for its plasticity or malleability. Thus, it is
important to roll the material in one direction in order that the
grains of nickel powder may approach the shape of filaments.
A desirable property of any cathode material is that it may be
readily degassed. Accordingly, it is advantageous to take steps to
ensure to the extent possible that hydrogen is the only gas
evolving during the degassing process. Thus, it is preferred to
conduct not only the sintering and annealing steps but also at
least the first rolling cycle in the presence of hydrogen since
hydrogen diffuses readily through hot nickel.
The cathode material as described above comprises a nickel
substrate with an active layer bonded to one of its surfaces.
However, it is to be understood that the substrate can have an
active layer bonded to both of its surfaces. Such a cathode
material is in general prepared in accordance with the method
described hereinabove. It is usually preferred, however, to deposit
the layer of nickel or nickel oxide powder and alkaline earth metal
carbonates first on one surface of the substrate followed by
sintering after which the same procedure is followed for the other
surface. It may be desirable to reverse the sintering and
compression steps in this embodiment since the adherence of the
layer to the substrate may be greater after the compression step.
Alternatively, the sintering and compression steps can be carried
out on one side after which a layer is formed on the other side.
This layer is then subjected to the sintering and compression steps
in the preferred order. A cathode material comprising a nickel
substrate with an active layer bonded to both of its surfaces is
particularly desirable for directly heated cathodes.
It is within the scope of the invention to use a very thin
substrate as compared to the active layer, e.g., a thickness ratio
of substrate to layer of 1 to 10, in preparing the cathode
material. Furthermore, if high percentages of nickel or nickel
oxide powder, e.g., from 70 to 80 weight percent, are used in
preparing the mixture with the carbonates, the substrate may be
omitted entirely. By fabricating the cathode material by these
methods, it is possible to obtain a homogeneous emitting sheet or
ribbon that has a high-ohmic resistance.
A better understanding of the invention can be obtained by
referring to the following example which is not intended, however,
to be unduly limitative of the invention.
EXAMPLE
Hollow cathodes with the emitting surface on the inside are
prepared in the manner described below.
A substrate in the form of a sheet of nickel one and one-half
inches wide and 12 inches long has a mixture of nickel powder and
barium, strontium and calcium carbonates deposited on one of its
surfaces. This is accomplished by first sieving nickel powder onto
a substrate surface followed by sieving a mixture of nickel powder
and barium, strontium and calcium carbonates onto the nickel
powder. The substrate has a thickness of 1 mm. and the ratio of
deposited layer thickness to substrate thickness is about 2 to 1.
The substrate with deposited layer is placed in a furnace
maintained at a temperature of 1,000.degree. C. and containing
hydrogen. The material is allowed to remain in the furnace for 30
minutes in the presence of hydrogen, at the end of which period
substantially all of the carbonates are reduced. The substrate with
adhering active layer is then placed in a hydraulic press whereby
it is subjected to a pressure of 10,000 p.s.i.a. The substrate with
bonded active layer is then cold rolled until such time as it can
no longer be worked. The material is then annealed by placing it in
a furnace containing hydrogen. The temperature in the furnace is
about 600.degree. C., and the material is allowed to remain in the
furnace for a time sufficient for it to attain this temperature.
The material is then removed from the furnace and the cold rolling
and annealing steps are repeated two more times. The substrate with
bonded layer has a desired thickness of 1.5 mm.
The sheet of cathode material is cut into six separate pieces, each
being about one and one-half inches by two inches in size. Each
piece is then bent into a cylinder having a diameter of about 1.27
inch and a height of about 1 1/2 inches. The active-layer forms the
inner surface of each of the cylinders. The abutting edges of each
cylinder are welded so as to provide a rigid structure. Insulated
heater wire is then attached to the outer surface of the cylinders
to provide means for indirect heating of the cathode material. The
cathodes so fabricated are then used in the manufacture of
gas-discharge tubes.
The cathode material of this invention is particularly suitable for
use in gas-discharge tubes, e.g., mercury and rare gas tubes, as
well as gas-laser tubes, such as an argon ion laser tube.
As will be evident to those skilled in the art, various
modifications of this invention can be made or followed in light of
the foregoing disclosure without departing from the spirit or scope
of the invention.
* * * * *