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Патент USA US2124752

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July'26, 1938.
K. E. scHmKus _
' 2,124,752
Filed June 25, 1934
IVE-167116;? }
' . 2W1: ESzihimkus,‘
Patented July 26, 1938
Kurt ’ E. ' Schimkus, Chicago, 111., assignor, by
mesne assignments, to P. R. Mallory & 00., Inc.,
Indianapolis, Ind., a corporation of Delaware
Application June 25, 1934, Serial No.'732,242
13 Claims. (01. 175-366)
additional sulphur being present in the form of
The invention relates to recti?ers and to a
process of making same and more particularly has the more or less unstable higher sulphide com
reference to recti?ers of the type known as dry
surface contact recti?ers.
Ageneral object of the invention is to pro.
I vide a novel recti?er having higher' e?lciency,
longer life, and a higher output capacity, and
I which is capable of withstanding a greater break-
down voltage than has heretofore been attained.
Furthermore the general aim is to provide a
novel process by which devices, which are sub
stantially uniform in all-material respects, may
be easily produced ona commercial scale in a
comparatively short time.
Another object is to provide, in_ a recti?er cell,
a rectifying ?lm having a manganese content and
which is of exceeding hardness and is capable
pounds of a metal.
More particularly stated, another object is to
provide an electronegative element for a recti
?er embodying an unstable metal sulphide of a
higher valence combination than a more stable
low valence sulphide of the metal wherebyv a re
serve of active but combined sulphur is ‘present
in said electronegative element to form and main 10
tain a rectifying sulphide ?lm.
In conjunction with the foregoing, another ob
ject is to provide a novel process for producing
- an electronegative velement containing as its prin- _
cipal ingredient a poly-sulphide compound of
Still another object resides in the provision of
a recti?er of this character which embodies an
of withstanding high temperatures. _
Another object is to provide an electronegative
element for a recti?er which includes manganese
in combination with one or more of the elements
electronegative element having; a high valence.
sulphur compound of a metal and an electro
positive element having a contact surface, for
classi?ed in Group VI, family B of the periodic
system, more particularly selenium, tellurium and
includes a compound (such as the oxide of- said
coaction with said electronegative element, which
metal) capable of being converted into the metal
sulphide by a reaction with part of the sulphur 25
Another object is to provide an electropositive content of said high valence sulphur compound.
element which embodies a metallic member hav
Other objects and advantages will become
ing, as a contact surface, a coating of a man- _ apparent in the following description and from
ganese compound, such as the oxide.
the accompanying drawing, in which:
A further object resides in the provision of a
Figure 1 is a side view of a recti?er embodying 30
30 new ‘and improved process for producing recti
features of the invention.
?ers of this type and particularly the separate
coacting elements of a recti?er cell. In this con
nection the novel process of producing the electro
negative electrode includes the reduction and
conversion of manganese oxide, preferably the
monoxide, in the presence of a member of ‘Group
VI, family ‘.8 of the periodic system. The im
' proved process of producing the electropositive
electrode includesv the step of forming a. man
ganese oxide ?lm or coating on a surface of a
Fig. 2 _is a top, plan view thereof.
Fig. 3 is a, sectional view on an enlarged scale
a ‘ cell.
Fig. 4 is a- distended perspective view showing 35
the several elements of a cell.
While the invention is susceptible of various
modi?cations and alternative constructions, I
have shown in the drawing and will herein de
scribe in detail the preferred embodiment, but
it is to be understood that I do not thereby intend
metal plate which is preferably of aluminum or to limit the invention to the speci?c form dis- ’
magnesium but may be a ductile alloy of either . closed, but intend to cover all modi?cations and
or both with manganese.
alternative constructions falling within the‘ spirit
Another object is to provide a process which ' and scope of the-invention as expressed in vthe 45
includes the step of forming arectifying ?lm
between the contacting surfaces of a manganese
compound ?lm .and the formed electronegative
element, which ?lm has a high manganese con
appended claims.
‘Referring to the drawing wherein a recti?er
construction has been shown in illustration of the
Ill designate a
the reference numerals
tent imparting hardness and a high heat resist f invention,
generally the individual cells of the ‘recti?er.
While four cells are herein shown, this number
50 ing characteristic thereto.
A further object is to provide a novel recti ‘ may be varied according to the characteristics
fying ?lm embodying a metal sulphide which has,
in a unit. The cells are preferably as
intimately associated therewith,- an available desired
sembled one upon the other and are separated
supply of additional sulphur for replenishing by contact plates ll which extend outwardly be 65
possible sulphur losses due to operation, such
yond the peripheries of?the cells. A plate l2 ‘ tent. .Use is made of this characteristic in form
similar to the contact plates-1| is disposed at
each end of the unit. The plates and cells are
axially apertured to receive a securing bolt It or
ing-and maintaining the rectifying ?lm.
Since ‘the manganese-sulphur combination is
vpreferred, further description will deal primarily
the like which is electrically insulated therefrom - with these materials. In producing the electro
in any suitable manner as by ‘a bushing M (Fig. ~ negative material, a quicker reaction can be ob
1). Engaging each of the plates I2 is a sturdy‘ tained if a manganese compound having quick
reaction'propertiels, such as the monoxide, is em
disk-like member I5 through which the bolt ex
tends, and these members serve as pressure. ployed. ,The quantity of sulphur is determined
10 transfer elements in the application of pressure
to the cells and plates as the structure is as
sembled. At one end a head It on the bolt bears
as being substantially that amount required to 10
complete a reaction which will produce the
highest valence sulphide compound of- man
ganese. The sulphur and manganese monoxide
threads on the other end of the bolt are engage are intimately mixed together, preferably in ex
ceedingly ?nely divided form, and a reaction
v15 able by a nut ll to secure the parts together un
therebetween is caused, as by igniting the mix
der pressure ample to insure good electrical con
tact therebetween. Washers l8 are preferably ture. During ignition, air should be excluded
against the associated member I! while screw
‘ interposed between the plates‘ l2 and the head ' in any suitable manner to prevent the formation v
l6 and nut ll, respectively. A mounting bracket
20 l9 may be securely clamped between the nut i1
and another nut 20 engaging the bolt. I
As may be seen in Figs. 1 and 2 the plates II
and I2 are similarly but irregularly shaped. In
this instance each plate has substantially the
25 form of an equilateral triangle and in assembly
the plates have their apexes staggered or mis
alined. Thus, the apexes constitute outward ex
tensions which, because of the irregular disposi
tion of the adjacent plates, are spaced apart a
.30 distance which is substantially greater than that
between adjacent plates. These plates are effi
cient heat radiating and disseminating means
and the misalinement of- the extensions increases
their capacity for transfer of heat. Thednterme
35 .diate piatés carry terminal screws 2i or the like
by which proper electrical contact with the unit‘
may be readily established.
Referring toFigs. 3 and 4 the structure and
the process of making the cells will be described.
' Each cell comprises a base plate 22 and two elec-.
trodes 23 and 24, these electrodes in this instance
being respectively electronegative and electropos
itive elements. The base plate 22 15a support
of oxides. Since a portion of the sulphur is lost
during the reaction, the resulting‘ material ap 20
pears to comprise a mixture of manganese sul
phide, in the several valence forms thereof; that
is to say, of the mono-, di- and tri-sulphides of
' manganese.
In addition to manganese and sulphur, a good 25
conductor may be added to increase the conduc
tivity of the electronegative element. Preferably
a metal is chosen'which when converted to a sul
phide retains its current conducting properties
and in addition the best results are obtained if 30
the metal is one which will form an alloy with
manganese. Carbon may also be used. Where
the conductivity increasing metal is employed,
the proportion thereof to the quantity of manga
nese monoxide used is not more, and is preferably 35
less, than equal parts. Inclusion of such a metal .
in a formula will, of course, increase the quantity
of sulphur necessary by the amount required to
convert the metal into its sulphide. Where
carbon is employed, however, the sulphur con 40
tent is not materially increased but an exces
sive quantity of carbon is provided since a large
part thereof is lost during ignition.
Mixtures of substances substantially accord- ‘
ing member for the other elements and perfects
ing to the following exemplary formulae have 45
electrical contact between the electronegative ele
ment 23 and the associated contact plate ll. been found to give satisfactory results:
Hence the plate 2? must be an electrical conducw
‘tor and should be capable of establishing an ef
Manganese (monoxide) __________________ .._ 59
?cient electrical connection between the parts" Copper '
____ __
50 it contacts. A steel plate coated with a thin ?lm Sulphur
of lead has been found satisfactory.
' The electronegative element 23 is in the form
of a slug comprised primarily of a chemical com
\ Pound or compounds from which a rectifying ?lm
Manganese (monoxide) ___________________ _.59
____ 52
55 may be obtained. According to the present in;
vention, a metal is combined with an element 'The several materials in ?nely divided form are
classi?ed in Group VI, family B of the periodic intimately mixed together and the mass is ig
system, to produce a material which may then nited to produce a mixture of the manganese
'niono-, di- and tri-sulphides. The iron or cop
be formed into the desired shape for use. Man
per which are exemplary of suitable conductivity 60
increasing metals are converted into their sul
properties (as willhereinafter be more fully ex
plained) is preferably employed as the metal phides. The reason for choosing a metal which
while sulphur, is chosen as the element from the I will alloy with manganese is that during ignition
the intense heat, which is generated by the re
periodic table classi?cation due to its inexpen
85 siveness and because its combining properties action; appears momentarily to alloy the 65
manganese and the metal so that upon subse
with manganese effect an advantageous result.
Manganese has the property of combining with quent conversion to the sulphidesv a more thor
ough, intimate‘ and uniform mixture results than
certain elements, of which sulphur. is one, in sev
eral different atomic relationships according to
could otherwise be obtained.
its several yalences. Barium has similar charac
After completion of the reaction, the material
is pulverized if necessary. and may then be
teristics and could be used in place of manga
nese. Of the manganese sulphide compounds, formed into shape by a compression operation in
the most stable isthe monoisulphide, the higher. a conventional type of press. It has been found
valence compounds being more or less unstable that the ?nely divided material may, without
.76 and tending to give up their excess sulphur'con
. the addition of a binder or similar agent, be 75
in a manganese mono-sulphide ?lm on said ele
ment. Therefore, a rectifying ?lm is formed on
the electropositive element and also on the‘ elec
formed into hard, impervious pieces, such as the
washer-like slug shown in Fig. 4, possessing ample
strength to withstand ordinary, somewhat care
less handling. Moreover a pressing operation
produces an element having substantially perfect
ly plane contact. surfaces whereby the element is
ready for immediate assembly‘ without further
tronegative element, and it has been found that
the two elements may be separated after the rec
tifying ?lm has been formed without materially
affecting the operation or e?iciency of the cell.
Fig. 3 is illustrative of a cell after formation and
The electropositive element in its preferred
the two ?lms are shown as one thickness, indi
cated at 26, since there is no de?nite separating 10
line unless the two elements are taken apart.
Upon separation, however, a rectifying ?lm will
10 form comprises generally a metallic current con
ducting strip having ‘on one surface thereof a
?lm of a compound which includes the principal
metal present in the electronegative element (in
be found on both elements. This is the reason
why cells produced by this process will withstand
exceedingly rough usage and treatment. More 15
over, the rectifying ?lm is extremely hard and
will withstand high temperatures and, it has
been found, is completely formed in a shorter
length of time than has heretofore been deemed
possible. Moreover all of the, sulphur from the 20
di- and tri-sulphide is not consumed in forming
this instance manganese) and is of such nature
15 as to combine readily with sulphur to produce va
rectifying ?lm.
A preferred compound is
manganese‘ oxide, and the ?lm is indicated at 25
(Fig. 3). The metal on which the strip is prefer
ably formed is aluminum or magnesium although
20 satisfactory results‘ may be obtained by using a
magnesium-manganese alloy, an alluminum
magnesium alloy, or an aluminum-manganese . the rectifying. Hence a reserve supply of active
combined sulphur is always available to maintain
' magnesium alloy. Since the metal must be duc
?lm during operation of the cell.
tile, the alloys contain less than approximately theThe
?lm thus formed functions to prevent a 25
current flow therethrough in one direction but
oxide ?lm may be formed on the metallic strip permits a current ?ow in the opposite direction.
in any suitable manner as, for example, by im
After the cells have been formed, a suitable num—
mersing a magnesium strip in a solution of man
are assembled into a recti?er structure, such
ganates which have been stabilized by the pres
as that shown in Fig. '1, although it is possible to 30
30 ence of a free alkali. In order to produce a ?rst assemble the individual elements of the cells
uniform coating of manganese oxide, it is im
such a structure and then form the cells to
portant that the surface of the metal strip to into
produce the rectifying ?lm. As is well under
be coated be absolutely clean. In practice, there
fore, one surface-of the metal strip is burnished stood, the relationships of the cells to each other
in the assembled unit determines whether the
35 or otherwise suitably cleaned before the strip unit is a half-wave or a full-wave recti?er. AS.
is immersed in the alkaline-manganate solution.
may be seen in Figs. 1 and 3 the plate 22 and the
This process of forming the electropositive ele
ment lends itself nicely» to quantity production, electropositive element 24 are of greater diameter
than the electronegative element 23. -Hence
since a sheet of the metal of considerable vsize can ‘
be cleaned and immersed to produce a uniform when pressure is applied through the large disk
IS the force is uniformly distributed
coating thereover, after which the coated sheet members
is rinsed, dried, and rubbed or otherwise ‘cleaned, across the contacting surfaces to bring every por
tion of such surfaces, and particularly those on
to remove excess particles of the film. Follow
the electropositive and electronegative elements,
ing this, a plurality of uniform electropositive
into intimate contact. In consequence a uniform 45
45 elements can be formed from the sheet by a
and evenly distributed rectifying ?lm is produced
stamping or like operation.
which covers the entire surface area of the elec
After the electropositive and electronegative
elements have been formed, the elements of the
celi'are‘assembled together with an electronega
tronegative element and enhances the output 'e?l
ciency of the device.
22 and an electropositive element 24 with the '
film covered side of the electropositive element
contacting the adjacent surface of the-electro
negative element.
comparative tests made between'a recti?er pro
duced‘ according to the present invention and sim
the output capacity of the commercial units'and _
electronegative and electropositive elements.
In the preferred embodiment herein described
the ?lm consists primarily of manganese sulphide
improved recti?er has been provided. By actual
tained that my device has approximately twice 55.
rent produces a hard crystalline ?lm 26 (Fig. 3)
of metal compounds (sulphides, selenides or tellu
rides, depending upon which element has been
00 used in the electronegative element) between the
ilar cell's now on the market, it has been ascer
The assembled cell is then
55 placed in a suitable clamping device and a form
ing current passed through the cell. This cur
in its most stable mono-sulphide form.
From the foregoing it will be evident that an 50
60 tive element 23 interposed between a base plate
It is to be noted that the contact surfaces of
both the electropositive and electronegative ele
ments have a high manganese content. During
the formation of the rectifying ?lm it appears
that the hard crystals are produced on both con
will stand aboutv twice the break-down voltage.
The instant devices will withstand long usage and
in operation are highly efilcient. By the im
proved process which has been described, recti-' 60
?ers which have exceedingly uniform character
istics may be quickly and easily produced on a
commercial scale, whereby- manufacturing costs
are materially reduced.
I claim as my invention:
1. A recti?er cell comprising, in combination,
an electrode embodying manganese combined
with one or more elements from Group VI, family
Bof the periodic system (selenium, tellurium,
sulphur) ,- and. a complementary electrode includ 70
ing one or more of the lighter electropositive
during the ?lm formation, into the more stable .metals and having a surface of manganese oxide
70 tacting surfaces. Theoretically, the di-v and tri
sulphide manganesecompounds are converted,
manganese-mono-sulphide and the excess or re
leased sulphur combines with the manganese of
?lm on the electropositive element resulting
for contact with said ?rst mentioned element.
2. The process of forming an electrode for a
rectifying cell which includes the steps of clean 76
ing a surface of a strip of an electropositive manganese oxide to the action of a solution of a‘
metal selected from the group magnesium, alumi *manganate stabilized by the presence of free
num and magnesium-aluminum alloy, depositing alkali to produce a manganese oxide ?lm on said
on said surface a coating of manganese oxide,
drying and cleaning said coating, and cutting
the strip to form a plurality of uniformly similar
9. A- recti?er of the sulphide dry surface ‘con
tact type formed from a ?rst electrode includinB
manganese oxide and a second electrode including
3. In the process of forming an electrode for
a rectifying cell the steps of reducing manganese
II) oxide to a high valent compound of manganese
manganese poly-sulphide, and having interposed
between them a hard vrectifying ?lm or layer
capable of withstanding high temperatures, said
and a member of Group VI, family B of the
periodic system, and forming an electrode from
?lm comprising the electrochemical reaction
product between said ?rst and second electrodes.
the resulting compound.
4. In the process of forming an electrode for
10. A recti?er cell comprising in combination,
an electrode embodying a metal from the group
a rectifying cell the steps of intimately mixing
?nely powdered manganese and sulphur in pro
portions substantially according to their com
including manganese and barium combined with
one or more elements from Group VI, family B,
of the periodic system, and a complementary elec
bining weights so as to produce a high valent
trode including one or more of the lighter electro-‘ ' '
manganese sul?de, igniting themixture in the
absence of air, and forming an electrode from the
oxide of said ?rst mentioned metal inengagement 20
resulting compound.
with the ?rst mentioned electrode.
5. The process of forming an electrode for a
rectifying cell which includes the steps of inti
positive metals and having a surface including an
11. A recti?er cell comprising in combination,
an electrode embodying a metal from the group
mately mixing ?nely divided ‘materials substan‘-‘ including manganese and barium combined with
tially according to the formula; at least ?fty per
one or more elements from Group VI, family 13, '
~ cent of manganese oxide, not to exceedthe same
of the periodic system, and a complementary elec
amount of a current conducting metal, and a
trode including one or moremetals from the group
member of Group'VI, family B of‘ the periodic including magnesium, aluminum and manganese
system in quantity at least sumcient to combine and alloys of the same and having a surface ?lm
30 completely with the other materials, effecting a
chemical reaction between the materials, and
forming an electrode of the resulting material.
including an oxide of the first mentioned metal. 30
12. A recti?er cell comprising in combination,
an electrode embodying a metal from the group
6. In a recti?er cell, the combination of an ' including manganese and barium combined with
one or more elements from the group including
electronegative element which predominately in
35 cludes the higher valence sulphide compounds of
manganese, and an electropositive element hav
ing a contacting surface including a manganese
compound capable of being converted into a low
valence sulphide compound of ‘manganese.
7. The process of forming an ‘electronegative
element for a rectifying cell which includes the
step of transforming an intimate mixture of
manganese monoxide and copper into the sul-v
phides thereof by ignition in the presence of a
quantity of sulphur in excess of that quantity
necessary to produce the lowest valence sulphides.
8. The process of forming an electrode for a
rectifying cell which includes the step of sub‘
iecting an electropositive metallic member of a
~50 character capable of receiving a surface ?lm of
sulphur, selenium and telluriurn in such propor 35
tions as to form a polyvalent compound thereof,
and a complementary electrode having a surface
which includes an oxide of said metal.
13. Arecti?er cell comprising in combination,
an electrode embodying a metal from the group 40
including manganese and barium combined with
one or more elements from the group including
sulphur, selenium and tellurium in such propor
tions as to form a polyvalent compound thereof,
and a complementary electrode including one or 45
more metals from the group including mag
nesium, aluminum and manganese and alloys of
the same and having a surface ?lm including an
oxide of the?rst mentioned'metal.
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