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Патент USA US2106753

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Patented Feb. 1, 1938
2,166,753
UNITED STATES PATENT OFFICE
1
2,106.15:
nuzc'mro mscnnacr: TUBE on LAMP
Anton Ieder'er. Vienna, Austria; Catherine Dan
zer and General Conrad Randa, executors of
said Anton Lederer, deceased, assignors to
Ernest Anton Lederer, Glen Ridge, N. J.
'
No Drawing. Application January 14, 1931, Se
rial No. 508,801. Benewed May 15, 1936. In
Austria June 27, 1930
26 Claims.
This invention relates to electric discharge
tubes or lamps. For obtaining particular light
phenomena from electric gaseous glow discharge
(Cl. 250-275)
These advantageous properties of the coating
are obtainable by sumcient heating in a particu
lar manner with the simultaneous removal of the
or are discharge it’ is necessary to coat one or
5 more electrodes of a gas-?lled discharge tube or
heating products and thus leading to a de?nite
stable final product. This latter, after comple
lamp with electron-emitting substances in order
tion of the heating or "activation” process, prob
ably contains in-all cases metallic barium or at
least barium sub-oxide besides, and in some cases
to obtain the desired luminous effects at a rela
tively low temperature but in contrast to tubes
for wireless 'telegraphy and telephony an ioniza
10 tion taking place of the gases and/or vapours
contained in the vessel. As a. matter of course,
other emitting oxides which may have been added
or the decomposition products thereof, or the 10
equivalent elements or compounds of the group
the substances employed must be heated by suit
of ‘the alkaline earth metals.
able means in order to render them effective.
ments as compared to the known methods and
If barium peroxide is used alone, one obtains
after treatment according to the present inven
tion a distinct departure from the white colour
electrodes of the high vacuum art, because in the
of the peroxides of the alkaline earth metals,
Therefore, there are di?erences in the require
v
case of gas-?lled discharge tubes or lamps special
and particularly a characteristic brownish col
precautions must be taken, which insure prompt,
oured product which apparently consists of bar- '
reliable and uniform operation. In this connec
.,-0 tion it is inter alia an important point that
the electron-emissive substances applied in the
ium metal and at least barium suboxide. This
colouration seems to be an essential condition in
order to obtain a refractory coating resistant to
tube or lamp are in such a condition or state
that a separation of gases or vapours therefrom
gaseous or are discharges even in cases where
is not easily possible. This is necessary for the
reason that with such luminescent discharge
tubes or lamps any contamination of the gas
and/or vapour ?lling must be avoided under all
circumstances.
Since Wehnelt’s proposals alkaline earth and
other oxide coatings for electron-emitting hot
electrodes have become common knowledge. ‘It
has furthermore been proposed to employ barium
peroxide and by separation of one half of its
oxygen to convert it to barium oxide.
The present invention is based on the knowl
edge that it is not su?icient to use these and
similar peroxides as such, but that it is necessary
to convert them into a stable state, if such hot
electrodes and particularly cathodes‘ are to be
40 used in gaseous discharge or luminescent tubes.
If these oxides. particu‘ariy the barium peroxide
vor barium oxide, are converted into stable con
dition, there is little danger of a further con
tamination of the gas ?lling, a feature which,
.15 with the gas-tubes referred to, is of great im
portance. This stable form or state is different
from the customary form used with high vacuum
electron tubes. It is true that there are certain
oxides of other materials which are also refrac
tory and which do not give off oxygen at all or
only with difficulty but they do not possess the
favourable property of a high emission of elec
trons as do those substances produced from
barium peroxide as original material and treated
according to the present invention.
other permanent or stable oxides had beenorig
inally included. It is not su?icient for gas
?lled discharge or luminescent tubes to use ordi 25
nary oxide coatings which are brought to lumi
nescence chie?y by an arc discharge, but it is
necessary that at least the darker coloured bar-.
ium- oxide or barium metal component must be
distinctly visible and noticeable, and by this char 30
acteristic this coating is believed to be distinct
from the customarily applied white coatings.
The reaction product obtained which, in all
probability, contains metallic barium, probably
also contains barium suboxide, as such is de 35
scribed as a brown substance in a treatise "Sur
la Preparation du Baryum" by M. A. Guntz
Annales de Chimie et de Physique 1907, (8) (10),
P. 437 11.).
It is possible that the brownish coating sub 40
stance above set forth may be usefully employed
for cathodes of tubes for wireless telegraphy and
telephony.
’
.
The product above set forth has the property
of reducing to the metal certain oxides capable 45
of participating in the emission of electrons.
Thus, for instance, said product converts thorium
oxide into highly emitting thorium metal which,
being not generally subjected to more than about
1000° C. at the operation temperature of the dis 50
charge tubes, can form a heat resisting and ad
herent coating of the electrode surface.
Zirconium oxide. which is not reduced by
barium, remains unchanged. However, inasmuch
as zirconium oxide which, as is known, is also an 55
2
2,106,768
emitting substance, does not give of! oxygen and
therefore does not cause any contamination, it
cannot become undesirable for the rare gas or
gases contained in the tube.
In carrying out the invention, care should be
taken that the formation and pyrogenous de
velopment of the sub-oxide of barium and/or
barium metal, namely of the substance charac
terized above takes place through its colour
10
change.
-
‘
For tubes for wireless telegraphy and teleph
ony it has been proposed to introduce into the
tube itself thev metallic electron emitting sub
stances and then to cause them to deposit on the
15 metal parts. However, for the purpose of the
present invention such process cannot be em
ployed, because not only are the required elec
trode or electrodes thereby covered with ‘the
metallic deposit but also the whole of the interior
2(1 surfaces of the tube.
In order to produce suitable coatings vwhich‘
at which some of the oxygen of the barium
peroxide escapes. By a further increase of tem
perature to probably about 1000° C. the remaining
oxygen may at least in part be removed. Finally,
the temperature of the electrode or the electrodes
is increased to nearly the melting temperature of
nickel. It will be observed that the originally
white coating becomes darker and apparently be
gins to ?ow. The heating should be then stopped.
- A coating of a dark brown colour will be left on
the electrode or electrodes which coating does not
give off any further as which coating is the de
sired one and is stable even in a gaseous discharge
or arc.
After the tube is furnished with the ?lling gas, 15
for instance, neon at a pressure of about 1 to 10
mm. mercury .column, the necessary operating
“voltage may be applied depending upon the con
struction or operating constants of the tube,
whereupon, when the hot electrodes are sum 20
ciently heated the gaseous or are discharge sets
remain stable during a long period of gaseous
in accompanied by an‘ intense light phenomenon.
or are discharges, for instance of hundreds of
bearing in- mind the aforesaid ?nal form of the
coating, the aim is to select a condition 0;‘ the
In order to ensure a reliable and durable ad
herence of the coating to the carrier it is ad
visable in some cases to add to the electron emit
ting main compound a small quantity of a highly
infusible metal or of a decomposable compound
basic or original materials such as to insure a
. thereof, whereby to provide a better adherence.
stable solid and durable coating. If, therefore,
the peroxides employed are applied alone or as
a mixture, they preferably have a certain particle
For instance, for such purpose with the above
hours duration, it is bene?cial to utilize basic
material of suitable form and'properties. Always
mentioned 3 parts of barium peroxide, 0.2 part 80
of nickel oxide may be admixed. Other sub
size, namely, the size of the particles should on . stances may be incorporated into the basic sub
an average be 0.004 mm. diameter or even less,
this being an order of size where Brownian molec
35 ular movement‘ of the suspended particles can
set in.
stance without damaging the emission effect
which in some cases'may thereby be even favour-'
ably influenced.
Y
.
35
_
Such ?ne division of the peroxides of barium,
Some ?nely divided thorium oxide may be ad
mixed with the basic substance, namely, in the
strontium or calcium, with which if desired may
be mixed also other emitting oxides having cer
4.0 tain qualities, as aforementioned, may be achieved
above example, barium oxide. Thus an equal
quantity or preferably one-third of the quantity
(of the peroxide used) of thorium oxide may be
During all these operations care should be taken
scribed. It will be observed that by the presumed
formation of barium metal and/or barium sub
by‘ grinding and, if desired, subsequent levigation.
to work as far as possible under exclusion of air,
45
.50
;
"
vcarbon dioxide, water and water vapour.
The following is an example of carrying out to
good effect the process of the present,‘ invention,
using barium peroxide as the original or basic
material. The barium peroxide is ?nely ground,
conveniently in wet condition, it being‘ advan
tageous to use amylacetate as a suspension liquid.
To insure ?rm adherence of such a suspensionon
thev emitting body, such as a nickel tube adapted
to be indirectly heated, a small quantity of a solu
tion of colloidin maybe added. For instance,
"three parts barium peroxide, 20 parts amylase
tate and 1/2 part of a 10% solution of colloidin
in acetone are well ground in such a way that the
particle size is on an average below 0.004 mm.
diameter, which may be achieved by very slow
60 grinding and subsequent ?ltering through a suit
able ?lter. If this suspension is ?nely sprayed on
to the electrode or electrodes, care being taken
' that one layer is dry before the next one is ap
plied, useful layers of several hundredths to one
65 tenth mm. thickness may readily be obtained.
After the electrode or the electrodes thus manu
factured is or are built in into the tube and the
added and then one may proceed as above de
oxide, 2. reduction of the thorium oxide also takes
place, the latter being reduced to thorium metal
which has a favourable electron emission, as is
known, and allows of a relatively high heating of
the coating.
'
'
The coating which was originally white and‘
subsequently becomes of a dark brown colour, 60
regarding the formation of barium metal and/or
barium suboxide, reduces the thorium oxide pres
ent to thorium metal and by further heating and
decomposition of the barium oxide the released
barium metal alloys with the thorium metal 55
forming a good, electron emitting, ?rmly ad
herent layer of almost black colour.
Other emitting oxides also may be admixed
with the basic metal but care should be taken to
use only such oxides or compounds which after 60
the glowing operation are no longer decomposable
at the temperatures used.
Forginstance, zir
conium oxide may be used, which substance re
mains in the coating unaltered. The amount of
such addition may be approximately equal to
the amount of the addition of thorium oxide.
Also cerium oxide, when added in small quan
latter is subjected to the usual preliminary heat
tities seems to influence the gaseous or arc dis
ing or baking at a temperature of vabout 400°
charge favourably, although the amount of the
addition may be very small. A few tenths of'a 70
part of cerium oxide are su?icient for admixing.
whilst being exhausted by a good vacuum pump,
preferably to a high vacuum, the activation of the
coating may be caused to set in, ‘and it will be ‘ with 3 parts of the original peroxide in order to
observed that when carefully further heating,
obtain favourable effects.
next to about from 600° to 800° C. a gaseous dis
It is evident that many other variations are
charge will take place, this being the temperature
possible, if the active oxides as indicated by 75
3 .
2,108,763
Wehnelt are considered and used, in which con
nection as a matter of course calcium and stron
tium and their compounds are to be taken into
consideration. Such active oxides are enu
merated in Wehnelt’s treatise: "Ueber den Aus
tritt negativer Ionen aus gliihenden Metallver
bindungen und damit zusammenhangende Ers
cheinungen.” (The Exit (Emission) of Ions from
Glowing Metal Compounds and Phenomena Con
10 nected Therewith.) Annalen d. Physik, IV. Folge,
1904, No. 8, p. 429.
The emitting substances described can also be
used on cathodes of tubes employed for wireless
telegraphy and telephony.
15
I claim:
1. Steps in the production of an electric illu
' cessively increased to nearly the melting point of
nickel.
-
5. A method for the production of an electric
discharge tube having at least two electrodes of
which at least one is adapted to emit electrons
when heated, which comprises providing said
electron emitting electrode 'with a coating’ of
least containing peroxide of an alkaline earth
metal, mounting said-electrode in a tube, exhaust
ing said tube to a relatively high vacuum, subject
ing said tube to preliminary heating while the
same is being exhausted, and then, whilst main
taining the vacuum, subjecting the emitting elec
trode to heat treatments at temperatures succes
sively increased to nearly the melting point of 15
nickel.
,
minating lamp having at least two electrodes of
6. A method for the production of an electric
which at least one is adapted to emit electrons
when heated, and a pure ?lling of at least a
discharge tube having at least-two electrodes of
20 monatomic or rare gas which consists in coating
said electron emitting electrode with a layer at
least containing barium peroxide, mounting the
electrodes in the vitreous bulb of the lamp, evac
uating said bulb, heating said electron emitting
25 electrode for several minutes at approximately
from 600° to 800° C., and whilst still maintaining
the vacuum heating the electron emitting elec
trode for a relatively short time to approximately
1200° C. so that the coating assumes essentially‘
30 a dark brown colour, and ?nally introducing the
rare or monatomic gas.
_
2. A method for the production of an electric
discharge tube having at least two electrodes of
which at least one is adapted to emit electrons
which at -least one is adapted to emit electrons
'when heated, which comprises providing said 20
electron emitting electrode with a coating at
least containing barium peroxide, mounting said
electrode in a tube, exhausting said tube to a
relatively high vacuum, subjecting said tube to
preliminary heating while the same is being ex 25
hausted, whilst maintaining the vacuum subject
ing the emitting electrode to heat treatments at
temperatures successively increased to remove
oxygen from the peroxide, and then, whilst still
maintaining the vacuum, subjecting the emitting 30
electrode to a heat treatment at a temperature
nearly the melting point of nickel.
'
'7. A method for the production of an electric
discharge tube having at least two electrodes of
when heated, which comprises providing said which at least one is adapted to emit electrons 35
electron emitting electrode with a coating at least when heated, which comprises providing said
containing barium peroxide, mounting said eiec- _ electron emitting electrode with a coating at
least containing barium peroxide, mounting said
tively high vacuum, subjecting said tube to pre-' electrode in a tube, exhausting said tube to a
relatively high vacuum, subjecting said tube to 40
40 liminary heating while the same is being ex
preliminary heating of about 400° C. while the
hausted, and then, whilst maintaining the vac
uum, subjecting the emitting electrode to heat same is being exhausted, whilst maintaining the
treatments at temperatures successively increased vacuum subjecting the emitting electrode to two
successive heat treatments one at a temperature
to nearly the melting temperature of nickel.
3. A method for the production of an electric of about 600° C. to 800° C. and the other at 45
discharge tube having at least two electrodes-of about 1000° C. to remove oxygen from the coat
which at least one is adapted to emit electrons ing, and then, whilst still maintaining the vacu
when' heated, which comprises providing said um, subjecting the emitting electrode to a heat
trode in a tube, exhausting said tube to a rela
electron emitting electrode with a coating at least treatment at a temperature near the melting
containing barium peroxide the average size of _ point of nickel.
50
8. Steps in the production of an electric dis
the particles of which is su?iciently small that
it exhibits Brownian movements, mounting said charge tube having at least two electrodes, of
emitting electrode in a tube, exhausting said tube which at least one is adapted to emit electrons
to a relatively high vacuum, subjecting said tube when heated, which consist in coating said elec
to preliminary heating while the same is being tron emitting electrode with a layer at least 55
containing barium peroxide, mounting the elec
exhausted, and then, whilst maintaining the vac
uum, subjecting the emitting electrode to heat trodes in a tube, heating said electrode in a main
treatments at temperatures successively in_
tained vacuum for a relatively long time at a
creased to nearly the melting temperature of
moderate temperature su?icient to-remove oxy
gen slowly from the barium peroxide, and then, 60
whilst maintaining the vacuum, heating the elec
trodes for relatively short periods at tempera
tures su?iciently increased that further oxygen
will be removed from the coating, the ?nal heat
ing being at nearly the melting point of nickel.
65
CO nickel.
4. A method for the production of an electric
discharge tube having at least two electrodes of
which at least one is adapted to emit electrons
when heated, which comprises providing said
electron emitting electrode with a coating at
least containing barium peroxide, mounting said
9. A process of making a thermionic active
electrode'in a tube, exhausting said tube to a
electrode which comprises supplying a coating
containing barium peroxide to an electrode, said
peroxide being employed in a ?nely ground con
dition suspended in amyl acetate, said amyl ace
tate having added thereto a solution of colloidin,
the particles of barium peroxide being on the
relatively high vacuum, subjecting said tube to
preliminary heating while the same is being ex
hausted, subjecting the emitting electrode, while
maintaining the vacuum, to further heat treat
ment at about 600° to 800° C. to remove oxygen
from the peroxide, and then, whilst still main
taining the vacuum, subjecting the emitting elec
trode to heat treatments at temperatures suc
average below 0.004 mm. in diameter, the result
ing suspension being sprayed on the surface of
the electrode, applying it in layers and allow 75
4
9,106,758
ing each layer to dry before applying the next
until the coating is of sufiicient thickness, there
upon building the electrode into a vessel, evacuat
in a tube, exhausting said tube to a relatively high
ing the latter to a high vacuum while heating
the electrode to a temperature approximating
400° C., thereupon, whilst retaining the vacuum,
raising the temperature progressively until oxy
gen escapes from the peroxide and ?nally, whilst
still retaining the vacuum, increasing the tem
10 perature until the coating assumes a brownish
vacuum, subjecting said tube to preliminary heat
ing while the same is being exhausted, and then,
whilst maintaining the vacuum, subjecting the
emitting electrode to heat treatments at tem
peratures successively increased at least to nearly
the melting point of nickel,
19. An electric dischargedevioe having at least
color.
-
' 10. An electric discharge device having atlleast
two electrodes of which at least one is adapted
to emit electrons when heated, said emitting elec
15 trode comprising a carrier adapted to be heated,
and an emitter formed at least from barium per
oxide and applied to said carrier and activated
in accordance with the process set, forth in
claim 2.
11. An electric discharge device having at least
two electrodes of which at least one is adapted to
emit electrons when heated, said emitting elec
- trode comprising a carrier adapted to be heated,
and an emitter formed at least from barium per
25 oxide and applied‘ to said carrier and acti'. ated in
accordance with the process set forth in claim 3.
electron emitting electrode with a coating con
taining barium peroxide, mounting said electrode
two electrodes of which at least one is adapted
to emit electrons when heated, said emitting elec
trode comprising a carrier adapted to be heated,
and an emitter formed at least from barium per
oxide and applied to said carrier and activated in 15
accordance with the process set forth in claim 18.
20. A method for the production of an elec
tric discharge device having at least two electrodes
of which at least one is adapted to emit electrons
when heated, which comprises providing said elec 20
tron emitting electrode with successive coatings
containing barium peroxide in suspended form,
each coating being dried before the next coat
ing is applied, mounting said electrode in a tube,
exhausting said tube to a relatively high vacuum, 25
subjecting said tube to preliminary heating while
the same is being exhausted, and then, whilst
12. An electric discharge device having atl-least
two electrodes of which at least one is adapted
to emit electrons when heated, said emitting elec
maintaining the vacuum, subjecting the emitting
and an emitter formed at least from barium per
melting point of nickel.
electrode at least to heat treatment at'a tempera
ture at least to nearly the melting point of nickel. 30
21. A method for the production of an electric
oxide and applied to said carrier and activated in discharge device having at least two electrodes of
accordance with the process set forth in claim- 4. which at least one is adapted to emit electrons
13. An electric discharge device having at least when heated which comprises the step of coat
35 two electrodes of which at least one is adapted ing said emitting electrode with a layer contain8 35
ing barium peroxide in finely divided suspended
to emit electrons when heated, said emitting elec
trode comprising a carrier adapted to be heated, ' form, the particle size being sumciently small
that Brown's molecular movement can take place,
and an emitter formed at least from barium per
oxide and applied to said carrier and activated in mounting said electrode in a tube, exhausting said
accordance with the process set forth in claim 5. tube to a relatively high vacuum, subjecting said 40
14. An electric discharge device having at least tube to preliminary heating while the same is
two electrodes of which at least one is adapted being exhausted, and then, whilst maintaining the
vacuum, subjecting the emitting electrode to heat
to emit electrons when heated, said emitting elec
trode comprising a carrier adapted to be heated, treatment at a temperature at least to nearly
30 . trode comprising a carrier adapted to be heated,
and an emitter formed at least from barium per
oxide and applied to said carrier and activated in
accordance with the process set forth in claim 6.
15. An electric discharge device having at least
two electrodes of which at least one is adapted
to emit electrons when heated, said emitting
electrode comprising a carrier "adapted to be
heated, and an emitter formed at least from
barium peroxide and applied to said carrier and
activated in accordance with the process set forth
55 in claim 7.
16. An electric discharge device having at least
.
22. A method for the production of an electric
discharge device having at least two electrodes of
which at least one is adapted to emit electrons
when heated, which comprises providing said
electron emitting electrode with successive coat 50
ings containing barium peroxide in ?nely divided
form, the particle size being sufficiently small
that Brown's molecular movement can take place
and each coating being dried before the next coat
ing is applied, mounting said electrode in a tube, 55
exhausting said tube to a relatively high vacuum,
subjecting said tube to preliminary heating while
two electrodes of which at least one is adapted
the same is being exhausted, and then, whilst
to emit electrons when heated, said emitting elec I maintaining
the vacuum, subjecting the emitting
trode comprising a carrier adapted to be heated,
electrode to heat treatment at a temperature in 60
and an emitter formed at least from barium per
creased at least to nearly melting point of nickel.
oxide and applied to said carrier and activated
23. An electric discharge device having at least
in accordance with the process set forth in
two
electrodes of which at least one is adapted to
claim 8.
‘
17. An electric discharge device having at least
two electrodes of which at least one is adapted
to emit electrons when heated, said emitting elec
trode comprising a carrier adapted to be heated,
and an emitter formed from barium peroxide and
applied
to said carrier and activated in accord
70
ance with the process set forth in claim 9.
emit electrons when heated, said emitting elec
trode comprising a carrier adapted to be heated, 65
and an emitter formed at least from barium per
oxide and applied to said carrier and activated in
accordance with the process set forth in claim 20.
24. An electric discharge device having at least
two electrodes of which at least one is adapted to 70
emit electrons when heated, said emitting elec
18. A method for the production of an electric _ trode comprising a carrier adapted to be heated, '
discharge device having at least two electrodes and an emitter formed at least from barium per
of which at least one is adapted to emit electrons oxide and applied to said carrier and activated in
76 when heated, which comprises providing said accordance with the process set forth in claim 21. 75
2,106,753’
25. An electric discharge device having at least
two electrodes of which at least one is adapted to
emit electrons when heated, said emitting elec
trode comprising a carrier adapted to be heated,
and an emitter formed at least from barium per
oxide and applied to said carrier and activated in
accordance with the process set forth in claim 22.
26. An electric discharge device having at least
5
two electrodes of which at least one is adapted to
emit electrons when heated, said emitting elec
trode comprising a‘ carrier adapted to be heated,
and an emitter formed at least from a peroxide of
an alkaline earth metal and applied to said car
rier and activated in accordance with the process
_set forth in claim 5.
ANTON LEDERER.
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