Aug. 10, 1937. F. M.

CLARK 2,089,683
ELECTRICAL CAPACTOR
Filed Nov. 30, 1934

Fig. 5. hig 4.
Blotting paper

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hank M. Clark,
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 Patented Aug. 10, 1937, 2,089,683

UNITED STATES PATENT OFFICE

2,089,683
ELECTRICA CAPACTOR
Frank M. Clark, Pittsfield, Mass, assignor to
General Electric Company, a corporation of
New York A

Application November 30, 1934, Serial No. 755,425

13 Claims, (C. 15-315)
The present invention is concerned with elec filled with the acid during the fabrication of the
trical capacitors or condensers and its object is capacitor. In the drawing two spacers 3 and 3
have been shown, the capacitor of Figs. 1 and 2
to improve the operating efficiency and reliabil being of the rolled type and it being desired that
ity of such devices.
It has been suggested heretofore to employ, as the spacer should be present in all cases between
relatively dilute aqueous solutions, acids and adjacent turns of the wound-up strip armatures.
salts in combination in electrolytic devices. The The spacers 3, 3’ which preferably consist
advantages of using the acid itself in concen of cheesecloth should be free from chlorides,
and may have a thickness between the limits
trated form as the solvent and suspending agent of about .0025 and .0055 inch, although this thick 9.
for a salt, heretofore have not been appreciated, ness is not critical. The thread count can be
nor have such combinations been used in thin varied over a wide range. I have found cheese
layers. or films between the armatures of capac cloth having, a thread count of 40 x 44 to be sat
itOrS. isfactory. A paper spacer having a porosity
In accordance with my invention the spaces similar to that of blotting paper may be used as 15
5 between the armatures of capacitors (which may
comprise closely spaced metal foils separated by shown at 4, Fig. 3. The thickness of the paper
a layer of porous material) are filled with a Con may be between the limits of .00075 and .001 inch.
centrated water-soluble organic acid containing The spacer may be perforated, that is, provided
in Solution or suspension a finely-divided solid with closely placed holes as shown at 5, Fig. 4.
material of good dielectric property which func It
20 tions has been determined that paper containing
one m. m. diameter perforations spaced 1 to 2
as an ionogen.
My invention will be more fully explained in m.m. apart is satisfactory. A spacer is not an ab
connection. With the accompanying drawing in Solutely essential part of the present invention and
which Fig. 1 is a perspective view of a completed may be omitted, the composition being spread 25
On the electrodes. Its use, however, is recome
25 capacitor; Fig. 2 illustrates a roll type of ca mended.
pacitor shown partly unrolled; and Figs. 3 and 4 . .
are diagrammatic representations of stacked ca oxideBefore the electrodes are assembled a film of
pacitors. w
may, and preferably should, be produced
While my invention has been described with thereon, preferably by electrolytic treatment in
accordance with well understood practice. While
30 particular reference to an impregnating mix the electrodes commonly consist of lengths of
ture containing acetic acid, the finely divided thin metal foil as shown in Fig. 2, it is permis
solid being ammonium borate, various other con sible
centrated organic acids and other resistance at 6, to use plates which may be flat, as indicated
7, in Fig. 3, or of corrugated, or other form.
modifying agents may be used. Propionic, The Spacer may be perforated as shown in Fig. 4.
35 acrylic, lactic, and butyric acids are examples of
A suitable electrolyte is employed for the pre
other aliphatic acids which are suitable for use liminary
in accordance with my invention. Such acids electrolytic oxidation treatment. For
are straight chain aliphatic acids having a max example, a Solution made by dissolving 80 parts
imum of four carbon atoms in the molecule. of boric acid and 2 parts of borax by weight in
40 Aromatic or cyclic type acids, such as cresylic 1000 parts of distilled water is suitable. These ,
acid (cresol) and carbolic acid (phenol) likewise constituents may be varied considerably without
may be used. The following salts may be used Seriously affecting the results. The oxidation
in combination with an organic acid: ammon treatment can be carried out entirely in one con
ium acid borate, sodium borate, sodium potas tainer, or the electrode material when consisting 45
45 sium tartrate (Rochelle salt), ammonium phos of long strips of foil, can be traversed successive
phate, sodium acetate, and ammonium acetate. ly through a series of electrolytic baths in differ
Referring to the drawing, the capacitor illus ent containers, the baths increasing in concen
trated by Fig. 2 comprises armatures or elec tration as the foil progresses from the first to
trodes , 2 of suitable metal, for example, alumi the last bath.
50 num, tantalum, or magnesium. The capacitor Preferably the electrolyte is heated during th
. forming
armatures ordinarily consist of aluminum foil process, a temperature of about 90 to 95
having a thickness of about .001 to .003 inch. C. being suitable. The voltage at which the elec
Between them is located a porous spacer 3 of trolytic treatment is carried out preferably should
be equal to or not more than about ten per cent
imbibitory material, such, for example, as cheese greater than the voltage at which the completed 55
cloth or porous paper, which is impregnated or
 2 2,089,683
capacitor is intended to be operated. For capac When anhydrous impregnating material is de
itors desired for alternating current operation sired the mixture of acid and resistance-modify
the treatment of the foil, plates, or other form of ing agent may be heated to about 100 C. While
electrodes, may be carried out either with alter stirring to drive off water. Ordinarily heating
5 nating or direct current. Preferably direct cur from 100 to 110° C. for at least fifteen minutes 5
rent is used, 'employing a voltage equal to or will produce an anhydrous condition. Preferably
slightly exceeding the peak of the alternating the described combination of acetic acid and the
current voltage at which the capacitors are salt is a turbid slowly settling suspension, some
intended to be operated. Aluminum foil in of the salt being dissolved in the acid.
10 tended for operation in the completed capacitor When the condenser assembly is to be in IC
with 110 volt alternating current may be oxidized pregnated either one of two alternative methods
by direct current treatment, the foil being made may be used. In accordance with one method,
the anode and a Woltage of 160 volts being applied the condenser assembly including the porous
between anode and cathode. Spacer is innersed in the electrolyte such as
15 The rate of the passage of the foil through the above prepared. During the impregnation the
electrolyte and the amount of current depends electrolyte may be heated to temperatures above
upon the conditions as Well understood. Ordi room temperature and as high as 100° C. After
narily a foil when the oxidizing treatment has about one hour immersion in the impregnating
been completed should not pass more than one liquid at this temperature, the capacitor is sub
20 ampere per square foot at 160 volts, direct cur jected for about one hour at the same tempera
rent, while immersed in electrolyte as above de ture while in the liquid to intermittently or con
scribed and at a temperature of 95° C. After the tinuously applied voltage. The voltage may be
foll has been oxidized, it may be dried and stored applied for about five seconds and then discon
in a dry environment until it is desired for use. " tinued for about five seconds. The object of this
25 The capacitors are assembled in accordance treatment is to 'cure' any defective or unoxidized
with well understood practice; for example, by Spots on the aluminum as may occur occasionally
rolling (Fig. 2), or stacking (Figs. 3 and 4), the at edges or elsewhere. It is desirable that this
oxidized foil and the spacer being in proper rela curing treatment be carried out at a temperature
tion. While it is necessary in capacitors in at least about as high as 60 to 75° C. but not
30 tended for alternating current use to have both higher than 100° C. -
armatures filmed or oxidized, it is sufficient when While alternating current application of volt
the capacitors are intended for direct current age is preferred at this stage, direct current ap
use to have but one foil or armature (the anode) plication may be used. For example, in the case
provided with an oxide film. The cathode need . of a condenser rated for operation at 10 volts
35 not be oxidized and in fact may consist of any alternating current, the curing treatment may
metal inert with respect to the electrolyte. Elec be carried out at 160 volts direct current. When
trical connections are made to the respective employing direct current it is necessary to reverse
armatures in accordance with well understood the polarity at intervals, say once each twenty
practice as by folding back one end of each foil seconds. When alternating current, application
40 and attaching to it strips 8 and 9 of desired width, is employed, then the curing treatment may be
for example, about, one-half inch, to make elec carried out at the voltage at which the capacitor
trical connection to exterior terminals. is intended to be operated, that is, its rated volt
When acetic acid is used as the impregnating age. When direct current voltage is used, it
material, it is used preferably in the anhydrous should equal in value the peak alternating cur
45 state (glacial acetic acid); although the presence rent Operating voltage. During the immersion
of a small amount of water is not excluded in all and voltage treatment period, the acid impreg
cases. In a copending application, Serial No. nating mixture when containing suspended crys
755,428 filled Nov.30, 1934, claims have been made tals, is stirred sufficiently to maintain a Sub
on electric capacitors containing a water-soluble, stantially homogeneous suspension of the crys
50 organic acid, such as acetic acid, and a substan tals. 50
tial amount (up to about 15 per cent) of water. In accordance with the second method of im
When it is desired to prepare ammonium acid pregnation, the capacitor assembly, while in a
borate as a preliminary step in the fabrication of dry state is impregnated with a concentrated
the capacitor, then about 250 grams of boric acid water solution of the Salt (for example, am
55 are triturated in 67 c. c. of concentrated aqueous monium acid borate) and thereupon the water is 55
ammonium hydroxide containing about 29% evaporated, leaving crystals of the salt in the
NH3, thereby forming fine crystals of the borate. fabric, or paper, between the capacitor arma
The trituration of this mixture is continued for tures. The dried capacitor assembly then is
a Sufficient period of time to cause such fineness
60 of subdivision of the crystalline product immersed acid. In
in the chosen concentrated organic
this case the acid likewise may be sat 30
(NHHB4O7) that when it is added to the acetic urated with the salt and may contain an excess
acid, or whatever other organic acid is used, a or undissolved portion of such salt in finely
slow settling, freely flowing, milky suspension divided form.
results. The ammonium borate may be formed A voltage treatment similar to the first de
65 by suspending boric acid in proper amount in the Scribed method of capacitor impregnation then 35
acetic acid and passing in gaseous ammonia while is applied. Upon completion of the voltage “cur
stirring. Chloride-free ammonium borate of ing' treatment the capacitors may and preferably
commercial source may be used. About 1 gram should be given a further soak in the impreg
molecule of the borate may be suspended in nating mixture for a period from 4 to 1 hour.
to approximately 3.7 gram molecules of acetic acid,
but on the other hand the amount of salt may be This further treatment insures stability in elec
trical characteristics.
reduced to the amount going wholly into solu After the capacitor has been impregnated it is
tion. Such a mixture contains free or uncon cooled to room temperature while still being
bined acid, regardless of whether or not an undis immersed in the acid impregnant. When the
75 - solved excess of salt is present. impregnation has been completed each capacitor
 2,089,688 3.
assembly has its voids filled with the acid impreg ticular capacitor assembly comprising Oxidized
nant.
aluminum foil and a cheesecloth or paper spacer,
After having been cooled the capacitors are I do not desire it to be understood as being limited
sealed in a container 0, Fig. 1, which may consist to What
this particular structure.
I claim as new and desire to secure by
5 of aluminum, and which is suitably insulated Letters Patent of the United States is: -
from the filling liquid. This may be accom 1. An electric capacitor comprising the com
plished by crimping on an aluminum top pro
vided with insulating bushings 2 and 3. A bination of film-forming capacitor armatures, a
porous spacer therebetween, and an impregnant
breather vent 4 to avoid excess internal pres substantially entirely of water-soluble O
10 sure may be provided. However, the treated con consisting
organic acid in an uncombined state and a resist
denser assembly may be totally surrounded in its ance-modifying agent, and having electrical re
container by wax which preferably should have sistivity less than 1x106 ohms per centimeter
a melting point between about 75 to 100° C., and cube.
should be unaffected chemically by the acetic 2. An electric capacitor comprising the combi 5
15 acid, or other liquid filler. A second topping nation of film-forming capacitor armatures, a
layer of Sealing compound may be applied con porous spacer therebetween, an electrolyte com
Sisting, for example, of a high melting asphalt.
prising a substantially anhydrous, water-soluble
External contacts, or terminals 5 and 6 are liquid
provided as usual. organic acid and a salt filling voids in said 20
20. In accordance with an alternative method of ity less said
spacer,
than
electrolyte having electrical resistiv
1X106 ohms per centimeter cube.
sealing the capacitor elements, after impregna 3. An electric capacitor comprising the combi
tion and voltage treatment, they are removed at
approximately 50° C. and dipped into a wax or nation of film-forming capacitor armatures, a
compound which melts at a temperature approx porous spacer therebetween, and concentrated
25
25 imating 75 to 100° C. and is not soluble in the acetic acid containing a salt in Suspension filling
impregnating liquid. By this treatment the voids in said spacer. - .
4. An electric capacitor comprising the combi- .
. Capacitor assembly is encased in Wax or com nation
pound. The assembly so encased then may be porous of film-forming capacitor armatures; a
spacer therebetween, and consisting of 30
put either singly or in groups into a container substantially
30 which is finally filled with the same wax or com in said spacer,anhydrous acetic acid filling voids.
said acid containing an exceSS of
pound and if desired given a final high melting
top Seal. salt.
Capacitors prepared in accordance with my 5. An electric capacitor comprising the combi
invention possess both high capacity and low nation of film-forming capacitor armatures, a
porous spacer therebetween, and a void-filling
35 power factor. The capacity of such capacitors liquid
or condensers is higher than that of present composition comprising ammonium borate
commercial forms of electrolytic capacitors. For and a chemical excess of acetic acid.
6. An electric device comprising the combina
example, at 110 volt alternating current Service
such electrolytic capacitors require about 8% to tion of closely adjacent armatures, at least one 40
40 9 square inches of armature surface for one of which is film-forming, a porous spacer there
microfarad capacity, whereas the herein de between, and an electrolyte consisting substan
scribed capacitors require from 7 to 7A square tially wholly of a water-soluble organic acid and
a resistance-reducing solid material filling voids
inches of armature Surface of one microfarad in said spacer, said electrolyte having electrical
capacity. The power factor of the acetic acid 45
45 capacitor at room temperature is as low as 3 to resistivity less than 1x106 ohms per centimeter
5% for 110 volt Service or even lower. No dis cube, the acid in said electrolyte being present
continuity in electrical characteristics is ob in 7.Substantial excess in an uncombined state.
An electric capacitor comprising the.combi
served over a wide range of temperature even nation of film-forming armatures, a Spacer there
if the range of temperature should include the 50
50 freezing point of the organic acid employed ins between and concentrated, uncombined crotonic
such capacitors. For example, the freezing point acid permeating said spacer, said acid being asso
ciated with a resistance-modifying material.
of acetic acid is 17° C. and both the power factor
and capacity show only a very slight temperature 8. An electric capacitor comprising the combi
variation over a range of minus 40° C. to plus nation of aluminum armatures, a porous paper
55 100° C. . spacer therebetween and concentrated uncom 55
While acetic acid has been particularly em bined crotonic acid permeating voids in Said
spacer, said acid containing sufficient resistance
phasized as suitable as a "mother liquid' for the
purposes of my invention, various other liquid modifying material to cause the resistivity there
acids of suitable resistivity (preferably below of to be less than 1x10 ohms per centimeter 60
60 1x108 ohms per centimeter cube) may be used. cube.
Chemical, derivatives of acids may be used as 9. An electrolyte Suitable for use With film
represented by lactic acid, hydroxy acrylic acid, forming electrodes consisting of the combination
crotonic acid, ethylene lactic acid and dihydroxy of a concentrated, substantially anhydrous ali
propionic acid. . phatic acid having a maximum of four carbon
65 Other examples are isobutyric acid, diethyl atoms in the molecule and a resistance-modify
acetic acid, iso-amyl acetic acid and iso-butyl ing salt.
acetic acid. In general all these acids are 10. An electrolyte suitable for use with film
characterized by water-solubility in varying de forming electrodes consisting of anhydrous acetic
gree. The electrical resistivity of the acid mix acid and a finely-divided salt. 70
70 ture should be less than 1.x 106 ohms per ceni 11. An electrolyte suitable for use with film
timeter cube. While I do not wish to have my
invention limited by any particular theory of forming electrodes consisting of the combination
of a concentrated, substantially anhydrous acid
operation, I may say that I believe theWhile
acid im
for . of the group consisting of acetic, water-soluble
pregnant functions as an electrolyte. acetic acid derivatives, propionic, butyric, acrylic,
75 purposes of illustration I have referred to a par
 4. 2,089,683
hydroxy acrylic, crotonic, lactic, ethylene lactic, 13. An electric capacitor comprising the CO
cresylic and carbolic acids and a resistance-modibination of film-forming armatures, a porous
fying salt. spacer therebetween and an impregnant consist
12. An electrolyte Suitable for use with film
forming electrodes consisting of the combination ing substantially of water-soluble, aliphatic acid
of a concentrated, substantially anhydrous wa in an uncombined state and a resistance-modi
ter-soluble organic acid and a Salt of the group fying agent, said impregnant having electrical
consisting of ammonium acid borate, sodium resistivity less than 1x106 ohms per centimeter
borate, Sodium-potassium tartrate, annonium cube.
10 phosphate, sodium acetate, and ammonium ace FRANK. M. CARK, O
tate.