An Improved Process for Treating Cups, Separating Partitions or Diaphragms used in Electric Batteries or Electrolytic Apparatus.
Year: 1892

page_text: Date of Application, 4th Oct., 1892
Complete Specification Left, 4th July, 1993-Accepted, 16th Sept., 1893
PROVISIONAL SPECIFICATION.
An Improved Process for Treating Cups, Separating Partitions
or Diaphragms used in Electric Batteries or Electrolytic
Apparatus.
I, ANTON JOSEPH LEHMAN of 32 Stone Street New York, in the County and
State of New York, United States of America, Gentleman, do hereby declare the
nature of this invention to be as follows:-
Previous to my invention attempts have been made to treat cups, diaphragms, and
the like, to be used in electric batteries or electrolytic apparatus so as to prevent or
retard the transmission of liquids through the pores or spaces and at the same time
still allow the current to be drawn from or passed through the cell or apparatus.
One of the methods in use is to take a porous clay cup and heat it and while hot
to partially paraffine or wax it. This method merely decreases the porosity of the
cup by filling the pores with an inert substance which in itself is not an electrolyte
and will not allow the current to pass through it. It will be seen at a glance that
if the cup be paraffined or waxed often enough it will eventually become an
absolutely non-porous cup and will not allow any current to be drawn from or
passed through it.
Still another process is to fill the pores with a jelly like substance. Now, all
jelly-like substances whether organic or inorganic owe their nature to the water
chemically retained and it is due to this water that they are jelly like. If the
water be removed either by evaporation or other means the water previously
retained will be driven off or absorbed, and if such a cup or diaphragm were used
in an electric battery with its pores filled with such a jelly like material, it after
losing its water would be as porous almost as it originally was.
Again if such a treated non-porous cup were used in an electric battery in which
any strong acid was used it in a short time, depending upon the thickness of the cup,
amount of acid, and strength of the acid, would cease to be a non-porous cup as the
affinity of strong acids for moisture of any kind is well known, the acid would
absorb or unite with the water of the jelly and the cup would be practically as
porous as it originally was, and there would now be nothing to prevent diffusion from
going on.
In yet another method porous diaphragms or cups were placed in batteries to
which the salt of a metal had been added so that the salt in solution in the excitant
surrounding the electro-negative pole of the cell would react upon the salt or base
in the solution around the electro-positive pole and thus form a precipitate in the
pores of the diaphragm.
There are two great objections to such a way of preventing diffusion or local
action, firstly, substances are added to the cell that are not necessary to the working
of said cell, thereby proportionately decreasing the life of the battery, secondly, the
diaphragms increase in resistance and if such cells are short circuited the diaphragms
in a very short time become so non-porous as to be of no use whatsoever. Such
cells may show quite a high E.M.F. after such short circuiting but the current
that can be drawn from such a cell is so slight if there is any at all as to be for all
commercial purposes where a large amount of current and low internal resistance is
necessary, valueless.
My invention relates to a process of treating cups, diaphragms, partitions and the
like so that the same will not be porous to the physical transfusion of liquids while
they will remain in such a condition that chemical action can pass through them.
The cups, etc., treated by my method have also the advantage in that they can
be treated again and again if through any cause the non-porosity of the cups, etc.

page_text: should in any way be effected, at the same time not appreciably increasing the
resistance of the cups, etc.
I will now point out some of the advantages that will be had if such a treated
cup be used in place of a porous one in an electric battery, as for instance a
salammoniac open circuit battery. Take for instance any salammoniac cell in
which the porous cup is filled with a mixture of carbon and manganese di-oxide into
which a carbon rod is inserted, which cup and contents is now placed in a solution
of ammonium chloride into which solution also a zinc rod is suspended. When such
a cell is in action some of the zinc is dissolved off, forming zinc chloride which being
soluble remains in solution while the ammonia is set free in the cup. Now, when the
zine chloride penetrates the cup and comes in contact with the ammonia, zinc hydrate
is precipitated and this precipitate increases the resistance of the cell until it
becomes so high that the cup and its contents must be replaced by a fresh one.
The zinc chloride and the ammonium chloride also unite to form the sparingly soluble
double salt of zine and ammonium chloride and these crystallize in the pores of the
cup and cause it to break and disintegrate, necessitating as before the replacing. of
the cup and its contents.
By replacing the porous cup with one of my treated or non-porous ones the zinc
chloride cannot come in contact with the ammonia and consequently no zinc hydrate
can be precipitated and as there are no pores for the double salt, ammonia and zine
chloride to crystallize in, the cup cannot crack or fall to pieces on that account.
By this change it will be seen that the efficiency and length of life of the cell is
increased.
Treated cups as made by me can also be placed in two fluid batteries when it is
desired to keep two fluids apart and by the use of such a cup, partition or diaphragm
or the like the greatest amount of useful energy can be obtained both from the zinc
and acid or whatever active material or materials are made use of.
Such cups, partition, etc., can also be placed in electrolytic apparatus when it is
desired that recombination be reduced to the minimum.
I will now describe the process I prefer in the manufacture of cups, partitions
or diaphragins to be used in electric batteries or in electrolytic cells or apparatus.
I take as a holder, a well baked porous clay cup or any similar substance and
place it in a saturated solution of barium chloride and leave it in this solution over
night. If it is desired to hasten the operation I place the cup in a boiling saturated
solution of the barium chloride and leave it in it till it has thoroughly soaked into
the cup and till no more air bubbles are seen to rise from the cup. I now gradually
allow the solution to cool until it is cool enough so that when a cup is taken out of
the solution it will remain wet, it must not be of such temperature that the cup
dries the minute it is removed from the solution. It should be about blood warm
so that when the cup is taken out of the solution it remains wet and while still wet
I immediately place it in a 10° Baumé strength of sulphuric acid, or in a saturated
solution of any soluble sulphate.
I find that about 10° Baumé sulphuric acid gives excellent results as the
resistance of the cup seems to be no more than if the cup had not been treated at
all. I find also that the precipitated barium sulphate is an amorphous non-
gelatinous one, it does not contain any combined water as in a jelly, consequently
such a cup when placed in strong acids has no water to be absorbed by the acid,
and such a treated cup retains the precipitate in a permanent condition which also
is a very good electrolyte.
I do not limit myself to the use of barium chloride for I can use if I like any of
the following as they all give excellent results.
I soak the cup in a saturated solution of barium chloride as in the previous case
and then place it in a saturated solution of oxalic acid when I get in the pores of
the cups, or partition an amorphous non-gelatinous electrolytic precipitate of
barium oxalate, or I can in place of the barium chloride use calcium chloride of such
a strength that it will easily soak into the cup and then place the soaked cup etc.,
in the saturated solution of oxalic acid as before and I in this case get an amorphous

page_text: non-gelatinous calcium oxalate, or, I can use as the first solution either hot or cold,
preferably hot, as such a hot saturated solution is much stronger, a saturated
solution of the proto-sulphate of iron and then as the second or precipitating
solution a saturated solution of the red prussiate of potash when I get a blue
amorphous non-gelatinous electrolytic precipitate of Prussian blue or I can use a
saturated solution of tungstate of soda and as the second solution any mineral acid
preferably nitric of ordinary strength.
I do not limit myself to these mentioned solutions but claim any amorphous
non-gelatinous precipitate whether precipitated in the pores or openings in any
holder as for instance a porous cup, diaphragm, or the like, or any amorphous
precipitate used as a partition through which the electric current can pass while it
prevents the transfusion of liquids and which precipitate can be made use of as a
filling, supported in any suitable way.
I do not limit myself to forming the precipitate in the pores of the supporting or
holding substance, for it may be introduced between or into such substances in
various ways which will be evident to any skilled in the art. Neither do I limit
myself to any particular form or construction of holder or support or to any
particular substance which can be precipitated or to any particular method of
precipitating the substance.
The amorphous non-gelatinous precipitate may be supported between sheets or it
may be precipitated in any porous or absorbent substance as felt, asbestos, parch-
ment, vegetable parchment, fibrite, kartavert, hard fibre or the like.
If it is not desired to use the cup at once, I dip the cup to keep it moist, until
wanted in a saturated solution either of the calcium chloride or magnesium chloride or
the cup can be wrapped up in a piece of paper or other absorbing material which
has been soaked in the deliquescent solution. In this way the cup can be shipped
to any part of the country if desired.
Dated this 4th day of October 1892.
F. W. BARKER,
Applicant's Agent.
COMPLETE SPECIFICATION.
An Improved Process for Treating Cups, Separating Partitions
or Diaphragms used in Electric Batteries or Electrolytic
Apparatus.
1, ANTON JOSEPH LEHMAN, of 32 Stone Street, New York, in the County
and State of New York, United States of America, Gentleman, do hereby
declare the nature of this invention and in what manner the same is to be
performed, to be particularly described and ascertained in and by the following
statement:—
My invention consists of a new and useful improved process for treating cups,
separating partitions or diaphragms used in electric batteries or electrolytic
apparatus and in the arts in which it is desired to have a cup, partition, or the
like to keep two liquids apart and I declare that the following is a full, clear,
and exact description which will enable others skilled in the arts to make and use
the same.
Previous to my invention, attempts have been made to treat cups, diaphragms,
and the like, to be used in electric batteries or electrolytic apparatus, so as to
prevent or retard the transmission of liquids through the pores or spaces and at
the same time still allow the current to be drawn from or passed through the cell
or apparatus.
One of the methods in use is to take a porous clay cup and heat it and while
hot to partially paraffine or wax it. This method merely decreases the porosity of
the cup by filling the pores with an inert substance which in itself is not an
electrolyte, and will not allow the current to pass through it.. It will be seen at

page_text: a glance that if the cup be paraffined or waxed often enough it will eventually
become an absolutely non-porous cup and will not allow any current to be drawn
from or passed through it.
Still another process is to fill the pores with a jelly-like substance. Now, all
jelly-like substances whether organic or inorganic, owe their nature to the water
chemically retained and it is due to this water that they are jelly-like. If the
water be removed either by evaporation or other means the water previously
retained will be driven off or absorbed, and if such cup or diaphragm were used
in an electric battery with its pores filled with such a jelly-like material, it after
losing its water would be as porous almost as it originally was.
Again if such a treated non-porous cup were used in an electric battery in
which any strong acid was used, it in a short time, depending upon the thickness
of the cup, amount of acid, and strength of the acid, would cease to be a non-
porous cup, as the affinity of strong acids for moisture of any kind is well known,
the acid would absorb or unite with the water of the jelly, and the cup would be
practically as porous as it originally was, and there would now be nothing to
prevent diffusion from going on.
In yet another method porous diaphragms or cups were placed in batteries to
which the salt of a metal had been added so that the salt in solution in the
excitant surrounding the electro-negative pole of the cell would react upon the salt
or base in the solution around the electro-positive pole and thus form a precipitate
in the pores of the diaphragm.
There are two great objections to such a way of preventing diffusion or local
action, first, substances are added to the cell that are not necessary to the working
of said cell, thereby proportionately decreasing the life of the battery; secondly,
the diaphragms increase in resistance and if such cells are short circuited the
diaphragms in a very short time become so non-porous as to be of no use whatso-
ever. Such cells may show quite a high E.M.F. after such short circuiting, but
the current that can be drawn from such a cell is so slight if there is any at all
as to be for all commercial purposes, where a large amount of current and low
internal resistance is necessary, valueless.
My invention relates to a process of treating cups diaphragms, partitions, and
the like so that the same will not be porous to the physical transfusion of liquids
while they will remain in such a condition that chemical action can pass through
them. The cups, etc., treated by my method have also the advantage in that they
can be treated again and again, if through any cause the non-porosity of the
cups, etc., should in any way be effected, at the same time not appreciably increasing
the resistance of the cups, etc.
I will now point out some of the advantages that will be had if such a treated
cup be used in place of a porous one in an electric battery, as for instance a sal
ammoniac open circuit battery. Take for instance any sal ammoniac cell in which
the porous cup is filled with a mixture of carbon and manganese di-oxide into
which a carbon rod is inserted, which cup and contents are now placed in a solution
of ammonium chloride into which solution also a zinc rod is suspended. When
such a cell is in action some of the zinc is dissolved off, forming zinc chloride
which being soluble remains in solution while the ammonia is set free in the cup.
"Now, when the zinc chloride penetrates the cup and comes in contact with the
ammonia, zinc hydrate is precipitated and this precipitate increases the resistance
of the cell until it becomes so high that the cup and its contents must be replaced
by a fresh one. The zinc chloride and the ammonium chloride also unite to form
the sparingly soluble double salt of zinc and ammonium chloride and these
crystallize in the pores of the cup and cause it to break and disintegrate, necessi-
tating as before the replacing of the cup and its contents.
By replacing the porous cup with one of my treated or non-porous ones the zinc
chloride cannot come in contact with the ammonia, and consequently no zinc hydrate
can be precipitated, and as there are no pores for the double salt, ammonia and
zinc chloride to crystallize in, the cup cannot crack or fall to pieces on that account,

page_text: By this change it will be seen that the efficiency and length of life of the cell is
increased.
Treated cups as made by me can also be placed in two fluid batteries when it is
desired to keep two fluids apart, and by the use of such a cup, partition, or
diaphragm or the like, the greatest amount of useful energy can be obtained both
from the zinc and acid or whatever active material or materials are made use of.
Such cups, partitions, etc., can also be placed in electrolytic apparatus where it
is desired that recombination be reduced to the minimum.
I will now describe the process I prefer in the manufacture of cups, partitions,
or diaphragms to be used in electric batteries or in electrolytic cells or apparatus.
I take as a holder, a well baked porous clay cup or any similar substance and
place it in a saturated solution of barium chloride and leave it in this solution over
night. If it is desired to hasten the operation I place the cup in a boiling
saturated solution of the barium chloride and leave it in it until it has thoroughly
soaked into the cup and until no more air bubbles are seen to rise from the cup.
I now gradually allow the solution to cool until it is cool enough so that when a
cup is taken out of the solution it will remain wet, it must not be of such a
temperature that the cup dries the minute it is removed from the solution. It
should be about blood warm so that when the cup is taken out of the solution it
remaius wet, and while still wet I immediately place it in a 10° Baumé strength of
sulphuric acid, or in a saturated solution of any soluble sulphate.
I find that about 10° Baumé sulphuric acid gives excellent results as the resistance
of the cup seems to be no more than if the cup had not been treated at all. I find
also that the precipitated barium sulphate is an amorphous non-gelatinous one, it
does not contain any combined water as in a jelly, consequently such a cup
when placed in strong acids has no water to be absorbed by the acid, and such a
treated cup retains the precipitate in a permanent condition which also is a very
good electrolyte.
I do not limit myself to the use of barium chloride for I can use if I like any of
the following as they all give excellent results.
I soak the cup in a saturated solution of barium chloride as in the previous case,
and then place it in a saturated solution of oxalic acid, when I get in the pores of
the cup, or partition, an amorphous non-gelatinous electrolytic precipitate of barium
oxalate, or I can in place of the barium chloride, use calcium chloride of such a
strength that it will easily soak into the cup and then place the soaked cup, etc., in
the saturated solution of oxalic acid as before, and I in this case get an amorphous
non-gelatinous calcium oxalate, or I can use as the first solution either hot or cold,
preferably hot, as such a hot saturated solution is much stronger, a saturated
solution of the proto sulphate of iron, and then as the second or
precipitating
solution, a saturated solution of the red prussiate of potash when get a blue,
amorphous non-gelatinous electrolytic precipitate of Prussian bine, or I can use a
saturated solution of tungstate of soda and as the second solution, any mineral acid
preferably nitric of ordinary strength.
I do not limit myself to these mentioned solutions, but claim any amorphous non-
gelatinous precipitate whether precipitated in the pores or openings in any holder
as for instance, a porous cup, diaphragm or the like, or any amorphous precipitate
used as a partition through which the electric current can pass while it prevents
the transfusion of liquids and which precipitate can be made use of as a filling,
supported in any suitable way.
I do not limit myself to forming the precipitate in the pores of the supporting or
holding substance, for it may be introduced between or into such substance in
various ways which will be evident to any skilled in the art.
Neither do I limit myself to any particular form of construction of holder or
support, or to any particular substance which can be precipitated, or to any
particular method of precipitating the substance.
The amorphous non-gelatinous precipitate may be supported between sheets or

page_text: it may be precipitated in any porous or absorbent substance as felt, asbestos,
parchment, vegetable parchment, fibrite, kartavert, hard fibre or the like.
(Fibrite is the trade name given to vulcanized wood fibre or pulp. It is made in
sheets and tubes and is extensively used in this country by all manufacturers of
electrical machinery and appliances. When dry it is a very good non-conductor of
electricity and is used in place of hard rubber because it is so much cheaper.
Kartavert is the trade name given to the same thing but manufactured by a
different house. This substance however becomes a very good conductor of
electricity if soaked or boiled in aqueous solutions.)
If it is not desired to use the cup at once, I dip the cup to keep it moist until
wanted in a saturated solution either of calcium chloride or magnesium chloride, or
the cup can be wrapped up in a piece of paper or other absorbing material, which
has been soaked in the deliquescent solution. In this way the cup can be shipped
to any part of the country if desired.
my
· Having now particularly described and ascertained the nature of said
invention, and in what manner the same is to be performed, I declare that what I
claim is :-
1. A separating diaphragm or partition for an electric battery or electrolytic
cell partially or wholly of an amorphous non-gelatinous precipitate, precipitated
before use in an electric battery or electrolytic cell, and which precipitate is not
dependent upon the solutions subsequently used in an electric battery or electrolytic
cell
.
2. A separating diaphragm or partition for an electric battery or electrolytic
cell, consisting of an amorphous non-gelatinous precipitate combined with a holder,
precipitated or impregnated before use in an electric battery or electrolytic cell,
which precipitate is not dependent upon the solutions subsequently used in an
electric battery or electrolytic cell, substantially as described.
3. A separating diaphragm or partition for an electric battery or electrolytic
apparatus consisting of a porous or absorbent substance impregnated with an
amorphous non-gelatinous precipitate, impregnated before use in an electric battery
or electrolytic cell,. and which precipitate is not dependent upon the solution
subsequently used in an electric battery or electrolytic cell for its treatment,
substantially as described.
4. A separating partition or diaphragm for an electric battery or electrolytic
cell consisting of a porous or absorbent substance or material, having its pores or
substance filled with an amorphous non-gelatinous precipitate, precipitated before
use in an electric battery or electrolytic cell, which precipitate is not dependent
upon the solution subsequently used in an electric battery or electrolytic cell for its
treatment, substantially as described.
5. A separating diaphragm or partition for an electric battery or electrolytic
cell, consisting of a porous substance, having its pores filled with an amorphous
non-gelatinous precipitate, and said precipitate being preserved in a moist state by
treatment with a deliquescent salt, substantially as described.
6. An improved process for treating cups, and separating partitions or diaphragms,
used in electric batteries or electrolytic apparatus, substantially as and for the
purposes hereinbefore described, and set forth.
Dated this 4th day of July 1893
F. W. BARKER,
Applicant's Agent.