IMPROVEMENTS IN THE ELECTRIC DEPOSITION OF COPPER AND BRASS
Year: 1868

page_text: LETTERS PATENT to William Henry Walenn, of 19, Talbot Road,
Tufnell Park West, Holloway, in the Parish of Islington, in the
County of Middlesex, Civil Engineer and Electrician, for the Inven-
tion of "IMPROVEMENTS IN THE ELECTRIC DEPOSITION OF COPPER AND
BRASS."
PROVISIONAL SPECIFICATION left by the said William Henry Walenn
at the Office of the Commissioners of Patents, with his Petition,
on the 24th December 1868.
I, WILLIAM HENRY WALENN, of 19, Talbot Road, Tufnel Park West,
Holloway, in the Parish of Islington, in the County of Middlesex,
Civil Engineer and Electrician, do hereby declare the nature of the
said Invention for "IMPROVEMENTS IN THE ELECTRIC DEPOSITION OF COPPER
AND BRASS," to be as follows:-
This Invention relates to improvements upon certain parts of that
set forth in Specification No. 1540 (A.D. 1857) and to other improve-
ments, as herein-after set forth.

page_text: The object of this Invention is to enable the electro-deposition of
copper and brass upon iron and other substances to be made with
less battery power, with greater economy, and more solidly and perfectly
than has hitherto been done.
A solution for electro-depositing brass is made as follows:---Crystallized
sulphate of zinc (1 part) and crystallized nitrate of copper (2 parts)
are dissolved in the smallest quantity of water that is possible. Sufficient
strong ammonia water is added to precipitate and then fully re-dissolve
the oxides. Then the purple tint of this solution is completely removed
by cyanide of potassium. The resulting solution should be left to stand
for a day or two, and may then be worked with from one to three
battery cells (Smee's preferred), using heat if a brass anode be employed.
It is however preferred to work this solution by either of the porous
cell arrangements herein-after described, the hydrated oxides of copper
and zinc being from time to time supplied, and, if necessary, ammoniuret
of copper being added.
Another solution for electro-depositing brass, chiefly useful where
heat is used, but also able to be employed cold with a porous cell
arrangement, is made as follows:-A "solvent solution" is first made,
consisting of,-
Cyanide of potassium (standard solution)
Nitrate of ammonium (standard solution)
Sulphate of ammonium (standard solution)
-
-
6 parts.
1 part.
2 parts.
The ingredients are
The "standard solution" of each salt consists of the salt in the solid
form dissolved in five times its weight of water.
mixed, and the whole is divided into three parts,-
Free solvent solution
Solution to dissolve cupric cyanide
Solution to dissolve zinc cyanide
- 1 part.
-
5 parts.
2 parts.
When the respective cyanides have been dissolved to saturation in the
portions appropriated to them the free solution is added thereto and
the whole is thoroughly mixed, ammoniuret of copper is then added,
and the finished solution is allowed to stand for a day or two. Instead
of using the cyanides of copper and zinc respectively to charge the
above-mentioned "solvent solution with copper and zinc, oxides,
carbonates, or any other suitable salt or salts, compound or compounds
of the metals, may be employed, or the "solvent solution may be
charged with metal from a brass anode by electric power.
"

page_text: If a solution to electro-deposit copper be required, instead of charging
the solution with about 1 part of zinc to 2 parts of copper the solution.
is charged with 1 part of zinc to 10 or 20 parts of copper.
This part of the Invention refers to any alkaline solution, but more
particularly to that containing cyanide of potassium and tartrate of
ammonium, and set forth in the Specification No. 1540 (A. D. 1857),
and to the two brass solutions described above. I am aware that the
addition of sulphate of zinc to acid solutions for electro-depositing copper
has long been known to improve the quality of the deposit and do
not include it in my Invention.
An improvement, which is applicable to all copper and brass solutions,
consists in the use of a porous cell arrangement in which the surface
of the solution next the zine or other dissolving plate is at a greater
elevation than that of the external or depositing solution.
The next part of my Invention refers to rendering alkaline copper
and brass electro-depositing solutions free from the evolution of hydrogen
gas, or nearly so, during electro-deposition, thus enabling the whole
of the electric power to be utilized and non-porous metal to be deposited.
This is accomplished by adding to either of the above-described solutions
the hydrated oxides of copper and zinc in sufficient quantity for the
purpose.
Another method is to add simply ammoniuret of copper:
In a third method the oxides of copper and zinc are dissolved in
ammonia water, and the resulting solution added to the depositing
solution.
My next improvement consists in applying to the copper and brass
solutions mentioned above, and included in the Specification No. 1540,
A.D. 1857, or in this Specification, being three brass solutions and the
same number of copper solutions, and those only, the method of working
them by the supply of the hydrated oxides of the metal or metals in
conjunction with the use of a porous cell to generate the electric power
or to receive the same from an adequate battery, the said oxides either
being stirred into the solution from time to time as required or supplied
from a tall porous cell containing an ammoniacal solution of the
said oxides that acts by the pressure of the column of liquid in the said
porous cell to force the ammoniacal liquid into the depositing solution
outside the porous cell. In conjunction with the said depositing
solutions, when no separate battery is used, I employ an amalgamated

page_text: zinc plate in the porous cell, immersed in one of the following
solutions :-
1. The "solvent solution" of the second brass solution.
2. A solution composed of,-
Cyanide of potassium (standard solution)
-
-
2 parts.
-
1 part.
Sulphate of ammonium (standard solution) -
3. A solution of an alkaline chloride.
4. A solution of an alkaline sulphate.
My last improvement consists in an acid solution for the electro-
deposition of copper, which has not hitherto been used for that purpose.
A few drops of bi-sulphide of carbon per gallon of solution (a larger
proportion may be used) are mixed with a solution containing one
pound of sulphate of copper to the gallon, and an ounce or two of
sulphate of zinc to the gallon; it is essential that this solution should
be acid. I prefer to work this solution with a porous cell arrangement
that has the surface of the inside solution much higher than that of the
depositing solution.
The proportions of the ingredients used in each of the solutions
mentioned herein may be varied to some extent without deteriorating
the quality of the results produced. The proportion of zinc and copper
in the respective depositing solutions should bear a close relation to the
proportion of these metals in the alloy deposited, but rather more zinc
may be started with to advantage.
Mere modifications of the solutious and processes are also included in
this Invention.
SPECIFICATION in pursuance of the conditions of the Letters Patent,
filed by the said William Henry Walenn in the Great Seal Patent
Office on the 23rd June 1869.
TO ALL TO WHOM THESE PRESENTS SHALL COME, I, WILLIAM
HENRY WALENN, of No. 19, Talbot Road, now called No. 76, 3
Brecknock Road, Tufnell Park West, Holloway, in the County of
Middlesex, Civil Engineer and Electrician, send greeting.

page_text: WHEREAS Her most Excellent Majesty Queen Victoria, by Her
Letters Patent, bearing date the Twenty-fourth day of December, in the
year of our Lord One thousand eight hundred and sixty-eight, in the
thirty-second year of Her reign, did, for Herself, Her heirs and successors,
give and grant unto me, the said William Henry Walenn, Her special
licence that I, the said William Henry Walenn, my executors,
administrators, and assigns, or such others as I, the said William
Henry Walenn, my executors, administrators, and assigns, should at
any time agree with, and no others, from time to time and at all
times thereafter during the term therein expressed, should and lawfully.
might make, use, exercise, and vend, within the United Kingdom of
Great Britain and Ireland, the Channel Islands, and Isle of Man, an
Invention for "IMPROVEMENTS IN THE ELECTRIC DEPOSITION OF COPPER AND
BRASS," upon the condition (amongst others) that I, the said William
Henry Walenn, my executors or administrators, by an instrument in
writing under my, or their, or one of their hands and seals, should
particularly describe and 'ascertain the nature of the said Invention,
and in what manner the same was to be performed, and cause the same
to be filed in the Great Seal Patent Office within six calendar months
next and immediately after the date of the said Letters Patent.
NOW KNOW YE, that I, the said William Henry Walenn, do
hereby declare the nature of my said Invention, and in what manner
the same is to be performed, to be particularly described and ascertained
in and by the following statement :-
This Invention relates to improvements upon certain parts of the
Invention set forth in Specification No. 1540 (A.D. 1857), and to other
improvements, as herein-after set forth.
The object of this Invention is to enable the electro-deposition of
copper and brass upon iron and other substances to be made with less
battery power, with greater economy, and more solidly and perfectly
than has hitherto been done.
A solution for electro-depositing brass is made as follows:-Crystal-
lized sulphate of zinc (1 part by weight) and crystallized nitrate of
copper (2 parts) are dissolved in the smallest quantity of water that is
possible. Sufficient strong ammonia water is added to precipitate

page_text: and then fully redissolve the oxides.
Then the purple tint of this
solution is completely removed by a standard solution of cyanide of
potassium. The resulting solution should be left to stand for a day or
two, and may then be worked with from one to three battery cells,
using heat if a brass anode be employed. It is, however, preferred to
work this solution by either of the porous cell arrangements herein-
after described, the hydrated oxides of copper and zinc being from time
to time supplied, and, if necessary, ammoniuret of copper being added.
Before adding the hydrated oxides it is advantageous to add as much
of the cyanides of the metals as will dissolve in the menstruum. Ammonia
water and a standard solution of cyanide of potassium should be added
occasionally to this depositing liquid in order to keep the salts of copper
and zinc well in solution. The hydrated oxides of copper and zinc are
mixed, and thoroughly incorporated in the proportion of two parts by
weight of the hydrated oxide of copper to one part of the hydrated
oxide of zinc before they are added to the solution. During working
little or no hydrogen should be evolved from the article.
A second solution for electro-depositing brass, chiefly useful where
heat is used, but also able to be employed cold with a porous cell
arrangement, is made as follows:-A "solvent solution" is first made
consisting of,
Cyanide of potassium (standard solution)
Nitrate of ammonium (standard solution)
Sulphate of ammonium (standard solution)
-
6 parts by measure,
-
1 part,
2 parts.
The "standard solution" of each salt consists of the salt in the solid
form dissolved in five times its weight of water; the standard solution
of cyanide of potassium referred to in the description of the first electro-
brassing solution is so made. Eight-ninths of the whole of the ingredients
provided are mixed in order to receive to saturation the cyanides of
copper and zinc previously mixed in the proportions of 3090 parts by
weight of cupric cyanide to 1795 parts of zinc cyanide; the remaining
one-ninth of the solvent solution is added as free solution to the eight-
ninths. This mixture is then treated to the hydrated oxides of copper
and zinc, as in the first solution, and the ammoniuret of copper is added
If it is found that this solution evolves hydrogen gas during deposition.
Previous to trial by the battery the solution should be allowed to

page_text: stand for one or two days. A few ounces (by measure) to the gallon
of ammoniuret of copper will suffice to prevent the evolution of
hydrogen gas. This method of mixing the solution is preferred to all
others.
A modification of this second electro-brassing solution is made by
mixing the whole of the solvent solution and then dividing it into three
parts-
Free solvent solution -
Solution to dissolve cupric cyanide
Solution to dissolve zinc cyanide
1 part.
5 parts.
2 parts.
When the respective metallio cyanides have been dissolved to saturation
in the portions of solvent solution appropriated to them the free solution
is added thereto, and the whole is thoroughly mixed; ammoniuret¸ of
copper is then added, and the finished solution is allowed to stand for a
day or two
Instead of using the cyanides of copper and zinc respec-
tively to charge the above-mentioned "solvent solution" with copper
and zinc, oxides, carbonates, or any other suitable salt or salts, compound
or compounds of the metals may be employed.
Another modification of this second electro-brassing solution, and one
very nearly equal in quality to that first described, consists in charging
the solvent solution with metal from a brass anode by electric power,
using four Grovo's cells of adequate size, and arranged for intensity for
the purpose.
After charging the solution with about two ounces of
metal per gallon the mixed cyanides are added, if it will dissolve any;
then as much of the mixed oxides as it will dissolve; and, finally, to
adjust the solution for the non-evolution of hydrogen, a small
quantity of ammoniuret of copper. This adjustment may or may not be
necessary.
A serviceable modification of the solvent solution of the second
electro-brassing solution consists in employing equal parts of cyanide of
potassium and sulphate of ammonium, and adding thereto one ounce
(by weight) of crystals of nitrate of ammonium per gallon. The nitrate
of ammonium is necessary, as it favours electric conduction, and tends
to keep the solution in working order.
If a solution to electro-deposit copper be required, instead of charging
the solvent solution with about one part of zinc to two parts of copper,

page_text: ime to time as required, or supplied from a tall porous cell containing
n ammoniacal solution of the said cyanides and hydrated oxides that
cts by the pressure of the column of liquid in the said porous cell to
orce the ammoniacal liquid into the depositing solution outside the
orous cell. When no separate battery is used an amalgamated zinc
late in the porous cell furnishes the requisite electric current. The
olution in the porous cell may be.
porous cell. When no separate battery is used an amalgamated zinc
plate in the porous cell furnishes the requisite electric current. The
solution in the porous cell may he-
1. The solvent solution" of the second brass solution.
2. A mixture containing cyanide of potassium and sulphate of
ammonium in solution, equal parts by weight preferred.
3. A solution of an alkaline chloride.
4. A solution of an alkaline sulphate.
When a separate battery is employed a brass or copper plate in the
porous cell as an anode, and immersed in the "solvent solution" of a
brass or copper solution, enables a portion of the said solution to be
charged with brass or copper, whilst the other portion is parting with
its brass to the cathode, and by the alternate use of these solutions as
depositing solutions continuous working may be obtained.
The last improvement consists in an acid solution for the electro-
deposition of copper, which has not hitherto been used for that purpose.
A few drops of bi-sulphide of carbon per gallon of solution (a larger
proportion may be used) are mixed with a solution containing one pound
of sulphate of copper to the gallon, and an ounce or two of sulphate of
zinc to the gallon; it is essential that this solution should be acid. The
effect of this solution is to deposit pure copper uniformly over the
article to be coated of a silky and bright appearance; the solution is
not liable to get out of order.
Having thus described the nature of my Invention, and the best
means with which I am acquainted for carrying the same into effect, I
desire it to be understood that I do not confine myself to the precise
details or proportions herein set forth, as they may be varied without
departing from the nature and object of my Invention; but I claim, the
improvements substantially as they are herein set forth, or any mere
modification thereof, whereby the electro-coating of iron or other articles
with copper or brass may be made with less battery power, with

page_text: greater economy, and more solidly and perfectly than has hitherto been
done.
In witness whereof, I, the said William Henry Walenn, have
hereunto set my hand and seal, this Twenty-third day of June,
in the year of our Lord One thousand eight hundred and sixty-
nine.
Witness,
SYDNEY D. HAMILTON,
11, Great James Street,
Bedford Row.
WILLIAM H. WALENN. (L.S.)