IMPROVEMENTS IN GALVANIZING OR COATING METALS BY ELECTRO-CHEMICAL AGENCY AND IN APPARATUS CONNECTED THEREWITH
Year: 1862

page_text: LETTERS PATENT to Charles Beslay, of Rue Menilmontant, Paris, in the
Empire of France, Gentleman, for the Invention of "IMPROVEMENTS IN
GALVANIZING OR COATING METALS BY ELECTRO-CHEMICAL AGENCY AND IN
APPARATUS CONNECTED THEREWITH."
Sealed the 29th August 1862, and dated the 28th June 1862.
PROVISIONAL SPECIFICATION left by the said Charles Beslay at the
Office of the Commissioners of Patents, with his Petition, on the
28th June 1862.
I, CHARLES BESLAY,of Rue Menilmontant, Paris, in the Empire of France,
Gentleman, do hereby declare the nature of the said Invention for "IMPROVE.
MENTS IN GALVANIZING OR COATING METALS BY ELECTRO-CHEMICAL AGENCY, AND IN
APPARATUS CONNECTED THEREWITH," to be as follows:-
My Invention relates to improvements on a former Patent granted to me,
and dated January 12th, 1859, No. 103, for coating or covering metals by
electro-chemical agency, and consists in the galvanization of metals, more
especially cast or other iron and steel, by indirect means at the ordinary tem-
perature with non-concentrated solutions, which I term galvanization in a cold
state.
Indirect means and affinity of metals.-The chief object of this Invention
is the galvanization of metals and alloys by means of other metals, observing
in the application of said metals the laws according to which they manifest
[Price 8d.]

page_text: the greatest affinity one for the other while in a metallic state. Thus, the
Invention consists in the practical application of the law of affinities between
metals to electro-chemical processes Experience has proved to me that there
exists great accord between the facility with which one metal combines with
another in fusion, and that with which a metal is deposited in a metallic state
by electro-chemical agency. Fusion and the electric current furnish, with
regard to affinity, identical results; for example, iron and tin, when fused, form
with facility a series of alloys, whether the iron or the tin predominate in
their formation and in the combination of metals, the alloy or product of the
combination is of a well defined homogeneous character. The same result is
not attained in combining iron with zinc, lead, or copper. Alloys of iron and
zinc have been but seldom used,the possibility of their production being even
denied, the same observation applies to iron and lead, while as regards iron
and copper also, it is well known that the two metals have very little affinity
for each other. In order to form combinations of metals, that is to say, alloys
in determined proportions, the agent I employ by preference in the majority
of, if not in all cases, consists of tin. For instance, zinc and iron in fusion
form but an indifferent alloy, whereas the result will be far better if I use iron,
tin,and zinc for the same purpose; tin, which may be alloyed with all ordinary
metals, and in any proportions, especially with zinc and lead, answers the
purpose inthe galvanizing process of an intermediate soldering or fixing metal.
The foregoing description indicates clearly what I mean bythetermindirect
method. I will now give other reasons in favour of this method. For example,
when coating iron with a thick layer of zinc, I superpose on the iron, which
is a ductile, slightly dilatable, and very elastic métal, a layer of zinc, which is
a metal possessing like properties in a veryзlight degree. But as the ductility,
elasticity, and dilatability increase inversely in the thickness of the zinc, if.
instead of a single layer of zinc of a given thickness, I substitute a layer of tin
"and then one of zinc, both together equalling the single layer of zinc, by means
of the intermediate metal (tin between iron and zinc) I obtain a covering
whose dilatability, ductility, elasticity, and adherent properties will be found
more assimilated to the iron than would be the case when employing a single
layer of zinc. From the local voltaic action produced by the deterioration of
a coating of zinc on iron, it results that the iron becoming exposed by the
destruction of the zinc covering oxidizes rapidly, especially below the surface,
while according to my Invention, the voltaic action being only between the
zinc and the tin which covers the iron, the oxidation is limited to the zinc
In the same manner when coating metals with lead, zinc, copper, or others, 1
first tin the article to be covered.

page_text: |Of the temperature and other conditions of the piles.-The process of
electro-chemical galvanization of metals leads me to consider the means
heretofore adopted. The question of temperature, which is of but slight
importance as regards precious metals, becomes one of great moment in the
present case. In fact, up to the present day, the galvanization of metals has
only been attempted on a small scale, and these experiments having little
reference to the commercial view of the case, recourse has been had to the
simplest means of obtaining a deposit of metal from a given solution, viz., by
heating said solutions as high as from 25 to 60 or 80° centigrade (90° to
150° or 200° degrees Fahrenheit). As the galvanization of metals in a cold
state could only be effected with advantage by operating simultaneously on
large quantities of metals, it results that in order to raise the temperature of
the solutions by heat, as above mentioned, special vessels and heating appa-
ratus would be required, the expense of maintaining which, together with the
consumption of fuel, would be alone sufficient to render the process unprofit-
able. It is thus a prime necessity to be enabled to operate at the ordinary
temperature. According to my Invention the solutions are prepared in such
manner that while offering but slight resistance to the galvanic current, the
operation can be carried on in any dry room at the ordinary temperature. I
may increase the action of the baths during exceptional cold weather by
increasing the force of the electric current; for this purpose I use piles of
peculiar arrangement with a single element, by which a continuous operation
sufficient for the galvanization of upwards of a thousand pounds weight of
articles at one time in two cubic yards of liquid solution can be effected.
These improved piles of my Invention are formed of a leaden vessel about four
feet in length, two feet in width, and five inches in depth. The bottom of
this vessel is provided with a thin sheet of copper, which is movable, and
turned up a little at the sides. I place two wooden rods about an inch in
diameter longitudinally on the bottom of the vessel, and on said rods I place
the thin sheet of zinc, to which the conductors are fixed.
There is no
diaphragm in this case, but one pile of this arrangement is equal to 12 or 15
elements of Daniels.
Of the solutions and their nature.-In electro-chemical applications, the
concentration of the solutions has heretofore been considered necessary as a
general rule to be invariably observed, in order to obtain a metallic deposit,
thus, in all works treating of electro-chemical manipulations, and in all
anterior Patents thedensity of the baths is always maintainedas being increased
to the maximum, whereas according to my Invention the weakness of the bath
is an indispensable condition in a commercial and economical point of view.

page_text: The solutions I use are of a minimum density of three degrees of Beaumé's
areometer, and do not exceed 5 or 6 degrees at the maximum. If the baths
become concentrated by the effects of lengthened evaporation to upwards of
5 or 6 degrees, I reduce them to their proper limit by adding water in equal
proportion to that evaporated. There is, besides another reason in favor of
the slightly concentrated solutions, which will be apparent from a chemical
point of view, it is that salts of tin, lead, and zinc are formed naturally in a
state in which they are much less liable to deterioration, and in conditions
favorable for receiving the influence of the electric current. My object, in
fact, is not to form in the baths either stannates, zincates, or plombates, which
have a great tendency in concentrated solutions to precipitate in a crystalline
state, and become more and more insoluble, sometimes forming gelatinous
deposits, and consequently presenting great resistance to electro-chemical
decomposition. The principal object of this part of my improvements, on the
contrary, is the formation of sub-salts of an alkaline or acidulated nature, which
are easily maintained in a soluble state in slightly concentrated solutions.
Among these subsalts I prefer those termed metastannates, protocyanides
of tin, either singly or combined, and other analogous salts with bases of zinc
or lead, also the subsulphates or protosulphates and subacetates of zinc, or
other metals combined together. I also use, in general, double combinations,
in very small proportions, of subsalts of the same metallic base. These double
combinations offer much less resistance to the current, and are much more
easily preserved from deterioration when the solutions are weak, consequently
the action or attacks on the anodes are made with more equality and
regularity.
SPECIFICATION in pursuance of the conditions of the Letters Patent, filed
by the said Charles Beslay in the Great Seal Patent Office on the 22nd
December 1862.
TO ALL TO WHOM THESE PRESENTS SHALL COME, I, CHARLES
BESLAY, of Rue Menilmontant, Paris, in the Empire of France, Gentleman,
send greeting.
WHEREAS Her most Excellent Majesty Queen Victoria, by Her Letters
Patent, bearing date the Twenty-eighth day of June, in the year of our Lord
One thousand eight hundred and sixty-two, in the twenty-sixth year of Her
reign, did, for Herself, Her heirs and successors, give and grant unto me, the
said Charles Beslay, Her special licence that I, the said Charles Beslay, my

page_text: executors, administrators, and assigns, or such others as I, the said Charles
Beslay, 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 GALVANIZING OR
COATING METALS BY ELECTRO-CHEMICAL AGENCY AND IN APPARATUS CONNECTED
THEREWITH," upon the condition (amongst others) that I, the said Charles
Beslay, 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 Charles Beslay, do hereby declare the
nature of my said Invention, and in what manner the same is to be per-
formed, to be particularly described and ascertained in and by the following
statement (that is to say) :-
My Invention relates to improvements on a former Patent granted to me,
and dated January 12th, 1859, No. 103, for coating or covering metals by
electro-chemical agency, and consists in the galvanization of metals more
especially cast or other iron and steel by indirect means at the ordinary tem-
perature with non-concentrated solutions, which I term galvanization in a cold
state:
Indirect means and affinity of metals.-The chief object of this Inventionis
the galvanization of metals and alloys by means of other metals, observing in
the application of said metals the law according to which they manifest the
greatest affinity one for the other while in a metallic state. Thus the
Iuvention consists in the practical application of the law of affinities between
inetals of electro-chemical processes. Experience and practice has proved to
me that there exist a great connection between the facility with which one
metal combines with another in fusion, and that with which a metal is
deposited in a metallic state by electro-chemical agency. Fusibility, the same
as the electric current, furnishes with regard to affinity identical results. For
example, iron and tin form, when fused, a series of alloys, whether the irou
or the tin predominate in their formation, and in this combination of metals
the alloy or product of the combination is of a well defined homogeneous
cliaracter. The same result is not attained in the combination of iron and
zinc, lead or copper. Alloys of iron and zinc have been but very seldom used

page_text: the possibility of their production being even denied; the same observation.
applies to iron and lead; while as regards iron and copper also it is well
known that the two metals have very little affinity for each other..
In order to form combinations of metals, that is to say, alloys in determined
proportions, the agent I employ by preference in the majority of, if not in all
cases, consists of tin. For instance, if zinc and iron in fusion form but an
indifferent alloy, it will not be so if I use irou, tin, and zinc for the same
purpose. Tin which may be alloyed will all ordinary metals and in any
suitable proportions, especially with zinc and lead, answers the purpose in the
galvanizing process of an intermediate fixing metal.
..
The foregoing description shows clearly what I mean by the term "indirect
method." I will now give other reasons in favor of this method. For example,
when coating iron with a thick layer of zinc I superpose on the iron; which is
a ductile but slightly dilatable and very elastic metal, a layer of zinc, which
is a metal possessing the properties of iron only in a very slight degree. But
as the ductility,elasticity, and dilatability increases inversely to the thickness
of the zinc, if, instead of a single layer of zinc of a given thickness, I substitute
a layer of tin and then one of zinc, both together equaling the single layer of
zine; by means of the intermediate metal (tin between iron and zinc) I obtain
a covering whose dilatability, ductility, and elasticity and adherent properties
will be found more assimilated to the iron than would be the case when
employing a single layer of zinc. From the local voltaic action produced by the
deterioration of a coating of zinc on iron it results that the iron, becoming
exposed by the destruction of the zinc covering, oxidizes rapidly, especially
below the surface, while according to my Invention the voltaic action being
only between the zinc and the tin which covers the iron limits the oxidation
to the zinc. In the same manner when coating metals with lead, zinc, copper;
or others, I first tin the article, to be covered.
Of the temperature and other conditions of the pile.—The process of electro-
chemical galvanization of metals leads me to consider the means heretofore
adopted. The question of temperature, which is of but slight importance as
regards precious metals, becomes one of great moment in the present case.
In fact up to the present day the galvanization of metals has only been
attempted on a small scale, and these experiments having little reference to
the commercial view of the case, recourse was had to the simplest means of
obtaining a deposit of metal from a given solution, viz., by heating said
solutions as high as from 25 to 60° and 80° centrigrade (90° to 150°or 200
Fahrenheit). As the galvanization of metals in a cold state could only be
effected with advantage by operating simultaneously on large quantities of

page_text: metal, it results that in order to raise the temperature of the solutions by heat
as above mentioned, special vessels and heating apparatus would be required,
the expense of maintaining which together with the consumption of fuel would
be alone sufficient to render the process unprofitable. It is thus a prime
necessity to be enabled to operate in the ordinary temperature according to
my Invention; the solutions are prepared in such manner that while offering
but slight resistance to the galvanic current, the operation may be carried on
in any dry room at the ordinary temperature. I may increase the action of
the baths during exceptional cold weather by increasing the force of the
electric current, for this purpose I use piles of peculiar arrangement with a
single element, allowing of a continuous operation sufficient for the galvani-
zation of upwards of a thousand pounds weight of articles at one time in two
cubic yards of liquid solution. These improved piles of my Invention are
formed of a leaden vessel about 4 feet in length, two feet in width, and 5
inches in depth. The bottom of this vessel is provided with a thin sheet of
copper, which is movable and turned up a little at the sides. I place two
wooden rods about an inch in diameter longitudinally on the bottom of the
vessel, and on said rods I place a thin sheet of zinc, to which the conductors
are fixed. There is no diaphragm, and one pile of this arrangement equals
12 to 15 elements of Danniels.
Of the solutions and their nature.- In electro-chemical applications the
concentration of the solution has hitherto been considered necessary as a
general rule to be invariably observed in order to obtain a metallic deposit,
thus in all works treating of electro-chemical manipulations and in all Patents
anterior to the present time, the density of the baths is always mentioned as
being increased to the maximum, whereas according to my Invention the
weakness of the baths is an indispensable condition in a commercial and
economical point of view. The solutions I use are of a minimum density or
three degrees of Beaumé's areometer, and do not exceed five or six degrees at
the maximum. If the baths become concentrated y the effects of lengthened
evaporation to upwards of five or six degrees, I reduce them to their proper
limit by adding water in equal proportion to that evaporated. There is
besides another reason in favor of the slightly concentrated solutions, which
will be apparent from a chemical point of view; it is that salts of tin, lead, and
zinc are formed naturally in a state where they are much less liable to
deterioration, and in conditions favorable for receiving the influence of the
electric currens. My object, in fact, is not to form in the baths either
stannates, zincates, or plombates, which have a great tendency in concentrated
solutions to precipitate in a crystalline state, become more and more insoluble,

page_text: sometimes forming gelatinous deposits, consequently presenting great re-
sistance to electro-chemical decomposition.
The principal object of this part of my improvements, on the contrary, is the
formation of subsalts, whether of an alkaline or acidulated nature, which are
easier to maintain in a soluble state in slightly concentrated solutions.
Among these subsalts I prefer those termed metastannates, protocyanides of
tin, either singly or combined, and other analogous salts with bases of zine or
lead, also the subsulphates or protosulphates and subacetates of zinc or other
metals combined together. I also use in general double combinations in very
small proportions of subsalts of the same metallic base.
These double combinations offer much less resistance to the current, and
are more easily preserved from deterioration when the solutions are weak,
consequently the shocks of the anodes are made with more equality and
regularity.
The foregoing is a description of the principal features of my Invention
for galvanizing metals by cold process, and which is suitable of practical
application.
In witness whereof, I, the said Charles Beslay, have hereunto set my
hand and seal, this Tenth day of December, in the year of our Lord
One thousand eight hundred and sixty-two.
Witness,
W. CLARK, Patent Agent,
53, Chancery Lane,
London.
CH. BESLAY. (L.S.)