Year: 1894

page_text: Date of Application (in United Kingdom), 24th Oct., 1894
Complete Specification Left, 20th July, 1895-4ccepted, 12th Oct.. 1895
АТИЩпиш
али
avo
I. PASCAL MARINO, Chemist, care of Mr. Vincent of 1 Avenue Victor Hugo,
at Vanves (Seine) France, do hereby declare the nature of this invention to be
as follows:
This invention refers to the composition of special and new electrolytes, (aqueous
solutions), for covering, directly, any metallic and metallised object with a bright
metallic layer of aluminium and of aluminium combined with tin, nickel, lead,
zinc, copper, silver, gold, platinum, etcetera, such coating being dense and
adherent.
An electrolyte suitable for depositing pure aluminium on metallic and metallised
objects is composed as follows :-
ARTICLE 1.
(a) I place in a receiver of porcelain, of glass, or of enamelled sheet iron, or
other material, some well washed hydrated alumina, obtained from a salt of
aluminium or from aluminiferous minerals.
I dissolve it in hydrochloric acid, or in ordinary sulphuric acid or its equivalent
until 1 obtain a clear solution.
I add to it an organic acid, as tartaric, citric, amylic, or a saccharine substance,
or a primary alcohol, or an albuminate, in order to maintain the alumina in
solution.
() I then treat this liquid with nitric acid, hydrofluoric, or other equivalent.
(c) Then I re-dissolve, entirely, the resulting coagulated substance in a solution
of potash or caustic soda.
(d) I then add some cyanure of potassium, about one-fourth of the weight of
the alumina employed, I boil it for fifteen or twenty minutes; the yellowish colour
of the liquid, after boiling, becomes dark brown.
I allow it to cool and I add hydrate of lime, of baryta, or other similar substance,
I filter and the bath is ready.
ARTICLE 2.
Bimetallic electrolyte suitable for depositing an alloy of aluminium and tin is
composed as follows:-
:-
I take the solution described in Article 1 up to paragraphs, (a) and (b). I add
to it the solution of a salt of tin (for example the fused protochloride of tin), I
heat, in order to obtain a complete and entire solution.
'מ

page_text: ARTICLE 3.
Bimetallic electrolyte for aluminium nickel, is composed as follows:-
I dissolve the oxide of 'nickel in a solution of potash or of caustic soda, I add it 5
to the compound described in Article 1 at paragraphs (a), (b) and (c). I take up.
the operations as described at paragraph (d) of the same Article 1.
In other cases as preferred I precipitate and I re-dissolve, by means of cyanure
of potassium; a solution of a salt of nickel, such as sulphate, citrate, carbonate, or
equivalent substance and I mix the liquid thus obtained with the solution described 10
in Article 1, at paragraphs (a), (b), (c), (d), but before heating it.
ARTICLE
Bimetallic electrolyte for aluminium-silver, is composed as follows:-
I dissolve a salt of silver, either cyanure, sulphate, chloride, or fluoride of silver,
by means of a solution of cyanure of potassium. I mix the whole with the
solution (d) of Article 1, but with the precaution not to heat it and not to add
bydrate of lime.

page_text: Another proceeding I may employ is, to take the aluminium bath described in
paragraphs (a), (b), (c), (d), of Artiole. 1 and I work it with soluble positive.plates
of silver.
_ Under Article 7 I only employ the sulphuric acid named in Article 1,
paragraph (a), to the exclusion of hydrochloric acid, because it is known that the
salts of silver are the reagents of chlorine, as chlorine is the reagent of silver.
aluminum describe in Article 1, paragraphs (a), (b), (c), (d).
ARTICLE 9.
Bimetallic electrolyte for aluminium-platinum, is composed. as follows:-
I dissolve a salt of-platinum, as the chloride, or other salt of platinum, in a
solution indicated in Article 8 and continue the operation as stated for gold.
Where I have not hereinbefore precisely stated the quantity of oxides and salts
intended to compose the above mentioned electrolytes, it is because. it should be
fixed according to the character to be given, to the metallic alloy, aimed, at ; for
example, if an alloy be required, of two parts of aluminium and one part of tin,
there should be put into the bath two parts of the equivalents of alumina and one
part of the salt of tin.
The whole of the nine electrolytes work either at the surrounding temperature,
or at a temperature which may vary from 40, to 80 degrees Centigrade, with, a very
strong current from a dynamo-electric machine.
The negative pole is put into contact with the articles to be coated, the positive
pole with the anodes, these anodes being soluble positive sheets of the same metal
as that which forms the base of the salts dissolved in the electrolyte, with the effect
of holding in solution the same quantity of metallic salt, for example, a soluble
sheet of aluminium, tin, nickel, lead, zinc, copper, silver, gold, platinum.
I may remark that aluminium deposits slowly under a weak current and
instantaneously under a powerful current.
It is practically impossible to give precise rules to include every case, but it is
always necessary to regulate the current in accordance with the capacity of the
bath, with the surface to be covered, sizes and arrangements of the anodes, of the
conductibility and degree of concentration of the bath, to obtain a bright, metallic
and adherent deposit.
Dated this 24th day of October 1894.
Improvements in and connected with the Electro-deposition of
Aluminium and Aluminium Alloys.
I, PASCAL MARINO, Chemist, care of Mr. Vincent of Avenue Victor Hugo,
at Vanves (Seine) France, do hereby declare the nature of this invention and in
what manner the same is to be performed to be particularly described aud
ascertained in and by the following statement :-
This invention refers to the composition of special and new electrolytes, (aqueous
solutions) for covering, directly, any metallic and metallised object with a bright

page_text: metallic layer of aluminium and of aluminium combined with tin, nickel, lead, zinc,
copper, silver, gold, platinum, etcetera, such coating being dense and adherent.
An electrolyte suitable for depositing pure aluminium on metallic and metallised
objects is composed as follows ;-
a-1 place in a receiver of porcelain, of glass, or of enamelled sheet iron, or
other material, some well washed hydrated alumina, obtained from a salt of
aluminium, or from aluminiferous minerals, of a weight of a kilogramme and a half
(1500 grammes).
I dissolve it in hydrochloric acid, or in ordinary sulphuric acid or its equivalent,
until I obtain a clear solution.
I add to it an organic acid, as tartaric, citric, amylic, or a saccharine substance,
or a primary alcohol or an albuminate, in order to maintain the alumina in solution
in the proportion of Tooth part by weight of the alumina employed, or 15 grammes.
I then treat this liquid with nitric acid, hydro-fluoric, or other equivalent
acid; in other words by stirring the quantity of acid until it begins to coagulate.
C- Then I re-dissolve, entirely, the resulting coagulated substance, in a solution
of potash or caustic soda for example, distilled water or rain water, potash or caustic
soda 100 grammes.
d-I then add some cyanure of potassium, about one fourth of the weight of the
alumina employed, I add distilled water until the volume attains the quadruple of
the original liquid formed of the alumina, acids, potash or caustic soda, I boil it for
fifteen or twenty minutes; the yellowish colour of the liquid, after boiling, becomes
dark brown.
I allow it to cool and I add 15 grammes hydrate of lime, of baryta, or other
alkaline earths, I filter and the bath is ready.
ARTICLE 2.
Distilled or rain water
Fused protochloride of tin
1 heat, in order to obtain a complete and entire solution.
500 grammes
150 gramines
I take up the operations as they are indicated in paragraphs (c) and (d) of
Article 1. In continuation refer to the different kinds of alloys in Article 10.
ARTICLE 3.
Bimetallic electrolyte for aluminium nickel is composed as follows-
1st Electrolyte. I dissolve the oxide of nickel in a solution of potash or of caustic 40
soda, for example
Distilled or rain water
Potash or caustic soda
Oxide of nickel
1000 grammes
75
""
200
وو
add it to the compound described in Article 1 at paragraphs (a) (b) and (c). I 45
take up the operations as described at paragraph (d) of the same Article 1.
2nd Electrolyte. In other cases as preferred I precipitate and I re-dissolve, by

page_text: Distilled water
Chloride of zinc
Potash or caustic soda
1000 grammes
-
200
"
->
400
"
and I continue the operation as it is indicated at paragraph (c) and (d) of
Article 1 after mixing. In continuation refer to the different kinds of alloys
in Article 10.
Sulphate of copper
Bi-carbonate of soda
200
250
"
"
which I collect in a hydrated state by decantation or by filtration, and I dissolve
it in a solution of potash or of caustic soda (water 200 grammes, potash or caustic
soda 150 grammes) which I mix with the solution indicated in paragraph (c)
of Article 1, after which the operations are continued as indicated in
paragraph (d).
;

page_text: 2nd Electrolyte. Or, if preferred, I..dissolve a salt of copper, for instance,
sulphate, citrate, cyanure of copper, etcetera, in cyanure of potassium, for
example
it, and I continue.
If I increase the quantity of copper so as to make it predominate over the
aluminium, I obtain a metallic layer of a yellow-gold colour (aluminium-bronze);
if, on the contrary, it is aluminium which predominates, I obtain a modification of
the colour furnished by the copper and the disappearance of the somewhat bluish
colour of the aluminium, the whole being transformed into a magnificent metallic
silver white colour.
In the presence of copper, aluminium deposits abundantly, so as to produce a
thick layer, uniform, and with perfect adherence on all metals.
ARTICLE .
Bimetallic electrolyte for aluminium silver is composed as follows-
1st Electrolyte. I dissolve a salt of silver, either cyanure, sulphate, chloride,
or fluoride of silver, by means of a solution of cyanure of potassium, for
example
Distilled water
Cyanure of silver
Cyanure of potassium
1000,grammes
100
300
"
I mix the whole with the solution (d) of Article 1, but with the precaution not to
heat it and not to add hydrate of lime.
2nd Electrolyte. Another proceeding 1 may employ is to take the aluminium
bath described in paragraphs (a) (b) (c) (d), of Article 1, and I work it with
soluble positive plates of silver placed at the positive pole, and the articles
to be covered with a coating of aluminium silver at the negative pole, in
connection with an electric dynamo machine of 10 volts power and a current
of 100 amperes.
Under Article 7 I only employ the sulphuric acid named in Article 1,
paragraph (a) to the exclusion of hydrochloric acid, because it is known that
the salts of silver are the reagents of chlorine, as chlorine is the reagent of
silver.
..Water
-
Chlorure or ammonure of gold
Cyanure of potassium
500 grammes
20
"
60
"
I add it to the bath prepared for the deposition. of pure aluminium described
in Article 1, paragraphs (a) (b) (c) (d), without adding bydrate of lime, or
harvta

page_text: Where I have not hereinhefore precisely stated the quantity of oxides and
salts intended to compose the above mentioned electrolytes, it is because it should
be fixed according to the character to be given to the metallic alloy aimed at; for
example, if an alloy be required, of two parts of aluminium and one part of tin,
there should be put into the bath two parts of the equivalents of alumina and one.
part of the salt of tin.
The whole of the nine electrolytes work either at the surrounding temperature
or at a temperature which may vary from 40 to 80 degrees Centigrade, with a very
strong current from a dynamo-electric machine, of an electromotive power of 10 volts.
and a current of 100 amperes.
The negative pole is put into contact with the articles to be coated; the positive.
pole with the anodes, these anodes being soluble positive sheets of the same metal
as that which forms the base of the salts dissolved in the electrolyte, with the effect
of bolding in solution the same quantity of metallic salt, for example, a soluble-
sheet of aluminium, tin, nickel, lead, zinc, copper, silver, gold, platinum.
I may remark that aluminium deposits slowly under a weak current and
instantaneously under a powerful current.
It is practically impossible to give precise rules to include every case, but it is
always necessary to regulate the current in accordance with the capacity of the
bath, with the surface to be covered, sizes and arrangements of the anodes, of the
conductibility and degree of concentration of the bath, to obtain a bright, metallic
and adherent deposit.
I should say that pure aluminium deposited by electrolytes according to my
invention possesses different and altogether superior properties to those of
commercial aluminium-and up to the present unknown-commercial aluminium is
strongly attacked by hydro-chloric acid and alkalies-aluminium deposited by me in
an electrolyte composed of hydro-chloric acid and alkalies, and as set out in my
Specification is not attacked in the same way by these re-agents, because it is
generated by them, and reduced to metal-it is in fact created in a liquid composed
of hydro-chloric acid alkalies and aluminium.
Having now particularly described and ascertained the nature of my said inven-
tion and in what manner the same is to be performed I declare that what I
claim as my "Improvements in the electro deposition of aluminium and aluminium
alloys" is
1. An electrolyte for depositing on metallic and metallised objects composed of
materials or aqueous solutions as described in Article 1, wherein pure aluminium is
utilised for the deposition of metals, whereby density, harduess and durability in the
coating are produced substantially as described.
2. An electrolytic bath suitable for the electro-deposition of various metals
composed of salts of aluminium, whereby I am enabled to deposit with great
rapidity various metals possessing physical properties, hardness, adhesiveness and
durability not heretofore obtained by other means and substantially as described.
3. The electrolyte for depositing pure aluminium on metallic and metallised
objects as specified with reference to Article 1 and paragraphs (a) (b) (c) (d).
herein.
4. The bimetallic electrolyte for depositing an alloy of aluminium and tin as
specified with reference to Article 2.

page_text: 5. The bimetallic electrolyte for depositing an alloy of aluminium and nickel as
specified with reference to Article 3.
6. The bimetallic electrolyte for depositing an alloy of aluminium and lead as
specified with reference to Article 4.
7. The bimetallic electrolyte for depositing an alloy of aluminium and zinc as
specified with reference to Article 5.
8. The bimetallic electrolyte for depositing an alloy of aluminium and copper as
specified with reference to Article 6.
9. The bimetallic electrolyte for depositing an alloy of aluminium and silver as
specified with reference to Article 7.
10. The bimetallic electrolyte for depositing an alloy of aluminium and gold as
specified with reference to Article 8.
11. The bimetallic electrolyte for depositing an alloy of aluminium and platinum
as specified with reference to Article 9.
Doted this 20th der of Jul 1805
BREWER & SON,
London and Leeds, Agents for Applicant.