IMPROVEMENTS IN AND IN THE MANUFACTURE OF PAINTS OR COMPOSITIONS FOR PREVENTING THE FOULING OF SHIPS' BOTTOMS
Year: 1878

page_text: LETTERS PATENT to William Clark, of Chancery Lane, in the County of Middle-
sex, Patent Agent, for the Invention of "IMPROVEMENTS IN AND IN THE
MANUFACTURE OF PAINTS OR COMPOSITIONS FOR PREVENTING THE FOULING OF
SHIPS' BOTTOMS." A communication from abroad by Charles Dubois, of Mar-
seilles Franco.
Sealed the 6th December 1878, and dated the 25th June 1878.
Scaled the 6th December 1878, and dated the 25th June 1878.
PROVISIONAL SPECIFICATION left by the said William Clark at the Office
of the Commissioners of Patents on the 25th June 1878.
WILLIAM CLARK, of Chancery Lane, in the County of Middlesex, Patent Agent.
"IMPROVEMENTS IN AND IN THE MANUFACTURE OF PAINTS OR COMPOSITIONS FOR
PREVENTING THE FOULING OF SHIPS' BOTTOMS." [A communication from abroad by
Charles Dubois, of Marseilles, France.]
This Invention relates to improved compositions for coating ships' bottoms to
prevent their becoming fouled by the adhesion of barnacles and marine vege-
tation.
The improved paint is composed of three principal ingredients, combined in the
following proportions, which have been found to give excellent results, both as
regards durability and as a protection against fouling
1st. Chlorinated oil or poisonous liquid
-
-
55 kilogrammes.
2nd. Sulphocyanide of copper, in powder or poisonous solid 30
"

page_text: as in some seas the molluscous or herbaceous element predominates more largely
than in others. In the former case the proportion of sulphocyanide should be
increased, and in the latter case, that is to say, for preventing the adhesion of
marine plants, the chlorinated oils will have the greatest effect, so that the pro-
portion of sulphocyanide of copper may be considerably reduced, or it may be even
omitted.
The Invention, therefore, consists in the employment in paints of compositions
for coating ships' bottoms of sulphocyanide of copper, mixed and coated with so-
called chlorinated oils; also the use of sulphocyanide of copper incorporated with
any description of paint for coating ships' bottoms; also the use of chlorinated oils
in paints of the kind, either alone or in combination with any known poisonous
solid other than sulphocyanide of copper.
The sulphocyanide of copper should be reduced to an impalpable powder, and is
colorless when perfectly pure, but as obtained in commerce it should be white, with
a slight rose or yellow tinge; if it possesses a greenish tinge, however, its poisonous
action would be greater, although it would be liable to set up an electric action,
which would be injurious to the hulls of iron vessels.
One of the great advantages, in an economical point of view, which is derived
from the use of sulphocyanide of copper in fine powder is that it obviates the
necessity of employing an oxide, such as zinc white, white lead, or other product
to give a body to the composition, as it may be used alone with the so-called
chlorinated oils or siccative or other oils, and being almost colorless the desired tint
may be given to the paint by the addition of ochres or other metallic oxides ordi-
narily used as coloring matters.
The poisonous liquid, to which I have given the generic name of chlorinated oil,
is an entirely novel product, specially prepared by incorporating chlorine, bromine,
or iodine (chemical products bearing similar properties to chlorine, and which, as is
well known, form part of the same group, and act in the same manner upon other
matters) in oils, essences, and resins, and generally all hydrocarbons, whether liquid
or solid, of animal, vegetable, or mineral origin, such as are generally employed in
paints.
2
The incorporation of chlorine, bromine, or iodine with the hydrocarbons may be
obtained by utilising any of the various apparatus or methods employed for effecting
the dissolution or combination of gaseous products with solid or liquid matters;
for example, columns may be employed, such as those in which ammoniacal water is
introduced, and streams of carbonic acid passed through it to produce carbonate of
ammonia.
In these apparatus the oil would take the place of the ammoniacal water, and the
chlorine, bromine, or iodine brought to a gaseous-state would replace the carbonic
acid, or vapours of chlorine, bromine, or iodine may be simply introduced into oily
liquids, prepared as herein-after specified.
The chlorinated liquids are composed of a mixture of solid matters dissolved in
oils or essences, and the liquids may be treated separately by the chlorine, bromine,
or iodine, and then mixed with the solid matters, which they dissolve; or the solid
matters may be first dissolved in the oils and essences, and the chlorine, bromine, or
iodine then added to the oils thus prepared in one or other of the ways above
mentioned.
"Proportions of the various matters of which the liquids are composed before.
being treated with chlorine gas or vapours of bromine or iodine: "
Resinous matters
30 kilos.

page_text: In order to convert the above three mixtures into so-called chlorinated oils,
which at same time form excellent paints for coating ships' bottoms, it is first
necessary to ascertain the density of each of the liquid compounds above given
(as owing to the commercial products being never precisely alike, either chemically
or physically, their densities are extremely variable), and then to pass through
them a current of chlorine gas, for example, until each of the mixtures indicated is
increased about 6 per cent. in density.
If, owing to the too considerable absorption of chlorine the liquid becomes too
thick, it should have the necessary fluidity imparted either by adding a certain
quantity of coal oil untreated with chlorine, or it may be a certain quantity of
chlorinated phenic acid or benzinc.

page_text: SPECIFICATION in pursuance of the conditions of the Letters Patent filed by
the said William Clark in the Great Seal Patent Office on the 24th December
1878.
WILLIAM CLARK, of Chancery Lane, in the County of Middlesex, Patent Agent.
"IMPROVEMENTS IN AND IN THE MANUFACTURE OF PAINTS OR COMPOSITIONS FOR
PREVENTING THE FOULING OF SHIPS' BOTTOMS." A communication from abroad by
Charles Dubois, of Marseilles, France.
This Invention relates to improved compositions or paints for coating ships'
bottoms to prevent the adhesion of barnacles and marine vegetation.
The following are the three chief ingredients thereof and the average proportions
in which they are used :-
:-
1st. A liquid anti-fouling or poisonous matter (herein called
"chlorinated oil," and prepared as hereafter described)
2nd. A solid anti-fouling or poisonous matter (sulpho-
55 per cent.
00
These proportions have given excellent results, both as regards the durability and
the anti-fouling qualities of the composition or paint, but it must be understood
that the proportions of ingredients Nos. 1 and 2 must necessarily be varied
according to the voyage, as in some seas the molluscous, and in others the herb-
aceous element predominates, and the proportion of the appropriate anti-fouling or
poisonous matter should be varied accordingly. The proportion of sulphocyanide
of copper should therefore be increased in the first case where mollusca predo-
minate, and in the second case as it is the (so-called) "chlorinated oils" which
have the greatest effect on marine vegetation, the proportion of sulphocyanide of
copper may be considerably reduced, or it may even be omitted altogether.
The sulphocyanide of copper to be employed should be reduced to an impalpable
powder; its color when perfectly pure is white, but as obtained in commerce the
white has a slight pink or yellow tinge; should it have a greenish tinge it would
still act very strongly as a poisonous or anti-fouling agent, but would in certain
cases have the disadvantage of causing galvanic action, which would injure the
hulls of iron vessels.
One of the great advantages, in point of economy, derived from the use of sulpho-
cyanide of copper in fine powder is that it obviates the necessity of employing an
oxide, such as zinc white or of white lead or other product to give body to the
composition or paint, as it may be used alone with the (so-called) "chlorinated
oils," or with other oils, whether drying or non-drying oils, and being almost white
the desired color may be given to the paint by the addition of ochres or metallic
oxides, generally used as coloring matters.
The liquid poison, which has been called by the generic name of "chlorinated
oil," is unknown in commerce, being an entirely novel product, specially prepared
for the manufacture of this anti-fouling composition or paint. It is prepared by
incorporating chlorine, or bromine, or iodine (the latter being chemical products
having properties analogous to chlorine, and all belonging to the same group, and
acting in the same manner upon other matters) with oils, volatile oils, and resins,
and generally all hydrocarbons, whether liquid or solid, of animal, vegetable,
or mineral origin, such as are generally employed in making paints.
The incorporation of the chlorine, bromine, or iodine with the hydrocarbons above
mentioned may be effected by utilising any of the various apparatus or methods
employed for effecting the solution or combination of gaseous products with solid
or liquid matters; for example, columns may be employed, such as those in which

page_text: currents of carbonic acid gas are passed through ammoniacal water to make car-
bonate of ammonia.
In these apparatus the oils would take the place of the ammoniacal water, and
the chlorine, bromine, or iodine in a gaseous state would take the place of the car-
bonic acid gas. Or vapors of chlorine, bromine, or iodine may be simply.made to
bubble through the oily liquids, prepared as heroin-after specified.
The chlorinated liquids are composed of a mixture of several solid matters
dissolved in oils or volatile oils, and the liquids may be treated separately with the
chlorine, bromine, or iodine, and then mixed with the solid matters, which they
dissolve; or the solid may be first dissolved in the oils or volatile oils, and the
chlorine, bromine, or iodine be then incorporated with the oils thus prepared in
one or other of the ways above mentioned.
Proportions of the various matters of which the liquids are composed before being
treated with chlorine gas or vapors of bromine or iodine:
Resinous matters
-
30 kilos.
"
In order to convert the above three mixtures into (so-called) "chlorinated oils
for the manufacture of anti-fouling composition or paint it is first necessary to
ascertain the density of each of the liquid mixtures or preparations above given (as
the commercial products never being precisely alike, either chemically or physically,
their densities are extremely variable), and then to pass through them a current of
chlorine gas, for example, until the density of each of the said mixtures or pre-
parations is increased about six per cent.
If, by absorbing too much chlorine, the liquid should become too thick, it should
be thinned down, either by adding a certain quantity of coal oil untreated
with chlorine, or a certain quantity of chlorinated phenic acid or chlorinated
benzine.
The (so-called) "chlorinated oils," prepared as above described, may either be
mixed with the sulphocyanide of copper, which has never been hitherto employed

page_text: as a poisonous or anti-fouling ingredient in paints for coating ships' bottoms; or
the said "chlorinated oils" may be incorporated with other poisonous matters; or
the sulphocyanide of copper may be added to other known paints for ships' bottoms
in which other poisonous ingredients are usually employed.
Having described the nature of the Invention and the manner of performing the
same, I declare that what I claim as the Invention to be protected by the herein-
before in part recited Letters Patent is,―
1st. The employment in paints or compositions for coating ships' bottoms of
sulphocyanide of copper mixed with (so-called)" chlorinated oils," prepared as herein
specified.
2nd. The use and application of sulphocyanide of copper as an anti-fouling or
poisonous ingredient in any description of paint for coating ships' bottoms, as
specified.
3rd. The use and application of the so-called chlorinated oil, prepared as herein
specified, as an anti-fouling. or poisonous liquid ingredient in paints for coating
ships' bottoms, as specified.
4th. The use and application of the so-called chlorinated oil, prepared as herein
specified, as an anti-fouling or poisonous liquid ingredient in paints for coating
ships' bottoms, containing any known anti-fouling or poisonous solid matter, other
than sulphocyanide of copper.
In witness whereof, I, the said William Clark, have hereunto set my hand
and seal, this Twenty-third day of December, in the year of our Lord One
thousand eight hundred and seventy-eight.
W. CLARK.