IMPROVE- MENTS IN CLEANSING AND COATING THE BOTTOMS OF SHIPS AND OTHER SUBMERGED SURFACES TO PREVENT OXIDATION, AND THE ADHESION OF MARINE ANIMALS AND PLANTS, ALSO IN COMPOSITIONS TO BE EMPLOYED FOR THESE
Year: 1865

page_text: LETTERS PATENT to Richard Percy Roberts, of No. 100, Kennington'
Park Road, in the County of Surrey, for the Invention of "IMPROVE-
MENTS IN CLEANSING AND COATING THE BOTTOMS OF SHIPS AND OTHER
SUBMERGED SURFACES TO PREVENT OXIDATION, AND THE ADHESION OF MARINE
ANIMALS AND PLANTS, ALSO IN COMPOSITIONS TO BE EMPLOYED FOR THESE
"
Sealed the 2nd March 1866, and dated the 9th September 1865.
PROVISIONAL SPECIFICATION left by the said Richard Percy Roberts
at the Office of the Gommissioners of Patents, with his Petition, on the
9th September 1865.
I, RICHARD PERCY ROBERTS, of No. 100, Kennington Park Road, in the
County of Surrey, do hereby declare the nature of the said Invention for
"IMPROVEMENTS IN CLEANSING AND COATING THE BOTTOMS OF SHIPS AND OTHER
SUBMERGED SURFACES, TO PREVENT OXIDATION AND THE ADHESION OF MARINE
ANIMALS AND PLANTS, ALSO IN COMPOSITIONS TO BE EMPLOYED FOR THESE PURPoses,”
to be as follows:-
This Invention has for its object improvements in cleansing and coating the
bottoms of ships and other submerged surfaces to prevent oxidation and the
adhesion of marine animals and plants, also in compositions to be employed
for these purposes.
It is well known that atmospheric and other influences produce upon iron
and other metals oxidation or rust, which is detrimental to iron ships, or ships
coated with iron, or ships coated with other metallic sheathing.
The principle of this Invention is therefore, first, the cleansing of the iron
or other metallic surfaces by chemical means, and afterwards the application

page_text: to the cleaned surface of suitable preservative composition as herein-after
described. The methods hitherto adopted for removing oxidation or rust from
such surfaces have been to cleanse the iron by scraping or mechanical means.
I, according to my Invention, cleanse the iron by dissolving, decomposing, or
removing the oxide or rust by chemical means, and for that purpose I employ
a solution of sal-ammoniac, or an ammoniacal solution, caustic potash, soda
or lime, camphine, petroleum, naptha, or other hydrocarbon or similar product,
or acid or acidulated water (or water which has been rendered acid by mixing
with it the farina of rye or other grain, and fermenting the mixture, may be
employed), or the surface may be exposed to the fumes of sal-ammoniac, or it
may be heated and rubbed with sal-ammoniac. I do not usually employ all these
substances and methods, but I am guided by the state or degree of oxidation
which has taken place. Judgment will, therefore, have to be used in the
processes for rendering the iron sufficiently clean, both to preserve the same,
and to render the surface fit to receive the composition; for example, I have
found a vessel to require only to be scoured with an ammoniacal solution, whilst
other vessels have been so badly oxidized or rusted as to have compelled me
to have recourse in succession to many of the means which have been
mentioned to remove, dissolve, destroy, or decompose the oxide or rust
sufficiently.
I have found when iron is not too much oxidized or rusted, that after the iron
has been well scraped it is well to scour it with an acidulated water, and after-
wards with an ammoniacal solution, and that this is sufficient for the purpose.
I prefer in using the acid solution to scour with sand or any similar material,
or to use a Bath brick, which is a useful auxiliary in the process, and I then
wash down with a solution of sal-ammoniac with a mop or other suitable
appliance. I have also found a vessel's bottom to require the use of many of
the above chemical solutions or chemicals which have been mentioned; thus,
] may use a solution of caustic potash, soda or lime (separate or together),
to remove grease or any extraneous matter, and afterwards wash or put on
camphine, petroleum, or similar product, and set fire to the same, or I may
rub or pass a red-hot iron over the surface, and then scour with acidulated
water worked with Bath brick, sand, or other auxiliary, and finally wash down
with solution of muriate of ammonia or sal-ammoniac. The iron may then be
dried with an open stove (I prefer a charcoal one), but this drying is not
positively necessary although I deem it desirable, as I prefer to use the coating
composition as quickly as possible after the iron is cleansed, that the naked
iron may be subject to as little atmospheric influence as possible. The
solutions or chemicals which have been mentioned may be mixed with any

page_text: may
suitable material to form a paste, which may be put and left upon the surface
of the iron for a time, or where camphine or similar product is used the paste
be put on and repeatedly saturated with the spirit, and then set fire to, or
a red-hot iron may be rubbed or laid. on or passed over the surface. Any of
the solutions may be made less liquid by adding any suitable substance to
make them into a paste. The sal-ammoniac used for the final washing I
prefer to be that which has been blackened by soot in the manufacture.
In preparing the coating composition, I first make a varnish consisting of,
say, 90 parts by weight of methylated spirit, 20 of shellac, and 2 of copal; to
the varnish I add in the proportion of from 1 to 5 parts by weight cyanogen,
cyanic acid, or hydrocyanic acid, their salts, or any of their definite chemical.
compounds. I also use iodine or bromine, their salts, or any of their definite
chemical compounds; or in place of using alone any one of the salts, two or more
together may be used. In using cyanogen, I pass a stream of that gas through
the varnish; -in using cyanic acid, I add that acid to the varnish; in using.
hydrocyanic acid, I add that acid to the varnish ;. in using iodine, I add iodine
to the varnish; in using bromine, I add bromine to the varnish. I prefer,
however, to use a salt or salts. In using a cyanogen salt, I prefer the chloride
of cyanogen, although other salts of cyanogen are nearly or quite as effective;
in using a cyanic acid salt, I prefer a sulphocyanate; in using a hydrocyanic
salt, the cyanide of ammonium or cyanide of zinc or other salt may be used;
in using an' iodine salt, I prefer the biniodide or deutioduret of mercury;
in using a bromine salt, I prefer the bromide of cyanogen.
Although I prefer to use the above, yet it may be found expedient where
the price of the composition is a question, to use cheaper or less expensive
salts, yet in using the above salts named as a preference the quantity employed
is small. The exact quantities would be determined by the length of voyage
to be made by the ship, and the sea or seas in which the ship or vessel may
have to pass; thus, a vessel going short voyages and continually running from
salt into fresh water, would not require the same expensive coating as vessels
going on longer voyages, or where there is a probability of the vessel being
becalmed. In the latter cases I should prefer to use a cyanogen salt or the
deutioduret of mercury, or both together.
Although this composition may be put on over other compositions, yet the
result could not with safety be depended upon, as the main principle of
cleansing and preserving the iron would be neglected. I consider that no
composition can be really effective except this preliminary principle of removing
sufficiently existing oxidation or rust is attended to. It must be apparent that
no mechanical means such as have hitherto been used to clean the iron can

page_text: be effectively employed. Not only do I consider oxidation or rust to be pre-
judicial to the iron, but also to any composition which may be put on or over
iron which has suffered from oxidation or rust. Two, three, or more coats
of the composition may be used. I prefer, however, from 4 to 6 coats,
according to the length and nature of voyage.
I prefer to put on as the first or first and second coats the varnish plain or
without any admixture, and for the remaining coat or coats I use varnish
mixed with other ingredients as already stated. Any of the compositions may
be put on one over the other, thus the third and fifth coats may be, say, a
cyanogen salt, and the fourth and sixth, say, the deutioduret of mercury
with or without another salt, or any other variation may be made either as
regards the number of the coat or coatings, or as regards the ingredient or
salt used in the composition or compositions; I prefer, however, to use the
deutioduret of mercury for the last coat or coats, either alone or in connection
with any of the other ingredients or salts used.
The deutioduret of mercury is insoluble or nearly so in either water or
alcohol, but is soluble in solutions of chloride of sodium, muriate of soda, or
sea water. I prefer, as above mentioned, to use the deutioduret of mercury
for the last coat or coats, as it presents a poison in a state soluble in sea water.
I, however, prefer to have another salt in connection with the same for the
latter or last coatings, and prefer the chloride of cyanogen.
A base may be
put into the varnish for cyanogen, cyanic acid, hydrocyanic acid, iodine, or
bromine to decompose and form a salt, or more than one may be used to form
a definite chemical compound or otherwise. I also use alone or in connection
with those poisons which have already been stated any narcotic, narcotic acrid,
or acrid poisons which have been thus classified by Dr. Paris, as stated
in a new Supplement to the latest Pharmacopoeias by James Rennie, M.A.
(London; Baldwin and Cradock, 1837). I have found the acrid poisons,
such as "aconite," the narcotic, such as "croton tiglium," and the narcotic
acrid, such as "oil of tobacco," to be most effective. In using these my object
is to act upon the nervous system or respiratory nerves or muscles of barnacles
and other living objects which may become attached to a ship or vessel. I
wish it, however, to be understood that in using the expensive poisons, I only
use them where the expense is of no object. The composition can be used for
either iron or coppered or wooden vessels, and for a coating for all materials
which are submerged. The improvements apply to the interior as well as to
the exterior parts of ships or other surfaces.

page_text: SPECIFICATION in pursuance of the conditions of the Letters Patent, filed
by the said Richard Percy Roberts in the Great Seal Patent Office on
the 9th March 1866.
TO ALL TO WHOM THESE PRESENTS SHALL COME, I, RICHARD
PERCY ROBERTS, of No. 100, Kennington Park Road, in the County of Surrey,
send greeting.
WHEREAS Her most Excellent Majesty Queen Victoria, by Her Letters
Patent, bearing date the Ninth day of September, in the year of our Lord
One thousand eight hundred and sixty-five, in the twenty-ninth year of Her
reign, did, for Herself, Her heirs and successors, give and grant unto me, the
said Richard Percy Roberts, Her special licence that I, the said Richard
Percy Roberts, my executors, administrators, and assigns, or such others as
I, the said Richard Percy Roberts, 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 "IM-
PROVEMENTS IN CLEANSING AND COATING THE BOTTOMS OF SHIPS AND OTHER
SUBMERGED SURFACES, TO PREVENT OXIDATION AND THE ADHESION OF MARINE ANIMALS
AND PLANTS, ALSO IN COMPOSITIONS TO BE EMPLOYED FOR THESE PURPOSES," upon
the condition (amongst others) that I, the said Richard Percy Roberts, 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 Richard Percy Roberts, do hereby
declare the nature of the said Invention, and in what manner the same is to
be performed, to be particularly described and ascertained in and by the
following statement thereof, that is to say:-
This Invention has for its object improvements in cleansing and coating the
bottoms of ships and other submerged surfaces, to prevent oxidation and the
adhesion of marine animals and plants, also in compositions to be employed
for these purposes.
:
The principle of this Invention is, first, the cleansing of the iron or other
metallic surfaces by chemical means, and afterwards the application to the
cleaned surface of suitable preservative compositions as herein after described.

page_text: The methods hitherto adopted for removing oxidation or rust from such
surfaces have been to cleanse the iron by scraping or mechanical means. I
according to my Invention, cleanse the iron by dissolving or removing the
oxide or rust by chemical means, and for that purpose I employ a solution of
sal-ammoniac or an ammoniacal solution of caustic potash, soda or lime,
camphene, petroleum, naptha, or other hydrocarbon, or acid or acidulated
water (or water which has been rendered acid by mixing with it the farina of
rye or other grain, and fermenting the mixture, may be employed), or the
surface may be exposed to the fumes of sal-ammoniac, or it may be heated
and rubbed with sal-ammoniac.
When using a solution of sal-ammoniac, I prefer to employ 2 pounds thereof
dissolved in each gallon of water; of ammonia I employ one pint to the gallon;
of potash one lb. to the gallon; of soda one lb. to the gallon; of lime one lb.
to the gallon. The acid I prefer to employ is the commercial sulphuric, and I
use from a pound to one pound to the gallon.. I scour the surface to be
cleansed with these solutions until it is sufficiently free from rust, and prefer
to use the solutions hot. When using the fumes of sal-ammoniac, I place
the salt of an iron sufficiently hot to vaporize it in close proximity to the
surface to be cleansed. I prefer to use about one oz. of sal-ammoniac per
square yard of surface to be cleansed, or the surface itself may be heated and
the sal-ammoniac rubbed upon it. The acid water from fermented farina
may be such as is commonly used for preparing iron plates. for tinning; it is
suitable when treating unmanufactured plates, and the plates should be soaked
in the liquor. When using camphine, petroleum, naptha, or other hydrocarbon.
I thoroughly moisten the surface with the hydrocarbon, and then ignite it or
pass a hot iron over it; I repeat the process as often as may be necessary.
I do not usually employ all these substances and methods for cleansing the
surface, but I am guided by the state or degree of oxidation which has taken
place; judgment will therefore have to be used in the processes for rendering
the iron sufficiently clean, both to preserve the same and to render the surface
'fit to receive the composition. For example, if the surface, is originally, very
slightly oxidized, it will require .only to be scoured with an ammoniacal
solution, whilst if badly oxidized or rusted, I have recourse in. succession to
many of the means which have been mentioned to dissolve or remove the
oxide or rust sufficiently. In ordinary cases, and when the plates are only
superficially oxidized, I prefer to proceed as follows:-I scour the surface with
acidulated water; I prefer, in using the acid solution, to scour with sand or
any similar material, or to use a. Bath brick, which is a useful auxiliary in the
process; and I then wash down with a solution of sal-ammoniac with a mop

page_text: or other suitable appliance. I have also found a vessel's bottom to require
the use of many of the above chemical solutions or chemicals which have been
mentioned; thus when the plates are badly-rusted and clogged with paint or
composition, I use a solution of caustic potash, soda, or lime (separate or
together) to remove grease or any extraneous matter, and afterwards wash
or put on camphine, petroleum, or similar product, and set fire to the same,
or I rub or pass a red-hot iron over the surface and then scour with acidulated
water worked with Bath brick, sand, or other auxiliary, and finally wash down
with solution of muriate of ammonia or sal-ammoniac. The iron may then
be dried with an open stove (I prefer a charcoal one), but this drying is not
positively necessary although I deem; it desirable, as I prefer to use the
coating composition as quickly as possible after the iron is cleansed, that the
naked iron may be subject to as little atmospheric influence as possible.
The solutions or chemicals which have been mentioned may be mixed with
any suitable material to form a paste, which may be put and left upon the
surface of the iron for a time; this process I prefer when a little delay is no
object, and where the best result is desired; in particular I find this method
of working applicable in the employment of sal-ammoniac. I bring the
solution of sal-ammoniac to the thickness of whitewash by mixing with it
whitening or chalk, and apply it with a brush. Where camphine or similar
product is used the paste may be put on and repeatedly saturated with the
spirit and then set fire to, or a red-hot iron may be rubbed or laid on or passed
over the surface. Any of the solutions may be made less liquid by adding any
suitable substance to make them into a paste. The sal-ammoniac used for
the final washing I prefer to be that which has been blackened by soot in the
manufacture. I find it frequently desirable, before deciding on which of
the processes above described to adopt for cleaning a surface, to try several of
them on small test portions of the surface.
In preparing the coating composition, I first make a varnish consisting of
gum or resin dissolved in a spirit solvent. I prefer, say, 90 parts by weight
of methylated spirit, 20 of shellac, and.2 of copal. To the varnish I add in
the proportion of from one to five parts by weight per cent. of cyanogen,
cyanic acid, or hydrocyanic acid, their salts, or any of their definite chemical
compounds. I also use iodine or bromine, their salts, or any of their definite
chemical compounds; or in place of using alone any one of the salts, two or
more together may be used. In each case I prefer to employ the larger
proportion, but for the sake of economy sometimes reduce the quantity to one
per cent. In using cyanogen, I pass a stream of that gas through the varnish;
in using cyanic acid, I add that acid to the varnish; in using hydrocyanic

page_text: acid, I employ Scheele's strength and add that acid to the varnish; in using
iodine, I add iodine to the varnish; in using bromine, I add bromine to the
varnish. I prefer, however, to use a salt or salts. In using a cyanogen salt,
I prefer the chloride of cyanogen, although other salts of cyanogen are nearly
or quite as effective; in using a cyanic acid salt, I prefer a sulphocyanate;
in using a bydrocyanic salt, the cyanide of ammonium, or cyanide of zinc, or
other salt may be used; in using an iodine salt, I prefer the biniodide or
deutioduret of mercury; in using a bromine salt, I prefer the bromide of
cyanogen. The exact quantities would be determined to some extent by
the length of voyage to be made by the ship and the sea or seas in which
the ship or vessel may have to pass; thus a vessel going short voyages, and
continually running from salt into fresh water, would not absolutely require
the same expensive coating as vessels going on longer voyages, or where
there is a probability of the vessel being becalmed. In the latter cases I
should prefer to use, say, a cyanogen salt or the deutioduret of mercury, or
both together.
Although this composition may be put on over other compositions, yet the
result could not with safety be depended upon, as the main principle of
cleansing and preserving the iron would be neglected. I consider that no
composition can be really effective except this preliminary principle of
removing sufficiently existing oxidation or rust is attended to. It must be
apparent that no mechanical means such as have hitherto been used to clean
the iron can be efficiently employed. Not only do I consider oxidation or
rust to be prejudicial to the iron, but also to any composition which may be
put on or over iron which has suffered from oxidation or rust. Two, three, or
more coats of the composition may be used; I prefer, however, from four to
six coats according to the length and nature of voyage.
I prefer to put on as the first or first and second coats the varnish consisting
of shellac, copal, and spirit without any admixture, and for the remaining
coat or coats I use varnish mixed with other ingredients, as already stated.
Any of the compositions may be put on one over the other; thus the 3rd and
5th coats may be, say, a cyanogen salt, and the 4th and 6th, say, the
deutioduret of mercury with or without another salt; or other variations may
be made, either as regards the number of the coats or coatings or as regards
the ingredient or salt used in the composition or compositions. Sometimes
for the sake of appearance I employ a coat of paint between the coats of plain
varnish and those containing the poisons. I prefer to use the deutioduret of
mercury for the last coat or coats, either alone or in connection with any of
the other ingredients or salts already mentioned.

page_text: The deutioduret of mercury is insoluble or nearly so in either water or
alcohol, but is soluble in solutions of chloride of sodium, muriate of soda, or
I prefer, as above mentioned, to use the dentioduret of mercury
for the last coat or coats, as it presents a poison in a state soluble in sea
water; I, however, prefer to have another salt in connection with the same for
the latter or last coatings, and prefer the chloride of cyanogen. A base such
as potash or soda may be put into the varnish for cyanogen, cyanic acid,
hydrocyanic acid, iodine, or bromine to decompose and form a salt. I also
use alone or in connection with those poisons which have already been stated,
narcotic and acrid poisons such as "aconite," "croton tiglium," and " oil of
tobacco;" these poisons I prefer to mix with the varnish in the proportion of
one per cent. by weight. Nux vomica or preparations thereof and acetate of
lead may also be used, the latter in the proportion of, say, five per cent. The
composition can be used for either iron or coppered or wooden vessels, and for
a coating for all materials which are submerged. The improvements apply to
the interior as well as to the exterior parts of ships or other surfaces.
What I claim is, first, the cleansing the bottom of an iron ship or other
surface by any of the methods herein-before described, and afterwards coating
the same with varnish composed of resin or gum dissolved in a spirituous
solvent, as herein set forth.
I also claim the compounding varnish composed of resin or gum dissolved
in a spirituous solvent with the several poisonous substances herein-before
mentioned, so as to make a composition suitable for coating the bottoms of
ships and other submerged surfaces.
In witness whereof, I, the said Richard Percy Roberts, have hereunto
set my hand and seal, this Eighth day of March, in the year of our
Lord One thousand eight hundred and sixty-six.
RICHARD P. ROBERTS. (L.s.)