IM- PROVEMENTS IN DRYERS, AND IN PREPARING DRYING OILS FOR OIL PAINTS, VARNISHES, AND OTHER USES
Year: 1853

page_text: LETTERS PATENT to Christopher Binks, of Albert Villa, North
Woolwich, in the County of Kent, for the Invention of "IM-
PROVEMENTS IN DRYERS, AND IN PREPARING DRYING OILS FOR OIL
PAINTS, VARNISHES, AND OTHER USES."
Sealed the 9th December 1853, and dated the 11th June 1853.
PROVISIONAL SPECIFICATION left by the said Christopher Binks
at the Office of the Commissioners of Patents, with his Petition,
on the 11th June 1853.
I, CHRISTOPHER BINKS, of Albert Villa, North Woolwich, in the
County of Kent, do hereby declare the nature of the said Invention
for "IMPROVEMENTS IN DRYERS, AND IN PREPARING DRYING OILS FOR OIL
PAINTS, VARNISHES, AND OTHER USES," to be as follows:-
The object of my Invention is to improve the drying properties of
linseed and other oils intended to be employed as dryers of oils and
oil paints, or applied in the composition of paints, varnishes, and other
compounds, in which good drying oil is an essential element; and my

page_text: Invention consists of the following methods of treating such oils, that
is to say:
Firstly, along with linseed or other drying oil I mix or grind up
some salt of manganese (as, for example, sulphate of manganese);
together with some reagent (as, for example, oxide of lead,) that has
the property of decomposing the manganese salt, by combining with
and abstracting its acid, whilst at the same time protoxide or hydrated
protoxide of manganese is liberated, or a compound formed with the
oil or some element of the oil and the manganese oxide. I then
expose this mixture to the action of atmospheric air, or of oxygen
gas, till sufficient oxygen has been absorbed by it, or the changes in
the oil resulting in its having acquired greatly increased drying pro-
perties be completed.
The result of this treatment of the oil is the formation interme-
diately of hydrated protoxide of manganese (or of a compound of the
manganese oxide with some clement of the oil) and of sulphate of
lead (when oxide of lead is the reagent employed), the former being
diffused through or combined with the oil, and the latter suspended as
an insoluble compound; and the result is, finally, after the absorption
of oxygen and other reactions, the production of a powerfully drying
oil.
This treatment of the oil I prefer to carry on under ordinary atmo-
spheric temperatures; but the operation may, if desired, be aided by
application to the mixture of heat.
The oil and these reacting materials are, during the operation, most
conveniently contained in shallow vessels, in order to expose a large
surface to the action of the air, and the mixture should be stirred from
time to time, or some convenient mechanical contrivance be applied for
agitating it, and alternately or continually exposing each particle to the
action of the air.
The relative proportions of oxide of lead and of sulphate of man-
ganese (when these are employed) I adjust according to the particular
effects upon the oil intended to be produced finally. When I wish to
bring to bear upon the oil the conjoint drying action of both oxide of
lead and oxide of manganese, or of the compounds formed by them

page_text: and some elements of the oil, I use the lead oxide in some excess above
the quantity requisite merely to neutralize the manganese salt present,
in which case the resulting oil holds both lead and manganese in com-
bination, or possesses, when finished, the superior drying and other
qualities due to the combined action of both compounds. But when J
wish to employ the lead oxide only intermediately, that is, as an agent
in the reactions between the elements of the manganese salt and the
oil, then I add the manganese sulphate either in the exact quantity
requisite to neutralize the lead oxide, or in some excess, so as fully and
finally to precipitate it as a sulphate.
The oil so treated speedily acquires a deep colour in the first instance,
clears readily on standing, and forms a rapidly drying oil applicable
to paints, for the manufacture of varnishes, &c., or for a dryer of other
oils or of paints, &c., &c.
For many uses, as when applied as a dryer or as a vehicle of many
kinds of pigments in the manufacture of paints, it is not necessary
before using the oil to separate the insoluble matters produced (such
as the sulphate of lead) in the act of treating the oil as above
described; the oil, together with all the products of the operation, can,
with great advantage, be used as a dryer or as a vehicle of pigments
in making paints or varnishes.
Secondly, in place of merely grinding together in the oil the salt of
manganese and the reagent, as just described, I previously form a
combination between the fatty acid of the oil and the reagent; as, for
example, when oxide of lead is the reagent, I heat together oxide or
hydrated oxide of lead and linseed or other oil, thereby producing the
well known compound of the oleic acid of the drying oil and oxide of
lead, and this compound I dissolve in a quantity of the oil to be ren-
dered more more drying, and then to this solution add the sulphate or
other salt of manganese, and expose the mixture to the action of air or
oxygen gas, as described generally in reference to the above or first
method, till sufficient oxygen has been absorbed, and the desired
changes and effects upon the oil are completed. The result in this
case (though, intermediately, the reactions leading to it are to some
extent different from those under the first method) is, as before, the
of

page_text: production of a powerfully drying oil; and the operations and relative
proportions of materials to be used are the same, and are adjusted in
the same manner as herein-before described.
I employ under the first method any other salt of manganese than
the sulphate therein specified, and any other reagent than the oxide of
lead that will yield, as the direct products of their decompositions or
reactions, protoxide or hydrated protoxide of manganese, or a combina-
tion thereof, with the elements of the oil, and at the same time a salt
or compound of the reagent capable of exercising no injurious influence
upon the oil or upon its drying properties. Thus, I employ the acetate
or the sulphite or the oxatate of manganese, and there are several other
salts of the protoxide that can likewise be employed; and as reagents
I employ baryta or lime or ammonia, and there exist several others
that are likewise applicable. And under my second method I do not
confine the practice of the Invention to the use of the compound
formed with the fatty acid of linseed or other drying oil and oxide of
lead, but employ at pleasure (or from having regard to any special
character of the oil to be finally produced, as when it is required to be
free from lead, and as such used as a vehicle or dryer of oxide or zinc
paints,) the like products formed of such fatty acid and the oxide of
baryta or lime or ammonia or other bases; and I employ in place
of the proto sulphate any other proto salt of manganese, as the sulphite,
the acetate, the oxatate, &c., &c., whose reactions result finally in
giving to the oil the high drying qualities described.
And I do not under either the first or second methods confine the
practice of my Invention to the use of salts of manganese only, but I
employ at pleasure, in place of the manganese salts specified, the cor-
responding salts of iron, and particularly the sulphate and the acetate,
though for most practical purposes I prefer to employ the salts of
manganese.
Thirdly, in place of the proto salts of manganese or of iron, I prefer,
in certain cases, to substitute salts of a higher oxide of either metal; as,
for example, for the proto sulphate of manganese under any of the
above methods, I substitute the sesqui sulphate of manganese, or any
other salt of the sesqui oxide of manganese. And in place of the

page_text: proto salts of iron I substitute in like manner salts of sesqui
sulphate of iron, as, for example, the persulphate of iron for the proto
sulphate.
And in those cases in treating the oil in which such per salts or
more highly oxodized salts are employed, the reactions between the
reagents used and the oil do not need the aid of exposure to air or to
oxygen gas to complete them, or to produce to an efficient extent
the required drying effects upon the oil, or the oil when mixed with
such materials does not require oxydation from the air or oxygen to
the same extent that it does when only the proto salts are employed;
consequently, such mixtures of the per salts with the reagents and the
oil may be used as dryers or as vehicles of paints, with or without
previous exposure to air or oxygen.
Fourthly, in place of liberating protoxide or sesqui oxide of manga-
nese or of iron, or of forming compounds with them and the elements
of the oil, or of so ordering the process that the oxide shall be made to
act in its nascent state upon the oil, I form the hydrated protoxide
or sesqui oxide of manganese or of iron separately, and then mix it
with the oil, and expose the mixture to air or oxygen till the required
changes have been produced; and such oil I use alone as a dryer of
other oils, or for the manufacture of paints, &c.; or I add to it, or com-
bine with it, when required, oxide of lead, or the drying compound of
fatty acid & oxide of lead, in order to secure the advantages of the
joint effects of the presence in or reaction upon the oil of both the lead
and manganese compounds.
Fifthly, my Invention consists in adding to linseed or other drying oil
some acetate of manganese or of iron, and then exposing this mixture
for some time at common temperatures, or, when aided by heat, to the
action of air or oxygen gas. The oil so treated gradually acquires
powerful drying properties, and is in other respects greatly improved
for application as a vehicle of pigments in the manufacture of paints,
or as a varnish oil, or as a dryer of other oils or paints. And, in place
of adding to the oil ready formed acetate of manganese or of iron, I
sometimes find it convenient to grind up with the oil acetate of lead,
or of baryta, or of lime, or other convenient acetate, together with some

page_text: salt of manganese or of iron, capable, by reaction of the acetate
present, of yielding acetate of manganese or of iron. And of such salts
I prefer to use the sulphate or sesqui sulphate of manganese or of iron.
In like manner, as above described, in reference to my other methods,
this mixture is exposed to the action of air of oxygen gas till the con-
sequent changes or reactions with the oil are completed. The resulting
highly drying oil may then be cleared, by standing, from all insoluble
compounds or deposits, or it may, for many purposes, be advantage-
ously employed, without previous separation from it of such insoluble
products, as for a vehicle of pigments in the manufacture of paints, or
as a dryer of oils or paints.
SPECIFICATION in pursuance of the conditions of the Letters Patent,
filed by the said Christopher Binks in the Great Seal Patent
Office, on the 10th December 1853.*
TO ALL TO WHOM THESE PRESENTS SHALL COME, I,
CHRISTOPHER BINKS, of Albert Villa, North Woolwich, in the County
of Kent, send greeting.
WHEREAS fler most Excellent Majesty Queen Victoria, by Her
Letters Patent, bearing date the Eleventh day of June, in the year of
our Lord One thousand eight hundred and fifty-three, in the sixteenth
year of Iler reign, did, for Herself, Her heirs and successors, give and
grant unto me, the said Christopher Binks, Her special licence that
I, the said Christopher Binks, my executors, administrators, and
assigns, or such others as I, the said Christopher Binks, my exccu-
tors, 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, ex-
ercise, and vend, within the United Kingdom of Great Britain and
Ireland, the Channel Islands, and Isle of Man, an Invention for "Im-
PROVEMENTS IN DRYERS, AND IN PREPARING DRYING OILS FOR OIL PAINTS,
VARNISHES, AND OTHER USES," upon the condition (amongst others) that I,
the said Christopher Binks, by an instrument in writing under my hand
and seal, should particularly describe and ascertain the nature of the

page_text: 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 Christopher Binks, 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, that is to say:
The objects of my Invention are, first, to improve the drying properties
of drying oils, and more particularly of linseed oil, in order to adapt
such oils for being employed as dryers of other oils and of oil paints,
as well as for all the applications in which good drying oil is a requisite;
and, secondly, to substitute effective and convenient methods of
operating upon such oils for the purpose of so improving their drying
properties, in place of the uncertain, objectionable, and dangerous
process of boiling oils as hitherto practised; and the nature of my
Invention is as follows:-
Firstly, I subject linseed or any other drying oil to the action of
certain metallic oxides, which, whilst in contact with such oils under
ordinary atmospheric temperatures, have the property, on exposure to
air or to oxygen gas, of absorbing oxygen, and of passing from a
lower to a higher state of oxidation, and in the act of this transforma-
tion, or as a consequence of it, of inducing upon the oil the peculiar
offects hereafter described.
Of such oxides I prefer to use the protoxide of manganese, and this
in form of the hydrated protoxide, and I carry on the operation with the
oil as follows: I take hydrated protoxide of manganese, and intimately
mix it with, or diffuse it through, the linseed or other oil intended to be
operated on. (From two to five parts of the oxide to one thousand parts
of the oil form convenient relative proportions, but within certain and
obvious limits the larger the relative proportion of the oxide to the oil
the more rapidly is the change upon the oil effected.) And then 1
expose this mixture to the action of atmospheric air or of oxygen gas,
until sufficient oxygen has been absorbed to produce upon the oil the
peculiar changes intended. The oil under this treatment gradually

page_text: changes color (passing from the yellow or greenish yellow of raw linseed
oil into the deep brown color peculiar to linseed oil that has been
toiled), and acquires, as these changes proceed, the superior drying
properties, and, finally, the characteristic flavour and smell of "boiled
oil." The protoxide of manganese itself assumes the dark color of a
sesqui oxide, and the excess of it floating in the oil readily subsides to
the bottom of the vessel so as to admit of the easy separation of the
clear oil from it. The dark rich color of the oil, and the amount of
drying power it has attained up to this point, can, if desired, be retained
and kept any length of time without further change, simply by excluding
all further access of atmospheric air or of oxygen from it. But on a
still further continued exposure of this deep rich colored oil to air or to
oxygen, it goes on to pass through another and further series of changes.
As it absorbs oxygen the drying power of the oil progressively increases,
and at the same time it passes from the condition of the deep rich brown
colored oil, just described as the result of the first stage, into a fine
straw or amber colored oil, which is the final result, and at which final
stage the oil has acquired the maximum drying power. Hence this new
method of treating oils effects the production at pleasure (according to
the extent to which the operations are carried) of two kinds of drying
oil, the one similar in appearance (but possessed of superior drying
and other properties) to ordinary "boiled" oil, and the other a powerfully
drying oil that has the peculiar advantage of possessing a fine light
straw or amber color.
I prefer, from the simplicity and convenience of the process, to carry
on the operations simply by exposing a mixture of the oil and the
oxide to the action of atmospheric air under ordinary atmospheric
temperatures, and to place the mixture in shallow vats, so as to expose
al large surface to the action of the air, and to stir or agitate the
mixture by hand occasionally. But the application of a temperature
superior to common temperatures quickens the operation, as does also the
passing through the mixture or through the cleared oil of atmospheric
air or of oxygen, and the application of any mechanical contrivances for
agitating the mixture so as to expose a larger surface to the action of the
air. Therefore in practice any of these adjuncts may be applied to the

page_text: operations with advantage, either in shallow vats or deeper vessels, if it
be desired to accelerate them beyond the rate obtained under ordinary
temperatures, or under the simpler conditions of the operations just
referred to.
If the oil resulting from the operations carried to the extent so far
described be still further oxygenized by a longer continuation of the
exposure to the action of air or of oxygen, it gradually passes from its
fluid state, or the state peculiar to ordinary linseed or boiled oil, into a
semi solid condition, in which state it constitutes a powerful and con-
venient form of dryer to be added to other oils, or to oil paints, and is
applicable with great benefit to a variety of other important purposes
in the arts.
Although I prefer to use the hydrated protoxide of manganese, I do
not confine myself thereto, as the protoxides of some other metals
may be substituted, as, for example, the hydrated protoxide of iron, &c.
Secondly, it is well known that oxide of lead forms a combination
with the oleic acid of drying oils, but that this composition as usually
produced has not hitherto been made applicable as an adjunct to drying
oils, or to oil paints, for the purpose of drying them. But I prepare a
light colored and fine drying oil containing lead in manner as follows:
I first form, in the usual manner, an oleate of oxide of lead from
linseed oil and litharge, or with hydrated oxide of lead, and then I
dissolve this, or a part of it, in a large excess of linseed or other drying
oil (from two to five parts of the oleate to one thousand of oil form
convenient relative proportions, though a larger proportion of the lead
preparation may in many cases be advantageously employed), and then
I heat this mixture till an excess of water (always present unless so
heated) is expelled from the mixture, upon which there results an oil,
having lead in combination with it, that after standing becomes trans-
parent, is of a light straw or amber color, and possesses powerful drying
properties. It is the presence of an excess of water in a solution of
the oxide of lead in an excess of oil that imparts to such a mixture as
is usually made its opaque appearance, and renders it an imperfect
dryer. And my Invention under this head consists in expelling the
water by application of heat to the solution of oxide of lead in oil

page_text: subsequently to the formation of the oleate, upon which, after standing
and subsidence of insoluble particles, a fine transparent amber colored
drying oil is procured.
Most conveniently in practice the process is conducted as follows:-
From one part to five parts of litharge are ground in a small quantity
of linseed oil, and then this mixture is diffused through one thousand
parts of linseed oil, some water is then added to the mixture, and it
is heated by steam or otherwise until the combination between the
oleic acid of the oil and the oxide of lead is completed, and, conse-
quently, a solution of oleate of lead is diffused through the excess of
oil present. The resulting mass is opaque and soapy looking, but on
further application of heat at or a little above 212° Farenheit the
excess both of free and of combined water is expelled and a compound
produced, which, on standing, form a fine amber colored drying oil.
For litharge and the addition of free water may, in this operation,
be substituted hydrated protoxide of lead without additional water,
under which condition the process is more rapidly completed than when
litharge and water only are employed.
The lead oil as so produced forms an excellent dryer of other oils,
and a most advantageous substitute (both as to its mode of preparation
and as to its properties) for ordinary "boiled" oil in all its uses and
applications. And, in like manner, with the oil produced by my first
process, a further exposure to air or oxygen (after formation of the
compound or preparation of the oil as just described) greatly increases
and improves its drying and other properties.
Thirdly, I form a fine drying compound oil, fit to be used as a dryer
and for all purposes wherein a quick drying oil is requisite, by mixing
together the finished oils resulting from my first process and that from
my second process as just described, a combination which I find to
yield an oil of very superior qualities.
Fourthly, in place of preparing, by a separate and previous operation,
the manganese protoxide as used under my first process, or by a sepa-
rate and previous operation preparing the new lead oil as under my
second process, I proceed with my operations as follows:-
Along with linseed or other drying oil I mix or grind up some salt

page_text: of manganese (as, for example, sulphate of manganese), together with
some reagent (as, for example, oxide of lead,) that has the property of
decomposing the manganese salt by combining with and abstrating
its acid, and of liberating at the same time protoxide or hydrated pro-
toxide of manganese. I then expose this mixture (in the manner and for
the same purposes, and, if desired, under the same modifications as to
temperature, application of mechanical agency for agitating it, and pass-
ing air through it, as are described under my first process,) to the
action of atmospheric air or oxygen till the required changes in the
mixture and effects upon the oil have been completed. I prefer,
though I do not confine myself to such proportions, to use such a
proportion of sulphate of manganese, or other salt of manganese,
as secures, on its decomposition, the presence in the oil of about from
1 to 3 parts of the hydrated protoxide to one thousand parts of the oil,
and the relative proportions of oxide of lead and of sulphate of man-
ganese (when these compounds are employed) I adjust according to
the particular effects upon the oil intended to be produced finally;
when I wish to bring to bear upon the oil the conjoint action of both
oxide of lead and oxide of manganese, or of any compounds formed
by them and any element of the oil, I use the lead oxide in some
excess above the quantity requisite merely to neutralize the manganese
salt present, in which case the resulting oil holds both lead and man-
ganese in combination, or possesses, when finished, the superior drying
and other qualities due to the combined action of both compounds; but
when I wish to employ the lead oxide only intermediately, that is, as
an agent in the reactions between the elements of the manganese salt
and those of the oil, then I add the manganese sulphate either in the
exact quantity requisite to neutralize the lead oxide, or in some
excess above that quantity, so as fully and finally to precipitate the
lead oxide as a sulphate. The oil so treated, whether the opera-
tion be so conducted as to yield a mixed lead and manganese oil,
or a manganese or oil only, speedily acquires a fine rich brown
colour in the first instance, and clears readily on standing, possesses
great drying powers as soon as it has taken the brown colour, and
on further exposure to air or to oxygen gradually bleaches, and

page_text: improves still further as it is further exposed in its drying power in
its general properties.
I employ under this fourth process any other salt of manganese than
the sulphate hitherto referred to, and any other reagent than the oxide
of lead for decomposing the manganese salt that will yield as the direct
products of their decompositions or reactions protoxide or hydrated
protoxide of manganese, or a combination thereof with elements of the
oil, at the same time a salt or compound of the reagent that exercises
no injurious influence with the oil, or upon its drying properties. Thus
I employ at pleasure the axitate or the sulphate on the oxalate of
manganese, and there exist several other salts of the protoxide that can
likewise be employed. And as reagents, in place of the oxide of lead,
I use at pleasure baryta, or lime, or ammonia, and there exist several
others that are applicable likewise.
Again, under this fourth part of my Invention, in place of merely
grinding together in the oil the salt of manganese and the reagent
to decompose it, as just described, I previously prepare the reagent
used by joining a combination between it and the fatty acid of linseed
oil. As, for example, when oxide of lead is the reagent I form, by well-
known processes, an oleate of lead with the oleic acid of linseed oil,
and this oleate I dissolve in a quantity of the oil to be rendered more
drying, and then to this solution add the sulphate or other salt of
manganese, and expose the resulting mixture to the action of air or of
oxygen, in the same manner as described generally in reference to the
immediately preceding and also to the first part of my Invention, till
the desired changes have been completed.
And, in place of the combination of the fatty acid with oxide of lead,
I employ at pleasure from regard to any special character of the
oil to be finally produced, as when it is required to be free from lead,
and intended to be used as a vehicle of oxide of zinc paints, the well-
known products formed of the fatty acid of linseed oil with oxide of
barium, or with lime, or ammonia, or some of the other known bases.
In place of using the proto salts of manganese or other metal, and
of obtaining by their decomposition, as just described, the liberation,
whilst in contact with the oil, of protoxide of the metal employed, I

page_text: prefer, in certain cases, to substitute salts of a higher oxide of the metal
used, as, for example, for the proto sulphate of manganese I substitute
sesqui sulphate or any other salt of the sesqui oxide of manganese.
And in place of the proto salts of iron I substitute salts of the sesqui
oxide of iron; as, for example, the persulphate in place of the proto
sulphate, in which cases respectively there is leberated in the oil by the
action of the reagents present sesqui oxide of manganese or of iron,
instead of the protoxide, as under the previous modification.
Fifthly, along with linseed or other drying oil I mix acetate or
nitrate of manganese, and leave these to react for some time, upon
which a peculiar change takes place in the oil, and it requires powerful
drying properties (from one part to five parts of either of these salts to
one thousand parts of oil are useful properties to employ). And, in
place of adding to the oil ready formed acetate or nitrate of manganese,
I produce either salt by decomposition whilst in contact with the oil;
as, for example, I grind up with the oil acetate of lead, or of baryta, or
of lime, or other convenient acetate, together with sulphate of manga-
nese, this yielding acetate of manganese and a sulphate of the base
employed. Or, I grind in the oil nitrate of lead, or of baryta, or of lime,
and to this add sulphate of manganese, producing, consequently, nitrate
of manganese and a sulphate of the base employed.
Agitation or increasing the temperature of the mixture facilitates the
operation, as does also passing through it atmospheric air or oxygen, in
this as in the former cases.
In witness whereof, I, the said Christopher Binks, have hereunto
set my hand and seal, this Tenth day of December, in the year
of our Lord One thousand eight hundred and fifty-three.
CHRISTOPHER BINKS. (L.S.)