IMPROVEMENTS IN PAINTS AND PIGMENTS
Year: 1848

page_text: TO ALL TO WHOM THESE PRESENTS SHALL COME, I, FRANCIS
GYBBON SPILSBURY, of Saint John's Wood, in the County of Middlesex,
Gentleman, send greeting.
WHEREAS Her present most Excellent Majesty Queen Victoria, by Her
Royal Letters Patent under the Great Seal of the United Kingdom of Great
Britain and Ireland, bearing date at Westminster, the Second day of
November, One thousand eight hundred and forty-eight, in the twelfth year of
Her reign, did, for Herself, Her heirs and successors, give and grant unto me,
the said Francis Gybbon Spilsbury, my exors, adññors, and assigns, Her
especial licence, full power, sole privilege, and authority, that I, the said
Francis Gybbon Spilsbury, my exors, adññors, and assigns, or such others as
I, the said Francis Gybbon Spilsbury, my exors, admors, or assigns, should
at any time agree with, and no others, from time to time and at all times
during the term of years therein expressed, should and lawfully might make,
use, exercise, and vend, within England, Wales, and the Town of Berwick-
upon-Tweed, and in the Islands of Jersey, Guernsey, Alderney, Sark, and
Man, and in all Her said Majesty's Colonies and Plantations abroad, my
Invention of "IMPROVEMENTS IN PAINTS AND PIGMENTS;" in which said Letters
Patent is contained a proviso, that I, the said Francis Gybbon Spilsbury, should
cause a particular description of the nature of my said Invention, and in what
manner the same is to be performed, by an instrument in writing under my
hand and seal, to be inrolled in Her said Majesty's High Court of Chancery

page_text: within six calendar months next and immediately after the date of the said
in part reciting Letters Patent, as in and by the same, reference being there-
unto had, will more fully and at large appear.
NOW KNOW YE, that in compliance with the said proviso, I, the said
Francis Gybbon Spilsbury, do hereby declare that the nature of my said In-
vention, and the manner in which the same is to be performed, are fully
described and ascertained in and by the following statement thereof, that is
to say:-
My Invention consists, first, of manufacturing pigments and paints from
lead by the application of tungstic acid.
Secondly, my Invention consists of manufacturing pigments and paints by
the application of soda and potash, oxides of tungsten.
Thirdly, my Invention consists of manufacturing pigments and paints by the
application of tungstate of iron and manganese.
Fourthly, my Invention consists of manufacturing pigments and paints from
lead by the application of antimonious acid and antimonic acid.
And, fifthly, my Invention consists of manufacturing pigments and paints
by the application of products of bitter aloes, acted on by nitric acid with
alkaline, earthy, and metallic bases.
In the manufacture of pigments and paints from lead, when tungstic acid is
used, I prefer to obtain the combination of tungstic acid with lead in the
following manner:-I take 100 lbs. of commercial tungstate of soda and
dissolve it in as small a quantity of boiling water as will effect the purpose, to
which solution I add a saturated solution of soluble salt of lead (such as the
acetate, nitrate, or chloride of lead,) as long as any precipitate falls. The pre-
cipitate having settled, the supernatent fluid is to be removed by a syphon or
otherwise; fresh water is then to be poured upon the precipitate, and the
same is to be well stirred up and again allowed to settle, and the clear liquid
again removed. This operation of washing is to be repeated with fresh quan-
tities of water until the water ceases to contract any taste from the precipitate.
And in order to remove the excess of lead, I pour over the washed precipitate
twenty-five pounds of acetic acid, specific gravity 1.05, or of nitric acid, specific
gravity 1-3, diluted with their bulk of boiling water. The mixture is allowed.
to stand forty-eight hours, agitating it from time to time. At the expiration
of that period the clear supernatent fluid is to be removed, and the precipitate
is again to be subjected to repeated washings, until the water that passes
off is tasteless. The precipitated matter is next to be ladled out on to frames
on which are stretched linen or horsehair cloths, where it is permitted to drain
until it assumes the consistence of moist clay, when it is to be passsed through

page_text: a color mill, after which I cut it into convenient sized lumps and place them
upon tiles made of any porous or absorbent material, and dry them in rooms
heated to about 150° of Fahrenheit. The pigment thus prepared may then be
mixed with vehicles in like manner to white lead, and such pigments and
paints made therefrom will be suitable to be used as substitutes for white
lead.
In carrying out the second part of my Invention, I prefer to take at the
rate of one hundred and eighteen parts of tungstic acid of commerce and fuse
it at a bright red heat in a crucible with fifty-three parts of calcined carbonate
of soda. When the mixture ceases to effervesce I add to the melted matters
more tungstic acid as long as fresh additions are dissolved, which is ascertained
by dipping an iron rod into the melted mixture after each addition, and if that
which adheres retains a whitish or cream color, more may be added, but if
the adhering matter is dark no more is to be added. This compound, having
been poured out on a cold plate of iron and afterwards reduced to a coarse
powder, is to be placed in a closed retort of iron or earthenware, set horizon-
tally across a furnace, like an ordinary gas retort. This retort is to have
inserted into its front end a pipe in order to admit hydrogen gas or carburetted
hydrogen; on the opposite end of the retort is to be fixed another pipe for
carrying off the gas and products. The object of this arrangement is to
permit a constant stream of hydrogen or coal gas to pass continually through
the retort, and over the heated materials contained in it, and out again into
the air. The ground compound of tungstic acid and soda having been spread
over the bottom of the retort is to be heated to a red heat, and it should bo
stated that the process will be accelerated by not permitting the materials to
flux. When the matters in the retort have thus become heated, the gas is to be
allowed to pass over the heated materials in a gentle stream for several hours,
and the materials are to be stirred from time to time, for which purpose I use
a rake, the handle of which passes air-tight through a stuffing box in the end
of the retort. At first dense vapours and steam will escape by the exit pipe.
These indications will gradually diminish, and when they have ceased altogether
the compound may be withdrawn from the retort. It is now to be thrown
into water contained in a convenient boiler of lead, or preferably of earthen-
ware, so that the water well covers it, and it is to be boiled, the boiling process
being repeated with fresh quantities of water as long as any taste is imparted
to the water; it is then to be boiled in dilute muriatic acid (muriatic acid of
commerce diluted with its weight of water) for about three hours. The dilute
acid is then to be removed and the matter washed with water; it is next to be
washed with an alkaline solution (one pound of carbonate of soda to a gallon

page_text: of water), after which it is to be again well washed with water, and it is then
to be removed and dried at a heat which should not exceed 112°. It will now
present the appearance of yellow metallic scales and bronze-colored powder.
These are to be sorted into different sized powders by passing through sieves
of different degrees of fineness. The fine pigment is to be ground, and is then
fit to be mixed with oil, turpentine, or other suitable vehicle; the coarser
scales are proper to sift upon surfaces which have been made adhesive by the
application of gold size or other size.
If instead of fifty-three parts of calcined carbonate of soda, as described,
above seventy parts of calcined carbonate of potash be substituted, and the
process followed out as described, the result will be a fine rich purple pigment,
which is to be sorted and treated as before explained. I would remark, in
respect to this part of my Invention, that I am aware that chemists have spoken
of combinations of the oxide of tungsten with soda; but the same has not
heretofore been manufactured into pigments and paints.
I will now describe the third part of my Invention. To make the rich
brown paint I take wolfram (native tungstate of iron and manganese) and grind
it with water to a smooth paste; this paste dried is a pigment, which may
either be sent into the market in this condition, or ground with linseed oil or
other vehicle to the state of a stiff paste like white lead, or mixed with
sufficient vehicle to make it into paint.
I will now describe the fourth part of my Invention. I take two hundred
parts of sulphuric acid of commerce and fifty parts of common crude metallic
antimony and boil the mixture in any convenient vessel not acted on by the
acid; the residuum is then heated to redness; add to it twenty-one parts of
calcined carbonate of soda and fuse these matters together; the resulting
mass is to be boiled with water, which will dissolve out the antimonite of soda
and leave a residuum of insoluble superantimonite of soda, which may be
melted up in a future operation with fresh soda to convert it into antimonite of
soda. To the solution of antimonite of soda is to be added a concentrated
solution of a neutral salt of lead, such as the acetate, nitrate, or chloride, until the
solution ceases to precipitate. The precipitated white powder is to be well
washed with water; the precipitate is then to be laid on frames with strained
haircloth and drained. The precipitate is to be ground and made into lumps
and dried upon absorbent tiles at a temperature of 150°. This pigment is to
be ground up with oil or other vehicle in like manner to white lead. To make
pigments or paints consisting of the antimoniate of lead, I deflagrate in a red-
hot crucible or in the bed of a reverberatory furnace heated to redness one
part of crude antimony (sulphuret of antimony) with five parts of nitrate of

page_text: soda; the residue is to be washed with boiling-hot water, when it will be
partially dissolved, and the clear supernatent liquid being poured off, is to be
gradually mixed with a concentrated solution of a neutral salt of lead, such as
the acetate, nitrate, or chloride, until the solution ceases to yield a precipitate.
This precipitate is to be washed like the last, laid out on frames of strained
cloth to drain, ground, and dried in lumps on absorbent tiles at a temperature
of about one hundred and fifty degrees. It is then a white pigment, to be
treated mixed with vehicles in like manner to white lead.
I will now describe the fifth part of my Invention. From the compounds of
earthy alkaline and metallic bases with the product arising from the continued
action of strong nitric acid upon the resin of bitter aloes I obtain various
shades of carmine. I take one part of bitter aloes and eight parts by weight
of nitric acid (specific gravity 1.3 to 1.5) and heat the mixture in a por-
celain or glass vessel until it ceases to react; I then distil the liquid from a glass
retort until six or seven parts of nitric acid have passed over into the receiver;
to the residue I add three or four parts more of fresh nitric acid of the same
specific gravity, and keep the whole at a temperature nearly boiling until gas
is no longer given off, which will require many hours. When cooled water is
poured upon the residue, which will cause a copious precipitate of golden
looking sand. This precipitate is to be well washed with water, and to two
hundred and thirty-three parts of it a boiling-hot solution of seventy parts of
dried carbonate of potash or fifty-four of calcined carbonate of soda is to be
added. The precipitate will dissolve in the hot solution, and on cooling
quickly there will be deposited a fine carmine red sediment; if slowly cooled
it will be deposited in coarse crystalline grains. In either case, after being
well washed in cold water the sediment is to be ground in a moist state to an
impalpable condition, and is then to be laid in small drops upon heated
absorbent tiles and dried at a temperature not exceeding one hundred and
fifty degrees, care being observed not to allow the heat to rise to any con-
siderable extent, or the matter is explosive. To procure the different shades, a
hot solution of the potash or soda carmine just described is to be mixed with a
hot solution of any earthy or metallic salt, as sulphate of magnesia, acetate of
lead, acetate of lime, nitrate of barytes, until a precipitate ceases to be formed.
These precipitates washed, dried, and ground in the same way as the potash or
soda carmine just described, will afford pigments of various hues.
Having thus described the nature of my Invention, and the manner of per-
forming the same, I would have it understood that I do not confine myself to
the details herein given, so long as the peculiar character of any part of my
Invention be retained; but what I claim is,-

page_text: First, the manufacture of pigments and paints from lead by the application.
of tungstic acid.
Secondly, I claim the manufacture of pigments and paints by the applica-
tion of soda and potash, oxides of tungsten.
Thirdly, I claim the manufacture of pigments and paints by the application
of tungstate of iron and manganese.
Fourthly, I claim the manufacture of pigments and paints from lead by the
application of antimonious acid and antimonic acid.
And, fifthly, I claim the manufacture of pigments and paints by the applica-
tion of products of bitter aloes acted on by nitric acid with alkaline, earthy,
and metallic bases.
In witness whereof, I, the said Francis Gybbon Spilsbury have hereunto
set my hand and seal, this Second day of May, in the year of our
Lord One thousand eight hundred and forty-nine.