Improvements in the Manufacture and Use of Paint..
Year: 1897

page_text: Date of Application, 19th Oct., 1897
Complete Specification Left, 18th Mar., 1898-Accepted, 2nd July, 1898
PROVISIONAL SPECIFICATION.
Improvements in the Manufacture and Use of Paint..
We, CHARLES EUGENE LEE, of New York City, State of New York, U.S.A.,
temporarily residing in Norfolk Street, Strand, in the County of London, Electrical
Engineer, and CHARLES FRANCIS LAWTON, ALBERT LINDEL LAWTON, and ARTHUR
WILLIAM LAWTON, all of Water Street, New York City aforesaid, Chemists,
do hereby declare the nature of this invention to be as follows:-
This invention has for its object the production of a water-mixed paint which
shall become insoluble in water as soon as the paint is dry; be capable of receiving
many different colours, and present greater resistance to the effects of rain, sunshine
and frosts than ordinary oil mixed paints.
To begin with we take oxide, hydrate, carbonate, chloride or oxychloride or
oxalate of lead, or the oxide or hydroxide of calcium, stroutium, barium,
magnesium, zinc or copper, and should it be lead that in this particular instance is
to be used instead of any of the other metals we take of the lead compound ten
pounds and mix it with from five to twenty pounds of very finely ground carbonate
of lime together with such pigments as are desired and in quantities according to
the nature of the color and depth of tint wanted, varying the quantity of carbonate
of lime according to these conditions.
In making the foregoing mixture, whatever metallic oxides or salts be used, we
so compound it that from ten to fifty per cent. of the solid or insoluble ingredients
shall be in the condition of hydroxide or hydrated silicate of one or more of the
metallic oxides or metallic salts present. For instance, a compound can be made of
ten pounds of carbonate of lead, five pounds of zinc hydroxide, Zn(OH)2 or
hydrated zinc silicate ZnSi0, + 2 H2O, and twenty pounds of very finely ground
carbonate of lime. These ingredients, together with coloring matter, should some
other color than white be wanted-are thoroughly mixed with ten to fifteen pounds
of water, and with fifteen to thirty pounds of a three to five per cent, water solution
of silica made by the well known diffusion or dialysis process of Graham. This last
ingredient being added and well stirred in, the whole mixture is then ground
through a paint mill, which finishes it.
It is a
This compound so made and ground we will call for convenience No. 1.
creamy paint-like liquid of variable consistence according to the amount of water
and the nature of the insoluble ingredients and colors that it contains.
The neutral solution of silica used in compound No. 1 is a thin, very mobile
solution, and does not turn to the coagulated condition until some time after it has
been mixed with the other ingredients. This is not to be confounded with the
transparent zinc ammonia soda silicate used in mixture No. 2.
Compound or mixture No. 2 is made by taking an eight to sixteen per cent. solution
in water of potash or soda silicate, singly or nixed, and adding to twenty pounds of
this alkaline silicate solution one half of a pound to one pound of a strong solution
of hydrated zinc oxide in strong aqua ammonia. This solution of zinc in aqua
ammonia will produce a white pulky clot in the alkaline silicate solution when first
added to it, but by vigorous stirring, the clot of compound zinc-sodium-ammonium

page_text: silicate so produced dissolves in the soda or potash silicate and ammonia, giving
a clear transparent solution of a compound alkaline and zinc silicate, the compound
silicate being kept in solution by the ammonia present and by the excess of potash
or soda silicate.
The reaction which ensues when the compound of zinc oxide and ammonia is
added to the silicate of soda or of potash in solution of mixture No. 2 may then be
possibly expressed thus:
.
As carbonate of ammonia dissolves oxide of zinc (and as carbonates, silicates and
borates re-act with other compounds in a manner having so many points of resem-
blance that chemists have placed carbonic, silicic and boric acids in a group (it is
possible that the ammonia present dissolves the silicate of zinc produced or the
compound silicate of zinc and soda whichever it may be, when the solution of zinc
oxide in ammonia is first added to the silicate of soda solution.
Compounds Nos. 1 and 2, though used for painting the same surface, must be
kept in separate vessels, and compound No. 1 must be well stirred up from the
bottom with a stick or paddle just before using.
To apply the paint the operation is as follows: Should a thin coat only be
desired, enough water is added to compound No. 1 to make it quite thin, and then
with a brush or atomizer the liquid is evenly applied over the surface of brick, wood,
stone, plaster or metal to be painted, and allowed to dry.
After mixture No. 1 has dried on the surface to which it has been applied, it is
gone over with a coat of the thin liquid No. 2, which quickly penetrates the dry
porous coat of No. 1 with which it reacts chemically, producing a hard, smooth,
tough, adherent compound, totally insoluble in water, hot or cold.
If lead carbonate, zinc hydrate, zinc silicate, and calcium carbonate be some
of the ingredients of coat No. 1, then possibly (we cannot assert with certainty)
the re-action will be as follows:
the calcium silicate represented in the first member of the equation being produced
by the water solution of silica coming in contact with the calcium hydrate in
mixing the materials for the first coat.
Where there is a mixture of basic oxides in the first coat, then there may be a
mixed reaction, but always we believe approximating the formulas given.
In effecting the decomposition of the sodium chloride, as hereafter mentioned,
in a water solution of silica by means of lead oxide without the use of heat, the
reaction may be expressed thus:
4 Si(OH) + 2 NaC1 + 2 PbO-
=
PbNa₂SO₁ + PbCl₂ + 8 H₂O.
10

page_text: be produced, it would be still less soluble. In this case the reaction would be
indicated by:
4 Si(OH), + 2 NaCl + 3 PbO = PbN₁₂S₁₁₁0 + Рb₂OC₁₂ + 8 H₂O.
10
Should a thick coat of paint be desired, less water is used in No. 1, and instead
of applying No. 1 first to the surface to be painted, as in the case just described,
No. 2 is used for the first coat. This quickly dries, and after it is dry, a coat
of No. 1 is laid over it, and after this second coat is dry, a coat of No. 2, making
the third coat, is laid over No. 1, which finishes the painting.
Should the surface to be painted be of a very porous absorbent nature, then to
make the work look even or free from spottiness, it will be necessary to grind the
transparent colorless No. 2 compound with material to give it body and then the
color desired for the finished paint. This can be done without difficulty if care is
used to avoid those ingredients which produce setting of the soluble silicate of
No. 2, but which setting ingredients are a necessary constituent of No. 1.
The material for giving body and color to No. 2, which can be used without
setting it, are finely ground carbonate of lime, sulphate of barium, magnesia
silicate, calcium silicate, zinc silicate &c. For colors which will not produce
setting in No. 2, there can be used peroxide of iron, green and blue ultramarine,
red lead, and nearly all the variously colored smalts or glass strongly colored by
being fused with various metallic oxides and then reduced to fine powder.
Instead of using, carbonate of lead in compound No. 1 as the setting material to
render the paint insoluble by the reaction between coats No. 1 and 2, other
compounds and salts of lead can be used, such as chlorides and oxchlorides of lead,
or chromate, manganate, fluoride, sulphate &c. of lead can be used, or the lead
compounds in No. 1 can be partly or entirely replaced by oxide, carbonate or
chromate of zinc, or by ferrous carbonate, or by copper compounds, such as oxide,
carbonate, or arsenicate of copper, or by those barium compounds which are
nearly insoluble but will react with an alkaline silicate.
Compound No. 2, however, as has been heretofore stated must not be mixed
with any substance like the above, which would react with the soluble silicate in
No. 2 before it could be applied to the surface to be painted.
The object in having some of the insoluble ingredients in No. 1 in the
condition of hydroxide and hydrate is because these hydrous compounds of metallic
oxides and salts give a certain plasticity and smoothness to the paint and also
cause these compounds to react more readily with the soluble silicate of No. 2
after No. 2 has been painted over No. 1.
The object in adding the water solution of silica to No. 1 is to coat each little
particle of solid matter in No. 1 with a coat of gelatinous silica insufficient in
quantity to saturate the lead or fixing substance in No. 1, but sufficient to bind
the particles of coat No. 1 together after the coat has dried on to the surface to
which it is applied.
The quantity of this gelatinous silica is not sufficient after the coat has become
dry, to stop the minute pores in the dried coat so as to prevent the penetration
of the soluble silicate of coat No. 2, but it is sufficient to bind coat No. 1 so that
it will not drag off or mix up in the brush when applying No. 2.
When the neutral or non alkaline water solution of silica is first mixed with
the other ingredients of No. 1 it gelatinizes at once if the ingredients are dry and
thickens the liquid greatly, but if the insoluble matters are previously ground with
a little water, the silica solution will take some time to gelatinize.
In some cases it is not necessary to dialyse out the sodium chloride produced by
the hydro-chloric acid's action on the alkaline silicate as in making a neutral water
solution of silica by the process of Graham, but the alkaline silicate can be diluted

page_text: with water enough to prevent precipitation and then rendered neutral by the
hydrochloric acid and mixed with other ingredients of No. 1 directly. Where
oxide of lead is one of the ingredients of No. 1, the sodium chloride introduced
in the neutral silica solution is decomposed by the lead with production of lead
chlorides and caustic soda, which react with the hydrous silica to produce an
insoluble double silicate of lead and soda with another portion of the lead oxide.
The object in using the ammonia solution of zinc in compound No. 2 is for the
reason that after this compound has been applied and the ammonia evaporated, all
of the potash or soda silicate left undecomposed by contact with the ingredients of
coat or compound No. 1, is rendered insoluble by the loss of its ammonia and the
production of an insoluble compound silicate of zinc, soda, and such other bases as
may be used. The function of the ammonia is to hold the silicate of zinc or the
double silicate of zinc and soda, in solution until the second coat (mixture No. 2)
can be applied, after which, by vaporization and escape of the ammonia, the
insoluble treble or quadruple silicate (according to the number of bases in the first
coat) is left behind.
Where the paint is required to be very hard and a perfectly white color is not
necessary,. three fourths of the carbonate of lime, sulphate of barium, silicate of
lime or other body given material in No. 1 can be replaced by finely ground
infusorial silica or diatomaceous marl, but when this infusorial silica is used the
quantity of it required to replace the other ingredients named is much smaller than
the lime or barium compounds required. This infusorial silica from some cause
produces a much greater thickening of soluble silicate solutions than do most
substances and if too much of it were used in compound No. 1 it would hinder the
proper penetration of the soluble silicate of compound No. 2 into dried coat
of No. 1.
We are aware of British patent to Blanc, No. 9803 of 1884, in which it is
proposed to bring slag and acid to the consistence of a jelly, which, after the acid
is removed, is added to paints, varnishes &c. By itself it is of no use, and is not
capable of being applied (by a brush, for instance) as a separate and distinct
coating, and has no chemical reaction with the paint or varnish in which it is mixed,
but unites therewith mechanically. By its mixture with paints or varnishes, its
porosity would be destroyed.
-
We are also aware of British patent to Ellis, No. 2645 of 1862, in which it is
proposed to render gelatinous silica soluble by means of silicate of soda or of potash,
or both; but this solution, however large the proportion of silica, is always a
silicate of the alkali used and always reacts alkaline. We use a neutral solution of
silica and its resulting gelatinous silica as a binding material for our first mixture
or coat, and not, as does Ellis, to dissolve again to produce an alkaline silicate
solution rich in silica.
Improvements in the Manufacture and Use of Paint.
We, CHARLES EUGENE LEE, of New York City, State of New York, U.S.A.,
temporarily residing in Norfolk Street, Strand, in the County of London, Electrical
Engineer, and CHARLES FRANCIS LAWTON, ALBERT LINDEL LAWTON, and ARTHUR
WILLIAM LAWTON, all of Water Street, New York City aforesaid, Chemists, do
hereby declare the nature of this invention and in what manner the same is to be

page_text: performed to be particularly described and ascertained in and by the following
statement -
This invention has for its object the production of a water-mixed paint which
shall become insoluble in water as soon as the paint is dry, be capable of receiving
many different colors, and present greater resistance to the effects of rain, sunshine
and frost than ordinary oil mixed paints.
In producing paint in accordance with this invention to begin with we take
oxide, hydrate, carbonate, chloride or oxychloride or oxalate of lead, or the oxide
or hydroxide of calcium, strontium, barium, magnesium, zinc or copper. Should
it be lead that in any particular instance is to be used instead of any of the other
inetals, we take of the lead compound say ten pounds and mix it with from five to
twenty pounds of very finely ground carbonate of lime together with such pigments
as are desired and in quantities according to the nature of the colour and depth of
tint required varying the quantity of carbonate of lime according to these
conditions.
In making the foregoing mixture, whatever metallic oxides or salts be used, we
so compound it that from ten to fifty per cent. of the solid or insoluble ingredients
shall be in the condition of hydroxide or hydrated silicate of one or more of the
metallic oxides or metallic salts present. For instance, a compound can be made
of about ten pounds of carbonate of lead, five pounds of zinc hydroxide Zn(OH),
or hydrated zinc silicate ZnSiO, + 2 H2O, and twenty pounds of very finely
ground carbonate of lime. These ingredients, together with coloring matter, should
it be desired that the paint shall be colored and not white are thoroughly mixed
with ten to fifteen pounds of water, and with fifteen to thirty pounds of a three to
five per cent. water solution of silica made by the well known diffusion or
dialysis process of Graham. This last ingredient being added and well stirred in,
the whole mixture is then ground through a paint mill, after which it is ready for
use.
The compound or mixture so made and ground we will hereinafter call, for
convenience, compound No. 1. It is a creamy paint-like liquid of variable con-
sistence according to the amount of water and the nature of the insoluble
ingredients and colors that it contains.
The neutral solution of silica used in this compound No. 1 is a thin, very mobile
solution, and does not turn to the coagulated condition until some time after it has
been mixed with the other ingredients. This solution is not to be confounded
with the transparent solution of zinc-ammonia-soda silicate used in the following
compound or mixture, No. 2..
Compound or mixture No. 2 is made by taking an eight to sixteen per cent.
solution in water of potash or soda silicate, singly or mixed, and adding to twenty
pounds of this alkaline silicate solution, one half of a pound to one pound of a
strong solution of hydrated zinc oxide in strong aqua ammonia. This solution of
zinc in aqua ammonia will produce a white bulky clot in the alkaline silicate solution
when first added to it, but by vigorous stirring, the clot of compound zinc-sodium-
ammonium silicate or zinc-potassium-ammonium silicate so produced dissolves in
the soda or potash silicate and ammonia, giving a clear transparent solution of a
compound alkaliue and zinc silicate, the compound silicate being kept in solution
The reaction
by the ammonia present and by the excess of potash or soda silicate.
which ensues when the compound of zinc oxide and ammonia is added to the
silicate of soda or of potash in solution of compound No. 2 may then be possibly
expressed thus

page_text: borates re-act with other compounds in a manner having so many points of
resemblance that chemists have placed carbonic, silicic and boric acids in a group) it
is possible that the ammonia present dissolves the silicate of zinc produced or the
compound silicate of zinc and soda whichever it may be, when the solution of zinc
oxide in ammonia is first added to the silicate of soda solution.
Compounds Nos. 1 and 2; though used for painting the same surface, must be
kept in separate vessels, and compound No. 1 must be well stirred up from the
bottom with a stick or paddle just before using.
To apply the paint the operation is as follows:-Should a thin coat only be
desired, enough water is added to compound No. 1 to inake it quite thin, and then
with a brush or atomizer the liquid is evenly applied over the surface of brick, wood,
stone, plaster or metal to be painted, and allowed to dry.
After mixture No. 1 has dried on the surface to which it has been applied, it is
painted over with a coat of the thin liquid No. 2, which quickly penetrates the dry
porous coat of compound No. 1 with which it reacts chemically, producing a hard,
smooth tough, adherent compound, practically insoluble in water, hot or cold.
If lead carbonate, zine hydrate, zinc silicate, and calcium carbonate be amongst
the ingredients of the coat of compound No. 1, then possibly (we cannot assert
with certainty) the reaction will be as follows:-
the calcium silicate represented in the first member of the equation being produced
by the water solution of silica coming in contact with the calcium hydrate in
mixing the materials for the first coat.
Where there is a mixture of basic oxides in the first coat, then there may be a
mixed reaction, but always we believe approximating the formulæ given.
In effecting the decomposition of the sodium chloride, as hereinafter mentioned,.
in a water solution of silica by means of lead oxide without the use of heat, the
reaction may be expressed thus :
4 Si(OH), +2 NaCl + 2 PbO = PbNa₁S₁₂O₁0 + PbCl₂ + 8 H₂O.
10
Should a thick coat of paint be desired, less water is added to compound No. 1,
and instead of applying No 1 first to the surface to be painted, as in the case just
described, Compound No. 2 is used for the first coat. This quickly dries, and
after it is dry, a coat of compound No. 1 is laid over it, and after this second coat
is dry, a coat of compound No. 2, making the third coat, is laid over No. 1, which
finishes the painting.

page_text: Should the surface to be painted be of a very porous absorbent nature, then to
make the work look even or free from spottiness, it will be necessary to grind the
transparent colorless compound No. 2 with material to give it "body" and then
the color desired for the finished paint. This can be done without difficulty if care
is used to avoid these ingredients which produce setting of the soluble silicate of
compound No. 2, but which setting ingredients are a necessary constituent of
compound No. 1.
Materials suitable for giving body to compound No. 2, which can be used
without setting it, are finely ground carbonate of lime, sulphate of barium,
magnesia silicate, calcium silicate, zinc silicate etc. For colours which will not
produce setting in compound No. 2, there can be used peroxide of iron, green and
blue ultramarine, red lead, and nearly all the variously colored smalts or glass
strongly colored by being fused with various metallic oxides and then reduced to
fine powder.
Instead of using carbonate of lead in compound No. 1 as the setting material to
render the paint insoluble by the reaction between the coats of compounds No. 1
and No. 2, other compounds and salts of lead can be used, such as chlorides and
oxychlorides of lead as herein before stated; or chromate, manganate, fluoride, or
sulphate etc. of lead can be used, or the lead compounds in compound No. 1 can be
partly or entirely replaced by oxide, carbonate or chromate of zinc, or by ferrous
carbonate, or by copper compounds such as oxide, carbonate, or arsenate of copper,
or by those barium compounds which are nearly insoluble but will react with an
alkaline silicate.
Compound No. 2, however, as has been heretofore stated must not be mixed
with any substance like the above, which would react with the soluble silicate in
compound No. 2 before it could be applied to the surface to be painted.
The object in having some of the insoluble ingredients in compound No. 1 in
the condition of hydroxide and hydrate is because these hydrous compounds of
metallic oxides and salts give a certain plasticity and smoothness to the paint and
also cause these compounds to re-act more readily with the soluble silicate of
compound No. 2 after compound No. 2 has been painted over compound No. 1.
The object in adding the water solution of silica to compound No. 1 is to coat
each little particle of solid matter in such compound with a coat of gelatinous
silica insufficient in quantity to saturate the lead or fixing substance in the said
compound but sufficient to bind the particles of a coat of such compound together
after the coat has dried on to the surface to which it is applied.
The quantity of this gelatinous silica is not sufficient after the coat has become
dry, to stop the minute pores in the dried coat so as to prevent the penetration of
the soluble silicate of the coat of compound No. 2 but it is sufficient to bind
the coat of compound No. I so that it will not drag off or mix up in the brush when
applying compound No. 2.
When the neutral or non-alkaline water solution of silica is first mixed with the
other ingredients of compound No. 1 it gelatinizes at once if the said ingredients
are dry and thickens the liquid greatly, but if the insoluble matters are previously
ground with a little water, the silica solution will take some time to gelatinize.
In some cases it is not necessary to dialyse out the sodium chloride produced by
the action of hydrochloric acid on the alkaline silicate; as in making a neutral
water solution of silica by the process of Graham, but the alkaline silicate can be
diluted with enough water to prevent precipitation and then rendered neutral by
the hydrochloric acid and mixed with other ingredients of compound No. 1 directly.
Where oxide of lead is one of the ingredients of compound No. 1, the sodium
chloride introduced in the neutral silica solution is decomposed by the lead with
production of lead chloride and caustic soda, which react with the hydrous silica to
produce an insoluble double silicate of lead and soda with another portion of the
lead oxide.
.
The object in using the ammonia solution of zinc in compound No. 2 is that after

page_text: this compound has been applied and the ammonia evaporated, all of the potash or
soda silicate left undecomposed by contact with the ingredients of the coat of
compound No. 1, shall be rendered insoluble by the loss of its ammonia and the
production of an insoluble compound of silicate of zinc, soda, and such other bases
as may be used. The function of the ammonia is to hold the silicate of zinc or the
double silicate of zinc and soda, in solution until the second coat (compound No. 2)
can be applied, after which, by vaporization and escape of the ammonia, the
insoluble treble, quadruple or other silicate (according to the number of bases in
the first coat) will be left behind.
Where the paint is required to be very hard and it is not necessary that it shall
be perfectly white, about three fourths of the carbonate of lime, sulphate of barium,
silicate of lime or other body giving material in compound No. 1 can be replaced by
finely ground infusorial silica or diatomaceous marl, but when this material is used
the quantity of it required to replace the other ingredients named is much smaller
than the lime or barium compounds otherwise required. The infusorial silica from
some cause produces a much greater thickening of soluble silicate solutions than do
most other substances, and if too much of it were used in compound No. 1 it would
hinder the proper penetration of the soluble silicate of compound No. 2 into the
dried coat of compound No. 1.
We are aware of British patent to Biane, No. 9803 of 1884, in which it is
proposed to bring slag and acid to the consistence of a jelly, which, after the acid
is removed, is added to paints, varnishes etc. By itself it is of no use, and is not
capable of being applied (by a brush, for instance) as a separate and distinct
coating, and has no chemical reaction with the paint or varnish in which it is
mixed, but unites therewith mechanically. By its mixture with paints or varnishes,
its porosity would be destroyed. We are also aware of British patent to Ellis,
No. 2645 of 1862, in which it is proposed to render gelatinous silica soluble by
means of silicate of soda or of potash, or both; but this solution, however large the
proportion of silica, is always a silicate of the alkali used and always reacts alkaline.
We use a neutral solution of silica and its resulting gelatinous silica as a binding
material for our first compound or coat, and not, as does Ellis, to dissolve again to
produce an alkaline silicate solution rich in silica.
Having now particularly described and ascertained the nature of the said
invention and in what manner the same is to be performed we declare that what
we claim is —
1. The herein described paint composition consisting of insoluble metallic oxide
or salt mixed with a neutral or non-alkaline solution of silica, the said composition
being capable of application without admixture with other substances, by means
of a brush, to the surface to be painted.
2. The herein described paint composition consisting of insoluble metallic oxide
or salt part of which is in the condition of a hydroxide or hydrate, mixed with
a neutral or non-alkaline solution of silica-the said composition being capable
of application without admixture with other substances, by means of a brush, to
the surface to be painted.
3. The herein described setting compound consisting of an alkaline silicate
solution containing zinc oxide and ammonia.
4. A paint comprising two compounds designed to act chemically one upon the
other the first compound consisting of insoluble metallic oxide or salt mixed
with a neutral non-alkaline solution of silica; and the second consisting of a
zinc-sodium-ammonium silicate solution, all substantially as described.
5. The process for producing a painted surface which consists in combining
with metallic oxide or salt when in suspension in water a non-alkaline solution
of silica in water and applying to this composition after application, another
compound comprising a zinc-sodium-ammonium silicate solution, substantially
as described.

page_text: 6. In the manufacture of mineral paint free from organic matter, the herein
described method of decomposing sodium chloride in a neutral water solution of
silica by bringing the sodium chloride into contact with a lead oxide, substantially
as set forth.
Dated this 18th day of March 1898.
For the Applicants,
W. LLOYD WISE,
46, Lincoln's Inn Fields, London, W.C., Chartered Patent Agent.