IMPROVE- MENTS IN IMPREGNATING, SATURATING, OR COATING THREADS, YARNS, AND FABRICS WITH METAL, WHICH PROCESS THE INVENTOR TERMS 'METALLIC DYEING
Year: 1853

page_text: LETTERS PATENT to Richard Archibald Brooman, of the firm
of Robertson, Brooman, and Company, of 166,Fleet Street, in the
City of London, Patent Agents, for the Invention of "IMPROVE-
MENTS IN IMPREGNATING, SATURATING, OR COATING THREADS, YARNS,
AND FABRICS WITH METAL, WHICH PROCESS THE INVENTOR TERMS
'METALLIC DYEING." "A communication from Charles Depoully, of
Paris.
Sealed the 27th October 1853, and dated the 2nd July 1853.
PROVISIONAL SPECIFICATION left by the said Richard Archibald
Brooman at the Office of the Commissioners of Patents, with his
Petition, on the 2nd July 1853.
I, RICHARD ARCHIBALD BROOMAN, of the firm of Robertson,
Brooman, and Company, of 166, Fleet Street, in the City of London,
Patent Agents, do hereby declare the nature of the said Invention
for "IMPROVEMENTS IN IMPREGNATING, SATURATING, OR COATING THREADS,
YARNS, AND FABRICS WITH METAL, WHICH PROCESS THE INVENTOR TERMS
'METALLIC DYEING,'" to be as follows:-
The Invention consists in imparting a metallic dye to fibrous sub-
stances and fabrics by the following process:-The threads, yarns or
ГР. 921

page_text: fabrics (having been deprived of any fatty or gummy matters they may
contain) are impregnated with a solution of some metallic salt (which
may easily be reconverted into a metallic state). When dry, the
threads or fabrics are submitted to the action of any de-oxydizing
. agent, such as salts or gases having a great affinity for oxygen, which
will reduce the solutions to the metallic state. The metal is thus made
to impregnate or enter into the pores of the threads or fabrics in a
state of minute subdivision, in which state the threads or fabrics
become good conductors of electricity, and are in a fit condition to
receive a coating or deposit of metal. The threads or fabrics are then
coated with a metallic surface by simple immersion in a properly
prepared bath, aided or not by a galvanic current (the electrotype
process).
SPECIFICATION in pursuance of the conditions of the Letters Patent,
filed by the said Richard Archibald Brooman in the Great Seal
Patent Office, on the 2nd January 1854.
TO ALL TO WHOM THESE PRESENTS SHALL COME, I,
RICHARD ARCHIBALD BROOMAN, of No. 166, Fleet Street, in the City of
London, Patent Agent, send greeting.
WHEREAS Her most Excellent Majesty Queen Victoria, by Her
Letters Patent, bearing date the Second day of July, in the year of
our Lord One thousand eight hundred and fifty-three, in the seventeenth
year of Her reign, did, for Herself, Her heirs and successors, give and
grant unto me, the said Richard Archibald Brooman, Her special licence
that I, the said Richard Archibald Brooman, my executors, adminis-
trators, and assigns, or such others as I, the said Richard Archibald
Brooman, 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 "IMPROVEMENTS IN IMPREGNATING, SATURATING, OR COVERING YARNS,
THREADS, AND FABRICS WITH METALS," communicated to me by a certain

page_text: foreigner residing abroad, upon the condition (amongst others) that I,
the said Richard Archibald Brooman, by an instrument in writing
under my hand and seal, 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 Archibald Brooman,
do hereby declare the nature of the said Invention, and in what manner
the same is to be performed, to be particularly described and ascer-
tained in and by this present Specification thereof as follows (that
is to say):
The said Invention consists of a mode or modes of impregnating,
saturating, or covering yarns, threads, and fabrics made of fibrous
materials with metals, so as to give them a metallic appearance, and
which Monsieur Depoully, the Inventor (who is a foreigner residing
abroad, and has communicated the said Invention to me), calls me-
tallic dyeing. For this purpose, the yarns, threads, or fabrics are im-
pregnated with a liquid holding in solution or in suspension therein a
metallic salt, metallic oxide, or compound containing a metal, which is
afterwards decomposed, so as to leave the metal contained in such salt
or oxide remaining amongst the fibres or filaments of the yarn, thread,
or fabric; after which (when required) the yarn, thread, or fabric is
introduced into a bath or liquid, holding in solution or in suspension
therein the like or some other metallic salt, oxide, or compound, for
the purpose of impregnating, saturating, or covering it with the metal
contained in such liquid, either in substitution or partly in substitution
for, orin addition to, the metal with whichitwas previously impregnated
or covered, and either with or without the aid of a galvanic battery.
In performing this Invention the yarns, threads, or fabrics are first
to be freed from any unctuous, fatty, or other matters which might
prevent them from becoming completely impregnated with the liquid
holding in solution or suspension the metallic salt, oxide, or compound.
For this purpose the yarns threads, or fabrics are introduced into a
warm caustic alkaline bath; after which they are washed, rinsed, and

page_text: dried, and then passed through rectified alcohol, ether, or other fluid
capable of dissolving and removing any resinous or gummy matters
which cannot be dissolved in the alkaline bath or water. The spirit
being expressed from the yarns, threads, or fabrics, they are then to be
saturated with a liquid holding in solution or in suspension therein
a salt, oxide, or compound containing the metal with which they are
to be impregnated, saturated, or covered; taking care, when a salt or
other compound is used; to select such a salt or other compound
containing the requisite metal for that purpose as will not injure the
fibres or filaments of the yarns, threads, or fabrics. For this
purpose
the Inventor employs ammoniacal solutions of metallic salts or
oxides; and when he intends to impregnate, saturate, or cover the
yarns, threads, or fabrics with silver, he prefers to use an aqueous
or alcoholic solution or mixture holding in suspension therein an oxide
of silver, which he forms as follows:-The nitrate of silver, being
dissolved in the menstruum, is decomposed by ammonia; and the
oxide of silver thus precipitated is redissolved by adding a sufficient
excess of the same alkali. The acid of the nitrate of silver, being
neutralized by the alkali, does not injure the fibres or filaments of the
yarns, threads, or fabrics in the same manner as would be effected by
a solution of nitrate of silver. The destructive or injurious action of
a metallic salt in solution may be diminished if not prevented by im-
pregnating the yarns, threads, or fabrics slightly with a preserving
substance, such as albumen, or any other substance which will not
prevent or interfere injuriously with the reduction of the salt or oxide,
and which will form a regular and continuous preserving coating upon
the fibres or filaments composing the yarns, threads, or fabrics.
The yarns, threads, or fabrics being then dried, the Inventor prefers
to effect the reduction of the metallic salt, oxide, or compound with
which the fibres or filaments of yarns, threads, or fabrics may have
been impregnated or saturated by a current of deoxydizing or reducing
gas, by which the metal may be reduced to a reguline state.
As
gas does not readily penetrate throughout every part of the fibres
of yarns, threads, or fabrics which it comes in contact with, the yarns,
threads, or fabrics are subjected to the action of the reducing gas in a

page_text: current, so that it may pass through, between, or amongst all the fibres
with greater facility.
For ensuring a more complete and uniform action of the gas upon
the metallic salt, oxide, or compound contained amongst the fibres
of yarns, threads, or fabrics, the apparatuses herein-after described as
applicable to that purpose may be used, or any other efficient means
for producing a uniform action of the gas may be adopted.
The reducing gas or agent which the Inventor prefers to use, is
phosphuretted hydrogen, or phosphorus in a state of vapour, contained
or dissolved in and conveyed along with a current of gas which does
not support combustion; and he prefers to make it dry or anhydrous, for
the purpose of causing the action of it to be more complete and uniform.
The phosphorus may be obtained in a state of gas or vapour for this
purpose by subliming it in a close vessel through which is passing a
current of hydrogen gas or other gas which does not support com-
bustion, so that the vapour of the phosphorus may be dissolved or
mixed with and carried away by the gas, or the gas may be charged or
loaded with phosphorus by causing gas to pass through a solution of
phosphorus in sulphuret of carbon or other solvent. The phosphuretted
gas may be produced in any other way which may be found to be most
convenient and economical. Thus, if phosphuretted hydrogen be re-
quired, it may be produced from some descriptions of iron or iron ores
which contain a proportion of phosphorus, adding some pieces of phos-
phorus to the iron if the iron should not contain enough; the gas
being generated by the action of dilute sulphuric or hydrochloric acid
upon the iron in the ordinary manner.
Arseniuretted hydrogen (or hydrogen holding arsenic in solution or
suspension therein) may also be used as the reducing agent; but in
consequence of its dangerous properties it is not recommended. The
mode of producing this gas is well known, and therefore need not be
described.
When the yarns, threads, or fabrics which have been metallized, or
impregnated, saturated, or covered with metal, in the manner which has
been described, are required to be still further impregnated, saturated,
or covered, or when some other metal is required to be added to the

page_text: metal first used or substituted for some part of it, the yarns, threads,
or fabrics are immersed in a bath or vessel containing a fluid holding
in solution or in suspension therein a metallic salt or oxide, or a com-
pound containing the required metal, which will not destroy or injure
the fibres or filaments of which the yarns, threads, or fabrics are
composed.
In some cases in which it is desired to substitute some other metal
for that with which the yarns, threads, or fabrics have been impreg
nated or covered, it will be sufficient to immerse the yarns, threads, or
fabrics in a solution of a salt containing the metal so to be substi-
tuted; the chemical affinity or affinities brought into action by the
contact of the metal contained in the yarns, threads, or fabrics with the
salt in solution being sufficient to cause a portion of the metal con-
tained in the yarns, threads, or fabrics to be replaced by a portion of
the metal contained in the solution, which latter may in such a case
be thus caused to be deposited upon the surface of the metal with which
the yarns, threads, or fabrics have been impregnated or covered, or
so much of that metal as may not be removed by this second process.
In other cases the desired substitution may be effected by causing
the solution of the requisite metallic salt or oxide to be mixed with
some other salt in solution, or incorrosive chemical agent, which will
produce the play of affinities requisite to cause a portion of the one
metal to be replaced by a portion of the other. In other cases, in which
the further impregnating or covering of the yarns, threads, or fabrics
cannot be effected, or conveniently effected, by means of the changes
produced by chemical affinities, recourse may be had to the aid of a
galvanic battery; the articles to be impregnated or covered being
placed in a bath containing the requisite materials, connected with the
proper pole of the battery, so as to produce the requisite deposit upon
the yarns, threads, or fabrics, in like manner as in performing the well-
known electrotype process. Thus, for "coppering," a solution of car-
bonate of copper and cyanide of potassium may be employed, taking
care not to use so much carbonate of coffer as to cause the decomposi-
tion of the cyanide of potassium. Any convenient apparatus may be
adopted for this purpose; but I have herein-after described apparatus

page_text: which is deemed suitable for that purpose, so as more clearly to shew
the manner in which this process may be performed.
The Drawings accompanying this Specification shew several kinds
of apparatus which may be used in performing the various parts of the
processes herein-before described or mentioned, but which apparatusitis
not intended to claim as forming any part of the Invention.
Figure 1, is a sectional view of an apparatus in which skeins of yarns
or threads are extended or placed apart for the purpose of being sub-
jected to the action of the reducing or deoxydizinggas or agent. A, is
a vessel in which the gas is disengaged; B, B¹, vessels in which the gas
is washed and purified; C, is a gasometer or vessel for containing the
generated gas; D, D¹, D", D, chambers for holding the skeins;
E, E', E, E, passages or perforated pipes for admitting the gas;
H, H, H, H, passages for conveying the gas away.
Figure 2, is a sectional view of an apparatus in which the matters to
be treated have the gas forced or drawn through them, the gas being
forced into one side of the vessel by pressure, or drawn out at the
other side, which may be affected as shewn in the Drawing, or by
any other convenient means, so that the gas may pass through the
articles contained in the vessel; I, is a pump for forcing the gas;
M, is a chamber for holding the articles to be operated upon. The
gas enters through a rose or spreader, so as to cause the gas to be
diffused throughout the whole of the chamber. The chamber is made
of a conical form at each of the ends at which the gas enters and
escapes, so that an equal amount of action of the gas may produced
on all parts of the articles contained in the chamber. P, is a cylinder
for holding the compressed substances. The gas may be collected in a
second holder or gasometer, so as to prevent waste.
Figure 3, is a sectional view of a tubular apparatus; Q, Q, are
tubes through which skeins of yarns or threads may be introduced
The gas may be forced or drawn through this apparatus in the same
manner as in the apparatus shewn in Figure 2.
Figures 4, and 5, exhibit apparatus suitable for treating fabrics. In
Figure 4, they are shewn stretched on rollers or cylinders; in Figure 5,
they are represented hung upon a frame arranged spirally, and are thus

page_text: introduced into the vessels in which they are to be subjected to the
action of the gas. These apparatus are only described as examples of
apparatuses suitable for carrying the Invention into effect, and are not
intended to be claimed as being any part of the Invention comprised in
the said Letters Patent.
It is important in practising this Invention to make arrangements
for frequently changing the positions of the threads, yarns, or fabrics
in the baths, in order to avoid any irregularity in the metallic deposit.
I now proceed to describe certain apparatus which may be employed
for this object.
Figure 6, is a sectional view of an apparatus for causing a metallic
deposit, by the aid of a galvanic battery, upon skeins of yarns or
threads or fabrics placed therein. For holding the metallic baths or
solutions a succession of vats is employed, the vats being made of
varnished wood, similar to those generally used by silk dyers. a, a, a,
are conductors connected with the positive pole of the battery; b, b, b,
are the skeins which are to be impregnated, saturated, or covered with
some metal, hanging on metal rods c, c, c, which form conductors,
bent at their ends and resting on metal rods d, d, which are placed
lengthwise on the upper sides of the wooden vats, and serve as con-
ductors of the negative pole of the battery. The conductors a, a, a, are
united together by rods f, f, f,f, placed on the side of the vats, and a
little above them, and form connections with the positive pole of the
battery. The manner in which these apparatus are to be employed is
very simple. It is only requisite to alter the position of the skeins from
time to time, and to turn them over so that the lower part may from
time to time be changed, so as to be at the top of the vat, in like
manner as is done by silk dyers. When the operation is concluded,
the separate skeins are to be lifted off one by one and carried away to
the cleansing vessel.
Figure 7, is a sectional view of another apparatus, in which the
skeins, instead of being hung on rods, are placed on two metal rollers
or cylinders C, C¹, which here act as the negative conductors. The
skeins are opened out and held on two small glass cylinders K, K¹,
turning on rods, and so arranged as to avoid or diminish friction.

page_text: Motion is imparted to the roller C¹, which carries a pulley M, made of
glass or other material not liable to be attacked by chemical agents.
The positive conductors are placed at a,al, all, within and without the
circuit made by the skein. The roller C, is put in connection with the
pole of the battery by means of a ring Q, attached to the conducting
wire. The whole apparatus is supported on a wooden frame, so con-
trived as to allow of its being removed and replaced when required.
Figure 8, represents an apparatus arranged for treating fabrics of a
considerable length, such as lace, blonds, ribbons, &c. C, C¹, are
cylinders acting as conductors. The fabric under treatment is rolled
successively from one cylinder on to another. a, a¹, are positive con-
ductors, above and below the unrolled portion of the fabric. Every
portion of this apparatus, as well as of the apparatus Fig. 7, except
the parts on which the threads, yarns, or fabrics rest, are covered with
an insulating coating.
:
Figure 9, is an apparatus suitable for impregnating, saturating, or
covering yarns, threads, or fabrics by immersion, without the aid of a
galvanic battery. A, is a copper boiler with double sides for generating
steam, in order that the temperature of the bath may be regular
throughout, as without this precaution the tone or covering, or
metallizing, may not be uniform. This generator or boiler may
revolve on a hollow axis B, to allow of the bath being emptied. The
steam is admitted through the hollow axis B. b, b, b, are the skeins,
which are suspended on a frame D, made of non-resinous wood, or of
gilded metal. This frame is carried by a band passing over a pulley,
which allows the workman to stir about the contents continually by
raising or lowering it in the bath. The generator A, must be com-
pletely gilt before it is used, which is done by boiling it in a gold
bath.
Having now described the nature of the said Invention, and the
manner in which the same is to be performed, I declare that I do not
intend to claim as of the said Invention any of the apparatus herein-
before described, and that, except as herein-after expressly mentioned,I
do not claim any of the processes herein described separately and apart
from the combination and application thereof in the manner herein

page_text: described and claimed as being any part of the said Invention, and
that I claim as of the said Invention,
Firstly, the impregnation, saturation, or covering of yarns, threads.
and fabrics with metals, by impregnating or saturating them with
fluids holding in solution or in suspension therein metallic salts or
oxides, or other compounds containing metals, and then decomposing
such compounds by means of a stream or current or any of the
deoxydizing or reducing gases herein-before mentioned, so as to reduce
the metal or metals contained in such salts, oxides, or compounds
respectively to a reguline state, as herein-before described.
Secondly, the impregnation, saturation, or covering of yarns,threads,
or fabrics with metals, by saturating or impregnating them with fluids
holding in solution or suspension therein metallic salts or oxides, or
other compounds containing metals, and after decomposing such
compounds so as to reduce the metal contained therein to a reguline
state, by the means aforesaid, or by any other convenient means,immers-
ing such yarns, threads, or fabrics in a bath or vessel containing a
fluid holding any metallic salt or oxide, or other compound containing
a metal or metals, so as, either with or without the aid of a galvanic
current, to impregnate or cover such yarns, threads, or fabrics with a
metal or metals, either in addition to the metal or metals with which
they may have been previously impregnated or covered, or in lieu of a
portion of such last-mentioned metal or metals, as herein-before
described.
In witness whereof, I the said Richard Archibald Brooman, have
hereunto set my hand and seal, this Second day of January,
One thousand eight hundred and fifty-four.
R. A. BROOMAN. (L.S.)