Improvements in the Production of Watermarks and other Designs and Impressions in or on Paper, Textiles, and other Materials.
Year: 1898

page_text: Improvements in the Production of Watermarks and other Designs
and Impressions in or on Paper, Textiles, and other Materials.
We, THOMAS ARCHIBALD GOODCHILD, of 125, Queen's Road, Dalston, N.E.,
Physician and Surgeon, and ARCHIBALD CAMPBELL TAIT BOND, of 3 Pemberton
Gardens, St. John's Park, Holloway, N., no occupation, do hereby declare the nature
of this invention to be as follows:-
Our invention relates to improvements in the production of watermarks and other
designs and impressions in or on paper, textiles and other materials and the objects
are to effect these results by simple means and by the application of electricity.
Particular phases of the process render it especially valuable for the printing of
cheques to guard against alteration of the amounts for which they are drawn. Our
invention consists essentially in providing two conducting surfaces connected with
opposite poles of a source of electricity one of the said surfaces bearing salient
designs or other matter and in pressing between the said conducting surfaces the
paper or other material which is to be impressed with the said design or other
matter, the paper or other material under pressure being previously superimposed
on an absorbant material moistened with plain water or with chemicals or a chemical
in solution, the character of the resulting impression varying with the absence or
presence of chemicals in the moistened material and with the material from which
the salient design is formed. The two conducting surfaces will generally be referred
to in this Specification as respectively the positive or negative conducting surface
according to the pole of the source of electricity with which the particular surface is
connected.
For the purpose of describing our invention it may be conveniently dealt with
under five heads, namely. (1) Wherein the design is produced as a disappearing
water-mark which can be revived as often as required. (2) Wherein the design is
produced as a permanently visible watermark. (3) Wherein the design is produced
in black on white or light paper or other materials. (4) Wherein the design is
produced in colour or colours on white or light paper or other materials. (5) Wherein
the design is produced in white or in other colours than the ground colour of dyed
paper or textile materials so as to obviate a second dyeing for the design.
(1) In producing a disappearing but repeatedly revivable watermark we provide a
platinum plate of suitable size or a plate of some other conducting material platinized
or having platinum inlaid therein and we connect this with the + pole of the source
of electricity. On this positive conducting surface we place absorbant material
saturated with plain water and on this we place the paper to be watermarked. This
paper we previously saturate with plain water and blot off or otherwise remove all
surplus moisture. Upon the paper we then press face downwards the negative
conducting surface bearing in salient features the design of the required watermark.
We leave the whole in close contact for a sufficient time, say ten seconds, and we
thus obtain in the paper a translucent watermark of the design on the negative
conducting surface. The watermark is of uniform brightness and exhibits all the

page_text: details of the design with great distinctness. As the paper dries the mark disappears
but may be revived as often as required by damping the paper.
=
'
(2) To produce the non-disappearing watermark we proceed in precisely the same
way as described under the preceding head but with these differences, namely, that
insead of saturating the absorbant material with plain water we saturate it with a
solution of sodium chloride (table salt) a twenty per cent. solution in water serving
very well, and secondly, that the time of contact is increased to say sixty seconds. In
this case the sodium chloride is decomposed by the electric current, chlorine appearing
at the electrode and sodium as hydroxide (MaHO) at the electrode which acts
on the paper. The change is 2 H₂O + 2 NaCl 2 Cl 2 NaHO. + H. Carbon elec-
trodes may be used instead of platinum ones, but for finely detailed designs platinum
is to be preferred. If carbon is used it should be of the sawn variety free from
particles which come off and stick in the paper. Most of the metals and some other
substances may be used instead of platinum or carbon at the side, but in the case
of other metals a slight stain may result from the action of the element or elements
liberated on the metal and this stain must be removed by suitable after treatment of
the paper. Carbon and platinum electrodes may be safely used together. Although
we have mention sodium chloride (which is cheap and gives good results) neverthe-
less we do not restrict ourselves to the employment of that one substance.
-
-
(3) To produce black designs on white or light coloured paper or other material we
provide a copper surface connected with the
pole of a source of electricity and
place thereon paper or other material moistened with water. Upon the paper we press
a salient design in silver connected with the + pole of the source of electricity and
leave them in contact for say from ten to sixty seconds according to the material. By
this means is obtained in the paper or other material a practically indelible black
impression of the salient silver design. Such a process is of service for marking linen
in the place of the usual marking ink. Instead of the copper negative conducting
surface a zinc, iron, lead or aluminium one may be employed with almost as good
results, the black image being probably a reduction of metallic silver in a very finely
divided state. As a modification 'the salient design may be on the copper or other
negative conducting surface the other conducting surface being a plain silver one con-
nected with the + pole. Again, the same result could be obtained by causing a
smooth cylinder of silver or of some material covered with silver, which silver is con-
nected with the + pole to travel over the paper or other material placed over the
salient design on the copper or other conducting surface. For embossing, the
salient design would be on the copper or other plate, the silver bearing a similar
design in intaglio.
(4) The production on the paper or other material of impressions in such colours
as purplé, violèt, black yellow, blue, terra cotta, green, grey, cherry red, pink and
red, depends on the chemical or chemicals in solution used to saturate the absorbant
material placed on the negative conducting surface and on the decomposition of the
chemical or chemicals by the current of electricity and the liberation of one or more
of its or their constituents or elements at the + pole acting on the material of the
face of the design, uniting with it and producing definite chemical compounds
which are merely intercepted by or deposited on the damped paper or other
material placed there to receive it or them. In some cases a compound may be
formed at the + pole which subsequently acts on the designs placed there. The
plate connected with the
pole may be of any material which is a good conductor
-
of electricity. The deposit in the paper or other material of a chemical may be
decomposed by the action of chemicals in solution or a gaseous state thus producing
another and distinct chemical compound of the metal used for the design. For
example, if on a copper negative conducting surface be placed a layer of absorbant
material saturated with a solution of hydrogen peroxide (H, O₂) and on this the
damped paper to receive the design and if on this paper be pressed a copper salient
design connected with the positive electrode there will be obtained after a few
seconds contact a yellowish brown copy of the design. The image is an oxide of
copper, the following being probably the reaction. H₂ O₂ + Cu H+ Cu O₂. The
=3

page_text: hydrogen being liberated at the
-
electrode and the oxygen at the moment of
disengagement at the + pole combines with the copper and forms the oxide. With
cobalt for the + electrode a blue colour is obtained due to the formation of oxide
of cobalt probably Co O. With iron for + electrode a reddish brown deposit is
obtained in the form of oxide of iron. Oxides of most of the metals can be got by
the direct combination of the elements by this process. An oxide of gold may be
deposited on paper in any design. The deposit is at first of a yellowish green colour,
which can he changed to a deep brown colour by submitting it to heat in any con-
venient manner. Light produces a similar result on this oxide. In a similar manner
designs may be deposited on paper simply by moistening it previously with oxides,
chlorides, carbonates, sulphides, prussiates bromides, chromates and iodides of the
metal used for the design, and in brief most of these combinations of the metals
with other clements known to chemistry can be brought about by this process and
deposited in any design on paper and other materials. Besides some combinations
which are obtained with difficulty in chemistry are brought about in a few seconds
by this process without any trouble. For example auric chloride which is usually
obtained by dissolving gold in nitro-hydrocloric acid we obtain by the direct com-
bination of chlorine with the gold in the following manner. On a copper or other
suitable negative conducting surface we place a layer of absorbant material saturated
with a solution of sodium chloride or other chloride. On this we put the paper
saturated with water & then damped off and over all we put the design in gold and
connected with the electrode. After about ten seconds contact a design in auric
chloride will be formed on the paper. In this the sodium chloride is decomposed
by the current, sodium hydroxide appears at the electrode and chlorine at
the electrode which at the moment of liberation unites with the gold design
and forms auric chloride. This auric chloride is intercepted by or deposited on
the damp paper or other material placed there to receive it. The action is
3 Na Cl. Au + 3 H₂ 0 =
=Au Cl, +3 Na H ( + H. The auric deposit can be
reduced by any of the reagents used for the purpose, say, ferrous sulphate solution,
the result being a greenish coloured image, which if burnished will have the lustre
of metallic gold.
2
-
Most of the colours obtained by our process are almost of equal distinctness on both
sides of the paper or other material and any which are not so at first can be made so
by subsequent treatment. Carbonates, sulphides, prussiates, chromates, oxides and
other salts of the metals can be obtained by this process, the colours depending on
the metal or material connected with the + electrode and on the nature of the
chemical solution if used.
(5) The obtaining of designs on dyed paper and textiles so as to have variety of
colour without second dyeing is practically only a particular application of the
processes described under the fourth head. For example, if upon a carbon or platinum
negative conducting surface we put a layer of absorbant, material saturated with
sodium chloride (Na. Cl.) and upon this put the textile fabric previously soaked with
water and the superfluous moisture blotted off and over this press a design in platinum
carbon or other suitable substance connected with the + pole of a source of electricity,
we obtain a design after some ten seconds contact, the colour of which will depend
on the nature of the dyed stuff used, chlorine appearing at the + electrode and
sodium hydroxide at the electrode. For example, the disengaged chlorine acting
on a cotton fabric dyed red produces a white copy of the design used. Acting on a
black fabric a reddish brown is the result and on a dark green mixture of silk and
cotton a yellow colour is produced.
By the processes described under heads 4 and 5 several distinct colours or groups
of colours may be produced at the same time either by using a metal for each colour
or by using one metal for the whole design and varying the chemical solutions to
saturate the absorbant material in different places or by using several absorbant layers
on the same plane each saturated with a different solution.
It is not always necessary to adopt the arrangements so frequently mentioned
above and involving the use of an absorbant layer saturated with the solution of a

page_text: chemical for other arrangements can, when suitable, be employed without departing
from the general features of the process. For example. A sufficiency of the chemical
solution can be placed in a non-conducting receptacle so as to saturate a porous carbon
or other suitable porous plate placed therein. The dyed paper or fabric previously
soaked with water and blotted off can be placed on the porous plate, the platinum or
other design connected with the + pole pressed on the fabric, and the negative
electrode dipped into the chemical solution or connected with the porous plate
placed therein. The electric current will pass, decomposing the chemical solution
and chloride in the case of sodium chloride will be disengaged at the design
connected with the + electrode, while if hydrogen peroxide be used oxygen will
be liberated. In other reducing reagents the element or elements required may be
made to do the same.
Several distinct colours can also be obtained by the use of the salts of aniline by
the previously described processes.
HUGHES & YOUNG,
23, Coleman Street, E.C., Agents.
Improvements in the Production of Watermarks and other Designs
and Impressions in or on Paper, Textiles, and other Materials.
We, THOMAS ARCHIBALD GOODCHILD, of 125, Queen's Road, Dalston, N.E., Physician
and Surgeon, and ARCHIBALD CAMPBELL TAIT BOND, of 3, Pemberton Gardens, St. John's
Park, Holloway, N., of no occupation, do hereby declare the nature of this invention
and in what manner the same is to be performed to be particularly described and
ascertained in and by the following statement :—
Our invention relates to the production of watermarks and other designs and
impressions in or on paper, textiles, and other materials and the object is to effect those
results by simple means and by the application of electricity. Our invention consists
essentially in providing two conducting surfaces connected with opposite poles of a source
of current electricity, one of the said surfaces bearing salient designs or other matter
and in pressing between the said conducting surfaces the paper or other material
which is to be impressed with the said design or other matter, the paper or
other material being previously superimposed on an absorbant material moistened
with plain water or with chemicals or a chemical solution, the character of
the result varying with the absence or presence of chemicals in the moistened
material and with the material from which the salient design is formed. The two
conducting surfaces will generally be referred to in this specification as respectively
the positive or negative conducting surface according to the pole of the source of
electricity with which the particular surface is connected.
For the purpose of describing our invention it may be conveniently dealt with
under four heads, namely, (1) Wherein the design is produced as a translucent water-
mark in or on manufactured paper which mark is invisible when the paper is dry and
becomes visible when it is moistened and can be repeatedly so made visible. (2)
Wherein a permanently visible translucent water mark on manufactured paper is
produced. (3) Wherein the design is produced as an opaque mark invisible when
the paper is dry and rendered visible when the paper is damped. (4) Wherein is
deposited in or on paper and fabric definite chemical compounds of the metals.
1. In producing a disappearing and repeatedly revivable translucent water mark
in or on manufactured paper we proceed as follows. Upon a platinum sheet or plate

page_text: forming the positive conducting surface we place a layer of absorbant material such
as blotting paper previously moistened with water. On this material we place the
paper which is to receive the watermark, the paper having been previously inoistened
through with water. We then press face downwards on the paper a platinum
design of the watermark and this design forms the negative electrode.
We keep
this negative electrode in contact with the paper for from five to ten seconds accord-
ing to the nature of the paper and the amount of electric current used. The result
on removal of the electrode is a distinct and translucent image of the design which
gradually fades as the paper dries and finally becomes invisible. The mark however
can be revived and made visible as often as the paper is immersed in water or
moistened in any other way.
We offer the following as the most probable explanation of the changes which take
place in the paper at the site of the water mark, the explanation being the result of
duly verified experiments. Ordinary drinking water contains saline substances in
solution and that used by us did so to the extent of twenty grains to the gallon.
These saline substances are decomposed by the passage of the electric current, acids
with free oxygen appearing at the positive electrode, while the alkalis in the form
of NaHO, KHO, etc. together with free hydrogen are liberated at the negative
electrode where they come in contact with the paper. The paper at these points of
contact is highly alkaline. It is more hydroscopic. We have reason to believe
however that the change is not limited to this but that this particular portion of the
paper or cellulose combines with an additional molecule of water thereby becoming
one or other of the glucoses. If we consider paper (cellulose) as CH10O+H₂O we
have CHO, a glucose or some body resembling it in chemical composition and
reaction. The action of nascent hydrogen on cellulose in the presence of alkalis may
play an important part in the change.
In the case of tinted paper we obtain the image as a white design or as an other-
wise contrasting image.
2. To produce the non-disappearing (perinanent) water mark we proceed in
precisely the same way as described under the preceding head but with these
differences, namely, that instead of saturating the absorbant material with plain
water, we saturate it with a solution of sodium chloride (table salt), a twenty per cent.
solution in water serving very well, and secondly that the time of contact is increased
to say sixty seconds. In this case the sodium chloride is decomposed by the electric
current, chlorine appearing at the positive electrode and sodium as hydroxide (NaHO)
at the negative electrode which acts on the paper. Carbon electrodes may be used
instead of platinum ones but for finely detailed designs platinum is to be preferred.
If carbon is used it should be of the sawn variety free from particles which come off
and stick in the paper. Most of the metals and some other substances may be used
instead of platinum or carbon at the negative side, but in the case of other metals a
slight stain may result from the action of the element or elements liberated on the
metal and this stain must be removed by suitable after treatment of the paper.
Carbon and platinum electrodes may be safely used together. Although we have
mentioned sodium chloride (which is cheap and gives good results) nevertheless we
do not restrict ourselves to the employment of that one substance. We would here
remark that when coloured paper is treated in the same manner a white copy of the
design is generally obtained on both sides of the paper, which occurs also when only
water is used.
3. To produce the opaque mark on paper, textile fabric and other materials we
proceed in the following manner. On a metal plate or other plate conductive of
electricity we place a layer of absorbant material saturated with a solution of barium
chloride (about 5 %) or other soluble salt of barium. On this we place the paper or
other material to be marked saturated with water but having bad superfluous
moisture removed. We connect this plate with the positive electrode of a source of
electricity.
Upon the paper or other material we press face downwards a design in platinum
connected with the negative electrode of a source of electricity and maintain contact

page_text: for some seconds. We have now a deposit in the paper or other material at the points
of contact with the design, of the hydroxide of barium. We next immerse this paper
or other material in dilute sulphuric acid, or in a solution of a soluble sulphate, for a
few minutes. The result is a deposit in the paper or other material of barium
sulphate, a practically insoluble salt. We thus obtain an indelible mark which varies
in appearance according to the nature of the material marked.
On white paper it is invisible in a dry state but visible in a moist condition of the
paper being white by reflected and dark by transmitted light. Made on translucent
paper it is seen, both in the moist and dry condition of paper as a dark by trans-
mitted and white by reflected light. On white silk in the moist and dry state it is
seen only by transmitted light and then appears dark.
4. In depositing in or on paper and fabric definite chemical compounds of the
metals, we place on a metal plate or other suitable surface conductive of electricity a
layer of absorbant material saturated with an electrically decomposable solution, one
or the other of whose elements is, in the nascent state liberated at the positive
electrode. This conductive plate or surface we connect with the negative electrode
of any suitable source of electricity. On the absorbant material we then place the
paper to receive the deposit or other material to receive the deposit having first
saturated it with water. In contact with the paper or other material we then place
a metal or metals connected with the positive electrode of a source of electricity.
By this means we obtain a deposit on the paper or other material of a compound or a
metal or of several distinct compounds simultaneously if more than one metal is used.
By this process is not only obtained the deposit in or on paper and other materials of
definite chemical compounds of the metals, but also in some cases their subsequent
decomposition into secondary compounds and in other cases their reduction to the
metallic state in the substance of the paper or other materials. This process depends
on the liberation at either electrode of an element or elements in the nascent state
and their power in this state of entering into direct combination with another element
or with other elements presented to them. For example, silk, paper and other
materials may be marked in a white design invisible in a dry, but very distinct when
the silk, paper or other material is damped with water by saturating the absorbant
material and material to receive the mark with a solution of biborate of sodium. In
this case the deposit is probably the oxide of boron.
Sometimes it is advisable to saturate the paper or other material with the same
solution as that used for saturating the layer of absorbant material.
Again if the absorbant material be saturated with a solution of a chloride, and
gold form the positive electrode on making contact in the manner described we have
a deposit in the paper or other material of auric chloride. In this case the nascent
chlorine enters into direct combination with the gold forming the positive electrode.
If ordinary water be used for saturating absorbant material and paper or other
material intended to receive the deposit we obtain a deposit of oxide of gold.
Further this auric chloride deposit may be reduced to the metallic state in the
substance of the paper or other material by suitable re-agents and then may be given
a metallic lustre by burnishing.
It is not always necessary to adopt the arrangements frequently mentioned above and
involving the use of an absorbant layer saturated with the solution of a chemical for
other arrangements can when suitable be employed without departing from the
general features of the process. For example; a sufficiency of the chemical solution
can be placed in a non-conducting receptacle so as to saturate a porous carbon or other
suitable porous plate placed therein. The paper or other fabric previously soaked
with water and blotted off can be placed on the porous plate, the platinum or other
design connected with the positive pole pressed on the paper or fabric, and the
negative electrode dipped into the chemical solution or connected with the porous
plate placed therein.
We may mention that the current of electricity employed by us in our experiments
was one of about one ampere at ten volts.
Having now particularly described and ascertained the nature of our said inven-

page_text: tion and in what manner the same is to be performed, we declare that what
we claim is :-
1. The process herein described for producing in or on manufactured paper a dis-
appearing but repeatedly revivable water mark which is invisible in a dry but visible
in a moist condition of the paper, the said process consisting essentially in
placing on a platinum sheet or plate forming the positive electrode a layer of
absorbant material or an equivalent saturated with water: in placing on this in a
moistened state the paper which is to be water marked and in pressing face down-
wards on the paper a salient or other platinum design forming the negative electrode
so that the current from a source of electricity may pass through that portion of the
paper which is in contact with the design in the negative electrode, the whole sub-
stantially as described in the above specification.
2. The process herein described for the production of a permanently visible water-
mark in or on manufactured paper the said process consisting essentially in pressing
the said paper in a moistened condition and superimposed on a layer of absorbant
material or an equivalent moistened with a solution of sodium chloride or other suit-
able substance between a platinum or carbon surface connected with the positive
electrode of a source of electricity and a platinum or carbon surface being in electrical
contact with a salient design of the required watermark connected with the negative
electrode of a source of electricity, the whole substantially as described in the above
specification.
3. For the production of indelible opaque marks in paper and other materials the
herein described process, dependent on the deposit in the paper or other material of
the hydroxide of barium and its subsequent conversion into barium sulphate in the
substance of the paper or other material, the said process consisting essentially in
placing upon a metal plate or other suitable conductor of electricity connected with
the positive electrode a layer of absorbant material or an equivalent saturated with a
solution of a barium salt and in placing on this the paper or other material to be
marked saturated with water, and in effecting the required deposit by pressing on the
paper or other material a conductor connected with the negative electrode of a source
of current electricity, the said deposit of barium hydroxide being converted into the
sulphate in the manner herein set forth, the whole substantially as described in the
above specification.
4. The process herein described for the deposition in or on paper and textile
fabrics of definite chemical compounds of the metals, the said process consisting
essentially in placing on a metal plate or other suitable surface conductive of elec-
tricity a layer of absorbant material or an equivalent saturated with an electrically
decomposable solution one or the other of whose elements is required at the positive
electrode in the nascent state, in connecting this plate with the negative electrode of
a source of electricity, in placing on this the paper or other material saturated with
water to receive the deposit and in placing in contact with this paper or other
material a metal or metals connected with the positive electrode of a source of elec-
tricity, the whole substantially as described in the above specification.
Dated this 25th day of May 1899.
HUGHES & YOUNG,
23, Coleman Street, E.C., Agents.