Improvements in or relating to the Ornamentation or Protection of Metallic Articles.
Year: 1892

page_text: Date of Application, 2nd Apr., 1892
Complete Specification Left, 2nd Jan., 1893-Accepted, 2nd May, 1893
PROVISIONAL SPECIFICATION.
Improvements in or relating to the Ornamentation or Protection of
Metallic Articles.
I, ERWIN NICOLAUS of Ortrand, in the Empire of Germany, Manufacturer,
do hereby declare the nature of this invention to be as follows:-
This invention relates to a process for the treatment of articles made of iron or
steel of varying thickness, with certain acids, or solutions of certain metals, so
that upon the surfaces of such articles there form oxides which may or may not
be combined with oxides of other metals, the result in either case being that
the metal articles thus prepared are durably decorated in different shades or
colours while at the same time they are made proof against wear and atmospheric
influences.
The oxides naturally forming upon iron and steel surfaces have the peculiarity
of varying in colour according to the degree of hardness or density of the metal,
forming what is generally known as blue, yellow, light or deep brown, and violet
rust. In combination with the oxides of other metals such as copper, zinc, nickel,
the rust is capable of assuming darker or lighter shades and hues and the idea of
this invention is to decorate objects of metal by taking advantage of the effects of
such combinations of oxides and by varying these effects according to the require-
ments of light and shade.
In order to obtain deeper or lighter shades it is necessary that the metal article
should be cast in such a manner as to present walls or portions of unequal
thickness. The parts which shall be of a lighter hue, when rust forms on their
surfaces, should be correspondingly thin-walled, and conversely, thicker walls are
required in those parts which when attacked by rust, are to acquire a darker
colouring; hardness varying in an inverse ratio to thickness.
When the metal-casting is formed it is covered or coated with dilute acids
adapted to accelerate oxidation. It is then allowed to dry for a few hours, where-
upon it is rubbed with a brush, which latter operation may be repeated several
times over according to the desired depth and durability of the hue to be produced.
The result will be that as oxidation sets in the article will become variously
coloured, in lighter or darker predetermined shades.
Instead of obtaining the variation of shades by varying the thickness of the
metal, it may be brought about by combining the oxide naturally forming on such
metal with oxides of other metals, such as copper, zinc or nickel. In this case acid
solutions of such metals are used instead of acids, the solution being first rather
concentrated and then gradually diluted.
The article is first coated with a more or less neutral solution which solution is
then gradually made stronger by the addition of acid. Care should however be
taken in this operation to avoid as much as possible putting acid on those parts to
which it is desired to give a light colouring. As in ordinary painting or shading,
more acid should be spread where the colouring is to be darkest.
In this manner variously coloured designs may be produced the different colours
being obtained by different mixtures of oxides.
An important condition is that the oxidizing process should be carried out in a
place or chamber in which the moisture of the air does not exceed 60% as
otherwise hard and rough oxidation would be produced and the effect spoiled.
If however the oxidation is allowed to be carried out in a place containing air
with from 70 to 90% of moisture, the rough rust resulting may be ground off and
then allowed to form again and so on until a hard protective crust forms on the
surface of the article.

page_text: To enable metal objects so treated, to withstand the effects of wear and weather
they are submitted to the following additional treatment,―
Each article is coated with a mixture of oil or varnish and of a farinaceous
substance which may or may not contain certain ferruginous varnishes or oxides
of iron. Such mixtures as these are well known to protect articles of metal from
rust. In this instance however it is intended by a similar action to protect
surfaces, which are oxidized already against injurious external influences. The
coating combines with the oxide of iron which is on or in the metal and the
thoroughness of this combination prevents it from scaling off or being readily
rubbed off in use.
If therefore the object so coated should happen to be damaged on the outside,
this will not cause the damaged part to be further destroyed by rust, as
rust cannot develop under the protective coating as it frequently does under-
neath the ordinary oil-paint coatings, thus practically destroying the whole: of
Euch coating:
The articles first decorated by oxidation, as aforesaid, are then placed in a
carefully closed vessel connected with an air-pump by means of which a more or
less complete vacuum can be produced therein. The pipe connecting the vessel
and pump is provided with a suitable cock for controlling the exhaustion of air.
In addition to this pipe another pipe leads to the said vessel and through this
second pipe is introduced by pressure or exhaustion the protecting liquid. This
supply pipe is connected with another vessel hermetically closed at the top and
containing the protecting liquid in question, it being heated underneath so as to
maintain the protecting material such as tar, tar-oil, or varnish anthracene oil,
creosote oil, or other oils in a liquid condition.
Upon creating a more or less complete vacuum in the vessel or chamber in which
the articles to be coated are placed, and opening the cock or tap in the supply
pipe, the protecting liquid will of its own accord enter the chamber or vessel
and the supply will be continued until the same pressure is attained in both
vessels. The cocks of both the supply pipe and the air-suction pipe are then
closed and a high pressure of say 8 to 10 atmospheres is produced and kept
up for 6 or 8 hours; steam, air, water or heat, being employed in producing
such pressure, which forces the protecting liquid into the very pores of the
metal which had been previously allowed to oxidize, and causes it thoroughly to
mix with the oxide.
The oxidation process above described besides producing the decorative effects
stated, when required present the more practical but none the less very valuable
advantages of rendering the metal bodies rough, porous and absorbent.
After a certain time the coating or impregnating apparatus is opened and the
articles treated therein are removed. The superfluous liquid is then allowed to
drip off and each object is dried in a place kept free from dust.
When it is desired to impart brilliancy to the whole or part of the metal article
this can be done by grinding or polishing off those parts and then re-coating them
with a fresh layer of oil.
Where it is intended in actual use to expose the article to the immediate contact
of air or water, it may after the impregnation process last described be immersed
in a cold bath of oil or of the same liquids which are used for the protective
impregnation.
Dated this 2nd day of April 1892.
W. P. THOMPSON & Boult,
Agents for the Applicant.

page_text: COMPLETE SPECIFICATION.
Improvements in or relating to the Ornamentation or Protection of
Metallic Articles.
1, ERWIN NICOLAUS of Ortrand, in the Empire of Germany, Manufacturer, 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:-
This invention relates to a process for the treatment of articles made of iron or
steel of varying thickness, with certain acids, or solutions of certain metals, so that
upon the surfaces of such articles there form oxides which may or may not be
combined with oxides of other metals, the result in either case being that the
metal articles thus prepared are durably decorated in different shades or colours,
while at the same time 'they are made proof against wear and atmospheric
influences.
The oxides naturally forming upon iron and steel surfaces have the peculiarity
of varying in colour according to the degree of hardness or density of the
metal, forming what is generally known as blue, yellow, light or deep brown,
and violet rust. In combination with the oxides of other metals such as copper,
zinc, brass, nickel, the rust is capable of assuming darker or lighter shades and
hues and the idea of this invention is to decorate objects of metal by taking
advantage of the effects of such combinations of oxides and by varying these effects
according to the requirements of light and shade.
In order to obtain deeper or lighter shades it is necessary that the metal article
should be cast in such a manner as to present walls or portions of unequal thickness.
The parts which shall be of a lighter hue, when rust forms on their surfaces, should
be correspondingly thin-walled, and conversely thicker walls are required in those
parts which, when attacked by rust, are to acquire a darker colouring; hardness
varying in an inverse ratio to thickness.
When the metal-casting is formed, it is covered or coated with dilute acids
adapted to accelerate oxidation. It is then allowed to dry for a few hours where-
upon it is rubbed with a brush, which latter operation may be repeated several
times over according to the desired depth and durability of the hue to be produced.
The result will be that as oxidation sets in the article will become variously
coloured, in lighter or darker predetermined shades.
Instead of obtaining the variation of shades by varying the thickness of the
metal, it may be brought about by combining the oxide naturally forming on such
metal with oxides of other metals, such as copper, zinc, or nickel. In this case
acid solutions of such metals are used instead of acids the solution being first
rather concentrated and then gradually diluted.
The article is first coated with a more or less neutral solution, which solution
is then gradually made stronger by the addition of acid. Care should however be
taken in this operation to avoid as much as possible putting acid on those parts to
which it is desired to give a light colouring. As in ordinary painting or shading,
more acid should be spread where the colouring is to be darkest.
In this manner variously coloured designs may be produced, the different colours
being obtained by different mixtures of oxides.
An important condition is that the oxidizing process should be carried out in a
place or chamber in which the moisture does not exceed 60% as otherwise hard
and rough oxidation would be produced and the effect spoiled.
If however the oxidation is allowed to be carried out in a place containing
from 70 to 90% of moisture, the rough rust resulting may be ground off and then
allowed to form again and so on until a hard protective crust forms on the surface
of the article.

page_text: To enable metal objects so treated, to withstand the effects of wear and weather.
they are submitted to the following additional treatment.
Each article is coated with a mixture of oil or varnish and of a farinaceous
substance which may or may not contain certain ferruginous varnishes or oxides of
iron. Such mixtures as these are well-known to protect articles of metal from
rust. In this instance however it is intended by a similar action to protect
surfaces which are oxidized already against injurious external influences. The
coating combines with the oxide of iron which is on or in the metal and the
thoroughness of this combination prevents it from scaling off or being readily
rubbed off in use.
If therefore the object so coated should happen to be damaged on the outside,
this will not cause the damaged part to be further destroyed by rust, as rust
cannot develop under the protective coating as it frequently does underneath
the ordinary oil-paint coatings, thus practically destroying the whole of such
coating.
The articles first decorated by oxidation as aforesaid are then placed in a
carefully closed vessel connected with an air-pump by means of which a more or
less complete vacuum can be produced therein. The pipe connecting the vessel
and pump
is provided with a suitable cock for controlling the exhaustion of air.
In addition to this pipe another pipe leads to the said vessel, and through this
second pipe is introduced, by pressure or exhaustion, the protecting liquid. This
supply pipe is connected with another vessel hermetically closed at the top and
containing the protecting liquid in question it being heated underneath so as
to maintain the protecting material, such as tar, tar-oil, or varnish anthracene
oil, creosote oil, or other oils in a liquid condition, or india-rubber solution.
Upon creating a more or less complete vacuum in the vessel or chamber in which
the articles to be coated are placed, and opening the cock or tap in the supply-
pipe, the protecting liquid will of its own accord enter the chamber or vessel, and the
supply will be continued until the same pressure is attained in both vessels. The
cocks of both the supply pipe and the air suction pipe are then closed and a
high pressure of say 8 to 10 atmospheres is produced and kept up for 6 or
8 hours, steam, air, water or heat, being employed in producing such pressure
which forces the protecting liquid into the very pores of the metal, which had
been previously allowed to oxidize, and causes it thoroughly to mix with the
oxide.
The oxidation process above described besides producing the decorative effects
stated when required present the more practical but none the less very valuable
advantages of rendering the metal bodies rough, porous and absorbent.
After a certain time the coating or impregnating apparatus is opened and the
articles treated therein are removed. The superfluous liquid is then allowed to
drip off, and each object is dried in a place kept free from dust.
When it is desired to impart brilliancy to the whole or part of the metal article,
this can be done by grinding or polishing off those parts and then re-coating them
with a fresh layer of oil.
Where it is intended, in actual use, to expose the article to the immediate contact
of air or water, it may after the impregnation process last described, be immersed
in a cold bath of oil or of the same liquids which are used for the protective
impregnation.
Having now particularly described and ascertained the nature of the said
invention and in what manner the same is to be performed, I declare that
what I claim is :-
1. The process of decoration of iron and steel articles consisting in so treating
them that the rust forming thereon is according to requirements of a lighter or
deeper shade or tone, the portions which are to remain light assuming the colours
or hues of copper nickel brass or the like while the shaded portions take the darker
colours of rust for which purpose the article to be decorated is either (a) cast in

page_text: such a manner that its thickness varies according to the deeper or lighter shades of
rust desired to appear on its different parts say for example thin where the colour
of the rust is to be lighter and thicker where it is to be deeper oxidation being
assisted by coatings of acids which after being applied are allowed to dry and are
then removed preferably by brushing or (6) coated with solutions of metal salts
e.g. salts of copper zinc nickel or brass taken first in the concentrated neutral
condition and then gradually diluted and acidified each coating being allowed to
dry and then brushed off.
2. The treatment of objects of metal decorated or oxidized in the manner
characterized in the preceding claim consisting in subjecting such objects or
articles after drying them well to high pressure maintained for several hours at
say 8 to 10 atmospheres in a tightly closed vessel or chamber partly filled with an
impregnating liquid such as oil tar coal-tar anthracene oil creosote oil or india-
rubber solution for the purpose of forcing the liquid into the body or substance of
the said articles and of causing it to mix with the pulverulent rust contained therein
so as to obtain a good strong colouring or coating on the said articles in keeping
with the purpose they are intended to fulfil.
Dated this 2nd day of January 1893.
W. P. THOMPSON & BOULT,
Agents for the Applicant.