The Production of Fast Colours on Animal Fibre by the Aid of Oxide of Titanium.
Year: 1896

page_text: Date of Application, 14th Mar., 1896
Complete Specification Left, 12th Dec., 1896-Accepted, 16th Jan., 1897
PROVISIONAL SPECIFICATION.
The Production of Fast Colours on Animal Fibre by the Aid of
Oxide of Titanium.
I JOSEPH BARNES of 149 Manchester Road, Accrington, Lancashire, Public
Analyst do hereby declare the nature of this invention to be as follows:-
This invention consists in producing fast colours on all kinds of animal fibre
such as woollen or silk threads, yarns, or fabrics by the aid of oxide of titanium.
When animal fibre is treated with a salt of titanium either by boiling, steeping, or
steaming, it is rendered capable owing to the fixation of oxide of titanium of being
coloured or dyed by certain colouring principles generally known as polygenetic
colouring matters such as haematein, tannin, & alizarin. The colours thus produced
are of considerable permanency and are generally different in shade from the colours
obtained in a similar manner by the aid of the metallic oxides hitherto used for
this purpose.
Dated this Thirteenth day of March 1896
The Production of Fast Colours on Animal Fibre by the Aid of
Oxide of Titanium.
I JOSEPH BARNES, of 149 Manchester Road, Accrington, in the County of
Lancaster, Public Analyst, 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 consists in producing fast colours on all kinds of animal fibre
(such as woollen or silk threads, yarns or fabrics for example,) by the aid of
oxide of titanium. When animal fibre or tissue is treated with a salt of titanium
either by boiling, steeping, or steaming it is rendered capable (owing to the fixation
of oxide of titanium) of being coloured or dyed by certain colouring principles
generally known as polygenetic colouring matters such as haematein, tannin, and
alizarin, &c. The colours thus produced are of considerable permanency and are
generally different in shade from the colours produced in a similar manner by the
aid of the metallic oxides hitherto used for this purpose.
Compounds of titanium have not hitherto been used as mordants for animal
fibre and I have found that oxide of titanium (TiO2) in a more or less hydrated
form such as TiO,, 2 H₂O, and even when more or less chemically united with
other oxides such as SO3 (sulphuric anhydride) P,O, (phosphoric anhydride)
C,O, (oxalic anhydride) CaO (calcium oxide) &c. serves when suitably fixed upon
or within the animal fibre as a good mordant for the mordant colours or what are
generally known as polygenetic colouring matters.
The whole series of alizarin colours, also coerulein, galleïn, tannin, as well as
logwood, and other so-called "wood colours" may be made to yield, by the
aid of oxide of titanium, lakes upon or within animal fibre which have the power
of withstanding to a considerable degree the action of soaping, or of light or
of both.

page_text: The shades of the titanium lakes so produced hold as a rule an intermediate
position between those produced by aluminium on the one hand and chromium on
the other.
The mordauting of wool (for example) may be carried out according to my
invention as follows:-
One ounce of titanium-tetra-chloride (TiCl), is placed in a large glass or
stoneware flask or bottle surrounded with cold water. Cold water is now allowed
to drop very slowly into the flask or bottle. The action of the water upon the
titanium chloride is very energetic and much heat is evolved so that care must be
taken to add the water slowly, say one drop every two or three seconds. The
addition of the water may be effected by the aid of a funnel with a glass or stone-
ware stop-cock. A pale yellow solid substance is formed by the first portions of
water and this is converted upon the further addition of water into a brownish
coloured fluid. When this stage is reached the addition of water may be quickened
care being taken however that the solution never becomes very hot. The total
amount of water added should be about two and a half ounces. The solution
thus prepared is poured into a porcelain or stoneware dish and four ounces of
ground cream of tartar are stirred into it. The dish is then heated on a water or
steam bath, the contents being stirred from time to time until the product has a
syrupy consistency and weighs six ounces.
For every ten ounces of wool I take of the mordant (prepared as above
described) from one to two and a half ounces according to the depth of shade
required and dissolve it in twenty pints of warm water. The wool which has
been previously wetted out is then immersed in the bath which is then brought
to the boil. After boiling one or two hours the wool is taken out, washed, and
is then ready for dyeing in the usual manner in a fresh bath with a mordant
colour.
In this manner shades may be produced as follows:-Alizarin produces from red
to maroon shades according to duration of heating in the dye-bath and to other
conditions, e.g. the addition of a lime salt. The final shade produced by a complete
and full dyeing is however a deep maroon.
Alizarin orange produces with a full mordanting & dyeing-scarlet.
brown.
Alizarin brown
"
"
Alizarin blue
"
"
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وو
"
blue-violet.
"
Coeruleïn
"
"
"
"
rich green.
Galloflavin
"
Alizarin yellow G.W."
Tannin
"
دو
وو
وو
"
"
"
"
"
"
Logwood
"
"
وو
رو
orange yellow.
brilliant yellow.
orange yellow.
deep black.
Instead of using cream of tartar for assisting the proper penetration and fixation
of the oxide of titanium in a suitable form within or upon the animal fibre or tissue
other materials such as tartaric acid, oxalic acid, hydro-fluoric acid, soluble fluorides,
soluble oxalates &c. which possess the property of preventing or retarding the
separation of oxide of titaniumn in an insoluble form when its solutions are heated,
may be made use of.
For the preparation of a suitable titanium mordant by the aid of oxalic acid
according to my invention I proceed as follows:-
A solution of oxide of titanium in aqueous hydrochloric or sulphuric acid is poured
into cold water containing ammonia in such quantity that there remains a distinct
smell of ammonia after the solutions are thoroughly mixed. The precipitate of
hydrated oxide of titanium thus formed is washed by decantation several times with
cold water and then thrown on to a filter and again waslied several times with cold
water and allowed to drain to a paste.
The percentage of ammonia oxide of titanium (TiO,) is then determined in a small
portion of this paste by the usual methods of quantitative analysis, and an amount
of crystallised oxalic acid taken which is equal to five times the weight of the

page_text: anhydrous oxide of titanium obtainable from the rest of the paste. The oxalic acid
is then dissolved in ten times its own weight of hot water and the paste is then
stirred into the hot solution. The liquor thus produced is used for mordanting wool
in the following manner.
A sufficient quantity of this last named liquor is mixed with a convenient quantity
of water to form a hath which shall contain from one to two parts of oxide of
titanium (TiO2) for every hundred parts of the wool to be mordanted. The woul
is then immersed in this bath and kept moving while the bath is heated up to a
temperature of 160 degrees Fahrenheit. The bath is kept at this heat for
half an hour or more. The wool is then removed and rinsed in water. It is then
ready for the dye bath.
Other alkalies such as soda or potash or those salts of soda, potash, or ammonia,
which possess an alkaline character e.g. the sulphites, sulphides, and carbonates of
these bases may be used instead of ammonia for precipitating the oxide of titanium
in a form suitable for re-dissolving in oxalic acid as above described. The
re-dissolving of the precipitated oxide of titanium may also be effected by means of
hydrofluoric, or tartaric and other organic acids either singly or conjointly and with
or without the aid of soluble fluorides, oxalates or tartrates, so long as a solution
is obtained which will not readily deposit oxide of titanium in an insoluble form
upon heating.
Insoluble oxide of titanium, e.g. that which has been strongly ignited or that
which is found in a native state such as rutile, or that which has been deposited by
builing a solution of its salts in water, may be brought into a soluble form by the
agency of strong sulphuric acid or bydrofluoric acid, or by fluxing with alkaline
bisulphates, alkalis, alkaline carbonates &c. in ways well known and described in
works on chemistry, and the compound of titanium thus obtained whether already
in solution or in a form readily soluble in acids may be used either at once in the
impure condition, or after removing impurities such as oxide of iron, for the
preparation of mordants as above described. It must be borne in mind however that
the presence of impurities, more especially iron, will modify the shades produced by
the various colouring matters.
Animal fibre or tissue may also be mordanted by steeping in a solid solution of
oxide of titanium; e.g.-silk may be mordanted by steeping for several hours in a
cold solution of oxide of titanium tetra-chloride (TiCl) with water as before described
and diluting the solution to 10 degrees of Twaddells' hydrometer.
Certain colouring principles, e.g.-tannin, may be mixed with the mordant
and the mixture used for the operations of mordanting and dyeing in a single
bath and also for printing in which latter process the colour and mordant
become fixed by a subsequent steaming operation. For some of these methods
however the mordant must contain little or no alkaline sulphates or chlorides,
otherwise, and more especially in the presence of tannin, an insoluble lake may be
formed before the colouring matter and mordant have an opportunity of entering
the fibre.
It will be evident that fast colours may be produced in other animal fibre or tissue
by the aid of oxide of titanium in an analogous manner.
Having now particularly described and ascertained the nature of my said inven-
tion and in what manner the same is to be performed I declare that what I
claim is :-
The production of fast colours upon animal fibre or tissue by the aid of oxide of
itanium substantially in the manner herein before described.
Dated this 11th day of December 1896.
GEO. DAVIES & SON,
4, St. Ann's Square, Manchester, Agents for the Applicant.