Processes for the Manufacture of New Chrome Mordanting Sub- stances, and for the Application thereof for Dyeing and Printing Purposes.
Year: 1889

page_text: Date of Application, 8th Jan., 1889
Complete Specification Left, 7th Oct., 1889-Accepted, 9th Nov., 1889
Chemist.]
Processes for the Manufacture of New Chrome Mordanting Sub-
stances, and for the Application thereof for Dyeing and Printing
Purposes.
I WILLIAM LLOYD WISE, of No. 46 Lincoln's Inn Fields, in the County "of
Middlesex, Consulting Engineer and Patent Agent, do hereby declare the nature of
this invention to be as follows:-
The chrome mordants which have hitherto been employed for mordanting cotton
fibre have the disadvantage that the oxide of chromium in such mordants is deposited
upon the fibre only with great difficulty and incompleteness, even when tedious
processes are adopted for the purpose.
Apart from the incomplete technical utilization of the chrome mordants heretofore
employed, it is difficult to obtain uniformly mordanted surfaces in fabrics beaten when
wet, and it is impossible to impregnate cotton yarn with the necessary quantity of
chrome oxide for dark shades by immersing such yarn once in a mordanting liquid
and subsequent fixing. In such a case it is necessary that the yarn be taken out of
the fixing bath (soda solution for instance) and placed into the mordanting bath
(for instance, a solution of chrome alum) several times in succession thus causing a
great expenditure of time and material.
Pieces beaten when wet had to be hung up for a long period steamed for two to
three hours, and very concentrated baths had to be used for fixing,
It has also been difficult heretofore to etch white patterns upon chrome-mordanted
fabrics by means of citric or tartaric acid. It was therefore necessary to produce a
chrome mordant which will impart the chrome oxide therein readily and completely
to the fabric, will always give uniform results and will produce, by etching with
organic acids, sharp patterns with a good white colour, that is to say to obtain a
chromium salt which, when brought upon the fibre, shall be quickly decomposed in
such a manner that the acid forming the solution becomes free, and the chrome oxide
is deposited in quantity upon the material in an insoluble condition.
The property of the new chrome mordant hereinafter described to produce by
means of organic acids, white patterns on the material is of the greatest importance.
This property enables cloth printers to produce a series of the most various fast and
novel articles.
My correspondent has found by experiment that the compound having the formula
Cr, (Cr O)+9 H, O, i.e. the normal chromate of chromic oxide obtained by
dissolving a molecule of chromoxydhydrate in three molecules of chromic acid,
carefully evaporating this solution, and crystallizing several times to long needle
crystals, was particularly suitable to fulfil the above requirements. The diluted
aqueous solution of this compound is decomposed by continued boiling, and the whole
of the chromic oxide is deposited in an insoluble state. When brought upon the
fibre and steamed for about fifteen minutes, this mordant is decomposed in such, a
manner that the whole of the chromic oxide is fixed, with the separation of the
chromic acid.
By merely rinsing the fibre in water, or better still in dilute soda solution, there is
obtained a very uniformly dyeing chroni-mordanted fibre or fabric is obtained.
Corrosion or injurious action of the free acid on the fibre is effectually obviated
by the addition of molecular amounts of sodium acetate or, better still, magnesium
acetate.
The new compound hereinbefore mentioned which in consequence of the large

page_text: quantity of unused chromic acid set free is less suitable for mordanting cotton, may,
in spite of its high price, be used with advantage to mordant silk which is to be dyed
with alizarine colours, as effects can be then produced such as cannot be obtained
with any other mordant hitherto in use:"
This mordant may also be advantageously used for mordanting sheep's wool, since
the whole of the chromium present in the trichromate as, chromic oxide (Cr, O3) and
chromic trioxide (Cr O₂), is readily and completely fixed, and the tartar ordinarily used
may be dispensed with.
The basic chrom-chromate Cr, (Cr O4)2 (OH), is also a good mordant if used when
-"freshly prepared, but the solution thereof does not maintain its good properties and
the price is at present much too high for its economical use.
A product suitable in every way for the purposes set forth is the sulphate chromate.
Cr, Cr O, SO, (OH), obtained by dissolving one molecule of chrome hydroxide in
one molecule of sulphuric acid and one molecule of chromic acid. Añalogous bodies
may be obtained by replacing the sulphuric acid with equivalent amounts of hydro-
chloric nitric or acetic acids.
: As chromic acid in the free state is too expensive to use experiments have been
made to produce soluble chromichromate compounds by means of double decomposition.
It was found that both normal as well as basic chrome..oxide salt. solutions (for
instance Cr, (SO4)2 (OH)2 &c.) when mixed with molecular amounts of soluble
chromates or bichromates, give mordanting liquids which remain clear, without the
deposition of a precipitate, even after standing for weeks, and which when mordanting
fibres act in an analogous manner to the pure chrom chromate mordants that are
prepared from chromhydroxide and the acids (chromic acid alone, or with the addition
of sulphuric acid, hydrochloric acid, &c.).
'
は
"
J..
These chrom chromate bodies obtained by dissolving chromhydroxide in chromic
acid with the addition of sulphuric acid, hydrochloric acid, &c. or by double decom-
position, are, by reason of the chromic acid contained therein very unstable chemical
combinations, which impart all their chromic oxide, by steaming for a short time, to
fibre such as cotton, sheeps wool, silk, etc. in a form that is well suited for dye a
matters.
When employed with mixed fabrics, good results may therefore be obtained by
mordanting once.
The following examples illustrate methods of producing mordants of the kind
herein before referred to.
PRODUCTION OF THE TRICHROMATE MORDANT (Cr, (Cr 0.);
From 1000 grammes of chrome alum (1 molecule), the hydroxide of 'chromium
is precipitated by means of 860 grammes of crystal = or 318 grammes of anhydrous
ammoniacal soda (3 molecules) and the chrome oxide paste so produced is after being
well washed and pressed dissolved by the aid of heat in 300 grammes of chromic
acid (3 molecules).
PRODUCTION OF SULPHATE CHROME MORDANT Cr, SO, Cr O. (OH),.
7
The chrome oxide paste obtained from 1000 grs. of chrome alum, is dissolved by
the aid of a gentle heat in 100 grammes of chromic acid (one molecule) and 98 grammes
of sulphuric acid (H, SO;) (one molecule).
1
7.
PRODUCTION OF SULPHATE CHROMATE-MORDANT Cг, SO̟, Cr O, (OH₂) BY BOUBLE (
DECOMPOSITION.
The chromoxide paste obtained from 1000 grammes chrome-alum is dissolved in
196 orammes of concentrated culebisnis
A

page_text: 4
(one molecule); 1945 grammos of potassium chromate K, Cr O, or 150 grammes of
sodium bichromate, Na, Cr. O, + 2 H; O (half molecule).
The following statements illustrate the application of these mordants in dyeing
and printing cotton fabrics.
APPLICATION OF THE CHROME-CHROMATE MORDANTS IN DYEING AND PRINTING
FABRICS.
In order to obtain the required darkest shades, it is necessary to impregnate the
fibre with about three per cent. of its weight of chromic oxide (Cr₂ O₂).
This requirement is fulfilled by suitably concentrating the mordanting liquids and
mordanting printing colours with a suitable proportion, say, for instance 200 grammes
of chrome-alum. p
.per litre..
By diluting with water, or by mixing the colours with thickening there may be
obtained from these original mordants, all necessary mordants and mordanting printing
colours may be prepared for producing light shades.
CLUMP MORDANTS FOR YARNS AND FABRICS.
1. Trichromate mordant.-Chromtrichromate is prepared from 200 grammes of
chrome-alum by dissolving the precipitate of chromoxyhydrate in chromic acid, then
adding 150 grammes of magnesium acetate of 16° Beaumé and the solution made up
with water to one litre.
2. Sulphate chromate mordant.-Sulphate chromate (Cr, SO, Cr O. (OH), is
prepared from 200 grammes of chrome-alum, by means of Cr O, and H, SO,
100 grammes of magnesium acetate of 16° Beaumé being added, and the whole made
up with water to one litre.
Both mordants may also be obtained by double decomposition as bereinabove
described.
i
3. Printing colour from sulphate chromate.-25 grammes of flour, 75 grammes of
wheat starch, 10 cubic centimetres olive oil, and 1 litre sulphate chromate (Cr, SO,
Cr O, (OH), prepared from 200 grammes of chrome alum, with Cr O, and H, SO, ;
with the addition of 100 grammes of magnesium acetate.
The substances are boiled together and when cold are stirred.
4. Printing colour from sulphate chromate by double decomposition.-25 grammes
of flour, 75 grammes of wheat starch, 10 cubic centimetres of olive oil, and 900 cubic
centimetres basic chrome sulphate Cr₂ (SO), (OH), prepared from 200 grammes
of chrome alum, are first. boiled then partly cooled after which there are added
39 grammes yellow potassium chromate and 100 grammes magnesium acetate of
16° Beaumé.
.
The colours print well and keep indefinitely.

page_text: steamed for about fifteen minutes in a low pressure steaming apparatus or they may
be suspended for twenty four hours in a chamber warmed to about 30° R.
By the action of steaming or suspending in a warin chamber the whole of the
chrome oxide present in the mordant is precipitated as strongly basic chromate in
insoluble form in the fibre.
The fabric is afterwards passed through a soda solution (1% crystal soda) at
about 60° R. for about three minutes, then washed or otherwise treated and dyed in
the ordinary manner.
The passage of the fabric through a weak soda solution after steaming, has not for
object (as in most chrome-mordanting processes heretofore employed) to precipitate
the chromic oxide in an insoluble form by the employment of hot concentrated
alkaline baths (alkali carbonates) but is intended to enable the more readily moistening
of the fibre (and also when colours are printed upon the same) so as to saturate the
excess of organic acids (and thus prevent flow)..
Dated this 8th day of January 1889.
W. LLOYD WISE,
Per F. J. B.
46, Lincoln's Inn Fields, London, W.C., 'Agent for the Applicant.
COMPLETE SPECIFICATION.
Processes for the Manufacture of New Chrome Mordanting Sub-
stances, and for the Application thereof for Dyeing and Printing
Purposes.
I, WILLIAM LLOYD WISE, of No. 46 Lincolns Inn Fields, in the County of
Middlesex, Consulting Engineer and Patent Agent, 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:-
Chrome mordant's such as heretofore employed for mordanting cotton fibre have
had the disadvantage that the oxide of chromium in them has been deposited upon
the fibre only with great difficulty and incompleteness, even when tedious processes
have been adopted for the purpose.
In addition to the incomplete utilisation of the chrome mordants heretofore
employed, it has been difficult to obtain uniformly mordanted surfaces in fabrics
beaten when wet ("Flatschen") and it has been impossible to impregnate cotton
yarn with the necessary quantity of chrome oxide for dark shades by immersing
such yarn once in a mordanting liquid and subsequent fixing. It has been necessary
to take the yarn out of the fixing bath (soda solution for instance) and place it
into the mordanting bath (for instance a solution of chrome alum) and vice versa
and this has involved a great expenditure of time and material.
Pieces-beaten-when-wet ("geflatscht") have had to be hung up for a long period
and steamed for two to three hours, and very concentrated baths have had to be
used for fixing.
It has also been difficult heretofore to form white patterns upon chrome-mordanted
fabrics by means of citric or tartaric acid. Hence the need of a chrome mordant
which should impart its chrome oxide readily and completely to the fibre, which
should always give uniform results, and which should produce, by the action of organic
acids, sharp patterns with, a good white colour, or, in other words, of a chromium
salt; which, when brought in solution into contact with the fibre or material to be
mordanted, should be quickly decomposed in such a manner that the acid effecting.
the solution would become free, and the chrome oxide be deposited in quantity upon
the material in an insoluble condition.
The property of the new chrome mordant hereinafter described, of producing by
means of organic acids, white patterns on the material, is of great importance :
and will enable cloth printers to produce a large variety of fast and novel articles.

page_text: My correspondent has found by experiment that the compound having the
formula Cr, (Cr 0₁), +9 H₂ O i.e. the normal chromate of chromic oxide, obtained
by dissolving a molecule of chromic hydrate in three molecules of chromic acid,
carefully evaporating this solution, and crystallising several times to long needle-
like crystals is particularly adapted to fulfil the above mentioned requirements.
The diluted aqueous solution of this compound is decomposed by continued boiling
and the whole of the chromic oxide contained therein is deposited in an insoluble
state. When brought into contact with the fibre or material to be mordanted and
afterwards steamed for about fifteen minutes, this mordant is decomposed in such
a manner that the whole of the chromic oxide therein is fixed, with the separation"
of the chromic acid. By merely rinsing in water, or better still in dilute soda
solution, a very uniformly dyeing chrome mordanted fibre or fabric can be obtained.
Corrosion or injurious action of the free acid on the fibre is effectually obviated by
the addition of molecular quantities of sodium acetate, or, better still, magnesium
acetate.
The new compound or mordant hereinbefore mentioned which, in consequence of
the large quantity of unused chromic acid set free is less suitable for mordanting
cotton, may, in spite of its high price, be used with advantage to mordant silk
which is to be dyed with alizarine colours, as effects can then be produced such as
cannot be obtained so far as I know with any other mordant hitherto in use.
The new mordant may also be advantageously used for mordanting sheep's wool,
since the whole of the chromium present in the trichromate, as chromic oxide (Cr, O₁)
and chromic trioxide (Cr O₁), is readily and completely fixed, and the tartar ordinarily
used may be dispensed with."
The basic chrom chromate (r, (Cr 0), (OH), is also a good mordant if used
when freshly prepared, but the solution thereof does not maintain its good properties.
and its price is at present much too high for its economical use.
A product suitable in every way for the purposes set forth is the sulphate-
chromate Cr. Cr O, SO, (OH), obtained by dissolving one molecule of chromic
hydrate in one molecule of sulphuric acid and one molecule of chromic acid.
Analogous bodies may be obtained by replacing the sulphuric acid with equivalent
quantities of hydrochloric, nitric, or acetic acids.
As chromic acid in the free state is very expensive, experiments have been made
to produce soluble chrom chromate compounds by means of double decomposition.
with the result that it has been found that both normal as well as basic chrom oxide
salt solutions for instance Cr, (SO4)2 (OH), &c. when mixed with molecular quantities
of soluble chromates or bichromates, give mordanting liquids which remain clear,
without the deposition of a precipitate, even after standing for weeks, and which,.
when mordanting fibres, act in an analogous manner to the pure chrom chromate
mordants that are prepared from chromic hydrate and the acids (chromic acid alone,.
or with the addition of sulphuric acid, hydrochloric acid, etc.).
The chrom chromate bodies obtained by dissolving chromic hydrate in chromic
acid with the addition of other acids such for example as sulphuric acid, or hydro--
chloric acid, or by double decomposition, are, by reason of the chromic acid
contained therein, very unstable chemical combinations, which impart all their
chromic oxide, by steaming for a short time, to fibres such as cotton, sheep's wool,.
silk and the like in a form that is well suited for dye matters.
Therefore when these are employed with mixed fabrics, good results can be obtained
by mordanting once.,
The following examples illustrate methods of producing some mordants of the kind
hereinbefore referred to.

page_text: soda or 318 grammes of ammoniacal soda (3 molecules), and the chromic hydrate paste
so produced is, after being well washed and-pressed, dissolved by the aid of heat in
300 grammes of chromic acid (3 molecules).
PRODUCTION OF SULPHATE CHROMATE-MORDANT Cr, SO, Cr O₁ (OH),.
4
The chromic hydrate paste obtained from 1000 grammes of chrome alum, is dissolved
by the aid of a gentle heat in 100 grammes of chromic acid (1 molecule) and 98 grammes
of sulphuric acid (H. SO,) (1 molecule)...
PRODUCTION OF SULPHATE CHROMATE MORDANT Cг, SO, Cr O (OH),
DECOMPOSITION.
06.
BY DOUBLE
The chromic hydrate paste obtained from 1000 grammes of chrome-alum is dissolved
in 196 grammes of concentrated sulphuric acid (2 molecules) and to the solution thus
obtained there is added 342.5 grammes of sodiuni chromate Na, Cr O + 10 H, O
(1 molecule); 194.5 grammes of potassium chromate K, Cr O₁; or 150 grammes of
sodium bichromate Na, Cr₂ 0, +2 H, O ( molecule).
The following description will illustrate the application of these mordants in dyeing'
and printing cotton fabrics.
APPLICATION OF THE CHROM CHROMATE MORDANTS IN DYEING AND PRINTING FABRICS.
In order to obtain the required darkest shades, it is necessary to impregnate the fibre
with about three per cent. of its weight of chromic oxide (Cr, O3). This requirement
is fulfilled by adopting a strength of mordanting liquids and mordanting printing
colors corresponding to the use of say for instance 200 grammes of chrome alum (the
starting substance) per litre.
By diluting with water, or by mixing the colors with thickening, there can be
obtained from these original mordants, all necessary, mordants and mordanting printing
colors for producing light shades.
المعدة
+02
5
CLUMP MORDANTS (“KLOTZBEIZEN") FOR YARNS AND FABRICS.
1. Trichromate mordant :-Chrom trichromate is prepared from 200 grammes of
chrome-alun by dissolving the precipitate of chromic hydrate obtained therefrom in
chromic acid, then adding 150 grammes of magnesium acetate of 16° Beaumé and
making up the solution with water to one litre.
0
2. Sulphate chromate mordant :-Sulphate chromate Cr. SO, Cr O. (OH), is pre-
pared from 200 grammes of chrome-alum, by means of chromic acid (Cr O3) and
sulphuric acid (H, SO.), 100 grammes of magnesium acetate of 16° Beaume being
added, and the whole made up with water to one litre."
r
Both mordants may also be obtained by doublo-decomposition as hereinabove
described.
.
3. Printing color prepared from sulphate chromate -25 grammes of flour,
75 grammes of wheat starch, 10 cubic centimetres of olive oil, and 1 litre of sulphate
chromate Cr, SO, Cr O. (OH), prepared from 200 grammes of chrome alum; with
chromic acid (Cr O3) and sulphuric acid (H, SO) and an addition of 100 grammes
of magnesium acetate are boiled together and stirred until cold.
4. Printing color prepared from sulphate chromate by double decomposition:-
25 grammes of flour; 75 grammes of wheat starch; 10 cubic centimetres of olive
oil and 900 cubic centimetres of basic chrom sulphate Cr, (SO), (OH), prepared
from 200 grammes of chrome alum, are first boiled.then cooled until lukewarm, after

page_text: which there are added to the mixture 39 grammes of yellow potassium chromate and
100 grammes of magnesium acetate of 16° Beaumé. The colors thus produced print
well and will keep.
Fabrics impregnated or printed with these mordants or mordanting colors are, for
the purpose of fixing the chrome oxide, after drying, steamed for about fifteen minutes.
in a low pressure steaming apparatus, or they may be suspended for twenty four hours
in a chamber warmed to about 30° Reaumur.
By the action of steaming or suspending in a warm chamber, the whole of the
chrome oxide present in the mordant is precipitated as strongly basic chromate in an
insoluble form in the fibre.
The fabric is afterwards passed through a soda solution (1% crystal soda) at
about 60° R. for about three minutes, then washed or treated thoroughly with cow dung
if necessary and dyed in the ordinary manner.
The passage of the fabric through a weak soda solution after steaming, has therefore
not for object (as in most chrome-mordanting processes heretofore employed) to
precipitate the chronic oxide in an insoluble form by the employment of hot concen-
trated alkaline baths (alkaline carbonates), but is intended to more readily effect
the moistening of the fibre to saturate the excess of organic acids and also
when colors are printed upon or recessed out of the same, to prevent their flowing
or running.
Having now particularly described and ascertained the nature of the said inven-
tion and in what manner the same is to be performed I declare that what I
claim is :
:-
1. The manufacture of a chrome mordanting substance hereinabove referred to
as chrom chromate by dissolving a compound of citromium in chromic acid as
described.
2. The manufacture of a chrome mordanting substance hereinabove referred to as
chrom chromate by dissolving a compound of chromium in chromic acid and sulphuric
or other acid as described.
3. The manufacture of a chrome mordanting substance hereinabove referred to as
chrom chromate by double decomposition between soluble chromium compounds and
soluble chromates or bichromates as described.
4. The use as a mordant in dyeing and printing on fibres or fabrics as hereinabove
described of a chrome mordanting substance such as hereinabove referred to as
chrom-chromate.
Dated this 7th day of October 1889.
W. LLOYD WISE.