Mordant Dyes

A mordant is a chemical binding agent that adheres well to both the fibers and the dye.
The word comes from the Latin mordere, which means to bite.
A mordant is a substance used to set dyes on fabrics by forming a coordination
complex with the dye which then attaches to the fabric. It may be used for dyeing fabrics.
A mordant is always a polyvalent metal ion. The resulting coordination complex of dye and
ion is colloidal and can be either acidic or alkaline.

Common dye mordants

Mordants are needed to set the color when using natural dyes. Different mordants will give
different results.

Alum: (Aluminum Potassium Sulfate)

This is the most widely used mordant. Alum is both a specific chemical compound and a
class of chemical compounds. The specific compound is the hydrated aluminium potassium
sulfate with the formula KAl(SO4)2.12H2O.
The formula of wider class of compounds known as alum is AB(SO4)2.12H2O.
Double sulfates with the general formula is A2SO4·B2(SO4)3·24H2O.
Copper: (Copper Sulfate)
This mordant is used to bring out the greens in dyes. It will also darken the dye colors,
similar to using tin, but is less harsh.
Chrome: (Potassium Dichromate, K2Cr2O7)
Chrome brightens dye colors and is more commonly used with wool and mohair than with
any other fiber. Extremely toxic: Chrome should not be inhaled and gloves should be worn
while working with chrome. Left over mordant water should be disposed of at a chemical
waste disposal site and treated as hazardous waste.
Iron: (Ferrous Sulfate)
Dulls and darkens dye colours. Using too much will make the fiber brittle.
Spectralite: (Thiourea Dioxide)
This is a reducing agent for indigo dyeing.
Thiourea dioxide is also called aminoiminomethanesulfinic acid and is
often abbreviated as TDO or TUD. Thiourea dioxide is a powdered
stable compound, which dissolves in water and decomposes gradually
to exhibit a reducing action.
Tara Powder: (Caesalpinia Spinosa)
Tara Powder is a natural tannin product. It is needed for darker colors on cotton, linen and
hemp.
Tartaric Acid: A must for cochineal. This mordant will expand the cochineal colors.
Tin: (Stannous Chloride)
Tin will give extra bright colors to reds, oranges and yellows on protein fibers. Using too
much will make wool and silk brittle. To avoid this you can add a pinch of tin at the end of
the dying time with fiber that was pre-mordanted with alum. Tin is not commonly used with
cellulose fibers.

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Mordants can be added before, during or after the dyeing process. Most recipes use
mordanting before dyeing.
The type of mordant used can change the colour of both the dye-plus-mordant solution and
influence the shade of the final product.

Mordant Dyes
Dyes which have no affinity towards textile fibers are attached with the fiber with the help
of mordants are known as mordant dyes.

Most commonly used mordants are inorganic chromium, so sometimes these dyes are called
chrome dyes. Chrome dye is an acid dye, which forms a chelate complex with chromium
atoms. Restricted use due to eco-toxicity problems.

These dye molecules have some mordant attracting groups which have some influence on
the metal ions. Mainly –OH or –COOH groups appear in neighboring position in azo dyes. A
metal equivalent takes the place of Hydrogen in the –OH or –COOH group each time.

The mordants have affinity both for fiber and dye. So dyes which have no affinity to fibers
can be applied by using a suitable mordant, as dyes have mordant attracting groups.

Fibers most readily dyed with mordant dyes are the natural protein fibers wool, modacrylic
and nylon fibers. In wool dyeing only chromium salt are of importance so mordant dyes
used for wool dyeing are usually called chrome dyes.

Properties of Mordant Dyes

1. Mordant dyes have no affinity for textile fibers. They are attached to the fibers with
the help of mordants. These mordants have affinity both for the dye and fiber.
2. Mordant dyes are capable of combining with metallic oxides to form insoluble color
lakes.
3. Mordant dyes may be natural or synthetic. Natural mordant dyes are obtained from
madder, cochineal, logwood etc. Synthetic mordant dyes are marketed as pastes or
powders.
4. Mordant dyes are mostly applied on natural protein fibers, nylon and modacrylic
fibers.
5. The light wash fastness of mordant dyes is very good with rating from 4-6.
6. Most mordant dyes are soluble in cold water.
7. The main feature of the mordant dye molecule is that there remains a metal ion
(mainly chromium) as a central atom which is bonded to neighboring –OH, -COOH,
or azo group.

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Functions of Mordant Dyes

1. As most natural dyes/mordant dyes have no affinity for a fiber, mordants act as
auxiliary chemicals to fix the dye with the fiber.

2. Mordants improve take-up quality of fiber.

3. They improve light and wash fastness properties.

4. Some mordants (FeSO4) darken the color, some (SnCl2) brighten the color, some
mordants help to obtain specific colors etc.

Classification of Mordant dyes

On the basis of origin there are two types of mordant dyes:

1. Natural mordant dyes

2. Synthetic mordant dyes

Natural Mordant dyes

Very few natural dyes are colour fast with fibres. So mordants are used to fix a dye with the
fibre. These dyes as derived from natural sources e.g., plants are natural mordant dyes.
Among the naturally occurring dyes aligerine (1,2-dihydroxy anthraquinone) is extracted
from the roots of madder. Alizarin produces red, pink, brown and yellowish brown colour
when treated with compounds of Al, Sn, Fe and Cu respectively.
Dyeing with natural mordant dye is a time consuming process. So they are used in a lesser
extent. In all these dyes chromium or other metals combine chemically with certain groups
present in dye and further bound by other forces.

Synthetic mordant dyes

As all synthetic mordant dyes are obtained from acid dyes, they are acid chrome dyes.
That is to say-

Acid colour + Cr Acid chrome

These dyes can coordinate easily with chromium. They can be dyed as acid dyes and
mordanted by after treatment with K2Cr2O7 or Na2Cr2O7. These acid chrome dyes are
extensively used for the dyeing of wool and polyamide fibres. They have good wet fastness
and most of them possess satisfactory light fastness. The commonest method of application
is to dye in an acid dye bath and when exhaustion is completed appropriate amount of
dichromate is to be added to the liquor. Then it is to be boiled for 30 min.

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Dyeing methods
The three methods used for mordanting are:

Pre-mordanting (chrome): The substrate is treated with the mordant and then dyed.
Meta-mordanting (metachrome): The mordant is added in the dye bath itself.
Post-mordanting (afterchrome): The dyed material is treated with a mordant.

The type of mordant used changes the shade obtained after dyeing and also affects the
fastness property of the dye. The application of mordant, either pre-, meta- or post mordant
methods, is influenced by:

The action of the mordant on the substrate: if the mordant and dye methods are harsh (e.g.
an acidic mordant with an acidic dye), pre- or post- mordanting limits the potential for
damage to the substrate.
The stability of the mordant and/or dye lake: the formation of a stable dye lake means that
the mordant can be added in the dye without risk of losing the dye properties (meta-
mordanting).
Dye results can also rely on the mordant chosen as the introduction of the mordant into the
dye will have a marked effect on the final colour.

Cream of Tartar (potassium hydrogen tartrate, KC4H5O6) is used as an assistant when

mordanting wool. It improves the consistency of the colour as well as the consistency
between batches. Cream of tartar should not be used in dyeing the wool with madder.

All fibres need to be well washed before being treated with a mordant. And whatever fibre is
being used it is very important not to overcrowd the vat. Mordanting (or dyeing) of 100
grams of fibre should be done in a 10 litre saucepan. The fibre should leave for at least 48
hours in the mordant bath. After taking the fibre from the bath, should be left for at least a
week before dyeing it. This ageing process is called batching and it improves the fastness of
the dye.

Brief description of methods of application

Pre-mordanting (chrome mordant process)
This is a two bath process. In this process the material is impregnated with an insoluble
chromium hydrate (Chromic Oxide Cr2 O3.2H2O) and then dyeing is done in a separate
bath.

Chrome hydrate is a hydrated form of chromic oxide bound with more or less two
molecules of water. It is insoluble in water and compatible with many organic materials.
Meta-mordanting (Chromate process)
In meta-chrome process dyeing and mordanting are carried out simultaneously in the same
bath. Here the mordant is present in the form of chromate which does not form the lake
with the dye and which is gradually converted into dichromate. The pH of the bath is kept
around 6-7. This method has the advantage of facilitating shading and requires less time
than the after chrome process. Chromates and dichromates are salts of chromic acid and
dichromic acid, respectively. Chromate salts contain the chromate anion, CrO42−, and
usually have an intense yellow color. Dichromate salts contain the dichromate anion,
Cr2O72−, and usually have an intense orange color.

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Post-mordanting (after-chrome process)
This is the oldest and the most common mordant dyeing process. Here the material is first
dyed with an acid dye and then mordanting with chromium is carried out in a separate bath
or mordanting can be done in the same after exhaustion of the dye has been completed.

Meta-chrome Dyeing Process

There are a certain number of acid mordant dyes which can be dyed and mordanted
simultaneously by using metachrome mordants. Meta-chrome mordants contain one part of
sodium or potassium dichromate with two parts of ammonium sulphate.
Common recipe:
2-5% metachrome mordants
5-10% Glauber salt
250-500gm/lit surface active agent
Scoured wool is treated in a bath containing the above chemicals at 40 °C for 20 min. After
20 min the dissolved dye is added and the liquor is brought to the boil over a period of 45
min and retained at this temperature for further 69-90 min.
In case of dyeing heavy shades it is advisable to complete exhaustion by adding 0.5-1%
acetic acid (40%) 30 minutes before the dyeing is finished. Ammonium acetate may be
used in place of ammonium sulphate in the mixture when using colours known to be unlevel
dyeing.
Advantages:
1. Dyeing is carried in one stage
2. High production
3. Easier shade matching
Disadvantages:
1. Range of shades is limited
2. In case of unlevel dyeing it is impossible to correct it

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Mordanting Cotton
Cotton is very time consuming to mordant. First it needs scouring and then it needs a three-
step process, with consecutive mordant baths of alum, tannin and then alum again.
Scouring Cotton
It is necessary to scour the cotton, even if it is to dye with indigo. Scouring removes the dirt
and grease that fibres accumulate during manufacturing and transit.

-Half fill a 10 litre stainless steel pot with water.

-Carefully add 35g soda ash into the pot.
-Place the wet fabric into the water and stir well with a spoon.
-Leave the spoon inside the pot, to prop the lid slightly open.
-Bring the water to the boil.
-Adjust the heat to low boil/hard simmer and allow the fibre to boil half covered for two
hours.
-Stir the fabric every 15 minutes to make sure it is being adequately scoured.
-After two hours remove the saucepan from the heat source and allow the fabric to cool
down until it can be safely removed from the water.
-Finally rinse the fabric.
-If necessary the process may be repeated.

Mordanting Cotton with Alum, Tannin & Alum

100g of fabric is used in a ten litre saucepan.

Total weights to mordant 100g of fabric:-

Alum : 50g (25g in each of Baths 1 & 3)

Soda Ash : 12g (6g in each of Baths 1 & 3)
Tannic Acid : 6g (for Bath 2 only)

Pre-wet 100g of cotton fabric in warm water for at least two hours.

Bath 1:
-Fill half of dye pot with water.
-Bring nearly to boil.
-Dissolve 25g of alum in a small container with boiling water.
-Slowly add alum to pot and stir well.
-Weigh out 6g of soda ash and add slowly and carefully to the water in the pot.
-Soda ash causes the water to bubble vigorously.
-When bubbles have subsided add more hot water to the pot.
-Add pre-wetted fabric.
-Heat to simmering point.
-Simmer for an hour.
-Stir fabric every fifteen minutes.
-Leave fibres in the pot for 24 hours.
-Wring well and dry.
-Leave the fabric to age for at least a week.
-When you are ready for the next step, wash the fibre well.

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Bath 2: (Tannin):
-Fill the pot 2/3 with hot water.
-Dissolve 6g of tannic acid in a small container with boiling water.
-Add tannic acid to pot and dissolve well.
-Add pre-wetted cotton.
-Simmer for one hour, leave for 24 hours.
-Wring well and dry.
-Leave the fabric to age for at least a week.
-Wash the fabric well.

Bath 3: (Second Alum Bath):

-Repeat alum mordanting as described for Bath 1.

Pure white areas:

Mordanting gives the fabric a pale yellow tinge. If area of pure white is needed, the area is
to be tied or masked before mordanting.

Dark colours:
To get dark colours dye the fabric, leave them to age for a week, wash fibres, re-mordant
with alum and soda ash and dye again. For really dark colours re-mordant using the three
step process.

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Mordanting Silk
-De-gummed silk, that is “Prepared for Dyeing” (PFD), silk should be used.
-Weigh the silk, using no more than 100g of silk for a 10 litre saucepan.
-Wash it by hand or by washing machine using silk washing liquid.
-Leave the silk to soak in hot tap water overnight.
-Next weigh the alum, using 6% of the weight of dry silk (i.e. for 100g of silk use 6g of
alum).
-Put the alum in a small container and pour boiling water into the container.
-Stir it well until the alum has dissolved.
-Fill a 10 litre saucepan ¾ full with hot tap water.
-Add the dissolved alum and stir well.
-Then add the pre-soaked fabrics, which are usually warm from the tap water.
-Leave the silk in the pot for 48 hours without adding any heat and stir gently and
occasionally.
-At the end of the 48 hours take the silk from the vat and leave it to dry.
-Keep it for at least a week before washing it and dyeing it.

Mordanting Wool
Scouring the wool
-Wool needs to be well scoured before it is dipped in the dye pot.
-To scour wool, fill a bowl with warm water (between 50 and 60 °C).
-Add some soap or washing liquid and leave the wool to soak for two hours or overnight.
-Rinse carefully.

Mordanting with alum

- 100g scoured wool (dry weight)

- 8g alum.
- 7g cream of tartar
- 10 litre stainless steel stock pot or saucepan.

-Weigh the wool and leave it to soak in water for at least an hour or even overnight.
-Fill a saucepan ¾ full of cold water.
-Pour boiling water into a small heatproof container and add the cream of tartar, stirring it
well until it has dissolved then add it to the saucepan.
-Pour boiling water in a small heatproof container and add the alum, stirring it well until the
alum has dissolved.
-Add the dissolved alum to the saucepan.
-Add the pre-soaked scoured wool to the saucepan.
-Raise the temperature of the saucepan slowly to a simmer (87 to 93 °C) for most wool.
Fine wools may need a lower temperature.
-Simmer gently for an hour. Make sure the fibres are submerged, and stir very gently and
occasionally.
-Leave the wool to cool in the saucepan.
-Dry the wool using a large colander.
-Put the wool on a towel and let it dry.
-If ready to dye, rinse the wool well to remove any unfixed alum.

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Alizarin dye
Among the few naturally occurring dyes madder is extensively used to produce bright red
shades. It is named as Turkey Red as it (madder red) was best dyed in Turkey.
Alizarin is an organic compound that is historically important as a prominent dye. It is an
anthraquinone originally derived from the root of the madder plant. In 1869, it became the
first natural pigment to be duplicated synthetically.

Dyeing of cotton with Alizarin

The dyeing procedure of cotton with alizarin dye (mordant dye) is described as below:

- Cotton fabric is boiled in the solution of

-- 1 part of TR oil
-- 10 parts of water
for 12 hours

TR Oil (Indole 3 acetic acid

- Fabric is dried at 60 °C for 20 minutes.

- Treated again with Aluminum acetate (10 °Tw) at 60 °C for 2 hours.

- Dry at 60 °C for 20 minutes..

- Again treated with two parts of Sodium phosphate and 10 parts of water at 40 °C for 20
minutes.

- 1-1.5% dye (owf) is added in the solution with Calcium acetate at 25 °C in 30 min.

- The fabric is hot rinsed (70 °C) for 30 min.

- Finally the fabric is washed with soap solution and water and then dried.

Draw the Dyeing Curve here

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Structures of Mordant Dyes
Examples of some synthetic mordant dyes are as below:

OH OH
N
N
N
N OH
O
O O + - S
+ - S S - + NaO
NaO ONa O
O O
N
O O

Acid Orange 10 Erichrome Black T

(Mordant Black 11)
[7-Hydroxy-8(phenylazo)-
[3-Hydroxy-4-(1-Hydroxy-2-naphthylazo)-
1,3-naphthalenedisulphonic 7-nitro-1-naphthalene sulphonic acid
acid disodium salt] sodium salt]

HO OH
O OH O
- +
N S ONa HO
N O
O
HO N
O O

Mordant Red 5 Acid Mordant Orange 14

[Sodium 3-[(2,4-dihydroxyphenyl)azo]- [1,2-Dihydroxy-3-nitroanthraquinone ]
4-hydroxybenzenesulphonate]

O N
O
O N
N OH

OH

Mordant Orange 1
5-(4-Nitrophenylazo)salicylic acid

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Colloid
Substance consisting of particles too tiny to be seen with the unaided eye (typically 1
nanometre to 10 micrometres), are substantially larger than atoms and ordinary molecules
and that are dispersed in a continuous phase. Both the dispersed phase and the continuous
phase may be solid, liquid, or gas; examples include suspensions, aerosols, smokes,
emulsions, gels, pastes, and foams. Dyes, detergents, polymers, proteins, and many other
important substances exhibit colloidal behavior.
Tannic acid, a specific commercial form of tannin, is
a polyphenol. The chemical formula for commercial tannic
acid is often given as C76H52O46, but in fact it contains a
mixture of related compounds. Its structure is based mainly
on glucose esters of Gallic acid.
Tannins are astringent, bitter plant polyphenols that either
bind and precipitate or shrink proteins. The astringency from
the tannins is what causes the dry and puckery feeling in the
Gallic acid
mouth following the consumption of unripened
(3,4,5-trihydroxybenzoic acid)
fruit. Destruction or modification of tannins with time plays an
important role in the ripening of fruit and the aging of wine.

Chemistry of Mordant dyes

Metachrome dyeing process

Extraction method of Alizarin

Cream of Tartar is an ‘Assistant’ that increases the

amount of alum absorbed by the wool. It can modify the
final colour, especially with cochineal and madder. Proper
Cream of Tartar (Potassium hydrogen tartrate) should be
used.

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Chemistry of Mordant Dyes

Transition metal ions (Fe+3) in aqueous solution can interact with anions (Cl-) to form simple
salts (e.g., FeCl3) or they can also combine with anions & neutral electron donors to form
complexes involving co-ordinate co-valent bonds (e.g., three K+ ions and one [Fe(CN)6]-3 ion
form K3[Fe(CN)6]. Coordinate co-valent bonds involve sharing

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