Adwait Mahesh Deshpande

Indigo Dyeing

Seminar

SUBMITTED TO THE

INSTITUTE OF CHEMICAL TECHNOLOGY

IN PARTIAL FULFILMENT OF THE

REQUIREMENTS FOR THE DEGREE OF

BACHELOR OF TECHNOLOGY

IN

DEPARTMENT OF FIBRES AND TEXTILE PROCESSING TECHNOLOGY

UNDER THE GUIDANCE

OF

Prof. Shukla

BY

Adwait Mahesh Deshpande

FINAL YEAR B. TECH- SEMESTER VII

INSTITUTE OF CHEMICAL TECHNOLOGY,

Deemed to be University

MATUNGA, MUMBAI- 400 019

SUBMITTED on 15th October 2010

1 Indigo Dyeing
 Adwait Mahesh Deshpande

Sr. No. Topic Page

No.
1 A Brief History Of Indigo Dyeing

2 Physical and Chemical properties

3 Synthesis Of the Indigo Dye

4 Dyeing Procedures for Polyester and Cotton

2 Indigo Dyeing
 Adwait Mahesh Deshpande

1. A Brief History of Indigo Dyeing

Indigo plants originate from different parts of the world and produce a colorfast, deep
blue dye. The plant was first domesticated in India during the Indus Valley period
between the fourth and the second millennium b.c. Many varieties of the indigo plant
exist throughout the world. One species originates from east and southern Africa, another
from tropical America. Indigofera tinctoria, believed to be native to Asia and now widely
distributed and naturalized all over the tropics. I.tinctoria is the species that was first
domesticated in India and predominantly cultivated over the centuries for commerce. The
name “indigo” is derived from the Greek for “of India” and refers to the Indian
subcontinent.

Indigo was mentioned in manuscripts dating as far back as the fourth century b.c. The
historical record of indigo is patchy, but references were made by Marco Polo who saw
indigo during a visit to the southern tip of India in 1298. Around this time, Arab traders
had introduced indigo to the Mediterranean region, where it became available in small
quantities. The cultivation of indigo on a large scale started in the sixteenth century in
India, particularly in the north.

During the Middle Ages indigo moved like other valuable articles of trade through
established caravan routes, primarily overland from India through Baghdad into Europe.
By the sixteenth century the Portuguese, and later the Dutch, had established trade routes
by sea to India, making indigo much more accessible to the average European. By 1516,
the Portuguese were importing large quantities of indigo (along with spices and other
valuable goods from eastern ports) by ship into Europe.

Indigo Arrives in Europe by Sea Trade

Soon after its appearance in European ports, the trade of indigo was inhibited by powerful
guilds in many European countries. Until indigo, the primary European source for dye was

3 Indigo Dyeing
 Adwait Mahesh Deshpande

the indigenous woad plant. Woad had been cultivated extensively in France, Germany and
England since the Roman Empire. European woad-growers and merchants saw indigo as
serious competition, since it was a better dye producing deeper, more colorfast blues.

Nevertheless, bans did not stop the flow indigo into Europe. Soon after the establishment of
Portuguese trade routes, Spain began cultivating indigo in its new world colonies, first setting
up plantations in the mid-1500s along the Pacific coast of Central America. By the close of
the seventeenth century, indigo was moving into Europe from east (Portuguese, Dutch, and
English) and west (Spanish). At this time, the French joined the fray with the establishment
of indigo plantations on the eastern part of modern day Haiti in 1697. When the German
woad industry eventually collapsed, a large population, whose livelihood depended on woad,
was plunged into abject poverty.

Indigo Plantations in the West Indies and South Carolina

By the late 1600s indigo was marketed legally in most European countries. Until this time,
India was the main supply of indigo for the British, who resented the monopoly on the dye
held by Indian traders and merchants. The British faced difficulties ensuring a regular supply
of indigo and controlling quality. The price of indigo also fluctuated drastically. The British
soon joined the Spanish and French, who were already cultivating indigo on plantations in
the new world. The British first established indigo plantations in its West Indian territories
(Jamaica), and then in its colonies in North America, most notably in South Carolina, as a
new source for the dye. Producing indigo was labor intensive and, in the West Indies and
American colonies, only possible through a system of slavery. Contemporary accounts
indicate that when prices were high, indigo dyestuff could be exchanged for slaves; it is said
that a planter in South Carolina could fill his bags with indigo and ride to Charleston to buy a
slave with the contents, “exchanging indigo pound for pound of negro weighed naked.”

Back to India

Soon after the loss of the American colonies and the drying up of French supplies of indigo,
Britain pressed for a return to India as a source. However, this time, they sought to control
production. In the nineteenth century, Bengal in northeastern India became the world’s main

4 Indigo Dyeing
 Adwait Mahesh Deshpande

source of indigo, by now in great demand to supply the textile industries of the Industrial
Revolution and to dye many European service uniforms. Throughout the century natural
indigo was far more valuable than any other dyestuff and Bengal’s indigo production far
outweighed that of the rest of the world. For the earlier part of the nineteenth century it may
be fair to say that the industry created gainful employment for Indians. But, after the first
quarter of the nineteenth century, Indians were generally forced to cultivate indigo on their
best land and faced exploitation and cruel maltreatment by British planters.

Denim and the Invention of Synthetic Indigo

The earliest known pre-cursor for jeans is the Indian export of a thick cotton cloth dyed in
indigo, in the 16th century, known as dungaree. Sailors of the time frequently used the fabric

5 Indigo Dyeing
 Adwait Mahesh Deshpande

to make clothing. For the past century, almost all indigo used in denim manufacturing has
been man-made. Synthetic indigo was first produced for commercial use in 1897, when the
German chemical company BASF (Badische Anilin und Soda Fabrik) introduced the dye
based on the findings of the Berlin chemist Adolf von Baeyer. BASF called its new product
“indigo pure.” Soon other European companies, including dyeworks in France and
Switzerland, began producing their own synthetic indigo, and natural indigo entered its final
irreversible decline on the international market. The situation of the peasants of India got
even worse with the chemical replication of indigo from the late 19th century onwards. The
pressures on the “planters” (British estate owners) to make a profit and survive in these
circumstances increased the pressure on those involved in indigo cultivation, extraction, and
processing.

6 Indigo Dyeing
 Adwait Mahesh Deshpande

2. Physical and Chemical properties

The first laboratory synthesis of indigo was achieved by Adolf von Baeyer in 1878, and
in 1883 he revealed the structural formula to Heinrich Caro, at that time head of the
research laboratories at BASF.

2.1 Physical Properties

The systematic name of indigo, also known as indigotin, is 2-(1,3-dihydro-3- oxo-2H-

indol-2-ylidene)-1,2-dihydro-3H-indol-3-one or 2,2 ´-biindolinylidene- 3,3´-dione. It
exists as blue-violet needles or prisms with a pronounced coppery luster. It sublimes
above 170°C as a red-violet vapor that condenses on cooling to form dark violet needles.
The melting point is 390.392°C.

Indigo is practically insoluble in water, dilute acids, and dilute alkalis, but slightly soluble
in polar, high-boiling solvents such as aniline, nitrobenzene, phenol, phthalic anhydride,
and dimethyl sulfoxide. Some polar solvents destroy indigo when it is dissolved in them
at the boil.

The dye is positively solvatochromic, the absorption maximum in a polar solvent such as
dimethyl sulfoxide being 620 nm, that is, 12 nm higher than in a nonpolar solvent such as
carbon tetrachloride. Characteristic of indigo is the unusually deep shade compared with
other conjugated systems of similar size. This is explicable in terms of the special
arrangement of the atoms in the basic chromophore and the high polarizability of the
charge distribution, which is strongly influenced by the ability of the molecule to form
hydrogen bonds.

Intra- and intermolecular hydrogen bonding are the explanation for indigo’s extremely
low solubility and high melting point. X-ray analysis and IR studies demonstrate the
existence of intermolecular hydrogen bonds in the solid state. The very long-wave IR
absorption of the carbonyl band at 1626 cm can be regarded as characteristic of the

7 Indigo Dyeing
 Adwait Mahesh Deshpande

indigo structure. By comparison, the carbonyl band of dehydroindigo is situated at 1724

cm. Bond orders and charge densities in the indigo molecule have been calculated
and compared with the results of X-ray analysis. These studies confirm the structural
formula and answer questions about the basic chromophore of the dye.

2.2 Chemical Properties

Indigo is very stable to light and heat. The molecule does not readily undergo
electrophilic or nucleophilic substitution. However, it can be successfully sulfonated
in concentrated sulfuric acid to give the tetrasulfonic acid, and halogenated in
nitrobenzene to introduce up to six halogen atoms.

Indigo is readily reduced by various reducing agents such as zinc dust, sodium dithionite,
hydroxyacetone, and hydrogen, or by electrochemical means. In an alkaline medium, a
salt (for example the sodium salt) of leuco indigo is produced, which can be converted by
acids to so-called indigo white.

Indigo (1)

8 Indigo Dyeing
 Adwait Mahesh Deshpande

The yellow-brown soluble vat form of indigo has affinity for animal and vegetable fibers,
making it possible for indigo to be used in dyeing. Upon oxidation with air, it forms blue
indigo again, fixed on the fiber. The dye tends to adhere mainly to the surface of cotton
fibers, whereas on the polypeptide fibers of wool or silk the bonding is more salt like.
This explains the fact that the fastness to light, rubbing, and washing are poorer on cotton
than on wool. The difference in shade between dyeing on the two fiber types is also due
to the different bonding mechanisms.

Oxidation of the indigo dye molecule results in formation of dehydroindigo. Oxidation

with permanganate or chromate splits the molecule, forming isatin. Oxidation and
reduction of the indigo system are accompanied by corresponding changes in the
spectroscopic properties.

3. Synthesis
For thousands of years, indigo was produced from plant material containing low
concentrations of indican, a precursor of the dye. Indican is split by enzymes and
converted to indigo by oxidation. Indigo can be synthesized from D-glucose by
genetically modified strains of coli bacteria, presumably by a process that resembles
biosynthesis in plants.

3.1 Chemical Synthesis

9 Indigo Dyeing
 Adwait Mahesh Deshpande

Synthetic indigo was made by A. von Baeyer in 1870 by treating isatin with phosphorus
trichloride and phosphorus in acetyl chloride. He obtained isatin by oxidizing indigo. The
first complete synthesis of indigo was achieved in 1878, when von Baeyer succeeded in
deriving isatin from phenylacetic acid.

First total synthesis of Indigo

Another synthetic route proposed by von Baeyer began with o-nitrocinnamic acid and led
to o-nitrophenylpropiolic acid, which could be converted to indigo directly on the textile
fiber with mild reducing agents under alkaline conditions.

For a few years o-nitrophenylpropiolic acid was sold commercially as “little indigo”.

Von Baeyer also synthesized indigo by a fascinatingly simple reaction between o-

nitrobenzaldehyde and acetone in alkaline solution. The product, o-nitrophenyllactic acid
ketone, splits off acetic acid and water and dimerizes to form indigo.

10 Indigo Dyeing
 Adwait Mahesh Deshpande

Hoechst and BASF tried to develop the von Baeyer processes industrially. However, a
breakthrough to a cost-effective industrial synthesis was not possible. The nitration step
was in each case insufficiently selective and therefore expensive.

Heumann I Process
In 1890 Karl Heumann published a synthetic method based on aniline. It involved reating
aniline with chloroacetic acid to form N-phenylglycine salt, fusing this in potassium
hydroxide to convert it to indoxylate (di-salt), and finally hydrolyzing and oxidizing the
indoxylate to indigo. Since the high reaction temperature (300° C) needed caused partial
decomposition, the yield (10% of theoretical) was too low for large-scale production.
Only the stoichiometric addition of sodium amide discovered by J. Pfleger of Degussa in
1901, as a highly effective condensing agent for the indoxylate melt, produced yields of
up to 90% at reaction temperatures of around 220°C. Hoechst and BASF launched this
process on an industrial scale.

After the ring-closure reaction, the yellow indoxylate present as the di-Na/K salt in the
alkaline melt is hydrolyzed with water. Oxidation of the monosalt of indoxylate takes
place in air at 80.90° C. A suspension of blue indigo results in an aqueous alkaline
medium. Small amounts of byproducts, such as aniline, Nmethylaniline, and anthranilic
acid, are also produced.

Indigo is isolated from the indigo suspension by cake filtration, washed with water, and
further processed into the various commercial forms of indigo or vat indigo. The mother

11 Indigo Dyeing
 Adwait Mahesh Deshpande

liquor from the filtration step can be regenerated and reused in the manufacturing process
as an anhydrous alkaline melt. N-Phenylglycine in the form of an alkali metal salt is the
starting material for the Heumann I synthesis.

Heumann PG salt synthesis

Heumann II Process
In the Heumann II process, starting from anthranilic acid, N-phenylglycine-o-carboxylic
acid, prepared from anthranilic acid and chloroacetic acid, is added in the form of the
alkali metal salt to a KOH/NaOH melt at 200°C to produce indoxylcarboxylic acid salt.
After hydrolysis and decarboxylation, the product is oxidized in air to yield indigo.

12 Indigo Dyeing
 Adwait Mahesh Deshpande

On account of the carboxyl group in the ortho position, ring closure occurs more readily
than in the case of N-phenylglycine salt. This makes it possible to attain yields of
between 70 and 90 %, even without the use of sodium amide. Isolation of indigo from the
suspension is carried out as in the Heumann I synthesis

by filtration, washing, and drying. This method was employed by BASF from 1897
onwards to produce and market the first synthetic indigo on an industrial scale. Indigo is
insoluble in aqueous alkaline media and to be useful in dyeing it must be converted into
soluble leuco indigo. In dyehouses this is done mostly by reducing it with sodium
dithionite in the presence of alkali.

The idea of liberating the dyer from the burden of vatting the dye and of integrating
this reduction step into the synthesis process is not new. For example, indigo can be
vatted with reducing agents that were commonly used in the past, such as zinc dust and
iron(II) sulfate. However, reduction with hydrogen in the presence of a catalyst such as
nickel or palladium is preferable, also from an ecological viewpoint.

Various forms of leuco indigo are available today. BASF Indigo Vat 60% Grains is
produced by evaporating to dryness an aqueous leuco indigo solution in the presence of
molasses. The molasses stabilizes the leuco indigo against oxidation. The resulting dye,

13 Indigo Dyeing
 Adwait Mahesh Deshpande

with an indigo content of 60 %, is a specialty product that, because it is so easy to use,

mainly finds application in the production of indigo dyeings for commercial art purposes.

Liquid commercial forms of leuco indigo are becoming increasingly significant. Thus, a
20% and, as new market standard, a 40% solution of an alkali metal salt of leuco indigo
are available. In addition to simple metering, the liquid dye allows dyehouses to dispense
with much of the sodium dithionite and alkali needed for dyeing with indigo granules.
Furthermore, the resin like residues produced by the reduction with hydrosulfite do not
occur.

Environmental Aspects
On account of its low solubility, indigo is degraded to only a very small extent in
biological wastewater clarification plants. However, over 90% is adsorbed onto activated
sludge and is thus eliminated from the wastewater. Indigo’s classification in Germany’s
official list of water-polluting substances is WGK 1, corresponding to the lowest
polluting potential. A strain of bacteria capable of degrading indigo was discovered by
the Hong Kong Institute of Biotechnology.

3.2 Biotechnological Synthesis

In General

Suitable plants for producing indigo are the indigo plant (Indigofera tinctoria ), woad (
Isatis tinctoria ), and Chinese indigo (Polygonium tinctorium). The latter is still grown on
the island of Shikoku in Japan and is used for blue dyeing. These plants all contain up to
0.8% of the glucoside indican. Enzymatic splitting of indican into indoxyl and glucose is
carried out in a fermentation vat containing a carbohydrate-based material, such as bran
or starch, and alkaline additives (potash, lime, or ammonia).

14 Indigo Dyeing
 Adwait Mahesh Deshpande

The enzyme responsible for cleaving indican is indoxyl- -D-glucosidase, which is formed
on the plant by microorganisms. The resulting indoxyl, which under alkaline conditions is
soluble in water, is discharged from the fermentation vat and oxidized to indigo by
operation. The insoluble dye is isolated by precipitation and air drying. The fermentation
mix can also be used directly for dyeing. The textile is impregnated with the fermenting
mash and then .blued. by oxidation in the air. This type of dyeing was carried out with
woad (Isatis tinctoria ). Pure indigo dye was not extracted from woad because of its low
content of indican.

Microbiological Synthesis

In the 1980s, indigo was successfully produced by microbiological techniques in the

USA. The development of a fermentation process involving genetically modified strains
of coli bacteria capable of forming usable amounts of indigo from D-glucose represented
a new, biosynthetic route to indigo.

Biotransformation of Indoles
It was reported in the technical literature as early as 1956 that bacteria are able to convert
indole to indigo. The bacteria use the enzyme naphthalene dioxygenase to oxidize indole
to indoxyl. Apparently the substrate specificity of this enzyme is not very pronounced, so
that besides naphthalene, which is oxidized to 1,2-dihydroxynaphthalene, it also accepts
indole as a substrate. Two process variants for carrying out this biotransformation are
described. In the first, the biotransformation is carried out in a homogeneous aqueous
system. The critical quantity is the indole concentration, since too high an indole
concentration causes the biomass to die off . In the second, the biotransformation is
carried out in a two-phase system. The biomass, containing the catalyst, is in the aqueous

15 Indigo Dyeing
 Adwait Mahesh Deshpande

phase, while the substrate is supplied in an organic solvent. In both process variants, the
indoxyl formed is spontaneously oxidized to indigo by atmospheric oxygen.

Bacterial De-Novo Synthesis

The basic idea behind this variant is to use the synthetic potential of bacteria to produce
the indole precursor. Although indole does not occur as an intermediate in bacterial
metabolism, it appears as an enzyme-linked intermediate in the biocatalytic
transformation of D-glucose to L-tryptophan. The crucial biosynthetic step is the
conversion of indole-3-glycerine phosphate to L-tryptophan by the enzyme tryptophan
synthase.

The essential stages of the multistep route used by nature to synthesize aromatic
amino acids were elucidated in the 1950s by studies on mutant bacteria (e.g. Aerobacter
and Escherichia coli): the cyclization of D-glucose to 5-dehydroquinic acid and the
formation of shikimic acid. The first aromatic compound in the reaction chain is
anthranilic acid:

Bioindigo -Shikimic acid path (simplified). Preparation of indigo by bacterial de novo synthesis.

16 Indigo Dyeing
 Adwait Mahesh Deshpande

Biotechnological techniques allow the genetic coding for the enzyme tryptophan synthase
in E. coli to be modified in such a way as to liberate the originally enzyme-linked
intermediate indole. If E. coli is simultaneously implanted with the coding for
naphthalene dioxygenase from the bacterium Pseudomonas putida, the modified
microorganism can convert the liberated indole directly to cis-indole-2,3-dihydrodiol,
which splits off water and is oxidized to indigo.

Indigoid Dyes
A problem in the biotechnological synthesis of indigo is the disposal of the large amounts
of biomass produced. Application as a fertilizer is not yet a ready option, because of the
possible liberation of genetically modified microorganisms. Alternative disposal
methods, such as an efficient clarification plant or incineration, are associated with
additional costs.

Commercial grades:
The following commercial forms of indigo are available worldwide:
In non reduced form as
1. indigo granules
2. indigo powder
3. indigo paste (alkaline)
In reduced form as
1. vat indigo 60%
2. vat indigo 40% (20 %) solution

17 Indigo Dyeing
 Adwait Mahesh Deshpande

4. Dyeing Procedures for Polyester and Cotton

Laboratory Scale dyeing

The typical dyeing procedure for polyester is 8g/L sodium hydrosulfite, 1g/L sodium
hydroxide, and 1 % owf indigo at 120°C for 30 minutes. After dyeing, the reduced indigo
in the polyester fabrics is air-oxidized at 100°C for over 10 minutes. The indigo dye is
reduced in aqueous solutions of 4 g/L sodium hydrosulfite (Na2S2O4), 2.88 g/L sodium
hydroxide (NaOH), and 30 g/L sodium sulfate (Na2SO4) at 50°C.

Cotton fabrics are put into the reduced indigo solution where the bath ratio is 50:1 and the
dye concentration is 0.05– 0.2 % owf. The cotton fabrics were dyed at 50°C for 30
minutes. After dyeing, the reduced indigo in the cotton is air oxidized at room
temperature for over 10 minutes, then washed with an aqueous solution of 5 g/L anionic
soaping agent at 80°C for 10 minutes.

Dyeing polyester fabrics with indigo dyes is successful under certain conditions, which
coordinate the rate of sodium hydrosulfite and sodium hydroxide. When the sodium
hydrosulfite concentration is 8 g/L, the optimum dyeing concentration of sodium
hydroxide is 0.5–1.0 g/L in the dye bath solution at 120°C. It seems that the role of non-
ionic reduced indigo formation is important in this dyeing method. The dyeing
temperature is effective, and well-dyed polyester fabrics are obtained at 120°C. The
maximum wavelength of polyester fabrics dyed with indigo is clearly different from that
of cotton fabrics. Polyester has a richer blue color than cotton when they are both dyed
with the indigo. The rub fastness of polyester dyed with indigo is superior to that of
cotton.

18 Indigo Dyeing
 Adwait Mahesh Deshpande

Industrial Scale Dyeing

Now processing and dyeing methods for indigo warps were introduced from 1978- 1987
to obtain a higher productivity and savings in dyeing or to achieve the required darker
shades (hard rock washing, super blue, soft denim), or softness of the yarn for final
finishing. The following table gives you a comparison of the possible processing stages
such as:

1. Indigo rope dyeing process

2. Indigo one sheet dye slashing
3. Indigo double sheet dyeing
4. Dye 1 for 6 (continuous dye slashing)
5. Dye 1for 6 with dyemer (continuous mercerization dyeing and sizing).

For the five major Indigo dyeing methods for the basic denim, super blue denim, soft
denim, stone wash denim, we also must take into consideration that a certain appearance
of the garments is only achieved after a certain washing method. (Chemical washing,
stone washing, hard rock washing), use of certain sizing agents (soft denim) or irregular
appearance in warp or weft direction by using a yarn with slubs and neps (antic denim).
The final finishing methods have influence on fabric construction and dyeing methods.

CONVENTIONAL CLASSICAL CONTINUOUS INDIGO ROPE DYEING

The classical rope dyeing system is very labour intensive and consists of:-

· Ball warping
· Indigo dyeing
· Rebeaming on long- chain-beamer
· Sizing

19 Indigo Dyeing
 Adwait Mahesh Deshpande

Yarn from the ring spinning machine is wound on automatic winding machines on to
a suitable package either cylindrical or 5057 cone. The winders are directly linked to
the ring spinning frames and the cops joint by splicing. OE yarns are directly creeled
up on the Ball warper.

The requires No. of ends (usually 380 – 420 ends) are assembled into a rope. These ends
are wound onto a core. The rope is guided similar as a cross wound package and wound
into a ball, length of ball approx. 12 – 15.000 meters. A lease is inserted at the start and
end of the rope. The facilitate Rebeaming every 1000 meters an additional lease is
inserted. Usually 18 – 24 ropes are simultaneously process on the rope dyeing machine.
Prior to dyeing, the ropes are boiled out and treated with caustic-soda and wetting agent
to remove from the cotton oil, impurities which could influence the fastness for the dye.
To dye with indigo, the ropes are immersed into the dye-bath. To dye in rope 30 – 60
seconds immersion (20 meters yarn) and 60 - 180 seconds are required for the oxidation
of the Indigo dyestuff to ensure that also ends in the centre of the rope are equally dyed.
Please note that squeezing pressure is important 5 tons as fastness of colour and shade
depends on even squeezing pressure. The comparatively long immersion and oxidation
time requires a comparatively expensive equipment of machinery.

In order to obtain the required deep shade of blue colour the ropes are 5 – 6 times
immersed in a sequence of dye boxes with an oxidation range then so called skying after
each dye box. (Indigo belongs to the group of the vat dyes which is watersoluble in
eeduced solution and becomes an insoluble pigment when oxidized.

Having passed the dyeing and oxidation rage the ropes are guided through 2 or 3 washing
boxes to wash off excessive loss pigments in the last box softener are added to ease the
opening of the ropes. They are dried in series of cans. The dried ropes which contain 380
– 420 ends are then deposited into large coilers Rebeaming with 300 – 380 ends per rope
is easer. These coilers are placed behind the long chain beamer where the Rebeaming and
opening of the ropes takes place. In order to guarantee even yarn tension through
rebeaming on to a back beam ready for sizing

20 Indigo Dyeing
 Adwait Mahesh Deshpande

the ropes are guided over a tension device which is placed approx. in 10 -11 meters
distance from the long chain beamer. Broken ends which very really happen process
of the rope are repaired at this process stage. Initially these machines were supplied
without yarn stop motion but are available now a days on special request. This is of
major importance as lost ends, fluff, 3 – tail ends and yarn remnants can cause inferior
performance in weaving.

The so prepared beck beams are now sized in a sizing machine preferably with 2 size
boxes. The size pick up varies between 8 – 10%. In Europe mainly modified starches
with binders are used, whilst in USA certain low % of PVA is applied sin combination
with starches by some companies. Depending on the final finishing process (washed
denim) with no filler also CMC gives excellent performance in weaving.

CONTINUOUS SLASHER DYEING

Contrary to the Indigo rope dyeing system, for the continuous slasher dyeing and sizing
back beams are used. That means that the total No of ends required for a weavers beam
are dyed, dried, sized and dried simultaneously. The back beam contains similar to rope
380 – 420 ends but distributed evenly over the width of 140 or 160 cm between the
flanges so the end lay parallel to each other, warp length 12 – 15.000 meters, similar to
the rope dyeing system the full No of ends are pretreated (washed) dyed in 4 dye boxes
and oxidized, no softener are used in the last wash box.
We must however consider that the squeezing effect is lower and therefore the danger
streakiness and shade variation from centre to out side is also higher. Consequently it
would be better to deduce the warping width rather to 140 cm instead of using warper
beams with 160 – 180 cm warping width. The immersion time in the dye boxes is approx.
10 – 15 seconds and time for oxidation 30 – 60 second. The final result is a weaver’s
beam. This system allows the installation of less expensive dye rage and less additional
preparatory machinery. One of the disadvantages in previous year when warp preparation
(knots, weak, thick places) was not kept at a very high level was that ends sown in the
dyeing range could cause major colour variation through machine stops.

21 Indigo Dyeing
 Adwait Mahesh Deshpande

DOUBLE SHEET CONTINUOUS DYEING

Patents applied for double shade dyeing by E. Godau date back as 1976. With the system
dyeing sizing is done in 2 operations. The main reason for dyeing of 2 sheets
simultaneously is achieved a more even dyed sheet, that means 8000 – 8200 end are
dyed, oxidized, dried and the full length of the warper’s beam 12.000 – 15.000 meters
flange diameter. These beams are transported with the aid of air cushions to the sizing
machine, and the yarn sheet sized in double size boxes. Immersion time and oxidation
time is the same as with continuous slasher dyeing.
With double sheet dyeing the linear warp thread density is doubled. Therefore:
Squeezing effect is increased; an even squeezing over the whole width is achieved,
Condensation and concentration of ends at one spot show compared to single sheet
dyeing no colour strips formation, streakiness or shading in the finished fabric. The
production out put of the dyeing is increased by 75%. Dyeing of 3 layers of yarn
simultaneously is possible but very difficult to control the beaming on 3 big warp
batches. Unfortunately the double sheet dyeing machine as well as the rope dyeing range
cannot be linked with a sizing machine which must be regarded as an advantage as the
processes of dyeing and sizing must be carried out separately.

Loop dye system 1 for 6

Similar to the sheet dyeing systems 10 – 16 warper’s beams with the total number of ends
required for the weaver beams are used. The warper’s beams are placed in a moveable
warp creel which can be loaded whilst one set is in rotation. The yarn sheet is guided to
the soaking bath through a feed-in system with tension compensation rollers. The soaking
bath has the task to prepare the yarn for the following dyeing operation.
The yarn sheet after having been immersed into a single indigo dye bath runs into a long
loop where oxidation takes place. As you can see from the slide the back beams are
inside the yarn sheet passes through the dye box as often as necessary to obtain the
required deepness of shade.

22 Indigo Dyeing
 Adwait Mahesh Deshpande

One of the advantages is:

Ideal utilization of Hydrosulphite is through squeezing 4 – 6 layers simultaneously and

oxidation of yarn in a comparatively long oxidation loop. After the oxidation the yarn
sheet is guided through 2 washing boxes into a yarn accumulator and finally on to a
series of drying cans, dried up to 25 – 30% final moisture content prior being immersed
into size boxes, dried and wound onto a weavers beam.
The molecules are controlled DC drive to maintain warp tensions. Temperatures are
automatically controlled as well as the PH value in the dye box. The automatic control
unit of the PH value supplies automatically hydrosulfite and caustic soda to stabilize the
present value from the start to end of a dye set.
All rollers are contact with the dyed sheet are fluted, they keep the sheet in position and
reduce deposit of dye and build-up of other deposit (fluff). In addition to width is
controlled by guides to ensure even distribution of the yarn layer over the whole width of
the dyed sheet.
All accumulators placed between washing boxes and drying cans guarantees a continuous
production of the dye range when a weaver beam has to be exchanged at the head stock.
The creels can be loaded with back beam with 1200 mm diameter which allows to warp
approx. 36.800 meters of yarn, count No 7, 5 (tex 78) or 50.000 m count No 10 (tex 60).
This means that depending on the count normally one cyl-spool is used in warping to fill
a warper’s beam.

WARPING SPEED

PRODUCTION
Speed varies between 1000 m/min, 35 m/min. No 5, 5 (tex 107) and 42 m/min. No
10 (tex 60)

23 Indigo Dyeing
 Adwait Mahesh Deshpande

MACHINE STOPS DURING SIZING

For 36800 m, 4 recorded on expansion comb.

WASTE OF MATERIAL
Approximately - 15-20 kg per set.

TIME REQUIRED FOR CHANGE OF SET

2 hours

Linear warp densities in the squeeze.

The linear density in the nip is calculated in the same manner as for sizing.
Q= linear thread density
F= ends in cm -1
D= diameter of yarn
D= 0,921 mm = 0,921 = 0, 29125
Nm 10 = 3.1622
Q= F x D

As already mentioned previously the warp density has an influence on colour fastness. A
higher squeezing effect is achieved due to the over laying of the watp ends this also gives
more side to side squeezing, therefore reduce strips formation. The high squeezing effect
results also in better, quicker and proper oxidation and better colour fastness.
It must be mentioned that recommended dip and oxidation times on warp dyeing ranges
are of little use if not the squeezing effect is taken into consideration. Under a given
squeeze pressure, for instance 500 kg the squeezing effect of the mentioned 4- dyeing
systems can be compared. We can see that similar squeezing effect can be achieved with
the loop dyeing system 1 for 6 (75%) as with rope dyeing 70 – 110%. Double dyeing
with 2 layers width with 150 cm gives approx. 80% squeezing effect, whilst single sheet
slasher dyeing varies depending on count between 100 – 130%.

24 Indigo Dyeing
 Adwait Mahesh Deshpande

As only one short indigo dye bath is deeded only one feeding tanks, no separate feeding
of chemicals is necessary.
Dye liquor is use in 1500 1 instead of 6-4500 1, therefore less chemicals in use at same
time.
· Lower power consumption.
· Fine counts can be dyed as well
· For dark shades, black shades or other shades needed by fashion, other indanthrene dye
stuff can be directly added into the indigo dye bath (indanthrene yellow or orange).

LOOP DYE 1 FOR 6 COMBINED WITH DYEMER

The demand for dark shades specially dark marine blue for super blue denims also led to
new ideas in indigo dyeing ranges have been increased between 8-15 dye boxes with
corresponding oxidation ranges. In some cases, Hydroxyacetone has been specially
treated with high frequency. Besides achieving a darker shaded with the desire greenish
touch it is very suitable for biological treatment.
In order to achieving ring dyeing, mercerized yarn has also been used. A mercerizing
prevents penetration of dye stuff into the inner code it is suitable for this purpose to
obtain an optical blue effect and superior colour fastness and behavior in washing.
Mercerizing is very costly, therefore new ways is continuous mercerizing and indigo
dyeing was found.

DYEMER

The dyemer range is integrated. For impregnation padder for hot caustic solution is
placed after the heating system. The yarn is guided over could cylinders and with an
adjustable roller the tension of the yarn sheet can be adjusted according to the required
tension prior to the scouring in 2 more boxes.
After having passed this, the yarn sheet is immersed into the dye box and the same
process as with the loop dye method is repeated.

25 Indigo Dyeing
 Adwait Mahesh Deshpande

INDIGO ROPE DYEING

SLASHER (INDIGOFLOW) DYEING

Indigoflow
We can explain the indigo flow dyeing tech as, every phase included the impregnation of
the yarn with the Leuco solution, in ALKALINE bath and at temperature relatively low
to oxidation it follows, after squeezing a pressure a passage in air to allow the Leuco to
oxidation and to become blue and therefore insoluble.

Oxidation
The oxidation is very important in the dyeing process; the purpose of the oxidation is
to get the permanent dye on the yarn and to eliminate the insolubility of the dye stuff in
the water.
According to the practical experience the average time for a perfect oxidation is about 60
seconds, this means that after the first dyeing/squeezing the yarn has to remain exposed
in the air for about 60 seconds before being dipped again in the second dyeing vat and so
on for all the following dyeing.
The dyeing mean time can be calculated in about 30/35 meters of yarn per minutes
therefore keeping as base the machine with eight dye vats. The total yarn in the oxidized
can be calculated as m 35 x 8 = 280 meters.
But Indigoflow with their special device “Rapidsky” only eight meters per dye vat of
yarn remain in the Rapidsky device. That means the total saving of yarn with Rapidsky is

24 x 8 = 216 meters.

FLEXIBILITY IN USE

The high degree of evolution that can be reached by completing the basic machine with
the mercerizing and an intermediate drying can group, a steamer and a special double
circuit system for bath circulation system, enabling separation of vats and that allows the
maximum flexibility in use. In addition to the classical indigo blue it thus possible to dye

26 Indigo Dyeing
 Adwait Mahesh Deshpande

the modern mercerized to dye the modern mercerized indigo blue and black, the new
indigo supper blue the per-dyed indigo, as well as the large range of colour denim with
sulphurs, indanthrene, naphtholes, direct, relatives and pigments dyes.

THE CIRCULATION SYSTEM

This system has a ingenious and perfect dye bath circulation system. Through a variable
flow pump, the dye bath is sent from the circulation vat to the first dyeing vat, and from
this by means of an overflow system with special conveyors/mixers, to the next vat and
so on until it falls back into the circulation vat, where it is filtered its temperature is
adjusted and colour Hydrosulphite and soda are automatically added. This system is very
simple and dose not required maintenance. Dye bath circulation vat, stainless steel made,
complete with interchangeable bucket filters, automatic level adjustment, temperature
control and dosing of colours, Hydrosulphite and soda.

ACCUMULATORS
This system have to Gravity accumulators for automatic storage of the dye yarn when the
slasher machines stops for beam change complete with finned stainless steel rollers for
synchronization and safety devices.

MERCERIZATION

Mercerization causes morphological and mechanical changes in the yarn thus increasing
its resistance and dye affinity (dye stuff) saving, mercerized warp makes it possible to
obtain a better texture handle and look as well as particular chromatic effect on the ready
made cloth.

MERCERIZED PROCESS
Mercerizing group consisting of soda process vat with circulation pump and filter, timing
cans neutralize and washing vats with 10 tons squeezing foulards, automatic feeding and
electronic yarn tension regulation devices.

27 Indigo Dyeing
 Adwait Mahesh Deshpande

TECHNICAL CHARACTERISTICS

1. Reduced capacity dye vat with semicircular bottoms and with only 2-3 large diameter
immersed rollers, to avoid the yarn breaking and tangling and to reduce the bath quantity.

2. Squeezing foulards with special rollers enabling a uniform squeeze effect over the
entire width under all pressure conditions.

3. In order to eliminate the cleaning operations and to help the colour oxidation this
system has special fining on the surface on the rollers of the oxidizers and accumulators.

4. Compactness, thus being accessible and easy to handle.

Ropes are stronger and less subjective to broken ends that, if they do occur, will tend to
pass through the machine. Ropes are braided from let-off creels to provide continuous
operation. Therefore there is no yarn waste from beam set splicing stops or shade tailing
from dye class changes. Standards pretreatment consists of counter flow scour/boxes.
Optional mercerizing section adds a caustic box plus skying rolls to provide proper
reaction time before washing. This adds important properties such as improved dye
affinity, fabric luster and strength as well as popular faction effects.

Rope dyeing is economical and well suited for processing chambers, dark shades, over
dye and fashion colours. These would include sulfur, reactive and vat dyes. Multiple dips
of indigo and proper oxidation time and in the skying section achieve depth of shade.
Basic range consists of eight box/sky sections. High production and/or deep fashion blue
ay require more sections.
Dyestuff preparation circulation and custom designed chemical and system allow full
flexibility for variation dyestuff application. Morrison’s color kitchen for caustic,
Hydrosulphite and indigo are supplied with filters and stand by pumps to allow

28 Indigo Dyeing
 Adwait Mahesh Deshpande

uninterrupted operation. Large diameter feed and return lines assure content level in the
each dye box.
After dyeing the ropes enter multiple wash boxes for rinsing and chemical application.
Ropes are than carefully dried to 6% moisture or steam heated drying cylinders. Coilers
lay the individual ropes into drums in a pattern to facilitate the subsequent rebeaming
operation.
The 350 plus ends per rope are blended during the rebeaming (post dye) stage, and then
further randomized when the twelve beams set are sized prior to weaving virtually
guaranteeing side/side colour uniformity.

SLASHER DYEING VS ROPE DYEING

Slasher Dyeing Rope Dyeing

Requires lesser floor Space Floor space required more than indigo flow
Is a continuous process or beam process It is not a continuous process, including
ball warping. Rebeaming critical.

The mercerizing process is easy and simple
Less man power required
The capacity of one dye Dye bath is 100
litres to save the expensive indigo dye
stuff. The dye bath has three rollers. (one is
bigger than the other two)
Mercerizing difficult due to rebeaming
More man power required for ball warping
and rebeaming
The dye baths are in customized shapes.
The capacityof dye stuff is 2.5 lits. The dye
bath have five rollers of the same size.

Yarn count allowed – 1-30 counts
Flexibility offered for different shades of
dyeing.
Any type of denim can be produced.
Cheaper than the rope dyeing technology
Yarn count allowed – 1-16 counts
Only blue and black colours can be dyed
onto the fabric.
Only classic denim can be produced.
We get it for a price of $ 2.85 per metre in
the international market.

29 Indigo Dyeing
 Adwait Mahesh Deshpande

30 Indigo Dyeing