(Wool, Silk, Nylon)

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Introduction
Acid dyes are so called because they are usually applied in acidic

condition
This dyes are applicable for those fibres which have amino

groups ( - NH2 -)
List of fibres that could be coloured with acid dyes
Wool Silk Nylon
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Properties of acid dyes

Acid dyes have molecular weights in the range 3001000 g mol1

The colour gamut of acid dyes is complete, including greens and blacks. The
shades

dyes are available as powders, grains and liquids for continuous dyeing, and as fine dispersions of the soluble types. Acid dyes produce a wide range of brilliant

The dyes have higher substantivity for wool , Silk or nylon. They do not have any affinity

to cellulosic fibres

They have a good affinity to protein and polyamide fibres

Usually used for dyeing of wool, silk and nylon

Fastness property of individual dyes varies

Care should be taken while dyeing mixture shades
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Properties of acid dyes

The selection of acid dyes for dyeing a particular material is

not an easy matter, given the wide range of textile products and fastness properties demanded. Manufacturers recommend groups of selected acid dyes for each type of application. Compatible dyes are selected to have similar rates of dyebath exhaustion, when applied together by the recommended procedure, and similar fastness properties. The dyes are available as powders, grains and liquids for continuous dyeing, and as fine dispersions of the soluble types.
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Properties of acid dyes

The rate of dyeing is a function of temperature
Each member has a specific temperature at which the rate of

dyeing and the exhaustion is maximum

Chemically acid dyes resembles the direct dye
After dissolution they produce

A coloured anion as DSO3 Colourless cation Na+

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Classification of Acid Dye

Classification by state of division i.e. size of dye molecule Molecularly split acid dyes
Aggregated acid dyes

Classification by the concentration of acid used in the dye bath

and the fastness properties of the dye

Levelling acid dyes Fast Acid dyes

Milling acid dyes

Super milling acid dyes

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 Molecularly split acid dyes

The dye gives a clear aqueous solution The individual molecule is ionized when dissolved in water

D SO3Na
acid

D SO3- +

Na+

Dyes are applied from baths containing sulphuric acid and formic

In absence of the acid they show a poor affinity to protein fibres

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 Aggregated acid dyes

These dyes, when dissolved in water, do not split into

individual molecules
The dye molecules join together to from clusters or aggregates Owing to their limited solubility, their solutions become turbid Increase in temperature, results increase in ionization

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1.Levelling Acid Dyes

Dyes have high levelling properties Dyeing wool with levelling acid dye requires sulphuric or formic

acid (24%) in the dyebath, along with Glaubers salt, Na2SO4.10H2O (510% owf). Considerable amounts of a strong acid are needed to achieve good exhaustion, Under such acidic dyeing conditions, levelling acid dyes have rapid strike for the wool because of the high concentration of cationic ammonium ion groups in the wool. They correspond to the molecularly split acid dyes

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2. Fast Acid Dyes

These are usually monosulphonated acid dyes of somewhat

higher molecular weight than typical levelling dyes.

The dye wool by essentially the same dyeing like levelling

acid dyes using acetic acid (13% owf) and Glaubers salt (510%owf).
They have reasonable migration at the boil. In some cases, a

levelling agent may be recommended.

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3. Milling Acid Dyes

These anionic dyes have higher molecular weights and greater

substantivity for wool than levelling or fast acid dyes. They usually only have one sulphonate group per dye molecule and therefore have lower water solubility.

Dyeing with milling dyes is carried out in the pH range from 5 to

7, usually starting in the presence of sodium acetate or ammonium sulphate. Acetic acid may be added later in the process to promote exhaustion by increasing the number of ammonium ion groups in the wool.

Milling acid dyes give dyeings with moderate to good washing

fastness, better than for levelling acid dyes.

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 When dyeing with milling acid dyes, Glaubers salt is never added.

Under typical dyeing conditions, at pH 6, it increases the exhaustion of such dyes and hinders levelling. The high concentration of sodium ions from the Glaubers salt helps to suppress the natural negative surface charge of the wool so that the dye anions are not repelled to the same extent and therefore have higher substantivity. The fibres negative surface charge is much less evident in acidic solution when the wool has an excess of cationic ammonium ion groups. This effect of Glaubers salt is exactly the same as that of added salts in cotton dyeing.

Because of the poor migration of milling acid dyes, level dyeing

initially depends upon gradually increasing the dyeing temperature, and then possibly decreasing the dyebath pH by addition of a small amount of acetic acid.
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4. Super-milling Acid Dyes

Dyeing wool with both types of milling dye in the presence of

sulphuric acid at pH 3 results in very rapid absorption and unlevel dyeing, with no chance of levelling by migration. Dyeing is therefore started at about pH 6.57.0. The rate of dye absorption is controlled by the gradual temperature increase of the dyebath, and later by a gradual decrease in dyebath pH to complete exhaustion, if required.
shades to mitigate the initial strike. The pH can be lower for dyeing loose fibre and tops where levelness is less critical since the fibres will be blended together during spinning. C, once the dye aggregates in solution begin to break up with increasing temperature. In the critical temperature range a decreased rate of temperature increase avoids uneven dyeing.
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The initial pH of the dyebath must be even higher for dyeing pale

Dyeing is slow below 60 C. It may, however, increase rapidly above 70

Characteristics of various types of acid dyes

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Chemical constitutions of some typical acid dyes

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Mechanism of dyeing
Abbreviations used
DSO3-Na+: The generalize formula of acid dye D: The colour component of the acid dye molecule DSO3-: The dye anion Na+: The sodium ion H+: Hydrogen ion Nylon: Nylon polymer W: wool polymer
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 The acids used in the dyebath range from sulphuric acid (dyebath

pH < 2.0) to ammonium acetate (dyebath pH > 6.5). Acid dyes are usually sodium salts of sulphonic acids, or less frequently of carboxylic acids, and are therefore anionic in aqueous solution. They will dye fibres with cationic sites. These are usually substituted ammonium ion groups in fibres such as wool, silk and nylon. These fibres absorb acids. The acid protonates the fibres amino groups, so they become cationic. Dyeing involves exchange of the anion associated with an ammonium ion in the fibre with a dye anion in the bath
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Mechanism of acid dyeing

Wool can be represented as

NH2 W COOH When dipped in water it becomes NH3+ W COO In presence of acid (say HCl) it becomes HCl = H+ + Cl NH3+ W COO- + H+ + ClCl- +H3N- W COOH Therefore, the dye will react as below DSO3Na DSO3- + Na+ DSO3- +H3N- W COOH
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Factors affecting the Acid Dyeing

Effect of electrolyte (Glauber Salt)

The added Glaubers salt acts as a retarding and levelling agent.

Sulphate and bisulphate ions inhibit the initial rapid strike of the dye by occupying and thus blocking ammonium ion sites in the wool. Dye anions of higher substantivity then gradually displace the sulphate and bisulphate ions. These anions, however, do have slight substantivity for the wool and will displace some absorbed dye in acidic solution. The presence of Glaubers salt thus promotes levelling and reduces the dyebath exhaustion. of Glaubers salt in an acidic bath at the boil. acid dye

Partial stripping of faulty dyeings is possible using 1520% owf

Salt functions as exhausting agent for milling and super milling
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Factors affecting the Acid Dyeing

Effect of temperature
No exhaustion takes place below 400 C Increase in temperature increases the rate of dyeing /

exhaustion

In each case of dye there is a specific temperature for which it

shows the maximum rate of dyeing

In case of milling and super milling the exhaustion starts at

600 C and reaches at maximum at 700 C

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Principle of application of Acid dye on Wool

Boil

Temperature (0C)

400 C

Rate of rise in temp at 10 C / min

Time (minutes) Check pH and add pre-dissolved dyes Add 10% Glaubers salt 2 4% H2SO4 (pH = 2.5 to 3.5)

Dyeing of protein fibres with molecularly dispersed dye or levelling acid dyes
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Principle of application of Acid dye on Wool

Boil Rate of rise in temp at 10 C / min Cool at 800 C and add 0.5 1 % HCOOH

400 Temperature (0C)

Time (minutes) Check pH and add pre-dissolved dyes

Add 1 3% CH3COOH (pH = 4.5 to 5.5)

Dyeing of protein fibres with milling acid dyes

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Principle of application of Acid dye on Wool

Boil Cool

400 C Temperature (0C)

Rate of rise in temp at 10 C / min

Time (minutes) Check pH and add pre-dissolved dyes Add ammonium acetate or sulphate 2 5 % based on depth of shade

Dyeing of protein fibres with super milling acid dyes

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Procedure for dyeing wool

Bath prepared at 400 C Acid (sulphuric acid 2%) is added to obtain the right dyeing pH Retarding agent is added (glauber salt )

Dyeing is continued at boil for 40 to 60 minutes

Dye bath temperature is raised gradually to the boil (at 10C /min)

Dye bath is circulated for 5 to 10 minutes

Rinsed with cold water and dried ** Note: 1) The dyeing time can be reduced if it is carried out at higher temperature 2) Excessive dyeing time, especially at temperatures above the boil, should be avoided to prevent the possibility of damage to the wool fibres

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Principles of Application of Acid Dye on Silk

980 C 30 90 minutes

Drop Bath 45 minutes

10 minutes
40 450 C A

10 minutes

A Acetic acid + Glauber salt (pH = 4 5) B Dye solution is added

B
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The dyeing cycle for acid dyes on silk

Application of acid dyes to Silk

Acid (Acetic acid 2%) and glauber salt are added to obtain the right dyeing pH ( 4 to 5) Dye solution is added Dye bath is circulated for 5 to 10 minutes

Dyeing is continued at higher temperature for 30 to 90 minutes

Dye bath temperature is raised gradually to the boil in 45 minutes**

Rinsed with cold water and dried ** It is advisable to control the dyeing at 80 to 850 C to preserve the lustre of silk

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Application of Acid Dyes to Nylon

Nylon fibres are characterized by end amino group (NH2), end carboxylic acid

(COOH) and interunit amide group along the chain ( - NHCO-)

Nylon NH2
Nylon polymer with terminal amino group

H+
Hydrogen ion

Nylon NH3+
Nylon polymer with positively charged terminal amino group

Nylon NH3+ + D-SO3Nylon polymer with positively charged terminal amino group Dye anion

Nylon NH3+ SO3- -D

Ionic bond formed between positively charged terminal amino group in nylon polymer and dye anion

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 Points to note
Nylon fibre is susceptible to uneven dyeing

Variation in molecular structure due to variation in the manufacturing process parameters Therefore, levelling agent is required

pH of the dye bath plays a prominent role

Uptake is low to moderate at pH 6 10 Uptake is moderate and constant at pH 2.5 6 Uptake is high for pH < 2.5

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Levelling agent in nylon dyeing

The inability of the dye to migrate from a heavily dyed portion of the

fibre material to a less heavily dyed one is the cause of uneven dyeing

Levelling agents are required to achieve better migration

Levelling agents function by

Lowering initial rate of dyeing (acting as retarding agent) Improve migration property of the dye
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 Glauber salt is mainly used as levelling agent

Pyridine can also be used as levelling agent which have the following

functions
Breaking down the dye aggregates and thus encouraging

molecular dispersion (solvent action) Being alkali it combines with the dye anion and retards ionisation via complex formation

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Types of levelling agents

Anionic levelling agent Cationic levelling agent Non ionic levelling agent

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 Anionic levelling agent

Have sulphonic acid group and combine with amino groups in

nylon; blocks the NH2 groups agent

But affinity of dye to nylon fibres is higher than levelling

With time and rise in temperature the dye replaces the

levelling agents completely

Therefore, though the initial rate of dyeing is slowed down,

but the exhaustion is not affected significantly

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 Cationic levelling agent

They have no affinity towards nylon fibres Forms a salt with the dye ions and does not allow it to react readily

with the ionic sites (end amino group)

Hence, the initial rate slows down As the temperature is raised the salts dissociates into ions The released dye anions are taken up by the fibre

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 Non anionic levelling agents

These agents have no affinity for the fibres Dye aggregates are broken down into single molecules Therefore the rate of dyeing is retarded and the migration

improves

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Method of Dyeing Nylon with Acid Dyes

For pH < 2 to 2.5, nylon has very high affinity towards acid dyes
But dyeing could not be carried out at this pH since degradation of nylon

is excessive
Acid dyes requiring strong acid are applied from a dye liquor containing 3 to

5% formic acid
Sulphuric acid is not used
It can cause degradation to nylon

Glauber salt is not used

It has no beneficial effect

Mainly non-ionic levelling agent is used

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 The material is entered cold and the dye bath is brought to the boil

The dyeing is continued at boil for 45 min to 60 min

This dye exhaust well in weaker acid and hence acetic acid could also be

used
The greater crystalline fibre structure of nylon compared with wool as

well as relatively lower no. of amino groups means darker shades are not obtained with acid dyes

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Fastness properties of acid dyes

The light fastness rating of acid dyes is 4 5
The electron arrangement in the chromophores of the acid

dye molecules is such that acid dye can resist the degrading effects of suns UV radiation for considerable time

The washing fastness is

2 3 for dyes with good levelling characteristics 3 -4 for dyes with average levelling characteristics 4 -5 for dyes with poor levelling characteristics
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 Note regarding wash fastness:

Acid dye molecules attach itself by ionic and hydrogen bonds

to nylon and wool fibre polymers. These bonds may be hydrolysed in water. Acid dye molecules which are held loosely or which are not penetrated the polymer sufficiently may be removed from the polymer system of wool and nylon during laundering.

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 Acid dyes are acidic in nature and so are resistant to acids. Being

acidic they will combine with alkalis such as those present in the detergents used for washing. The result is that the excess or loosely attached dye molecules combine with the alkaline detergent and are removed from the textile material

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Irregularities of Nylon Dyeing

Barr: It is the visual difference in colour depth, and

possibly of hue, along the length of dyed nylon filaments in a fabric caused by physical and chemical variations in the polymer. This gives a continuous pattern of colour stripes seen in the course direction in circular knits, as warp streaks in warp knits, or as weft or warp streaks in woven materials.

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Sources of Barr in Nylon

Chemical End Groups: Chemical irregularities in nylon filaments

are mainly from a non-uniform distribution of the polymer amino groups, which causes variations in the rate of dye up-take and particularly the equilibrium dye content of the filaments. Polyamide formation is reversible and the amino group content may change as additional polycondensation or hydrolysis occur when the nylon is at high temperatures during processes such as heat setting or texturing. The number and distribution of amino groups may also vary because of their oxidation during processing Orientation and Crystallinity of Polymer X-section & Surface Roughness of the Fibre Non-uniform Texturing Non-uniform Knitting Tension
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FABRIC
Barre line (Woven) Barre line (knitted)

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Questions???
Why are acid dyes called so? State any four of their properties How acid dyes are classified? Explain the mechanism of dyeing wool with acid dye What do you mean by molecularly split acid dye? Discuss the factors that affect the acid dyeing of protein fibres Explain the mechanism of an anionic levelling agent in the acid dyeing of nylon List the fastness properties of acid dyes. What is Barre ? How it can be removed?
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