Sulphur Dyes 018-RIFAT

Dyeing: Dyeing means applying color-producing substances to materials such as fibers, yarns, or fabrics to give them a
lasting color. The color must remain during use, washing, and exposure to light.

Materials commonly dyed:

• Textile fibers (cotton, wool, silk, etc.)

• Plastic films
• Anodized aluminum
• Fur, wood, paper, leather
• Some foodstuffs

Process of Dyeing:

• The colorant (dye) is dissolved or dispersed in a liquid medium, usually water.

• The fiber or fabric is then brought into contact with this dye solution.
• Initially, the dye molecules attach to the surface of the fiber.
• True dyeing occurs when dye molecules penetrate into the inner part of the fiber and become fixed there.

The main goal of any dyeing process is deep and uniform penetration of color into the material.

Properties of Dyes:
Dyes are coloring substances that can dissolve in water (permanently or temporarily) and have the ability to attach to textile
fibers.

Properties:

• Soluble or made soluble in water during dyeing.

• Have chemical affinity to one or more fibers under specific conditions of temperature and pH.
• Must produce intense color.
• Must be absorbed and retained by fibers.
• Should have adequate fastness — meaning the color must resist washing, light, and other treatments during fabric
use.

Pigments:
Pigments are water-insoluble coloring substances. They are mainly used in paints, inks, and plastics rather than in dyeing.
However, pigments can be applied to textiles if mixed with a binder (adhesive substance) that helps them stick to the fiber
surface.

Difference between Dye and Pigment:

Dye Pigment
Soluble or made soluble in water Insoluble in water
Has chemical or physical affinity to fiber No natural affinity to fiber
Absorbed into the fiber Stays on fiber surface using a binder
Produces bright and intense colors Color intensity depends on binder and fabric
Generally has good fastness May wash off without a binder
Mainly used for textile dyeing Mainly used in paints, inks, plastics; textiles with binder
Colors fibers by absorption or chemical reaction Colors fibers by physical adhesion only
Penetrates inside the fiber Remains on the surface
Some dyes can be removed or fade Pigments are stable but not absorbed
Requires fiber compatibility Requires a binder to fix on fiber
Sulphur Dyes – Introduction

• Sulphur dyes are widely used for black and brown shades on cellulosic materials (cotton, viscose, etc.).
• Their chemistry is similar to vat dyes — both use oxidation to develop final color.
• Though reactive and azoic dyes can also give similar shades, sulphur dyes are cheaper and more suitable for dark
shades.
• These dyes contain disulphide (S–S) linkages in their molecular structure.
• The dyeing is done in an alkaline medium (usually with sodium sulphide).
• They are used in both dyeing and printing.

General Chemical Structure:

→ where “S–S” is the disulphide linkage connecting two chromophores (color-bearing parts).

Properties of Sulphur Dyes:

• Water-insoluble in their original form.

• Must be reduced (made soluble) before application.
• Oxidation after dyeing develops the final color.
• Work best in alkaline conditions.
• Addition of electrolytes (salts) helps better dye absorption.
• Have average fastness to washing and light.
• Mainly suitable for black and brown shades.
• Applied to cotton, viscose, and staple fibers.
• Dyeing temperature: 80–95°C.
• Low cost and widely available.

Reasons for Use on Cellulosic Materials:

1. High Affinity to Cellulose:

o When reduced to their soluble leuco form, sulphur dyes have strong attraction (substantivity) to cellulose
fibers.
o This allows the dye to penetrate and fix well inside the fiber structure.
2. Alkaline Dyeing Conditions:
o Cellulosic fibers are stable in alkaline conditions.
o Sulphur dyeing requires an alkaline medium (using Na₂S and Na₂CO₃), which does not damage cellulose.
3. Good Fastness on Cellulose:
o After oxidation, the dye becomes water-insoluble inside the fiber, giving good wash fastness and decent
light fastness on cotton and viscose.
4. Economic for Dark Shades:
o Sulphur dyes are cheap and especially effective for black, brown, and navy shades, which are in high
demand for cotton fabrics.
5. Compatibility with Cellulosic Fiber Structure:
o The porous and hydrophilic nature of cellulose helps the leuco dye solution to easily penetrate the fiber
before reoxidizing into its colored form.
Exhaustion in Dyeing:
During dyeing, dye molecules gradually move from the solution to the fiber. This process is called exhaustion.

As dyeing continues, dye concentration in the bath decreases while absorption increases.

Main Steps in Dyeing with Sulphur Dyes / Mechanism of Sulphur Dyeing:

The dyeing of sulphur dyes involves five main stages. Each step is important for developing proper color and fastness.

1. Reduction:
o The water-insoluble dye is converted into a water-soluble leuco form using a reducing agent (e.g., sodium
sulphide).
o This allows the dye to dissolve and penetrate the fiber.
2. Application:
o The soluble dye solution is applied to the fiber through exhaust or continuous dyeing methods.
o The fiber absorbs the dye molecules.
3. Rinsing:
o The dyed fabric is rinsed to remove loose or unfixed color before oxidation.
4. Oxidation:
o The absorbed leuco dye is oxidized back into its insoluble colored form, either by air exposure or using
chemical oxidizing agents.
5. Soaping:
o The dyed material is soaped in hot water with detergent to remove surface dye, increase brightness, and
improve color fastness.

Advantages:

• The color does not bleed during washing.

• The dyed fabric does not stain other garments.
• Low cost and easily available.
• Provides good wash fastness.
 • Suitable for dark shades, especially black and brown.
• Simple application process.
• Can be used for both dyeing and printing.

Disadvantages:

• May show poor rubbing fastness.

• Hypochlorite bleach can easily destroy the color.
• Bronziness of shade – fabric may show dull or shiny brown areas.
• White spots can appear if dyeing is uneven.
• Tendering (weakening) of cellulose during storage.
• Poor rubbing fastness – dye can rub off easily.
• Bleaching sensitivity – color destroyed by chlorine bleach.

Common Auxiliaries Used in Sulphur Dyeing:

Auxiliaries are chemicals added to improve dyeing performance and quality.

1. Reducing Agents:
o Convert the insoluble dye into a soluble (leuco) form so it can penetrate the fiber.
o Common types: Sodium sulphide (Na₂S), Sodium hydrosulphide (NaHS), Ammonium sulphide ((NH₄)₂S),
Sodium dithionite (Na₂S₂O₄), Glucose (C₆H₁₂O₆) – an eco-friendly alternative.
o Usually used in amounts 1–3 times the dye weight.
2. Alkali:
o Helps solubilize the sulphur dye and neutralizes acids formed during reduction.
o Common types: Caustic soda (NaOH), Sodium carbonate (Na₂CO₃), or a mixture of both.
3. Antioxidants:
o Prevent premature oxidation of the dye in the bath.
o Improve stability of dye liquor.
o Reduce problems like bronzing or uneven color.
o Common types: Sodium polysulphide, Sodium borohydride.
4. Sequestering Agents:
o Prevent unlevel dyeing and poor rubbing fastness caused by metal ions (like Ca²⁺, Mg²⁺) present in water or
fabric.
5. Wetting Agents:
o Improve fabric wettability and dye liquor penetration.
o Some non-ionic wetting agents can reduce dye uptake in exhaust dyeing, so they must be used carefully.
6. Neutral Electrolytes (Salts):
o Promote dye exhaustion (help the dye leave the solution and enter the fiber).
o Usually, 20–50% on weight of fabric (owf) salt is used.
o Too much salt can cause bronziness (shiny brown patches).
7. Oxidizing Agents:
o Convert the soluble leuco dye back into its final insoluble, colored form.
o Common examples: Oxygen (from air or water), Hydrogen peroxide (H₂O₂), Sodium dichromate
(Na₂Cr₂O₇) in acetic acid solution, Sodium bromate (NaBrO₃).

Oxidation:
Oxidation is a chemical process in which a substance loses electrons or gains oxygen (or both).
In sulphur dyeing, oxidation converts the soluble leuco form of the dye (colorless or light-colored) back into its insoluble
colored form inside the fiber.

Purpose of Oxidation:

• To develop the final color on the fabric.

• To make the dye insoluble and permanent inside the fiber.
 • To ensure good wash fastness of the dyed material.

After-Treatments:
After dyeing, some chemical treatments can improve the brightness and fastness of the color.

Common after-treatments include:

1. Hydrogen peroxide (H₂O₂) — for oxidation and brightness.

2. Copper sulfate (CuSO₄) + Acetic acid (CH₃COOH) — improves rubbing fastness.
3. CuSO₄ + CH₃COOH + Sodium dichromate (Na₂Cr₂O₇) — for stronger shades.
4. Sodium carbonate (Na₂CO₃) — helps neutralize acids and fix color.

Stripping of Sulphur Dyes:

Stripping means removing color from fabric when re-dyeing or correcting faults.

Process:

• Carried out at high temperature (90–95°C) using a reducing bath.

• Typical bath contains: 4.5–9 g/L sodium hydrosulphide, 2–3 g/L sequestering agent.
• This removes about 10–20% of the color.
• Adding polyvinyl pyrrolidone can remove an additional 10–20%.
• After stripping, it is best to re-dye from a fresh bath.

Environmental Issues:

• Sulphur dyes are highly polluting due to toxic sulfide reducing agents (like Na₂S).
• Effluents can cause odor, water pollution, and corrosion.
• Use of sulphur dyes is decreasing in Western countries.
• Still widely used in South Asian textile industries due to low cost.

Recent Improvements:

• Use of glucose as a mild, eco-friendly reducing agent.

• Development of low-sulfide and zero-sulfide dyeing processes.
• Electrochemical reduction methods are being researched to replace toxic chemicals.
 Azoic Colors

• Azoic colors are not ready-made dyes.

• They are formed inside the textile by a chemical reaction between two components:
1. Naphthols (colorless or lightly colored)
2. Diazo compounds (soluble diazotized bases)

Process

1. Naphtholation
o Naphthols are first applied to the textile.
o They have some affinity for cellulosic fibers.
2. Coupling
o The treated fabric is then reacted with a soluble diazotized base.
o This forms the intense azo color inside the fiber.

• The reaction occurs inside the fiber, making the dye permanent.
• The process ensures good fastness properties (wash, light, perspiration).
• Azoic colors are also called “Coupling Dyes” because the color forms by coupling reaction.

Properties of Azoic Colors

• Water insoluble dye – forms inside the fiber.
• Composed of two components:
1. Naphthol component
2. Diazo component
• Color formation requires coupling of these two components.
• Coupling is done in alkaline conditions.
• Mainly used for cellulosic fibers (cotton, viscose).
• Relatively inexpensive compared to other dyes.
• Dyeing process has two steps:
1. Naphthalization
2. Coupling
• Longer application time is required.
• Can produce very bright and vivid shades.
• Fastness properties: Good to excellent (wash, light, perspiration).

Azoic Color Application Steps

1. Naphtholation

• First step: Treat the textile with naphthol solution.

• Method: Padding is preferred because naphthols have low affinity for cellulosic fibers.
• Depth of dyeing is expressed as grams of naphthol per liter (like padding recipes).
2. Development / Coupling

• The naphtholated fabric is treated with a diazonium bath for 20–30 minutes.
• The final color develops during this step.
• The amount of diazotized base depends on:
o The quantity of naphthol applied
o The coupling ratio

After-Treatments in Azoic Dyeing

After-treatment is essential for achieving proper shade and fastness in azoic colors.

1. Removal of Mechanically Held Pigments

• During development, some pigment forms in the bath.

• Fabric may pick up loose pigments on its surface.
• After-treatment removes these pigments to prevent uneven color and staining.

2. Production of Normal Shade

• Some naphthol–diazo combinations change tone during soaping:

o Example: Naphthol AS-TR + Fast Orange GC → turns yellower
o Naphthol AS-TR + Fast Orange GR → develops bluer tone
• Standard soaping ensures the correct, intended shade.

3. Achieving Normal Fastness

• Soaping improves fastness to light and chlorine.

• Many naphthol–base combinations show better fastness after proper soaping.
• Soaping at the recommended temperature is therefore essential.

Advantages of Azoic Colors

• Strong shades in orange, red, dark blue, and black.
• Can produce certain bright blue full-depth shades not achievable by other dyes.
• Applicable to various textile forms (yarn, fabric, garments) and machines, even short batches.
• Excellent shade reproducibility.
• Good fastness properties (wash, light, chlorine).
• Low dyeing cost.

Disadvantages of Azoic Colors

• Application process is complicated and time-consuming.
• Requires many chemicals that must be stored.
• Poor rubbing fastness.
• Limited range of available hues, making shade matching difficult.
• Final shade appears only after coupling.
• Shade correction is difficult once developed.
 Reactive Dye
Reactive dyes are dyes that chemically react with the fiber to form a covalent bond. After dyeing, the dye
becomes a permanent part of the fiber.

• Reactive dyes contain a reactive group.

• This reactive group forms covalent bonds with:
o –OH groups of cellulose fibers (cotton, viscose).
o –NH₂ groups of protein fibers (wool, silk).
• Because the dye reacts with the fiber, it is called a reactive dye.

Properties of Reactive Dyes

• Highly water-soluble.
• The reactive group forms a covalent bond with the fiber, making the dye a permanent part of the fiber.
• Mainly used for cellulose fibers (cotton, viscose) and also for protein fibers (wool, silk, polyamide).
• Available in powder, liquid, and print paste forms.
• Can produce all types of shades, including bright and deep shades.
• Dyeing is done in an alkaline medium (around pH 11.5).
• Shows good wet fastness (wash and perspiration).
• Has good brightness and good rubbing fastness.
• Cost is relatively low compared to other dye classes.
• Dyeing process is simple and easy to control.
• 10–40% of the dye may hydrolyze during dyeing (becomes non-reactive).
• Very popular and widely used in Woven, Print, and Knit (WPI) industries in Bangladesh.

Reasons of being Popular

• Ability to produce bright shades of wide range.
• High leveling quality.
• Good washing fastness.
• Good light fastness.
• Simple dyeing method therefore one stage dyeing.
• Low temperature dyeing (below 1000C)
• Lower cost, i.e. cheaper.

Principles of Dyeing
1. Migration
o Dye molecules move from the dyebath (liquor) to the fiber surface.
o This process improves with higher temperature and auxiliaries (chemicals that help dyeing).
2. Diffusion
o Dye moves from the fiber surface into the inside of the fiber.
o Assisted by agitation (movement of fiber or bath) and heat.
3. Fixation
o Dye molecules become attached to the fiber by physical forces or chemical bonding.
o Strength of bonding can be weak or strong depending on dye type.
4. Role of Heat
 o Most dyeing processes need heat for dye migration, diffusion, and fixation.
o Heat is usually supplied by steam (direct or indirect).

Characteristics of Reactive Groups

• Reactive groups do not give color; color comes from the chromogen part.
• Halogen-containing groups (like chlorine) are more reactive than vinyl sulphone groups.
• More reactive groups → higher fixation/binding with fiber.
• Reactive dyes can show up to 90% exhaustion (absorption).
• Molecular weight of reactive groups: 69–211 g/mol.
• Higher molecular weight → higher reactivity.
• Chlorine gives medium reactivity and is cost-effective.
• Fluorine gives the lowest reactivity and lowest hydrolysis rate.
• Vinyl sulphone groups become more reactive when temperature and pH increase.
• Sulphone groups have high solubility, but they are less stable.
• Low molecular weight reactive dyes are usually hot brand dyes (need high temp).
• Low-affinity reactive dyes are used in pad dyeing methods.

Assistants Used for Dyeing with Reactive Dyes

1. Salt

• Neutralizes the negative charge on the fiber surface.

• Helps push the dye from the solution into the fiber, increasing dye absorption.

2. Alkali

• Maintains the required pH (alkaline condition) of the dye bath.

• Works as a fixing agent, helping the dye form covalent bonds with the fiber.

3. Urea

• Helps achieve the desired shade by improving dye solubility and penetration.

4. Soaping

• Removes unfixed dye from the fiber surface.

• Improves wash fastness and increases brightness and shade stability.
•

Chemistry of Dye and Cellulose

1. The –OH groups of cotton cellulose take part in the chemical reaction with the reactive group of the
dye.
2. Reactive dyes react more easily with cellulose –OH groups than with water.
 3.
o Activation energy for dye–water reaction: 16.4–26.2 kcal.
o Activation energy for dye–cellulose reaction: 9.2–15.8 kcal.
o Since dye–cellulose needs lower energy, it happens more easily and dominantly.

4. Higher activation energy = slower reaction.

5. Dye does react with water, but only to a small extent (causing hydrolysis).
6. The covalent bond between reactive dye and cellulose is stronger than:
▪ Hydrogen bonds
▪ Van der Waals forces
▪ Metal coordination bonds
7. Effect of Extreme pH
o Very acidic or very alkaline conditions cause hydrolysis, breaking the dye–fiber bond.
o This results in poor wash fastness.

Dyeing Mechanism of Reactive Dye

1. Exhaustion (Dye Absorption)

• Salt (electrolyte) helps the dye move from the dyebath to the fiber surface.
• The fiber absorbs the dye and the dye gets concentrated on the fiber.

2. Fixation

• In presence of alkali, the reactive group of the dye forms a covalent bond with the fiber’s –OH groups.
• Dye becomes a permanent part of the fiber.

3. Wash-off

• Removes all unfixed or hydrolyzed dye from the fiber surface.

• Improves wash fastness, brightness, and shade stability.
Application: Important Factors for Dyeing Cellulosic Fibers
1. Dyeing Temperature

• Higher temperature increases dye migration, diffusion, and reactivity.

• Different reactive dye brands (cold/medium/hot) require different temperatures.

2. Amount of Alkali

• Alkali creates the alkaline condition needed for fixation.

• Too little alkali = low fixation.
• Too much alkali = more hydrolysis (wastage of dye).

3. pH of the Dye Bath

• Reactive dyes need high pH (alkaline) for proper reaction with cellulose.
• pH affects both reactivity and dye stability.

4. Electrolyte (Salt) Concentration

• Salt helps overcome the negative charge of the fiber.

• Increases dye exhaustion (dye absorption into the fiber).

5. Time of Dyeing

• Sufficient time is needed for:

o Exhaustion
o Diffusion
o Fixation
• Longer time improves fixation but may increase hydrolysis.

6. Liquor Ratio

• Lower liquor ratio = higher dye concentration, better exhaustion.

• Higher liquor ratio = more water, slower dye uptake.

Dyeing Temperature
• Temperature affects both physical and chemical processes in dyeing.
• When temperature increases:
o Affinity ↓ (dye is less attracted to fiber)
o Hydrolysis ↑ (more dye wasted)
o Fixation ↓
o Diffusion ↑ (dye enters fiber faster)
• Below 20°C, no fixation occurs.
Dyeing Time Depends On
• Depth of shade (darker shade = more time)
• Reactivity of selected dye (low-reactive dyes need more time)

Electrolyte (Salt) Concentration Depends On

• Liquor amount (M:L ratio)
• Shade % (darker shade → more salt)

Factors Affecting pH
• Optimum pH varies depending on dye type.
• Dyeing time (longer time may need pH adjustment)
• Dyeing temperature (higher temp may change pH requirement)

Factors Affecting Amount of Alkali

• Depth of shade (darker = more alkali)
• Material-to-liquor ratio (M:L)

Factors Influencing Performance of Reactive Dyes

1. Dye-Related Factors

• Molecular Structure: Determines solubility, reactivity, shade, and dyeing behavior.

• Number of Reactive Groups: More groups → better fixation and wash fastness.
• Type of Reactive Groups: Highly reactive groups fix fast; less reactive groups give better leveling.
• Molecular Size: Large molecules → slower diffusion but better light fastness; small molecules → faster
penetration.
• Sulphonic Acid Groups: More groups → better solubility; too many can reduce fiber affinity.
• Ratio of Sulphonic Acid to Aromatic Carbons: Controls balance between solubility and fiber affinity.
• Hydrophobic-Hydrophilic Balance: Ensures dye dissolves well and absorbs into fiber efficiently.
• Impurities/Additives: Salts, moisture, and by-products can affect shade and dyeing consistency.

2. Fiber/Material-Related Factors

• Type of Fiber: Reactivity, absorbency, and crystallinity affect fixation and shade.
• Macro-Structure: Yarn, fabric, or garment form affects liquor penetration and uniformity.
• Micro-Structure: More amorphous regions → easier dye penetration; more crystalline → slower
diffusion.
• Material Preparation/Damage: Proper scouring, bleaching, and mercerization improve absorption and
levelness.
• Exposure to External Agents: Heat, chemicals, and microbes can damage fiber and reduce dye
performance.
Exhaustion of Reactive Dyes
The dyeing of cotton with reactive dyes generally occurs in two stages: Primary Exhaustion and Secondary
Exhaustion.

1. Primary Exhaustion
• Occurs at neutral conditions (before adding alkali).
• Glauber’s salt (Na₂SO₄) is added to promote dye absorption.
• Dye molecules move from the dyebath to the fiber surface.
• This stage depends on diffusion; dye can migrate freely.
• Fixation does not occur yet, so the dye is not chemically bonded.

Key Points:

• Dye absorption reaches equilibrium gradually.

• The initial rate of dyeing is fast and then decreases over time.
• Dyeing curve: starts at 0% exhaustion → increases → slows down as equilibrium is approached.

2. Secondary Exhaustion
• Occurs after adding alkali (e.g., soda ash).
• Alkali initiates fixation by reacting the dye’s reactive groups with cellulose –OH groups.
• No further migration of dye occurs; it reacts chemically with the fiber.
• Stirring/circulation may be required to balance fixation rate and prevent uneven dyeing.

Key Points:

• Dye molecules are now chemically bonded to the fiber.

• Exhaustion % may increase slightly during this stage.
• Dyeing curve shows dye fixation over time.

Mixing of Reactive Dyes

1. Different Reactive Groups:

• Don’t mix dyes with different reactive groups (e.g., VS, MCT).
• Each group needs different temperature, pH, and time.
• Mixing can cause uneven color and poor results.

2. Levelling Conditions:

• Levelling means slowing down the dye reaction.

• It allows the dye to spread evenly on the fiber before it fixes.
Continuous Method –

Continuous Dyeing of Cellulosic Fabrics (Reactive Dye) – Pad-Dry-Thermofix Process

1. A-frame – Fabric is unwound and fed into the line.

2. Scray (J-box) – Temporary storage/buffer for smooth operation.
3. Pad – Fabric is impregnated with dye liquor using nip rolls.
4. Infrared Pre-Dry – Removes surface moisture to prevent dye migration.
5. Hot Flue Treatment – Main drying chamber for near-complete dryness.
6. Batching Option – Allows controlled accumulation of fabric if needed.
7. Wash – Removes unfixed dye, alkali, and other chemicals.
8. Dry – Final drying of fabric before batching or finishing.

Stripping of Reactive Dyes

Stripping is done to correct uneven dyeing by removing dye from the fabric.

1. Partial Stripping
• Removes some dye to adjust the shade.
• Chemicals used:
o Acetic acid: 5–10 parts + water 1000 parts
o Or Formic acid: 2.5–10 parts + water 1000 parts
• Temperature: 70–100°C
• Time: Until the desired shade is achieved

2. Full Stripping
 • Removes all dye from the fabric.
• Chemicals used:
o Sodium hypochlorite (NaOCl): 1% at room temperature
o Sodium hydrosulphite (Na₂S₂O₄): 1% at boiling temperature
• Time: 30 minutes

Hydrolysis of Reactive Dyes

Hydrolysis occurs when a reactive dye reacts with water instead of fiber, making it unfixable.

1. Halogen-Containing Reactive Dye

Reaction:
D–R–Cl + H₂O → D–R–OH + HCl
• The chlorine group reacts with water instead of cellulose.

• Produces hydrolyzed dye which cannot fix to fiber.

2. Activated Vinyl Sulphone Dye

Reaction:
D–F–CH₂–CH₂–OSO₃H + H₂O → D–F–CH₂–CH₂–OH + H₂SO₄
• The vinyl sulphone group reacts with water.

• Produces hydrolyzed dye that cannot bond with fiber.

Key Point:
• Hydrolysis reduces fixation, shade strength, and wash fastness.

• Control factors: temperature, pH, and dyeing time.

Prevention of Hydrolysis
1. Control Temperature
o Hydrolysis increases with temperature.
o During dye dissolution and application, temperature should not exceed 40°C.
2. Separate Preparation
o Prepare dye solution and alkali solution separately.
o Mix them just before use to minimize hydrolysis.
3. Avoid Prolonged Storage
o Do not keep the mixed dye–alkali solution for a long time.
o Long storage leads to more hydrolysis and reduced fixation.
Classification of Reactive Dyes
Reactive dyes can be classified based on three controlling parameters:

1. Alkali-Controllable Reactive Dyes

o Optimal fixation temperature: 40–60°C
o Exhaustion in neutral salt solution: Low before alkali addition
o Reactivity: High during alkali addition → requires careful control for level dyeing
o Alkali dosing: Must be controlled
o Example: Vinyl Sulphone (VS) reactive dyes

2. Salt-Controllable Reactive Dyes

o Optimal fixation temperature: Around 80°C
o Exhaustion at neutral: Relatively high → need careful salt addition for level dyeing
o Recommended practice: Portion-wise addition of salt at controlled rate

3. Temperature-Controllable Reactive Dyes

o React with cellulose at temperatures above boiling (>100°C)
o Self-levelling by nature
o Rate of temperature rise controls fixation
o Example: Kayacelon React dyes

Other Special Types

1. High-Fixation Reactive Dyes
o Normal fixation: ≤70%
o Some are acid-fixable, which improves fixation
o Dyes with more than one reactive system are possible
o Technologically challenging due to substantivity and diffusibility issues
2. Acid-Fixable Reactive Dyes
o React only under catalyst + dry heat
o Example: Calcobond dyes (American Cyanamid)
o Procion T dyes are another example
3. Neutral-Fixation Reactive Dyes
o React at high temperature (>130°C)
o Suitable for single-bath dyeing with disperse dyes
o High temperature helps with diffusion of large dye molecules
o Slightly higher reactivity than VS type

Dyeing Faults in Reactive Dyeing

1. Uneven Dyeing – Color is not uniform across the fabric.
2. Batch-to-Batch Shade Variation – Different batches have slightly different shades.
 3. Patchy Dyeing – Irregular spots or patches of color.
4. Roll-to-Roll / Meter-to-Meter Variation – Shade differences between rolls or lengths of fabric.
5. Crease Marks – Lines formed due to folds during dyeing.
6. Dye Spots – Localized spots of excess dye.
7. Wrinkle Marks – Uneven color due to wrinkles in fabric.
8. Softener Marks – Stains or streaks caused by uneven softener application.

Advantages of Reactive Dyes

• Full color range – can produce all shades.
• Brilliant, bright colors with high wash fastness.
• Varying reactivities – suitable for different temperatures, including cold dyeing.
• Versatile application methods – batch, semi-continuous, continuous.
• Covalent fixation – dye becomes a permanent part of fiber.
• Relatively inexpensive to apply (though the dyes themselves can be costly).
• Incomplete hydrolysis is minimized with proper control.

Disadvantages of Reactive Dyes

• Wash-off required to remove unfixed dye (for high wash fastness).
• High salt requirement – can affect the environment and watercourses.
• High pH needed for fixation – may require careful handling.
• Some dyes contain AOX compounds – potentially harmful to the environment.

Importance of Washing Fastness (WF)

Major Issues

• Loss of color / fading during laundry.

• Staining of other fabrics due to dye transfer.
• Fabrics are exposed to mechanical action, water, detergents, and heat, which can "beat" dye out of the
fiber.

Fate of Dye in Wash Water

1. Re-adsorbs onto the original fiber → minimal problem.

2. Adsorbs onto other fabrics → causes staining.
3. Remains in water → wasted dye, environmental concern.
Degree of Staining Depends On

• Affinity of dye for original fiber

• Affinity for adjacent fibers
• Affinity for water (staying dissolved in solution)