Key Surfactants & their applications in Textile Processing

BY:

SANKET VALIA
RICHA KHARD
 Abstract
Surfactants form a unique class of chemical compounds. This review provides an
introduction to the nature and physical properties of surfactants, emphasizing their ability to
radically alter surface and interfacial properties and to self-associate and solubilize
themselves in micelles. These properties provide the means to apply surfactants in wet-ability
modification, detergency, and the displacement of liquid phases through porous media on one
hand, and to stabilize dispersions (including foams, froths and emulsions), or to destabilize
dispersions (again including foams and emulsions) on the other hand. These in turn lead to a
vast array of practical application in textile processing that includes desizing, scouring,
bleaching, mercerization dyeing and many more.

Introduction
The term surfactant is derived from the words surface active agent. Surfactants provide
remarkable benefits in many textile wet processes. A surface active chemical is one which
tends to accumulate at a surface or interface. Clearly, the chemical processes that take place
at the solid/liquid surface between textile fibers and water often determine the success or
failure of the process. Examples of important events in textile chemical processes that
involve interaction of surfaces include wetting, dispersing, emulsification, chemical or dye
adsorption on fibers, adhesion, vaporization, sublimation, melting, heat transfer, catalysis,
foaming and defoaming. Specific functions of surface active agents include scouring,
wetting, rewetting, softening, retarding dyeing rate, fixing dyes, making emulsions,
stabilizing dispersions, coagulating suspended solids, making foams, preventing foam
formation and defoaming liquids.
If the droplet of water is in contact with a solid such as a fabric, its shape will also be
affected by the surface tension at the solid/liquid interface.
Surface active agents interfere with the ability of the molecules of a substance to interact
with one another and, thereby, lower the surface tension of the substance. Surfactants used in
industrial applications usually cause a dramatic decrease in surface tension when used at low
concentration. Chemically, surfactants are amphipathic molecules. Therefore, a surfactant
molecule has both hydrophilic and hydrophobic characteristics.

The hydrophobic group in a surfactant for use in aqueous medium is usually a hydrocarbon
chain but may be a fluorocarbon or siloxane chain of appropriate length. The hydrophilic
group is polar and may be either ionic or nonionic.
Since surfactant molecules have both hydrophilic and hydrophobic parts, the most attractive
place for them in water is at the surface where the forces of both attraction and repulsion to
water can be satisfied. One other way that surfactants interact to satisfy natural forces of
attraction and repulsion between molecules is by formation of micelles. Surfactant
molecules aggregate in water forming micelles. Micelles consist of hydrophobic interior
regions, where hydrophobic tails interact with one another. The hydrophobic regions are
surrounded by the hydrophilic regions where the heads of the surfactant molecules
interact with water.

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Surfactants:
· It reduces the surface tension of a solvent.
· Due to surface tension, wetting of fibre surface does not take place thoroughly and quickly.
· Surfactant doesn’t removes the surface tension but reduces it.
· They are widely used in scouring.
· Chemically surfactants are long chain of organic compounds contain both hydrophobic and
hydrophilic component.
· The concentration at which no further reduction in surface tension occurs is known as
critical micelle concentration.
· The good surfactant should have hydrophobic and lyophilic balance (HBL).
Types (Classes) Of Surfactants
Surfactants fall in the following classifications according to the nature of the hydrophilic
group:
• Anionic: hydrophilic head is negatively charged;
• Cationic: hydrophilic head is positively charged;
• Nonionic: hydrophilic head is polar but not fully charged; and
•Amphoteric: molecule has both positive and negative groups; charge depends on
pH of the medium.
Anionic surfactants
They are the most widely used of the four classes. Important types of anionic surfactants are
Carboxylates, Sulfonates, Sulfates and Phosphates.
Carboxylates: Most carboxylate surfactants are soaps. Soaps are alkali metal salts of fatty
acids. Fatty acids are carboxylic acids derived from or contained in animal or vegetable fats
or oils. They contain linear hydrocarbon groups and may be either saturated of unsaturated.
Those with less than 10 carbons are soluble in water to have good surface activity. Those
with more than 20 carbons in a linear configuration are insoluble in water to use in aqueous
medium. Soaps are effective as cleaning agents in aqueous medium. Since soaps are
relatively weak acids, the free acid is liberated in acidic medium. The free acids are insoluble
in water. Therefore, soaps are only effective in alkaline medium. Soaps can be made by
neutralization of free fatty acids by alkali metals hydroxides by alkaline hydrolysis
(saponification) of fats and oils. Fatty acids are produced by alkaline hydrolysis
(saponification) of fats. The soap (fatty acid solid) thus formed is separate from the glycerol
byproduct by neutralization of the alkali or addition of salt to precipitate the soap.
Sulfonates: Since the sulfonate group is a strong acid, the sulfonate surfactants are soluble
and effective in acidic as well as in alkaline medium. The calcium and magnesium salts are
soluble in water, so sulfonate surfactants are not greatly affected by hard water.
Since the sulfonate surfactants are resistant to hydrolysis by both hot acid and alkali, they are
very useful for textile scouring formulations. Since sulfonation is relatively inexpensive,
sulfonate surfactants are found in high-volume products. Sulfonated lignin is a very good
dispersing agent for solids in water and finds textile applications mainly as a dispersing agent
in specialty chemicals and dyes. Lignin sulfonates are unsuitable for many applications
because of their dark color and because they do not produce much lowering of the surface
tension of water. Esters of sulfosuccinic acid, such as dioctyl (2-ethylhexyl) sulfosuccinate
(DOSS), are excellent fast-wetting surfactants. Sulfosuccinate ester surfactants are very
soluble in water. They do not emulsify oils so they are not good scouring agents. They are
soluble in organic solvents making them useful in dry cleaning.
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Sulfates: The sodium salt is most common although salts with diethanolamine,
triethanolamine or ammonia are used in cosmetics and shampoos. Sodium lauryl sulfate is an
excellent foaming agent. Foaming properties are enhanced when some unsulfated fatty
alcohol is retained in the product.
Phosphates: Phosphate esters of fatty alcohols are useful surfactants. Resistance of
phosphate surfactants to acid and hardness ions is poor. Because of these limitations and their
relatively high cost, phosphate surfactants are mainly specialty products. Since phosphate
surfactants are excellent emulsifiers under strongly alkaline conditions, they are effective for
scouring of oil and wax from textile materials
Cationic surfactants:
· They are unsuitable for use as detergent or wetting agents.
· The hydrophobic part of the molecule of the cationic surfactant is the organic ammonium or
pyridinium compound containing one or more hydrophobic residues as shown below.
· Cationic surfactants are mainly used as softeners, leveling agents, retardants in
dyeing, water repellent bacteria growth inhibitors and emulsifiers.
Non-ionic surfactants:
· They do not contain an ionisable group and have no electrical charge.
· They do not contain an insoluble group.
1. EO-PO ethers
2. EO-PO esters
3. Thioethers.
4. Sorbitan ethers.
· Non-ionic surfactants are free from precipitation and redeposition onto the fabric and can be
safely used.
· It also permits the caustic to act as a lime soap detergent.
Advantages: 1. Excellent compatibility.
2. Good wetters and rewetters.
3. God emulsifiers.
4. Excellent oil solubility.
Amphoteric surfactants:
· Amphoteric surfactants are may be of cationic, anionic or non-ionic depending upon the pH
of the aqueous solution.
· Amphoteric surfactants offer an excellent degree of lubrication, corrosion, inhibitor and
wetting action and provide a protective colloid for silk and wool.
· Major use is in scouring and dyeing of protecting chafting, crack and crow’s feet.
· They are comparatively expensive and some of them are not heat stable and hence cannot
be used at elevated temperature.
Surfactant as a wetting agent:
 Interfacial tension b/w textile fibre and the liquor are high hence wetting may be
affected.
 One of the functions of surfactant is to reduce surface tension.
 Water surface tension is 72 dynes/cm. It is possible to bring down the surface tension
of water from 72 dynes/cm to 28 dynes/cm.

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  A lone oxygen atom in the water contains a pair of electrons which is balanced
correspondingly large positive charge in the hydrogen atom.
 The structure of the water has a great dipole moment and also the molecule ‘stick’ to
another when water is in the liquid phase.
 It is a mixture of clusters of tetrahedral linked water molecules and a single molecule
occupying space b/w the cluster.
 The energy of the hydrogen bond is even greater than that of any other molecular
interaction.
 All these factors either alone or together make the wetting of textile difficult.
 When surfactant soap is dissolved in water the hydrocarbon chain (tail), tries to get
away from water medium due to its hydrophobicity to the surface.
 The hydrophilic grouping just dip in the water at the surface and sodium cation is in
the vicinity of negatively charged carboxyl heal.
 Thus structure of the water distorted and decreases the free energy of the system.
 In other means micelles with their hydrophobic grouping directed towards the interior
of the cluster and their hydrophilic group directed towards the solvent.
 Wetting agent also displaces the air from the microphores of the cotton by the water.
 Liquid spread as a continuous film instead of remaining as drops.
 If q is less than 90 degree, the oil will tend to spread over the fibres.
 If q is greater than 90° the oil will tend to form a globe which easily detached from
fibres.
 The surfactant reduces the values of cos q.

Surfactant as detergent:

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  The function of the detergent is to remove the dirt and dust particles and other
constituents.
 Detergent keeps the soil in dispersed or suspended form in scouring solution and
prevents redeposition on the fabric.
 When detergent is added, the soil hydrophobe either dissolves into the soil or orient
along the fabric surface.
 Micelle is due to unfavorable interactions.
 The polar "heads" of the micelle, due to favorable interactions with water, form a
hydrophilic outer layer that in effect protects the hydrophobic core of the micelle.
 The compounds that make up a micelle are typically amphiphilic in nature, meaning
that not only are micelles soluble in protic solvents such as water but also in aprotic
solvents as a reverse micelle.
 Because of the hydrophile, the edges tend to associate with water and thus the
removal of soil from the fabric starts.
 The oil disperses as droplets and the dirt is held in suspension with the droplets. The
suspended soil particles with its shealth of oriented soap molecules assume a net
negative charge similarly to the globe of soap.
 The electrostatic charge of repulsion b/w particles and the fibre play a major role in
redeposition.
 CMC (carbomethyl cellulose) and PVP (pyrolidon) can act as anti redepositing
agents.
 The most important consideration in scouring is the critical micelle concentration
CMC of the surfactant.
 The detergency is at maximum while surface tension and inter facial tension are at
their minimum.
 CMC concentration is that how much amount of detergent is required.

Surfactant as emulsifier:
· An emulsion is a mixture of two or more immiscible (unblendable) liquids.
· Emulsions are part of a more general class of two-phase systems of matter called colloids.
· The terms colloid and emulsion are sometimes used interchangeably, emulsion tends to
imply that both the dispersed and the continuous phase are liquid.
· In an emulsion, one liquid (the dispersed phase) is dispersed in the other (the continuous
phase).
· An emulsifier (also known as an emulgent) is a substance which stabilizes an emulsion by
increasing its kinetic stability.
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· In some cases, particles can stabilize emulsions as well through a mechanism called
Pickering stabilization.
Theory of surface activity and detergency:
· Surface activity generally related to the balance b/w hydrophobic and hydrophilic portions
of the molecule.
· If hydrophobic characteristic of the surfactant is increased, aqueous solubility decreases and
oil solubility increases.
· The balance b/w the hydrophobic and hydrophilic moieties of the surfactant is critical factor
in determining its major characteristics.
· This is referred as HBL value and is generally use in expressing the characteristics of a
surfactant and it is of particular value in describing the emulsion formation.
· For some general purpose the HBL can be used qualitatively (referring, for instance to low,
medium or high HBL).

Quantifying scale:
· Covers a range of values from zero to 20 hydrophobic and hydrophilic portions.
· The value of 10 approximately representing the point at which hydrophilic and hydrophobic
portions are in balance.
Examples:-
1. HBL 4-6
· Hydrophobic group presents.
· Suitable for water-in oil emulsions.
2. HBL 7-9
· Good wetting properties.
3. HBL 8-18
· Typical for surfactant to give oil-in water emulsion.
Surfactants Applications in Textile Processing
Some of most important applications of surfactants in textile processing are:
Wetting
When treating textiles by immersion in aqueous solutions it is essential to ensure that air be
displaced quickly and thoroughly from between the fibers or filaments so as to establish
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contact between the textile surfaces and the treatment bath. Success depends on a number of
factors:
1- Different fibers vary in wettability because of their different chemical structures. For
example, according to presence of polar groups in cotton fibers, they wet easily but polyester
filaments are wetted only with difficulty.
2- Geometric arrangements of fibers in yarn and fabric influence wettability of the material.
Wetting of compact fabrics is more difficult.
3- Presence if impurities (wax, soils, etc.) influence wettability of fabrics. For example, while
raw cotton contaminated with wax is very difficult to wet, scoured and bleached cotton is
wetted very easily.
Some commercially available wetting agents which are used in textile processing (Sizing,
Dyeing, Printing, etc.) include surfactants in their compositions:
1. Phosphoric Esters
2. Alkylaryl Ethoxylates
3. Diisooctyl Sulfosuccinates
4. Fatty Alcohol Ether Sulfate
5. Alkylaryl Polyglycol Ether Sulxzfate
Detergency
Scouring processes remove foreign materials from the fibers and are more difficult for
natural fibers such as cotton and wool than synthetic fibers. For example, impurities of cotton
(sizing agents, wax, pectines,) are up to 20% and for wool (wax, grease, dust, soil) are up to
50% of weight of fibers.
Surfactants constitute the most important group of detergent components, and they are
present in all types of detergents. Some commercially available detergents which are used in
textile processing include anionic and nonionic surfactants in their compositions
1. Carboxylic Acids and Salts
2. Sulfuric Acid Derivatives
3. Sulfonic Acids and Salts
4. Alkoxylated Alcohols
5. Alkanolamides
6. Ethoxylated Fatty Acids
Dispersing Agents
Insoluble dyes applied in the form of aqueous dispersions are used in a large number of
dyeing and printing processes. Dispersants are required to produce the dye preparation for
these processes and to stablize the finely dispersed state during application. Powdered
dispersion and vat dyes contain 50-80% of these products. To maintain the stability of the
dispersion throughout the dyeing or printing process, additional dispersant is added to the dye
bath. The dyes in print pastes must be in a completely dissolved or very finely divided form,
otherwise problems could arise during the printing processes, resulting in uneven prints.
Dispersing agents can cause insoluble dyes to become finely dispersed during the preparation
of the print paste, and stablize this state of dispersion.
Some of the most important surfactants used as dispersing agents are listed below:
1. Alkali Metal Derivatives of Unsaturated and Aromatic Hydrocarbons
2. Alkali Metal Alcoholates
3. Anhydrous Alkali Metal Soaps of Higher Fatty Acid
Antistatics
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The rapid growth of the synthetic fiber industry has greatly emphasized the importance of
antistatic finishes. Cotton and viscose rayon under normal humidity conditions do not
generate static electricity to any troublesome extent. Acetate rayon and wool generate static
electricity more readily, and necessitate precautionary measures in the mills where they are
fabricated. Different types of antistatic finishes are based on increasing of the electrical
conductivity of the fiber surface. Antistatic compounds are not only applied at the mill but
are also sold for use by laundries and dry cleaners and for home use, to be applied as a final
rinse after laundering. Antistatic compounds are also used for spray application to rugs,
carpets, upholstery, auto seat covers, etc. Similarly charged textiles repel each other and are
attracted by conductors nearby, by machine parts, or by the human body, in which the
opposite charge is produced by induction. The latter effect is well known to occur in
underwear made from man-made fibers and charges are induced in adjacent garments,
causing them to stick to the body. By walking over non-conducting floor covering, the body
potential can be raised and an electric shock may be felt when an earthed object is touched.
Small and harmless though these shocks are to human beings, they may cause difficulties in
the operation of electronic equipment. Cationic surfactants are quite widely used as antistatic
agents. Commercial antistatics are included surfactants with following structures:
1. Cationic or Neutral Nitrogenous Compounds
2. Polyhydroxy and Polyethenoxy Nonionic Compounds
3. Long Chain Phosphates, Phosphonates Derivatives
4. Sulfonated Oil and Sulfonated Ester Emulsions
Softeners
Softeners are of great importance in textile processing and, these days, almost every single
textile piece leaving a textile mill is treated with a softener. The aim of this treatment is to
achieve a soft handle to facilitate the processability and improve wearability. The chemical
nature of softeners can either be cationic, anionic or non-ionic. Most of the long-chain
quaternary ammonium salts, particularly those in which the straight 18 C chain is present,
have a marked softening action on cellulosic fabrics.
1. Cationic Surfactants
2. Anionic Surfactants
3. Nonionic Surfactants
Leveling Agents for Dyeing
Leveling agents promote uniform distribution of the dye in the textile in the exhaustion
dyeing process, so that the dyeing is level, with a uniform shade and depth of color. Leveling
agents act mainly by reducing the dyeing rate, increasing the rate of migration of the dye
within the textile, and improving the compatibility of dyes.
Example of using leveling agents “retarders” are in dyeing of polyacrylonitrile fibers with
cationic dyes. Cationic surfactants are recommended for this purpose. These cationic
surfactants compete with cationc dyes for anionic dye sites of fibers, so retard dye sorption.
The most important leveling agents (surfactants) for different fibers are listed below:
1- Leveling agents for dyeing cellulose fibers with vat and direct dyes
Ployglycol Ether
Phosphoric Esters
Alkyl aryl Sulfonate
2- Leveling agents for wool dyeing with acid dyes
Alkyl Amine Ployglycol ether sulfate
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Ethoxylated fatty acid amide derivative
Alkyl Amine Polyglycol ether
Fatty Amine Polyglycol ether
3- Leveling agents for dyeing Polyamide fibers
Fatty Amine Polyglycol Ether
Alkyl Amine Ethoxylate
Polyglycol Ether derivatives and sulfonate
4- Leveling agents for dyeing polyester fibers with disperse dyes
Modified Phosphoric Acid Esters
Alkyl Phenol and Fatty Acid Ployglycol Ethers
Carboxylic Acid Alkyl Esters
5- Leveling agents for dyeing polyacrylonitrile fibers with cationic dyes
Quaternary ammonium compound
Quaternary Fatty Acid Amine
Water-Repellents
The term water-repellents, as applied to fabrics, means that the fabric retains its air
permeability but resist the passage of liquid water. A large number of variations on the above
general principle depend on forming a water-soluble long-chain compound which can be
applied to the fabric from aqueous solution and which is heatlabile, so that on drying and
heating a water-insoluble, water-repellent finish is generated on fabric surface. The water
solubility of the long-chain compound may be due to a cationic or an anionic solubilizing
group or in some cases even to a nonionizing group.
Some of the most important surfactants which are used for making fabrics water-repellent:
1. Cationic Surfactants
2. Methylol Stear Amides , Methylene Distear Amide
3. Pyridinium Compounds

Summary
The Various unit operations of textile industry offer numerous opportunities for
advantageous use of surface active agents. As a consequence, a large number of such
products is used in textile processing than in any other industry. Beginning with the invention
of the sulfated oils about 1870, and continuing to the present decade, almost all new surface
active products have been developed with a view toward specific textile applications. During
the conversion of textile fibers into various forms of textiles, from scoured fibers or filaments
through to yarns or fabrics, some processes involve treatments in aqueous solutions. The use
of water as a medium for textile processing ideally requires that liquid wets the fiber surfaces
quickly and uniformly, and here surfactants play a useful role. In addition, surfactants may be
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required for detergency, achievement of level dyeing, and so on, and the choice of a
particular surfactant for a particular purpose depends on its ability to interact with fibers
and/or other components in the system. Textile finishing is any treatment applied to fabric
(after weaving process) to improve its properties such as desizing, scouring, beaching,
dyeing, printing, specific finishing (softening finishes, crease resistant finishes, water
repellent finishes). Active matters of most textiles finishing processes are surfactants. In most
instances, the fact that the finishing compound happens to be surface active has little to do
with its application or its utility as a finish. In order to make a fabric water-repellent or to
give it a soft handle, it is expedient to apply long-chain fatty or oily compounds to the fiber
surface. One of the practical methods for depositing and attaching fatty chain compounds on
a fiber surface is to introduce a solubilizing group into the fatty molecule. The resulting
compound is then water-dispersible and can be applied from an aqueous medium in
controlled concentrations. The introduction of certain solubilizing groups may even confer
substantivity, thus facilitating and strengthening the attachment of the finish to the fabric.

References:

1. “Surfactants in textile processing” Colourage Volume 56, Issue 2, February 2009,

Pages 39-46
2. Fainerman V. B., Mobius D., Miller R. (Ed.), "Surfactants : Chemistry, Interfacial
Properties, Applications", Elsevier Science B. V., 2001
3. Hummel D. O., "Handbook of Surfactant analysis", John Wiley & Sons, LTD, 2000
4. Datyner A., "Surfactant in Textile Processing", Marcel Dekker, Inc., 1983
5. Khosravi A., Gharanjic K., “Dyeing of Synthetic Fibers”, Jahad Publisher, 1374
(Persian)
6. Seyed Esfehani M.H.,”Textile Finishing”, Vol. 1, Tohid Publisher, 1377 (Persian)
7. Sohozade Abyane M. ,”Textile Printing”, safar Publisher, 1372 (Persian)
8. Sisley “Encyclopedia of Surface Active Agents”, Page:18

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