Studies on Wetting Agents

Scope of Work
Wetting Agents are an integral part of most processes in the Textile Industry. Their application extends right from the fabric preparatory stage to the finishing stage. Hence an understanding of the types of wetting agents and their use in specific application is of invaluable importance.

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Studies on Wetting Agents

SURFACTANTS1,2,3,4
The word Surfactant is coined from the expression "surface active agent". As the phrase implies, a surfactant molecule possesses surface activity, a property associated with the chemical structure of the molecule. The characteristic feature of a surfactant molecule is its two ends attached by a covalent bond. The two ends have diametrically opposed polarities. The non-polar end is lyophilic (strongly attracted to organic molecules) while the strongly polar end is lyophobic (having little attraction for organic molecules) yet strongly hydrophilic (water loving). Duality of polarity causes the molecule to align itself with respect to the polar nature of the surfaces it contacts.

These two structures in the same molecule form a special amphiphilic molecular structure. It possesses special surface activity and is known as a surfactant. A surfactant used in a penetrant testing agent can increase wetting, penetration into a discontinuity and the solubilizing or emulsification for washing functions.

Surfactants have an amphiphilic molecular structure. Hydrophilic groups may be cationic (organic amines — especially with three hydrocarbon chains attached to the nitrogen atom), anionic (fatty acids or sulfates with hydrocarbon chains) or nonionic (organic compounds with oxygen containing groups such as alcohols, esters and ethers). Hydrophobic or lipophilic (oleophilic) groups may be large, straight or branched chain hydrocarbons, cyclic hydrocarbons, aromatic hydrocarbons and/or combinations of them.

Such a molecular structure poses a double property: one part can dissolve in water and the other can dissolve in oil like materials and tries to escape from water. When put into water, the hydrophilic groups dissolve in the water and the oleophilic groups close and associate together to form a hydrol or micelle structure holding some oil (micelles may be microscopic and submicroscopic spherical globules of one liquid in another; some may also be colloids). These micelles look like a tiny ball with the oil loving ends turned inside the ball and the water loving ends covering the outside. An oleophilic micelle particle can increase the retention of water in organic compounds.

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Studies on Wetting Agents These compounds can also reduce the surface tension of the liquids into which they are placed. Materials that reduce the surface tension of liquids are known as surfactants. These compounds may improve the wetting ability or the water washability of penetrants when added to them.

Physical Chemistry of Surfactant Solutions:

When a surfactant is put into an oil/water interface, it can reduce interface tension and form an emulsifying colloid or a single liquid phase, rather than two liquid phases. When surfactants' hydrophilic property is stronger, they can form water occluded oil colloids. When the oleophilic property is stronger, they can form oil occluded water colloids.

When soap (sodium oleate) molecules are added to pure water one molecule at a time, the first few molecules align at the air/water interface and the hydrocarbon tails orient toward air. The driving force for this alignment is the non-polar tails seeking to associate themselves with the most non-polar interface it can find, in this case air. As additional molecules are added, they too will align at the water/air interface until all of the surface area is completely packed. As more molecules are added, they are forced into the bulk of the water, floating about as individual molecules until a saturation level is reached. At this point, called the Critical Micelle Concentration, soap molecules agglomerate into water soluble clumps (Micelles), where the lyophobic tails are associated with themselves and the hydrophilic heads are surrounded by water molecules. These sequences of events are diagrammed as below. The first beaker represents close packing of surfactant molecules at the surface. The second beaker represents the condition before micelle formation. The third beaker shows the formation of micelles.

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Studies on Wetting Agents Orientation of Surfactant Molecules in Water

Critical Micelle Concentration A plot of soap concentration verses water's surface tension is shown in the figure below. It takes very little surfactant to quickly lower the surface tension. At some low concentration, the plot levels off and maintains the low surface tension valueregardless of how much more soap is added. The concentration where the curve levels off is called the critical micelle concentration (CMC). The literal meaning of CMC is the minimum concentration of soap required to form micelles. Increasing the soap concentration beyond this point simply increases the number of micelles in the solution.

Plot of Surface Tension verses Concentration

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Studies on Wetting Agents Spreading of Water on Smooth surfaces

Absorbability and Wetting – Out5,6 Absorbability and Wetting-out both refer to the entrance of liquid into a yarn or fabric. Absorbability is the ability of the fabric to take up a liquid. Wetting – out is a technical term meaning the ability of a liquid to enter a fabric and displace the air from the capillary spaces. Both terms refer to the same phenomenon but absorbability refers to the fabric and wetting-out to the liquid. Two factors are important in absorbency: the total amount of liquid absorbed and the rate of absorption of the liquid. Sometime one factor is measured and sometimes the other.

Absorbability is also related to the warmth of a fabric if a fabric is permeable to air but does not absorb water, evaporation of perspiration takes place from the skin and skin temperature falls. This is the phenomenon which occurs when nylon fabrics are worn. If the fabric absorbs the perspiration, however, the evaporation takes place from the fabric and not from the skin; therefore, chilling does not occur.

The methods used in testing fabrics for absorbency and testing wetting- out agents (or penetrants) are: 1. Surface tension: This does not take capillary action into account and so is not always comparable with practical results. 2. Sinking time of a tuft of fiber or yarn or a patch of cloth.

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Studies on Wetting Agents 3. Drave’s method. This is a standard method of the A.A.T.C.C. 4. Capillary travel method. The rate of absorption is measured in this method.   Wick –up or modified Weireck method Haven’s method

5. Absorption from a wet solid surface such as a wet brick or tile. The total absorption is measured in this method. 6. Absorption on immersion in a liquid. The total absorption is measured in this method. 7. Absorption on sparing with water. This is a standard method of the A.S.T.M. The rate and amount of absorption are measured in this method. Drave’s Method5,6: Drave’s method which is a standard method of the A.A.T.C.C, is an elaboration and improvement on the method above. It measures the time required for a standard skein to sink in a solution of wetting agent when the skein, carrying a standard weight, is held below the surface of the wetting solution by an anchor. The sinker consists of No.IO copper wire, 2½ inches in length, bent into the form of a hook. The weight of the sinker should be 3.00 grams. It is also desirable to use hooks of 1.50 grams and 6.00 grams in order to obtain a complete description of the wetting properties.

The sinker is fastened by a fine, strong thread at a distance of 1 inch from an anchor which should weigh at least 40 grams. A five-gram skein of gray, two-ply cotton yarn is folded once to form a loop, the sinker and anchor are attached, and the opposite end of the skein is cut through with shears. The wetting solution in a graduated cylinder with a capacity of 500 cubic centimeters is brought to 25º C, 50º C, or 90º C according to the conditions under which it is to be used, and the skein is dropped in.

The time elapsing between the entrance of the skein and the moment when the weighted skein starts to sink (when the tread between the sinker and anchor slackens) is measured with a stop watch. Wetting agents are tested in concentrations of 1, 2, 5, 7, 10, 20 grams per liter and the results plotted.

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Studies on Wetting Agents If this method is to be used for testing yarns or fabrics for wetting –out, a 1½ gram sinker or even a ½ gram sinker may be used, since the three-gram sinker may be too heavy for samples which wet-out readily. CLASSIFICATION OF SURFACTANTS1,4 Surfactants are classified according to use, to ionic charge and to chemical structure. A. By Use  Wetting Agents: The ability of a liquid to spread on a smooth solid surface is dependent on the polar nature of the solid and the surface tension of the liquid. More about the thermodynamic relationships will be brought up in the chapter on water and oil repellents. A non-polar solid surface such as paraffin wax or Teflon will cause a drop of pure water to bead-up and not spread. Water containing surfactants on the other hand will easily spread on paraffin surfaces and have lower contact angles on Teflon. Surfactants used this way are called wetting agents, or penetrating agents when used to wet out repellent fabrics. Penetration of fabrics is a function of surface wetting, however fabric assemblies have a volume of air entrapped in the void formed spaces. Before a liquid can move in, the air must move out. Penetrants facilitate this process.  Detergents are surfactants that help remove soils from solid surfaces. Over and above reducing water's surface tension, detergents must adsorb onto the soil's surface to aid in spontaneous release. Detergents must also keep the soil suspended to prevent redeposition.  Emulsifying Agents are surfactants that convert water-insoluble oils into stable, aqueous suspensions. The lyophilic part of the surfactant molecule is absorbed by the oil droplet and the lyophobic head is oriented outward, surrounding the droplet with a hydrophilic sheath. Ionic surfactants add another dimension to the stability of emulsions, they set up a charge-charge repulsion field which adds to keeping the droplets separated.  Dispersing Agents function in a manner similar to emulsifying agents. The difference is that solid particulate matter, rather than insoluble oils, is dispersed.

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Studies on Wetting Agents The nature of the lyophilic part of the surfactant molecule must be such that it adsorbs onto the particle's surface. Surfactant molecules must be matched with their intended use.

B. By Ionic Charge     Anionic: Those that develop a negative charge on the water solubilizing end. Cationic: Those that develop a positive charge on the water solubilizing end. Non-Ionic: Those that develop no ionic charge on the water solubilizing end. Amphoteric: Those that have both a positive and negative charged group on the molecule.

SURFACE ACTIVE AGENTS

IONIC

NONIONIC

ANIONIC

CATIONIC AMPHOTERIC

Anionic Surfactants: When a surfactant like sodium stearate is dissolved in water, it ionizes into sodium cations and stearate anions: CH3- (CH)2-COONa CH3-(CH2)16-COO- + Na+

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Studies on Wetting Agents The sodium cation is comparatively very small and the stearate anion is dominating ion in the solution, because of its larger size. Therefore, this surfactant is called as anionic surfactant. Some of the important chemical types are given in the following: 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. Sulphated vegetable oils Sulphated fatty acid esters Sulphated esters of low molecular weight aliphatic acids Fatty acid esters of sulphonated alcohols Sulphonated substituted fatty acid amides: Alkyl aryl sulphonates Aliphatic alcohol sulphates Secondary alcohol sulphates Sulphated alkyl phenol-ethylene oxide condensates Phosphate esters

Cationic surfactant: In contrast to the anionic surfactants we have the cationic surfactants. For example when pyridine is reacted with concentrated hydrochloric acid, it forms pyridinium chloride, which also ionizes in water. If the hydrogen attached to the pyridinium cation is replaced by a C16 hydrocarbon chain, the resulting cetyl pyridinium chloride attains balanced water solubility and water insolubility and hence becomes surface active compound thus reducing the surface tension of water. In water it ionizes into a larger cation and a smaller anion:

C15H30-CH3 (C5H5N ) Cl+

C15H30-CH3 H2O (C5H5N )
+

+ Cl-

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Studies on Wetting Agents Since the cation is dominant ion the compound is called a cationic surface active agent or a cationic surfactant. Cationics have a strong affinity for dyes and therefore they are used as a stripping agent or dye fixing agent. They also have a strong affinity for cellulosic fibre and can be used as fabric softeners or water repellents. surfactants are given below: 1. Fatty acid amides and their derivatives 2. Quaternary ammonium salts 3. Fatty amine salts 4. Pyridinium and substituted pyridinium salts 5. Cyclic (imidazolinium) derivatives 6. Alkylol amide salts 7. Dicyandiamide-formaldehyde Important cationic

AMPHOTERIC SURFACTANTS These are the surfactants when dissolved in water ionizes and produce large segments carrying both ionic and anionic charges. For example aminocarboxylic acids ionize in water to give zwitterions. H3N+(CH2)n-COO-

H2N-(CH2)n-COOH

The amphoteric surfactants have an outstanding feature that they can behave as a anionic as well as cationic surfactant. They have an affinity to wool and cellulose. In alkaline solution they behave as anionics, whereas in acidic medium they behave as cationics. At pH 7 they behave as non ionic surfactant.

NONIONIC SURFACTANT These are other kind of surfactants which are soluble in water and also reduce the surface tension of water. However they do not ionize in water. Hence they are called nonionic surfactant. For example reaction between stearic acid and ethylene oxide gives polyester: CH3-(CH2)16-COOH + 6 CH2 O CH2 CH3-(CH2)16-COO-(CH2-CH2-O)6H

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Studies on Wetting Agents The oxygen atom of the oxyethylene unit is sufficiently hydrophilic and such six atoms provide the required degree of hydrophilicity to balance the hydrophobicity of the stearyl tail of the compound. With the balanced water solubility and water insolubility, the resulting compound acquires surface activity, even though it does not ionize in water. Many nonionic surfactants are based on the reaction of ethylene oxide with certain hydrophobes. The word hydrophobe is used to define a water insoluble, lyophilic molecule which will be converted into a surfactant by appropriate reactions. Some important examples are given below 1. 2. 3. 4. 5. Alkyl phenol condensates Fatty alcohol condensates Fatty acid condensates Fatty amine condensates Fatty amide condensates

Water Solubility of Ethoxylated Nonylphenol Water solubility of ethoxylated compounds is a function of hydrogen-bond formation between water molecules with ether oxygens. The greater the number of ether groups, the greater the number of hydrogen-bonding sites for solubilizing the compound. The relationship between water solubility is shown in the figure. As the number of moles of ethylene oxide increases for a given hydrophobe, the solubility of the compound increases. Solubility as a Function of Ethylene Oxide Content

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Studies on Wetting Agents 4. Hydrophilic-Lypohilic Balance (HLB) For a molecule to function as a surfactant, it must have the proper balance of water and oil solubility. The molecule must not be too water soluble otherwise it will not form micelles, yet at the same time it must be sufficiently soluble to do its job. The solubility of a surfactant molecule in water verses oil depends on the water solubilizing group.

The surfactant molecular hydrophilic or oleophilic strength may be expressed as the hydrophile lipophile balance (HLB) value. When the HLB is less than 10, the oleophilic property is stronger. When the HLB is greater than 10, the hydrophilic property is stronger. An HLB of 3 to 6 can form a water/oil colloid. An HLB of 8 to 18 can form an oil/water colloid. An HLB of 13 to 15 increases the washability function and an HLB of 15 to 18 possesses a solubilizing function for a penetrant.

When the hydrophilic group is in the middle of the surfactant molecular configuration, the wetting function is better than when it is at the end. When the hydrophilic group is at the end of the surfactant molecular configuration, the washing activity is better than when it is in the middle.

A comparison of some other surfactant properties is useful. If the surfactant structure remains chemically similar and has the same molecular size, the wetting and penetrant function of the surfactant is better with branched than nonbranched oleophilic group configurations. As the surfactant molecular size becomes smaller, the wetting and penetrant function is better. As the oleophilic group's branched configuration becomes larger, the washing and dispersion function of the surfactant is better.

SELECTING A SURFACTANT: Choosing the correct surfactant to have a particular effect is not difficult. The properties required for a particular application can be formulated into a product using the following as a guide:

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Studies on Wetting Agents  Ethylene-Oxide Content The function a surfactant performs is related to the hydrophilic portion of the molecule. The greater the ethylene oxide content, the more water loving is the surfactant. Generally, the number following the surfactant's name is an indication of the ethylene oxide content. 

Moles of EO Function 1-3 4-6 7 - 12 > 12 Emulsify small amounts of water in oil as the major portion. Emulsify small amounts of oil in water as the major portion. Cleaning action, dirt removal. Special properties such as solubilizing and suspending.

In some formulations it is desirable to include more than one surfactant, for instance in laundry applications where dirt and oil have to be removed. A surfactant with 1 - 3 moles E.O will remove oils in fabrics, while a surfactant with 7 - 12 moles E.O will aid in the removal of dirt and particulate matter. 

HLB To Function The Hydrophilic/Lipophilic balance is a more precise measure of a surfactant's function.

HLB VALUE FUNCTION 3-6 7-9 8 - 15 12 - 15 15-18 Water in oil emulsifier Wetting Agent Oil in water emulsifier Detergency Solubilizer, hydrotrope

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Studies on Wetting Agents  Cloud-Point Surfactants must remain in solution to perform their role. Unlike salts which dissolve more readily in hot water, nonionic surfactant solubility has a temperature limit called the cloud point. This is the temperature at which a surfactant drops out of solution causing the solution to become turbid. Surfactant activity and surfactant performance are usually greatest just below the cloud point. Hence if you are formulating say a textile scouring agent to be used in hot water at about 75 degrees C. then a surfactant with a cloud point of something around 70-73 Degrees would be suitable. An important exception to this rule is in the area of defoaming.

Cloud point is influenced by the structure of the hydrophobe and the degree of ethoxylation. Temperature too has an influence on hydrogen bonds, as the temperature increases, H-bonds rupture. At some elevated temperature, enough of them will have broken to cause a cloud of insolubility to form. Eventually the surfactant will separate into an insoluble layer floating on water. Cloud point of a given hydrophobe is influenced by the number of ether units available to hydrogenbond with water. In the figure cloud point is plotted against temperature

Cloud Point versus Moles of Ethylene Oxide

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Studies on Wetting Agents  Foam-requirements In some applications foam is undesirable. At temperatures above a surfactants Cloud Point the minute droplets of precipitated surfactant can act as a "bubble breaker". Hence in textile dying and auto dishwashing applications where foaming is undesirable a surfactant which is soluble in cold water but precipitates out in hot water has interesting effects. Chlorine and Propylene Oxide capped nonionic surfactants find application in this area.

Table of Desirable Properties vs Ionic Nature

Desired Property Foam Detergency Mildness

Anionic

Non-ionic

Cationic

Amphoteric

Best Better Variable

Good Good Good

Poor Fair Poor

Better Good Best

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Studies on Wetting Agents

References
1. Tomasino Charles, Chemistry and Technology of fabric, Preparation and Finishing, NCSU 2. http://pharmcal.tripod.com/quicklnk.htm 3. http://periodicals.wanfangdata.com.cn/qikan/periodical/jxsyhg/jxsy2001/0102/01 02mle.htm 4. Shenai V.A, Technology of Textile Processing, VOL 5, Sevak Publications, Mumbai, 2002 5. Skinkle J.H, Textile Testing, Chem. Publication Co., NY 6. Jay C Harns, Detergency Evaluation ant Testing, Interscience Publishers, Inc., NY, 1954 7. Paul R., Naik S. R., Textile Dyer and Printer, 30(5),16,1997 8. Paul R., Naik S. R., Textile Dyer and Printer, 30(5), 13,1997 9. Shelke Vinod, Colourage, 48 (1), 25, 2001 10. Schmitt B., Prasad A. K., Colourage, 45 (10), 20,1998 11. Kochavi D, Vidibaek T, Cedroni D, American Dyestuff reporter, (9), 24, 1990 12. Micheal Tyndall R., American Dyestuff Reporter, (5) ,22,1990 13. www.rossari.com 14. http://science.ntu.ac.uk/research/EnzyTex/TitleCo2.html#Contents 15. http://www.touchofcotton.com/fabricsmart 16. Paul R., Naik S. R., Textile Dyer and Printer, 30(10), 17,1997

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