Surfactants in paint

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Paint has four major components: pigments, binders, solvents, and additives. Pigments serve to give paint its color, texture, toughness, as well as determining if a paint is opaque or not. Common white pigments include titanium dioxide and zinc oxide. Binders are the film forming component of a paint as it dries and affects the durability, gloss, and flexibility of the coating. Polyurethanes, polyesters, and acrylics are all examples of common binders. The solvent is the medium in which all other components of the paint are dissolved and evaporates away as the paint dries and cures. The solvent also modifies the curing rate and viscosity of the paint in its liquid state. There are two types of paint: solvent-borne and water-borne paints. Solvent-borne paints use organic solvents as the primary vehicle carrying the solid components in a paint formulation, whereas water-borne paints use water as the continuous medium. The additives that are incorporated into paints are a wide range of things which impart important effects on the properties of the paint and the final coating. Common paint additives are catalysts, thickeners, stabilizers, emulsifiers, texturizers, biocides to fight bacterial growth, etc.

Contents

The word surfactant is short for surface active agent. [1] Surfactants are compounds that lower the surface tension of a liquid, the interfacial tension between two liquids, or the interfacial tension between a liquid and a solid. In solutions this behavior is known as wetting, and it occurs as a result of surfactants adsorbing to the air/water interface. [2] Soluble surfactants are also capable of forming micelles and other aggregate structures in solution, leading to a stabilizing effect in latex paints. Surfactants in paint are used to change many end properties of a dried paint, as well as to emulsify paints in their liquid state.

Role of surfactants in paint

 % TiO2 by volumeModulus of Elasticity (MPa)Modulus of Elasticity: Surfactant Removed (MPa)
08.96.0
1322.922.4
2560.289.1
38169.8416.8
Elasticity of a latex paint is affected by presence of surfactant. [3] Note the effect changes dependent on TiO2
concentration.

Positive Effects

Surfactants affect a wide array of physical properties in paints. Surfactants affect the behavior of a paint not only during the lifetime of the formed coating but also the initial aggregation and film formation of the paint. Surfactants are also used to stabilize the dispersion of polymer particles during emulsion polymerization in paints and other applications. The mechanical stability, freeze-thaw stability and shelf-life of paints are all improved by the addition of surfactants. The addition of surfactants to paint also allow the paint to coat a surface more easily because surfactants increase the wetting of a solution. [4]

Negative Effects

The addition of surfactants does not always have a positive effect on all properties. The water resistance of the coating can be decreased with surfactant addition since surfactants can be very water-soluble and will easily wash out of a coating. [3] This problem of moisture resistance is particularly prevalent problem for art conservation, as well as problems with adhesion, loss of optical clarity, and dirt pickup caused by polyether surfactants in contemporary acrylic emulsion used in artworks bearing acrylic coats. [5] While the type and amount of surfactant determine what properties will be affected, other chemicals in a paint can alter the overall effect the surfactants may have on the paint. [6] Elasticity has been found to either increase or decrease in latex paints depending on the amount of TiO2 present. [3]

Emulsification

A surfactant micelle around a polymer chain. Surfactant around a polymer chain in a latex paint.png
A surfactant micelle around a polymer chain.

Latex paints (emulsion paints British English, not to be confused with latex rubber) are an emulsion of polymer particles dispersed in water. Macroemulsions in latex paint are inherently unstable and phase separate, so surfactants are added to lower interfacial tension and stabilize polymer particles to prevent demulsification. [7]

Anionic surfactants such as sodium dodecyl sulfate are most commonly used for stabilizing emulsions because of their affinity for hydrogen bonding with the aqueous medium. Nonionic surfactants are rarely used alone due to their inferior efficiency in creating stable emulsions in comparison to anionic surfactants. Because of this, non-ionic surfactants are usually used in tandem with anionic surfactants and impart a second method of colloidal stabilization through steric interference of the van der Waals forces amid polymer and pigment particles. Latexes that require stability over large pH ranges use larger nonionic to anionic surfactant ratios. Cationic surfactants are least commonly used because of their high cost, inefficient emulsifying capability, and undesirable effects on initiator decomposition. [8] High speed application, low temperature storage, shear stresses from pumping, and other extreme storage or application conditions can cause the failure of a surfactant to adequately stabilize a paint dispersion.

The thermodynamic explanation for demulsification is the gain in Gibbs Free Energy resulting from lowering the total area of high energy surface interactions.

The energy gained from demulsification is dependent on the total area of interface and the surface tension of that interface. Surfactants lower the surface tension (γ) and thus gibbs energy is gained from demulsification. This slows the process of demulsification and stabilizes the latex paint.

The size of the droplets of dispersed polymer in a latex paint can be modeled with the following equation:

The radius of a droplet in the emulsion is dependent on surfactant length, Ls, volume fraction of dispersed phase, φd, and volume fraction of surfactant, φs. [7]

Classification of surfactants

There are three main categories of surfactants used in paint —ionic, polymeric and electrosteric. [6]

According to head group composition

Sodium Dodecyl Sulfate, a common anionic surfactant. Sodium laurylsulfate V.1.svg
Sodium Dodecyl Sulfate, a common anionic surfactant.

The head group classification of a surfactant is determined by the head group ion type. Ionic surfactants derive their amphiphilicity from a charged hydrophilic head group and tend to be small, low molecular weight molecules. Ionic surfactants will stabilize particles suspended in a paint by electrostatic repulsion and are easily adsorbed and desorbed from a surface due to their small size. [6]

Anionic head groups are negatively charged, and commonly used in cleaning products. Anionic surfactants can be found in products such as shampoos, laundry detergents, and soaps because of their ability to remove dirt from soft mediums such as fabric. Anionic surfactants are easily suspended in water due to the polarity of the charged head group. However, hard water can deactivate the molecule. Some of the more commonly used anionic head groups are sulfates and ethoxylates.

Cationic head groups have a positive charge and cationic surfactants are used in several different applications. One common use for cationic surfactants is in fabric softeners. Cationic head groups are also added to laundry detergent in conjunction with anionic surfactants because they help to improve the dirt removal properties of the anionic surfactants. Cationic head groups also increase the disinfecting properties of household cleaners. Some common cationic surfactants head groups include amines and quaternary ammonium ions. Among the many types of surfactants, cationic surfactants are very useful corrosion inhibitors due of their protective effectiveness in neutral and acidic media. [9]

Nonionic head groups have no charge and they function very well as grease removers. Nonionic surfactants are commonly used in detergents, soaps, and household cleaners. In solutions of hard water, nonionic surfactants are used to help limit the deactivation of ionic surfactants caused by the calcium and magnesium ions. Some common nonionic surfactant head groups include fatty acids and glycols.

According to tail composition

Hydrocarbon chains are long chains which consist of a carbon backbone hydrogen substituents, making them very hydrophobic. Hydrocarbon chains alone form waxes and oils and retain these characteristics when they are incorporated into surfactant. A good example of surfactants containing a hydrocarbon chain are lipids, which form cell membranes.


Alkyl ether chains are similar to hydrocarbon chains, except with oxygens incorporated within the backbone as well as carbons. There are two alkyl chains commonly used in surfactants: polyethylene oxide and polypropylene oxide. Polyethylene oxide chains have an oxygen and two carbon (-O-CH2-CH2-)n repeating unit and has an increased hydrophilic character compared to hydrocarbons. Polypropylene oxide has the same backbone structure as polyethylene oxide but with a methyl group substituent of one of the carbons, and this structure has hydrophobicity between hydrocarbons and polyethylene oxides.

Fluorocarbon chain tails consist of a carbon backbone that has fluorine substituents instead of hydrogens. Fluorocarbons help to lower the surface tension of water and other solvents because of their lipophobic nature even in harsh conditions such as low pH. When fluorocarbons are incorporated into surfactants they are used as stain repellents and incorporated into coatings in order to decrease surface defects.

Silicon - Oxygen bonds resist chain breakdown from hydrolysis and will prevent cracking in paints. Siloxane Polymer.PNG
Silicon - Oxygen bonds resist chain breakdown from hydrolysis and will prevent cracking in paints.

Siloxane chains consist of a backbone which contains alternating oxygen and silicon atoms. Surfactants with siloxane tails have been found to resist hydrolysis and prevent breakdown polymer chains which can cause cracking in the paint and are thus used in products such as cosmetics, deodorants, defoamer, and soap. [10]

Problems with surfactant use

Environmental issues

Surfactants can destabilize toxic organic compounds in paint which can enter the environment and have negative effects. [4] Water-soluble surfactants can wash out of dried paints and enter the environment. Some of these surfactants are directly toxic to animals and the environment as well as increase the ability of other toxic contaminants present to enter the environment. [11]

Cost

The cost of surfactants is partially dependent on the crude oil market. As a stock ingredient for production of surfactants, paints highly dependent on surfactants will be affected by this market.[ citation needed ] More intricate surfactants with larger, more difficult to synthesize structure are more expensive to produce and have a greater effect on end market price of their applications. As a result, simple, easy to produce and more environmentally friendly surfactants are used more widely. [12]

See also

Related Research Articles

<span class="mw-page-title-main">Paint</span> Pigment applied over a surface that dries as a solid film

Paint is a liquid pigment that, after applied to a solid material and allowed to dry, adds a film-like layer, in most cases to create an image, known as a painting. Paint can be made in many colors and types. Most paints are either oil-based or water-based, and each has distinct characteristics.

<span class="mw-page-title-main">Surfactant</span> Substance that lowers the surface tension between a liquid and another material

Surfactants are chemical compounds that decrease the surface tension or interfacial tension between two liquids, a liquid and a gas, or a liquid and a solid. Surfactants may function as emulsifiers, wetting agents, detergents, foaming agents, or dispersants. The word "surfactant" is a blend of surface-active agent, coined c. 1950.

In polymer chemistry, emulsion polymerization is a type of radical polymerization that usually starts with an emulsion incorporating water, monomers, and surfactants. The most common type of emulsion polymerization is an oil-in-water emulsion, in which droplets of monomer are emulsified in a continuous phase of water. Water-soluble polymers, such as certain polyvinyl alcohols or hydroxyethyl celluloses, can also be used to act as emulsifiers/stabilizers. The name "emulsion polymerization" is a misnomer that arises from a historical misconception. Rather than occurring in emulsion droplets, polymerization takes place in the latex/colloid particles that form spontaneously in the first few minutes of the process. These latex particles are typically 100 nm in size, and are made of many individual polymer chains. The particles are prevented from coagulating with each other because each particle is surrounded by the surfactant ('soap'); the charge on the surfactant repels other particles electrostatically. When water-soluble polymers are used as stabilizers instead of soap, the repulsion between particles arises because these water-soluble polymers form a 'hairy layer' around a particle that repels other particles, because pushing particles together would involve compressing these chains.

<span class="mw-page-title-main">Micelle</span> Group of fatty molecules suspended in liquid by soaps and/or detergents

A micelle or micella is an aggregate of surfactant amphipathic lipid molecules dispersed in a liquid, forming a colloidal suspension. A typical micelle in water forms an aggregate with the hydrophilic "head" regions in contact with surrounding solvent, sequestering the hydrophobic single-tail regions in the micelle centre.

Lipophilicity, refers to the ability of a chemical compound to dissolve in fats, oils, lipids, and non-polar solvents such as hexane or toluene. Such non-polar solvents are themselves lipophilic, and the axiom that "like dissolves like" generally holds true. Thus lipophilic substances tend to dissolve in other lipophilic substances, but hydrophilic ("water-loving") substances tend to dissolve in water and other hydrophilic substances.

Microemulsions are clear, thermodynamically stable isotropic liquid mixtures of oil, water and surfactant, frequently in combination with a cosurfactant. The aqueous phase may contain salt(s) and/or other ingredients, and the "oil" may actually be a complex mixture of different hydrocarbons. In contrast to ordinary emulsions, microemulsions form upon simple mixing of the components and do not require the high shear conditions generally used in the formation of ordinary emulsions. The three basic types of microemulsions are direct, reversed and bicontinuous.

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<span class="mw-page-title-main">Amphiphile</span> Hydrophilic and lipophilic chemical compound

An amphiphile, or amphipath, is a chemical compound possessing both hydrophilic and lipophilic (fat-loving) properties. Such a compound is called amphiphilic or amphipathic. Amphiphilic compounds include surfactants. The phospholipid amphiphiles are the major structural component of cell membranes.

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Adsorption of polyelectrolytes on solid substrates is a surface phenomenon where long-chained polymer molecules with charged groups bind to a surface that is charged in the opposite polarity. On the molecular level, the polymers do not actually bond to the surface, but tend to "stick" to the surface via intermolecular forces and the charges created by the dissociation of various side groups of the polymer. Because the polymer molecules are so long, they have a large amount of surface area with which to contact the surface and thus do not desorb as small molecules are likely to do. This means that adsorbed layers of polyelectrolytes form a very durable coating. Due to this important characteristic of polyelectrolyte layers they are used extensively in industry as flocculants, for solubilization, as supersorbers, antistatic agents, as oil recovery aids, as gelling aids in nutrition, additives in concrete, or for blood compatibility enhancement to name a few.

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An oil dispersant is a mixture of emulsifiers and solvents that helps break oil into small droplets following an oil spill. Small droplets are easier to disperse throughout a water volume, and small droplets may be more readily biodegraded by microbes in the water. Dispersant use involves a trade-off between exposing coastal life to surface oil and exposing aquatic life to dispersed oil. While submerging the oil with dispersant may lessen exposure to marine life on the surface, it increases exposure for animals dwelling underwater, who may be harmed by toxicity of both dispersed oil and dispersant. Although dispersant reduces the amount of oil that lands ashore, it may allow faster, deeper penetration of oil into coastal terrain, where it is not easily biodegraded.

Macroemulsions are dispersed liquid-liquid, thermodynamically unstable systems with particle sizes ranging from 1 to 100 μm, which, most often, do not form spontaneously. Macroemulsions scatter light effectively and therefore appear milky, because their droplets are greater than a wavelength of light. They are part of a larger family of emulsions along with miniemulsions. As with all emulsions, one phase serves as the dispersing agent. It is often called the continuous or outer phase. The remaining phase(s) are disperse or inner phase(s), because the liquid droplets are finely distributed amongst the larger continuous phase droplets. This type of emulsion is thermodynamically unstable, but can be stabilized for a period of time with applications of kinetic energy. Surfactants are used to reduce the interfacial tension between the two phases, and induce macroemulsion stability for a useful amount of time. Emulsions can be stabilized otherwise with polymers, solid particles or proteins.

Polyelectrolytes are charged polymers capable of stabilizing colloidal emulsions through electrostatic interactions. Their effectiveness can be dependent on molecular weight, pH, solvent polarity, ionic strength, and the hydrophilic-lipophilic balance (HLB). Stabilized emulsions are useful in many industrial processes, including deflocculation, drug delivery, petroleum waste treatment, and food technology.

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Waterborne resins are sometimes called water-based resins. They are resins or polymeric resins that use water as the carrying medium as opposed to solvent or solvent-less. Resins are used in the production of coatings, adhesives, sealants, elastomers and composite materials. When the phrase waterborne resin is used, it usually describes all resins which have water as the main carrying solvent. The resin could be water-soluble, water reducible or water dispersed.

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References

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