Surfactant Basics Page 1 of 8

Surfactant Basics

Here you’ll find answers to many of the most commonly asked questions regarding DOW
surfactants. For answers to your specific technical questions, please go to Contact Us, or contact us
via phone at the numbers below. One of our technical experts will provide an answer by return
email.

Telephone:
In the United States and Canada, call 1-800-447-4369.
In other global areas, call +1-989-832-1560

For answers to general questions on DOW surfactants, please select:

1. What is a surfactant? Why are surfactants used in cleaners and detergents?

2. What is surface tension? Why is it important?
3. What is the critical micelle concentration?
4. What is HLB? How is it applied to formulate emulsions?
5. How can I control or modify the foam in an application?
6. What is cloud point? Why is it important?
7. What is a hydrotrope?
8. How can I choose the best surfactant?
9. Are there special grades of DOW surfactants (USP, NF)?
10. What tests are commonly used to evaluate cleaners and detergents?
11. How are surfactants used in emulsion polymerization?
12. Do anionic and nonionic surfactants function differently in emulsion polymerization?

1. What is a surfactant? Why are surfactants used in cleaners and detergents?

A surfactant (surface active agent) is a molecule that, when added to a liquid at low concentration,
changes the properties of that liquid at a surface or interface. Surfactants are used in cleaners and
detergents to:

z Improve wetting / spreading

z Provide detergency by solubilizing and suspending soils (particulate, oily)
z Produce, modify or control foam
z Emulsify / disperse (e.g., silicone, wax)
z Couple or compatibilize formulation components
z Modify viscosity

The general structure of a surfactant includes a hydrophilic portion and a hydrophobic portion as
shown in the schematic below.

Schematic of a Surfactant
The hydrophilic end is water-soluble and is usually a polar or ionic group. The hydrophobic end is

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water-insoluble and is usually a long fatty or hydrocarbon chain. This dual functionality, hydrophobic
and hydrophilic, provides the basis for characteristics useful in cleaner and detergent formulations,
including surface tension modification, emulsification, foam, and cloud point. Surfactants are
generally characterized by the hydrophilic group into the following categories:

Surfactant Categories
Type Charge Product Name Product Type
TRITON™ and
Nonionic None Ethoxylates, Alkoxylates, Glucosides
TERGITOL™ Surfactants
TRITON and DOWFAX* Sulfates, Sulfonates, Disulfonates, Phosphate
Anionic -
Surfactants Esters, Sulfosuccinates
Cationic + Quaternary ammonium salts
Amphoteric +/- Betaine

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2. What is surface tension? Why is it important?

The ability of surfactants to reduce the surface tension of water to a low value is a fundamental
characteristic that results in highly efficient and effective performance in a wide range of
applications. By changing the surface tension of a solution, the surfactant makes the solution wet
better. Instead of beading up, the solution will spread over the surface or penetrate more rapidly into
fibers.

Surfactants change the surface tension of water by breaking up the forces holding the water
molecules together at the interface. Surface tension is usually expressed dynes/cm or mN/m. Two
surface tension measurements commonly performed provide two different types of data.

Equilibrium surface tension (typically of an aqueous surfactant solution) indicates how effective a
surfactant is at reducing the surface tension of water (72 dynes/cm). For example, a 0.1% aqueous
solution of TERGITOL TMN-6 (90%) Surfactant has an equilibrium surface tension of 26 dynes/cm,
which indicates excellent wetting properties.

Dynamic surface tension measures how rapidly a surfactant reduces the surface tension of a
solution. Dynamic surface tension data provides information on how rapidly surfactant molecules
that are present in the sample can diffuse to and orient at a newly created surface. In very short
time, the surface tension of the solution will be near that of pure water (72 dynes/cm) since the
molecules have not had time to diffuse and orient at the surface. In longer time, the surface tension
will approach the equilibrium surface tension value. TERGITOL TMN Series Surfactants lower the
surface tension rapidly. Typical values for dynamic surface tension for TERGITOL TMN-6 (90%)
Surfactant are 36 dynes/cm at a bubble frequency of 4 bubbles/sec or 0.25 s for a 0.1% aqueous
solution at 25°C.

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3. What is the critical micelle concentration?

A micelle is an aggregated unit composed of a number of molecules of a surface active material as

shown in the drawing below. Micelles solubilize dirt and oils by lifting these soils off the surface and
dispersing them into solution. Micelle formation enables emulsification, solubilization, and dispersion
of otherwise non-compatible materials. Critical micelle concentration (CMC) is the surfactant
concentration at which an appreciable number of micelles are formed and thus remove soils (see
drawing below).

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A micelle Critical micelle concentration

Critical micelle concentration (CMC) is a measure of surfactant efficiency. A lower CMC indicates
less surfactant is needed to saturate interfaces and form micelles. Typical CMC values are less than
1% by weight (e.g., TRITON X-100 Surfactant has a CMC of 0.0130%). To obtain optimal cleaning
performance, concentrations of 1-5% are common. This concentration is higher than that needed to
achieve micelle formation; therefore, providing a reservoir of additional surfactant molecules to form
micelles. These micelles solubilize and disperse soils leading to detergency. CMC values provide a
valuable guideline for comparing surfactant detergency. Other formulation components and
temperature may affect micelle formation.

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4. What is HLB? How is it applied to formulate emulsions?

HLB (Hydrophile-Lipophile Balance) is an empirical expression for the relationship of the hydrophilic
(“water-loving”) and hydrophobic (“water-hating”) groups of a surfactant. The table below lists HLB
values along with typical performance properties. The higher the HLB value, the more water-soluble
the surfactant.

The HLB system is particularly useful to identify surfactants for oil and water emulsification. There
are two basic emulsion types:

z Water-in-oil (w/o): water is dispersed in oil

z Oil-in-water (o/w): oil is dispersed in aqueous phase, most common emulsion type.

Water-in-oil emulsions (w/o) require low HLB surfactants. Oil-in-water (o/w) emulsions often require
higher HLB surfactants.

Surfactant selection for an o/w emulsion can be simplified if the HLB system is applied. Oils have
required HLB numbers that identify the HLB necessary to give good o/w emulsification. Often the oil
supplier can provide the required HLB value. Alternatively, there are a number of compiled lists in
the literature on the required HLB for common waxes and oils. Since overall chemical structure (e.g.,
branched, linear, aromatic) is also a variable, a number of different surfactants with the required
HLB should be examined. Not all surfactants having the same HLB value may be acceptable for an
o/w emulsion. HLB values for surfactants can be calculated for simple alcohol ethoxylates. If a
surfactant is not a simple alcohol ethoxylate, the HLB value must be determined experimentally.
HLB values are additive; therefore, if two different surfactants or oils are present, the HLB will be the
weighted average of the HLB values for each component. Example: An oil (HLB = 10.5) is a
component in an aqueous cleaning solution.

There are several choices for surfactants. TRITON X-45 might be considered since it has an HLB
value of 9.8; however, it is dispersible (not soluble) in water. Another choice is a blend of TRITON X-
35 (HLB = 7.8) and TRITON X-100 (HLB = 13.4), a combination that will be water-soluble. HLB
values are additive, so to achieve the required HLB value, use the weighted average of the HLB
values for each surfactant. Required HLB = 10

Surfactant family: TRITON X Series

.....................(0.5 TRITON X-35)(7.8) + (0.5 TRITON X-100)(13.4) = 3.9 + 6.7 = 10.6

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A 1:1 blend of TRITON X-35 and X-100 Surfactants provides the required HLB value.

HLB Values and Properties

HBL Property Examples of Selected Surfactant
<10 Oil soluble
>10 Water Soluble
4-8 Antifoaming agent TERGITOL 15-S-3
7-11 Water-in-oil emulsifier TERGITOL 15-S-5
12-16 Oil-in-water emulsifier TERGITOL 15-S-7, 15-S-9, 15-S-12, 15-S-15
11-14 Wetting agent TERGITOL 15-S-7, 15-S-9
12-15 Detergent TERGITOL 15-S-7, 15-S-9, 15-S-12
16-20 Stabilizer TERGITOL 15-S-20, 15-S-30, 15-S-40

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5. How can I control or modify the foam in an application?

Foam can be both an advantage and a disadvantage. In some applications, such as car wash or
hand dishwash, high foam may be desirable. In other applications (e.g., latex paint, automatic
dishwash), foam is less desirable and can hinder detergency. Careful surfactant selection can lead
to optimal levels of foam.

Two common methods used to measure foam levels are the Ross-Miles and Waring or Hamilton-
Beach blender foam tests. The Ross-Miles foam test (ASTM D1173-53) generates foam under low-
agitation conditions and is generally used for moderate- and high-foam surfactants. The blender
tests generate foam under high agitation in a blender, which is appropriate for low-foam surfactants.
Both tests gather data on initial foam height and foam decay (e.g., height of foam over time). Foam
decay provides information on foam stability.

In general, anionic surfactants provide high levels of foam, and nonionic surfactants provide
moderate to low foam heights. For formulations in which foam levels are desired to be high, choose
a high-foaming surfactant, such as TRITON X-200 Surfactant. For low-foam formulations, use a low-
foam surfactant such as the TRITON CF and DF Surfactant product lines or TERGITOL MinFoam
1X or 2X Surfactants. In addition to simply providing different levels of foam, surfactants can provide
different foam characteristics. For example, some surfactants provide stable foams (TRITON X-200
Surfactant, TRITON X-100 Surfactant), while other surfactants provide foams that break fast and
collapse quickly (TRITON QS-15 Surfactant). The structure of the foam varies as well. Some
surfactant foams have porous, very open structures, while others have dense, lathery foams
(TRITON X-200 Surfactant). Surfactants can also have unique foam-profile triggers. TRITON RW
Surfactants have foam profiles that are pH dependent. At alkaline pHs these surfactants provide
foam, but after appropriate chemical treatment, these surfactants provide little to no foam as shown
in the following photograph.

Surfactants can also be used to control foam or have defoaming properties. For example,
surfactants that are dispersible or slightly soluble in water can act as defoaming agents in a
formulation (TERGTIOL L Series Surfactant). Other surfactants are useful for controlling foam
resulting from food and protein soil defoaming (TRITON CF-32 Surfactant,).

TRITON RW-150 Surfactant Foam

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Aqueous solutions of TERGITOL RW-150 Surfactant (0.1% aqueous) at pHs ranging from basic (pH
= 13) to acidic (pH = 2) were shaken to sow that at basic (higher) pHs this surfactant provides foam,
while at low pHs this product has lost its surfactancy.

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6. What is cloud point? Why is it important?

Cloud point is the temperature above which an aqueous solution of a water-soluble surfactant
becomes turbid (see photograph below). Knowing the cloud point is important for determining
storage stability. Storing formulations at temperatures significantly higher than the cloud point may
result in phase separation and instability. Wetting, cleaning and foaming characteristics can be
different above and below the cloud point. Generally, nonionic surfactants show optimal
effectiveness when used near or below their cloud point. Low-foam surfactants should be used at
temperatures slightly above their cloud point.

Cloud points are typically measured using 1% aqueous surfactant solutions. Cloud points range
from 0 to 100°C (32 to 212°F), limited by the freezing and boiling points of water. Cloud points are
characteristic of nonionic surfactants. Anionic surfactants (with negatively charged groups) are more
water-soluble than nonionic surfactants and will typically have much higher cloud points (above 100°
C). The presence of other components in a formulation can depress or increase the solution's cloud
point. For example, the addition of a coupler or hydrotrope can increase the cloud point of a solution,
whereas builders or other salts will depress the cloud point temperature.

For low-foam applications, the cloud point of the surfactant should be just below the use
temperature. For example, the cloud point of TRITON CF-32 Surfactant is 23°C (73.4°F). This
surfactant should be used around 25-28°C (77-82°F) for maximum efficacy. For standard foam
applications, the cloud point of the surfactant should be just above the use temperature. For
example, the cloud point for TRITON X-100 Surfactant is 66°C (150°F). This surfactant should be
used at <66°C (150°F).

Cloud Point of TRITON CF-32 Surfactant Water solubility of a nonionic surfactant varies inversely
with temperature. A solution of TRITON CF-32 surfactant is clear at 20°C but is cloudy at 40°C.

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7. What is a hydrotrope?

A hydrotrope is a substance that improves the solubility of surfactants in water, particularly those
systems containing high levels of builders or alkalinity. Couplers, like solvents and more-soluble
surfactant classes, can also be used to increase solubility. Hydrotropes are a special class of
couplers requiring relatively low levels for solubilization of surfactants. Builders or other electrolytes
will depress cloud point temperature or solubility of surfactants in aqueous systems. Hydrotropes
can be used to adjust the cloud point of the formulation. A higher concentration of hydrotrope
generally leads to higher cloud points. The hydrotrope does not contribute to or detract from the
performance of surfactant or builder.

The choice of hydrotrope is based on the builder levels and requirements for each specific
application. The following phosphate ester-based products are particularly efficient hydrotropes.

TRITON H-55 surfactant: solubilizes surfactants into moderately to highly built detergents

TRITON H-66 surfactant: solubilizes surfactants into low to moderately built detergents;solubilizes
low-foaming nonionic surfactants into highly built detergents

TRITON QS-44 surfactant: solubilizes surfactants at use-concentration levels and into low built
detergents; provides surface activity (e.g., detergency, wetting, foaming)

DOWFAX C6L Surfactant: solubilizes surfactants at use-level concentrations, especially useful in

the presence of hypochlorite bleach.

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8. How can I choose the best surfactant?

Several surfactants may be appropriate in a given application. Final surfactant selection will depend
on your specific requirements, end-use application, and what properties are most important in your
application. Surfactants can serve many functions in a formulation, but rarely can a single surfactant
fulfill all these roles. To facilitate correct selection, decide what role the surfactant plays (e.g.,
provide foam, emulsification, wetting, detergency, stabilization) in an application, and select the
surfactants that most closely match your requirements. For further assistance in selecting the best
surfactant, refer to our surfactant guides:

Specialty Surfactants Reference Chart (283KB PDF)

TERGITOL NP Surfactants Reference Chart (291KB PDF)

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Surfactant Product Finder

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9. Are there special grades of DOW surfactants (USP, NF)?

None of the DOW surfactants are USP or NF grade products.

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10. What tests are commonly used to evaluate cleaners and detergents?

Three general classes of measurements can be used to fully evaluate cleaners and detergents:
physical properties of the formulated product, product performance, and some measure of consumer
satisfaction. Desired test characteristics include an ability to discriminate between different
formulations, accuracy, convenience, and reproducibility. The physical properties of the formulation
include product form (e.g., solid, liquid, gel), viscosity for liquids or dry flow for powders, foam, cloud
point, surface tension, and pH. Long term physical and chemical stability of the formulation must
also be considered. Stability testing might include freeze-thaw stability, high/low temperature
stability, shelf stability, and stability in package.

To evaluate product performance, carefully design controlled tests to mimic the end application. Soil
and surface selection that mimics or reproduces the soil and surface to be cleaned is critical.
Screening tests might measure wetting, detergency, spotting/filming, anti-soil deposition or soil
tolerance. When acceptable formulations are identified, field or in-use testing should be done.

Standard industry methods for both physical property and detergent testing are available from:

z American Association of Textile Chemists and Colorists (AATCC),

One Davis Drive, P.O. Box 12215,
Research Triangle Park, NC 27709-2215
Phone: (919) 549-8141
www.aatcc.org

z American Society for Testing and Materials (ASTM)

100 Barr Harbor Drive
West Conshohocken, PA 19428-2959
Phone: (610) 832-9585
www.astm.org

z Chemical Specialties Products Association (CSPA)

1913 Eye St., NW
Washington, D.C. 20006
Phone: (202) 872-8110
www.cspa.org

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11. How are surfactants used in emulsion polymerization?

Surfactants are involved in different steps of latex manufacturing and are essential for latex
stabilization. Prior to the onset of polymerization, surfactants are used to reduce the interfacial
tension between monomers and the aqueous phase. Surfactant selection is dependent upon the
system to be emulsified. During nucleation, surfactant micelles help solubilize monomers and
provide sites where polymerization occurs. Particle nucleation is controlled by the
monomer/surfactant ratio. Due to their ability to stabilize small particles by electrostatic repulsion,

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anionic surfactants are generally used for nucleation. Blends of anionic and non-ionic surfactants
are often used during polymerization to stabilize the formulation for a specific application and to
ensure latex stability during storage and transport.

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12. Do anionic and nonionic surfactants function differently in emulsion polymerization?

Yes. Anionic surfactants are adsorbed on the latex particles, surrounding them with a coulumbic
charge that provides an energy barrier. This barrier limits coalescence and destabilization. Anionic
surfactants are sensitive to the presence of salts in the system. Nonionic surfactants achieve
stabilization of the latex by surrounding the particles with a hydrated layer of surfactant. This layer
acts as a steric barrier to particle coalescence. Nonionic surfactants are generally less efficient in
providing latex stability than anionic surfactants. However, the hydrated layer around the particle is
considerably less sensitive to electrolytes and to freezing.

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