Basics of Surfactants

Chemical Structure

Water: Hydrophobic part Hydrophilic part

Oil: Lipophilic Lipophobic

The balance between the two parts decisive for

the properties of the surfactant!!
 Surfactants

Surface active molecules

Air
orientate themselves in the
interface between two phases.
Water

When the surface is saturated

with surfactants they start to
form spherical globules in the Air
water, which are called Oil
micelles.

Interfacial tension
Water
 Types of Surfactants

The Hydrophobe The Hydrophile

¾ Fatty acids ¾ Nonionic types
ƒ Ethoxylates
¾ Fatty amines
ƒ Glucosides
¾ Alkyl phenols ¾ Cationic types +
¾ Fatty alcohols ƒ Quaternary, tertiary and
¾ Etc…. primary amines
_
¾Anionic types
ƒ Acids, phosphonic groups
ƒ Sulphonates etc…
_
¾Amphoteric types +
ƒGlycinates, propionates
ƒBetaines
 Functions of Surfactants

™ Dispersing ™ Conditioning
™ Aggregation ™ Emulsification
™ Hydrophobation ™ Colloid stabilization
™ Wetting ™ Water retention
™ Disinfection ™ Anti-corrosion
™ Rheology control ™ Foaming/Defoaming
™ Thickening
 Why Use Surfactants in Cleaning?

The main tasks of surface active agents for cleaning are to:

9 reduce the surface tension of water to get

wetting properties and to release soil from surfaces.

9 emulsify fatty material

9 disperse solid particles and pigment (“dirticles”)

 Nonionic Surfactants

H
O O
x Alcohol ethoxylate
X=4

HO
HO O

O Alkylpolyglucoside
H OH
O
dp
Nonionic Surfactants

(CH2CH2O)n H
N Amine ethoxylate
(CH2CH2O)m H

O(CH2CH2O)n H
Alkyl phenol
ethoxylate

OH Alkanolamide
N

H
 NP-Ethoxylates
Distribution of Ethylene Oxide – NP10

Unreacted alcohol %
14

12
* A narrow distribution is good
10 for foam control
8
* Very little unreacted alcohol,
6 so odour is low

4 * Not readily biodegradable

0 1 2 3 4 5 6 7 8 9 1 0 1 1

0 4 8 12 16 18 Moles EO
 Distribution of Ethylene Oxide in
Different Standard Alcohol Ethoxylates

Unreacted alcohol %
16

14
C1215-3
12 * A broad distribution of
moles of EO results in
10
higher foam
C1415-7
8 * The fewer moles of EO
6
the worse the odour

4 C1415-11 * Unreacted alcohol can

be significant
2

0
0 4 8 12 16 20 24 Moles EO
 Benefits of Narrow Range
Ethoxylated Alcohols

Unreacted alcohol %
20

15 * Narrow EO distribution for

foam control

10
* Low odour

* Readily biodegradable

5 * Good cleaning performance

0
0 4 8 12 16 Moles EO
 The Cloud Point of Nonionics

¾ The temperature at which a nonionic water solution

becomes cloudy

¾ The solution becomes heterogeneous and separates into

two phases upon further increase in temperature
 Water Solubility of Nonionics

H H
O O Hydrogen bond
H H
C-C-O-C-C-O-C-C-O-C-C-O-C-C-OH
H H
O O
H H

Hydrogen bonding between oxygen atoms in ethoxylation units and

water, cause water solubility.
The more ethoxylation the more water soluble.
 Effect of Temperature

H H
O O
H H

C-C-O-C-C-O-C-C-O-C-C-O-C-C-OH

H H
O O
H H

The temperature where a nonionic forms two less soluble phases in

water, is called the cloud point
Cloud Points of Nonionics

Cloud point, oC

100

80

60

40

20

0 4 8 12 16 20 Moles EO
 Cloud Points of Nonionics

100
75
Cp10NaCl 50
25
0
NP
100
75 C1618
Cp0 50 C1214
25
0 EO
100 5 10 15 20 25 30
75
Cp25BDG 50
25
0
 Influence of Cloud Point on
Soil Removal

Removal, % NP-10 Cloud point is 55-60oC

120

100

80
30oC
60 75oC
58oC
40

20

0
0.025 0.05 0.1 0.25 Concentration, %
CMC ~0.005%
 HLB - Hydrophilic Lipophilic Balance

Low HLB values High HLB values

The lipophilic The hydrophilic
(hydrophobic) part is dominating
part is dominating
 HLB According to Griffin
(only for nonionic surfactants)

% Ethylene oxide in the molecule divided by 5

Example: Molecular weight/g/mol:

C11-alcohol + 7 EO C11H23-OH = 172
EO = 44

C11-7 = 172 + (7 x 44) = 480

308 x 100
EO-content = 64.1%
480

64.1
HLB = 12.8
5
 Cloud Point – HLB-value
Different Hydrophobes

Cloud point, oC
100

80

C14-15
60

40
NP
C9-11
20

0
11 12 13 14 HLB
 HLB – Application Areas

HLB Griffin Application areas

3-7 Water in oil emulsions (W/O)
7-10 Wetting agents
12-15 Detergents
15-18 Dispersing agents
10-18 Oil in water emulsions (O/W)
 Nonionic Surfactants

¾ Adjustable foaming

¾ Insensitive to hard water

¾ Good emulsifying properties

¾ Good dispersing properties (high number of EO)

¾ Compatible with other types of surfactants

Cationic Surfactants (1)

-
+ (CH2CH2O)n H Cl Ethoxylated
N -
(CH2CH2O)m H CH3SO4 quaternary
CH3

+ CH3 Dialkyl
-
N Cl
CH3 quaternary
Cationic Surfactants (2)

O
+ CH3
O -
O N Cl Ester ”quat”
CH3
O

CH3
-
+ Benzalkonium
N CH2 Cl
chloride
CH3
 Substantivity

Adsorptive properties of cationic

surfactants and related nitrogen
derivatives

Adsorption, particularly onto solid

surfaces.
Attraction between the positive
charge on the nitrogen atom –
negative charge surfaces

+
N ........... .......... ...........
........... ............ ........... Surface modification
 Cationic Surfactants

Substantivity leads to the following functions:

¾Softening

¾Anti-static properties

¾Lubrication

¾Corrosion inhibition

¾Adhesion

¾Hydrophobation
 Cationic Surfactants

Properties/Functions

¾Substantivity ¾Bactericidal

¾Softening ¾Corrosion inhibition

¾Thickening ¾Foam boosting

¾Dispersing ¾Hydrotroping

+
 What is Surface Tension?

ƒ The work/force needed to create more surface area!

ƒ The stronger bonds the higher surface tension and
the more energy needed
What is Surface Tension?

• The water molecules in the

surface orientate themselves so
they are ”holding hands” due to
the hydrogen bonds between
oxygen and hydrogen atoms.
Hydrogen bond This is a relatively strong force.

• This force is manifested in

Surface Tension. For water it is
typically ~72 mN/m
Surface Tension (in mN/m) of
Some Liquids at 25oC

Mercury 480
Water 72
Blood 56-61
Ethanol 22
n-Hexane 18
 The Influence of Surfactants
on Surface Tension

The surfactants orientate

themselves in between the water
molecules and disturb their
Weaker hydrogen “hand-holding”. The force is then
bond lowered.

For some surfactants the surface

tension can be reduced to ~30
mN/m or even lower.
 Wetting

Bad wetting, high Good wetting, low

surface tension, big surface tension, small
contact angle contact angle

Contact angle reduction is the key!

 Substrate

• Type of material
• CST (Critical Surface Tension)

Material mN/m
Glass >73
Polystyrene 32
Polypropylene 28
Teflon 18
Water 72

To wet a surface, the surface tension of the liquid

should be below the Critical Surface Tension (CST)
Critical Micelle Concentration (CMC)

Interfacial tension

Equivalent conductivity
Osmotic pressure
Surface tension

CMC Concentration
 CMC (Critical Micelle Concentration)

Below the CMC, the molecules are

free, swimming around seeking
areas to attach and forming mono-
molecular layers to (adsorb)

Above the CMC, they form the

mono-molecular layer. When all the
area has been covered they stick to
one another instead, forming the
micelles. The more you add, the
more micelles you form.

The surface tension now does not

decrease with increased surfactant
addition. The micelles form and
disintegrate 1000 times per second
Below CMC Above CMC
 Structures of Micelles

Spherical Rod-shaped or Lamellar

cylindrical

The structure and shape of a micelle depends on:

– Temperature
– Concentration
– Type of surfactants
– Electrolytes
– Other water soluble organic compounds (e.g. alcohols)
 CMC is Affected by Other
Components in the Solution

Surfactant adsorption and aggregation (CMC) depends on:

9 Type of surfactant ionics higher, longer tails lower

9 Temperature ionics small increase, nonionics

decrease with temperature

9 Salts usually reduction with increase (salt)

9 Co-surfactants increase or decrease; in some mixtures

a synergistic reduction of CMC

9 Co-solvents usually increase

 CMC for Some Surfactants

Surfactant CMC/mM at 25oC

Anionic
• n-C10H21SO4-Na+ 33,0
• n-C12H25SO4-Na+ 8,20
• n-C14H29SO4-Na+ 2,05

Nonionic
• C12H25(OC2H4)3OH 0,052
• C12H25(OC2H4)5OH 0,064
• C12H25(OC2H4)8OH 0,109
 Conclusions CMC and Micelles

¾ Micelles make insoluble material soluble in water.

¾ The structure of the micelles can affect the viscosity of
the solution.
¾ Micelles are reservoirs of surfactants.
¾ If not above CMC, the cleaning solution gets
depleted of surfactants and cleaning power is lost!!
Emulsions

When an oil is added to water

containing a surfactant, the oil is
surrounded by surfactant

Oil amid the oil loving tails of the

surfactant

Water loving heads of the surfactant

bonding with water molecules
 Emulsification

Oil emulsified
¾ Surfactants allow us to mix substances of in water
different nature

¾ Very important applications:

– Food industry
– Lubricants
– Paints
– Polymerization
– Cosmetics
Repulsion forces
between the head
groups avoid
coalescence of the
droplets
 Real Soil

Pigment: Grease:
* Dust * Mineral Oil
* Graphite * Vegetable Oil
* Carbon Black * Animal Fat
* Etc
 How Surfactants Work

The hydrophobic (lipophilic)

chain is attracted by the soil
and penetrates it

The surfactants force the soil

to open and to detach from
the surface

The soil is detached from

the surface
Degreasing - Emulsification
 Solubility versus Degreasing

¾ When surfactants are highly water soluble:

ƒ the driving force for the surfactants to leave the water phase and
penetrate the oil phase (grease) is low
ƒ few molecules leave the water phase
ƒ high surfactant concentrations are required

¾ When surfactants are poorly water soluble:

ƒ the driving force to go to the oil phase is strong
ƒ almost all molecules leave the water phase
ƒ low concentrations do great job

¾ Best surfactant to remove oils and fats is nonionic

Dispersing of Solid Particles
in Liquid

1. Wet the particles

ƒ reduce the surface tension

2. Break the particle clusters

ƒ mechanical work

3. Prevent re-aggregation and

sedimentation of the particles
ƒ steric interaction
ƒ electrostatic forces
 Pigment Removal

¾ Most particles and surfaces are given a negative surface

potential in water

¾ An increase of the pH means and increase of the

repulsion between pigment and surface

OH - OH - OH -
 Detergency

Pigment removing capacity on cotton at different pH,

without surfactant
40
Pigment remo val, %

20

0
2 4 6 8 10 12 14 pH
Dispersing

Repulsion of the head groups

avoid coalescenece and
precipitations of the particles

Surfactants adsorbing on hydrophobic particles

 Disperse Hydrophobic Particles
with Electrostatic Forces
Repulsing
forces
_ __ _
_ _ _
_ _ _ _ _
_ _
_ _
_ _ _

_
_ _ _ _ _
_ _ _
_ _
_ _

Dispersing agent: the same charge as the particle

Disperse Hydrophobic Particles
with Steric Interaction

Nonionics

Dispersing agent: big hydrophilic group

 Required Effects when Cleaning

¾ Wetting
ƒ The cleaner has to get in contact with soil and surface

¾ Emulsification
ƒ Removal of soils (oils, greases, proteins, fats)

¾ Dispersion
ƒ Removal of dust, earth, etc
ƒ Avoiding redeposition of solid particles