THE HLB SYSTEM

A TIME SAVING GUIDE TO

SURFACTANT SELECTION

Presentation to the Midwest chapter

of the Society of Cosmetic Chemists
March 9th 2004
WHAT DO WE MEAN BY
SURFACTANT SELECTION
• First - selecting between the available chemical
types
– anionic,
• Negative charge
– cationic,
• Positive charge
– amphoteric
• Charge depends on pH
– Nonionic
• No charge
WHAT DO WE MEAN BY
SURFACTANT SELECTION
• Second – once having selected the chemical
family
– You must select a surfactant or surfactant pair
with the correct solubility for your unique
application
WHAT DO WE MEAN BY
SURFACTANT SELECTION
• How does surfactant solubility affect
performance ?
– For example ( very general rules )
• You need high water solubility for cleansing and
detergency
• You need medium solubility for spreading and
dispersion
• You need low solubility for invert emulsions and
coupling immiscible oils
• You need a blend of solubilities for O/W
emulsions
WHAT DO WE MEAN BY
SURFACTANT SELECTION
• Is there a way to predict surfactant solubility by
merely looking at its chemistry?
– Yes ( for the most part )
– Almost all “soaps” have medium to high solubility
in water & low solubility in oils/fats
– Almost all anionics such as S.L.S. are highly
water soluble & low solubility in oil/fats
– Almost all cationics and amphotrics are highly
water soluble
– Nonionics’ water solubility can be predicted by
their HLB
What do we mean by “HLB”

• All surfactants must have an oil loving portion

and a water loving portion or they would not
have surface activity
• The ratio of the oil loving portion to the water
loving portion is what we call its balance
• We measure this balance based on molecular
weight
• “HLB” stands for
– HYDROPHILE / LIPOPHILE / BALANCE
What is the HLB “system” story

• The “system” was created as a tool to make it

easier to use nonionic surfactants
• In general it applies to nonionic surfactants only
• The basic principle of the system is:
– Surfactants have an HLB value
– Applications for surfactants have an HLB
requirement
– Matching the requirement with the value saves
time and money
What are the common ways of
surfactant selection?
• Try what has worked in the past

• ask a co-worker

• use your instinct

• try everything
– there are thousands available
• The HLB System
Why use the HLB System

• It tells us something about the chemistry of the

surfactant

• when you know about the chemistry of the

surfactant you can predict how it will behave

• being able to predict how a surfactant will

behave will save you time ( $$$$$ )
Short background of the HLB
System
• It was invented 55 years ago by
William C. Griffin of the Atlas Powder Company ( bought
by ICI in 1971 )

• The letters HLB stand for

– Hydrophile Lipophile Balance

• It was / is intended as a large scale road map to good

emulsification performance

• It was invented for use with NONIONIC surfactants in

particular
What is the chemistry of a
nonionic surfactant ?
• Each surfactant has a hydrophilic group and a
lipophilic group
– must have both or it would not be surface active

• the hydrophilic group is usually a polyhydric*

alcohol or ethylene oxide

• the lipophilic group is usually a fatty acid or a

fatty alcohol

– * polyhydric- an alcohol with OH’s attached

What is the chemistry - cont.

• The relationship ( or balance ) between the

hydrophilic portion of the nonionic surfactant to
the lipophilic portion is what we call

HLB
• All nonionic surfactants have an HLB Value
What is the HLB “system” ?

• Nonionic surfactants have an HLB “value”

• applications for surfactants have an HLB

“requirement”

• matching the HLB “value” of your surfactant

with the application “requirement” will give good
performance

• it is that simple
How do we determine the HLB
“value” of a surfactant ?
• We calculate the water loving portion of the
surfactant on a molecular weight basis and
then divide that number by 5

• this keeps the HLB scale smaller and more

manageable
– the working scale is from 0.5 to 19.5

• this number is then assigned to the nonionic

surfactant
Here is an example of an HLB
value calculation
• our product BRIJ ® 98 INCI name : oleth-20 is a 20 mole
ethoxylate of oleyl alcohol
• we calculate the molecular weight of the 20 moles of
ethylene oxide ( one mole ETO =44 )
– 20 x 44 = 880
• we add this number to the molecular weight of the oleyl
alcohol
– 880+ 270 = 1150 ( the mol. wt of BRIJ 98 )
• What percentage of 1150 is 880 ?
– 880/1150 = 76.5%
• 76.5% divided by 5 = 15.3
• 15.3 is the HLB value of BRIJ 98
Important to remember !

• The HLB value is an indication of the solubility

of the surfactant

• the lower the HLB value the more lipophilic or

oil soluble the surfactant is

• the higher the HLB value the more water soluble

or hydrophilic the surfactant is

• this surfactant solubility property is an indicator

of its likely end use
Important to remember, cont.

• HLB values are calculated for nonionic

surfactants only
• the HLB value is the molecular weight percent
of the water loving portion of the nonionic
surfactant - divided by five
• What does it mean when you hear of an anionic
with an “HLB” for 40 or so?
– This number is a relative or comparative number
and not a mathematical calculation
Examples of matching HLB
values to application needs
• mixing unlike oils together
– use surfactants with HLB’s of 1 to 3
• making water-in-oil emulsions
– use surfactants with HLB’s of 4 to 6
• wetting powders into oils
– use surfactants with HLB’s of 7 to 9
• making self emulsifying oils
– use surfactants with HLB’s of 7 to 10
• making oil-in-water emulsions
– use surfactant blends with HLB’s of 8 to16
• making detergent solutions
– use surfactants with HLB’s of 13 to 15
• for solubilizing oils ( micro-emulsifying ) into water
– use surfactant blends with HLB’s of 13 to 18
What is a required HLB as
opposed to an HLB value ?
• Each lipophilic ingredient used in O/W
emulsions has what we call a “required” HLB

• these “required” HLB’s have been determined

by a simple experiment

• a list of these “required” HLB’s is available from

us
– see our HLB Booklet
 Another way to think of
“required” HLB
• The HLB value of the surfactant that provides
the lowest interfacial tension between

– Your unique oil phase

• AND

– Your unique water phase

• Is your “required” HLB

Some general required HLB
rules for O/W emulsions
Class Required HLB

Vegetable oil family 6

Silicone oils 8-12

Petroleum oils 10

Typical ester 12
emollients
Fatty acids and 14-15
Alcohols
How do we determine the “required’
HLB of a lipophilic ingredient?

• We run a simple practical test

– eight small experiments
• Materials need for this test:
– an HLB “kit”
– about 200 grams of your oil
– eight small jars
– the instructions
– and a little bit of time
What is an HLB “kit” ?

• A series of jars of nonionic surfactant blends

– HLB 2 8% SPAN®80 / 92% SPAN 85
– HLB 4 88% SPAN80 / 12% SPAN 85
– HLB 6 83% SPAN 80 / 17% TWEEN® 80
– HLB 8 65% SPAN 80 / 35% TWEEN 80
– HLB 10 46% SPAN 80 / 54% TWEEN 80
– HLB 12 28% SPAN 80 / 72% TWEEN 80
– HLB 14 9% SPAN 80 / 91% TWEEN 80
– HLB 16 60% TWEEN 20 / 40% TWEEN 80
How do we run the practical test
to determine a required HLB
• We prepare eight simple emulsions
– each with the same amount of oil
– each with the same amount of surfactant but with a
different HLB value
– each with the same amount of water and mixing
• we observe which emulsion appears to be the
most stable
– stable - meaning here the one least separated or the one
that separates last
• the HLB value of the surfactant used in this
emulsion is the HLB requirement for that
particular oil phase
Separation curves will look
something like this

120
100
80
60
40
20
0
4 8 12
6 10 14
How is knowing the required
HLB useful for a formulator
• One you know the required HLB of individual
oils it is easy to mathematically calculate the
required HLB of a mixture of oils

• knowing the required HLB of an oil or an oil

mixture means that you can use the least
amount of surfactant to achieve emulsification
Directions for using the HLB system to
select surfactants for an O/W emulsion

• Look at your formula

• determine which are the oil soluble ingredients
– this does not include the emulsifiers
• weigh each of the weight percents of the oil
phase ingredients together and divide each by
the total
• multiply these answers times the required HLB
of the individual oils
• add these together to get the required HLB of
your unique blend
For example

• A simple O/W lotion formula

– mineral oil 8%
– caprylic/capric triglyceride 2%
– isopropyl isostearate 2%
– cetyl alcohol 4%
– emulsifiers 4%
– polyols 5%
– water soluble active 1%
– water 74 %
– perfume q.s.
– preservative q.s.
Calculations:
add up the oil phase ingredients
– mineral oil 8%
– caprylic/capric triglyceride 2%
– isopropyl isostearate 2%
– cetyl alcohol 4%
» 16
– emulsifiers 4%
– polyols 5%
– water soluble active 1%
– water 74 %
– perfume q.s.
– preservative q.s.
Calculations:
divide each by the total to get the
contribution to the oil phase

• Mineral oil 8 / 16 = 50%

• caprylic/cap. trig. 2 / 16 = 12.5%

• isopropyl isostearate 2 / 16 = 12.5%

• cetyl alcohol 4 / 16 = 25%

Calculations for HLB of this
unique blend
Oil phase contribution X required equals
ingredient HLB of
ingredient
Mineral oil 50.0% 10.5 5.250

Caprylic 12.5% 5 0.625

cap. Trig.
Isopropyl 12.5% 11.5 1.437
isostearate
Cetyl 25.0% 15.5 3.875
alcohol
Total 11.2
How do we use this information
to our advantage?
• We know that as a starting point we should
select a surfactant system with an HLB value of
~11.2

• For the surfactant system we recommend that

you use a blend of at least two surfactants
– reason
• experience has shown the benefit
• mixtures of a low HLB and a high HLB surfactant
give better coverage at the interface
• a blend of two surfactants is typical
How do we use this information
to our advantage? ( Cont. )

• The correct HLB value usually translates to

superior stability at a lower use level. For
example:
– our unique formula with a surfactant blend at
HLB 11.2 at a 4% use level will most likely give
longer stability at elevated temperatures than 5%
of a blend at either HLB 10.2 or 13.2
Surfactant choice
considerations:
• Chemical type
– ester VS ether
– lipophilic group, e.g. lauryl VS stearyl
• Physical form
– liquid VS solid VS beads
• FDA “status” ( if any )
– is there an N. F. monograph
• Price VS function
• Blend VS single surfactant
• Efficiency of the surfactant
A very general recommendation
for o/w emulsions
• For topical O/W emulsions (the most common
type) we recommend:
– nonionics based on stearyl alcohol or stearic
acid
• the high molecular weight and high melting point
of the C-16/18 portion gives superior anchoring in
the dispersed oil droplets
• blends of steareth-2 with steareth-21 are the most
useful ( in our opinion )
– these are low and high HLB stearyl alcohol
ethoxylates
For Example :
ethoxylated fatty alcohol at HLB 15

Fatty alcohol Hydrophilic Lipophilic mol. Total mol.

mol. Wt. Wt. wt.

STEARYL
811 270 1081
OLEYL
805 268 1074
CETYL
726 243 969
LAURYL /
DODECYL
559 186 745
How do we calculate HLB value
of a surfactant blend ?
• Simple arithmetic, for example:
– a 50 / 50 blend of steareth-2 and steareth-21

– 50% times the HLB value of the steareth-2

• 0.5 X 4.9 = 2.45
– 50% times the HLB value of the steareth-21
• 0.5 X 15.5 = 7.75
– 2.45 + 7.75 = 10.2
Summary

• HLB is a number system that lets you know

how oils and surfactants will likely interact
• Surfactants have an HLB value
– the higher the number the more hydrophilic
– the lower the number the more lipophilic
• Oils and applications have an HLB requirement
• Matching the HLB value with the requirement
will give good performance
• It is not rocket science
– just a very useful time saving general guide
How to get in touch with me
( as of March 2004 )
• Web page
– www.uniqema.com
• Postal address here in the USA
– Uniqema Corporate Center
– 900 Uniqema Boulevard
– New Castle DE
– 19720-2790
• Customer service here in the USA
– 302-574-5872
• Me ( in the USA )
– Philip Haw,
– E-mail [email protected]
– phone 302-574-8415