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HLB & Emulsion Stability

By- Vidya Jain & Disha Pandya


R&D, Zydus Wellness Ltd.
Date : 12.03.2019
What is Emulsion?

• Emulsion: Thermodynamically unstable system containing 2


immiscible liquids. An emulsion is a two-phase system
prepared by combining two immiscible liquids, in which small
globules of one liquid are dispersed uniformly throughout the
other liquid.
• Thermodynamic instability is due to-
1.large increase in surface energy that results from the
combination of interfacial tension and large surface
area of the dispersed phase
2. The different densities of the two phases.
• The thermodynamic stability can be achieved by use of
emulsifiers / surfactants which reduce interfacial tension
significantly making the 2 liquids miscible.
Types of emulsions
• o/w: continuous / external phase-Water and dispersed /
internal phase- oil
• w/o: Continuous /external phase – Oil and dispersed /
internal phase- water

Reasons of emulsion
destabilization
• Coalescence
• Creaming

Fig 1.0-Effect of rate of coalescence on emulsion type. Davies


Theory Rate 1:O/W coalescence rate. Rate 2: W/O
coalescence rate.
Emulsion stabilization mechanism

Fig 2.0-Types of films formed by emulsifying agents at the oil–


water interface. Orientations are shown for O/W emulsions
What is HLB?
• Hydrophile Lipophile Balance:
• In 1949, William C. Griffin developed the Hydrophile-Lipophile
Balance System or the HLB System whereby emulsifying or
surface-active agents can be categorized on the basis of their
hydrophilic to lipophilic balance.
• HLB is a numerical system used to describe the relationship
between the water-soluble and oil-soluble parts of a nonionic
surfactant.
• Emulsifiers often have a hydrophilic portion (head) and a
lipophilic portion (tail) with one or the other being more or less
predominant.

Fig. 3.0 Types of surfactants


What is HLB?

• The HLB values have been assigned from 1-40 but commonly
used emulsifiers fall in the range 1-20.
• Each emulsifier is assigned a HLB value/number indicative of
the substance polarity.
• Higher hydrophillicity- Higher water solubility- High HLB
towards 20. Higher Lipophillicity-higher oil solubility- Low HLB
towards 1
• SPANS( Sorbitan Esters) have low HLB values. Tweens (POE
derivatives of Sorbitan Esters) have High HLB values
HLB Scale showing Surfactant function
HLB Value –Function of surfactant as per
Griffin’s Scale
HLB Value Type of emulsifier Type of emulsion promoted
0-10 Lipophillic emulsifiers w/o
10-20 Hydrophillic emulsifiers o/w

• The phase in which Emulsifier has higher solubility tends to form external phase

HLB Value Function of surfactant/ emulsifying agent


1-3 Antifoaming agent
4-6 w/o emulsifying agents
7-10 Good wetting agents
8-18 O/W emulsifying agents
13-15 Detergents
10-18 Solubilizers

Sr no Type of emulsion Weighed HLB value of oil phase


1. Oil in water 8-16
2. Water in Oil 3-8
HLB-calculation
• The HLB value of a nonionic surfactant, having the Hydrophilic group
like polyhydric alcohol (-OH) or Ethylene Oxide (EO) or POE as a
hydrophilic part, can be calculated with the equation-

HLB= E / 5
E: Percentage by weight of ethylene oxide units

• HLB value of fatty acid esters of polyhydric alcohols such as Glyceryl


Monostearate is calculated with that equation-

HLB= 20 [1-(S / A)]

S: Number of ester saponification


A: Acid number of the fatty acid
HLB Values of common emulsifiers
HLB Values- water dispersibility
HLB, R-HLB and Emulsion

• R-HLB: During selection of emulsifier by application of HLB


system, it is required to take into consideration the presence /
absence of polarity in the material to be emulsified.
Depending on the polarity the required HLB of oil phase
changes.
• R-HLB: HLB Value required by a material to be emulsified
effectively to form a stable emulsion.
• R-HLB varies depending on emulsion to be formed is O/W or
W/O.
• Griffin after lot of experimentation established R-HLB list of
many oil and oil phase ingredients.
HLB, R-HLB and Emulsion
• R HLB values of some common emulsion ingredients
HLB, R-HLB Calculation
• HLB values are algebraically additive.
• by using a low HLB surfactant with a high HLB surfactant it is possible to
prepare blends having HLB values intermediate between those of the two
individual emulsifiers.
• O/W Emulsion
Liquid petrolatum (Required HLB 10.5) 50 g
Emulsifying agents 5g
Sorbitan monooleate (HLB 4.3)
Polyoxyethylene 20 sorbitan monoleate (HLB 15.0)
Purified Water qs. 100 g
Total % of oil phase =50% and water phase=50%
Oil Phase %w/w R-HLB value Part RHLB
component
Liquid petrolatum/ 50 10.5 10.5*50/50=10.5
mineral oil heavy
HLB, R-HLB Calculation
Alligation method to arrive at proportion of emulsifiers:
Sorbitan monooleate(SMO) (HLB 4.3) 15.0-10.5=4.5 PARTS
(SPAN 80)
RHLB 10.5

POE20 SMO(HLB 15.0) 10.5-4.3=6.2 PARTS


(Tween 80) Total =4.5+6.2=10.7 parts

Blend of [4.5parts of Sorbitan Monooleate+6.2 parts of POE20sorbitan


monooleate]= mixed emulsifier of RHLB 10.5
Since Emulsifying agent assumed qty= 5 g
4.5x+6.2x=5.0
10.7 x=5.0
X= 5.0/10.7=0.4673
Thus qty of SMO= 4.5X=4.5*0.4673=2.1
Qty of POE20SMO= 6.2X= 6.2*0.4673= 2.897=2.9
HLB, R-HLB Calculation
• The same effective RHLB can be achieved by many different
combinations of emulsifiers.

• Griffins HLB system can help identify the Emulsifier system that
can provide RHLB demanded by the system but not the exact
concentration of emulsifier.
Baby Lotion
HLB Calculation Baby Lotion
16% Oil Phase
70% water phase
14%excipients

%w/w % weight
R-HLB contribution of
Components Value oil phase part RHLB
C*R-HLB
W C /100
Cetyl Alcohol 15.5 2.5 15.63 2.42
Biophilic HM B
(Hydrogenated
lecithin (and)
12.5 3.00 18.75 2.34
C12-16 alcohols
(and) Palmitic
acid)
Heptyl
7.5 3.5 21.88 1.64
Undecylenate Assumed of cyclomethicone 7.5
VCO 8.0 1.0 6.25 0.50
Oleosoft O-4 5.56 1.5 9.38 0.52
dicaprylyl
9.0 2.5 15.63 1.41
carbonate assumed of diisopropyl adipate 9.0
Perfume 8.0 1.0 6.25 0.50 essential oils ( 6-10)
Tocopherol
6.0 1.0 6.25 0.38
(Vitamin E)
Total Oil Phase
16 100.00 9.71
(%w/w)
HLB Calculation Baby Lotion

RHLB 9.71
Emulsifier by
part Mixed emulsifier
Biophillic HMB % of
HLB Emulsifier Actually used
12.5 9.71-5.5 4.21 60.14 4.00
9.71
GMS SE HLB
5.5 12.5-9.71 2.79 39.86 3.00
7.0 100.00 7.0