Hydrophilic-Lipophilic Balance (HLB) in
Cosmetic Formulation
Introduction to HLB Theory
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The Hydrophilic-Lipophilic Balance (HLB) is a fundamental concept in emulsion science
that quantifies the balance between the hydrophilic (water-loving) and lipophilic (oil-loving)
portions of surfactant molecules. Developed by William Griffin in 1949, the HLB system
provides a numerical scale from 0 to 20 that helps formulators predict and control emulsion
behavior in cosmetic products.
Chemistry Behind HLB
Molecular Structure and HLB
Surfactants and emulsifiers consist of two distinct parts: a hydrophilic head group and a
lipophilic tail. The HLB value reflects the relative size and strength of these portions. The
molecular weight ratio between the hydrophilic and lipophilic segments determines the
overall HLB value.
The fundamental chemistry involves:
• Hydrophilic groups: hydroxyl (-OH), carboxyl (-COOH), sulfate (-SO4), and
polyethylene oxide chains
• Lipophilic groups: hydrocarbon chains, typically fatty acid derivatives
HLB Calculation Methods
Griffin's Original Method: For polyethylene glycol derivatives: HLB = 20 × (Mh/M)
Where:
• Mh = molecular weight of hydrophilic portion
• M = total molecular weight
For fatty acid esters: HLB = 20 × (1 - S/A)
Where:
• S = saponification number of ester
• A = acid number of fatty acid
Davies Method: HLB = 7 + Σ (hydrophilic group numbers) – Σ (lipophilic group numbers)
This method assigns specific numerical values to different chemical groups, providing more
precision for complex molecules.
HLB Scale and Applications
HLB Value Ranges and Functions
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The HLB scale correlates specific ranges with emulsion types and applications:
• HLB 1-3 : Antifoaming agents
• HLB 4-6 : Water-in-oil (W/O) emulsifiers
• HLB 7-9 : Wetting agents
• HLB 8-18 : Oil-in-water (O/W) emulsifiers
• HLB 13-15 : Detergents
• HLB 15-18 : Solubilizers
Critical Packing Parameter
The HLB concept relates to the critical packing parameter (CPP), which predicts aggregate
structure based on molecular geometry:
CPP = V/ (A × lc)
Where:
• V = volume of hydrophobic chain
• A = area of hydrophilic head group
• lc = critical chain length
Different CPP values correspond to different aggregate structures and HLB ranges.
HLB in Cosmetic Formulation
Emulsion Type Selection
The choice between water-in-oil and oil-in-water emulsions depends on the required HLB of
the oil phase and the available emulsifiers:
Water-in-Oil Emulsions (HLB 4-6):
• Heavy creams and ointments
• Barrier creams
• Makeup bases
• Products requiring occlusive properties
Oil-in-Water Emulsions (HLB 8-18):
• Light moisturizers
• Lotions
• Cleansing products
• Most modern cosmetic emulsions
Required HLB Concept
Each oil or oil blend has a characteristic "required HLB" value representing the HLB needed
for optimal emulsification. This concept allows formulators to:
1. Determine the required HLB of oil phases
2. Select appropriate emulsifier systems
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3. Blend emulsifiers to achieve target HLB values
Blending Emulsifiers for Optimal HLB
When a single emulsifier doesn't provide the required HLB, blending multiple emulsifiers can
achieve the target value:
HLB blend = (HLB A × %A) + (HLB B × %B)
Where percentages represent the weight fraction of each emulsifier in the blend.
Choosing the Right Emulsifier Based on HLB
Step-by-Step Selection Process
1. Determine Oil Phase Required HLB:
• Test different HLB values with the specific oil blend
• Identify the HLB that produces the most stable emulsion
• Common required HLB values for oils range from 4-12
2. Select Emulsifier System:
• Choose emulsifiers compatible with the formulation pH and other ingredients
• Consider regulatory requirements and labeling preferences
• Evaluate cost and availability
3. Calculate Emulsifier Blend:
• Use mathematical blending to achieve required HLB
• Typically combine low HLB (4-6) and high HLB (12-16) emulsifiers
• Maintain total emulsifier concentration between 2-8% typically
Practical Emulsifier Selection Guidelines
For W/O Emulsions:
• Primary emulsifiers: Sorbitan esters, glyceryl stearate, cetyl alcohol
• HLB range: 4-6
• Often combined with co-emulsifiers for stability
For O/W Emulsions:
• Primary emulsifiers: Polysorbates, ceteareth-20, steareth-21
• HLB range: 8-16
• May require secondary emulsifiers for enhanced stability
Specialty Considerations:
• Natural/organic formulations: Plant-based emulsifiers with appropriate HLB
• Sensitive skin products: Gentle emulsifiers with minimal irritation potential
• High-performance products: Emulsifier systems providing additional benefits
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Factors Affecting HLB in Formulation
Temperature Effects
Temperature significantly impacts HLB behavior:
• Higher temperatures generally favor higher HLB emulsifiers
• Phase inversion temperature (PIT) relates directly to HLB
• Emulsification often performed at elevated temperatures then cooled
pH Influence
pH affects the ionization state of emulsifiers:
• Ionic emulsifiers show pH-dependent HLB changes
• Nonionic emulsifiers remain relatively stable across pH ranges
• Buffer systems may be necessary for consistent performance
Ionic Strength and Electrolytes
Salt concentration affects emulsifier performance:
• High ionic strength can destabilize O/W emulsions
• May require HLB adjustments or alternative emulsifier systems
• Particularly important in formulations with high active concentrations
Oil Phase Composition
Different oils require different HLB values:
• Polar oils (esters, alcohols): Higher required HLB
• Nonpolar oils (hydrocarbons, silicones): Lower required HLB
• Mixed oil systems: Weighted average required HLB
Advanced HLB Applications
Microemulsions and Nanoemulsions
Ultra-fine emulsions require precise HLB optimization:
• Narrow HLB ranges for transparent systems
• Often require co-surfactant systems
• Specialized measurement techniques for characterization
Pickering Emulsions
Solid particle-stabilized emulsions represent an alternative to traditional HLB-based systems:
• Particles act as emulsifiers
• Contact angle determines emulsion type
• Growing interest in cosmetic applications
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HLB Limitations and Alternatives
While HLB remains valuable, limitations include:
• Temperature dependence not fully captured
• Limited applicability to modern complex emulsifiers
• Alternative methods like hydrophilic-lipophilic deviation (HLD) provide enhanced
predictive capability
Quality Control and Testing
HLB Verification Methods
Emulsion Stability Testing:
• Microscopic examination for droplet size distribution
• Centrifuge testing for phase separation
• Temperature cycling for accelerated aging
Conductivity Testing:
• Distinguishes between O/W and W/O emulsions
• Monitors phase inversion
• Simple quality control method
Rheological Measurements:
• Viscosity profiling
• Yield stress determination
• Temperature-dependent behavior
Troubleshooting HLB-Related Issues
Common Problems and Solutions:
• Phase inversion: Adjust HLB or emulsifier concentration
• Poor stability: Optimize HLB match or add stabilizers
• Inadequate viscosity: Modify emulsifier system or add thickeners
The HLB system remains a cornerstone of cosmetic emulsion formulation, providing both
theoretical understanding and practical tools for creating stable, effective products. While
modern formulation has expanded beyond traditional HLB limitations, the fundamental
principles continue to guide emulsifier selection and system optimization in contemporary
cosmetic development.
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