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HLB & Emulsification

Description of Hydrophile, Lipophile Balance and use of HLB in Producing Emulsions

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Introduction to HLB: Surfactants are often characterized by their hydrophilic/lipophilic balance or HLB. High HLB values indicate good water, or polar solvent solubility, of the surfactant while low HLB values are indicative of good solubility in non polar systems, such as oil. The water loving, or hydrophilic character, of a surfactant is determined by the polarity of the head group. Typical head groups found in Akzo Nobel Surfactant products include, amine, quaternary ammonium, ethoxylate, sulfate, phosphate and carboxylate. The polarity of the head group may be altered in some cases by altering the pH or by increasing the degree of ethoxylation, e.g. increasing the ethoxylation levels increases the water loving character of the surfactant, and thus the HLB increases. Conversely, increasing the size of the fatty tail, or propoxylation of the head group will decrease the HLB. The Hydrophile, Lipophile Balance, (HLB) system is a useful tool in finding a suitable emulsifying system A vast number of emulsifiers (surfactants) are available to the formulator and the HLB system can be used as a guide to narrow the selection to those best suited to his specific system. The following discussion covers the determination of HLB of a surfactant: HLB Calculation: HLB calculation for nonionic products is obtained with the Griffin formula: HLB = 20 MW H/(MW H + MW L) = wt% hydrophile / 5 MW H = mol. wt. of hydrophile MW L = mol. wt. of hydrophobe Example: C10-8EO Hydrophobic part: CH3(CH2)9-OH Hydrophilic part: [CH2CH2O]8 MW = 158 MW = 352

HLB for C10-8EO = 20 x 352 / (352 + 158) =13.8

For ionic surfactants, the HLB values of individual surfactant molecules can be calculated applying the Davies formula. According to this formula the HLB is derived by summing the hydrophilic/hydrophobic contributions afforded by the structural components of the surfactant. HLB = (Hydrophilic group contributions) (Hydrophobic group contributions) + 7 Group contributions are listed in tables A - D. Tables A, B & C provide the group contributions of the hydrophilic groups and table D gives the contribution of the hydrophobic groups. Akzonobel uses Griffin formula for nonionic surfactants and Davis formula for ionic surfactants. Readers should be aware of the limitation of HLB for emulsion or microemulsion formulation development. HLB values reported in the literature are typically referred to the values at room temperature. As temperature varies, the HLB value of a surfactant may also vary. For example, an alcohol ethoxylate displaces a lower HLB at higher temperature. That is why nonionic surfactants usually produce a W/O emulsion or microemulsion at higher temperature.

Table A: anionic hydrophilic group contributions hydrophilic group HLB contribution hydrophilic group COO- Na+ 19.1 SO3- Na+ O - SO3- Na+

HLB contribution 20.7 20.8

Table B: cationic and betaine hydrophilic group contributions

Hydrophilic group HLB contribution Hydrophilic group HLB contribution NH2+- CH2 - CH2 - CH2 NH3+ 2 Cl38.6 CH3 / > N+ Cl22.5 \ CH3 CH3 19.2 N+- CH2 Cl CH3 CH2 - CH2 OH N+- CH3 Cl24.9 CH2 - CH2 OH CH2 CH2 OH / NH+- CH2 - CH2 - CH2 NH+ 2 Cl \ CH2 - CH2 - OH CH2 - CH2 OH 41.4 CH2 - CH2 OH l 2 3.8 NO (at pH = 3) L CH2 - CH2 OH CH3 N+- CH2 - COO38.0 CH3

NH3+ Cl20.0 >NH2+ Cl20.0 CH3 N+- CH3 Cl22.0 CH3 CH3 / > N+ Cl19.7 \ CH2 - CH2 - CH2 OH N+ H Cl21.9 CH2 - CH2 OH CH3 CH3 N+- CH2 - CH2 - CH2 - N+- CH3 2 Cl CH3 CH3 43.5 CH3 l 21.0 NO (at pH = 3) l CH3 CH3 N+- CH2 - COOH Cl24.1 CH3

Table C: cationic and nonionic hydrophilic group contributions hydrophilic group HLB hydrophilic group contribution NH2 > NH CH3 / N \ CH3 9.4 9.4 NH - CH2 - CH2 CH2 NH2

HLB contributi on 17.4

CH2 - CH2 OH / 8.5 N \ CH2 - CH2 OH 11.3

CH2 - CH2 OH / N - CH2 - CH2 - CH2 - N \ CH2 - CH2 OH CH2 - CH2 OH

O C - NH2

9.6

COOH OH

20.2 2.1 1.9

O CH2 - CH2 O CH2 - CH2 OH

1.3 0.33 0.95

Table D: hydrophobic group contributions hydrophobic group HLB contribution hydrophobic group CH3 0.475 CH = (unsaturated) CH2 0.475 CH2 - CH - (branched) 0.475 CH2 CH O CH3

HLB contribution 0.475 1.66 0.15

Example Calculation: The following calculation is based on tetradecyl trimethyl ammonium chloride: Tetradecyl trimethyl ammonium chloride has the following structure: CH3 l CH3 - (CH2)13 - N+- CH3 l CH3

Cl-

Group contribution of the hydrophobic groups: CH3 0.475 - CH2 0.475 Group contribution of the hydrophilic group: CH3 l - N+- CH3 l CH3

Cl22.0

HLB = 22.0 - (14 x 0.475) + 7 = 22.4 Surfactant Mixtures: In this case, the HLB value of a surfactant system is the weight average values of the respective surfactant components. For example, a mixture of 40 % Armeen 12D (HLB = 11.7) and 60 % Arquad 16 (as 100 % active) (HLB = 21.4) gives the following HLB value: HLB = (0.4 x 11.7) + (0.6 x 21.4) = 17.5

Cationic HLB Values: The Akzo Nobel fatty amine products have surfactant properties that can offer emulsifing properties. In literature HLB values for this class of surfactants are hardly found. Following is a list of HLB values for these products:

Table 1: HLB values of Akzo Nobel fatty amines and derivatives (accuracy: 10%). Some products convert to amine salts in acid conditions, and their resulting HLB depends on the pH. The following table is segmented by pH for those products that convert to salts. Products whose HLB are independent of pH are given in the far right column.

HLB at pH >9 Armeen 12D Armeen CD Armeen 16 Armeen HTD Armeen HT Armeen OD Armeen 18D Armeen 2C Armeen 2HT Armeen DMCD Armeen DM16D Armeen DMHTD Armeen DMOD Duomeen C Duomeen T Duomeen O Triameen YT Ethomeen C/12 10.7 10.2 8.8 8.3 8.3 8.2 7.9 4 0.1 9.3 7.9 7.3 7.2 18.2 16.3 16.2 24.2 12.1

HLB at pH <8 Armeen 12D Armeen CD Armeen 16 Armeen HTD Armeen HT Armeen OD Armeen 18D Armeen 2C Armeen 2HT Armeen DMCD Armeen DM16D Armeen DMHTD Armeen DMOD Duomeen C Duomeen T Duomeen O Triameen YT Ethomeen C/12 21.3 20.8 19.4 18.9 18.9 18.8 18.5 14.6 10.7 19.9 18.5 17.9 17.8 39.4 37.5 37.4 56 21

HLB independent of pH Armac C Duomeen TDO Arquad 12 Arquad C Arquad 16 Arquad HP Arquad HT Arquad S Arquad DMCB Arquad NF Arquad 2C Arquad 2HT Duoquad T Ethoquad C/12 Ethoquad HT/25 Ethoquad O/12 Ethoquad O/15 Ethoquad 18/25 22.9 25.9 23.3 22.8 21.4 20.8 20.9 20.8 21.7 21 17.1 13.2 42.4 25.7 28 23.7 24.6 27.6

Table 1 (continued): HLB values of derivatives (accuracy: 10%), continued HLB at pH >9 Ethomeen C/15 Ethomeen C/25 Ethomeen T/15 Ethomeen T/20 Ethomeen T/30 Ethomeen S/12 Ethomeen 18/15 Ethomeen O/12 Ethoduomeen T/25 Ethomid O/15 Aromox 14DW-970 Aromox C/12 Aromox DMC Aromox T/12 13.3 16.4 11.1 12.8 16.1 10.1 10.7 9.8 23.1 11.2 18.6 21.8 21.9 19.9 HLB at pH <8 Ethomeen C/15 Ethomeen C/25 Ethomeen T/15 Ethomeen T/20 Ethomeen T/30 Ethomeen S/12 Ethomeen 18/15 Ethomeen O/12 Ethoduomeen T/25 Ethomid O/15 Aromox 14DW-970 Aromox C/12 Aromox DMC Aromox T/12 23.7 27 21.7 23.4 26.7 20.7 21.3 20.4 44.3 21.8 21.4 24.6 24.7 22.7

Nonionic HLB Values: Our nonionic surfactants offer a wide range of HLB values. These products have HLB reported by the Griffin method. Nonyl Phenol Alkoxylates: Witconol nonyl phenol based nonionic surfactants are used in many industries. They are very good at wetting, dispersion, and emulsification. Table 3: Product Name WITCONOL NP-40 WITCONOL NP-90 WITCONOL NP-100 WITCONOL NP-200 WITCONOL NP-400 HLB 8.9 13 13.1 16 17.8

Alkyl Alkoxylates: The Ethylan family contains other nonionic surfactants.

Table 4: Product Name

ETHYLAN 1005 ETHYLAN 1008 ETHYLAN 1206 ETHYLAN 25-3 ETHYLAN 324 ETHYLAN DA-4 ETHYLAN LA-230 ETHYLAN SN-70 ETHYLAN SN-90 ETHYLAN TD-60

HLB
11.6 14 9.5 8 8 10.5 17 12 12.9 11.4
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Ethoxylated Castor Oil: The Emulpon trade mark is for our castor oil ethoxylates. These are best for emulsifying oil in water, or water in oil. Table 5: Product Name EMULPON CO-200 EMULPON CO-360 EMULPON CO-550 Fatty Esters: We also offer a line of fatty esters under the Witconol product name. These products find use as emulsifiers and dispersants in a variety of industrial and consumer applications. The following HLB data for these products is reported using the Griffin method. Table 6: Product Name WITCONOL 14 WITCONOL H-31A WITCONOL H-32 WITCONOL H-33 HLB 6 12.5 10 8.4 HLB 10.2 13.5 14.4

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Emulsification by HLB: In order to emulsify a mixture of water and oil one or more emulsifiers is required. Each surfactant system (pure or mixture) can be characterized by an HLB value. Each oil/water system can be characterized by a so-called required HLB value. This value depends on the nature of the oil and the product application. Basically, there are two types of product application. In one type water dominates; the oil forms droplets. This is designated as a oil in water (O/W) system. In the other type it is reversed. The system is essentially water in oil (W/O). The HLB system predicts the optimum emulsion stability when the HLB value of the surfactant systems matches the required HLB of the oil/water system. The required HLB is the value at which enhanced emulsion stability will be attained. Optimization of the performance can be achieved by only including surfactant systems with similar HLB values. The following figure illustrates the effect of different surfactant systems on the stability of an emulsion. It shows the matching of the surfactant system HLB and the required HLB of the oil/water system. For each surfactant system emulsion stability reaches a maximum at the same HLB value. Figure #1
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preformance in arbitrary units

30 20 10 0 9 10 11 12 13 14 15 HLB of surfactant mixture 6 7 8 A C B

Idealized model of enhanced performance. Regardless of the surfactant mixture (A,B or C) at the required HLB of the system performance is enhanced. This effect may be stronger (example C) or less pronounced (example B).
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When To Use the HLB System: The HLB model can be used for applications including emulsification, detergency, solubalization and other applications. Typically a HLB value will dictate these properties, as shown in table 7:

Table 7: Suggested HLB values for a number of applications Defoaming of aqueous systems 1-3 Detergency & cleaning 12 - 15 W/O emulsification 3-6 O/W emulsification 8 - 28 Solubilization 11 - 18 Wetting 7-9 Procedure for Using the HLB System: The HLB system allows for a straightforward approach. Good results can be achieved in three steps. First of all the required HLB of the formulation system must be identified. Then, the best surfactant ingredient must be found. Several (mixtures of) ingredients, all having an HLB equal to the required HLB, must be included. The choice is determined by the test result. The final step is varying the amount.

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Determine Required HLB: For ordinary oil in water (O/W) or water in oil (W/O) emulsification the required HLB are given in tables 8 (O/W emulsification) and 9 (W/O emulsification). TABLE 8: Required HLB for O/W emulsions of a variety of oils ( 1)* Acetophenone 14 Ethyl Aniline 13 Mineral Spirits Arachidyl 7 Ethyl Benzoate 13 Mink Oil Propionate Benzene 15 Fatty Acids 14-16 Nitro Benzene Benzonitrile 14 Fatty Alcohols 11-16 Nonylphenol Bromobenzene 13 Fenchone 12 o-dichlorobenzene Butyl Stearate 11 Glycerol 13 Palm Oil Monostearate Carbon 16 Hydrogenated 6-7 Petrolatum Tetrachloride Peanut Oil Castor Oil 14 Isopropyl 11-12 Petroleum Naphta Myristate Chlorinated 12-14 Isopropyl 14 Pine Oil Paraffin Lanolate Chlorinated 12-14 Isopropyl 11-12 Propene, tetramer Paraffin Palmitate Chlorobenzene 13 Jojoba Oil 6-7 Rapeseed Oil Corn Oil 10 Kerosene 12 Silicone Oil Cottonseed Oil 5-6 Liquid Lanolin 9 Soybeen Oil Cyclohexane 10 Lauryl Amine 12 Styrene Decyl Acetate 11 Mehadin Oil 12 Toluene Diethyl Aniline 14 Methylphenyl 7 Trichlorotrifluoro Silicone Ethane Diisooctyl 13 Methyl Silicone 11 Tricresyl Phthalate Phosphate Diisopropyl 9 Mineral Oil 9-12 Xylene Adipate Diisopropyl 15 Benzene Dimethyl 9 *LITERATURE Silicone VALUES Table 9: required HLB for W/O emulsions of a number of oils ( 1)* Gasoline 7 Kerosene 6 Mineral Oil *LITERATURE VALUES

14 5 13 14 13 10 7-8 14 16 14 6 7-8 6 15 15 14 17 14

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It is likely that your oil system is not listed in the tables. In these cases one has to determine the required HLB value. In essence such determination consists of three steps. However the salinity, pH and temperature of these steps must be consistent. First, choose a surfactant system containing at least two surfactants with a significant difference in HLB value. Then, the product formulation? must be made? including this surfactant system. It must be done several times. Each time the surfactants must be mixed in another ratio in order to create different HLB values. Finally, the performance must be determined and plotted vs. the HLB (as shown in Figure 1). A maximum will appear in the plot. The corresponding HLB maximum is equal to the required HLB. One can then use statistical methods to determine the optimal level of ingredients for your formula. If no maximum value is noted in the above procedure then one can deduce that HLB is not essential to your formulation. To make choices of the surfactants more easily, table 10 provides indicative values of required HLBs of most common applications. Table 10: indicative required HLB for a number of applications defoaming of aqueous systems 13 detergency & cleaning 12 15 W/O emulsification 36 O/W emulsification 8 28 Solubilization 11 18 Wetting 79

FURTHER READING The HLB System, a Time Saving Guide to Emulsifier Selection, ICI Americas Inc., version 1980 Davies, J.T. & Rideal, E.K., Interfacial Phenomena, 2nd ed., p 371, Academic Press, London, 1963 Lin, I.J. & Marszall, L., Tenside Det., 15, 243 (1978) O Boen Ho, J. Colloid Interface Sci., 198, 249 (1998)

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HLB & Emulsification

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2011 Akzo Nobel Surface Chemistry LLC Publication: SC-11-02

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