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Technical Information Surface Chemistry
HLB & Emulsification
Description of Hydrophile, Lipophile Balance and use of HLB in Producing Emulsions
According to this formula the HLB is derived by summing the hydrophilic/hydrophobic contributions afforded by the structural components of the surfactant. HLB = Σ (Hydrophilic group contributions) – Σ (Hydrophobic group contributions) + 7 Group contributions are listed in tables A . The Hydrophile. Lipophile Balance. such as oil. The following discussion covers the determination of HLB of a surfactant: HLB Calculation: HLB values of individual surfactant molecules can be calculated applying the Davies formula. The polarity of the head group may be altered in some cases by altering the pH or by increasing the degree of ethoxylation. (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.D. The water loving. 2 . of the surfactant while low HLB values are indicative of good solubility in non polar systems. or propoxylation of the head group will decrease the HLB. increasing the size of the fatty tail. or polar solvent solubility. of a surfactant is determined by the polarity of the head group. phosphate and carboxylate. e. Tables A.g. and can accommodate the types of products we offer. High HLB values indicate good water.Introduction to HLB: Surfactants are often characterized by their hydrophilic/lipophilic balance or HLB. ethoxylate. and thus the HLB increases. B & C provide the group contributions of the hydrophilic groups and table D gives the contribution of the hydrophobic groups. quaternary ammonium. increasing the ethoxylation levels increases the water loving character of the surfactant.. sulfate. or hydrophilic character. Conversely. Akzo Nobel Surfactants uses the Davies formula as it is a wide scale of 0 – 40. amine. Typical head groups found in Akzo Nobel Surfactant products include.
CH3 Cl24.7 20.SO3.7 19.0 – NH2+.0 38.5 │ \ CH3 CH3 CH3 CH3 / │ > N+ Cl19.Table A: anionic hydrophilic group contributions hydrophilic group HLB contribution hydrophilic group – COO.CH2 –.Na+ 19.0 │ │ CH3 CH3 3 .6 CH3 CH3 │ / – N+.CH2 – OH CH2 .CH2 – NH3+ 2 Cl>NH2+ Cl20.CH2 – OH CH3 CH3 CH2 – CH2 – OH │ │ / – N+.1 – SO3.CH2 – OH l l 2 3.8 21.9 – N+.CH2 .1 – N+.CH2 .CH2 ∅ Cl\ │ CH3 CH2 .CH2 .N+.Na+ HLB contribution 20.CH2 – OH CH2 .CH2 – OH CH3 CH3 │ │ – N+.CH2 – NH+ 2 Cl│ │ │ \ CH3 CH3 CH2 .CH3 2 Cl– NH+.4 CH3 CH2 .CH2 .9 │ │ CH2 .8 Table B: cationic and betaine hydrophilic group contributions Hydrophilic group HLB Hydrophilic group HLB contribution contribution – NH3+ Cl20.0 > N+ Cl22.0 –N→O –N→O (at pH = 3) (at pH = 3) l L CH3 CH2 .CH2 .CH3 Cl22.CH2 .5 41.COO38.2 – N+.OH CH2 .Na+ – O .∅ CH2 .CH2 .COOH Cl24.CH2 – OH │ │ – N+– H Cl21.CH2 .CH2 – OH 43.CH2 .
475 – CH = (unsaturated) – CH2 0.CH2 .NH2 9.4 17.CH2 – O – – CH2 .CH2 .66 0.1 1.2 2.475 – CH2 .CH2 – OH 1.3 \ \ CH3 CH2 .4 – NH .CH2 .CH2 – OH / – N .(branched) 0.CH2 – OH / / –N 8.475 – CH2 – CH – O – ⏐ ⏐ CH3 HLB contribution 0.CH2 – CH2 – NH2 > NH 9.33 0.4 CH3 CH2 .CH2 .CH2 – OH CH2 .CH2 – OH CH2 .15 4 .3 0.∅ – CH .CH2 – OH O ║ – C .9 –O– – CH2 .N ⏐ \ CH2 .475 1.95 Table D: hydrophobic group contributions hydrophobic group HLB contribution hydrophobic group – CH3 0.6 – COOH – OH 20.Table C: cationic and nonionic hydrophilic group contributions hydrophilic group HLB hydrophilic group HLB contribution contribution – NH2 9.5 –N 11.
0 .Example Calculation: The following calculation is based on tetradecyl trimethyl ammonium chloride: Tetradecyl trimethyl ammonium chloride has the following structure: CH3 l CH3 .4) gives the following HLB value: HLB = (0. the HLB value of a surfactant system is the weight average values of the respective surfactant components.7) + (0.6 x 21.CH3 l CH3 Cl- Group contribution of the hydrophobic groups: CH3 0.475 .(CH2)13 .4) = 17.5 5 .N+.475 Group contribution of the hydrophilic group: CH3 l .7) and 60 % Arquad 16 (as 100 % active) (HLB = 21.475) + 7 = 22. a mixture of 40 % Armeen® 12D (HLB = 11. For example.(14 x 0.4 Surfactant Mixtures: In this case.0 HLB = 22.CH3 l CH3 Cl22.4 x 11.N+.CH2 0.
The following table is segmented by pH for those products that convert to salts.3 22.8 21.8 18.6 10.5 37.3 7.9 20.9 18. 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 10.5 14.8 8.9 23.3 20.7 28 23.Cationic HLB Values: The Akzo Nobel fatty amine products have surfactant properties that can offer emulsifing properties.8 39.7 21 17.9 4 0.1 9. Products whose HLB are independent of pH are given in the far right column. Following is a list of HLB values for these products: Table 1: HLB values of Akzo Nobel fatty amines and derivatives (accuracy: ± 10%).9 18.8 19.1 13.4 20. and their resulting HLB depends on the pH.2 7.6 6 .3 16.3 7.9 25.4 37.8 21.6 27.4 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 22.2 42.3 8.2 8.3 8.5 17. Some products convert to amine salts in acid conditions.2 16.1 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 21.7 10.7 19.9 7.4 18.8 20.7 24.2 12.9 18.9 17. In literature HLB values for this class of surfactants are hardly found.4 25.2 24.2 18.
1 10.3 16.7 27 21.1 11.7 22.7 20.7 23.4 44.7 21.8 21.4 11.8 16.4 26.4 24.1 12.Table 1 (continued): HLB values of derivatives (accuracy: ± 10%).1 10.6 24.8 21.8 23.3 21.3 20.2 18.7 7 .6 21.9 19.7 9. 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 13.9 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.
9 13 13. They are very good at wetting.4 8 . Nonyl Phenol Alkoxylates: Witconol™ nonyl phenol based nonionic surfactants are used in many industries. and emulsification.5 17 12 12. dispersion. Table 3: Product Name WITCONOL NP-40 WITCONOL NP-90 WITCONOL NP-100 WITCONOL NP-200 WITCONOL NP-400 HLB 8.9 11.8 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 11.1 16 17.6 14 9.5 8 8 10.Nonionic HLB Values: Our nonionic surfactants offer a wide range of HLB values.
Ethoxylated Castor Oil: The Emulpon™ trade mark is for our castor oil ethoxylates. These are best for emulsifying oil in water.5 10 8.5 14. These products find use as emulsifiers and dispersants in a variety of industrial and consumer applications. Table 6: Product Name WITCONOL 14 WITCONOL H-31A WITCONOL H-32 WITCONOL H-33 HLB 6 12. or water in oil.4 HLB 10.2 13. 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.4 9 .
Figure #1 40 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. The required HLB is the value at which enhanced emulsion stability will be attained. 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.B or C) at the required HLB of the system performance is enhanced. It shows the matching of the surfactant system HLB and the required HLB of the oil/water system. 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. Basically. the oil forms droplets. The system is essentially water in oil (W/O). there are two types of product application. Optimization of the performance can be achieved by only including surfactant systems with similar HLB values. This is designated as a oil in water (O/W) system. This effect may be stronger (example C) or less pronounced (example B). For each surfactant system emulsion stability reaches a maximum at the same HLB value. This value depends on the nature of the oil and the product application. In the other type it is reversed.Emulsification by HLB: In order to emulsify a mixture of water and oil one or more emulsifiers is required. 10 . In one type water dominates. The following figure illustrates the effect of different surfactant systems on the stability of an emulsion.
15 W/O emulsification 3-6 O/W emulsification 8 . The final step is varying the amount. the best surfactant ingredient must be found. as shown in table 7: Table 7: Suggested HLB values for a number of applications Defoaming of aqueous systems 1-3 Detergency & cleaning 12 .When To Use the HLB System: The HLB model can be used for applications including emulsification. detergency. must be included. Then. Good results can be achieved in three steps. The choice is determined by the test result. Several (mixtures of) ingredients. 11 . all having an HLB equal to the required HLB.18 Wetting 7-9 Procedure for Using the HLB System: The HLB system allows for a straightforward approach.28 Solubilization 11 . solubalization and other applications. Typically a HLB value will dictate these properties. First of all the required HLB of the formulation system must be identified.
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 6 12 .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).
. 198. version 1980 Davies. However the salinity.. Academic Press... Colloid Interface Sci. “Interfacial Phenomena”.J. pH and temperature of these steps must be consistent. If no maximum value is noted in the above procedure then one can deduce that HLB is not essential to your formulation.T.. p 371.K. One can then use statistical methods to determine the optimal level of ingredients for your formula. London. table 10 provides indicative values of required HLB’s of most common applications. & Marszall. First. ICI Americas Inc. Each time the surfactants must be mixed in another ratio in order to create different HLB values. In essence such determination consists of three steps. 249 (1998) 13 . J. The corresponding HLB maximum is equal to the required HLB. 243 (1978) O Boen Ho. Finally. 2nd ed. To make choices of the surfactants more easily. choose a surfactant system containing at least two surfactants with a significant difference in HLB value. Then. Tenside Det. E.. It must be done several times. the performance must be determined and plotted vs. & Rideal. L. the HLB (as shown in Figure 1). 1963 Lin. J.It is likely that your oil system is not listed in the tables. In these cases one has to determine the required HLB value. Table 10: indicative required HLB 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 FURTHER READING • • • • “The HLB System. the product formulation? must be made? including this surfactant system. I. a Time Saving Guide to Emulsifier Selection”. A maximum will appear in the plot. 15.
and should refrain from any unauthorized use. as to the products’ merchantability or fitness for any particular purpose. or that any suggested use will not infringe any patent. samples or assistance please contact your local sales representative or the Akzo Nobel Customer Service Department at: Akzo Nobel Surface Chemistry LLC 525 W. Akzo Nobel Surface Chemistry LLC and its affiliates. by preliminary tests or otherwise. distribute and/or photocopy this document only if unaltered and complete. You may not copy this document to a website.akzonobelusa. however.HLB & Emulsification Customer Service For additional information. The information contained herein supersedes all previously issued bulletins on the subject matter covered. The user may forward. including all of its headers and footers. Nothing contained herein shall be construed as granting or extending any license under any patent.com All information concerning these products and/or all suggestions for handling and use contained herein are offered in good faith and believed to be reliable. the suitability of these products for his purposes. Van Buren Street Chicago IL 60607-3823 (800) 906-9977 (312) 544-7000 http://www. Buyer must determine for himself. make no warranty as to the accuracy and/or sufficiency of such information and/or suggestions. ©2008 Akzo Nobel Surface Chemistry LLC Publication: SC-08-06 14 .surface.
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