AkzoNobel Tb HlbEmulsions

Akzo Nobel Surface Chemistry LLCTechnical Information Surface Chemistry HLB & Emulsification Description of Hydrophile, Lipophile Balance and use of HLB in Producing Emulsions http://surface.akzonobel.com 1 phosphate and carboxylate. increasing the size of the fatty tail. and thus the HLB increases. e. such as oil. (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.g. The Hydrophile. wt. of hydrophile MW L = mol. amine. 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. The water loving.8 2 . Typical head groups found in Akzo Nobel Surfactant products include. of a surfactant is determined by the polarity of the head group. High HLB values indicate good water. Conversely. or hydrophilic character. ethoxylate. or propoxylation of the head group will decrease the HLB. of the surfactant while low HLB values are indicative of good solubility in non polar systems.Introduction to HLB: Surfactants are often characterized by their hydrophilic/lipophilic balance or HLB. or polar solvent solubility. sulfate. Lipophile Balance. increasing the ethoxylation levels increases the water loving character of the surfactant. wt. 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. The polarity of the head group may be altered in some cases by altering the pH or by increasing the degree of ethoxylation. quaternary ammonium. For ionic surfactants.8 3 . B & C provide the group contributions of the hydrophilic groups and table D gives the contribution of the hydrophobic groups. the HLB value of a surfactant may also vary. HLB values reported in the literature are typically referred to the values at room temperature.D. HLB = Σ (Hydrophilic group contributions) – Σ (Hydrophobic group contributions) + 7 Group contributions are listed in tables A .SO3. the HLB values of individual surfactant molecules can be calculated applying the Davies formula. an alcohol ethoxylate displaces a lower HLB at higher temperature. According to this formula the HLB is derived by summing the hydrophilic/hydrophobic contributions afforded by the structural components of the surfactant.1 – SO3.Na+ HLB contribution 20.Na+ 19. Akzonobel uses Griffin formula for nonionic surfactants and Davis formula for ionic surfactants.Na+ – O . Readers should be aware of the limitation of HLB for emulsion or microemulsion formulation development. For example. Table A: anionic hydrophilic group contributions hydrophilic group HLB contribution hydrophilic group – COO. That is why nonionic surfactants usually produce a W/O emulsion or microemulsion at higher temperature. Tables A. As temperature varies.7 20. 6 CH3 / > N+ Cl22.0 >NH2+ Cl20.CH2 – OH CH3 CH3 │ │ – N+.CH3 2 Cl│ │ CH3 CH3 43.OH CH2 .N+.7 \ CH2 .CH2 – OH CH2 – CH2 – OH / – NH+.CH2 .CH2 – NH+ 2 Cl│ \ CH2 .CH2 .CH2 – OH l 2 3.9 │ CH2 .CH2 – OH │ – N+– H Cl21.COO38.1 │ CH3 4 .CH2 .CH2 ∅ Cl│ CH3 CH2 .CH2 .CH2 .0 –N→O (at pH = 3) l CH3 CH3 │ – N+.CH2 – OH CH3 │ – N+.0 │ CH3 CH3 / > N+ Cl19.0 CH3 │ – N+.Table B: cationic and betaine hydrophilic group contributions Hydrophilic group HLB contribution Hydrophilic group HLB contribution – NH2+.CH2 .CH2 – OH 41.4 CH2 .2 – N+.CH2 – NH3+ 2 Cl38.CH3 Cl24.0 │ CH3 – NH3+ Cl20.CH2 .CH2 – OH │ – N+.CH2 .5 CH3 l 21.COOH Cl24.∅ CH2 .CH2 .CH2 –.5 \ CH3 CH3 │ 19.8 –N→O (at pH = 3) L CH2 .9 │ CH2 .CH3 Cl22. CH2 – OH / – N .6 – COOH – OH 20.33 0.N  \ CH2 .∅ – CH .15 5 .66 0.CH2 – OH CH2 .1 1.CH2 – CH2 – NH2 HLB contributi on 17.475 – CH2 .3 0.475 – CH2 – CH – O –   CH3 HLB contribution 0.CH2 .475 1.CH2 – OH / 8.9 –O– – CH2 .475 – CH = (unsaturated) – CH2 0.2 2.CH2 – OH 1.3 CH2 .4 CH2 .CH2 .NH2 9.95 Table D: hydrophobic group contributions hydrophobic group HLB contribution hydrophobic group – CH3 0.CH2 – O – – CH2 .(branched) 0.4 – NH .4 9.CH2 .CH2 – OH O ║ – C .5 –N \ CH2 .CH2 – OH 11.Table C: cationic and nonionic hydrophilic group contributions hydrophilic group HLB hydrophilic group contribution – NH2 > NH CH3 / –N \ CH3 9.CH2 . 5 6 .0 HLB = 22.0 .N+.6 x 21.CH3 l CH3 Cl22.475 .7) + (0.CH3 l CH3 Cl- Group contribution of the hydrophobic groups: CH3 0. a mixture of 40 % Armeen® 12D (HLB = 11.4) = 17.(14 x 0. For example.(CH2)13 .Example Calculation: The following calculation is based on tetradecyl trimethyl ammonium chloride: Tetradecyl trimethyl ammonium chloride has the following structure: CH3 l CH3 .CH2 0.475) + 7 = 22.475 Group contribution of the hydrophilic group: CH3 l .4 x 11.4) gives the following HLB value: HLB = (0.N+. the HLB value of a surfactant system is the weight average values of the respective surfactant components.7) and 60 % Arquad 16 (as 100 % active) (HLB = 21.4 Surfactant Mixtures: In this case. and their resulting HLB depends on the pH.6 7 .8 20.3 8.3 22.2 18.2 42.9 7.8 21. 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 10.9 20.5 14.9 4 0.9 18.4 18.9 18.4 37.1 13. In literature HLB values for this class of surfactants are hardly found.2 8.7 28 23. Following is a list of HLB values for these products: Table 1: HLB values of Akzo Nobel fatty amines and derivatives (accuracy: ± 10%).3 7.8 19.8 18.2 12.7 21 17.7 19.9 23.4 25.8 8.2 24.9 18.3 7.3 8.Cationic HLB Values: The Akzo Nobel fatty amine products have surfactant properties that can offer emulsifing properties.7 10.2 7.9 25. Some products convert to amine salts in acid conditions.7 24.6 27.8 21.6 10.8 39.4 20.1 9. Products whose HLB are independent of pH are given in the far right column.5 17.2 16.3 16. The following table is segmented by pH for those products that convert to salts.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 17.1 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 20.5 37. 8 16.7 20.8 21.6 24.8 21.3 16.2 18.7 27 21.7 21.7 23.3 20.Table 1 (continued): HLB values of derivatives (accuracy: ± 10%).7 9.4 11.1 10.7 22.8 23.1 11.7 8 .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 23.4 26.3 21. 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 13.1 12.9 19.1 10.4 44.4 24.6 21. Nonyl Phenol Alkoxylates: Witconol™ nonyl phenol based nonionic surfactants are used in many industries. These products have HLB reported by the Griffin method.1 16 17.9 11. 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.Nonionic HLB Values: Our nonionic surfactants offer a wide range of HLB values.8 Alkyl Alkoxylates: The Ethylan™ family contains other nonionic surfactants.6 14 9. They are very good at wetting. Table 3: Product Name WITCONOL NP-40 WITCONOL NP-90 WITCONOL NP-100 WITCONOL NP-200 WITCONOL NP-400 HLB 8.9 13 13.4 9 .5 17 12 12. and emulsification. dispersion.5 8 8 10. The following HLB data for these products is reported using the Griffin method.4 HLB 10. Table 6: Product Name WITCONOL 14 WITCONOL H-31A WITCONOL H-32 WITCONOL H-33 HLB 6 12.5 14. 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 are best for emulsifying oil in water.4 10 . These products find use as emulsifiers and dispersants in a variety of industrial and consumer applications.Ethoxylated Castor Oil: The Emulpon™ trade mark is for our castor oil ethoxylates.2 13.5 10 8. or water in oil. 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. This effect may be stronger (example C) or less pronounced (example B). Basically. the oil forms droplets. The system is essentially water in oil (W/O). For each surfactant system emulsion stability reaches a maximum at the same HLB value. It shows the matching of the surfactant system HLB and the required HLB of the oil/water system. Each surfactant system (pure or mixture) can be characterized by an HLB value. In the other type it is reversed.B or C) at the required HLB of the system performance is enhanced. Optimization of the performance can be achieved by only including surfactant systems with similar HLB values. 11 . This is designated as a oil in water (O/W) system. Regardless of the surfactant mixture (A.Emulsification by HLB: In order to emulsify a mixture of water and oil one or more emulsifiers is required. This value depends on the nature of the oil and the product application. The required HLB is the value at which enhanced emulsion stability will be attained. 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 following figure illustrates the effect of different surfactant systems on the stability of an emulsion. In one type water dominates. there are two types of product application. Each oil/water system can be characterized by a so-called “required HLB” value. detergency. The choice is determined by the test result. The final step is varying the amount.28 Solubilization 11 . the best surfactant ingredient must be found.18 Wetting 7-9 Procedure for Using the HLB System: The HLB system allows for a straightforward approach. all having an HLB equal to the required HLB. First of all the required HLB of the formulation system must be identified. Good results can be achieved in three steps. as shown in table 7: Table 7: Suggested HLB values for a number of applications Defoaming of aqueous systems 1-3 Detergency & cleaning 12 . Typically a HLB value will dictate these properties. solubalization and other applications.15 W/O emulsification 3-6 O/W emulsification 8 . 12 . Then. must be included.When To Use the HLB System: The HLB model can be used for applications including emulsification. Several (mixtures of) ingredients. 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 13 .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). In essence such determination consists of three steps. First. Tenside Det. the HLB (as shown in Figure 1). Then. 1963 Lin. 2nd ed. table 10 provides indicative values of required HLB’s of most common applications. 249 (1998) 14 . If no maximum value is noted in the above procedure then one can deduce that HLB is not essential to your formulation. Finally. J. pH and temperature of these steps must be consistent. It must be done several times.K.. 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. “Interfacial Phenomena”. 15. L. In these cases one has to determine the required HLB value. A maximum will appear in the plot. version 1980 Davies.T. Each time the surfactants must be mixed in another ratio in order to create different HLB values. & Marszall.. p 371. the performance must be determined and plotted vs. Academic Press. 243 (1978) O Boen Ho.. However the salinity. London.J... E. To make choices of the surfactants more easily.. choose a surfactant system containing at least two surfactants with a significant difference in HLB value. 198. The corresponding HLB maximum is equal to the required HLB. ICI Americas Inc. a Time Saving Guide to Emulsifier Selection”. & Rideal. Colloid Interface Sci.It is likely that your oil system is not listed in the tables. the product formulation? must be made? including this surfactant system. I. J. One can then use statistical methods to determine the optimal level of ingredients for your formula. as to the products’ merchantability or fitness for any particular purpose. including all of its headers and footers. make no warranty as to the accuracy and/or sufficiency of such information and/or suggestions. or that any suggested use will not infringe any patent. ©2011 Akzo Nobel Surface Chemistry LLC Publication: SC-11-02 15 . distribute and/or photocopy this document only if unaltered and complete. The user may forward.HLB & Emulsification Customer Service For additional information. the suitability of these products for his purposes. however. Akzo Nobel Surface Chemistry LLC and its affiliates. You may not copy this document to a website. and should refrain from any unauthorized use. samples or assistance please contact your local sales representative or the Akzo Nobel Customer Service Department at: Akzo Nobel Surface Chemistry LLC 525 W. 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