Industrial Formulator Training

Rene Haensel Goldschmidt GmbH / Industrial Specialties Industrial Formulator 09.01.2007

Emulsion Technology
Introduction - Dispersed Systems - Emulsifier - HLB - Use of co-emulsifier - Paste Method

A good adjusted emulsifier system does not only stabilize the emulsion, it furthermore provide film building and wetting properties.
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Emulsion Technology
Dispersing Agent Dispersed Substance

Gas

Liquid Solid

Fog Smoke

Liquid

Gas Liquid Solid

Foam Emulsion Suspension Solid Foam

Solid

Gas

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Emulsion Technology

During the production of an emulsion two immiscible fluids are mixed, causing a rise in the surface are of the dispersed phase. As this generates an increase of the interfacial tension, the total energy of the system is increased and therefore the stability of the system decreases.

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Emulsion Technology

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Droplet Formation

W=dA*y W = Work (required to increase the surface of the dispersed phase, to achieve finely dispersed droplets) dA= Increase of surface y = Interfacial tension
The lower the interfacial tension is, the lower is the energy which is needed to create new surfaces. A low interfacial tension is necessary to achieve self-emulsifying properties and stable finely dispersed emulsions.
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Emulsifier
Emulsifier are surfactants which are amphipathic,
containing hydrophobic groups and hydrophilic groups Emulsifier adsorb at the interface between oil and water and reduce the interfacial tension Emulsifier shall stabilize the interface (the emulsion) by protecting from coalescence

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Emulsifier

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O/W and W/O emulsions

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Emulsifier
Nonionic Emulsifier (our product range for Metal Working Fluids) Anionic Emulsifier Kationic Emulsifier Amphoterics

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General Rule (W. D. Bancroft, 1913): hydrophile (water soluble or dispersable) emulsifiers => O/W emulsions lipophile (oil soluble) emulsifiers => W/O emulsions

Bancroft, W.D., J. Phys. Cehm. 17, 515,518 (1973).

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Hydrophilic Lipophilic Balance

HLB
10
0

HLB
20
10
0

HLB
10
20

20

W
O W

Emulsifiers with an HLB value of less than 10 are mainly oilsoluble (lipophilic) ---> Emulsifier for W/Oemulsions
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Transition point from lipophilic to hydrophilic being situated approx. around the HLB value 10

Emulsifiers with an HLB value higher than 10 are mainly watersoluble (hydrophilic) ---> Emulsifier for O/Wemulsions
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The HLB System

HLB: Hydrophile Lipophile Balance

PEG-20 Stearate

HLB 15

PEG-100 Stearate

HLB 19

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HLB System according to W. C. Griffin

Result of many years' experimental work (lots of emulsion tests): HLB Value 1.5 3 3 7 8 13 12 Attention: Attention: 8 9 18 15 18 Use as Antifoaming agent W/O emulsifier Wetting agent O/W emulsifier Wash active substance Solubilizer for aqueous systems

The system was originally developed for nonionic substances: The system was originally developed for nonionic substances: Fatty acid esters of polyalcohols (glycerin, sorbitol and so on) and Fatty acid esters of polyalcohols (glycerin, sorbitol and so on) and their ethoxylates, ethoxylated fatty alcohols and fatty acids their ethoxylates, ethoxylated fatty alcohols and fatty acids
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Calculation of the HLB value

1) Fatty acid esters of polyalcohols (also ethoxylated)

HLB = 20 (1 - SV/AV) HLB = 20 (1 - SV/AV)

SV = Saponification value of the ester AV = Acid value of the fatty acid

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Calculation of the HLB Value

2) Ethoxylated fatty alcohols and fatty acids
HLB = E/5 HLB = E/5
E = Weight % of the PEG part

Example:

PEG-20 Stearate

PEG-20 = 20 x 44 g/mol = 880 g/mol Stearic acid = 284 g/mol Weight % PEG part = 880/(880 + 284) x 100 = 76 % HLB = 76/5 = 15

Attention: Attention:

The equations are not valid for ionic substances and for nonionic The equations are not valid for ionic substances and for nonionic substances which contain propylene glycol, butylene glycol, nitrogen, substances which contain propylene glycol, butylene glycol, nitrogen, sulfur and so on. sulfur and so on.
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Calculation of HLB

Example: Determination of the HLB value of an emulsifier mixture

Tagat V 20 Tegin OV HLB 8.4 HLB 3.3

Mixture of Tagat V 20 and Tegin OV with a ratio of 0,83 : 0,17: Mixture of Tagat V 20 and Tegin OV with a ratio of 0,83 : 0,17: HLB = 0.83 x 8.4 + 0.17 x 3.3 = 7.5 HLB = 0.83 x 8.4 + 0.17 x 3.3 = 7.5

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Estimating the HLB Value of an Emulsifier with the help of Solubility Tests in Water (5 %)

HLB 1 4 4 6 6 8 8 10 10 13 > 13

Behaviour in Water Not dispersible in water Very poor dispersibility Turbid dispersion after vigorous shaking Stable turbid dispersion Opaque to translucent solution Clear colloidal solution

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How to find a suitable emulsifier for metal working fluids

Required HLBs for O/W emulsions

-Emulsifier should have similar HLB values to that of the respective oils in order to achieve maximum stabilization Example Sunfloweroil required HLB approx. 8 Paraffinicoil required HLB approx. 11 Rapeseedoil required HLB approx. 8 Mineraloil required HLB approx. 10-12 Petroleum required HLB approx. 14 - The desired HLB number of the emulsifier can also be achieved by mixing hydrophobic and hydrophilic surfactants
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How to emulsify a base oil for metal working fluids

Incorporate the emulsifier/emulsifier blend into the oil phase Example:

85% Canola Oil + 15% Emulsifier Blend Blend 1: 15% Tagat V 20, HLB: 8.4; + 85% Canola oil Blend 2: 13% Tagat V 20 + 2% Tegin OV, HLB: 7.7; + 85% Canola Oil Blend 3: 11% Tagat V 20 + 4% Tegin OV, HLB: 7,0 + 85% Canola Oil

Incorporate the concentrate in water

- The metal working emulsions are usually diluted between 5 10% in water. The concentrate has to be self-emulsifyable. (low shear)

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Adjustment of the required HLB value

11% Tagat V 20 4% Tegin OV 85% Canola Oil

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13% Tagat V 20 2% Tegin OV 85% Canola Oil

15% Tagat V 20 85% Canola Oil

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Adjustment of the required HLB value

The optimized HLB leads not only to a finely dispersed Emulsion, furthermore the film building and wetting properties of an emulsion are improved

13% Tagat V 20 2% Tegin OV 85% Canola Oil

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11% Tagat V 20 4% Tegin OV 85% Canola Oil

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Base oil 85 % Rape seed oil 45 - 65 % Oleic acid content 85 % Sunflower oil ~ % Oleic acid content 90 % Trimethylol propane trioleate 90 % Paraffinic oil (BP) C/A: 7 %, C/N: 25 %, C/P: 68 % 90 % Naphthenic oil e. g. Nynas T 22 C/A: 10 %, C/N: 43 %, C/P: 47 %

Emulsifier blend 10.5 % TAGAT V 20 + 4.5 % Oleic acid 12.5 % TAGAT V 20 + 2.5 % TEGIN O V 10.5 % TAGAT V 20 + 4.5 % TEGO SMO V 10.5 % TAGAT V 20 + 4.5 % TEGIN O V 10.0 % TAGAT V 20 10.0 % TEGO STO 85 V 10.0 % TAGAT TO V 8.5 % TAGAT TO V + 1.5 % TEGIN O V 5.0 % TAGAT TO V + 5.0 % TAGAT V 20 5.0 % TAGAT V 20 + 5.0 % FAE + 5 EO 14.0 % TAGAT V 20 + 1.0 % Oleic acid 14.0 % TAGAT V 20 + 1.0 % TEGIN O V 9.0 % TEGO STO 85 V + 1.0 % TEGO STO V

HLB Value
(calculated)

7.6 7.2 6.9 8.4 11.0 11.3 10.0 9.9 8.7

55 % Rape seed oil 45 - 65 % Oleic acid content 30 % Naphthenic oil C/A: 11 %, C/N: 45 %, C/P: 44 % 90 % Hydrocrack oil

8.1 10.0

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Preparing of an emulsion using high energy (e.g. paste method)

- Emulsions which consist of Silicone oil, Silane emulsions, Silicone resins, OMS as dispersed phase - Emulsions with high volume ratio of inner phase

Example
4 .0 % 4 .0 % 4 0 .0 % 5 1 .8 % 0 .2 % E m u ls ifie r A E m u ls ifie r B O ilp h a s e W a te r P re s e rv a tiv e

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Emulsification

Turbine - Stirrer

Mizer - Blade

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Emulsification by paste method

Addition of components
100 90 80 70 60 50 40 30 20

Viscosity of mixture
100 90 80 70 60 50

water

Oil phase

40 30 20

Emulsifier A
10 0

Emulsifier B
10 0
1 2 3 4 5 6 7

water
w ater emulsifier A emulsifier B oilphase preservative

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Stability of emulsions

Creaming

Flocculation

Phase inversion

Coagulation

Ostwald ripening

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Stability of emulsions

Coalescence of 2 droplets

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Stability of Emulsions Centrifuge Quick test to find out if the emulsion tends to separate. The emulsion is filled in a glas tube and treated in a labcentrifuge. If the emulsion is not stable phase separation can be monitored

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Stability of Emulsions Vibrating -test Gives information if the emulsion is sensible to impacts during transport. Due to these impacts coalescence of the emulsion, especially on the surface may happen.

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Stability of Emulsions

Stability at higher temperature

a) Gives information what happens to the emulsion due to thermal stress

during storage or transport. In the summer emulsions can be heated up to 50 C during transport on truck. b) This test often is made to determine the shelf life within a short time. e.g. 4 weeks at 50C = 6 month at R.T. (????)

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Emulsion
Emulsion: A disperse system consisting of several phases which arises through the mixing of two liquids which are not soluble in each other (e.g. mineral oil and water). One liquid forms the inner or disperse phase, distributed in droplet form in the carrier liquid (the outer or continuous phase). The emulsifyable metalworking fluids are frequently oil in water emulsions (O/W), i.e., oil forms the inner phase. During the production of an emulsion two immiscible fluids are mixed, causing a rise in the surface area of the dispersed phase. As this generates an increase of the interfacial tension, the total energy of the system is increased and therefore the stability of the system decreases. Among the parameters, who determine whether a system made from oil, surfactant and water form an O/W- or a W/O-emulsion, are: type of surfactant, salt content type of oil (polarity, viscosity) volume ratio: oil : water Oils of higher viscosity are more prone to form the coherent phase than oils of lower viscostiy The tendency of a phase to form the coherent one increases with its volume ratio. Due to geometrical limitations the volume ratio of the coherent phase has to exceed a certain minimum value. This can be derived from the volume demand of the closest sphere packing of the droplets of the dispersed phase.
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Emulsion
Emulsifier: An emulsifier also know as surfactant or surface active material is a substance which stabilize interfaces in emulsions. Emulsifier are usually organic compounds that are amphipathic, meaning they contain both hydrophobic groups (their "tails") and hydrophilic groups (their "heads"). Therefore, they are typically sparingly soluble in both organic solvents and water. Emulsifier reduce the surface tension of water by adsorbing at the air-water interface. They also reduce the interfacial tension between oil and water by adsorbing at the liquid-liquid interface. Many surfactants can also assemble in the bulk solution into aggregates that are known as micelles. The concentration at which surfactants begin to form micelles is known as the critical micelle concentration or CMC. When micelles form in water, their tails form a core that is like an oil droplet, and their heads form an outer shell, or corona, that maintains favorable contact with water. When surfactants assemble in oil, the aggregate is referred to as a reverse micelle. In a reverse micelle, the heads are in the core and the tails maintain favorable contact with oil.

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Emulsion

How to find the right emulsifier? Emulsifiers should have similar HLB values to that of the respective oils in order to achieve maximum stabilization. Mineral oil has an assigned HLB of 4 when a water-in oil emulsion is desired, and a value of 10,5 when an oil in water emulsion is to be prepared. Accordingly, the HLB number of the emulsifier should also be around 4 and 10,5, respectively. The desired HLB numbers can also be achieved by mixing lipophilic and hydrophilic surfactants. (see HLB) Example: Determination of the HLB value of an emulsifier mixture Emulsifier A: HLB 3.8 Emulsifier B: HLB 16.4 Mixture of A and B with a ratio of 40 : 60: HLB = 0.4 x 3.8 + 0.6 x 16.4 = 11.36

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Emulsion
The "required HLB value can only be a guideline, as the result of emulsification fundamentally depends on: Amount of emulsifier Phase weight ratio of the emulsion Electrolyte content of water Emulsification temperature Emulsification method For the choice of the emulsifier not only its correct HLB value is important, but also the choice of the suitable chemistry. An experimental determination of the HLB value only makes sense with standards whose HLB values are correct.

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Emulsion
HLB: HLB stands for hydrophilic lipophilic balance. Surfactants with a low HLB are more lipid loving and thus tend to make a water in oil emulsion while those with a high HLB are more hydrophilic and tend to make an oil in water emulsion. General Rule (W. D. Bancroft, 1913): hydrophile (water soluble or dispersable) emulsifiers => O/W emulsions lipophile (oil soluble) emulsifiers => W/O emulsions Attention: The system was originally developed for nonionic substances: Fatty acid esters of polyalcohols (glycerin, sorbitol and so on) and their ethoxylates, ethoxylated fatty alcohols and fatty acids.

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Emulsion
Ethoxylated fatty alcohols and fatty acids HLB = E/5 E = Weight % of the PEG part

Example:

PEG-20 Stearate

PEG-20 = 20 x 44 g/mol = 880 g/mol Stearic acid = 284 g/mol Weight % PEG part = 880/(880 + 284) x 100 = 76 % HLB = 76/5 = 15

Attention: The equations are not valid for ionic substances and for nonionic substances which contain propylene glycol, butylene glycol, nitrogen, sulfur and so on.

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