SURFACTANTS - EMULSIFIERS

An emulsion is a mixture of two or more immiscible (un-blendable) liquids. Emulsions are p of a more g q part general class of two-phase systems p y of matter called colloids. Although the terms colloid and emulsion are sometimes used interchangeably, emulsion tends to imply that both the dispersed and the continuous phase are liquid. In an emulsion, one liquid (the dispersed phase) is dispersed in the other (the continuous phase)

A. Two immiscible liquids, not yet emulsified. emulsified B. An emulsion of Phase II dispersed in Phase I. C. The unstable emulsion progressively separates. D. The D Th surfactant ( f t t (purple outline around l tli d particles) positions itself on the interfaces between Phase II and Phase I, stabilizing the emulsion

Emulsions are made up of a dispersed and a continuous phase; the boundary between these phases is called the interface. Emulsions tend to have a cloudy appearance, because the many phase interfaces scatter light that passes through the emulsion. Emulsions are unstable and, thus, do not form spontaneously. The basic color of emulsions is white. If the emulsion is dilute, the Tyndall effect will scatter t e light a d d sto t t e co o to blue; if y da e ect scatte the g t and distort the color b ue; it is concentrated, the color will be distorted toward yellow.

Microemulsions and nanoemulsions tend to appear clear due to the small size of the disperse phase. Energy input through shaking, stirring, homogenizing, or spray processes is needed to initially form an emulsion. Over time, emulsions tend to revert to the stable state of the phases comprising the emulsion, an unstable emulsion that will quickly separate unless p g , q y p shaken continuously. Whether an emulsion turns into a water-in-oil emulsion or an oil in water water in oil oil-in-water emulsion depends on the volume fraction of both phases and on the type of emulsifier. In general, the Bancroft rule applies: Emulsifiers and emulsifying particles tend to promote dispersion of the phase in which they do not dissolve very well; for example, proteins dissolve better in water than in oil and so tend to form oil-inl t i di l b tt i t th i il d t dt f il i water emulsions (that is they promote the dispersion of oil droplets throughout a continuous phase of water).

There are three types of instability: flocculation, creaming, and coalescence. Flocculation describes the process by which the dispersed phase comes out of suspension in flakes. Coalescence is another form of instability, which describes when small droplets combine to form progressively larger ones. Emulsions can also undergo creaming, th migration of one of th substances E l i l d i the i ti f f the b t to the top (or the bottom, depending on the relative densities of the two phases) of the emulsion under the influence of buoyancy orcentripetal force when a centrifuge is used.
Orijinal Emlsiyon Flokulasyon Koalesens

Kremleme

Krlma

Surface active substances (surfactants) can increase the kinetic stability of emulsions greatly so that, once formed, the emulsion does not change significantly over years of storage. Surfactants are compounds that lower the surface tension of a liquid, the interfacial tension between two liquids, or that between a liquid and a solid. Surfactants may act as detergents, wetting agents, emulsifiers, foaming agents, agents and dispersants.

Surfactants reduce the surface tension of water by adsorbing at the liquid-gas interface They liquid gas interface. also reduce the interfacial tension between oil and water by adsorbing at the liquid liquid liquid-liquid interface.

A micelle the lipophilic tails of the micellethe surfactant molecules remain on the inside of the micelle due to unfavourable interactions. interactions The polar "heads" of the heads micelle, due to favourable interactions with water, form a hydrophilic outer layer that in effect protects the hydrophobic core of the micelle. The compounds that make up a micelle are typically amphiphilic in nature, meaning that not only are micelles soluble in protic solvents such as water but also in aprotic solvents as a reverse micelle.

Surfactant classification according to the composition of their head: nonionic, anionic, cationic, Amphoteric (pH dependent).

Uses Of Surfactants

1. Emulsifiers

Water In Oil - L W I Low Hlb Oil In Water - High Hlb

2. 2 3. 4. 5. 6. 7. 8.

Foam St bili F Stabilizers Lipid Crystal Modifiers Wetting Agents Solubilizers Starch Complexers Protein Modifiers o od Detergents

Interaction Of Surface A i Agents With I i S f Active A Wi h Food Components

1. Lipids 2. Water 3. 3 Starch 4. Protein 5. Air 6. I 6 Ions

MOST SURFACTANTS INVOLVE INTERACTONS WITH LIPIDS

Why do we add surfactants to foods ?

Orange Drink
Solublizer for colors Stabilize orange oil Possible cloud

Bread

Loaf volume Entrap gas, Soften, Soften Reduces staling g

CSL, PS 60, DATEM

EMULSIFIERS IN BREAD BAKING

During mixing

Improves wetability Improves distribution of shortening Interacts with starch, protein and fat Decreased mixing time Decreased shortening usage g g Improved mixing tolerance Improved physical characteristics of the dough

Results in:

EMULSIFIERS IN BREAD BAKING

During fermentation

Results in better gas retention R l i b i Improved gas retention d Improved loaf volume Decreased water l D d t loss Finer, more uniform texture Increased softness Less staling

During baking

During Storage

Pudding

Emulsification Wetting agent in powder Texture modifier

Ice cream

Emulsion stability and destability, Foam stability,

Candy Bar

Lecithin to stabilize fat crystals "bloom", control viscosity and thus coating

Cookie

Control spread

protein and fat interaction

Note: altering sugar may be a bigger factor

Surfactants 172

Listed Under Multipurpose Additives

Dioctyl Sodium Sulfosuccinate Glyceryl Tristearate Hydroxylated Lecithin Methylglucoside- Coconut Oil Ester Oxystearin Sodium Lauryl Sulfate Sodium Stearyl Fumarate

Surface Active Agents

Acetylated Monoglycerides Succinylated Monoglycerides Ethoxylated Mono And Diglycerides Polysorbate 60 Polyoxyethylene (20) Sorbitan Monostearate Aka Tween 60 Polysorbate 65 P l P l b t Polyoxyethylene (20) S bit th l Sorbitan Tristearate Polysorbate 80 Polyoxyethylene (20) Sorbitan Monooleate

Surface Active Agents

Sorbitan Monostearate Aka Span Calcium Stearoyl-2- Lactylate Sodium Stearoyl-2-Lactylate Lactylic Esters Of Fatty Acids y y Lactylated Fatty Acid Esters Of Glycerol And Propyleneglycol py gy Glyceryl-Lacto Esters Of Fatty Acids Polyglycerol Esters Of Fatty Acids

Surface Active Agents

Propylene Glycol Mono- And Diesters Of Fats And Fatty Acids Propylene Glycol Alginate Sucrose Fatty Acid Esters Fatty Acids

Affirmed GRAS Emulsifiers

Diacetyl tartaric acid esters of mono- and diglycerides. diglycerides Glyceryl monooleate. Glyceryl monostearate. l l Glyceryl behenate. Lecithin Mono- and diglycerides. gy Monosodium phosphate derivatives of monoand diglycerides gy

Mono & diglycerides

Most commonly used Generally as mono & di Highly lipophilic with HLB values range from 1 to 10 p produced by transesterification of glycerol and triacylcerides y gy y used in bakery products, frozen desserts, icings, toppings, and peanut butter

Sources MonoMono and diglycerides occur naturally as food fat constituents, and are constituents also formed from triglycerides, being normal products of fat metabolism, during the digestion and absorption of food. As such, they are always found in conjunction with triglycerides, glycerol and some free fatty acids subject to the manner in which they have been roduced. They are p y produced commercially by a) heating triglyceride fats with an y y ) g gy excess of glycerol, or b) direct esterification of glycerol with fatty acids. The resulting composition is dependent upon the proportion of glycerol and temperature conditions used. The mono-ester is usually in the range 3060%. The composition of the product will vary according to conditions, but conditions glyceryl monostearate and glyceryl distearate are often major components.

Function in Food Emulsifiers are used to disperse fat droplets in water or water droplets in fat. Because they act at the surface between the fat and the water, they are also B h h f b h f d h h l known as surface-active agents or surfactants. Monoglycerides and mixtures of mono- and diglycerides are by far the most important commercially of all the food surfactants known; in Europe, they represent no less than 50% of the total food emulsifier market and, in addition, p , , the monoglycerides are important intermediates in the manufacture of DATEMs (diacetyl tartaric acid esters of monoglycerides) and other emulsifiers. Mono- and diglycerides are used widely in a great many products and are the surfactant type most used in bread. Performance characteristics are controlled by the skilful combining of alpha-mono-, beta mono di and tri glyceryl esters alpha mono beta-mono-, ditri-glyceryl of mixtures of fatty acids. In bread, the effectiveness of the emulsifier is dependent upon its total monoester content as, in this application, the performance of th alpha- and betafractions are similar and superior to either f f the l h d b t f ti i il d i t ith the di- or triglycerides.

Benefits In the production of bread, the contribution made by the surfactant is to enable the gluten in the dough to remain plastic and pliable so that, during that the kneading process, the strands of gluten can form a smooth extensible film, ensuring that the correct texture is produced in the finished product. As a general rule, volume and texture are of the utmost importance in baking. For example, it can be shown that, in cake making, the air bubbles in the batter that contribute to volume are enclosed in films of protein in which the fat is dispersed. The action of the surfactant is to improve the production of the initial air bubbles, ensuring their uniformity and thereby an improved texture of the finished baked product. Typical Products Bread, cakes and other baked goods; cereals, puddings; fresh pasta, instant (mashed) potatoes; frozen desserts, ice cream and soft-serve; desserts confectionery, e.g. chewing gums, toffees, caramels; and fats, e.g. margarines and shortenings.

Polysorbates

Polyoxyenthyene esters of sorbitan monoesters Polysorbate 60

polyoxyethylene sorbitan monostearate or TWEEN 60 - HLB = 14.9

oil toppings, cake mixes, and cake icing Polysorbate 65

polyoxyethylene sorbitan tristearate Permitted in ice cream, frozen custard polyoxyethylene sorbitan tristearate Special dietetic foods, fat soluble vitamine

Polysorbate 80

Sorbitan monostearate
sorbitan monostearate approved for food use - HLB = 4.7 - used in conjunction with polysorbates in oil toppings, cake mixes, etc. t i k i t
-

Stearoyl Lactylates

an ionic, hyddophylic emulsifier lactic acid ester of monoglyceride with sodium or calcium form strong complex with gluten in starch and f t l ith l t i t h d especially valuable in baked products

Lecithin

A mixture of phospholipids including phosphatidyl cholines, cholines phosphatidyl ethanolamines inositol ethanolamines, phosphatides, etc Can be chemically modified by provide a wide range of HLB values f various applications l for i li ti widely used in baked goods, low-fat baked goods, chocolate, instant foods, confectionery products, and cooking spray , yp , g p y

Sources Lecithin is a mixture or fraction of phospholipids, which are obtained from animal or vegetable foodstuffs (mainly soya and egg) by physical processes. i l bl f d ff ( i l d )b h i l They also include hydrolysed substances obtained by the use of enzymes. The finished product must not show any residual enzyme activity. A number of different lecithins or lecithin fractions are available.

Function in Food Phospholipids are the active ingredients of lecithin and have a two-part molecular structure. One part is lipophilic (high affinity to fat/non-polar phase) and the other is hydrophilic (high affinity to water/polar phase). phase) The phospholipids tend to dissolve in fat and disperse in water. This surface activity i th b i for th majority of lecithin applications and allows the ti it is the basis f the j it f l ithi li ti d ll th formation of both water-in-oil and oil-in-water emulsions. Besides nutritional benefits, phospholipids have the following functional properties in food products: emulsification and stabilisation of oil-in-water or water-in-oil emulsions; release and anti-spattering effects; adjustment of the ; p g ; j flow properties in chocolate masses; improvement of the wettability of instant products; as well as optimisation of the gluten network of baked goods.

Benefits Lecithin allows the production of fine, stable emulsions with little fine aggregation or coalescence. It is also used in chocolate manufacture to modify the flow characteristics of liquid chocolate y q for both blocks and coating. Lecithin is used on the surface of powders to improve instant properties. In bakery applications, lecithin i l ithi is used to increase the extensibility of the gluten in bread dt i th t ibilit f th l t i b d making, and in batters to improve the overall distribution of ingredients in cakes and to assist the release of wafers from hot iron moulds. Typical Products Margarines, dressings, chocolate and confectionery items, instant powders po de s and bakery goods. bake goods

Emulsifier Usage in U.S. (millions of pounds)

Emulsifier Mono&Di Lecithins MG Polysorb. CSL/SSL SorbMS PG ester

Bread Cake mix 116 13.2 1.5 27 23 1 0.5 1 .75 .1 10

M,SD,S * 30.5 10 2.5 .75 .25 2 1.8

Total 200 42.5 25 8 30 14.3

*Margarine, salad dressings, shortenings

Sorbitan Monostearate
Calcium Stearoyl-2- Lactylate Sodium Stearoyl-2-Lactylate

Emulsifier Usage

Product % of total US Bread and Rolls 49 Cake Mixes 11 Cookies and crackers 7 Sweet goods and icings g g 3 Margarine, dressings, shortenings 14 Confectionaries 6 Deserts and toppings 3 Dairy products 3

The Hydrophilic-lipophilic balance of a surfactant is a measure of the degree to which it is hydrophilic or lipophilic determined lipophilic, by calculating values for the different regions of the molecule All surfactants must have an oil loving portion and a water loving portion or they would not have surface activity The ratio of the oil loving p g portion to the water loving p g portion is what we call its balance We measure this b l W thi balance b based on molecular weight d l l i ht HLB HLB stands for
HYDROPHILE / LIPOPHILE / BALANCE

Hydrophillic Lipophillic Hydrophillic-Lipophillic Balance (HLB)

This is a concept for choosing emulsifiers. The value of HLB ranges from 1-20 1-20. Low HLB emulsifiers are soluble in oil while high HLB emulsifiers are soluble in water..

Bancroft's Rule
The type of emulsion (i.e. oil in water or water in oil) is dictated by the emulsifier and that the emulsifier should be soluble in the continuous phase. Low HLB emulsifier s are soluble in oil and emulsifier's give rise to water in oil emulsions

What i h H B Wh is the HLB system story The system was created as a tool to make it easier to use system nonionic surfactants In general it applies to nonionic surfactants only g pp y The basic principle of the system is: Surfactants have an HLB value Applications for surfactants have an HLB requirement A li ti f f t t h i t Matching the requirement with the value saves time and money

What is the chemistry of a nonionic surfactant ? Each surfactant has a hydrophilic group and a lipophilic y p g p p p group must have both or it would not be surface active the hydrophilic group is usually a polyhydric* alcohol or th h d hili i ll l h di * l h l ethylene oxide the lipophilic group is usually a fatty acid or a fatty alcohol * polyhydric-an alcohol with OHs attached p y y The relationship ( or balance ) between the hydrophilic p portion of the nonionic surfactant to the lipophilic portion p p p is what we call HLB All nonionic surfactants have an HLB Value

How do we determine the HLB value of a surfactant ? We calculate the water loving portion of thesurfactant on a molecular weight basis and then divide that number by 5 l l i ht b i d th di id th t b b this keeps the HLB scale smaller and more manageable the working scale is from 0 5 to 19 5 0.5 19.5 this number is then assigned to the nonionic surfactant

HLB VALUES OF SOME FOOD EMULSIFIERS

EMULSIFIER HLB VALUE Oleic acid * 1.0 Acetylated monoglycerides 1.5 Sorbitan trioleate 1.8 Glycerol dioleate y 1.8 Sorbitan tristearate 2.1 Propyleneglycol monostearate 3.4 Glycerol Monoleate 3.4 Glycerol monostearate 3.8 38

HLB VALUES OF SOME FOOD EMULSIFIERS

EMULSIFIER HLB VALUE Acetylated monoglycerides (stearate) 3 8 3.8 Sorbitan monooleate 4.3 Propylene glycol monolaurate 4.5 45 Sorbitan monostearate 4.7 Calcium stearoxyl 2 lactylate * stearoxyl-2-lactylate 5.1 51 Glycerol monolaurate 5.2 Sorbitan monopalmitate 6.7 Soy lecithin 8.0 Diacetylated tartaric acid esters y of monoglycerides 8.0

HLB VALUES OF SOME FOOD EMULSIFIERS

EMULSIFIER

Sodium Stearoyl lactylate * Sorbitan monolaurate ) Polyoxyethylene (20) sorbitan tristearate Polyoxyethylene (20) sorbitan trioleate Polyoxyethylene (20) sorbitan monostearate Sucrose monolaurate Polyoxyethylene (20) sorbitan monooleate

HLB VALUE 8.3 8.6 86 10.5 10 5 11.0 14.9 15.0 15.0

HLB VALUES OF SOME FOOD EMULSIFIERS

EMULSIFIER Sodium Stearoyl lactylate * Sorbitan monolaurate ) Polyoxyethylene (20) sorbitan Polyoxyethylene (20) sorbitan Polyoxyethylene (20) sorbitan Sucrose monolaurate Polyoxyethylene (20) sorbitan Polyoxyethylene (20) sorbitan HLB VALUE 8.3 83 8.6 tristearate 10.5 trioleate 11.0 monostearate 14.9 15.0 monooleate 15.0 monopalmitate 15.6

Stokes' Law

Creaming or sedimentation is proportional to: i l

1. Diameter of the particle squared 2. Difference in density between the particle and the continuous phase 3. 3 Viscosity of the continuous phase

And inversely proportional to:

Stokes Law

Rate = [Diameter squared x density difference x g] / [16 x viscosity] How can we change diameter? How can we change density difference? How can we change viscosity?

Amylose Complexing Index

Distilled Monoglycerides

From hydrogenated lard (65% MS, 30% MP) From hydrogenated soy oil (85%Mono Stearate) From unhydrogenated lard 45% Mono olein From soy oil (55% mono olein)

92 87 35 28

Acetylated mono glycerides Saturated Mono and Di glycerides (50% mono) Steroyl-2-lactylate Sodium Steroyl-2-lactylate Calcium Steroyl-2-lactylate Lactylated monoglycerides y gy Diacetyltartaric esters of monoglycerides

0 42 79 72 65 22 49

Basic Rules
1. For emulsions, if you don't have A clue, use At 5% Of The fat. 2. 2 Use unsaturated emulsifiers with unsaturated fats. 3. Mixtures work better than a single g emulsifier when stabilizing foams And emulsions.

Basic Rules
4. Bancroft's Rule
Emulsion S bili I F E l i Stability Is Favored By Solubility In The d B S l bili I Th Continuous Phase i.e. High HLB----> oil/water Low HLB-----> water/oil

5. HLB and most other rules go out the window when protein and (sometimes) polysaccharides enter the system. 6. 6 Only saturated monoglycerides complex with starch.

Basic Rules

4. Bancroft's Rule

Emulsion S bili I F E l i Stability Is Favored By Solubility In The d B S l bili I Th Continuous Phase i.e. High HLB----> oil/water Low HLB-----> water/oil

5. HLB and most other rules go out the window when protein and (sometimes) polysaccharides enter the system. 6. 6 Only saturated monoglycerides complex with starch.

Basic Rules

7. Emulsifier forms affect functionality.

flakes fl k vs powder vs hydrates vs gels d h d l

8. Many functions are due to affects on polymorphism. l hi 9. Emulsifier preparations frequently contain unsaturation and may be an important nsat ation ma impo tant contributor to off flavors. 10. 10 Emulsifier preparations are seldom pure and thus variation from manufacturer to manufacturer may be substantial. substantial

Basic Rules
11. When you find a non-obvious usage of emulsifiers, emulsifiers the function is often related to interaction with starch or protein. 12. 12 Order of addition may be very important. important 13. Processing steps like homogenization may substantially change the function of emulsifiers.