Soap Technologies The Fundamental Principles of Soap Formulations and Structures

Norman Hall Contina Consultancy Service

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March 2006 Mumbai 1. The Objectives The objectives of this first talk are to show: How individual chain length soaps from an oil blend will interact to create lather and some other user properties How processing influences the arrangement of individual chain length soaps within the bar and how that arrangement can influence user properties, hardness and translucency. A simple procedure to select and blend alternative oils for soaps

2. Terminology used in the soap business This talk aims to give that audience a first introduction to the fundamental principles of soap formulation and manufacture. As with most technical topics it will be necessary to introduce words or phrases which, through common use over many years, have become part of the soapmaker-speak i.e. jargon. It should always be remembered that there is usually a corresponding science-speak explanation. For example, a first question can be What is the Lye Limit Concentration (LLC) which would be used for deciding the concentration of washing liquid to be used when removing glycerine by-product from an 80/20 tallow/ coconut soap made from oils? Within that sentence are several examples of soapmaker-speak. The question could be phrased in science-speak i.e. At what concentration of sodium chloride solution will common ion and ionic strength effects of the electrolyte sodium ions completely displace from solution the sodium soaps of the weak fatty acids created from a blend of 80 parts of tallow and 20 parts of coconut oil? The answer is that 80/20 soaps will be completely insoluble in a 10.8% solution of NaCl.

There will be several other examples of jargon arising during this presentation. Hopefully they will be explained or should be obvious from the context in which they are used. The emphasis of this presentation is on toilet soap - but soap is soap. In the emerging and developing nations very often laundry soap is used for both personal washing and for household cleaning. Whether a bar is called laundry soap or toilet soap will often depend more on the shape and wrapping of the product, or how we advertise it and will not always depend on the product formulation. 3. The Basic Chemistry The fundamental principles of soap compositions and performances are generic and apply to all soaps. The chemistry of soap making is very simple Soaps are the salts of (mainly) Carbon Number C10 to C18 saturated and unsaturated fatty acids. The source of the fatty acids is always a blend of natural triglyceride oils. However, relatively few manufacturers make soap by neutralising a blend of fatty acids. Most create soap directly from the blend of oils. To make soap directly from oil, a blend of glyceride oils is reacted with strong sodium hydroxide solution to give the soap plus glycerine and a lot of heat. Separating the soap from the glycerine by-product is not easy, and may not even be necessary. Fats/ Oils R1COOCH2 R2COOCH R3COOCH2 + 3 NaOH + Caustic Soda Soaps R1COONa R2COONa R3COONa + + Glycerine CH2OH CHOH CH2OH

The alternative is to split the triglyceride oil into fatty acids and glycerine using high temperatures and high pressures. In this case the fatty acids and glycerine can easily be separated. The separated fatty acids are normally distilled, blended and the neutralised with NaOH solution to form soap.

Fats/ Oils R1COOCH2 R2COOCH R3COOCH2

+ Water

Fatty Acids R1COOH

Glycerine CH2OH

+ 3 H2 O

R2COOH R3COOH

CHOH CH2OH

Distillation Fatty Acids + Caustic Soda NaOH Soaps + Water H2O

R1,2,3COOH +

R1,2,3COONa +

Whether it is better to make soap by classical saponification or by a fatty acids route involves consideration of economics, supply chain issues, raw material and finished product qualities. Important issues can be the availability of process operation skills and equipment spares. 4. Glycerides The alkyl chains R1, R2 and R3 on the triglyceride molecule of the oil or fat will include both saturated and unsaturated fatty acid types of different carbon atom chain lengths (Carbon Numbers) e.g. CH2-O-CO-(CH2)x-CH3 CH-O-CO-(CH2)y-CH=CH-(CH2)z-CH3 CH2-O-CO-(CH2)x-CH3 (saturated) (unsaturated) (saturated)

In the example shown the triglyceride has 2 saturated fatty acid chains (say palmitic, C16) and one unsaturated fatty acid chain (say oleic, C18:1). Several different combinations of saturation/ unsaturation and chain length are possible on a given glycerine backbone, giving oils of widely different characteristics especially melting points. These differences are very important for Edible applications where the oils are used as triglycerides, but are much less important for soap applications because in soapmaking all the fatty acid chains are separated from the glycerine backbone. For soaps the important factors are only The relative proportions of saturated to unsaturated fatty acids (Iodine Value grams of iodine reacting with the unsaturation in100g of oil or fat) The lengths of the fatty acid chains (Carbon Number)

The proportions of saturated and unsaturated fatty acids and the chain lengths of those acids are a characteristic of the oil or oil blend used for making soap. Why use a mixture of oils ? A blend of oils is almost always used to make toilet soaps or laundry soaps. The most common oils are Coconut oil (CNO) or Palm Kernel oil (PKO) - understandably, generally called nut oils Tallows (AT or T) or Palm Oils (PO) - these are generally called non-nut oils To get the best performance from soaps you need both types of oils ie non-nut oil and nut oil. Tallows or Palm Oils provide - Long chain length fatty acids (C16/ C18 palmitic acid and stearic acid) which give soaps that are insoluble and do not lather but these virtually insoluble soaps o add to lather stability o add hardness and so make the soap solid To put the insolubility of sodium stearate into context calcite is more soluble in water at 25C than is sodium stearate. Lather stability is to a large extent governed by the rate at which a liquid film drains under gravity from between the air bubbles. When the liquid film becomes so thin at any point that the film sides touch then the bubbles burst. Any mechanism that slows the rate of liquid drainage will increase lather stability. When the liquid film contains insoluble particles these can sometimes bridge the film sides and cause premature lather instability. This can happen with very large particles of filler materials. However, the particles of insoluble soaps are very small and asymmetric. There are two consequences of this asymmetry First, in the same way that sticks of wood flowing in a moving river will align with their longest axis parallel to the river flow, so the insoluble asymmetric particles of sodium stearate and sodium palmitate will align so that their long axis is parallel to the flow of liquid draining from between the bubbles of lather. The narrow axis of the stearate/ palmitate particles is very small so it is unlikely that the particles will bridge the film sides until most of the liquid has drained. Second, and most important, at the junctions between the air bubbles there is a region of much slower liquid flow. This is the Gibbs Plateau. In this region motion of the particles of sodium stearate/ palmitate will become much more random, like wooden sticks floating randomly in a slow moving pond of water.

Just as sticks floating in a slow pond can cause a log-jam that inhibits the water flow, so the particles of sodium stearate/ palmitate can collect in the Gibbs Plateau to an extent that they will block the flow of liquid draining from the lather. In effect this increases the time taken for the bubble film sides to touch and for the bubbles to burst and so increases lather stability Tallows or palm oils also provide long chain length unsaturated fatty acids (mainly C18:1) which give soaps with reasonable solubility but only moderate lather stability and rather poor lather volume.

The moderate lather stability of sodium oleate from tallows or palm oils is improved significantly by the lather stabilising effect of insoluble sodium stearate/ palmitate soaps provided by the same oils. This means tallow soap or palm oil soap alone can give a reasonable amount of lather and have good lather stability provided the use temperature is high enough to dissolve the sodium oleate ie is over 25-30C. The nut oils provide: Short chain length fatty acids (especially C12, lauric acid) that give soaps of moderate solubility, but with high lather when they are dissolved.

Solubility can be increased by using soap at a higher temperature, but sodium laurate does not dissolve significantly until over 40C. However, another important mechanism helps sodium laurate to dissolve at a much lower temperature. 5. The Importance of the Oleate : Laurate Eutectic It is a common but mistaken idea that nut oils make soap lather because the C12 soap has a high lather. It is true that C12 soap has a higher than C18 soap (which effectively does not lather at all) and a higher lather than C18:1 soap. However, the lather of a soap containing both tallow/ palm and nut oil is much higher than that of C12 soap alone. The reason is fundamental to many aspects of the performance of soap tablets. When a system contains both C12 and C18:1 fatty acid soaps together, the mixture has a much higher solubility than the solubilities of either of the individual components. A 1:1 mixture of C12 sodium soap and C18:1 sodium soap is very soluble and has a very high lather. This mixture will also make the soap softer. For example, the Krafft Temperatures (Tk )** of Sodium C12 soap (sodium laurate) = 42oC Sodium C18:1 soap (sodium oleate) = 28oC ** Krafft Temperature = temperature at which solubility = c.m.c. (Appendix 1)

But the Krafft Temperature of the 1:1 mixture is < 0oC

Mixtures of C12 soap and C18:1 soap are : very soluble high lathering
60 40 60

10% solids

40 20 0

Tk/oC

20 0 Eutectic Mixture

Na Laurate

Tk = Krafft Temperature

Sodium Oleate

which means it is very soluble even in cold wash water, and so lathers quickly and gives a good amount of lather. 6. Eutectics
This special property of a mixture of materials having properties very different from those of any of the components is called a Eutectic property. Eutectics are usually created when the molecules of two (or more) of the materials in a mixture have totally different shapes or sizes. If two molecules have totally different shapes/ sizes they cannot pack together neatly. Effectively each molecule "poisons" the other so that it cannot crystallise normally, and the abnormal crystals have higher solubility C12 saturated soaps have a straight molecule chain of carbons C18:1 unsaturated soaps usually have a "U" shaped (cis) carbon chain

In (almost) all soap tablets there will be more soap derived from C18:1 fatty acids than from C12 fatty acids i.e. most soap tablets contain more sodium oleate than sodium laurate. It therefore follows that as the C12 content is increased i.e. as the soap contains more nut oil, so the amount of 1:1 oleate : laurate mixture will increase, and the lather will increase. There is however the potential effect of increasing soap softness with increasing nut oil level. The explanation of why this could happen, but why it does not happen to any significant extent can be explained in the basis of the first of two models relating soap structure and properties.

7. Soap Structure - Performance Models There are two models of soap structure that can be useful. o Model 1- A very simple macro model based on solid soap to liquid soap phase ratios. This model is used to explain many aspects of processing characteristics o Model 2 - A molecular model which considers the crystallisation changes occurring during soap drying and subsequent processing, and which can be used to explain aspects of the user properties of soaps. Soap structure models are useful because they provide ways in which you can more easily visualise the links between formulation processing characteristics user properties 8. Model 1 The Macro Model Soap bar hardness at constant moisture content and electrolyte content is a function of the balance between Solid (insoluble) soaps mainly Na C16 and C18 saturated fatty acid soaps (sodium palmitate/ stearate) but with some content of Na C12 saturated fatty acid soap (sodium laurate) when this has not had an opportunity to form the 1:1 eutectic mixture with Na C18:1 unsaturated fatty acid soaps (sodium oleate). Soluble soaps dissolved in the free water content of the soap bar. These are mainly the very soluble 1:1 oleate : laurate eutectic soaps, plus some free Na C18:1 soap, sodium oleate plus electrolyte, glycerine etc
The very simple macro model Soap hardness at constant moisture content is a function of the balance between : Solid / insoluble soaps : Softer/ soluble soaps

Na C16/ 18 and any undissolved C12

solid phase :

C12 / C18:1 eutectic + excess C18:1/18:2 in the water of the bar

liquid crystal phase in the bar water

more solid/less liquid = harder more liquid/ less solid = softer

The simple bar chart model of soap structure and hardness can be very useful to explain many formulation and processing effects, and will be referred to several times. The model simply shows a schematic balance between the solid soaps and the dissolved soaps. In real life the liquid phase will be up to about a 25% solution of dissolved soaps, and such a high concentration soap solution will have a Solution Liquid Crystal structure. This means that although the soaps are dissolved, the molecules of soaps will have arranged into large domains of micelles, and these have a regular packing structure. In most soaps that structure will be an hexagonal close packed arrangement of cylindrical or rod micelle domains. Although it has a structure the liquid phase remains mobile and fluid. Therefore, the more liquid phase there is in a soap, relative to solid phase, the softer the soap will be. 8.1 The Model Predictions of Effects from Formulations/ Process Changes Some of these will be obvious, but try to think of how the model explains the effects. a. Higher Temperature At a higher temperature more soap will dissolve from the solid phase into the liquid phase. The liquid phase volume will increase in size relative to the solid phase, and the soap should be softer. b. Higher Water Content in the soap There are two effects. First, the extra water will directly increase the liquid phase volume, Second, the liquid phase will (potentially) be able to dissolve more soap giving a further increase in liquid phase volume.

Both actions will lead to a softer soap, so a relatively small change in soap water content (say 1-2%) can have a big influence on product softness. c. More Electrolyte in the soap By common ion and ionic strength effects, electrolytes (usually sodium salts of stronger acids) will salt-out soaps from solution in the liquid phase. The result will be less liquid phase volume and more solid phase, and a harder soap. The hardening effect of electrolyte can be large eg an increase from 0.5% NaCl in soap to 1% NaCl will almost double the soap hardness from typically 2 x 10^5 N/M2 to 3.8 x 10^5 N/M2. The effect is large because all of that electrolyte will be dissolved in only the free water of the soap typically 10% water. The overall 0.5% electrolyte is therefore

present as a 0.5 x 100/10 = 5% solution, and the 1% electrolyte as a 10% solution. That is a big difference Always think of soap component concentration effects in this way d. More Nut Oil in the Soap Oil Blend Clearly, if a higher % nut oil in a soap gives more lather because it allows the formation of more 1:1 oleate : laurate eutectic, then this same mechanism should mean that a higher nut oil content will give a softer soap. If all else is equal, then this is true. However, all else is not normally equal. During manufacture soap is washed with a strong solution of NaCl to remove the glycerine byproduct. As the soap nut oil content increases so a higher concentration of NaCl solution is needed to effectively separate soap from the glycerine lye and the residual soap will always contain more of the NaCl. This will increase the soap hardness. The softening effect of the eutectic and the hardening effect of the electrolyte just about balance out, and in practice a higher nut oil content does not give a softer or harder soap as nut oil is increased up to about 40% in a blend with 60% tallow or palm oil. Above 40% nut oil the tallow or palm oil no longer provides enough C18:1 to form more 1:1 eutectic. The additional C12 therefore stays as solid phase and the soap will quickly get very hard as the % nut oil increases beyond 40%. e. Free Fatty Acids To improve their performance some toilet soaps can be made to contain significant amounts of free fatty acids (superfatting), typically more than 5%. Such free fatty acids can be as part of the solid phase or can be solubilised in the liquid phase. If in the liquid phase they will pack within the micelles and because they do not have a strongly polar head group they will dilute the charge density at the micelle surfaces. The result is that the usual cylindrical or rod micelles can form a different, more stable structure a lamellar structure. A lamellar liquid phase structure can inherently hold more dissolved soap, and is much less viscous than an hexagonal liquid phase. The result is a larger liquid phase volume, and certainly a lower viscosity liquid phase and a softer soap. f. Glycerine Glycerine is very soluble in water and so will always locate in the liquid phase. The first few % of glycerine added-to, or left-in, soap will simply increase the size of the liquid phase (slightly) and will give a slightly softer soap. Up to about 1% glycerine can have this effect in a toilet soap, perhaps 2% in a laundry soap.

At higher levels of glycerine, say 6% such as would be present if you did not remove any of the glycerine residual from soap making, the effective concentration of glycerine in the liquid phase becomes very high. It can be close to 40% in toilet soap ie 6% glycerine in 10% free water = (6/ 10+6) x 100 = 37.5% Soap will not dissolve is strong solutions of glycerine, and if glycerine is added or increased to levels over about 2% some dissolved soaps will be displaced from the liquid phase and will become solid phase. In effect, a high level of glycerine acts like an increased level of electrolyte. g. Minerals Added to Soaps At moderate levels (say 5%, perhaps higher) any minerals will simply be dispersed evenly between both solid and liquid phases and will have little influence on soap hardness. At higher levels (say over 10%) minerals can disrupt the packing of the soap crystal domains which are the solid phase. Such disruption can lead to the domains being able to slide over each other more easily and giving the impression of a softer soap. The softness is however due to weakness in the solid phase rather than to any change in solid to liquid ratio. An observation, is that with any level of almost any mineral then over time (say at least 2 months) there will be an increase in product hardness greater than that which may be associated with any water loss. There is no proper explanation of this effect. A simple explanation is that slowly the mineral will bind some of the free water in the bar. This is possible, but would probably depend on the amount of heating the mineral was given after extraction from the ground. h. Perfume Acts very like free fatty acids ie quickly softens soap, probably because some of the polar ketone and aldehyde components quickly migrate into the liquid crystal phase. As more perfume components migrate into the liquid phase in the hours/ days after soap manufacture it is probable that the liquid crystal phase can also change from viscous hexagonal to more fluid lamellar structure. This is an area in need of research. 9. Model 2 - The Molecular Model This model considers the crystallisation changes occurring during soap drying and subsequent processing, and which can be used to explain aspects of the user properties of soaps.

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The mixture of oils from which soaps are made have a wide range of saturated and unsaturated fatty acid chain lengths from below C8 to greater than C20. For the purposes of this model we will consider only the three major chain length groups: - Sodium Palmitate/ Stearate - Sodium Oleate - Sodium Laurate NaP/St NaOL NaL C16/C18 C18:1 C12

Soapmaking by normal alkali saponification, washing and fitting produces a liquid neat soap phase with a 70% solution of soap at 100oC minimum. This neat soap has no formal crystal structure, or at least no solid crystal structure. To make toilet soap noodles the neat soap is pre-heated to typically 135- 145oC and is sprayed into a vacuum chamber where it loses water to become 85% soap with around 12% water. During the vacuum spraying process the soap is cooled and solidified very, very quickly (0.5 sec) from say140C to below 50C. This sort of very rapid cooling and solidification does not give enough time for optimum crystallisation Effectively, the soaps of all the different chain lengths crystallise into a meta-stable solid phase. Only some of the most soluble chain length soaps (NaOL) will remain in the residual water of the soap. Although it does not have the most stable arrangement/ packing of the mixed chain length soaps the solid phase produced at the drier does always have a defined way in which all the long carbon chains of the fatty acid parts of the molecules pack together. Detail of this structural arrangement can be seen using X-ray diffraction techniques. In the company for whom I worked the structure of the solid phase formed immediately after drying is called Kappa phase (Omega phase by Procter & Gamble). Remember that Kappa phase will contain all the soap chain lengths: Kappa phase = Na P/St, NaL and even some NaOL. Remember from one of the earlier parts of this presentation that the best lather is obtained from Na laurate (NaL) but only when it is dissolved by forming the 1:1 eutectic with NaOL. Directly from the drying stage almost all the NaL is locked up in the solid Kappa phase, and so soap directly from the drier has relatively poor lather. The question is how do we free the NaL from the solid phase so that it can form the eutectic with NaOL dissolved in the liquid phase? The answer is to provide an energy of activation in the form of work energy. Applied work will allow the meta-stable Kappa phase to release some NaL into the liquid phase, where it will form the thermodynamically more stable eutectic with NaOL.

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As soon as some eutectic forms in the liquid phase so the liquid phase contains more soap and is a better oleophilic solvent and so (if work energy continues to be applied) it will more easily dissolve even more NaL from the solid phase. This process is self-perpetuating so long as the work energy continues to be applied. In the limit all the NaL could move out of the solid Kappa phase into the liquid phase. As this movement of NaL progresses so it leaves holes in the Kappa phase structure and makes it weak. As more and more NaL moves from the Kappa phase to the liquid phase so eventually the Kappa phase structure starts to collapse and then re-crystallise.

We do not only mix/mill/refine soap in order to evenly distribute perfumes, colour etc. We mix and mill/refiner soap in order to change the crystal phase structure and to give soap with better user properties

9.1 The nature of the phase to which Kappa phase will recrystallise will depend on the type of soap. Especially it will depend on the solvent power of the liquid phase ie the water content and whether it contains any solubilised free fatty acids. If the water content of a 90/10 to 70/30 type soap is at or above 15% (preferably 18%) then with enough work energy almost all of the sodium laurate will move from the solid Kappa phase into the liquid phase. If enough NaL moves from the solid to the liquid phase to be able to cause a solid phase restructure, then the solid phase will crystallise to the phase called Zeta phase (Beta by Procter &Gamble) Remember that Zeta phase will now contain only NaP/St soaps because all or most of the NaL has moved into the liquid phase. A characteristic of Zeta phase is that the crystal size is very small. This means there is less scattering (diffraction/ reflection) of incident light and so high Zeta phase soaps are often translucent. Scattering is also minimised when there is a minimum difference in Refractive Index (RI) between two surfaces ie at the solid phase/ liquid phase boundary. Glycerine has a high RI (1.5) close to that of soap so a high glycerine content in the soap (in the liquid phase) will increase the RI of the liquid phase to closer to the RI of the solid phase and so will always enhance the optical effect of translucency.

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It is relatively easy to get toilet soaps to form some Zeta phase by applied work energy. A higher water content (at least 16% rather than the usual 13%) will help the movement of NaL from the solid to liquid phases and with enough work energy can result in almost complete conversion from Kappa phase to Zeta phase. High zeta phase soaps will always have better lather properties because the liquid phase will contain a much higher proportion of the high lathering NaOL: NaL eutectic mixture. 9.2 Limitations 9.2.1 Nut Oil contents If the soap has less than 10% nut oil (equivalent to about 5% sodium laurate) then even if all the NaL moves from the solid phase to the liquid phase this movement will not give enough distortion to the Kappa phase to cause any major recrystallisation to Zeta phase. If the soap contains more than 30-35% nut oil then even when the liquid phase contains as much NaL as is possible there will still be enough NaL remaining in the Kappa phase to keep that phase stable. 9.2.2 Water Content Most toilet soap has about 20% nut oil and about 13% water content, and only trace amounts of free fatty acids. Even if the maximum realistic amount of work energy is applied to such a soap formulation only part of the NaL will move from the solid Kappa phase into the liquid phase. There is simply not enough solvent power in 13% water to move enough of the NaL to cause the Kappa phase to fully recrystallise to Zeta phase. Normal soaps therefore contain only a limited amount of Zeta phase and are not translucent. 9.2.3 Fatty Acids An Additional Note about Superfatted Soaps (A short diversion that can be passed-over unless the reader has a special interest in the subject. The topic will be discussed again in a later talk) If the soap being worked contains > 5% free fatty acids then both the solid phase and the liquid phase structures will change. The liquid phase structure will contain a lot of solubilised free fatty acids and, as explained earlier, this will cause the liquid phase structure to become lamellar rather than hexagonal. Under the influence of work energy (mixing or milling) the movement of NaL from the solid phase to the liquid phase is exactly the same as for non-superfatted soap, and so the

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Kappa phase changes to become more and more NaP/St only. However, when this structure collapses it forms a phase with crystals much larger than those in the Kappa phase (rather than much smaller as is the case with Zeta phase). These larger crystals are long and ribbon-like, and highly inter-twined and are described as Delta phase. If these ribbon-like Delta phase crystals can be formed in the soap due to work energy input then there can be significant advantages for the final soap performance. Especially the mush can be lower. You can only get Delta phase to form in superfatted soap if all work energy is input at below (ideally) 38C, certainly below 40C All soap mush is Delta phase, whether it forms from a soap in which the solid phase is Kappa, Zeta or already Delta phase. During soap mush formation water will penetrate into the soap bar. If the bar solid is Kappa phase (NaP/ST + NaL) then during the relatively long soap/ water contact time to form mush the NaL will dissolve out into the surrounding water, leaving the residual NaP/St to recrystallise into Delta phase in the presence of a lot of water. That water becomes trapped amongst the long, ribbon-like crystals of the Delta phase and gives a high mushing product. Net result Kappa phase soaps inherently have high mush. If the solid phase is Zeta phase then there is no NaL present to dissolve out into the surrounding water but eventually, by Oswald ripening, the small Zeta phase crystals will grow into the long, ribbon-like crystals of Delta phase, and will still trap the penetrated water. This growth probably takes a longer time to create Delta phase than does the formation from Kappa phase because of NaL-loss induced re-crystallisation. All else being equal a Zeta phase soap can therefore take longer to give the impression that it is a high mushing product. All is normally not equal. To encourage the initial formation of Zeta phase a soap will normally have a higher water content, and probably also a high glycerol content if it is to be a translucent soap. The higher water content or the glycerol content will both give a much higher level of water penetration, and these will more than compensate for and slightly longer mushing time due to the transformation from Zeta to Delta phase. Net result highly worked soaps can have a slower formation of high mush, but usually other formulation changes give significantly increased mush. If the solid phase is already Delta phase because the soap contained free fatty acids and was worked at below 38C then the mush will be lower than from soaps with Kappa or Zeta solid phase. The pre-formed Delta phase does not trap the penetrated water in the same way that it traps water when the Delta phase forms due to mushing.

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10. Oil Blending So far we have seen that For a good toilet soap you need both a non-nut oil and a nut oil in the formulation (typically 80/20 ratio) Soap user properties and processing behaviour are governed by the way in which the soap is processed ie temperature and shear (work energy) and by some elements of the formulation eg moisture, electrolytes, glycerine etc.

However, all of these are fairly constant for a given factory. Importantly, the soap properties and processing will depend very much on the natures of the fatty acids present as soap and therefore on the types of oils used to give that mixture of fatty acids. Optimum oil type selection is important because of cost, availability and for product performance. Most soaps are made using something like an 80/20 blend of a non-nut oil and a nut oil. Commonly the oils are: Coconut oil Palm kernel oil Tallows Palm oils CNO PKO AT or T PO (and commonly POs for Palm Stearine)

Note that coconut oil and palm kernel oil are reasonably well defined materials although fractionated or topped versions may be available as by-products of the Edibles business. [The author warns that topping to remove some or even all of the glycerides containing very short chain lengths (C6-C10) can give a an oil with undesirable properties. Although the residual oil will now contain a higher proportion of C12 fatty acids the lather properties of a resultant soap may be much poorer than expected. The reason is that the very short chain length fatty acid soaps have a vital role in initiating the formation of the initial liquid crystal phase that will eventually hold the high lathering oleate:laurate eutectic. If the short chain soaps are missing it is much more difficult for applied work energy to help the oleate:laurate eutectic to form so soap lather can be less than optimum.] In contrast, tallow and palm oil are group names and the fatty acids compositions of oils from these groups can be very variable.

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10.1 Nut Oils For soap with 10 - 30% nut oil, coconut oil and palm kernel oil can be considered interchangeable in terms of their contributions to user properties such as lather, wear and mush. Relative to coconut oil PKO does have slightly more colour because some carotenes from the palm fruit are usually extracted with the PKO, a higher Iodine Value (more C18:1) but has much better odour and colour stability because it contains natural antioxidants Coconut oil of the right quality can be good, very good, but there are limited supplies of the best qualities and most is used in Edible products. The majority of coconut oil used in soap is less than premium quality. All coconut oil contains a small amount of C10 hydroxy fatty acids. With time these can cyclise to give a distinctly odorous 5-decanolide (-C10 lactone) which has the typical old coconut odour. Some average quality coconut oil and the soap derivatives are also shown to contain the odorous materials guaiacol (o-methoxyphenol) and 2-dodecanone. Overall, PKO is a better soap making oil than CNO 10.2 Non-nut Oils 10.2.1 Tallow Tallow, is defined as a material containing over 50% fat derived from the bodies of land animals. The remaining 49% of tallow can be anything so long as the product meets material specifications for colour, titer etc. As such - the compositions of tallows are as variable as the types of land animals. The majority of tallow does come from cattle but there are many types of cattle Different breeds of cattle product tallows with different fatty acids compositions and other characteristics Different diets and climates experienced by cattle produce tallows with different characteristics

An important characteristic is the relative proportion of saturated fatty acids and unsaturated fatty acids.

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This characteristic can be best expressed directly as Iodine Value (IV) and for traded tallow that will vary from about 38 for tallow from Brazil to an average of 47 for Europe/ East coast USA to 53 for some USA tallow from the Gulf region. [The ratio of saturated to unsaturated fatty acids is also commonly expressed as the indirect measure of Titer (approximately the solidification temperature of the fatty acids). Iodine Values 38, 47 and 53 correspond approximately to Titers of 46, 42 and 38C] An Iodine Value range 38-53 is big and would result in soaps with quite different hardness and user properties. 10.2.2 Palm Oil Although there are some small variations in the compositions of palm oils grown in different continents, whole palm oil has a very constant composition around the world. This is because many of the trees are from cloned plants and climate/ soil qualities affect yield rather than fatty acids composition. Whole palm oil usually has an Iodine Value of 53-55, indicating that it is quite like a softer type of tallow. However, much palm oil is fractionated into Palm oleine (POf) Typical Iodine Value 58 and widely used as edible oil. However, please note that there can be opportunities to use some palm oleine in oil blends for soap. Palm stearines (POs) Fractionation by different companies produces a range of palm stearines having different Iodine Values. Traded true POs may have IVs 33 to 38 but often the traded material will also contain some palm oil blended with POs and the IV can be up to 50.

10.3 Blending Oils for Soap Given that there is such a wide range of non-nut oils available how best can the blend be selected? Rules such as INS (Iodine Value Saponification Value) are well established but the author has always contended that for day to day use the rules can be made much simpler. The proposition is that the type and % of nut oil in a soap is usually fixed by Cost Availability The nut oil % in peer products in the market

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Therefore most oil blending options need only consider the non-nut oil component of the blend. The procedure is to blend to a target Iodine Value for the non-nut oil fatty acids blend. A good target is Iodine Value 45-50, usually IV 45. A simple equation will then indicate how to blend non-nut oils of different IVs. For example, to blend a lower IV oil (harder oil) with a higher IV oil (softer oil) to a selected target IV IV soft oil - IV target % harder oil = -------------------------- x 100 IV soft oil - IV hard oil Examples: 1. An extreme example 80/ 20 type soap made using palm stearine (POs) , cottonseed oil (CTO) and coconut oil (CNO) POs IV = 38, CTO IV = 110. Let the blend target IV = 47 in this case. % harder oil = 110 - 47 -------------- x 100 = 87.5% 110 - 38

The non-nut oil is therefore 87.5% POs of IV 38 and 12.5% Cottonseed oil of IV 110. Blending this with 20% coconut oil gives an overall blend composition of 70 POs/ 10 CTO/ 20 CNO The processing characteristics and user properties of soap from such a blend will be fully comparable with those from regular 80/20 soaps made using conventional tallow and coconut oil. 2. A less extreme example A less extreme and more practical example is to blend whole palm oil with palm stearine. Whole palm oil with IV 53 gives quite a soft soap for modern high speed finishing lines and it is useful to blend whole palm oil with some (cheaper) palm stearine. Whole PO = IV 53 % harder oil = POs = IV 33 (a hard type of stearine) 53 - 47 -------------- x 100 = 30% 53 - 33

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The non-nut oil blend is therefore 70% whole palm oil and 30% IV 33 POs and for an 80/20 type soap that means an overall blend of 56 PO/ 24 POs/ 20 CNO Many other examples are possible eg Hard POs IV 33 + Soyabean oil IV 133 = 91 POs/ 9 BO Hard Brazilian/ Argentinean tallow IV41 + whole palm oil = 75 Tallow/ 25 PO Palm stearine IV 35 + Lard IV 65 = 67 POs / 33 LA Hard tallow IV 40 + Sunflower oil IV 135 = 92 Tallow/ 8 SF All of these are examples of soaps known to have been produced. Because of local circumstances the IV target may have been different for each example. This simple blending rule has never failed but does have limitations The calculations get complex if more than two oils are involved The simple rule does not cope with using hydrogenated oils likely to contain significant amounts of trans fatty acids eg C18:1 trans (elaidic acid) has the same IV as C18:1 cis (oleic acid) but the fatty acids and their soaps have very different properties oleic Mpt 14oC, elaidic Mpt 42oC Using IV does not distinguish between C18:1 and C18:2 and really there should be some limit on C18:2 in an overall blend It can be sensible to also impose a limit on the total % of oxidation-vulnerable C18:3 (mainly from using soya oil)

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Appendix 1
Krafft Point (Krafft Temperature) At low temperatures a saturated surfactant solution will be in equilibrium with solid surfactant. The solubility will be low because the temperature is too low for micelles to form. At the Krafft Point (Krafft Temperature) micelles will form and the surfactant can then dissolve into the micelles rather than into the water. The surfactant therefore suddenly becomes much more soluble, as is shown in the following curve for sodium decylsulphonate.

CMC (critical micelle concentration) is mainly determined by the hydrophobic group of a surfactant but the Krafft Point depends strongly on the nature of the detergent head group and the length of the hydrocarbon chain. The hydrocarbon parts have to be in a liquid state for micelles to form. Solidification of the hydrocarbon chain is favoured by the cohesion between hydrocarbon chains, which increases with their length. Hence, the Krafft Point increases with increased hydrocarbon chain length. E.g. C10 SO3Na 22 C C12 SO3Na 34 C C14 SO3Na 43 C C16 SO3Na 52 C C18 SO3Na 60 C

Solidification can however be hindered if the hydrophilic head group is large enough to prevent the carbon chains from getting close enough for effective cohesion. The cross section of a typical carbon chain is about 0.22 nm2. For a typical micelle the head group

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area must be greater than 0.5 nm2. A head group of cross section much less than 0.5 nm2 will tend to stabilize the solid hydrate ie it will raise the Krafft Point. The effect of head group size can be seen below C16 SO4Na 38 C C16 SO3Na 52 C C16 N(CH3)3Br 26 C

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