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Interesting study on SLES helping cetyl alcohol bind hair
I always thought fatty alcohols were added to shampoos because of their slip and mild conditioning properties
or that they were an early low-poo attempt as surfactant molecules attract fatty alcohol carbon chains, rendering them unavailable for attracting hair oils.This study says that SLES-fatty alcohol ‘gel networks’ help hair bind cetyl/stearyl alcohols
The gel-netrowk is crucial, if it’s missing, fatty alcohol deposition won’t happen
https://www.deepdyve.com/lp/wiley/gel-network-shampoo-formulation-and-hair-health-benefits-pQODAsekXoColloidal Gels Formed by Dilute Aqueous Dispersions of Surfactant and Fatty Alcohol
This study says that the gel-network is formed by mixing water, fattyl alcohols, and just some SLES (not too much SLES yet as it won’t form the gel-network)
(please look up the study in Google, it links to an immediate download pdf at springerling.com ,I’m unable determine a direct link address)This patent suggents that
1 SLS doesn’t form the network as well as SLES
2 Mix equal parts of SLES and fatty alcohols, water, wait for the gel-network to form
and only then dilute with all other shampoo ingredients.
https://data.epo.org/publication-server/rest/v1.0/publication-dates/20170726/patents/EP2763748NWB1/document.pdf
(please check the patent legal status, and don’t infringe any patents. Post meant just for scientific discussion purposes). -
25 Replies
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In the first study
Gel network shampoo formulation and hair health benefits.Marsh JM1, Brown MA2, Felts TJ1, Hutton HD2, Vatter ML1, Whitaker S1, Wireko FC1, Styczynski PB1, Li C1, Henry ID1.AbstractOBJECTIVE:The objective of this work was to create a shampoo formula that contains a stable ordered gel network structure that delivers fatty alcohols inside hair.METHODS:X-ray diffraction (SAXS and WAXS), SEM and DSC have been used to confirm formation of the ordered Lβ gel network with fatty alcohol (cetyl and stearyl alcohols) and an anionic surfactant (SLE1S). Micro-autoradiography and extraction methods using GC-MS were used to confirm penetration of fatty alcohols into hair, and cyclic fatigue testing was used to measure hair strength.RESULTS:In this work, evidence of a stable Lβ ordered gel network structure created from cetyl and stearyl alcohols and anionic surfactant (SLE1S) is presented, and this is confirmed via scanning electron microscopy images showing lamella layers and differential scanning calorimetry (DSC) showing new melting peaks vs the starting fatty alcohols. Hair washed for 16 repeat cycles with this shampoo showed penetration of fatty alcohols from the gel network into hair as confirmed by a differential extraction method with GC-MS and by radiolabelling of stearyl alcohol and showing its presence inside hair cross-sections. The gel network role in delivering fatty alcohol inside hair is demonstrated by comparing with a shampoo with added fatty alcohol not in an ordered gel network structure. The hair containing fatty alcohol was measured via the Dia-stron cyclic fatigue instrument and showed a significantly higher number of cycles to break vs control.CONCLUSIONS:The formation of a stable gel network was confirmed in the formulated shampoo, and it was demonstrated that this gel network is important to deliver cetyl and stearyl alcohols into hair. The presence of fatty alcohol inside hair was shown to deliver a hair strength benefit via cyclic fatigue testing.© 2017 Society of Cosmetic Scientists and the Société Française de Cosmétologie.
https://www.ncbi.nlm.nih.gov/pubmed/28594472
Free preview at:
https://www.deepdyve.com/lp/wiley/gel-network-shampoo-formulation-and-hair-health-benefits-pQODAsekXo?key=bioportfolioBy SLES1S I guess they meant SLES 1 Ethylene Oxide mol, didn’t they?
They first mixed and heated just some (not all) of the SLES with stearyl and cetyl alcohol to allow for the gel-network to form itself, allow to cool off
and only then, all other shampoo ingredients were added:Shampoo formulation
The gel network was made with 11% of SLES1S surfactant, 8% stearyl alcohol and 4% cetyl alcohol and 77% deionized water where all ingredients were first heated together to a temperature between 75 and 90 C and then cooled to room temperature. This process formed the gel-premix.
A small amount of this pre-mix, 2.3% fatty alcohol by weight of the final shampoo, was then dispersed in a typical shampoo containing other benefit agents such as surfactants, silicones and polymers.
https://www.deepdyve.com/lp/wiley/gel-network-shampoo-formulation-and-hair-health-benefits-pQODAsekXoIt certainly looks interesting and worth trying, even though 2.3% would normally seem like a lot in a shampoo without gel networks.
Also interesting to try SLES + dimethiconol since the latter has some -OH groups, although two of them one on each side, and with a silicon chain, instead of carbon like fatty alcohols.
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Interesting, didn’t think it could have that benefit, I always saw it as a stability ingredient. It would be interesting to see a comparative against other emulsifying waxes.
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I will try this. I don’t have stearyl alcohol but I do have cetearyl alcohol which is a mixture of cetyl and stearyl so it should work.
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While cetyl alcohol + surfactant -only can be used
fatty alcohol mixtures yield more stable gelsColloidal Gels Formed by Dilute Aqueous Dispersions of Surfactant and Fatty Alcohol…The SDS/CA/water system was chosen to keep the model as simple as possible although it is well known that mixtures of fatty alcohols, for example, of CA and stearyl alcohol (SA), yield more stable gels…
…A chain length mismatch of the alcohol molecules as in the commonly used mixtures of cetyl and stearyl alcohol helps to prevent crystallization…
https://www.springer.com/cda/content/document/cda_downloaddocument/9783319151281-c2.pdf?SGWID=0-0-45-1504288-p177222117So, yes
you can use a cetyl + cetearyl alcohol mix to match the cetyl+stearyl percentages used in the study, as @Belassi just suggested.By the way, in this study they used
Sodium dodecyl sulfate = Sodium lauryl sulfate = SLS
instead of SLES -
That’s useful to know, thanks. I was wondering whether to try SLS as well as SLES because the SLES I have here is the type with 2 mols of EO. I will also try ALS because that’s directly compatible with the surfactant blend I use.
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I think there’s something wrong here. I need some help.
According to what I read, you use 12% cetyl/stearyl and 12% SLES. And then you add 2% of that to the shampoo formula.
So I just tried 12% cetearyl + 12% of ALS + water Q/S and I am glad I only made 500mL because as it is cooling down, it is “forming a gel network” with a vengeance. It’s becoming a solid! -
I should think so, but because of the probable reduction in foaming due to the extra fatty alcohols, I would not reduce the surfactant %.
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OK. Now it has cooled down completely I have a VERY thick white gel. Is this what they mean by the “gel network”? And as to dispersing it in a shampoo? I will persevere…
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@Belassi there are 2 studies and 1 patent
all with slightly different percentages, which one are you talking about?for the study where they used SLES:
Gel network shampoo formulation and hair health benefits
Shampoo formulation
The gel network was made with 11% of SLES1S surfactant, 8% stearyl alcohol and 4% cetyl alcohol and 77% deionized water where all ingredients were first heated together to a temperature between 75 and 90 C and then cooled to room temperature. This process formed the gel-premix.
A small amount of this pre-mix, 2.3% fatty alcohol by weight of the final shampoo, was then dispersed in a typical shampoo containing other benefit agents such as surfactants, silicones and polymers.
https://www.deepdyve.com/lp/wiley/gel-network-shampoo-formulation-and-hair-health-benefits-pQODAsekXo
(you can preview the full study there for 5 minutes for free, or register for a free-trial, credit card required but not charged after the free-trial expires)It says 11%, but I don’t think 12% you used is going to change the end result
You can also fine tune by checking the stearyl/cetyl alcohol ratio in the cetearyl-alcohol batch that you have, adding a bit extra cetyl-alcohol as required to perfectly match the 8%/4% used in the study.
Although I don’t think it’s going to make it any different.Now they added 2.3% total fatty alcohols in the shampoo, not 2.3% of the gel network.
So, if the gel network has 12% fatty alcohols in it ( 8% stearyl + 4% cetyl)
you need:
2.3 / 0.12 = 19.17% gel-network in the shampoo in order to get 2.3% total fatty alcohols from it.As to verify if calculations are correct:
19.17% gel-network multiplied by 12% of it are fatty alcohols = 2.3% total fatty alcohols in the shampoo.
(you can always use less of it, as they usually use high amounts in studies, so effects are clearly seen. i.e. you can use only 1% or 0.5% total fatty acids in the shampoo, as many recipes already do).This 19.17% gel-network has 11% of SLES on it
so it’s adding 2.11% SLES to the shampoo.For comparison, you can just mix all shampoo ingredients together, without making the gel-network first
(make sure to add the 2.11 SLES previously mentioned)
but we probably know the end result in advance = undissolved fatty alcohols.Again, you can preview the full study for 5 minutes for free at deepdvye.com
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The other study advises to cool it off slowly,
to better form the network
so it doesn’t hurt to try it that way.For dissolving it in water,
for every 19.17 g of the gel-network, add 30.83 mL of water
in order to get a 50% mix in the final shampoo.
If it doesn’t dissolve by tomorrow with occasional stirring, it’s likely going to need a high shear blender.@Perry are these ones the same thing as lamellar gel networks?
https://knowledge.ulprospector.com/4712/pcc-lamellar-gel-network-technology-a-primer/ -
I used the first study but I only added 2% of the gel network. Even that was enough to produce an increase in viscosity. I tried the result and even at 2% it has a conditioning effect.
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2% gel-network = 0.24% total fatty acids in the shampoo
I wonder if gel-networks are the main “secret” behind the hard-to-replicate conditioning effect of big-name products:
LGNs are important because MOST oil-in-water skin-care emulsions sold globally are based on LGNs stabilized with polymers. MOST hair conditioners sold globally are also based on LGNs. The peroxide phase of many two-part hair-dye formulations and many cream depilatories and hair relaxers are also LGN-based.
https://knowledge.ulprospector.com/4712/pcc-lamellar-gel-network-technology-a-primer/
The word ‘most’ is the key here.… Under the right conditions, these mixtures have been found to form lamellar crystal mesophases and gel networks that can greatly increase viscosity by converting the micellar structure into the lamellar one capable of forming vesicles and, at the same time, confer stability upon emulsions…
https://books.google.com.ua/books?id=FAYNAwAAQBAJ&pg=PA565&lpg=PA565&dq=“cetyl+alcohol”+lamellar+gel+network+shampoo&source=bl&ots=sttMizm2cK&sig=XSIJNnab1Qn_WHBtMqFDylKOwD8&hl=en&sa=X&ved=0ahUKEwifu7bjyKHbAhUHJVAKHYT-BFY4ChDoAQgxMAI#v=onepage&q=”cetyl%20alcohol”%20lamellar%20gel%20network%20shampoo&f=false
(Sorry for the long link. I don’t know how to make it shorter, yet still redirecting to the same page in the book).This one touts gel networks as THE key ingredient:
…Similar to the function of coacervates in shampoo, lamellar gel network in conditioner is the key factor for the slippery and smooth feel of wet hair…
https://books.google.com.ua/books?id=HGp_CwAAQBAJ&pg=PA606&lpg=PA606&dq=lamellar+gel+network+shampoo&source=bl&ots=DW-VCYytJP&sig=4q8NPzeDp5y3Q98WBnI4RrjsMcg&hl=en&sa=X&ved=0ahUKEwin2NyJ0aHbAhXQfFAKHVu7DbMQ6AEIZDAN#v=onepage&q=lamellar%20gel%20network%20shampoo&f=falseThis one says that fatty alcohols are THE most deposited ingredient by conditioners.
It also mentions a strictly controlled heating and cooling process to make the gel network:
…The process starts as an emulsion of the surfactants and alcohols in water. The materials then go trough a strictly controlled heating and cooling process: the application of heat causes the solid compounds to melt, and the solidification process enables a setting of the lamellar assembly molecules in a fully extended conformation, creating a lamellar gel network. When this networks interacts with the hair surface, the high concentration of fatty alcohols make it the most deposited ingredient group, followed by the silicones and cationic surfactants. Typical deposition levels for cationic surfactant, fatty alcohol and silicone are around 500-800, 1000-2000, and 200 ppm, respectively. Typical concentrations are approximately 2-5, 5-10, and 1-10 wt%, respectively…
https://books.google.com.ua/books?id=IaNtd8VwWNQC&pg=PA15&lpg=PA15&dq=lamellar+gel+network+shampoo&source=bl&ots=ODjH1HfujO&sig=roakteBRFWz0l1iEdWObxzg0u-U&hl=en&sa=X&ved=0ahUKEwj8kf6o0aHbAhUGbFAKHTr7Be04ChDoAQglMAA#v=onepage&q=lamellar%20gel%20network%20shampoo&f=falseThese articles/books also say that cationic surfactant deposition works better when there are lamellar gel networks.
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That’s useful. I am going to continue with this.
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I’d go with higher % actives to form a solid. I’ll give it a shot if I can get any alcohol from a supplier, I don’t want to buy a bag.
How hot you went and how much torque did you use?. I remember a chemist complaining about the temperature of the reactors when making NFs, they were about 250°C.
Anyone has experience in this?. Im wondering now if this could work with milder surfactants, or maybe CAPB.
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@Belassi this patent implies that it should become solid
as it doesn’t make sense to pass a liquid trough a mill:Preparation of the Gel Network Pre-Mix
To prepare the gel network pre-mix, the water is heated to about 74 °C and the fatty alcohol and secondary surfactant (e.g. Sodium Laureth Sulfate) are added to it. After incorporation, this mixture is passed through a mill and heat exchanger where it is cooled to about 32°C. As a result of this cooling step, the fatty alcohol, the secondary surfactant, and the water form a crystalline gel Network
Gel Network Pre-Mix Example
Table of Gel Network Premix Example
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Thanks Gunther, I hadn’t noticed that. I did prepare it exactly as described but using ALS. It formed a very thick liquid at 80C and as it cooled, it became a very thick white solid.
I’m going to try this with one or two of our shampoos and see. -
Interesting, the shampoo formula for Pantene back in the early 2000’s contained Stearyl Alcohol, Cetyl Alcohol and ALES + ALS
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I added
77% deionized water
11% SLES
12% cetearyl alcoholI didn’t dissolve SLES first, heat water or melt stearyl alcohol first.
I just poured everything together at room temperature
and warmed it up in a water-bath to about 77 C while stirring.
Some bubbles appeared.
Then allowed it to air cool while still in the water-bath.
BTW I used a pewter cup, as I feared it would become solid and I could break a beaker.The end result looks like a whithier and thicker buttercream but it didn’t become solid.
I washed my hands with it and it didn’t lather at all. It was really conditioning and left a tiny, bright coat on my hands despite it being a quick wash.
It seemed to dissolve in water, with a cloudy, creamy whitish color, and some latter. You can even hear its bubbles crackling.
I’ll rinse my hair with it tomorrow
and leave the rest standing still, to see if stearyl alcohol precipitates out of solution or something.Then I will try predissolving SLES in water before warming it all from room temperature, so I don’t have to stir SLES that hard and make bubbles in the process.
@Belassi I got a totally different result (cream)
What concentrations, warming/mixing/cooling-off protocol did you use?
Were you able to dissolve the solid in water? -
I used the same proportions except I used ALS. I melted the cetearyl and raised the temp of the surfactant and water to 80C. Then added the cetearyl to the surfactant, stirred a while, added the water, mixed until a homogeneous thick liquid, allowed to cool. Thick white solid results. I was able to dissolve the solid in shampoo.
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As @Perry said, Pantene shampoos do contain cetyl and stearyl alcohol
NOURISHING BLENDS
SHAMPOO
…and Lipids (Stearyl Alcohol, Cetyl alcohol) that act like hair’s natural, healthy oils.PURIFYING INGREDIENTS
SHAMPOOCleansing Complex: Sodium Laureth Sulfate, Cocamidopropyl Betaine, Sodium Lauryl Sulfate, Cocamide MEA. -
In this P&G patent they used a fatty alcohols mixture + either SLES or Behentrimonium Cl.
- Preparation of the Gel Network Pre-Mix
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[0256]To prepare the gel network pre-mix, about 20% of the water is heated to about 74° C. and the fatty amphiphile and the secondary surfactant (e.g., Behenyltrimethylammonium chloride (Varisoft BT-85) or Sodium Laureth Sulfate) are added to it. After incorporation, this mixture is passed through a mill and heat exchanger where it is cooled to about 35° C. As a result of this cooling step, the fatty amphiphile, the secondary surfactant, and the water form a crystalline gel network.
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[0257]For mixtures of different fatty amphiphiles, it may be beneficial to pre-mix the fatty amphiphile materials before incorporation into the water. This can be done by co-melting the different fatty amphiphiles together and utilizing this melt or cooling into a solid phase and incorporating this into the heated water along with the secondary surfactant. Another variation could be to co-melt the one or more fatty amphiphiles and the secondary surfactant before incorporation into the water. Some gel network compositions with chain melt temperatures between about 27° C. to about 35° C. will need to be cooled below 27° C. to ensure the lamellar phase structure is froze.
https://patents.google.com/patent/US20060024256A1/en
They tried pre-forming the gel-network along some esters like glyceryl distearate/stearate/palmitate, PEGs, sorbitans, but they don’t mention how they compared to plain SLES+fatty alcohol+water.
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This patent by Unilever claims that glyceryl mono stearate, CTAC and Quaternium 90 Bentonite helps network stability.
Although very few commercial products have Q90B in them, so it didn’t make it to the market.…We have surprisingly found that conditioning gel phases or gel networks comprising a particulate are more stable in the presence of glyceryl monostearate…
https://encrypted.google.com/patents/WO2009112420A1?cl=en—
It doesn’t hurt to try making the gel network along some Glyceryl monostearate, to see if it works.
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It does seem like quite a good way of incorporating some refatting effect at low cost without destroying the foam profile. I think it also thickens to some extent.
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@Belassi did you try washing your hands with it?
Either with the bare gel-network, or its solution?I did, to get a feel for it
and it leaves a smooth, waxy layer. -
Yes, by itself I agree with you. In a body wash at 4% content it had a skin conditioning effect.
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