lamellar gel network

BrendaMBrendaM Member
Hello
I discovered an article ulprospector highlighting the effect of LGNs in hair conditioners.( said article being https://knowledge.ulprospector.com/8959/pcc-hair-conditioner-formulations/). 
In the comment section, someone asked what would be the optimum ratio of low HLB vs high HLB to formulate a daily, economical conditioner. To which the author replied, Typically 1-1.5% Quat (high HLB) and 3-5% Cetearyl alcohol (low HLB) or a ratio of around 25-30%.
Based on the above, what would be the same ratios for: 
a daily leave-in conditioner
a detangler
a deep treatment

 I'm also struggling with this part under factors affecting LGN performance
" Ratio of high HLB to total surfactant has a significant impact on viscosity and the conditioning properties. For optimum conditioning, this ratio should be ~30%."
Is it possible for someone to elaborate with an example?

Comments

  • zeteinzetein Member
    It seems all conditioners are based on quaternium surfactant + fatty alcohols = LGNs
  • AbdullahAbdullah Member
    BrendaM said:
    Hello
    I discovered an article ulprospector highlighting the effect of LGNs in hair conditioners.( said article being https://knowledge.ulprospector.com/8959/pcc-hair-conditioner-formulations/). 
    In the comment section, someone asked what would be the optimum ratio of low HLB vs high HLB to formulate a daily, economical conditioner. To which the author replied, Typically 1-1.5% Quat (high HLB) and 3-5% Cetearyl alcohol (low HLB) or a ratio of around 25-30%.
    Based on the above, what would be the same ratios for: 
    a daily leave-in conditioner
    a detangler
    a deep treatment

     I'm also struggling with this part under factors affecting LGN performance
    " Ratio of high HLB to total surfactant has a significant impact on viscosity and the conditioning properties. For optimum conditioning, this ratio should be ~30%."
    Is it possible for someone to elaborate with an example?

    Suppose you have 5% total surfactant (BTMS+fatty alcohol). 30% of it should be BTMS which equals 1.5% in formula.
    So 1.5% BTMS and 3.5% fatty alcohol. 
  • AbdullahAbdullah Member
    What i don't know is if they were talking about weight percentage or molecular weight percentage?
  • PharmaPharma Member, Pharmacist
    Basically all conditioners and many other cosmetic products which contain considerable amounts of fatty alcohols, free fatty acids, glyceryl monoesters of fatty acids, fatty acid-2-lactylates, and other similar derivatives are highly likely to contain LGNs.
    The % given are nearly always weight-%, however, what really counts is the mol-ratio (= number of molecules) of surfactant (or emulsifier, nearly no matter wheter anionic, cationic, or nonionic, as long as the hydrophilic head group is rather small) to 'LGN promotor'. Anything from 6:1 to 1:6 (whole numbers preferred) is possible, high viscosity tends to be at a ratio of (approximately) 1:3 to 1:6. Ratios from 1:1 to 1:6 tend to be mostly LGN whilst ratios between 6:1 and 1:1 will result in mixed type emulsions (part micellar system, part LGN). Ratios of 1:>6 will result in a third phase composed of LGN promoter which doesn't do much good nor feel that great, simply put, it's blobs of fatty alcohol floating in the soup.

    BTW LGNs are a type of 'emulsion' which is not compatible with the HLB system and can not be calculated/predicted using the HLB system. Fatty alcohols allegedly have HLB values although these are only apparent values. They are not emulsifiers and therefore can't have HLB values (neither are they oils/fats and therefore can't have required HLB values either). Fatty alcohols are not considered emulsifiers nor co-emulsifiers in the proper sense, they are a species on their own (= LGN promotors or so). Glyceryl monoesters and other LGN promotor on the other hand can be emulsifiers/co-emulsifiers and can have HLB or HLD values.
    The mention of high and low HLB emulsifiers is hence incorrect. Correct would be emulsifier (doesn't matter which HLB) plus LGN promotor at a correct molecular ratio. Depending on several factors (which aren't calculable by conventional means), the 'best' ratio of the two depends on both partners (including head and tail), not on any hydrophilic-lipophilic difference/balance.
    Where the article is right, anything which intercalates with lamellar crystalline structures can decrease viscosity. This concerns mostly unsaturated and branched hydrocarbon chains on either, the emulsifiers and the LGN promotors as well as some emollients (e.g. ester oils).
  • zeteinzetein Member
    How did (Cetearyl Olivate and Sorbitan Olivate) work? Which one plays TEA-Stearate and which one plays Stearic Acid?
    They are two lipophilic morculars unlike traditional lipophilic+hydrophilic combination. And being derived from olive oil makes them very unsaturated, which would hinder lamellar crystalline structure.
    How ever it still became one of the workhorses for liquid crystal cream advertising.
  • AbdullahAbdullah Member
    edited June 4
    @Pharma thanks a lot for such explanation.

    Some more questions

    All in mol ratio
    1. What is the best ratio for maximum emulsion stability?
    2. What is the best ratio for maximum conditioning in hair conditioner?
    3. Can liquid emulsifier like polyglyceryl-4 laurate+ GMS or fatty alcohol make LGN products?
    4. Can SLS or SLES+ GMS or fatty alcohol make LGN product?
    5. If GMS is used as LGN promotor, what should be counted as it's molecular weight?
    For example

    GMS is 358.57g/mol(google search
    GMS with 40% mono, 50% di & 5% tri is 500.512g/mol (my calculation)
    GMS with 90% is 385.215 g/mol(my calculation)

    So if i am using GMS with 40% mono, should i count it as 500.512 g/mol or 358.57 g/mol?

  • BrendaMBrendaM Member
    @Abdulla thank you for the example

    @Pharma if I were to design an experiment to determine which mole ratios would work with the various surfactants and 'LGN promoters' that I have, how would I go about it?
  • PharmaPharma Member, Pharmacist
    edited June 4
    Very well observed. Olivem 1000 is a gread example of an exception wherein seemingly everything contradicts the possibility of an LGN. I honestly don't know the true answer and was wondering too. Looks like there are two kinds of LGNs: the one people usually refer to is the α-gel network (a liquid crystall) which follows the mentioned rules and there are non-α-gel networks such as those formed for example by the branched-chain fatty alcohol 2-octyldodecanol which are said to be non-crystalline (couldn't find any reliable information). Neither could I find anything in literature which would shed any helpful insight in the matter of Olivem 1000. Cetearyl olivate and sorbitan olivate are very similar to one another and are therefore likely to assemble (well, they have to or it wouldn't work so nicely). Cetearyl olivate is a liquid ester wax similar to jojoba oil which doesn't have an HLB but an required HLB value and sorbitan olivate aka Span 80 which is a very low HLB emulsifier... My guess is that they form an 'inverse' lamellar phase. If you invert lamellar phases, you end up with another lamellar phase... basically, both are the same and by definition, both are liquid crystals. How one would obtain such a structure without the crystallinity... I honestly don't know but it does seem possible based on reason and it also seems possible that this combo actually works though it's 100% against the rules. Obviously, the HLB system in this case is as useless as it is with all LGNs.
    Regarding the other Q: TEA stearate = 'high HLB' emulsifier and stearic acid = LGN promotor. Totally follows the rules.
  • PharmaPharma Member, Pharmacist
    @BrendaM As one nearly always does in developing cosmetics: trial and error.
    Experimental setup depens on what you have, what you want, and how much time and effort you are willing to invest. Basically, you start with a formulation low in LGN promotor and subsequently add more until you hit the feel and stability you heart desires (if you don't, switch the basic formulation and start anew).
  • PharmaPharma Member, Pharmacist
    Abdullah said:
    ...
    All in mol ratio
    1. What is the best ratio for maximum emulsion stability?
    2. What is the best ratio for maximum conditioning in hair conditioner?
    3. Can liquid emulsifier like polyglyceryl-4 laurate+ GMS or fatty alcohol make LGN products?
    4. Can SLS or SLES+ GMS or fatty alcohol make LGN product?
    5. If GMS is used as LGN promotor, what should be counted as it's molecular weight?
    For example

    GMS is 358.57g/mol(google search
    GMS with 40% mono, 50% di & 5% tri is 500.512g/mol (my calculation)
    GMS with 90% is 385.215 g/mol(my calculation)

    So if i am using GMS with 40% mono, should i count it as 500.512 g/mol or 358.57 g/mol?
    1. As said, the optimal ratio of a given formulation (if said formulation even has one) depends on the formulation itself and can not be calculated.
    2. See N° 1.
    3. AFAIK laurate is the short end of hydrocarbon chains which still forms liquid crystals. However, the low melting point becomes an issue and may result in very fluidic liquid crystals.
    4. Yes
    5. Yes (is't still an estimate because all the other cosmetic ingredients are oft not pure and have only average MW but that's usually close enough).
  • AbdullahAbdullah Member
    Pharma said:
    Abdullah said:
    ...
    All in mol ratio
    1. What is the best ratio for maximum emulsion stability?
    2. What is the best ratio for maximum conditioning in hair conditioner?
    3. Can liquid emulsifier like polyglyceryl-4 laurate+ GMS or fatty alcohol make LGN products?
    4. Can SLS or SLES+ GMS or fatty alcohol make LGN product?
    5. If GMS is used as LGN promotor, what should be counted as it's molecular weight?
    For example

    GMS is 358.57g/mol(google search
    GMS with 40% mono, 50% di & 5% tri is 500.512g/mol (my calculation)
    GMS with 90% is 385.215 g/mol(my calculation)

    So if i am using GMS with 40% mono, should i count it as 500.512 g/mol or 358.57 g/mol?
    1. As said, the optimal ratio of a given formulation (if said formulation even has one) depends on the formulation itself and can not be calculated.
    2. See N° 1.
    3. AFAIK laurate is the short end of hydrocarbon chains which still forms liquid crystals. However, the low melting point becomes an issue and may result in very fluidic liquid crystals.
    4. Yes
    5. Yes (is't still an estimate because all the other cosmetic ingredients are oft not pure and have only average MW but that's usually close enough).
    Thanks
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