Cosmetics Ingredients are not all the same

by Perry Romanowski
As a beginning chemist, one of the most frustrating things for me as I started my career was
the product ingredient lists. While all the products had cosmetic ingredient listings, the
ingredient were rarely things that I learned about in college. The cosmetics industry just does
not use the same naming system for ingredients as the one you learned in college.
The college system of naming is the IUPAC system. The great thing about this system is that
it allows you to figure out the chemical structure of any material from its name alone.
Unfortunately, it also leads to incredibly long names for the ingredients so it isnt practical to
use it for naming cosmetics.
The cosmetic system is the one created by the PCPC and listed in the INCI Dictionary. They
use a whole different set of naming conventions which lead to shorter names but also make it
impossible to ascertain most ingredients structures from the name. Oh well, you dont really
need to know the molecular structure to be a good cosmetic chemist.

Ingredients are not the same

One of the things I wanted to point out in this post is that not all ingredients are the same
even if they have the same name. To understand why, lets look at an ingredient like Sodium
Lauryl Sulfate (SLS).
SLS is a pretty straightforward molecule. It is a surfactant with a 12-carbon chain backbone
attached to a SO4 group and ionically bonded with a sodium ion.
But when you buy Sodium Lauryl Sulfate from one supplier, you might not be getting the
same chemical as when you buy your ingredients from another supplier. Why?
It turns out that this is because of the way sodium lauryl sulfate is produced. To create SLS,
you react Lauryl Alcohol with Sulfur Trioxide gas. This is further neutralized with Sodium
Hydroxide to produce SLS. The key part of this reaction is the Lauryl Alcohol and the way
that it gets produced.

Lauryl Alcohol
Lauryl alcohol can be obtained from a number of sources including from the fatty acids of
plant oils and crude oil. Unfortunately, these sources are a mixture of fatty acids and it is
incredibly difficult to isolate only the C12 molecules. So, instead of starting the production of
SLS with pure Lauryl Alcohol, most companies start with a mixture that is mostly Lauryl
Alcohol but contains a number of other residual fatty alcohols.
Therefore, the chemical properties and quality of the SLS will vary from raw material
supplier to raw material supplier depending on the quality and type of starting material for
their SLS. The more pure the starting Lauryl Alcohol source, the better controlled the SLS
end properties will be.

This same thing applies to most any other cosmetics ingredients that you might use. Its pretty
rare that a cosmetic ingredient is pure. It is nearly always a mixture of the main ingredient
you want and some residual ingredients that you might not.
Tagged as: cosmetics ingredients, raw materials

HLB The Easiest Way to Create An Emulsion

by Kelly Dobos
As a cosmetic chemist you will undoubtedly be asked to make products that require you to
combine materials that arent easily compatible. Fortunately, there is a system that can help
you get started.
Cosmetic Emulsions

Emulsions are one of the most common forms of cosmetic products. You find them in skin
lotions, make-up, and even hair products. By definition an emulsion is a dispersion of two or
more immiscible materials, where one phase, also know as the internal phase, is dispersed in
the continuous or external phase. Cosmetic emulsions are classified as oil in water (O/W),
water in oil (W/O) and water in silicone (W/Si). Multiple emulsions such as oil in water in oil
(W/O/W) are also possible. Oil in water emulsions are the most common due to preferable
cost and light skin feel.
In order to create an oil in water emulsion (one that remains stable for a long enough time),
work must be done to overcome the interfacial tension between the two phases. This can be
achieved by mixing; however mixing even at very high rates is not enough to provide long
term stability. An emulsifier or combination of emulsifiers is needed to stabilize droplets of
the dispersed phase. For example, simple oil in vinegar salad dressings will separate rapidly
without the use of an emulsifier like mustard.
Using Surfactants

In this industry, we use surfactants to create emulsions. Surfactants are molecules that have a
hydrophobic (oil soluble) and an effective hydrophilic (water soluble) portion. They act as
emulsifiers by significantly lowering the interfacial tension and decreasing the coalescence of
dispersed droplets.
HLB Formulating

Figuring out what surfactant to use for any specific formula will be a challenge you face as a
cosmetic chemist. There is a great deal of research on surfactants and their behavior. But
studying the thermodynamic equations and phase diagrams associated with surfactants can be
a daunting task, not to mention the number of surfactants available to the formulator is vast.
Luckily for us, William C. Griffin developed a way to streamline the selection of surfactants
by utilizing the ratio of the hydrophobic to the hydrophilic portion of the molecule. This
method is referred to as the HLB (Hydrophile Lipophile Balance) method. Griffin first
presented this method at meeting of the Chicago Chapter of the Society of Cosmetic
Chemists in 1949 and it is still widely used today. He published the method shortly there
after.1 (A bit of trivia for you, the Chicago Chapter was the first chapter formed in Society of
Cosmetic Chemists)
The HLB method applies to nonionic (uncharged) surfactants but attempts have been made to
broaden the concepts to other surfactant types including silicone surfactants. And using the

HLB system to create emulsions is quite simple. All you have to do is calculate the HLB
number of your surfactant, then the Required HLB for the oil phase and match the two
numbers.
Determining the HLB of a surfactant

A typical nonionic emulsifier (e.g. Laureth-4) contains an ethylene oxide groups or

polyhydric alcohol hydrophilic portions with a fatty alcohol hydrophobic portion. The HLB
for a nonionic surfactant can be calculated as follows:
HLB = Weight % Hydrophile/5
Example 1: HLB calculation for Laureth-4
Molecular weight of ethoxylate portion = 176
Molecular weight of lauryl alcohol = 186
Wt. % Hydrophile = (176/(176+186)) x 100 = 48.6%
HLB = 48.6/5 = 9.7
Based on the calculation, surfactants with high HLB values will be more water soluble and
those with low HLB values are more oil soluble. Division by 5 just allows for a compact,
easy to use scale. The calculation is simple, but you wont usually have to figure it out since
most surfactant HLB values are readily available through literature references and surfactant
suppliers.
Calculating HLB of oil phase

Each lipophilic ingredient in the oil phase has its own required HLB. These required HLB
values are determined experimentally, however a method utilizing solubility parameters has
been proposed by Vaughan and Rice.2 Required HLB values for some common oil phase
ingredients are available to the formulator in literature. The Reqd HLB values are
approximate and can vary by about 1 unit. It is also important to keep in mind that cosmetic
emulsions often have complex oil phases with several components. The required HLB of an
oil phase mixture can be calculated by first calculating the percent of the oil phase each
ingredient contributes. This percentage is then multiplied by the required HLB for each of
those ingredients and the results are summed.
Example 2: Calculation of required HLB for an oil phase mixture
The oil phase is 10% of the total formulation and consists of:
4% Shea butter, 40% of the oil phase. Reqd HLB of 8.

3% Jojoba oil, 30% of the oil phase. Reqd HLB of 6.5.

3% Sunflower seed oil, 30% of the oil phase. Reqd HLB of 7.
Total required HLB:
Shea butter contribution 0.4 x 8 = 3.20
Jojoba oil contribution 0.3 x 6.5 = 1.95
Sunflower oil contribution 0.3 x 7 = 2.10
Total Reqd HLB = 7.25
You can now select emulsifiers to match the required HLB of the oil phase and create an
emulsion. A blend of high and low HLB surfactants is often used to achieve the desired value
in part because of demonstrated effectiveness and efficiencies in packing at the interface. The
HLB for the surfactant blend is calculated in same manner as the required HLB for a blend.
Example 3: Calculation of HLB for a surfactant mixture
The surfactant mixture is a 70/30 blend of Steareth-2 and Steareth-21.
Total HLB:
Steareth-2 contribution 0.7 x 4.9 = 3.43
Steareth-21 contribution 0.3x 15.5 = 4.65
Total HLB = 8.08
In order to match the HLB of a particular oil phase, it is easiest to set up a spreadsheet with
the calculation and vary the percentages of each emulsifier in increments of 5% to find the
right ratio.
Limitations of HLB

Although a very useful tool, the HLB system does have some limitations. For example
additional water phase ingredients are not considered but still may impact the stability. The
method also does not provide information as to how much surfactant is needed, but 2 to 4%
surfactant is a good starting point to begin further optimization for stability. So it is important
to keep in mind that the HLB system is not absolute in prediction of your formulations
behavior, but a very good starting point for achieving emulsification.
References

1. Griffin WC; Calculation of HLB Values of Non-Ionic Surfactants, Journal of the Society of
Cosmetic Chemists; 1954. Vol. 5, pp 249-235
2. Vaughan, C.D. Rice, Dennis A.; Predicting O/W Emulsion Stability by the Required HLB
Equation; Journal of Dispersion Science and Technology; 1990. Vol. 11 (1), pp 83 91.

COA Savvy
by Kelly Dobos

Raw materials arrive with a certificate of analysis (COA) meant to ensure the product
conforms to certain specifications that contribute to end performance and that the material
has not degraded or become contaminated. COAs are also very important to review when
starting to work with a new or unfamiliar material because parameters covered on the COA
can help you understand how the material will function in a formulation and warn you of
potential pitfalls. Since the meaning of many of the terms on a certificate of analysis are not
obvious, below are some common COA characteristics with information about what they
mean when it comes to formulation.

Common Certificate of Analysis Terms

Ash Content Describes the inorganic content of a material. In ash content analysis the
sample is charred and the remaining ash is expressed a percentage of the initial sample
weight. Most minerals are converted to oxides, sulfates, phosphates, chlorides or silicates.
This information is important when working with ingredients that may be sensitive to metal
salts.
Iodine Value Measures the degree of unstaturation in fats and oils. The lower the iodine
value the lower the degree of double bonds and the more solid the material will be. Double
bonds may be stronger than single bonds, but they are more reactive, making iodine value a
good indicator of stability. Using a material with a higher iodine value may require the
addition of an antioxidant and special care in storage.
Peroxide Value Oxidation during storage and heating causes decomposition and off-odors
in fats and oils. Peroxide value analysis measures the concentration of hydroperoxides
generated in the first steps of the oxidative process.
Refractive Index (RI) Measures how much the speed of light is reduced when it travels
though a specific medium. A raw material will have a narrowly defined range for RI. RI
matching can also be used to create clear formulations.
Penetration In this test method a needle or cone is pushed into a solid or semi-solid sample
with a standard weight. The main determinant of penetration is the hardness of the material.
But it can also be telling of the crystalline structure and yield properties. These properties are
important when using waxes to stabilize some W/O emulsions or for controlling the
properties of lipsticks.

Saponification (Sap) Value Indicates the mean molecular weight of triglycerides. In the
test, the amount of potassium hydroxide needed to saponify (make soap from) 1 gram of a fat
or oil is determined. Triglycerides with longer fat chains have a low saponification value
because there will be less fat chains to saponify in a 1 gram sample than a sample with many
short chain triglvycerides. Sap values are important for making soap and soap-stabilized
emulsions. Saponifcation values for NaOH are also available but most commonly reported by
KOH, so be sure to check the test method referenced on the COA.
Unsaponifiable Matter Content While sap value describes fat chain length,
unsaponifiable matter content is a measure of the other organic components contained in fats
and oils. This may be contaminant like mineral oil or naturally occurring sterols, tocopherols,
pigments, etc. This test involves the saponification of a sample followed by dilution and
extraction with an organic solvent.
Hydroxyl Value Triglycerides in fats and oils are subject to hydrolytic rancidity. Hydroxyl
value measures the free OH groups formed by cleavage of fat chains from the glyceride
molecule that occur with hydrolysis. The hydroxyl value can be used as an indication of the
quality of the material.
Acid Value Similar to hydroxyl value, acid values measures hydrolytic rancidity by
measuring the free fatty acids have been liberated from their ester linkage with a parent
glyceride molecule by titration with a base. High hydroxyl and acid value numbers indicated
rancidity.