EXAMENSARBETE INOM TEKNISK KEMI,

AVANCERAD NIVÅ, 30 HP
STOCKHOLM, SVERIGE 2021

Medical White Oil in

Cosmetic Applications
HANNA DUBECK SCHÖMER

KTH
SKOLAN FÖR KEMI, BIOTEKNOLOGI OCH HÄLSA
By: Hanna Dubeck Schömer
22-06-2021

Supervisor: Emma Öberg

Examiner: Mark Rutland
Abstract
Moisturizers are the most prescribed products in dermatology, and the most common type of
moisturizer delivery systems are lotions and creams. These are emulsions and often contain
medical white oil (MWO) due to their protective properties and excellent skin compatibility.
The MWO used in cosmetics have traditionally been paraffinic. However, as naphthenic oils
often have been proven to create better emulsion stability, this thesis aimed to compare Nynas
AB s new MWO, N-MWO, with a paraffinic oil, P-MWO, with similar properties regarding
their emulsion stability. The two oils were compared by analyzing their emulsion stability
using a rheometer and a Mastersizer 3000 while varying the following factors: type of oil,
type of emulsifier, emulsifier concentration, and with and without perfume. The two
emulsifying systems used were the commercial product Promulgen D from Lubrizol and the
combination of Tween 80 and Span 20. Better emulsion stability and smaller droplet size
distribution were obtained when a higher content of Promulgen D was added. However, a
higher concentration of Tween 80 and Span 20 did not have the same favorable effect. The
results showed that the addition of perfume had no effect, while the type of emulsifier
influenced the emulsion stability the most. The samples made from Supela 240 and Tween 80
and Span 20 phase separated. This was more likely due to P-MWOs incompatibility with
these emulsifiers as oil type did not influence the emulsion stability when Promulgen D was
used as an emulsifier.
Keywords: Medical white oil, naphthenic oil, paraffinic oil, emulsion stability, rheology,
droplet size distribution
Sammanfattning
Fuktbevarare är de produkter som oftast skrivs och rekommenderas av dermatologer, och den
vanligaste typen av fuktgivare är lotioner och krämer. Dessa produkter är emulsioner, vilka
ofta innehåller medicinsk vit olja (MWO) på grund av deras skyddande egenskaper samt
enastående hudkompabilitet. Traditionellt så har de MWO som används varit parafinska. Då
naftenoljor ofta har visat sig ha bättre emulsions stabilitet, har detta examensarbete ämnat att
jämföra emulsions stabiliteten för Nynas ABs nya MWO, N-MWO, med en parafinsk
motsvarighet, P-MWO. Jämförelsen av de två oljorna genomfördes genom att variera följande
faktorer: olje- och emulgator typ, koncentration av emulgator samt både med och utan
parfym. De två emulgator system som användes bestod av Promulgen D (en kommersiell
produkt från Lubrizol) samt kombinationen av Tween 80 och Span 20. Bättre
emulsionsstabilitet och mindre droppstorlek och fördelning utficks då högre koncentration
Promulgen D användes. En högre koncentration av Tween 80 och Span 20 gav dock inte
samma gynnsamma effekt. Resultaten från samtliga tester påvisade att emulsions stabiliteten
inte påverkades utav parfym. Det som istället gav störst påverkan var typ av emulgator. De
prover som innehöll P-MWO samt Tween 80 och Span 20 fasseparerade. Detta berodde dock
troligen mer på att P-MWO inte var kompatibel med dessa emulgatorer eftersom oljetypen
inte påverkade emulsionsstabiliteten när Promulgen D användes som emulgator.
Nyckelord: Medicinsk vit olja, naftenolja, paraffinolja, emulsionsstabilitet, reologi,
droppstorleks fördelning
Table of Contents
1. INTRODUCTION ............................................................................................................................................. 1
1.1 GOAL OF THE THESIS...................................................................................................................................... 1
1.2 OUTLINE OF THESIS REPORT........................................................................................................................... 1
2. BACKGROUND ............................................................................................................................................... 1
2.1 OIL ................................................................................................................................................................ 2
2.1.1 Paraffinic oils ........................................................................................................................................ 2
2.1.2 Naphthenic oils ...................................................................................................................................... 3
2.1.3 Hetero atoms ......................................................................................................................................... 3
2.1.4 Medical White oils ................................................................................................................................. 3
2.2 THE REFINERY PROCESS ................................................................................................................................. 4
2.3 IMPORTANT PROPERTIES OF OIL ..................................................................................................................... 5
2.4 SKIN .............................................................................................................................................................. 6
2.4.1 Epidermis .............................................................................................................................................. 8
2.4.2 Dermis ................................................................................................................................................... 9
2.4.3 Hypodermis ......................................................................................................................................... 10
2.5 MOISTURIZERS ............................................................................................................................................ 10
2.5.1 What is a moisturizer? ......................................................................................................................... 11
2.5.2 Properties of a moisturizer .................................................................................................................. 11
2.5.3 Importance of pH................................................................................................................................. 13
3. THEORY ......................................................................................................................................................... 13
3.1 DESTABILIZATION OF EMULSIONS ................................................................................................................ 14
3.2 STABILITY OF EMULSIONS ............................................................................................................................ 15
3.2.1 Physical hindrance .............................................................................................................................. 15
3.2.2 Electrical hindrance ............................................................................................................................ 16
3.3 CREATING EMULSIONS ................................................................................................................................. 16
3.4 HLB-VALUES............................................................................................................................................... 17
3.5 INFLUENCE OF EMULSIFIERS ........................................................................................................................ 19
3.6 OILS ............................................................................................................................................................. 19
3.7 EMULSIONS OF MOISTURIZERS IN PRACTICE................................................................................................. 21
3.7.1 PIT value ............................................................................................................................................. 21
3.7.2 Formulations used in this project ........................................................................................................ 23
3.8 ANALYSIS OF EMULSION STABILITY IN THIS PROJECT ................................................................................... 26
3.8.1 Droplet size distribution ...................................................................................................................... 27
3.8.2 Rheology .............................................................................................................................................. 28
4. METHOD ........................................................................................................................................................ 31
4.1 DECIDING HLB OF OIL ................................................................................................................................. 31
4.1.1 Required HLB for N-MWO .................................................................................................................. 32
4.1.2 Required HLB for P-MWO .................................................................................................................. 33
4.1.3. PIT value ............................................................................................................................................ 34
4.2 STABILITY TESTS ......................................................................................................................................... 34
4.2.1 Droplet size distribution ...................................................................................................................... 34
4.2.2 Rheology .............................................................................................................................................. 35
4.3 HOW TO CREATE EMULSION ......................................................................................................................... 35
5. RESULTS AND DISCUSSION...................................................................................................................... 38
5.1 PIT .............................................................................................................................................................. 38
5.2 TEST OF MASTERSIZER METHODOLOGY ....................................................................................................... 39
5.3 RHEOLOGICAL TESTS ................................................................................................................................... 39
 5.3.1 Frequency sweep ................................................................................................................................. 40
5.3.2 Thixotropic test .................................................................................................................................... 42
5.3.3 Application test .................................................................................................................................... 44
5.3.4 Amplitude sweep .................................................................................................................................. 46
5.3.5 Storage stability ................................................................................................................................... 50
5.3.6 Thermal loop ....................................................................................................................................... 53
5.4 MASTERSIZER TESTS .................................................................................................................................... 55
5.5 VISUAL ANALYSIS........................................................................................................................................ 59
5.6 FORMULATION ............................................................................................................................................. 61
6. CONCLUSIONS ............................................................................................................................................. 62
7. SUGGESTIONS FOR FUTURE WORK ..................................................................................................... 64
8. REFERENCES ................................................................................................................................................ 66
9. APPENDIX ...................................................................................................................................................... 70
9.1 OIL .............................................................................................................................................................. 70
9.2 METHOD ...................................................................................................................................................... 70
9.3 HLB TESTS .................................................................................................................................................. 70
9.4 FREQUENCY SWEEPS .................................................................................................................................... 76
9.5 MASTERSIZER .............................................................................................................................................. 77
1. Introduction

1.1 Goal of the thesis

Nynas AB has developed a new medical white oil (MWO). MWO are commonly used in
cosmetic emulsions. The oils used have, in these cases, traditionally been paraffinic. Studies
have shown that naphthenic oils provide better emulsion stability than paraffinic oils in many
cases. It was consequently interesting to compare the new MWO, N-MWO, with a paraffinic
oil with similar properties, P-MWO.
The aim of this thesis can be described in three parts. Firstly, it was to come up with basic
formulations to create the moisturizers of the previously mentioned oils. In parallel to this, the
aim was to compare the emulsion stability varying four different factors of importance for
emulsion stability, to see what factor mattered the most. These factors included: type and
concentration of emulsifier, perfume or no perfume, and the type of oil used in the sample.
The final aim of the project was to figure out a way of analyzing the emulsion stability of the
samples with the analytic tools available at Nynas.

1.2 Outline of thesis report

Some background concerning moisturizers, skin, oil, and oil refinery are firstly described.
Thereafter, the theory behind emulsion stability, the stability tests made, and the reasoning
behind the choice of emulsifiers. Following this, the methodology and the formulations used
are described, and the results are presented and discussed. Finally, the conclusions concerning
the projects along with possible future work are presented.

2. Background
To apply oils and fats to moisturize the skin is almost an instinct and has probably been done
throughout mankind s existence. A large variety of products can be utilized to moisturize the
skin. Examples of these include gels, oils, ointments as well as creams, and lotions. The latter
ones being the most common delivery systems for moisturizers. These are typically composed
of a two-phase emulsion. An emulsion is a system with two immiscible liquids. One of the
phases is continues while the other phase is dispersed in the continues phase. Commonly, one
of the phases is a water phase while the other is an oil phase. The system can be classified as
either oil-in-water (o/w), which is the most common type of system for creams, while the
other is classified as water-in-oil (w/o). An o/w system entails that the dispersed phase is an
oil phase while water is the continuous phase. The opposite applies to w/o. (1)
A common ingredient used in moisturizers, which you very well may find as an ingredient in
your creams and lotions, is paraffin oil that often is called mineral oil, which is a derivative
from petroleum. They are used for their great skin tolerance, distinct caring, protective
properties, as well as their broad range of viscosities. Even if the words paraffin oil and
mineral oil are used so interchangeably that they seem to be synonyms, this is not the case.
White mineral oil is not necessarily paraffin oil, instead, it is a definition of an oil s purity.
White mineral oils are purified to the extent where they are allowed to be used in food. (2)

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Nynas have produced a new product that is a mineral oil that goes under the name N-MWO.
As Nynas use naphthenic crude oil this mineral oil will be of naphthenic character. They are
looking into potential applications for their oil and are interested in its potential in cosmetics.
As many cosmetic products are emulsions where emulsion stability is of great importance
naphthenic medical white oil is thought to have an advantage against paraffinic oil as
naphthenic oils are known to create more stable emulsions. (3) Consequently, this thesis aims
to make stable o/w emulsions and compare its stability to paraffinic mineral oil to see if
naphthenic mineral oils can be used in moisturizers. The paraffinic oil used has similar
properties to N-MWO and is called P-MWO.

2.1 Oil
Millions of years ago, plants and animal remains were buried in primeval mud under oceans,
lakes, and swamps. After being subjected to enormous heat and pressure, the remains formed
petroleum-saturated rock. To only form petroleum-saturated rocks is not enough if large
enough quantities for commercial use are desired. Four criteria must be fulfilled for this to
occur: there must be a reservoir rock, source rock, and cap and seal. The source rock is
usually a sedimentary rock containing much organic matter. When the decaying matter forms
crude oil, the oil travels to the reservoir rock containing many small pores where the oil can
be stored. The trap prevents the oil from emerging from the reservoir while the seal is entirely
impermeable and hinders the oil from penetrating the trap or traveling around it. (4) This long
process creates crude oil, which today is the main feedstock for the petrochemical industry
that produces products such as plastics, solvents, fuels, base oils, and bitumen. It is also the
largest energy source in the USA. (5)
Crude oil can be characterized in different manners. One way is by its geological sources,
such as sandstones and limestones. Another way of characterizing crude oil is by its chemical
composition. Crude oil is a complex mixture of various hydrocarbons. These hydrocarbons
can be paraffinic, naphthenic, olefins, and aromatic. The oil also contains heteroatoms such as
low amounts of sulfur and traces of nitrogen and oxygenated compounds. (4) To characterize
the oil, thermal methods can be used to give insight into the number of carbons present in the
chain on average. To characterize the chemical structure in closer detail, however, FT-IR or
GC-MS can be used. These techniques can determine aromatics' oil concentration, cyclic
hydrocarbons and/or saturated hydrocarbons, and the hydrocarbons boiling points. (6) These
are further a technique used by Nynas for this purpose. (7) The chemical composition is not
dependent on its geological age nor origin. Generalizations that can be made in one region are
not valid for another. (4)
In this project, the new medical white oil N-MWO that has been refined at Nynas AB from
naphthenic crude oil was used. It was compared to a medical white oil of paraffinic character.
The chemical composition of these oils is described more in detail below.

2.1.1 Paraffinic oils

Paraffinic crude oil has high wax content and only a small amount, if any, of asphalt. They
contain a high percentage of paraffin hydrocarbons (8) that are straight or branched alkane or
iso-alkane chains. The ratio between iso-alkanes and alkanes vary between samples, and the
general chemical formula for paraffinic oils is CnH2n+2. Most of the paraffinic chains contain
between one and 35 carbons. A smaller amount, however, contains up to 60 carbons. (4) The
applications for paraffinic oils are many. These include candles, lamp oils, in the textile

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industry, cosmetics, as a laxative, lubes (these oils tend to have larger quantities of good
lubricants than others because of the high viscosity index (VI)), and of course fuels as these
oils can produce large amounts of low octane petrol. (8) (9)

2.1.2 Naphthenic oils

In contrast to paraffinic crudes, naphthenic crudes usually contain little or no wax while
containing asphalt residues, and while the viscosity of paraffinic crudes remains relatively
stable during temperature changes, naphthenic crudes viscosity vary a lot with temperature.
(8) Naphthenic hydrocarbons are composed of saturated hydrocarbons as cycloalkanes or
cycloparaffins, and alkane chains connected to these with the general chemical formula of
𝐶 𝐻2 . Naphthenic oils can contain several rings, but for them to be classified as such, at least
one closed ring structure is present. The percentage of naphthenic in crude oil in the world is
between 30 and 60%. The rings usually contain five or six carbons. For oils with higher
boiling points, it is common with more than one ring structure; as many as ten rings have been
observed, and the rings are often connected. (4) The applications for naphthenic crude oils are
diverse and plentiful. The naphthenic crudes can be used to make asphalt for roads and
roofing and high octane petrol oils and burning oils. (8) They can be used to produce
lubricants, adhesives, antifoaming agents, as agents in industrial explosives, printing ink,
membrane separators in batteries, as a plasticizer in rubber, and due to their very low
dielectric constant, as transformer oils.(10)

2.1.3 Hetero atoms

As previously stated, crude oil contains a small amount of inorganic matter. The sulfur
content ranges between 0.1 and 10 weight percent. They are in the form of thiols, thiophenes,
sulfides, and disulfides. It only contains small quantities of nitrogen, about 0.9%wt, and an
even smaller amount of oxygen (between 0.06 to 0.4%wt). The oxygens are often present as
acids in alkanes and cycloalkanes. (4) The heteroatoms are, in other words, integrated into the
oil molecules, and despite their low concentration, they can change the properties of the oil
noticeably.

2.1.4 Medical White oils

Medical white oils, or as they are also known in the cosmetics industry, mineral oils, are
highly refined oils and waxes. They are generally odorless, colorless, and tasteless liquids or
opaque waxes. (11) Owing to these unique properties, they have many applications. Such as
cosmetics, adhesives, sealants, food additives, denature adhesive creams, pharmaceutic
products, and insect repellants. (2) White oils are a specific class of mineral oils, and as they
are used in pharmaceutics, food, and cosmetics, these need to be highly pure. To be highly
pure means that the polyaromatic hydrocarbons and other impurities are reduced to only
traces to meet the specific requirements stipulated by international and European
pharmacopeia monographs. Further, the refinery process of mineral oils should act according
to good manufacturing practices and quality assurance controls (EU GMP, Directive
2003/94/EC and ISO 9001 or ISO 14001). The final product is, as always, when concerning
refined oils, a complex mixture of hydrocarbons. The highly lipophilic white oil is composed
of hydrocarbon chains of different structures and sizes ranging between 14 and 90 carbons in
the hydrocarbon chains. The white oils viscosity and melting point vary with these
characteristics. (11)

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As the chemical composition of white oils can vary greatly while the applications are highly
specific, and thus require specific chemical properties, the necessity for classification is great.
The Joint FAO/WHO Expert Committee on Food Additives (JECFA) has classified the oils
according to their viscosity, carbon number at 5% boiling point, and average molecular
weight. Further, JECFA and the European Food Safety Authority (EFSA) evaluated the safety
profile, and their acceptable daily intake was decided, which is called their ADI value.
Mineral oils with an ADI value consequently are of food-grade mineral oil and are approved
to be used in food and food additives. The classifications mentioned can be seen in Table 1.
(11)
Table 1. The classifications made of mineral oils by JECFA. Information recreated from (11)

Kinematic Average Carbon number at Acceptable daily

viscosity molecular 5% boiling point intake (ADI,
at 100°C (mm²/s) weight (g/mol) mg/kg)

Microcrystalline 11 500 C25 0-20

waxes
High viscosity 11 500 C28 0-12
mineral oils
Medium viscosity 8.5-11 480-500 C25 0-12
Class I
Medium-low 7.0-8.5 400-480 C22 None
viscosity Class II
Medium-low 3.0-7.0 300-400 C17 None
viscosity Class III

This project will concern cosmetics, an area in which mineral oils are used widely. As
mentioned earlier, the viscosity of mineral oils can vary greatly, and this can be a perk as the
oil can be chosen to regulate the product's viscosity. Further, they have lubricating and
protecting properties and are dermatologically well tolerated. They are used in many products
including, including lipstick, creams, lotions, hair gels, and ointments. Their concentration,
depending on their application, can be from one to 99% in these products. The cosmetic
regulations in Europe are rigorous. Consequently, only highly refined mineral oils and
microcrystalline waxes of the pharmaceutical grade, furthermore, comply with the
specifications of the European Union cosmetics regulation EC/1223/2009 as well as the
European Pharmacopeia are allowed to be used for skin applications. (11)

2.2 The refinery process

The crude oil is transported to Nynas refineries via ships, after which it is stored in cisterns.
The first step of the production is distillation. Depending on the type of oil that is distilled,
either vacuum distillation or atmospheric distillation can be used. As the oil used at Nynas is
classified as heavy, vacuum distillation is performed as the applied vacuum allows lower
boiling points. This is beneficial as the oil goes through thermal decomposition (also known
as cracking) around 350°C. During the distillation process, the oil is separated based on its
density. The oil is during this phase heated so that it is evaporated into gas phase. It begins to

4
travel up in the column. As it goes up in the column, the temperature decreases, and once the
temperature is decreased to the oil's boiling point, it condensates. The lower density oils, the
distillates, have the lowest boiling points and will travel furthest up in the colon, while the
heaviest fractions, bitumen, have the highest boiling points and will be at the bottom of it. (7)
(12)
The second step used at Nynas is hydrotreating, during which the distillates are treated with
hydrogen gas in the presence of a catalyst. The goal of this is to remove aromaticity as well as
sulfur, nitrogen, and oxygen. The catalyst enables the hydrogen saturation of unsaturated
molecules. It removes sulfide by forming hydrogen sulfide, oxygen by producing water, and
nitrogen by creating ammonium. As heteroatoms give the oil its dark color, the color becomes
lighter with an increased degree of hydrotreatment. Sulfur contamination provides a yellow
color. (7) (12) Aromatic compounds are unwanted since they are classified as carcinogenic
and genotoxic substances. Saturated hydrocarbons have not been assessed as either
carcinogenic and genotoxic. (11) Previously, in 2.1.4 Medical White oils, it was mentioned
that these impurities needed to be expelled from the white mineral oils, and this is how it is
done. The naphthenic oils have a higher activity than paraffinic oil; it is more demanding to
treat naphthenic oils than paraffinic oils.

2.3 Important properties of oil

Viscosity
Describes a liquid's resistance to flow. It can be thought of as the molecules' resistance
between one another. The property is temperature-dependent, increased temperature results in
decreased viscosity. Unit for kinematic viscosity is .

Density
Density is also temperature-dependent as most materials undergo an expansion during a
temperature increase. If increased pressure is applied the oil will be more compressed and
thus have an increased density. Thus, both pressure and temperature are usually specified
when density is decided for a substance.
Pour point
Is the lowest temperature at given conditions where the substance still flows. Generally, a
higher viscosity results in a higher pour point. Paraffinic oils generally contains more wax
than naphthenic oils. As the temperature of a paraffinic oil decreases the wax in it begins to
form crystals, which ultimately results in the oil reaching its pour point. In the case of
naphthenic oils, the crystals form at lower temperatures than for paraffinic oil, if at all.
Instead, the viscosity increases as the temperature decreases until the naphthenic oil reaches
its pour point. Therefore, naphthenic oils usually have lower pour points than paraffinic oils.
Aniline point
In the standard method ASTM D611 for determining Aniline point, an equal amount of oil
and aniline (𝐶 𝐻5 𝑁𝐻2 are mixed. Due to the oil s hydrophobic properties and anilines
hydrophilic properties the liquids normally are immiscible. With increasing temperature,

5
however, the solubility increases. The aniline point is thus the temperature at which the
liquids are miscible. It serves as a means to indicate the solubility of the oil.
Boiling point distribution
The boiling point can be correlated to the number of carbons in hydrocarbon compounds. By
determining the boiling point distribution of an oil, it is, through the use of standardized
tables, possible to decide the molecular weight distribution of the oil. An example of this can
be seen in Figure 4 where the boiling point distribution is visualized in a graph for N-MWO
and P-MWO. This property has implications not only for the oil distillate but also for the
crude oil itself. The boiling point distribution can be decided through the method ASTM
D2887, a standard method that uses GC as a method of analysis.

2.4 Skin
The skin envelops the entire body and does so with a great fit. The perfect fit and it being
almost hairless in relation to other species make it an attractive feature unique for humans. It
is often referred to as the largest organ of the body. Even if the surface area is not always the
largest, it is the heaviest organ. The skin is of utmost importance and has many functions:
preventing the body from dehydrating, regulating the body temperature, and protecting the
body from the environment while simultaneously communicating with it. (13) Only after
understanding the skin's response to various stimuli and its properties and functions is it
possible to formulate products that can improve or maintain it. (14)

The most distinctive structural difference is between hairy and glabrous skin. (13) Glabrous is
present in the palms of our hands and the soles. Its epidermis, Figure 1, is much thicker than
for hairy skin. Further, the sense organs are trapped inside the dermis, and there are no hair
follies or sebaceous glands. In hairy skin, the hair follies and sebaceous glands are all present,
while the sense organs are not trapped in the dermis. (14)

6
 Figure 1. The cross section of the skin (15)

As previously stated, the functions of the skin include protection and communication with the
environment. Part of the protection includes an acidic pH, ranging between 4 and 6, which
contrasts to the pH of the inside of the body, ranging between 7.2 and 7.5. The more acidic
environment results from the epidermis producing amino acids and lactic acids and the acidic
components in sweat and sebum. This is known as the acidic mantel and is, with the help of
the microflora present, able to act as a chemical buffer, detoxifying agent, and bacteriostat;
thus, both chemical and microbial attacks can be resisted. (16) (14) The skin can further aid in
the protection from UV light, dehydration, and due to its viscoelastic properties, help resist
mechanical traumas. These properties are primarily lost when exposed to water, solutes, or
solvents for a prolonged time. The skin's ability to communicate and control the body is
essential for humans to adapt to a new environment. The skin can communicate temperature,
pressure, pain, odor, and sexual stimuli which the brain can coordinate the signals. For
example, the body's temperature and water content are controlled by the sweat glands and the
circulatory system. (14)

To gain a better understanding of the skin, it is crucial to gain knowledge of its composition.
Essentially it can be said that the skin is composed of three layers: the epidermis, dermis, and
hypodermis that can be seen in Figure 1. (15)

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2.4.1 Epidermis
The epidermis is composed of many layers of avascular cells and needs to be provided with
nutrition from the blood vessels in the dermis. The epidermis makes up a barrier that protects
the body from the invasion of pathogenic foreign particles that potentially are infectious. (15)
The epidermis varies in thickness. In hairy skin, it is between 75 to 150 µm while in glabrous
skin can be up to 4 mm. It is responsible to form the stratum corneum (SC), seen in Figure 2,
a protective layer residing at the outmost surface of the epidermis. SC is composed of dead
cells that stick together with the help of a lipid material to form a water-resistant layer. (14)

Figure 2. The structural composition of the epidermis. Modified from (15)

The epidermal, seen in Figure 2, is continuously renewed in a process known as keratinization, in which the
basal cells (keratinocytes) are multiplied through mitosis and produce keratin as they are pushed up. (14) As the
cells travel upwards to the spinous layer, they take a flatter shape. The cells contain many desmosomes in these
cell layers, which connect the cells. (17) In the granular layer, the cells are flattened as they lose their
mitochondria, ribosomes, and nucleus and are filled with keratin. The degraded organelles are degraded into
something commonly referred to as the natural moisturizing factor (NMF) that acts as a water reservoir in SC. It
is this reservoir that keeps it flexible and soft. The composition of NMF can be seen in

Table 2. (14)

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 Table 2. The percentual amount of the components making up the natural moisturizing factor (14)

Substance Percentual amount [%]

Free amino acids 40

Mineral salts 16

2-Pyrrolidone carboxylic acid 14

Lactate 12

Sugars, organic acids, peptides 11

Urea 4

Urocanic acid 3

When the keratinized flattened cells (corneocytes) reach the surface of SC, they are dead and
water-resistant flakes, which stick together with the help of lipid bilayers. The lipid bilayers
are thought to have many purposes. These include corneocyte adhesion, hydration, and
reduction of transepidermal water loss. Their composition can be seen in Table 3. As the
corneocytes travel up through the SC, the cells become more haphazard, and the desmosomes
become scarcer. Consequently, the top of SC consists of dead skin flakes that will be worn off
due to wear and tear in a process known as desquamation. It occurs at the same rate as the
basal cells are renewed. (14) The process from cell renewal and desquamation is called
turnover time and takes between 52 to 75 days. (18)
Table 3. The composition of the lipid bilayers between the corneocytes. (14)
Lipid Composition [%]

Ceramides 55

Free fatty acids 20

Cholesterol 15

Cholesterol esters 10

2.4.2 Dermis
Beneath the epidermis (as seen in Figure 1) is the dermis functioning as its supportive frame.
It contains blood vessels and supplies the epidermis with nutrients; it further supports the
skin's sweat glands, hair follicles, and sensory nervous system. While the epidermis consists
of a cellular structure, the dermis consists of consecutive tissue (other examples of this type of
tissue include bones and cartilage). The consecutive tissue of the skin is composed of a pretty
dense network of protein fibers entrenched in a viscoelastic and hydrophilic gel, which is
called the ground substance. The ground substance is made up of water, salt, and
glycosaminoglycans that form complexes with proteoglycans. An example of these is

9
hyaluronic acids that are important for the hydration of the tissue as they can carry large
amounts of water. The fibroblasts (cells) are responsible for the tissue's maintenance,
synthesis, and replacement. Collagen constitutes 30% of the dry weight of the dermis and is
the primary constituent of the protein that gives the skin its high tensile strength and is
parallel to the skin surface. The other constituent of the protein bundle is the elastin protein,
which gives the skin its elastic property. (14)
Only mammals have sweat glands. As shown in Figure 1, they reside in the dermis and can be
classified as eccrine or apocrine sweat glands. The apocrine glands are associated with hair,
are controlled by sex hormones, and consequently activated during puberty. They can be
found in the ear canal, axilla, breasts, and anogenital area. The liquid formed by the gland is
odorless, but as bacteria break down the liquid more than a hundred volatile substances are
formed, which are perceived as foul-smelling, especially in the axilla. There are over three
million eccrine glands distributed over the body. While emotions activate the apocrine glands,
the eccrine glands react only to thermal stress, except for some areas such as the palms of the
hands, soles of the feet, and the axillae. They are, along with the blood vessels of the skin,
controlled by the nervous system and are used to maintain a body temperature of 37ºC. The
sweat is composed of water and salt and serves to cool down the body by evaporating. (14)
The skin is the largest sensory organ of the body and is employed as an open communication
channel between the environment and the body. This is of importance for cosmetics. For
example, the skin feel during and after application will make the customer favor one lotion
over another. Someone with dry skin may, for example, may prefer a heavier lotion as it
makes the skin feel better than a lighter one, although it is not the more suited product for the
skin. This feeling will sway the customer into buying this product. The external stimuli can be
classified as either thermal or tactical. Further, they can be classified as pleasant or
unpleasant. The signal will travel through the spinal cord and be interpreted by the brain. (14)

2.4.3 Hypodermis
The third and final layer seen in Figure 1 is the hypodermis. The cells in the hypodermis are
used to store fat that can be utilized as an energy reserve. The fat also serves the purpose of
insolating the body and acting as a buffer against impact. Further, this fat gives the body its
contour. (14)

2.5 Moisturizers
Moisturizers are used by almost everyone and are the most prescribed product of
dermatologists. It aims to maintain skin integrity and make the skin look more appealing.
There are many different types of moisturizing products, including so-called stay-on products
such as ointments, creams, lotions, gels, and oils. Other methods of treatments such as bath
oils are also possible. However, creams are the most common types of delivery systems for
moisturizers. These are often composed of emulsions, which will be further described in 3.
Theory. The ratio between the water and oil phase is vital in moisturizers, and the droplet size
of the dispersed phase ranges between 1 and 100 µm, which results in white color for the
emulsion. o/w emulsions are more common in this application than w/o emulsions. The oil
concentration usually ranges between 15 and 30%. An increased oil concentration may result
in increased greasiness of the cream. New, more proficient emulsifiers enable a decrease in
the oil concentration, even in w/o emulsion. (1)

10
A good moisturizer is easy to spread across the skin, does not irritate the skin, can easily be
rubbed in without soaping, and leaves the skin smooth instead of sticky. It should also have a
pleasant scent, either through the appliance of fragrance or, if no fragrance is applied, there
should not be any fatty base odor. (14)

2.5.1 What is a moisturizer?

Generally, moisturizers can be divided into the following groups:
1. Day preparations.
2. Night preparations.
3. Hand and body lotions.
4. All-purpose products.
5. Barrier creams.
Day preparations are generally light o/w that is easy to spread. They usually contain stearic
acids and leave the skin with a wet feel. Night preparations are much thicker and are usually
classified as w/o. They leave a sticky feeling on the skin, usually owing to the wax content,
and do not look appealing on the skin. The benefit of w/o is that when oil makes up the
continuous phase, it has direct contact with the skin's surface, without any detergent action. It
can thus easily spread out over the skin to create the occlusive layer while trapping the water
droplets on the skin. It is also more resistant to wash-off. Hand and body lotions have similar
formulations to the day preparations and are more often lotions instead of creams to ease the
utilization of the product. This can be done by increasing the viscosity of the water phase.
This type of preparation contains large amounts of humectant, sorbitol, and glycerol. All-
purpose products are creams and lotions that can be used all over the body as moisturizers
and even as cleansing creams. They have a light texture and are easily spread. Barrier
creams not only moist the skin, but further protect it from being permeated by things like
water, dirt, and defatting solvents. Its formulation is dependent on what the cream is to protect
the skin from, but the oil content generally seems to be relatively low, at around 10%. It can
further be said that paraffinic oils (going by various names such as mineral oil, paraffinum
liquidum, and paraffin) can be found in all of the different applications mentioned above. (14)
Most of the different applications mentioned earlier can be creams or lotions. This definition
is highly arbitrary. In an interview with Lena Hällstig, she stated that the definition for lotions
and creams varied largely but claimed that it generally could be said that the difference lies in
the viscosity. A cream is a type of moisturizer with a viscosity high enough for the cream not
to drip from the container if it were turned upside down. On the other hand, Lotions are of
much lower viscosity and would instantly begin to flow if the jar was tilted. (19)

2.5.2 Properties of a moisturizer

The most important properties of a moisturizer are its emollience, occlusion, and moisture
retention. (20) To retain moisture, humectants are used, which are ingredients with the ability
to keep things moist. It accomplishes this by attracting water by forming hydrogen bonds with
it. Consequently, the humectant draws water from the dermis to the epidermis. (21)
Humectants can typically be urea, an NMF of the skin, or glycin. (14) This results in
increased water concentration in stratum corneum (SC). (20) This is beneficial as SC owes its
flexibility and softness to water. If SC lacks water, it becomes brittle and stiff, and no lipids or
oils can soften it. (22)

11
Mineral oils do not possess the ability of humectants as they are too large to penetrate the skin
and further are hydrophobic and thus will not attract water. Mineral oils do, however, inhibit
the other two qualities. As previously mentioned, the oil molecules are far too large to
penetrate the skin and instead stay on top of the skin. Consequently, emollience is created
through the occlusion. To clarify this further, the oil in itself does not affect the hardness of
SC, but in combination with water (which is the case for emulsions), the oil can trap water on
the skin surface due to its occlusive properties. The trapped water is then able to improve the
SC flexibility, i.e., emollience. (21)

For occlusion to occur, the molecules need to align, thus creating a thin film. According to
Rawlings (21), it is beneficial for the chains (the author speaks explicitly of alkyl chains) to be
of similar length as the aligning will be more proficient and thus create adequate protection
inhibiting other molecules from penetrating it. Further, Rawlings claims that alkyls are more
efficient in creating the protective palisade than structures containing cyclic structures. This
is because the cyclic molecules prevent the constant build-up of the occlusive layer. The
imperfection of the occlusive layer created by the straight paraffinic chains is due to different
chain lengths of the paraffin oil. They may all be straight, but in the case of P-MWO, they
range from 23 to 44 carbons (seen in Table 6). (21) This heterogeneity of chain length would
result in imperfections in the palisade. Due to the different chemical compositions of
paraffinic and naphthenic oils, P-MWO should be better at creating an occlusive layer than N-
MWO.

Another critical aspect of occlusive is its substantivity (the ability of the oil to stick to the
skin). If the oil at the top of the skin is depleted fast, the substantivity is not very good. The
depletion occurs through diffusion. Either by penetrating the skin or through lateral diffusion
at the skin s surface. Mineral oils are too large to penetrate the skin, but they can perform
lateral diffusion, unlike wax. Their substantivity is, however, good enough. It should further
be noted that it is essential to have large enough quantities of oil in the formulation. If these
are too small, the occlusivity and substantivity will be insufficient. (21) When the cream is
applied, its components are either digested, evaporated, stay on the skin, absorbed into it, or
detach when in contact with other material. Therefore, studies have concluded that after eight
hours, only 50% of the moisturizer is left on the skin. (22)

Transepidermal water loss (TEWL) is a measurement that indicates the water lost through the
skin through diffusion and evaporation. The diffusion can be reduced by changing the
viscosity of the oil.

Moisturizers change both the tactile and the appearance of the skin. The combination of
substances results in the initial feel of the product. Meaning how it spreads out on the skin, the
friction of the skin, how quickly it is absorbed, and how the skin looks and feels after usage of
moisturizer. Directly after the application of moisturizer, an increase in water content occurs
in SC. (1) This is both because the product contains water, which is absorbed into SC, and
because of the oils' occlusive effect, which results in a build-up of water in SC, although this
process is more delayed. (22) The outmost layer of the skin is composed of flakes of dead
cells, and the lack of moisture within and between them makes the skin look flaky. The
moisturizer fills the spaces between the skin flakes and makes the skin look less flaky and
smoother. After this, the mechanisms of the skin are changed. The increased hydration will

12
enable the degradation of desmosomes that keeps the corneocytes together. Another possible
benefit may be the possibility of strengthening a previously weakened skin barrier. (1)

Both the aesthetic and the stability of moisturizers are affected by concentration and type of
oils, emulsifiers, and humectants. Furthermore, the pH affects these properties, and most
creams have a pH ranging from between 3 to 8. Emulsifiers effect on the skin has not been
studied much; however, non-ionic emulsifiers are expected to be less irritating than ionic ones
despite the non-ionic emulsifiers also interacting with the skin barrier function. (1) Table 4
shows the theoretical composition of a moisturizer.

Table 4. Shows the typical concentrations of the essential components in emulsions

Essential for stability Percentage in moisturizers [%]

Water 80

Oils 20

Emulsifiers 5

Preservatives 0.5

2.5.3 Importance of pH
As previously mentioned, the effect of pH needs to be considered. The pH is a critical factor
in barrier homeostasis, as antimicrobial defense and the integrity and cohesion of SC. The
skin's pH ranges between 4 and 6. Both endogenous and exogenous factors have an impact on
the skin's pH. (16) Soaps are examples of exogenous factors. They are often alkaline, and
when it is applied on the skin its pH increases. A study proved that the application of o/w
moisturizer with pH 5 after soap exposure resulted in a more rapid decrease of pH than when
the moisturizer was not applied. Moisturizers thus seem to have the ability to decrease the pH.
It is therefore of great importance for the skin that the product has the correct pH value. (23)
Considering the pH range of the skin and the fact that many companies (such as Eucerin and
CeraVe) use pH 5, this study constructed moisturizers with pH 5. Instead of simply acidifying
the moisturizer with an acid, a buffer should be employed so that the skin s pH is
decreased and maintained at the desired pH. The skin has a large buffer capacity. It is,
therefore, necessary for the buffer in the moisturizer to also have a large buffer capacity. (24)
There are plenty of buffer pairs being used. A pair used in moisturizers is citric acid and
sodium citrate. According to Paula s Choice, a website rating ingredients in cosmetics, this is
a good option. (25) Therefore, this buffer pair is used to create a moisturizer with a pH of 5
for this project.

3. Theory
This project aimed to compare the emulsion stability of moisturizers created with paraffinic
respectively naphthenic oils. This section is consequently centered around emulsion stability
and ways to analyze emulsion stability.

13
3.1 Destabilization of emulsions
If only water and oil are present, the emulsion will not be stable. The droplets will collide, and
the emulsion will break down. There are various mechanisms responsible for the breakdown
of the emulsion. These are visualized in Figure 3.

Figure 3. Shows the breakdown of an emulsion.(26)

The creaming and sedimentation visualized in Figure 3 occur due to density differences
between the oil and the water phase. Because the oil phase usually has a lower density than
the water phase, creaming is more common than sedimentation in o/w systems. During the
flocculation, droplets aggregate together as they enter a secondary minimum where it is
energetically favorable for the droplets to stick together to form aggregates while maintaining
their integrity. Flocculation, sedimentation, and creaming are all reversible mechanisms, and
if high shear mixing is applied, the emulsion can return to its original shape. This is not the
case for coalescence. In this case, the droplets merge irreversibly to form larger droplets. If
the secondary energy minimum, in the case of flocculation, is too low, there may be no real
distinction between flocculence and coalescence. Another degrading mechanism is called
Oswalled rippling. In this mechanism, small droplets, which have a larger area to volume ratio
than larger ones, lose material to the larger droplets. This occurs through the diffusion of the
dispersed phase through the continuous phase. This mechanism mainly occurs for unstable oil
phases, which usually are smaller hydrocarbons rather than larger ones. (26)

Paraffinic hydrocarbon chains are highly insoluble in water, and thus Oswald ripening is quite
unlikely. It should further be noted that paraffin chains often are solid at room temperature,
and thus paraffin emulsions often are particle dispersions the particles' high rigidity results
in the unlikelihood of coalescence. The destabilization of paraffines thus mainly occurs
through flocculation or sedimentation. (27) In the case of P-MWO (and N-MWO), they are
both liquids at room temperature and thus will not create particle dispersion.

14
3.2 Stability of emulsions
An emulsion system is very futile, and the droplets last only for a few moments. For example,
if an o/w system with droplets of 1µm in a 1:1 water-oil ratio system where the droplets move
with a velocity of 40 mm/day, then the halftime of the droplet can be calculated to be 0.77s.
This is naturally not stable enough to be of any use for any products. Consequently, stabilizers
along with the water and oil phase must be used. The velocity of the droplets, and thus the
velocity of the coalescence is influenced by the following factors: (26)

The square of the radius of the droplet

The density difference between the dispersed and the continues phase.

The inverse of the viscosity of the continues phase.

If a potential energy barrier is introduced the half-life can increase from being less than a
second to be days or even several years.(26) There are two types of stabilizers: ones that
physically hinder coalesces and ones that create electrical repulsion between the droplets. (28)

3.2.1 Physical hindrance

A few examples of physical hindrance are stated below.
Steric stabilization

Is sometimes referred to as polymer stabilization. A non-ionic polymer or surfactant is used

for steric stabilization. For steric stabilization to be successful it is of importance that the
continuous phase has a high solubility for the polymer chain. The repulsion is entropy-driven
as an entanglement of the polymer chains results in a decrease in entropy. (26) This
stabilization is more robust than electrostatic stabilization as works in both aqueous and non-
aqueous phases, are uninfluenced by salt concentration and volume fraction. They will,
however, break down at high temperatures or pressure. Another factor that can result in
coalescence of particles is a decrease in solvation of the polymer. Hence this is such an
important factor to take into account when constructing the system. (29)

Particle stabilization

Particles can also be used to stabilize emulsions. These particles should have a 90° contact
angle to the oil droplet and should project themselves equally in both mediums. It is common
to use hydrophobic proteins at their isoelectric point for this application. (26)

Stabilization by Lamellars liquid crystals

Emulsions can be stabilized by covering the surface with layers of surfactants making up
lamellar liquid crystals. This provides a stable emulsion that can be stable for a long duration.
This at a low energy demand as this is a so called spontaneous emulsification .(26)

As earlier mentioned an emulsion can be stable through electrostatic repulsion as well, an

example of this is stated below.

15
3.2.2 Electrical hindrance

Electrostatic stabilization

Ionic surfactants, both anionic and cationic are used for this application. Often in combination
with polyelectrolytes. This is based on electrostatic repulsion. As when the headgroups get
closer so does the double layer. When this happens the volume of the counterions becomes
more restricted, consequently, the entropy decreases. Hence repulsion. (26) There are also,
however, attractive forces present in the emulsion, which responds to the Van der Waal forces
between the droplets. These two opposing forces make up the DLVO theory, which is of great
importance in the case of electrostatic stabilization. (28)

3.3 Creating emulsions

As mentioned above, various methods can be used to stabilize emulsions, but all the
stabilizers are not optimal. The following stabilizers are large and subsequently diffuse too
slowly: Proteins at their isoelectric point, large polymers, and lamellar liquid crystal.
Consequently, these are not good at forming emulsions. On the other hand, surfactants with
their low molecular weights are suitable for this purpose and are called emulsifiers for this
reason. The requirements for surfactants to create emulsion: (26)

1. Reduce surface tension between the oil and the water phase and diffuse rapidly to the
newly created interphase.

2. The new surface will only be stable against coalescence if surfactants cover it with a
monolayer rapidly.

There are two possible routes to create emulsions. One is nucleation and growth, where
particles were built up from molecules. The other one is called grinding or emulsification,
wherein bulk material is dispersed into smaller droplets. Thermodynamically speaking, the
free energy of formation of this process is governed by surface tension and entropy, as can be
seen in Equation 1.

∆𝐺 𝛥𝐴𝛾1,2 𝑇𝛥𝑆 Equation 1

When droplets are dispersed, the oil phase s area increases (ΔA). 𝛾1,2 represents the surface
tension between the oil and the water phase (which can be decreased with emulsifiers), T is
the temperature, and Δ𝑆 is the change in entropy. Thus, the entropy increases during the
dispersion as this results in less confinement and more disorder. Usually, ΔA 𝛾1,2 is much
larger than 𝑇ΔS and thus emulsification is not a spontaneous process. The energy required for
emulsification is, however, much larger than solely the thermodynamic ΔA 𝛾1,2 energy. This
is because it does not consider that, as droplets are created, the surface created contains a
curvature. This can be calculated through the Young-Laplace equation Equation 2. (28)
1 1 Equation 2
∆𝑃 𝛾1,2

16
Equation 2 describes how the surface must deform before droplet can break out and be
created. In Equation 2, ∆𝑃 is the Laplace pressure while 𝑟1and 𝑟2 are the principle radiuses.
The droplets formed will depend on the velocity of the flow. A laminar flow creates larger
droplets than turbulent flow does, and the distribution is further slower.(28)

It is not only the velocity of the stirring and the interspatial energy that effects the distribution
but also the viscosity of both the phases, the shear of the system and the pressure of the
droplets.(28)

3.4 HLB-values
This project, as is common in cosmetics, used a non-polar surfactant as the emulsifier.
Surfactants are composed of two parts a hydrophilic part and a hydrophobic or lipophilic part.
The ratio between these in the surfactants is called the hydrophilic-lipophilic balance or HLB.
(30) Depending on its HLB value the surfactant will be more or less hydrophilic. Generally, it
can be said that water-soluble emulsifiers create o/w while oil-soluble emulsifiers create w/o
emulsions. This concept is known as the Bancroft s rule. This is qualitative and calculations
can be made to classify their hydrophilic behavior in solution. It was Griffin that introduced
the term HLB to make it quantitative. This was further extended by Davies formula, which
took into consideration that different groups were differently polar. Either Davies or Griffin's
HLB values can be helpful when choosing an emulsifier. In line with Bancroft s reasoning
high values (between 8 and 18) are appropriate when creating an o/w system, as this project
aims to do. Because these numbers correspond to more hydrophilic values, which is
appropriate when the continuous phase is aqueous. The scale is, however, not applicable when
the emulsification is performed at high temperatures or when the product is stored at low
temperatures. (26)

How to calculate HLB value of emulsifier:

𝑀𝑤 𝑜𝑓 ℎ𝑦𝑑𝑟𝑜𝑝 ℎ𝑖𝑙𝑖𝑐 𝑝𝑜𝑟𝑡𝑖𝑜𝑛 Equation 3

𝐻𝐿𝐵 =
𝑀𝑤 𝑜𝑓 ℎ𝑦𝑑𝑟𝑜𝑝 ℎ𝑖𝑙𝑖𝑐 +ℎ𝑦𝑑𝑟𝑜𝑝 ℎ𝑜𝑏𝑖𝑐 𝑝𝑜𝑟𝑡𝑖𝑜𝑛 𝑥5

How to calculate a blend of emulsifiers:

𝐻𝐿𝐵 𝐻𝐿𝐵1 % 𝐻𝐿𝐵2 % Equation 4

Oils have their HLB-value, the value that results in the lowest surface tension and thus the
most stable emulsion system. When the HLB-value is known this can be matched to an
appropriate surfactant. Thereafter calculate the concentration of surfactant required.

Surfactants with HLB-values below 9 are of lipophilic character, surfactants with HLB values
above 11 are of hydrophilic character while the values in between are of intermediate
character. The HLB can be said to be a good indicator as to what system will be created. If it
will be o/w or w/o for example. It further is an indicator of how chemically efficient the
surfactant or the blend is for its specific task. The efficiency between the different HLB
ranges mentioned earlier vary. This is, however, not owing to the HLB value but rather the

17
surfactants' chemical structure as well as the material being emulsified. When creating a w/o
emulsion the surfactant should mainly be hydrophobic at HLB values around 4-6. When an
o/w emulsion is desired the surfactant should mainly be hydrophilic and thus have an HLB
value in the range of 8-18. (31)

When choosing an emulsifier, it is not only important to consider whether the desired product
is o/w or w/o, but also the specific HLB for the product in question. Paraffinic oils (medium
viscosity) for instance have an HLB of 9. It would thus be useless to try emulsifiers that
collectively would create an HLB values of 8 or 13. It is, however, not only the HLB that
needs to be considered concerning the choice of emulsifier. Even if the correct HLB value is
chosen for the emulsifier it may be from the wrong chemical family and thus for this reason
not work. It is, however, a good place to start. Naphthenic mineral oil approximately has an
HLB of 11-12. It should be noted that the HLB values are dependent on the concentration of
the product as well as the type of emulsion. In this case, the products need to have a lower
concentration than 20% in an o/w emulsion. (31)

Even if choosing an emulsifier with the correct HLB it is equally important to choose the
correct chemical type. Unsaturated lipophilic chains seem to attract unsaturated oils while
saturated lipophilic chains attract saturated oils. Even if both emulsifiers have the correct
HLB value the emulsifier that attracts the oil chains will create more stable emulsions. (31)
Further, it is beneficial to choose more than one surfactant and that the ones chosen to have
different HLB values. Through Equation 3 the composition of the surfactant blend can be
adjusted so that the desired HLB value would be reached. This is because different surfactants
have different critical packing parameters (CPP) which means they pack differently at the
interphase. This would result in better packing. (32)

As stated above the HLB values of typical paraffinic and naphthenic medium mineral oils are
known. It was, however, not completely certain that these values were correct for N-MWO
and P-MWO. Especially since N-MWO is closer to being considered a medium than a light
oil (68 cSt at 40 °C). As the usage of the correct HLB value can result in more stable
emulsions with less usage of emulsifiers the HLB value for both P-MWO and N-MWO was
experimentally decided. (33)
To test the HLB value of an oil, the emulsifiers Tween and Span can be used. These are two
families of emulsifiers that often are used in industry. They are convenient because Span is
of a more lipophilic character while Tween is of a more hydrophilic character. As a result,
these two emulsifiers can create the desired HLB value. The emulsifiers are numbered and
can, for example, be called Tween 80. These numbers indicate to what chemical family the
emulsifier belongs. The numbers between 20 - 29 (called 20s for simplicity) indicate that they
are laurate-ester, the number 40s indicate that they are palmiate-esters, number 60s stearates,
and 80s oleates. For the HLB test, a matching HLB pair should be used because the test
should be made of Tween and Span that belong to the same chemical family. As an example,
the matching pair Tween 80 and Span 80 could be used. (33) An excess of emulsifiers should
be used. About 10-20 wt% of the oil phase should in this case consist of emulsifiers. The
emulsifiers should be mixed into the oil phase. It is important that this part is performed as a
like as possible for all the samples. (33) To obtain the desired HLB value the percentage of
each emulsifier that is to be used can be calculate by using Equation 5 and Equation 6.

18
 100 Equation 5
𝐴%

𝐵% 100 𝐴% Equation 6

In Equation 5, x represents the desired HLB value. 𝐻𝐿𝐵 and 𝐻𝐿𝐵 are the known HLB
values for the emulsifiers from the Tween and Span series.

3.5 Influence of emulsifiers

Emulsifiers are generally classified as cationic, anionic, and non-ionic. The anionic
emulsifiers have the most considerable potential to interact with the lipids and proteins of the
skin. Consequently, they have the most considerable ability to harm SC by disrupting its
permeability and dehydrate it, as well as cause skin irritation. This does not apply to all
anionic emulsifiers, however. The negative effects of anionic emulsifiers can be decreased by
either neutralizing them by partially neutralizing them with cationic emulsifiers or by diluting
the anionic emulsifier with a non-ionic emulsifier. (34) Another problem concerning anionic
emulsifiers in the case of moisturizers is that many of them only are effective at relatively
high pH values above 8. (35) Thus, these would be ineffective in a moisturizer with a pH of
around 5.

Cationic emulsifiers can have both positive and negative effects on the skin. The positively
charged emulsifier can bind to the negatively charged proteins of the skin and consequently
resist wash-off. Through this, moisturization can be prolonged, which is beneficial for dry
skin. Some cationic emulsifiers have cytotoxic effects and can cause damage to SC even at
low concentrations. Some examples of these toxic cationic emulsifiers are benzalkonium
chloride, stearalkonium hectorite, behentrimonium methosulfate, stearalkonium chloride,
quaternium-15, quaternium-19, and quaternium-23. (34) Cationic emulsifiers are effective at
low pH, which is beneficial for moisturizers. (35)

Non-ionic emulsifiers are usually less irritating for the skin than charged emulsifiers. TEWL
measurements do, however, imply that some of these may cause microscopic damage in SC.
This is probably due to non-ionic emulsifiers having been proven to interact with the lipids of
SC. (34) An important aspect of non-ionic emulsifiers is that they are, due to their lack of
charge, independent of both pH and water hardness. By choosing an appropriate HLB value
the emulsifier can be made to fit the emulsion in question perfectly. (35) At a given HLB
value, the stability of the emulsion against coalescence increases with the molar mass of the
non-ionic emulsifiers as this leads to an increased volume, which results in a a more
considerable steric repulsion. (36)

3.6 Oils
This chapter will disclose more information concerning the oils that have been used in this
project. Two oils have been used for creating emulsions. One is paraffinic (P-MWO), and the
other naphthenic (Nynas N-MWO). In Table 5, the identities of the oils can be seen.

19
 Table 5. Shows the properties of the N-MWO and P-MWO. The methods used in the analysis can be found in
Table 25

Analysis Unit N-MWO P-MWO

Clear & Clear &
Appearance Bright Bright
Density, 15°C kg/m3 0.884 0.869
Viscosity, 40°C (Stabinger) mm2/s (cSt) 68.3 68.7
Pour point °C -39 -15
Aniline Point °C 110 120.6
Viscosity-Gravity-Constant (VGC) 0.820 0.7998
Carbon-Type Composition, CA % -2.1 -1.4
Carbon-Type Composition, CN % 43.2 33,8
Carbon-Type Composition, CP % 58.9 67.6
Saybolt Colour >+30 >+30

As mentioned in the introduction, oil during the refining process is separated based on boiling
point into different distillates. Generally, the boiling point of the molecule indicates the
number of carbons in the molecule. This is described in ASTM D2887 - 16a Standard Test
Method for Boiling Range Distribution of Petroleum Fractions by Gas Chromatography. Had
the oil fraction had one specific boiling point the number of carbons in the hydrocarbon
chains would be about the same. This is not the case. Instead the oil fraction has a range of
boiling points. In Figure 4, the boiling point with the respective mass fraction of the
naphthenic and paraffinic oil can be seen.

Boiling Point Distribution

14
12
Fraction mass % / Signal

10 N-MWO
8 P-MWO
6
4
2
0
300 350 400 450 500 550
BP C

Figure 4. Shows the boiling point distribution for N-MWO and P-MWO.

N-MWO is notably seen to have a larger range than that of P-MWO. Further, P-MWO has a
higher set of boiling points making its fraction have longer hydrocarbon chains. When

20
comparing the boiling points to the table of ASTM D2887 - 16a, the chain lengths of the oils
can be found. These are shown in Table 6.

Table 6. Shows the chain length distribution of the paraffinic respectively naphthenic oil

Shortest chain length Longest chain length Most abundant chain

length

P-MWO 23 44 36

N-MWO 19-20 41-42 28-29

3.7 Emulsions of moisturizers in practice

In Table 4 a general formulation for moisturizers is described. The following questions are to
be answered:
Will an o/w, w/o, or w/o/w be used?
What emulsifier will be used?
o The reasoning behind the choice of emulsifier (HLB value, chemistry, Etc.)
What concentration of each component was used?
How is the emulsion prepared?
The droplet size and the droplet size distribution play an important role in both the stability,
functionality and physical properties of an emulsion. Consequently, the droplets should be as
monodispersed as possible.(37) For a stable emulsion, the polydispersity needs to be low, and
the droplet size needs to be very small. For this to occur, high shear, temperature above the
melting point, and the kraft point for the surfactants need to be applied. (27) For this,
highspeed blenders, colloid mills, and high-pressure homogenizers have traditionally been
used. These are, however, very energy demanding, and both the emulsion distribution and
droplet sizes are difficult to control. Membrane emulsification consumes less energy while
creating a monodispersed emulsion with droplet sizes that are easier to control. Its low
disperse phase throughput results in low productivity, however. (37) For this project, the
blender: Yellow line with 500 rpm rotation was used.
Paraffins usually have a melting point ranging from 40 to 70 °C and are thus solid at room
temperature. It is because of this reason the temperature needs to be high when creating
paraffin emulsions. The temperature needs to be above their melting point to liquefy them.
(27) For the oils used in this project, however, the oils are liquid at room temperature. It is,
however, not solely for the melting of oils that the temperature needs to be increased, but also
for the sake of the melting point of the emulsifiers. (27)

3.7.1 PIT value

Another concept concerning the temperature to be taken into account is the phase inversion
temperature (PIT), which is the temperature at which an o/w emulsion becomes a w/o
emulsion. In other words, the temperature at which a phase inversion occurs. PIT is a
common phenomenon for o/w emulsions with non-ionic emulsifiers (with ethylene-oxide
chains) and occurs because as the temperature increases, the hydration forces between the

21
hydrophilic portion of the emulsifier and water decrease. With this, the emulsifier's water
solubility decreases. The hydration forces decrease with temperature until the hydrophilic-
lipophilic properties balance at the PIT. Consequently, it can be said that PIT represents a
measure of the HLB value of the emulsifiers in the given system. (38)
Phase inversion entails a sharp change in physical properties as the dispersed phase (oil
phase) goes from being just that to a coherent phase at the PIT. At the PIT, the now coherent
oil phase coexists with the coherent water phase. Every hydrodynamic movement will change
the interface and form of the coherent phase and be accompanied by large energy
consumption. Because of this, the viscosity will be much more considerable at the PIT. At
temperatures far above PIT, the viscosity will decrease as the coherent water phase becomes
dispersed droplets that move freely in the solution. The changed properties include
conductivity, interfacial tension, viscosity, and light transmission. It is thus possible to
measure PIT in several manners. (38) PIT can be determined through conductivity if a small
amount of electrolyte is added to the emulsion. o/w emulsions can conduct electricity. The
conduction will increase with increasing temperature until reaching the PIT, where the
conductivity drastically drops as w/o forms (which does not conduct electricity). Shinoda and
coworkers discovered that the PIT temperature is related to the HLB of the surfactants. The
droplet size decreases with increasing temperature (until PIT, that is), and it can be said that
the droplet size depends on both HLB and temperature. The temperature dependency is owed
to the fact that surface tension decreases with temperature until PIT is reached, as shown in
Figure 5. If the storing temperature is 20 to 65ºC lower than the system's PIT temperature,
relatively stable o/w emulsions can be obtained. (36)

Figure 5. Shows how the surface tension varies with increased temperature.

When the emulsifiers, the oil, and the water phase have been adequately mixed, the
temperature must be rapidly decreased since the emulsion is more prone to coalescence close
to the PIT temperature. If the temperature is decreased rapidly, the droplet size remains small,
and the system is stabilized. (36) The components with high melting points (such as the
emulsifiers or oil phase) will once again be solidified. In this case, it will be the emulsifiers
that are solidified. The temperature decrease needs to be rapid so that the emulsion is not
destabilized, and the surfactants desorbed. Traditionally, when making an emulsion, ionic
surfactants have been used. However, recent studies have found that a mixture of ionic/non-
ionic surfactants can create even more stable emulsions. The stabilization occurs both due to
electrostatic repulsion and steric hindrance. The emulsion can be more stable as it obtains a
larger storage modulus and smaller droplets. The multilayers of surfactants created around the
droplets at a much lower concentration than what usually is observed could be the reason for

22
good stabilization. (27) In cosmetics, however, it should be kept in mind that ionic surfactants
may irritate the skin. Thus, these need to be chosen with caution to ensure a safe and non-
irritant product. (34)

3.7.2 Formulations used in this project

Moisturizers can be prepared as both o/w and w/o and can be both creams and lotions. For
this project, it was decided to make an o/w lotion with two different sets of emulsifiers used to
create lotions. Each emulsifier set created a basic recipe for a formulation the two
formulations are called Formulation A and Formulation B.
Formulation A
Formulation. A used Promulgen D (commercial product from Lubrizol), a non-ionic
emulsifier with an HLB value of 15, efficiently creates o/w emulsions and is compatible with
a wide pH range. Promulgen D is a mixture of Cetearyl alcohol (a mixture of Cetyl alcohol
and Stearyl alcohol that is seen in Figure 6) and Ceteareth 20 (a type of ethoxylated Cetearyl
alcohol seen in Figure 6) and Ceteareth 20 (which is a type of ethoxylated cetearyl alcohol
seen in Figure 7). (39) (40) (41) The melting point of Promulgen D is between 47-55 , and it
is a ubiquitous ingredient in cosmetics. (39) As a result, it was found appropriate for the use
of the project. Due to the emulsifier being solid at room temperature, the o/w emulsion
created with Promulgen D has quite a high viscosity. The moisturizer created with Promulgen
D, oil, water, and buffer consequently had similar viscosity to be considered lotions and
creams. Subsequently, extra ingredients were unnecessary to thicken the emulsion.

Figure 6. Chemical structure of Stearyl alcohol (18 carbons) and Cetyl alcohol (16 carbons).

Figure 7.Chemical structure of Ceteareth-20. n represents the number of ethylene oxide groups, 20 in this case.
The rest of the chain is differently long depending if it is combined with a Cetyl or Stearyl alcohol.

Formulation B
Formulation B used the set of emulsifiers from the Tween and Span series, which was the
series used to perform the HLB test. This series was chosen because they are often used in
industry, and their chemical characteristics are known. It should be noted that these are also
used in cosmetics, even though not as frequently as Promulgen D, and that they meet the
safety standards required to be used in cosmetics. Furthermore, the Tween and Span series is
often employed in research to analyze emulsion stability. Thus, many studies could help
explain what emulsifiers from the Span-Tween series were to be used. Many studies have
used the combination Span 80 and Tween 80, and the combination Span 20 and Tween 80 to
form emulsions containing mineral oil.

23
Consequently, these combinations were compared in the literature study. The emulsifiers that
were chosen for the experimental part of the project were Span 20 and Tween 80. The
reasoning behind this choice is seen below.
The emulsifying agent Span 80 has an HLB value of 4.3, is lipophilic, viscous, and tends to
form w/o emulsions, which in this case is not desired. Tween 80 has an HLB value of 15 and
is a derivative of Span 80. Because the hydroxyl groups, on the sorbitan ring are exchanged
with the bulky polyoxyethylene groups the emulsifier is hydrophilic by nature. As a
consequence of its higher water solubility, it tends to form o/w emulsions, which is desired in
this project. Both emulsifiers have good chemical stability and good compatibility with other
ingredients. They are recognized as safe and are approved to be used in multiple cosmetic,
pharmaceutical, and food products as they are nonirritant and have low toxicity. (42) The
molecular structures of Span and Tween 80 can be seen in Figure 8.

Figure 8. The molecular structure of Tween 80 (to the left) and Span 80 (to the right).

The safety of Tween 80 has already been mentioned. However, the same applies to Span 20,
meaning it is not toxic nor irritant and consequently safe to be used in food, pharmaceutical,
and cosmetic products. The molecular structure of Span 20 can be seen in Figure 9. (43)

Figure 9.The molecular structure of Span 20.

An illustration of how Span 20 and Tween 80 would look at the oil-water interphase can be
seen in Figure 10. The chemical structure of the surfactant is vital as the hydrophobic tails of
the surfactants interact differently well with the oil. Combining two surfactants can result in
the surfactant blend being more compatible with the oil phase. The combination of Span 20
and Tween 80 is illustrated in Figure 10. The different lengths of hydrophilic and hydrophobic
parts can further result in better packing at the interphase a better packing, resulting in a
more stable emulsion. (43)

24
 Oil

Water

Figure 10. Illustrates Span 20 and Tween 80 at the oil-water interphase, where the oil phase is above the blue
line and the water below it. The illustration was created by using MolView.

As can be seen in Figure 11 the Tween 80 and Span 80 combination tended to form w/o
emulsions. As this was not desired in this project, Span 20 and Tween 80 combination is
better as this combination tends to form o/w as seen in the same figure. (43)

Figure 11. Phase diagram of mineral oil with Tween 80 and Span 20 as emulsifier seen to the left, and the phase
diagram with Tween and Span 80 as emulsifiers to the right. Modified from (43)

Because Tween 80 and Span 20 are liquid at room temperature, an emulsion created through
these would give a much too low viscosity to generate the one needed for a cream or even a
lotion. As it is desired to make a cream or a lotion, a thickener is necessary. Carbopol® Ultrez
30 (commercial product from Lubrizol used for lotions and creams and in this report will be
referred to as Carbopol 30) is a polyacrylic acid polymer. It will not only thicken the phase
but further help in stabilizing the emulsion. The chemical structure of the monomers Carbopol
30 is made up of can be seen in Figure 12. (44)

25
 Figure 12. Chemical structure of the monomers that make up Carbopol 30.

As a dry powder, the polyacrylic acid is crosslinked with itself and tightly coiled up into coils
with diameters of about 2-7 µm. This is illustrated in Figure 13. When immersed in water that
does not contain any electrolytes, Carbopol 30 is hydrated and dilated slightly, but not enough
to thicken the water phase. This is numbered as step II. in Figure 13. The emulsion is
thickened with the addition of a strong base (in this project, KOH was used) as this will
deprotonate the acrylic acid groups resulting in the polymers charged groups begin to repel
one another. (44) (45)

Figure 13. Illustrates Carbopol 30 during the neutralization process

Further, the polymer can crosslink using, for example, non-ionic emulsifiers or glycine. This
thickens the emulsion further, which results in another benefit as this gives the emulsion a
higher yield point. Because of this, the polymer gel can suspend particles such as oil droplets.
This increased yield point hinders coalescence, and thus the gel can stabilize the emulsion
through steric stabilization. In contrast to gels created using other polymers, the gels created
using Carbopol 30 have little to no thixotropic property. They are also quite viscoelastic.
Consequently, the gels quickly recover their original structure after a mechanical force is
applied to them. (44) (45)

3.8 Analysis of emulsion stability in this project

Emulsion stability depends on both the emulsion composition and the processing conditions
used for producing it. These aspects will influence the droplet characteristics, including their

26
size, interaction, charge, concentration, and rheological behavior. These properties can be
analyzed with various analytical and experimental methodologies. It can generally be said that
these methodologies can be divided into the following sections: visual and microscopy
observation, rheology as well as particle size, and charge analysis. (28)
Visual observation is probably the easiest, cheapest, and fastest way to determine emulsion
stability. It is possible as emulsion instability often can be seen by the naked eye due to phase
separation. The gravitational separations (creaming and sedimentation) can be observed.
Other separation phenomena, such as Ostwald rippling, flocculation, and coalescence, cannot
be observed, however. (28) Visual observation is consequently valuable when deciding if an
emulsion has separated or not (which can be helpful when determining the HLB value). To be
more precise, other analytical tools need to be used.
Microscopical observations can be valuable as droplets smaller than 100 µm cannot be seen
with the naked eye. Further, more separation mechanisms can be determined than through
visual observation as the amplification can give results concerning both the droplet's
dimension and their distribution. Several different types of microscopes can be used. Some of
these include optical, electron, fluorescent, and confocal microscopy, as well as AFM. There
are, however, many downsides to using microscopical observation. They are often time-
consuming as well as subjective, which makes them difficult to standardize between
laboratories. For reliable data, numerous analyses on different parts of the sample are
required. Moreover, preparations such as dilution and slide-spreading are often required,
which may change the original structure of the emulsion. Therefore, it is optimal to combine
information from other sources (such as surface charge and particle size). (28)
Charge analysis is another method used to determine the stability of emulsions. When the
surface of droplets is electrically charged, they repel other charged droplets of the same
charge. Both the sign and the magnitude of the charge depend on the emulsifiers' ionization
characteristics that are absorbed at the surface. The surface charge can further be affected by
the pH and other charged particles that can be present. Two commercially available
instruments are electroacoustic spectroscopy and microelectrophoretic techniques. The latter
technique often includes a light scattering instrument, and to avoid backscattering of light, the
sample needs to be diluted. Electroacoustic spectroscopy can analyze samples with higher
particle concentration (up to 50%). (28)

3.8.1 Droplet size distribution

According to stokes law (Equation 7) the stability of an emulsion is dependent on the particle
size of the dispersed liquid. v represents the velocity of the droplet with radius r. 𝜌 represents
the density of the oil and the water phase while 𝜂 represents the viscosity of the continues
phase. (28)
𝜌2 𝜌1 Equation 7
𝑣 2𝑔𝑟 2
9𝜂1

Equation 7 implies that the smaller the particle the more stable the emulsion. Further, the
more monodisperse the droplets are the more resistant it is towards creaming. It is therefore of
interest to determine the droplet size distribution of the emulsions created in this project. A
way of doing this is through light scattering, which will be used for this project. The
instrument used is a Mastersizer 3000, which measures droplet size distribution. It is
automatic and can quickly and easily obtain valuable information. It is, however, important to

27
input the correct physical information concerning the sample, such as the correct refractive
index. Further, the concentration cannot be too high and must be diluted. (28) The dilution of
the emulsion may result in the obtained data not being representative of the real system. It is
also important that the sample measured is properly dissolved in the solvent (deionized water
in this case) as the instrument can otherwise measure the particle size of the undissolved
emulsion lumps instead of the oil droplet size.
The data obtained from the mastersizer tests is a curve showing the droplet size distribution in
a graph, but also the 𝐷 10, 𝐷 50, and 𝐷 90, which represents the cumulative particle size
distribution at 10, 50, and respectively 90%. The droplet size distribution of the sample is
commonly called SPAN, which is a dimensionless number. It can be calculated by using
Equation 8. (46)

𝐷 90 𝐷 10 Equation 8
𝑆𝑃𝐴𝑁
𝐷 50

3.8.2 Rheology
The feel of a moisturizer on the skin and how long it can be stored are essential properties for
all moisturizers. These can be studied with rheological measurements. (47) Rheology
concerns the relationship between force, deformation, and time. The sample is deformed in a
controlled manner when studying rheology, while its reaction is studied. The sample will
respond to deformation in one of three possible ways. Its response depends on whether it is a
viscous, elastic, or viscoelastic material. This is, in turn, dependent on what happens to the
deformation energy of the sample. Energy cannot disappear or be created only converted into
different forms of energy, First law of thermodynamics. In ideal viscous material, all the
deformation energy is converted into heat, and as a result, the sample begins to flow. It will
never regain its previous shape, and thus the material is irreversibly deformed. In the case of
an ideally elastic material, all the deformation energy is stored within the sample structure.
Consequently, the previous structure of the sample can be fully recovered. A sample is
seldom either entirely viscous or elastic but usually a combination. This is termed
viscoelastic. Viscosity (has the unit Pa s) is a measure of resistance to flow within the
material. One could say it is the friction between molecules. The viscosity of a sample gives
information concerning its flow properties. For example, when being pumped from a bottle or
applied on the skin. Elasticity is a measure of a sample s degree of structure. The higher value
of elasticity, the more network structure and/or internal bonds exist in the material. The value
of elasticity gives information concerning its storage stability. (48)
In this project, the moisturizers produced were liquid. A liquid is a substance that
continuously changes its shape and will take the shape of its container. This stands in contrast
to a fully elastic solid that reaches a constant deformation level that depends on the inflicted
level of stress. All the deformation energy is stored in the material and used to recover the
original shape of the material. A liquid can either be defined as a Newtonian or a non-
Newtonian liquid. A Newtonian liquid is an entirely viscous liquid and thus has no elastic
properties, and the viscosity is a material constant. The viscosity of a Newtonian liquid only
changes with temperature and pressure. A non-Newtonian liquid s viscosity depends not only
on the previously stated factors but also on the flow rate. The duration of the flow can
influence the viscosity of a non-Newtonian liquid, and consequently, the non-Newtonian
liquids are classified as either time-dependent or time-independent. A moisturizer is a non-

28
Newtonian liquid as they inhibit elastic properties. Creams and lotions are emulsions in which
there are weak interactions between the molecules. When shear is imposed on the moisturizer,
the molecules are reversibly deformed to take up less space. Consequently, the viscosity will
decrease with increasing shear. When the shear ceases, the moisturizer begins to go back to its
original shape. This will, however, in most cases take time. Thus, lotions and creams are time-
dependent non-Newtonian liquids. You may have noticed this concept yourself. When you
put a finger into a jar of face creams, the structure is deformed. When the finger is removed,
the cream begins to go back to its original shape slowly. The concept wherein the viscosity of
the liquid decreases as a function of the shear stress and time, and the original form is not
recovered immediately, is termed thixotropic. (48)
Some important rheology concept includes strain (deformation), shear stress σ (force per
unit area), and shear rate 𝛄 (deformation per unit time). An approximate shear rate for rubbing
lotion on the skin ranges between 10 000 to 100 000 𝑠 1 . Viscosity can be calculated through
Equation 9. In contrast, elasticity G of an ideally elastic material subjected to simple
oscillatory flow can be calculated through Equation 10. (48)

σ Equation 9
γ

σ Equation 10
𝐺
γ
Other essential concepts include storage modulus G’ and loss modulus G’’. The fraction
between loss modulus and storage modulus is phase angle tan δ. The storage modulus defines
the degree of elasticity in the sample. The higher the value, the more elastic the sample is. The
loss modulus is defined as the energy lost as the material is deformed. The phase angle is the
quota between storage and loss modulus and the concept separating in and out of phase
oscillatory shear. For ideally elastic material, tan is zero, while it is 90 for entirely viscous
material and 45 for an ideally viscoelastic material. At this point, G is equal to G when the
sample behaves as an ideal viscoelastic material. When G is larger than G , the sample
behaves more elastically, and when the opposite is true, it behaves more like a viscous
material. (48)
This project performed the following tests: frequency sweep, amplitude sweep, thermal loop,
thixotropic, and application test.
Frequency and amplitude sweep
Frequency and amplitude sweep are oscillatory tests that are used to characterize linear
viscoelastic behavior. The sample is, through these tests, subjected to a dynamic, frequency-
dependent oscillatory shear. The shear must be within the linear viscoelastic region (LVE) of
the sample. The sample is subjected to increasing frequency for frequency sweeps while
amplitude (strain) is kept constant. The viscoelasticity of the sample can thus be studied.
Through a frequency test, it is also possible to observe the sample at rest. The relation
between storage and loss modulus with increasing frequencies gives information about the
sample structure, as shown in Figure 14. For a weak gel, tan displays a low change. If the
variable increases slightly at low-frequency values, this indicates inferior long-term stability.
(48)

29
 Figure 14. Frequency sweep diagrams for week and strong gel.

Amplitude sweeps can either be stress or strain sweeps. During these tests, the sample is
subjected to increasing shear amplitudes while the frequency is kept constant. These tests are
performed to determine the LVE region and the rest structure of the sample and,
consequently, be used to determine the storage stability of the product. The broader the LVE
range of the sample is, the more homogenous the particle size distribution is, making it more
stable. (48) The broader it is, the more mechanical resistance it can resist without the structure
of the sample being affected. (49) The lower the LVE of the storage modulus value, the lower
degree of elasticity of the sample. Consequently, the better the sample is at resisting
molecular attraction, and as a result, the better it is to resist aggregation. (36) The yield point
is the value where the value of the storage modulus has decreased by 5% compared to the
storage modulus of the LVE region, and it marks the end of the LVE region. The flow point is
the stress value at the crossover of storage and loss modulus, representing the force necessary
for the material to flow. (47)
Storage stability
The structure of the material can be influenced with time as phase separation can occur. A
storage stability test is a way of analyzing the change in rheological properties with time. The
sample is, during this test, stored for a period (a month, for example). After this, an amplitude
sweep is performed. In semi-solid systems, such as creams and gels, the two phases can
separate if the formulation is unstable. When the phase with lower viscosity is separated from
the phase with higher viscosity, the viscosity and elasticity of the bulk will increase.
Therefore, the storage modulus of the LVE region can increase. (48)
Thixotropic test
A thixotropic test is also a frequency sweep and can be employed to quantify the thixotropy of
the sample. A thixotropic material is a material in which structure breaks down during shear,
which causes the viscosity to decrease, but over time the structure is recovered, and the
viscosity increases. So-called loop-tests are performed to study this behavior. During these
tests, the sample is subjected to increasing, and after a certain point, decreasing shear stress
during a specific time. The larger the area between the up and down viscosity curves, the
more thixotropic the sample is. (48)
Application test
The viscosity of non-Newtonian materials depends on the acting shear rate. The model that is
the most frequently used is the power law, Equation 11. K is the consistency coefficient with

30
the unit 𝑃𝑎𝑠 , and it is an estimation of the material s viscosity at low shear rates. The higher
the K value, the higher the viscosity at the lowest shear rate for the sample. n (unitless) is
called the flow index and indicates how much the viscosity of the material has changed with
changing shear rate. For shear-thinning liquid n<1, for shear thickening n>1 and for
Newtonian liquids is equal to 1. In the case of shear-thinning liquids, the smaller the n value,
the more the viscosity of the liquid decreases with increasing shear rates. (48)

𝜎 𝐾∗γ Equation 11. Power law

Thermal loop
According to Stoke s law (Equation 7), the resistance against instability mechanisms resulting
from the flocculation decreases with increasing viscosity. As rheological properties include
the flow properties of an emulsion, rheology can be used to study these and thereby determine
physical properties, such as flow point and thermal and chemical stability. (50) While an
amplitude and frequency sweep can analyze the emulsion's mechanical properties and
structure, a thermal loop test can be performed to investigate the structural change of a sample
with varying temperatures. (47) A moisturizer can be carried in a handbag, stored in a car,
inside the bathroom cabinets, Etc. Therefore, it is exposed to a large variety of temperatures.
As the properties of materials change when subjected to varying temperatures, it was decided
to study the structural changes and the sample's thermal stability with a thermal loop. The
properties impacted by temperature fluctuations are storage stability G and loss modulus G .
The relative structural change ( ) for the properties can thus be studied with Equation 12. The
maximum G or G value of each cycle is compared to the first cycle. (51)
/
, Equation 12
∆ /
,

Some of the factors that can influence the rheological properties of an emulsion are the
viscosity and the chemical composition of the continuous phase. Examples of these include
electrolyte concentration, pH, the volume fraction of dispersed phase, the elasticity of
emulsifier film (that is dependent on the emulsifier type and concentration) finally, droplet
characteristics such as size distribution, concentration, internal viscosity as well as particle-
particle interaction. (50)

4. Method
4.1 Deciding HLB of oil
Two chemical families from the Tween and Span series were tried when deciding the HLB for
the oils: Span and Tween 80 and 20. According to theory, an excess of emulsifier was used as
the emulsifiers made up 20% of the oil phase, which corresponds to 4g. Moreover, 20 wt% of
the emulsion was made up of the oil phase, 20g, while the water phase was 80g. The HLB
value of Span 80 is 4.3 while it is 15.0 for Tween 80. For Span 20, the HLB value is 8.6,
while the HLB value of Tween 20 is 16.7.
For each HLB value 16g of emulsifiers was made instead of the 4 g needed for one HLB
value test. The emulsifying mixtures were made by mixing them in an Erlenmeyer flask. It

31
was mixed with a magnet stirrer at 40 . When the mixture of emulsifiers had been properly
mixed, and there were no air bubbles in the mixture, 4g of the emulsifying mixture was added
to 16 g of either N-MWO or P-MWO. This was mixed with a spoon at 30-35ºC until mixed.
80g of the water phase was added to a 250 ml beaker. The water phase was composed of
deionized water and HCl to set the pH of the water phase to 5. The water phase was mixed at
300 rpm while the oil phase was added slowly. After all the oil phase had been added the
blend was stirred at 700 rpm for 10 minutes. Thereafter it was poured into a vial and
photographed. The photographs were taken immediately after the emulsion was poured into
vials. Pictures were also taken five days after emulsification. These results can be found in
Appendix.

4.1.1 Required HLB for N-MWO

In Table 7 the HLB values created using Span and Tween 80 along with the composition of
the emulsifiers are seen, (both in percentage and in mass).
Table 7. Shows the HLB values used to test the HLB value of N-MWO with the corresponding composition of
Tween and Span 80.

HLB Span 80 of Tween 80 Span 80 Tween 80

E [%] of E [%] [g] [g]
10 46.73 53.27 7.5 8.5
11 37.38 62.62 6.0 10.0
11.5 32.71 67.29 5.2 10.8
12 28.04 71.96 4.5 11.5
12.5 23.36 76.64 3.7 12.3

The HLB tests were also performed using Span and Tween 20 to see if the different chemistry
of these emulsifiers could have a beneficial impact on the emulsion stability. The HLB values
used for N-MWO can be seen in Table 8.
Table 8. The HLB values used to test the HLB value of N-MWO with the corresponding composition of Tween
and Span 20.

HLB Span 20 of Tween 20 Span 20 [g] Tween 20

E [%] of E [%] [g]
10 82.72 17.28 13.2 2.8
11 70.37 29.63 11.3 4.7
11.5 64.20 35.80 10.3 5.7
12 58.02 41.98 9.3 6.7
12.5 51.85 48.15 8.3 7.7

32
The samples were photographed directly after emulsification as well as seven days later.
These photographs can be seen in Appendix. Through these tests it was decided that HLB 12
was the best fit for N-MWO

4.1.2 Required HLB for P-MWO

The same procedure as described directly above was used to test the HLB value of the P-
MWO. As it was found in litterature that medium paraffinic oils gave HLB values of about 9,
a slightly modified HLB series was tested to cover lower HLB values than for N-MWO, these
values are found in Table 9. (33)
Table 9. Shows the HLB values used to test the HLB value of P-MWO with the corresponding composition of
Tween and Span 80.

HLB Span 80 of Tween 80 Span 80 [g] Tween 80

E [%] of E [%] [g]
9 56.07 43.93 7.0 9.0
10 46.73 53.27 8.5 7.5
8.5 60.75 39.25 6.3 9.7
11 37.38 62.62 10.0 6.0
9.5 51.40 48.60 7.8 8.2

The HLB tests were also performed using Span and Tween 20 to see if the different chemistry
of these emulsifiers could have a beneficial impact on the emulsion stability since Span and
Tween 20 also are common emulsifiers in the cosmetic industry. The HLB values used for P-
MWO can be seen in Table 10. It should be noted that as the HLB value of Span 20 is 8.6 and
therefore limits the HLB-range for the Tween Span 20 mixture to 8.6, instead of 8.5, as in
Table 9. Consequently, the HLB 9 mixture also contains a high amount of Span 20.
Table 10. Shows the HLB values used to test the HLB value of P-MWO with the corresponding composition of
Tween and Span 20.

HLB Span 20 of Tween 20 Span 20 [g] Tween 20

E [%] of E [%] [g]
8.6 100 0 16 0
9 95.06 4.94 15.2 0.8
9.5 88.89 11.11 14.2 1.8
10 82.72 17.28 13.2 2.8
11 70.37 29.63 11.3 4.7

The samples were photographed directly after emulsification as well as seven days later.
These pictures can be seen in Appendix. From these tests it was decided to use HLB 9.5 for P-
MWO in Formulation B.

33
4.1.3. PIT value
As previously mentioned, the properties of the emulsion change radically when the
temperature reaches the PIT value. Some of these properties are easier to analyze with the lab
instruments at hand than other. The first attempt that was made to decide the PIT value for N-
MWO was through the emulsion s conductivity change with temperature. This test was
carried out by preparing an emulsion at low temperature (just above melting point of
Promulgen D and at 40ºC for Tween 80 and Span 20). The emulsions were heated from room
temperature to 94 ºC in an oil bath while both the temperature and conductivity was measured
with a conductive meter for every 1°C. As the viscosity changes radically at the PIT value a
rheometer was used to investigate the viscosity change as the temperature was changed from
room temperature to 94ºC when amplitude and frequency was kept constant.

4.2 Stability tests

The samples emulsion stability was studied by testing their droplet size distribution along
with their rheological properties using a Malvern Mastersizer 3000 (wet cell) that uses the
technique of laser diffraction.

4.2.1 Droplet size distribution

The droplet size distribution was analyzed to determine the particle size along with their
distribution. Since the emulsions in this project was relatively viscous and to ensure that the
dilution of the emulsion would give significant data when executing the real tests, three
different lotions were highly diluted differently and analyzed in the Masterziser. If the
different dilutions were to give the same droplet size distribution along with the same droplet
sizes, it would be evident that the dilution would not give a bias in the measurement and then
the Mastersizer could be used for the project.
For this test two commercial hand lotions were used: Vaseline intensive care Healthy hands
Stronger Nails (Moisturizer 1) and DAX Hand och Hudkräm (Moisturizer 2). They both
contained white mineral oil (INCI paraffin oil). The latter lotion had similar composition as
the one to be created in this project (Formulation A). Finally, a thick moisturizer created with
promulgen D and P-MWO made by Emma Öberg (Moisturizer 3) was also tested.
A study diluted 0.5 g of lotion with 3 ml of water and thereafter 4.5 ml more before being
injected into a Mastersizer 2000.(27) Similar dilutions were thus made, these can be seen in
Table 11. Shows the dilution scheme for the three lotions.
Table 11. Shows the dilution scheme for the three lotions.

Moisturizer 1 Moisturizer 2 Moisturizer 3

Mass of lotion [g] 0.5 0.52 0.53
First dilution [ml] 4 4 3
Second dilution [ml] - - 4

Moisturizer 1 and 2 were only stirred with a spoon briefly as their viscosity were much lower
than Moisturizer 3, which was extremely thick. This moisturizer was stirred with a magnet
rod for three hours. After the dilution was finalized a milky fluid was produced. This could be
injected into the Masterziser 3000. Different amount of the moisturizers was injected into the
Mastersizer to give different degrees of obscuration i.e. different concentrations.

34
4.2.2 Rheology
All the following rheological tests were performed around two hours after the emulsification,
except the storage stability test. The instrument used was a stressed-controlled Anton Paar
DSR MCR 302. The measuring geometry used was plate/plate with a diameter of 24.985 mm,
and the gap used during all measurements was 2 mm. This was advised by the knowledgeable
Annika Sahlström. The temperature was controlled with a temperature cooler,
VISCOTHERM VT 2.
Amplitude sweep
The amplitude sweep was performed at 23 (a common temperature to have in a bathroom)
at an angular frequency of 1 Hz at strains from 0.01 to 100% the same day as the samples had
been produced.
Storage stability investigated by amplitude sweep
An amplitude sweep was performed with the same parameters as the ones mentioned above
two weeks after the emulsification of the samples.
Frequency sweep
It was performed at 23 with angular frequencies ranging from 0.1 to 10 Hz and a strain of
0.1% the same day as the samples had been produced.
Application test
A temperature of 28 was used (as an estimation of the surface of the skin temperature) the
shear rate was varied between 10 and 100 𝑠 1 .
Thixotropic test
The thixotropic test was performed at 23 . The test varied shear rate from 10 to 100 1/s and
from 100 to 10 𝑠 1 .
Thermal loop test
The thermal stress was simulated by exposing the sample to 15 thermal cycles varying the
temperature from -20 to 30 (normal temperatures during a year in Sweden) for every cycle.
The strain was kept at 0.1% and the frequency at 1 Hz.

4.3 How to create emulsion

The methodology used in this project was to compare the emulsion stability for emulsions
while varying certain factors and keeping the rest constant. The varied factors include oil
type, if perfume is added or not, the concentration of emulsifiers, and the type of emulsifiers.
The type of emulsifier used determined the other components used in the emulsion resulting
in two formulations. These different formulations will henceforth be called Formulation A
(Promulgen D as emulsifier) and Formulation B (with Span 20 and Tween 80 as emulsifiers).
The composition of these formulations can be seen in Table 12. Different components are
required depending on the emulsifier used because Promulgen D is solid at room temperature
and, consequently, will thicken the emulsion into a thick cream or lotion. However, Tween 80
and Span 20 are liquid at room temperature and will not do the same for the emulsion.
Instead, the emulsion would be left as thin as milk. Therefore a thickener was needed,

35
Carbopol-30, a commercial product from Lubrizol. Carbopol 30 is extremely sensitive to
electrolytes. Consequently, a buffer cannot be used in combination with Carbopol-30, while
the pH of the water phase will be buffered with citric acid and sodium citrate to pH 5 for
formulation A. To homogenize the emulsion a mechanical mixer was used (Yellowline by
𝐼𝐾𝐴® OST Basic Overhead Stirrer). During the emulsification a 4-blade propeller was used.

Table 12. Shows the composition of Formulation A and B

Formulation A Formulation B

Oil content [% by weight] 25 25

Water content [% by weight] Up to 100 Up to 100

Emulsifier Promulgen D Span 20 and Tween 80

Cross polymer None Carbopol 30 (0.2%)

pH regulator Buffer: Citric acid sodium KOH

citrate

The Span 20 and Tween 80 emulsifiers used the HLB 9.5 for P-MWO and 12 for N-MWO.
The ratios of the emulsifiers used to create Formulation B can be seen in the Appendix in
Table 26. The emulsifiers were added to the oil phase as this seems to be the custom. Before
being added to the water phase, the oil phase was heated to 65-70 and stirred using a
magnetic stirrer and a heating plate. The temperature of the water phase was controlled by
immersing the beaker into an oil bath (𝐼𝐾𝐴® -WERKE HB4 basic, with silicone oil) where the
water phase was heated to 65-70ºC. As many of the methodological steps differed between
Formulation A and B, see Figure 15 to clarify the methodology.

Figure 15. Emulsification process briefly explained for Formulation A and B.

36
The first step for formulation Formulation A was to drip the oil phase into the water phase
using a pipet, while the water phase was stirred at 500 rpm once both the water and oil phases
had reached 65-70 . Then, after all the oil phase had been added, the sample was stirred at
500 rpm for 10 minutes. For Formulation B, 0.2g of Carbopol 30 needed to be added to the
water phase before this step. So Carbopol 30 was added carefully to the water phase while the
deionized water, which made up the water phase, was stirred. Then, when all the Carbopol 30
had been added, it was stirred at 500 rpm for 5 minutes. After this step, the oil phase was
added to the water phase the same way it had been for Formulation A.

For Formulation B the pH of the solution needed to be increased to inflate the polymers after
emulsification. Therefore, the sample was first cooled to about 60-65 then 7 ml of KOH
(pH 12.2) was added while the sample was stirred at 300 rpm. Once the base had been added,
the sample was stirred at 300 rpm for 3 minutes.

If perfume was to be added to the sample, it was added after this. Once the sample had been
cooled to about 60 , 56 l of pure lavender oil was added while stirred at 300rpm. After the
addition, the sample was stirred at the same rate for 1 minute.

As earlier mentioned, three factors were be varied separately for both Formulations A and B.
This includes varying if the oil used was N-MWO or P-MWO, the emulsifiers' content, and if
the perfume was added. The list for the composition of the samples created for both
Formulation A and B can be found in Table 13 and

Table 14.
Table 13. The composition of the different samples created by Formulation A. (emulsifier used for this
formulation: Promulgen D).

Content of
Sample Oil emulsifier [%] Perfume

1A N-MWO 4 With

2A P-MWO 4 With

3A N-MWO 6 With

4A P-MWO 6 With

5A N-MWO 4 Without

6A P-MWO 4 Without

7A N-MWO 6 Without

8A P-MWO 6 Without

37
 Table 14. The composition of the different samples created by Formulation B (emulsifier used for this
formulation: Tween 80 and Span 20).

Content of
Sample Oil emulsifier [%] Perfume

1B N-MWO 4 With

2B P-MWO 4 With

3B N-MWO 6 With

4B P-MWO 6 With

5B N-MWO 4 Without

6B P-MWO 4 Without

7B N-MWO 6 Without

8B P-MWO 6 Without

5. Results and discussion

The results and discussion is divided into the following parts: PIT, test of the mastersizer
methodology, rheological tests, mastersizer measurements, visual test, and reflections
concerning the formulation. Only a few replicates were made. This was because a sample
took too long to produce, and due to corona restrictions, the time possible to be in the lab was
shortened to three days a week. The replicated samples, termed sample x No 2, had the
highest degree of difference from one another in terms of formulation to gain a generalized
insight into how reliable the results were for all samples.

5.1 PIT
Neither the conductivity and temperature curve nor the viscosity and temperature curve had
any similarities to theoretical ones. This is because the content of ethylene-oxide chains in
Promulgen D is far too low. Consequently, this concept is irrelevant for it. Instead, all that
could be seen for the emulsion prepared with Promulgen D was a steep decline in viscosity
and conductivity at 55ºC. This may be because the emulsifier used, Promulgen D, is solid
until 55ºC. Consequently, the viscosity will increase with temperature as the solution is
liquified, which may influence the conductivity. For the Tween and Span series, the ethylene-
oxide chain was probably not long enough. Further, the sorbitol group probably should be
avoided if it is desired to create an emulsion via the PIT method.
As none of the emulsifier systems had a PIT value, the temperature for the emulsification
process was chosen based on what is common to be used in industry when making
moisturizers. The temperature chosen was 65-70ºC and was, as seen in 4.3 How to make
emulsions, used for all samples.

38
5.2 Test of mastersizer methodology
The results obtained can be seen in Figure 16, Figure 17, and Figure 18. It can clearly be seen
that different degrees of obscurations (or dilutions) results in the same droplet size
distribution. Consequently, the Masetersizer 3000 can be used in the project to determine
droplet size distribution for the emulsions created.

Figure 16. Graph showing the droplet size distribution for three different dilutions of Moisturizer 1

Figure 17. Graph showing the droplet size distribution for three different dilutions of Moisturizer 2

Figure 18. Graph showing the droplet size distribution for three different dilutions of Moisturizer 3

An interesting aspect of the droplet size distribution is that Moisturizer 2 and 3 only have one
peak while Moisturizer 1 has two. This could be because Moisturizer 1 had been used for
several months and frequently taken outside. The different shape of Figure 16 to Figure 17
and Figure 18 could thus be that Moisturizer 1 had been exposed to much temperature change
and thus made the droplet size less monodisperse. To draw these conclusions for certain one
must naturally perform tests to have as a reference before the moisturizer is used, but it is an
interesting possibility which is in accordance with theory.

5.3 Rheological tests

In this section, all the rheological tests are presented and discussed. The first tests, frequency
sweep, application, and the thixotropic tests, describe the sensory experience and give
39
knowledge concerning the properties of the sample. The amplitude sweep, storage test, along
with the thermal loop, give information concerning emulsion stability.

5.3.1 Frequency sweep

The frequency sweeps made for four of the samples from Formulation A can be seen in
Figure 19 and Figure 20, while figures for the rest of the samples can be found in Appendix
on page 76. For all samples of Formulation A, storage modulus is always larger than loss
modulus as seen in Figure 19.

Rheoplus

3
10

1A Sample 2A nr 1 30 mars 1

2A PP25-SN24228; [d=2 mm]

5A G'' Loss Modulus

6A G' Storage Modulus

Sample 1A 7 April 1

PP25-SN24228; [d=2 mm]

G'' Loss Modulus

G''
G' Storage Modulus
2
10 Sample 5A nr 3 14 April 1

PP25-SN24228; [d=2 mm]

G'
G'' Loss Modulus

G' Storage Modulus

Sample 6A nr 2 16 April 1

PP25-SN24228; [d=2 mm]

G'' Loss Modulus

G' Storage Modulus

1
10
0,1 1 Hz 10
Frequency f
Anton Paar GmbH

Figure 19. Frequency sweep for 1, 2, 5 and 6A showing storage and loss modulus.

These curves in Figure 19 are almost parallel displaced, but not entirely as the loss factor tan
can be seen decreasing with increasing frequency values, Figure 20. These factors indicate
that all samples from Formulation A are weak and stable gels. As tan , Figure 20, does not
increase at low-frequency values, there is no indication from the frequency test that any
samples from Formulation A should have bad storage stability.
Rheoplus

0
10

1A 5A
2A 6A Sample 7A nr 2 26 mars 1 Sample 3A 8 April 1
3A 7A PP25-SN24228; [d=2 mm] PP25-SN24228; [d=2 mm]
4A 8A tan( ) Damping Factor tan( ) Damping Factor

Sample 2A nr 1 30 mars 1 Sample 5A nr 3 14 April 1

PP25-SN24228; [d=2 mm] PP25-SN24228; [d=2 mm]

tan( ) Damping Factor tan( ) Damping Factor

Sample 4A 31 mars 1 Sample 6A nr 2 16 April 1

tan( )
PP25-SN24228; [d=2 mm] PP25-SN24228; [d=2 mm]

tan( ) Damping Factor tan( ) Damping Factor

Sample 1A 7 April 1 Sample 8A nr 2 16 April 1

PP25-SN24228; [d=2 mm] PP25-SN24228; [d=2 mm]

tan( ) Damping Factor tan( ) Damping Factor

-1
10
0,1 1 Hz 10
Frequency f
Anton Paar GmbH

Figure 20. Frequency sweep made of all the Samples from Formulation A showing loss factor plotted against
frequency.

40
The frequency sweeps made for four of the samples from Formulation B can be seen in Figure
21 and Figure 22. The rest are found in Appendix in section 9.4 Frequency sweeps. For all
samples of Formulation B, storage modulus is always larger than loss modulus. Furthermore,
these curves are almost parallel displaced, but not entirely as the loss factor tan fluctuates
quite a lot, Figure 22. This may be due to the Formulation B's viscosity being much lower
than the one of Formulation A, but the same strain (0.1%) was used for both Formulations. As
can be seen in the amplitude sweep in 5.3.4 Amplitude sweep in Figure 25 the storage and
loss modulus fluctuates greatly at low strains for Formulation B. It may consequently have
been beneficial to use a higher strain for the samples made of Formulation B.
Rheoplus

3
10

1B Sample 5B 29 April 1
2B PP25-SN24228; [d=2 mm]
5B G'' Loss Modulus
6B G' Storage Modulus

Sample 1B 5 maj 1
2
10 PP25-SN24228; [d=2 mm]

G'' Loss Modulus

G''
G' Storage Modulus

Sample 2B 6 maj 1

PP25-SN24228; [d=2 mm]

G'
G'' Loss Modulus

1 G' Storage Modulus

10
Sample 6B nr 2 11 maj 1

PP25-SN24228; [d=2 mm]

G'' Loss Modulus

G' Storage Modulus

0
10
0,1 1 Hz 10
Frequency f
Anton Paar GmbH

Figure 21. Frequency sweep made of Sample 1, 2, 5 and 6B showing storage and loss modulus.

The storage modulus always has larger values than the loss modulus for all samples from
Formulation B. Moreover, the graphs in Figure 21 are parallelly displaced. Consequently, all
samples made from Formulation B are weak and stable gels. In Figure 22 the values of tan
fluctuate greatly. Despite the fluctuations, the trend line of each of these curves are horizontal
at low frequencies, and no slight increase of tan is seen for most of the samples from
Formulation B. The only sample where a slight increase could be seen was sample 1B
excepted. Other than that, none of the frequency sweeps made for Formulation B indicate any
slight increase of tan . According to this test, only sample 1B may potentially have bad
storage stability.

41
 Rheoplus

0
10

Sample 5B 29 April 1
1B PP25-SN24228; [d=2 mm]
2B
tan( ) Damping Factor
5B
Sample 1B 5 maj 1
6B
PP25-SN24228; [d=2 mm]

tan( ) Damping Factor

Sample 2B 6 maj 1
tan( )
PP25-SN24228; [d=2 mm]

tan( ) Damping Factor

Sample 6B nr 2 11 maj 1

PP25-SN24228; [d=2 mm]

tan( ) Damping Factor

-1
10
0,1 1 Hz 10
Frequency f
Anton Paar GmbH

Figure 22. Frequency sweep made of sample 1, 2, 5 and 6B Samples from showing loss factor plotted against
frequency.

It can be noted that samples with lower content of emulsifier, seen in Figure 22, fluctuate a
little more than the samples with a higher emulsifier content, Figure 49 in Appendix in section
9.4 Frequency sweeps.

5.3.2 Thixotropic test

Three examples of thixotropic tests are seen in Figure 23. The area that determines the
samples degree of thixotropy is the triangular area seen to the left of the graph s intersection,
marked in red for the reference lotion.

1A
2A
Reference

Figure 23. Thixotropic test made for sample 1 and 2A as well as the reference lotion.

The thixotropic areas can be found in

42
Table 15 and Table 16. For Formulation A, it can be seen that a higher concentration of
Promulgen D results in a larger area, meaning a higher degree of thixotropy, which means that
the samples with higher content of Promulgen D take a longer time to recover their original
structure. The thixotropy of the reference lotion is quite similar to the samples with the higher
Promulgen D content, although its value is slightly lower. Neither the addition of perfume nor
the oil type seems to influence the thixotropy of the samples.

Table 15. Showing the area between the curves created in the thixotropic measurement for Formulation A

Sample Area

1A 140

1A No 2 197

2A 84

3A 447

4A 516

5A 99.1

6A 75.7

7A 600

8A 368

8A No 507

Reference lotion 391

As the gel in Formulation B is created by Carbopol 30 that creates structures with little to no
thixotropy, low thixotropic values were expected. As shown in Table 16 none of the samples
created with N-MWO were thixotropic at all, while the samples created using P-MWO were
slightly thixotropic. Consequently, it takes the samples made of P-MWO a slightly longer
time to regain the original structure. As a result, Span 20 and Tween 80 combined with
Carbopol 30 will result in a more thixotropic material when combined with P-MWO than with
N-MWO. The same thixotropic behavior difference between the oils was not observed with
Formulation A. Therefore, it is likely that it is the combination of Tween 80, Span 20,
Carbopol 30, and the oils that influence the thixotropic behavior.

43
Table 16. Showing the area between the curves created in the thixotropic measurement for Formulation B

Sample Area

1B 0

1B No 2 0

2B 24.8

3B 0

4B 25.8

5B 0

6B 41.8

6B No 2 16.8

7B 0

7B No 2 0

8B 29.1

The samples created with P-MWO from Formulation B may have a higher degree of
thixotropy than those made of N-MWO. They still, however, have a much lower degree of
thixotropy than all samples from Formulation A. Even sample 6B, which was twice as
thixotropic as its replicate, had a much lower degree of thixotropy than the samples from
Formulation A.

A more thixotropic material will take a longer time to regain its original structure, which may
be a bad thing. The Reference lotion (a commercial product) has the same degree of
thixotropy as the samples with the highest Promulgen D content. As a result, the fact that N-
MWO from Formulation B has the lowest thixotropy does not necessarily mean that these
have better emulsion stability.

5.3.3 Application test

An example of the appearance of two application tests can be seen in Figure 24. A power-law
function was fitted to the graphs to obtain the K and n values. These values, along with the 𝑟 2
values, are displayed in Table 17 for Formulation A and in Table 18 for Formulation B.

44
 Rheoplus

2 1
10 10

1A
1B Sample 1A 7 april 1

PP25-SN24228; [d=2 mm]

Shear Stress

σ G'
G'

G''
Storage Modulus

Loss Modulus
Pa Pa Pa Sample 1B nr 2 26 Maj 1

G'' PP25-SN24228; [d=2 mm]

Shear Stress

G' Storage Modulus

G'' Loss Modulus

1 0
10 10
10 1/s 100
.
Shear Rate
Anton Paar GmbH

Figure 24. Application test made of sample 1A and 1B.

For all samples prepared from both formulations the n value was below 1. Consequently, all
the samples are shear thinning. It can further be said that all n values from Formulation A
along with the Reference lotion, Table 17, are smaller than the n values for Formulation B, are
smaller than the n values for Formulation B, Table 18. As a result, the viscosity changes at
low frequencies are larger for Formulation A (and the Reference lotion) than for Formulation
B. This means that the lotion feels less rich when applied on the skin for Formulation A
than Formulation B.

Table 17. The K and n value obtained from the power law for the samples from Formulation A. The 𝑟 2 vale of
the power law curve.

Sample K n 𝒓𝟐

1A 7.6411 0.2361 0.94

1A No 2 9.7984 0.2491 0.97

2A 9.1354 0.2701 0.91

3A 19.445 0.2984 0.99

4A 23.412 0.2956 0.99

5A 6.9697 0.2226 0.92

6A 7.785 0.2046 0.91

7A 22.143 0.2581 0.99

8A 16.11 0.2361 0.97

8A No 2 19.147 0.3361 0.99

Reference lotion 33.846 0.2084 0.99

45
The K values of Formulation A, Table 17, seem to be influenced by the Promulgen D content,
as a higher concentration generates a higher K value. Even the highest K values of the
samples from Formulation A still have a lower K value than the Reference lotion. As for the
samples made from Formulation B, Table 18, the samples made from N-MWO have a larger
K value. This means that N-MWO has a higher viscosity at a low shear rate in Formulation B
and that a higher Promulgen D generates the same effect. On the other hand, none of the
samples created have higher viscosity at low shear rates than the Reference lotion.

The problem with this test, in this case, is that one of the formulations, Formulation B, is
extremely sensitive to electrolytes. In practice, when applied to the skin, the salts that exist on
the skin will shield the deprotonated acid groups of the polyelectrolyte. Consequently, it will
curl up, which will lead to a very low viscosity of the lotion.

Table 18. The K and n value obtained from the power law for the samples from Formulation B. The 𝑟 2 value of
the power law curve

Sample K n 𝒓𝟐

1B 8.9799 0.4951 0.999

1B No 2 14.633 0.4208 0.999

2B 12.58 0.3518 0.992

3B 18.079 0.4299 0.999

4B 9.769 0.3758 0.995

5B 9.7181 0.4539 0.999

6B 5.509 0.5543 0.994

6B No 2 5.3117 0.5624 0.994

7B 16.981 0.4366 0.999

7B No 2 15.371 0.4580 0.999

8B 10.573 0.3379 0.994

5.3.4 Amplitude sweep

In Figure 25 an amplitude sweep for sample 1A and 1B can be seen. The figure was added to
exemplify the appearance of an amplitude sweep. The data of importance, namely the yield
point, flow point along with the storage modulus of the LVE region can be viewed in Table
19 and Table 20.

46
 Figure 25. Amplitude sweep made on sample 1A and 1B. The yield point is marked with a red square while the
flow point is marked with a red circle.

The graph, Figure 25, of sample 1B has fluctuating storage and loss modulus at low strain
values. This is true for all samples from Formulation B, while none of the samples from
Formulation A have this appearance. The reason behind fluctuating values can be the low
strain at the beginning of the amplitude sweep, resulting in the rotor moving very slowly,
which is difficult to control. This can result in fluctuating values. Furthermore, an amplitude
sweep is performed by controlling the strain, but for the rheometer used for this project, the
parameter controlled was stress. Therefore, the instrument constantly must convert the stress
values to strain values. At low amplitude, this would result in fluctuating values. Formulation
A may not have been affected by this since all samples have a much higher viscosity and
subsequently give rise to larger storage and loss modulus signals than Formulation B does. A
weak signal often leads to fluctuating values.

47
Table 19. The flow point, yield point as well as the storage modulus of the LVE for Formulation A. Values were
obtained directly after emulsification

Sample Flow point [Pa] Yield point [%] G [Pa]

1A 3.044 0.128 210.4

1A No 2 8.401 0.16 335.2

2A 2.887 0.116 229.8

3A 21.41 0.241 724.7

4A 19.12 0.200 1362

5A 3.052 0.175 192.0

6A 3.59 0.126 137.74

7A 21.9 0.329 933

8A 15.88 0.174 520

8A No 2 20.29 0.288 1135

Reference lotion 39.8 1.19 602.88

From Table 19 it can be seen that the emulsifier concentration highly influences the viscosity
of samples from Formulation A. A higher concentration results in a higher viscosity. Further,
during manufacturing, it was noted that the viscosities of Formulation A were highly
dependent on the stirring time and its velocity. This resulted in the samples of Formulation A
being challenging to reproduce, as clearly is the case for samples 8A and 8A No 2, Table 19.
More concerning this can be bound in 5.6 Formulation. Since the viscosity of the samples
created in Formulation A are so dependent on the stirring, the flow point along with the yield
point may also vary greatly. Consequently, it is difficult to draw certain conclusions. The
yield point of sample 8A No 2 is more than 0.1 percentual units larger than that of 8A. This is
quite a large difference considering that what otherwise can be seen in Table 19 is that the
yield point is about 0.1 percentual units larger for the samples with 6% Promulgen D than
those with 4%. As only one replicate was made, the exact deviation for the yield point of
Formulation A is hard to deduce. It is, however, with this in mind, impossible to determine
which oil created the emulsions with the best, meaning those with the largest value, yield
points.
Concerning the flow points, 5 Pa differed between sample 8A and its replicate, which is quite
a considerable difference. The flow point seems to follow a pattern, however, where perfume
addition does not influence it. In contrast, emulsion concentration certainly does since much
higher flow points were obtained for samples with the higher Promulgen D concentration.

48
Another trend observed is that the flow point is slightly higher for the samples created with N-
MWO from Formulation A than P-MWO from the same formulation for all samples except 5
and 6A. The difference is, however, minimal and maybe even too small to be significant. A
higher flow point makes the moisturizer more viscid, making the moisturizer feel richer in
its texture.
Table 20. The flow point, yield point as well as the storage modulus of the LVE for Formulation B. Values were
obtained directly after emulsification

Sample Flow point [Pa] Yield point [%] G [Pa]

1B 15.81 1.56 46.53

1B No 2 19.48 1.51 105.58

2B 13.84 1.52 69.01

3B 28.39 4.34 129.64

4B 12.24 1.24 55.51

5B 10.37 1.23 51.04

6B 9.513 1.13 58.54

6B No 2 17.26 1.29 88.05

7B 22.63 2.26 107.71

7B No 2 21.97 3.69 102.73

8B 9.177 1.32 51.45

Three replicates were made for Formulation B. Sample 1B s replicate had twice as large a
value for storage modulus in the LVE region. Sample 7B and 7B No 2 had about the same
storage modulus value. In contrast, 6B had a storage modulus value of 30 Pa, or 50% lower
than its replicate. While the flow points were similar between replicates and originals from
samples 1 and 7B, they differed greatly for 6B. Furthermore, the rheometer gives slightly
different values (can differ +/- 10 Pa) for storage modulus between different measurements of
the same samples. With this in mind, the storage modulus of the LVE region should probably
be about the same regardless of oil type, emulsifier concentration, and whether it contained
perfume or not in the case of Formulation B.
The yield point of all the samples of Formulation B is around 1.2 to 1.5% except for 3B and
7B (along with 7B No 2) that have slightly higher yield points. This would indicate that a
higher concentration of emulsifiers would result in higher yield points in the case of N-MWO.
A higher yield point would result in a more homogeneous sample, which likely is more stable.
A higher yield point further shows that the sample has a higher inner resistance to structural
change, resulting in more stable emulsions.

49
The factor that influenced the properties measured in the amplitude sweep the most was the
type of emulsifier used. The yield points for Formulation B, Table 20, are greatly larger than
the those of Formulation A, Table 19. The flow points of Formulation B were not influenced
by the concentration of the emulsifier like the flow points of Formulation A, where the values
of the flow points for Formulation B are similar to the flow points of Formulation A that had
the higher Promulgen D content. Finally, the storage modulus is much lower for all samples
of Formulation B. Even the lowest storage modulus from the samples of Formulation A had
twice as high a storage modulus as the sample with the highest storage modulus of
Formulation B. A lower storage modulus may indicate the sample being more stable as its
lower elasticity results in better resistance towards molecular attraction. It also results in it
resisting aggregation better. Consequently, the amplitude sweep seemed to indicate that the
samples made from Formulation B were more stable than those from Formulation A.

5.3.5 Storage stability

The change in storage modulus and the change of yield point can be seen in Table 21 for
Formulation A and in Table 22 for Formulation B. The change of storage modulus was
calculated by subtracting the value obtained at emulsification, Table 19 and Table 20, with the
value obtained two weeks later. The difference in yield point was calculated in the same way.
The storage value of the LVE region and the yield point values measured directly after
emulsification, found in Table 19 and Table 20, were subtracted from the values measured
two weeks after emulsification. Since sample 6B was the first sample made from Formulation
B, it was believed that this must have been a particularly bad sample since it phase separated
after only three days and that it should be discarded due to being produced poorly. Therefore,
no storage stability tests were made on sample 6B.

50
 Table 21. The change in storage modulus and yield point from the day of emulsification to t weeks later for
formulation A

Sample Change in G Change in

yield point

1A 399.6 -0.0549

1A No 2 119.1 -0.0400

2A 405.6 -0.0456

3A 309.3 0.101

4A -317 -0.018

5A 262.4 -0.0814

6A 373.6 -0.0378

7A 73 -0.06

8A 342.8 -0.173

8A No 2 -83 -0.079

For Formulation A, the storage modulus increased in value two weeks after emulsification, as
seen in Table 21, for almost all samples except samples 4A and 8A No 2, which decreased
slightly. However, in the case of 8A No 2, the decrease is not large enough to be significant.
Instead, the structure of the sample probably is unchanged. As earlier mentioned, the viscosity
is difficult to reproduce due to the manufacturing method. Consequently, the change observed
in storage modulus in Table 21 can be said to be very slight for most samples, but no clear
correlation can be seen between oil type, addition of perfume, or even emulsifier
concentration. The slight increase in storage modulus could indicate that some of the water
phase had separated from the emulsion giving the bulk a slightly higher viscosity.

Furthermore, the yield point decreases slightly for all samples except 3A. However, the
decrease is so slight that it is insignificant, especially since the margin of error seems to be +/-
0.1. In conclusion, two weeks of storage do not seem to influence the storage stability of
Formulation A. It would have been beneficial to perform the storage stability test after a
longer time to see if the stability would have been influenced. This was not possible since the
study was too short, and there was not enough time for a longer test.

51
 Table 22. The change in storage modulus and yield point from the day of emulsification to two weeks later for
Formulation B

Sample Change in G Change in

yield point

1B -4.65 0.98

1B No 2 2.88 0.17

2B -16.97 -0.562

3B 16.26 -1.3

4B -30.14 -1.086

5B -5.16 0.23

6B No 2 -39.99 -0.838

7B 13.18 1.63

7B No 2 12.92 -0.77

8B -7.71 -0.22

As seen in Table 22, the storage stability tests showed that most of the samples from
Formulation B decrease in storage modulus, except for samples 3B, 7B, and 7B No 2, which
increased slightly in viscosity. Sample 1 and 5B decreased so slightly that the viscosity of the
samples probably was unchanged during this period. However, the samples created with P-
MWO decreased greatly in viscosity, as discussed in the chapter concerning visual analysis.
All samples created with P-MWO had phase-separated after two weeks. The samples were
homogenized with a spoon slightly to get a representative sample. As mentioned earlier, the
viscosity of the bulk should increase if the phase with lower viscosity separates from the bulk.
In this case, it was, however, the oil phase that separated from the bulk. Therefore, the
viscosity is much lower for the oils created with P-MWO

There is no correlation between either perfume content or emulsifier concentration concerning

the change in yield point. For all samples prepared with P-MWO the yield points decreased.
For N-MWO the samples' yield points increased slightly for all samples except 3B and 7B No
2. As the samples prepared with P-MWO all phase-separated, their emulsion stability
obviously was poor; it was thus expected of them to have a lower yield point after two weeks.
As seen in Appendix in Figure 34 and Figure 35 the samples created with N-MWO looked
visually pleasing and should have better emulsion stability than the P-MWO samples. Even if
most of the yield points increased slightly, the yield point of sample 3B decreased more than
the P-MWO samples. Therefore, the method of comparing yield points two weeks after
emulsification may be ineffective when evaluating emulsion stability. Instead, a month later

52
would probably have been more effective. Moreover, it would probably have been better if
only the bulk would have been analyzed two weeks later. A pipet could have been used only
to extract the sample from the bulk.
Finally, it can be said that the storage stability after two weeks was quite similar for all
samples of Formulation A and the samples made of N-MWO of Formulation B since the
storage modulus as well as the LVE region did not change greatly over the span of two weeks.
The indication that samples made from Formulation A should have worse emulsion stability
than those of Formulation B is thus wrong.

5.3.6 Thermal loop

The relative structural change value differed between the replicates and the original sample.
The samples with replicates are thus displayed separately from the samples without replicates
to give clarity. The relative structural value for the samples without replicates from
Formulation A are displayed in Figure 26. The samples with replicates are seen in Figure 27.

2,5
Relative change of structure

2
2A

1,5 3A
4A

1 5A
6A
0,5 7A
Ref. L
0
1 3 5 7 9 11 13 15
Datapoint Number No, i

Figure 26. Relative change of structure strength during 15 thermal cycles for the samples from System A that do
not have any replicates. The reference lotion (Ref. L) is also seen.

Sample 8A and its replicate, Figure 27, have similar values, while 1A and its replicate differ
more. This is, however, due to the values of the two first cycles deviating much. Except for
those values, the relative structural change would have been quite similar to its replicate.
None of the samples from Formulation A experience much relative structural change, seen in
Figure 28 and Figure 29 except for samples 1A and 4A. The reason these samples deviate
more is unknown. As most of the graphs have similar appearances, no conclusions can be
drawn concerning emulsifier content, oil type, nor the effect of perfume. It should further be
noted that the reference lotion, Figure 26, varies greatly in its relative structural change during
the test. As this is a commercial product this should indicate that all samples from
Formulation A are quite thermally stable.

53
 1,2

1
Relative change of structure

0,8

1A No 2
0,6
1A
8A No 2
0,4
8A

0,2

0
1 3 5 7 9 11 13 15
Datapoint No, i

Figure 27. Relative change of structure strength during 15 thermal cycles for the samples from System A and
their replicates

The graphs of the relative structural change for Formulation B are seen in Figure 28 (for
samples without replicates) and in Figure 29 (for samples with replicates). When comparing
the results for the relative structural change for Formulation A and B, it becomes evident that
the change, generally, is much less for Formulation A than for Formulation B.

4,5

4
Relative change of structure

3,5

3 2B
3B
2,5
4B
2
5B
1,5
8B
1

0,5

0
1 3 5 7 9 11 13 15 17
Datapoint No, i

Figure 28. Relative change of structure strength during 15 thermal cycles for Formulation B, the samples
displayed did not get replicated

As previously seen, the relative change of structure for the first sample from the formulation
(1B in this case) can be seen deviating greatly from its replicate, just like 1A did. The other
replicates of the samples from Formulation B, Figure 29, had a similar relative change of
structure to the original sample.

54
 8

7
Relative change of structure
6

5 1B No 2
1B
4
6B
3 6B No 2

2 7B No 2
7B
1

0
1 3 5 7 9 11 13 15 17
Datapoint No, i

Figure 29. Relative change of structure strength during 15 thermal cycles for Formulation B, the samples were
the replicated ones

As previously mentioned, the results from Formulations A and B are distinctly different. The
results within each system are, however, much more similar. For neither formulation, any
correlation between the samples' structural change can be found for either the concentration of
emulsifier, perfume addition, or type of oil. It can, however, be established that the structural
change is nonexistent for Formulation A while Formulation B, Figure 28, undergoes structural
change. Consequently, the greatest impact of the structural change is the type of emulsifier.
The thermal loop test is an excellent test to gain knowledge in emulsion stability. However, it
would have been preferred if similar emulsifying systems had been used to draw conclusions
concerning the oils. If correct conclusions are to be drawn regarding the emulsion stability for
the different oils, it is also vital that replicates are created as the results can be seen varying
greatly for the replicates.

5.4 Mastersizer tests

The plots made of the samples from Formulation A are seen in
Figure 30 and Figure 31. The peaks of the samples made with a higher Promulgen D, Figure
31, content are narrower than those with the lower Promulgen D content
Figure 30).

1A
2A
5A
6A

55
 Figure 30. The droplet size distribution of the sample with the lowest content of emulsifier from Formulation A
i.e. sample 1, 2, 5 and 6A

In contrast with the samples created with P-MWO, in Figure 31, the samples with a higher
concentration of Promulgen D made with N-MWO generated very small droplets that are
below 1 µm. These droplets are too large to be micelles (as these range between 10 and 100
nm) created by the surplus emulsifier. Instead, it may indicate that N-MWO form very small
drops, at very low quantities, when containing a higher content of emulsifier (behavior also
seen for 7A No 2).

3A
4A
7A
8A

Figure 31. The droplet size distribution of the sample with the highest content of emulsifier from Formulation A
i.e. sample 3, 4, 7 and 8A

The droplet size distribution can also be analyzed by comparing the 𝐷 10, 𝐷 50, and 𝐷 90
values. When applying these values, Table 23, into Equation 8 the droplet size distribution, or
SPAN, can be calculated. From Table 23 it can be seen that a higher Promulgen D content
generates a more monodisperse sample, although the difference is relatively small. Once
again, neither the perfume nor the oil type seems to influence the emulsion stability. As for
the droplet size distribution after the thermal loop seems to have been relatively uninfluenced.

56
 Table 23. Showing the droplet size distribution for Formulation A on the day of emulsification as well as after
the thermal loop

𝐷 10 [µm] 𝐷 50 [µm] 𝐷 90 [µm] SPAN 𝑆𝑃𝐴𝑁*

1A 8.47 52.7 178 3.23 3.19

1A No 2 8.90 37.7 133 3.29 -
2A 12.4 57.8 202 3.28 2.83
3A 4.59 23.7 76.6 3.04 3.93
4A 6.57 22.3 71.0 2.89 2.21
5A 8.38 38.4 140 3.44 2.69
6A 11.3 46.2 147 2.94 2.73
7A 4.13 23.7 66.5 2.63 2.57
8A 8.78 31.1 87.6 2.53 2.68
8A No 2 8.54 43.7 124 2.63 -
Reference 3.29 7.03 13.5 1.45 -
lotion
*SPAN measured after the thermal loop

The droplet size distribution plots for the samples made from Formulation B are seen in
Figure 32 and Figure 33. The samples made with P-MWO, Figure 32, have a much
monodisperse droplet size distribution. Further, the main peak of the samples in Figure 32 are
of a much smaller droplet size than the main peak for the samples made of N-MWO in Figure
33.

2B
4B
6B
8B

’
Figure 32. The droplet size distribution of the samples made from P-MWO with system B i.e. sample 2, 4, 6 and
8B

The droplet size distribution is much more polydisperse for the samples made with N-MWO,
Figure 33. Two peaks are seen for all the samples. A larger number of droplets can be seen at
the peak of smaller droplet sizes for 3 and 7B, meaning the samples with higher emulsifier
content.

57
 1B
3B
5B
7B

Figure 33. The droplet size distribution of the samples made from N-MWO with system B i.e. sample 1, 3, 5 and
7B

The 𝐷 50 are considerably smaller for the samples made using P-MWO than for those
created using N-MWO as seen in Table 24. The same is true for 𝐷 90, but not for 𝐷 10. In
this case the samples with N-MWO are slightly smaller. The droplet size distribution or
𝑆𝑃𝐴𝑁 was also much lower for the samples with P-MWO than the ones with N-MWO.
Further, all the samples from Formulation B (except for 6B) have a narrower droplet size
distribution than the ones created with Formulation A.
Table 24. Showing the droplet size distribution for Formulation B on the day of emulsification as well as after
the thermal loop

𝐷 10 [µm] 𝐷 50 [µm] 𝐷 90 [µm] 𝑆𝑃𝐴𝑁 SPAN*

1B 3.66 36.1 62.7 1.63 2.92
1B No 2 0.654 18.8 59.8 3.14 2.43
2B 3.55 7.41 14.4 1.47 2.96
3B 0.643 35.7 74.5 2.07 2.86
4B 1.26 2.29 4.54 1.42 3.8
5B 0.881 20.0 62.2 3.07 3.09
6B No 2 3.69 7.27 13.8 1.39 4.10
6B 4.06 16.7 72.0 4.07 6.50
7B 0.693 26.8 61.6 2.27 2.45
7B No 2 1.08 30.04 69.8 2.28 2.78
8B 3.92 6.88 12.2 1.20 3.10
*SPAN measured after the thermal loop

As previously mentioned, 𝐷 10 are very small for Formulation B, and are much smaller than
those found in Formulation A. The small droplet sizes may be attributed to Carbopol 30.
When dry, the size is about 2 to 7 µm, and when hydrated it expands slightly. Carbopol 30
was dilated when the base was added during emulsification, but Carbopol 30 is extremely

58
sensitive to electrolytes. If electrolytes are present, they will shield the deprotonated acid
groups (responsible for the polymer's dilation as they repel one another due to their negative
charge). Much water was used to dilute the sample to analyze it with the mastersizer, and
even if the water was meant to be deionized, it might not have been entirely so. As the amount
of water used to dilute the sample, enough electrolytes may have been added to make the
polyelectrolytes curl back together.
After the thermal loop it can be seen, Table 24, that the droplet size distribution for the
samples of Formulation B increases much more for the samples created with P-MWO than for
the ones created using N-MWO. This contrasts with the results from the thermal loop where
no differences between the samples based on oil type could be seen. Suppose it had been so
that the droplet size had increased greatly more for one of the oils. Then this should have been
seen in the results of the thermal loop.
For Formulation B the samples made with P-MWO obtained a much lower 𝐷 50, they further
had a much more monodisperse droplet size distribution than the samples made with N-
MWO. The smaller the particle size, the more stable the emulsion. The more monodisperse
the droplets are, the more resistant it theoretically should be towards creaming. These results
should indicate that the most stable emulsions created during this project were made from P-
MWO form Formulation B; this is known to be the exact opposite. These samples phase-
separated, which probably occurred through creaming and preceded to coalescence.
Consequently, this test seems to be either flawed and that it does not show the true droplet
sizes, or the smaller droplet sizes did not have the positive effect expected in this case.
The mastersizer test seems to highlight discernable differences in emulsion stability, such as
the case for 6B, which was so poorly made that it phase-separated after only three days
instead of a week. The test consequently can differentiate terrible samples such as 6B. For
sample 6B, the test results proved the SPAN value was much larger than all samples made
from P-MWO and even more polydisperse than the most polydisperse sample from
Formulation A, which had a much higher degree of polydispersity than Formulation B. It is
good that terrible emulsion stability can be detected. However, to ensure that accurate
conclusion are drawn concerning the emulsion stability when the emulsion stability is not
extremely bad, it is difficult to determine the emulsion stability by only looking at the droplet
size distribution directly after emulsification. Instead, the droplet size distribution should also
be analyzed later to see how it changes with time. This would probably give a more accurate
representation of storage and emulsion stability.
The other possibility is that the droplet sizes of the samples made of Formulation B of P-
MWO indeed generated much smaller droplet sizes, which may be due to the emulsifying
composition being mainly being composed of Span 20. This may result in a different surface
activity, which subsequently generates small droplets that were unstable. The solution to this
could also be to analyze the droplet size distribution more than once. In this case, the increase
of the droplet size that occurred would be seen.

5.5 Visual analysis

For the emulsions made of P-MWO of Formulation B, a phase separation can clearly be seen
two weeks after emulsification, as can be seen in Figure 34 and Figure 35. In this case,
creaming seems to have occurred as there is a layer at the top that is see-through and slightly
yellowish (which is the color of the emulsifiers Tween and Span in Formulation B). Owing to

59
the color of the top layer and the fact that P-MWO has a lower density than water, the
separated phase is likely oil and emulsifier.

Figure 34. Picture taken two weeks after emulsification of sample 1, 2 and 4B. Sample 1B is to the far left and
sample 4B to the far right.

Figure 35. Picture taken two weeks after emulsification of sample 1, 2, and 4B. Sample 1B is to the far left and
sample 4B to the far right.

The Formulation B emulsions created with N-MWO did, on the other hand, not phase
separate during the observed time. As an example of Formulation B with N-MWO as the oil
in the oil phase, a picture was taken of sample 1B two weeks after emulsification as can be
seen in Figure 34 and Figure 35. This could be the result of N-MWO being better at creating
emulsions than P-MWO. However, as the phase separation did not occur in Formulation A, it
is more likely the result of the emulsifiers of Formulation B being less compatible with P-
MWO than N-MWO. The correct HLB value was used for the oils, but as previously stated,
emulsion stability can also be negatively affected by choice of chemical type.
When comparing the pictures taken during the HLB test of P-MWO (Figure 43, Appendix) to
N-MWO (Figure 37, Appendix) when prepared with Span and Tween 80 it can be seen that P-
MWO is stable over a larger HLB range than N-MWO when Span and Tween 80 are used as
emulsifiers. This may be due to the chemistry of the paraffinic oil being more compatible with
the Span and Tween 80 series. The Span and Tween 80 series is made up of oleates. The
Tween and Span 20 series was, on the other hand, much more compatible with N-MWO than
P-MWO. The sample made with P-MWO that had the HLB 8.6 was exteremly lumpy, and the
phase seperation was very evident. When Span and Tween 80 were used in combination with
P-MWO as emulsifiers, HLB 8.5 worked well as seen in Figure 43. This may be because P-
MWO is not chemically compatible with Span 20. Since Span 20 have an HLB value of 8.6 it
could not be combined with Tween 20, which has an HLB value of 16.7, to create a blend
with HLB 8.6. The lumpiness and phase separation could be due to only one emulsifier being
used instead of two since two types of emulsifiers often give better critical packing parameter

60
values. For Formulation B, Tween 80 in combination with Span 20 was used as emulsifiers.
However, only 14% of the emulsifier mixture was composed of Tween 80; the rest was made
up of Span 20. This strengthens the argument that bad emulsion stability was due to chemical
incompatibility between P-MWO and the emulsifiers of Formulation B

5.6 Formulation
As emulsion stability may be influenced by pH (even though both Promulgen D and Tween
and Span, in theory, should not be affected by pH greatly), the pH was supposed to be the
same for both formulations. Calculations were made to increase the pH of Formulation B to
exactly 5, but when measured with a pH meter, this value was too low. The correct pH was
then looked for experimentally using a pH meter at first, but when the gel created by Carbopol
30 got too thick, the pH meter could no longer measure. pH indicator paper was then used, but
it was difficult to determine the pH. By doing this, it was decided that a volume of 7 ml KOH
(pH 12.2) would give a pH that was around 5. Meanwhile, the water phase of Formulation A
was buffered to precisely pH 5. Consequently, the two formulations did not have the exact
same pH but probably similar enough for the emulsion stability to be unaffected.
The viscosity of the samples made from Formulation A is highly sensitive to the stirring rate
used during the emulsification process. Promulgen D is solid at room temperature. If the
sample is not stirred enough when cooled from 65-70 to room temperature, the layer closest
to the air interphase will stiffen faster than the bulk. Consequently, it will obtain a much
higher viscosity than the bottom layer, making the sample heterogenous. This may be because
some water evaporates during cooling, and if this water only comes from the top layer, this
part will obtain a higher viscosity than the bulk. This is due to water being the phase with the
lowest viscosity, which would result in the remaining top layer having a higher viscosity. The
viscosity differences seen between replicates could also be the result of production time. If the
sample takes longer to produce, more water evaporates, and as the emulsifier is solid, the
sample produced obtains a larger viscosity than those produced during a shorter time. This is
problematic since the reproducibility decreases for Formulation A. Therefore, a solid
emulsifier is difficult and undesirable to work within this scale where everything is done
manually and no evaporation protection is used.
The addition of perfume never seemed to influence the emulsion stability nor the rheological
properties. A very concentrated lavender oil was added. Despite the small quantity used, the
moisturizers smelled plenty. Consequently, the small contribution would probably have
sufficed in terms of the scent in a commercial product. For the purpose of the study, it still
would have been interesting to have added 0.1 wt% instead of 0.05 wt%. This amount was
meant to be added at first. However, when the first sample with this concentration was
created, it had such a low viscosity that it was believed that the perfume had an enormous
impact. It was, however, because this sample had been stirred more during cooling (avoiding
the surface hardening due to water evaporation), unlike the previous unperfumed samples
made. Through this, it was wrongfully assumed that the lower concentration of 0.05 wt% had
to be used for the project's continuance.
Moreover, the factor that resulted in the most prominent difference relating to emulsion
stability and other rheological properties was the choice of emulsifier. Promulgen D has a
melting point of 47-55 . Therefore, it stabilizes the emulsion not only by steric hindrance
but also by being solid at room temperature. This gives it naturally a higher viscosity where
an increased amount of Promulgen D will result in a higher viscosity as an increased amount
of the emulsifier means more solids in the sample. This is difficult to compare with Tween
and Span that are liquid at room temperature and for which viscosity depends on Carbopol 30.

61
Even if it can be said that it is difficult to compare the two formulations due to the different
chemical properties of the emulsifier, it was precious to investigate the influence of
emulsifier. If only Formulation B had been made, the conclusion that N-MWO was much
better than P-MWO for creating emulsifiers would have been drawn. As two different
emulsifiers were used, it can instead be said that the oils seem to behave quite similarly. This
may be because even if one of the oils is paraffinic and the other is naphthenic, they share
many other properties: viscosity, density, and chain length. MWO is severely hydrotreated,
decreasing the chain's naphthenic properties compared to process oils that are less
hydrotreated and do not classify as white mineral oils. It would have been better to use
emulsifiers with similar properties instead, such as two different series from Tween and Span
(with Carbopol 30) or two emulsifiers that became solid at room temperature.

6. Conclusions
The conclusions made for the frequency sweep and the applications and the thixotropic test
are presented as bullet points below.

All samples from all formulations created weak gels. No indications of bad storage
stability could be seen for any samples except 1B, but not its replicate. As the
frequency sweep did not predict any of the samples made of P-MWO from
Formulation B to have bad storage stability, it cannot solely be relied on to determine
storage stability.

Regarding the thixotropic tests. Higher content of Promulgen D (for Formulation A)

resulted in a more thixotropic material. None of the samples made of N-MWO from
Formulation B were thixotropic, while all samples made of P-MWO were slightly
thixotropic. Neither the oil type nor the perfume affected the thixotropy.

Through the application test, it was discovered that all samples were shear thinning.
The viscosity changes at low frequencies were more considerable for the samples from
Formulation A and the reference lotion than for Formulation B. For Formulation B the
samples made with N-MWO had higher viscosities at low shear rates than the samples
made with P-MWO. For Formulation A, it was the samples with the highest
Promulgen D content that had the highest viscosities at low shear rates.
The tests mentioned did not result in any knowledge concerning emulsion stability.
The application test was further misleading as the gel created in Formulation B would
collapse when in contact with the skin based on its sensitivity to electrolytes.
The conclusions made for the tests that analyzed emulsion stability and comments concerning
the formulations are stated in bullet points below.
Amplitude sweep
Emulsifier type influenced the measured parameters the most. Formulation B had
much lower storage modulus values, while Formulation A had much lower LVE
regions and flow points. These factors indicate that samples made with Formulation A
would have a worse emulsion stability than those made of Formulation B.
The preparation of Formulation A influenced the viscosity of the samples much.
Making it difficult to draw conclusions concerning yield points. It can, however, be
said that a higher Promulgen D content resulted in a higher storage modulus value and
flow point. No difference could be seen with regards to oil type nor perfume.

62
 Formulation B was uninfluenced by all the factors varied regarding its storage
modulus and flow point. However, it could be seen that when N-MWO was combined
with a higher emulsifier content, its LVE was longer. Meaning these emulsions
potentially were more stable.

Storage stability test

The storage modulus increased slightly, generally, for Formulation A while the yield
point decreased for all samples after two weeks, compared to starting values. The
changes were, however, so small that they were insignificant. Consequently, all
samples from Formulation A have as good storage stability two weeks after
emulsification.
The storage modulus and the LVE region for the samples made with P-MWO with
Formulation B decreased significantly. Proving that the samples made with P-MWO
with Formulation B had much poorer storage stability.
The storage modulus increased slightly for samples made of N-MWO with a higher
emulsifier content for Formulation B while decreasing insignificantly much for the
samples of lower emulsifier content after two weeks of storage. There seems to be no
significant difference in the LVE region for the samples made with N-MWO.
The indication from the amplitude sweep that samples made from Formulation A
would have worse stability than those made of Formulation B is consequently not true.
Thermal loop
Neither of the samples from Formulation A undergoes much relative structural
change. Formulation B does, however. Between the samples from the same
formulations, no conclusions can be drawn, and the relative structural change mainly
depends on emulsifier type.
Mastersizer tests

The droplets size distribution was unpretreated for all samples from Formulation A
and the samples made from N-MWO from Formulation B after the thermo loop. On
the other hand, the droplet size distribution increased greatly for the samples made of
P-MWO from Formulation B.

The only difference in droplet size distribution for Formulation A can be seen for the
samples with different emulsifier content. According to theory, the higher the content,
the more monodisperse the distribution was (and the more stable it should be,
according to theory).

For Formulation B, the samples made with P-MWO obtained the smallest and the
most monodisperse droplet size distribution of all the samples created. These results
should indicate that the most stable emulsions created during this project were made
from P-MWO of Formulation B. As all of these phase-separated, this is known to be
the exact opposite. To assure that accurate conclusions are drawn, more mastersizer
measurements should be performed with time.

63
 The droplet size distribution was more polydisperse and the 𝐷 50 larger for the
samples made with N-MWO than those made of P-MWO of Formulation B. These
parameters were, however, smaller respectively more monodisperse than the samples
of Formulation A.

The reason for the small droplet size of P-MWO of Formulation B may be either that
the test gave incorrect result, but it is more probable that the emulsifiers created small
droplet sizes due to their surface activity.

Visual analysis

The samples made from P-MWO of Formulation B phase-separated, but it is not

necessarily due to the oil having worse emulsion stability properties and instead more
likely that P-MWO is incompatible with Span 20.

Sample 6B phase-separated after only three days instead of approximately a week like
it did for the other samples that phase-separated during the observed time. The quality
difference could be seen in many of the tests: the droplet size distribution was twice as
large for 6B than for 6B No 2, and also larger than all the other samples made. Its
storage modulus value was 50 % lower than its replicate, and the same was true for the
flow point. The relative structural change was a bit larger for 6B than for its replicate,
but the difference was not striking. These test results are intriguing since the
rheological and droplet size distribution indicate that the sample structure differs
greatly from the replicate.
Formulations

The pH value of Formulation A was not identical with that of Formulation B, but this
did not likely influence the emulsion stability.

When producing Formulation A, stirring and production time probably influence the
rheological properties greatly. Primarily when cooled to room temperature.

The emulsion stability seems to have been entirely uninfluenced by perfume content.
It would have been better if a more considerable quantity had been added to see if that
affected the stability. The factor that influenced all properties analyzed in this project
the most was the type of emulsifier.

Because the emulsifiers' properties varied so much, it was challenging to deduct what
oil gave the highest emulsion stability. Emulsifiers of more similar properties should
have been chosen.

7. Suggestions for future work

If it is of interest to further compare the emulsion stability of oils, it would be beneficial to use
emulsifiers of similar characteristics for the different formulations. This, owing to the results
encountered through these tests, mostly showed that the choice of emulsifier was the property
that changed the emulsion stability, rheological properties, and droplets size distribution the
64
most. Thus, emulsifiers with similar rheological properties (solid or liquid at room
temperature) should be used in future work. It would be preferred is to use liquid emulsifiers
(such as Tween and Span) and use a thickener such as Carbopol 30. A larger emulsifier
concentration would (potentially) increase the emulsion stability without increasing the
viscosity, which is the case when using solid emulsifiers. The emulsifiers that were liquid at
room temperature further resulted in a higher degree of reproducibility, making it easier to
draw conclusions regarding emulsifier concentration and emulsion stability. To further ensure
the correctness of the conclusions, more replicates (preferably three of each sample) should be
made. These should be made to ensure reproducibility along with the accuracy of the results
produced.

The application and thixotropic tests are unnecessary to perform if only the emulsion stability
is of interest. However, they provide information concerning rheological properties that still
may be of interest as these are essential properties for the consumer. These tests are not very
time-consuming to perform, but it should be noted that they are excessive if only the emulsion
stability is of interest.

Further, performing the storage stability tests after a more extended period than two weeks
would be more appropriate, perhaps a month. An additional storage test could also be
performed two months after emulsification to see the changes in storage stability over time.
Moreover, it would be good to perform tests analyzing the droplet size over time as well.
Maybe analyzing the droplet size distribution after one and two months as well as directly
after emulsification. This way, the change of the distribution would be visible.

65
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9. Appendix
9.1 Oil
Table 25. Shows the test method used to analyze the oils

Properties/Composition
Analysis Unit Test Method
Appearance ASTM D 4176
3
Density, 15°C kg/m ASTM D 4052
2
Viscosity, 40°C (Stabinger) mm /s (cSt) ASTM D 7042
Pour point °C ASTM D 7346
Aniline Point °C ASTM D 611
Viscosity-Gravity-Constant
(VGC) ASTM D 2501
Carbon-Type Composition, CA % ASTM D 2140
Carbon-Type Composition, CN %
Carbon-Type Composition, CP %
Saybolt Colour ASTM D 156

9.2 Method
Table 26. The percentage of Tween and Span used to create Formulation B

Oil Tween 80 [%] Span 20 [%]

N-MWO 53 47
P-MWO 14 86

9.3 HLB tests

The samples prepared using N-MWO with Tween and Span 80 as emulsifiers can be seen
below.

70
 Figure 36. Shows the emulsions created with N-MWO oil and Span and Tween 80 as emulsifiers. Images were
taken directly after mixture.

When looking at Figure 36 it can be seen the HLB 10 already had much more foam at the top,
which indicates creaming. The others had similar apperance directly after the emulsification.
Five days later as can be seen in Figure 37.

Figure 37. Shows the HLB value tests for N-MWO after five days

A HLB 12 sample was made for N-MWO with Tween and Span 80 as emulsifiers with a
neutral water phase and a water with pH 5. These were photographed five days after being
preppared, as can be seen in Figure 38, and as can be seen the emulsdion preppered at pH 5 is
less stable than the one at a neutral pH.
Figure 38. The emulsion created by N-MWO with Span and Tween 80 as emulsifiers after
five days. The left sample was made with a water phase of pH 5 while the right sample has a
neural water phase
The samples preppared using Tween and Spn 20 can be seen in Figure 39 where it becomes
evident that HLB 10 with Tween and Span 20 is not an appropriate HLB value for N-MWO.
Both HLB 12 and 12.5 produced more foam than HLB 11 while HLB 11.5 produced the least
foam.

71
 Figure 39. Shows the emulsions created with N-MWO oil and Span and Tween 20 as emulsifiers. Images were
taken directly after mixture.

When comparing these results to the samples made with Span and Tween 20, seen in Figure
36 it can be seen that the spabity is quite similar exept for HLB 10, which has a much lower
stability when Span and Tween 20 were used in comparision to when Span and Tween 80 was
used. The emulsions can be seen in Figure 40 seven days after emulsification.

Figure 40. HLB value tests for N-MWO with Tween and Span 20 as emulsifiers after seven days.

In Figure 40 it is evident that HLB 10 is not suited for N-MWO, it is however, still unclear
which of the other HLB values that are best suited. Consequently, a light was shone at the

72
bottom of the sample to see which sample had the most phase separation. This can be seen in
Figure 41.

Figure 41. Seven days after emulsification of N-MWO with Span and Tween 20 as emulsifiers. A lamp was
placed behind the sample to highlight the degree of phase separation.

The more see-through the lower part of sample is, Figure 41, the more water it is composed
by, and thus the less degree of emulsification in that bottom part of the sample there is. The
sample that is the least see-through has HLB 12. HLB 12 created one of the most stable
emulsions when using Span and Tween 80 as well, Figure 37, this is also on accordance with
the theoretical value (33). Consequently, the HLB that seems to be the most appropriate for
N-MWO is 12.

Figure 42. Shows the HLB tests made on P-MWO.

The samples were photographed five days later, and the result can be seen in Figure 43. From
this picture the sample with the least phase separation is HLB 9 or 8.5. As this is a medium
heavy paraffinic oil, this is in accordance with theory.

73
 Figure 43. Emulsions made of P-MWO and Span and Tween 80 as emulsifiers. Picture taken five days after
emulsification

The samples created using P-MWO and Tween and Span 20 are seen below.

Figure 44. Shows the emulsions created with P-MWO oil and Span and Tween 20 as emulsifiers. Images were
taken directly after emulsification.

The samples were photographed seven days later and are seen in Figure 45. It is clear that
HLB 8.6 is not the appropriate HLB value for this composition, but the other HLB values are
quite similar to the ones created using Tween and Span 80. To determine the HLB for P-
MWO a flashlight was used to illuminate the bottom of the samples to see which was the most
stable emulsion. These pictures can be seen in Figure 46.

74
 Figure 45. P-MWO with Span and Tween 20 as emulsifiers. Picture taken seven days after emulsification.

In Figure 46 it can be seen that HLB 9 and 11 clearly are not appropriate for P-MWO. HLB
9.5 and 10 have better and more similar degree of stability, but HLB 9.5 seems to be a little
more stable.

Figure 46. Seven days after emulsification of P-MWO with Span and Tween 20 as emulsifiers. A lamp was
placed behind the sample to highlight the degree of phase separation.

75
9.4 Frequency sweeps

Figure 47. Frequency sweep made of Sample 3, 4, 7 and 8A showing storage and loss modulus.
Rheoplus

3
10

Sample 7B nr 2 23 April 1

PP25-SN24228; [d=2 mm]

G'' Loss Modulus

G' Storage Modulus

Sample 8B 28 April 1
2
10 PP25-SN24228; [d=2 mm]

G'' Loss Modulus

G''
G' Storage Modulus

Sample 4B 7 maj 1

PP25-SN24228; [d=2 mm]

G'
G'' Loss Modulus

1 G' Storage Modulus

10
Sample 3B 10 maj 1

PP25-SN24228; [d=2 mm]

G'' Loss Modulus

G' Storage Modulus

0
10
0,1 1 Hz 10
Frequency f
Anton Paar GmbH

Figure 48. Frequency sweep made of Sample 3, 4, 7 and 8B showing storage and loss modulus.

76
 Figure 49. Frequency sweep made of sample 3, 4, 7 and 8B Samples from showing loss factor plotted against
frequency.

9.5 Mastersizer

Table 27. Showing the droplet size distribution for Formulation B after the thermo loop

𝐷 10 [µm] 𝐷 50 [µm] 𝐷 90 [µm] SPAN

1B 0.910 25.3 74.8 2.92
1B No 2 2.41 19.4 49.5 2.43
2B 3.19 11.7 37.9 2.96
3B 0.542 20.9 60.3 2.86
4B 3.19 7.94 33.4 3.8
5B 0.570 12.0 37.7 3.09
6B 4.90 16.9 74.2 4.10
6B No 2 5.78 33.7 225 6.50
7B 1.55 19.6 49.7 2.45
7B No 2 3.22 31.2 90.0 2.78
8B 0.881 19.0 59.6 3.10
*SPAN measured after the thermo loop

77
 Table 28. Showing the droplet size distribution for Formulation A after the thermo loop

𝐷 10 [µm] 𝐷 50 [µm] 𝐷 90 [µm] 𝐷 𝛥∗

1A 5.43 28.6 96.7 3.19
1A No 2
2A 11.3 73.5 218 2.83
3A 2.55 29.6 119 3.93
4A 10.6 32.2 81.8 2.21
5A 11.9 55.7 162 2.69
6A 12.6 44.4 134 2.73
7A 8.32 31.3 88.6 2.57
8A 6.25 24.9 73.0 2.68
8A No 2 - - - -
*SPAN measured after the thermo loop

78
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