INTRODUCTION OF EMULSION

EMULSION
• Emulsion
• Emulsions are dispersions made up of two
immiscible liquid phases
• which are mixed using mechanical shear and
surfactant. Particle size of
• this conventional emulsion grows continuously
with time and hence fi nally separation occurs
at gravitational force thus these emulsions are
• thermodynamically unstable
• Theories: According to the surface-tension theory of
emulsification, the
• emulsifiers or stabilizers lower the interfacial tension
between the two
• immiscible liquids, reducing the repellent force
between the two liq uids and diminishing the
attraction between the molecules of the same
• liquid2
• The oriented-wedge theory assumes the formation
of mono molecular layers of the emulsifying agent
which are curved around the
• droplet of the internal phase of an emulsion
• Types3
• Following are different types of emulsions
• Water-in-oil (w/o)
• Oil-in-water (o/w)
• Water-in-oil-in-water (w/o/w)
• Oil-in-water-in-oil (o/w/o)
• Methods of preparations4
• • Dry Gum Method: Triturate mixture of emulsifier and
oil with addi tion of water which will form primary
emulsion. Further add water to
• dilute and mix continuously to form emulsion.
• • Wet Gum Method: Initially triturate oil with water and
then with
• emulsifier to form primary emulsion. Further add water,
dilute and
• mix to form emulsion.
• • In Situ Soap Method: Take oil and lime water (calcium
hydroxide so lution). Mix with stirring to form emulsion.
• • Mechanical Method: Take oil, water and emulsifier
together, mix well
• and stir by machine to form emulsion
• ONE of the most interesting characteristics
• of emulsion polymerization is the produc tion of high molecular
weight polymer with
• simultaneous rapid rate of reaction. The most
• plausible current attempts to explain this consist
• in attributing an abnormally low value to the
• rate of mutual termination of growing free
• radicals due to the high viscosity of the poly merization locus (i.e.,
the swollen polymer parti cles).l However, a more attractive
explanation is
• offered by a consideration of the kinetics of free
• radical reactions in isolated loci when the free
• radicals originate in a medium outside of the
• loci of reaction, or are generated by reaction of
• substances which come from the outside medium
• Harkins2 has recently discussed the locus of
• the emulsion polymerization reaction and the
• function of the various phases present. His
• discussion may be briefly reviewed as follows.
• During emulsion polymerization there are four
• phases which play an integral role in the over-all
• process. The water phase normally contains the
• "catalyst," or more properly, chain initiator; it
• is probable that the initial formation of free
• radicals takes place here.
• Dispersed in the water
• of polymerization of a single free radical. Thus the rate
• of emulsion poiymerization. the concentration of monomer
• in the lor;i, and the number of loci present provide the
• information needed for calculating the chain propagation
• constant for the monomer.
• A simplified treatment is given for approximating the
• number of reaction loci (polymer particles) produced in
• emulsion polymerization when the rate of polymerization
• per locus is constant (see case 2 above). The law obtained
• indicates that the number of particles should increase with
• the soap concentration (3/5ths power) and with the rate of
• formation of free radicals (2/5ths power), but should
• decrease with increasing rate of growth of the free radicals
• (-2/5ths power
• Thus, the problem of the kinetics of emulsion
• polymerization is twofold. There is the problem
• of determining what factors govern the rate of
• polymerization in a single swollen polymer
• particle and also there is the problem of
deter mining how many such polymer particles are
• formed. Part I of this discussion is concerned
• with the first, while Part II presents a simplified
• discussion of the factors determining the number
• of reaction loci produced in emulsion
polymer ization.
Causes of emulsion
As most of oilfields enter the high water cut stage, crude oil
pro duction is declining. Low-permeability reservoirs are the
most pro mising development direction for improving oil
production. In such
reservoirs, the water displacement efficiency is low, and the
residual oil
saturation is high, which leads to low oil recovery (Zhao et
al., 2015;
Shangguan et al., 2015; Yuan et al., 2014; Tian et al., 2012;
Dou and
Yang, 2012). Conventional methods to improve the recovery
of low permeability reservoirs have advantages and
disadvantages, but all
have failed to enhance oil recovery. Therefore, further
investigation is
required to provide theoretical guidance for the efficient
development
of low-permeability reservoirs
• Researchers have investigated the details of low
oil-water interfacial
• tension (IFT) in low permeability reservoirs,
which is similar to that of
• conventional oil. Alternatively, the formation of
oil-in-water (O/W)
• emulsions has also been suggested as a
possible recovery mechanism,
• and researchers have hypothesized that O/W
emulsions may plug water
• channels, leading to an improved volumetric
sweep of the reservoir
• (Bryan and Kantzas, 2009; Dong et al., 2009;
Mirchi et al., 2017).
•.
• Therefore, the formation of water-in-oil (W/O)
emulsions has been
• proposed as a possible recovery mechanism (Liu
et al., 2016). These
• emulsions are expected to be more viscous than
water, thus improving
• the mobility ratio and sweep efficiency of the
flood. To improve the oil
• displacement efficiency, the crude oil
emulsifying ability of the dis placement system
must be improved. Liu et al. have developed an
al kali/surfactant oil displacement technology
(Dong et al., 2009; Liu
• et al., 2006a; Chen et al., 2013).
• Experimental
• 2.1. Materials
• The oil was obtained from Changqing Oilfield,
(China). The visc osity, density, and four
components of the oil were analyzed and are
• shown in Table 1. The oil had a viscosity of 3.4
mPa s and a density of
• 0.83 g/cm3 at 50 °C. Alkylphenol polyoxyethylene
(OP-10) was an in dustrial product provided by
Haian Petrochemical Co., Ltd. The AP-P4
• polymer was purchased from Sichuan Guangya
Chem Co., Ltd and its
• chemical structure is shown in Fig. 1. In addition,
the salinity of the
• simulated formation water is 22784 mg/L
• 2.2. Oil displacement experiments
• The core was 2.5 cm in diameter and 7.5 cm in length.
The experi mental procedure was as follows: first, the
water permeability of the
• core was measured in the presence of the formation
water, and the core
• was subsequently saturated with the crude oil. The
injected oil was
• continued until water production almost ceased (oil
saturation >
• 99%). Then, the core was flooded by the formation
water until the oil
• production became negligible (oil saturation < 1%).
Followed by a 0.5
• pore volume (PV) chemical slug, the chasing water was
injected until no
• oil produced. The injection rate of the slugs was 0.2
mL/min
• 2.3. Emulsification test
• Eight milliliters of the aqueous solution containing different
con centrations of emulsifier was added to a tube, and
then, 2 mL of crude
• oil was carefully transferred to the top of the aqueous
solution using a
• syringe to minimize the mechanical disturbance. For a set
of tubes, each
• tube was turned very gently from a vertical to a horizontal
position to
• mix the oil and water phases at 50 °C. The emulsions were
examined
• using a XSJ-2 microscope (Chongqing Photoelectric
Instrument Co.,
• Ltd.). The emulsion droplet size distributions were
analyzed using an
• LS-13-320 laser diffraction particle sizing analyzer
(Beckman Coulter
• 2.4. Rheological measurement
• Viscometric measurements were carried out using an
Anton Paar
• MCR 302 rheometer at 50 °C with shear rate ranging
from 0.1 to 1000
•s
• −1
• . Dynamical shear measurements were performed with
the same
• rheometer and measuring system at 50 °C in order to
determine the loss
• (G″) and storage (G′) moduli of the FE flooding as a
function of fre quency ranging from 0.01 to 10 Hz. It
should be noted that all dyna mical measurements
were preceded by an oscillation strain sweep to
• identify the linear viscoelastic region. All of the
measurements were
• performed in the linear response region.
• 2.5. Determination of interfacial tension
• Determination of the interfacial tensions between
surfactants aqu eous solution and crude oil were
measured at 50 °C using the spinning
• drop interfacial tensiometer of dataphysics SVT20.
• 2.6. Micromodel test
• A glass-etched micromodel was used as the
porous medium to in vestigate the
microscopic displacement mechanisms of FE
flooding. The
• steps for the micromodel test are as follows: (1)
saturating micromodel
• with brine; (2) displacing brine with oil; (3)
flooding brine until the
• water cut reaches up to 98%; (4) 0.5 PV
chemical flooding at 0.003 mL/
• min; (5) resuming brine injection until the water
cut up to 98% again.
• All the dynamic processes were videotaped
STATISTICS OF THE
EMULSION
• This research presents the results of statistical
significance tests for evaluating the main effect of
water diesel emulsion usage (containing 2%, 5%,
8% and 10% by vol.) and engine load on the engine
performance
• and emission parameters. To exclude inevitable
random errors of measurements, the mean values
of
• measured data were compared using Duncan's
multiple range tests (MRT).
• RT). The decrease in heating value
• and increase in fuel density and viscosity were observed with
increasing water content. Although the fuel
• pour point decreased with water presence, but it didn't depend to
water percentage. The combustion of
• emulsions significantly decreased the engine power and torque at
1% probability level (P < 0.01) due to
• the reduction in the heating value of emulsions. The lowest brake
specific fuel consumption (BSFC) was
• observed for E2. Generally higher brake thermal efficiency was
found for emulsions due to more com plete combustion. The
significant decrease (P < 0.01) in combustion temperature for E5,
E8 and E10,
• increased the engine CO and decreased its CO2. Emulsion usage
decreased engine NOx through reducing
• combustion temperature when compared to neat diesel. As a whole,
E5 with highest improvement in the
• engine HC, NOx and CO2 could be the best suggestion to decrease
undesirable engine emission.
• Results and discussion
• 3.1. Fuel specifications
• The specifications of water-diesel emulsion
were measured and
• given in Table 4. It could be noted that
increasing water presence in
• diesel engine decreased the heating value of
fuel. Yang et al. [4]
• reported lower heating value for emulsion
comparing to neat
• diesel. As presented in this table, the kinematic
viscosity, dynamic
• viscosity and density of the blends increased
with increasing water
• percentage in emulsions.
• Similar results for viscosity [15] and
• density [6] were reported. The pour point decreased
due to the
• presence of water in diesel. However, the value of
water percentage
• in emulsions didn't have any effect on fuel pour
point. So, it could
• be concluded that pour point just depended to
droplet structure
• Engine emissions
• The comparison of mean values of engine CO
emission versus
• fuel blends and engine load using Duncan's MRT
was shown in
• Fig. 6. The results showed significant increase in
engine CO emis sion at 1% probability level for E5
and E10. Mazlan et al. [40] re ported higher CO
emissions for water-diesel emulsion than neat
• diesel for a light-duty truck. The increase could be
attributed to the
• water presence in the fuel, which slows down the
oxidation process
• of CO to CO2 by decreasing the combustion
temperature.
• The presence of water in emulsions containing 5 volumetric
• percentage of water and greater, decreased the combustion
• temperature and resulted significant decrease (P < 0.01) in the
• engine CO2. The lowest amount of CO oxidation to CO2 yielded
• highest O2 and lowest CO2 emission for E5 and E8.
• 5) Smallest engine HC emission for E5 (P < 0.01) could illustrate
the
• best micro explosion process for this emulsion.
• 6) The combustion temperature reduction and enhancement of
• air/fuel mixing due to the presence of water, decreased signifi-
• cantly (P < 0.01) the engine NOx emission for emulsions when
• compared to neat diesel. The more the engine operated closer
to
• full load, the slower the engine NOx increased.
• As a whole, it was found that the main effect of
fuel on the
• engine performance and exhaust emission
parameters were totally
• dependent to water content of emulsion.
Analyzing the data using
• Duncan's MRT showed the optimum result for
emulsion containing
• 5 volumetric percentage of water and
suggested it as the best
• alternative for neat diesel.
•.
• Statistical analysis could be recommended in a
wide range of
• research methods about emulsions to exclude
inevitable random
• errors and find the real main effect of
independent factors. Per forming significance
tests using Duncan's MRT could be used for
• water-diesel micro-emulsion and 3-phase
emulsion (e.g. biodiesel diesel-water). The
differences between emulsions prepared by
• different additives could be investigated using
Duncan's MRT
ADVANTAGES AND
DISADVANTAGES OF THE
EMULSION
• Advantages5
• • To solubilise hydrophobic or oil soluble drugs
• • To enhance drug absorption through
• • To enhance topical absorption of drugs
• • To mask the disagree able taste and odour of
drugs
• • To enhance palatability of nutrient oils
• Disadvantages
• • Less stable as compared to other dosage
forms
• • Possesses short shelf-life
• • Creaming, cracking (breaking), flocculation
and phase inversion are
• common problems observed during storage of
emulsions
• INTRODUCTION
• Purification of emulsified oil contaminated waters
• (doil droplets < 5 μm) cannot be carried out by
conventional
• water treatment methods (such as gravity separation,
cen trifugation, skimming, etc.), but membrane filtration
can be
• a suitable method to eliminate macro- and even
nanoscale
• oil droplets (Chakrabarty et al. ; Abadi et al. ; Yi
• et al. ). Microfiltration (Abadi et al. ; Shokrkar
• et al. ; Yang et al. ) ensures higher fluxes,
meanwhile
• ultrafiltration (Chakrabarty et al. , ; Masoudnia
• et al. ) results in higher purification efficiency,
• membrane fouling is a major problem in both cases
• (Padaki et al. ), which causes flux reduction and
• increases the cost of these procedures, preventing the
econ omical utilization. Therefore, the suppression of
fouling is
• one of the most important aspects in terms of
developing
• advanced membrane separation techniques.
• Nanotechnology-based methods can be used to
prepare
• highly hydrophilic and/or low-fouling membranes (Van
der
• Bruggen ; Fischer et al. ; Yin & Zhou ; Islam
• et al. ; Kovács et al. ),
• Production of the oil-in-water (o/w) emulsion
• O/w emulsions (coil ¼ 100 mg L1
• ; ddroplets < 1.5 μm) were
• prepared in two steps, using crude oil (provided by
MOL
• Nyrt.; Hungary), and ultrapure water (PureLab Pulse,
• ELGA Labwater, UK). Intensive stirring (35,000 rpm,
• 1 min) of crude oil and water was followed by 10 min
ultra sonic homogenization (Hielscher UP200S,
Germany) at
• 25
C (using maximal amplitude and cycle). For the
photo catalytic experiments 20 ppm oil
concentration was set by
• the dilution of the emulsion.
• CONCLUSIONS
• Both TiO2 and CNT coatings resulted in significant
• reduction of total resistances during the ultrafiltration of
• oil-in-water emulsions. Surprisingly, the TiO2/CNT compo site
modified membrane resulted in by far the highest flux
• and therefore the lowest total resistance; moreover, the
• ratio of reversible and irreversible resistances was also
• the most beneficial in the case of the composite covered
• membrane. In addition, the composite had increased
• photocatalytic activity (both for oily and water-soluble
• contaminants), which is beneficial from the point of
regener ation properties of the contaminated membranes.
Based on
• the presented results, detailed investigations about the
utiliz ation of TiO2/CNT modified membranes in o/w
emulsion
• separation are highly promising.
CONCLUSION OF WARNING/
MESSAGE /ADVICE/STEPS
• Objective: The Health Star Rating (HSR) is a
voluntary front-of-pack nutrition labelling
system
• that rates products from ½ to 5 stars (five
being healthiest). The Chilean Warning Label
system
• displays warnings on foods high in sugar,
saturated fat, sodium, or energy. We aimed to
• evaluate alignment between the systems
• Methods: New Zealand packaged products (n=13,868)
were classified according to the two
• systems. Alignment was assessed by cross-checking
the number of products meeting the
• criteria for warnings against star ratings. Products
with no warnings but an HSR <2, or with >1
• warning but an HSR of ≥3.5 were considered outliers
• Results: Two-thirds of products met the criteria
for at least one warning. There was a
significant
• positive relationship between the number of
warnings and mean HSR: 0 warnings = HSR
• 3.77±.0166 (p<0.001), 1 warning = HSR
2.70±.0206 (p<0.001) and >1 warning = HSR
2.00±.0160
• (p<0.001). The systems were non-aligned for 1,
117 products (8%)
• Conclusion: HSR and the Chilean Warning Label
systems are broadly aligned. Non-alignment is
• due to the Chilean system restricting warnings
to foods containing added ingredients and HSR
• awarding points for positive components.
• Implications for public health: These results
could be helpful in informing improvements to
• the HSR system.
• Key words: nutrition labelling, food labels,
Health Star Rating, Chilean Warning Labels
• Summary of key findings
• We investigated how New Zealand packaged
• foods and beverages would rate under the
• Chilean Warning Label system and how this
• system would align with the current HSR.
• The study found that a warning label for high
• energy content (37% of products) would be
• the most common, followed by warnings for
• high sodium (34%), sugar (33%) and saturated
• fat (29%) contents. The study also found
• that two-thirds (n=9,359) of products would
• meet the criteria for at least one warning. The
• analysis indicates a broad alignment between
• the HSR system and the Chilean Warning
• Label system, but approximately one in 12
• (8%) of products were found to be outliers
• (non-aligned).
THE END
UROOJ FATIMA
LIAQUAT UNIVERSITY OF MEDICAL AND HEALTH
SCIENCE JAMSHORO
PHARM-D
2ND YEAR STUDENT
EMAIL: uroojfatima007777@gmail.com
TOPIC:EMULSION
SUMMARY
ARTICAL.1
• WENDELL V. SMITH AND ROSWELL H. EWART
• General Laboratories, United States Rubber
Company, Passaic, New Jersey
ARTICAL.2
• Haishun Fenga
• , Wanli Kanga,b,∗
• , Liming Zhanga
• , Jun Chena
• , Zhe Lia
• , Qiong Zhoua
• , Hairong Wua
ARTICAL.3
• Santosh Nemichand Kale1
• ,Sharada Laxman Deore2
•1
• Department of Pharmaceutical Sciences, Shri
Jagdish Prasad Jhabarmal Tibrewala University,
Rajasthan, INDIA.
•2
• Department of Pharmacognosy, Govt College of
Pharmacy, Amravati, INDIA.
 ARTICAL.4
• Gábor Veréb (corresponding author)
• Viktória Kálmán
• Szabolcs Kertész
• Sándor Beszédes
• Cecilia Hodúr
• Zsuzsanna László
• Institute of Process Engineering, Faculty of
• Engineering,
• University of Szeged,
• Moszkvai Blvd. 9, Szeged H-6725,
• Hungary
• E-mail: verebg@mk.u-szeged.hu
ARTICAL.5
• Fredrik Söderlund,1,2 Helen Eyles,3 Cliona Ni
Mhurchu3,4
• 1. Stockholm University, Sweden
• 2. Karolinska Institute, Sweden
• 3. National Institute for Health Innovation,
University of Auckland, New Zealand
• 4. The George Institute for Global Health, New
South Wales, Australia
Stars versus warnings: Comparison of the
Australasian Health Star Rating nutrition labelling
system with Chilean Warning Labels
Fredrik Söderlund,1,2 Helen Eyles,3 Cliona Ni Mhurchu3,4

U
nhealthy diet is a leading preventable
risk for poor health worldwide,
and a major contributor to non-
communicable diseases such as type-2
diabetes mellitus, cardiovascular diseases
and some cancers.1 In New Zealand, dietary
risk factors are the leading cause of health
loss accounting for 9.4% of total disability-
adjusted life years (DALYs).2 In 2017/2018,
32% of New Zealand adults (15 years and
older) and 12% of children aged 2–14
years were obese.3 The healthcare costs
attributed to overweight and obesity in New
Zealand were estimated to be NZ$623.9
million in 2006 and are likely to be greater
now given increases in obesity rates over
the intervening period.4 In an attempt to
reduce obesity through helping consumers
make informed choices, the World Health
Organization (WHO) recommended the use
of food labelling in their Global Strategy on
Diet, Physical Activity and Health published in
2004.5 Today, the focus of food labelling has
shifted towards front-of-pack (FOP) labelling,
which can provide additional and/or more
interpretive information compared with
traditional back-of-pack labelling schemes,
and may help the consumer to identify
healthier foods more easily. In 2015, the
WHO regional office of Europe published the
European Food and Nutrition Action Plan 2015–
2020, promoting the “use of interpretative,
consumer-friendly labelling on the front of
packages”.6
The Health Star Rating (HSR) system is a
voluntary FOP nutrition label in Australia and
Abstract
Objective: The Health Star Rating (HSR) is a voluntary front-of-pack nutrition labelling system
that rates products from ½ to 5 stars (five being healthiest). The Chilean Warning Label system
displays warnings on foods high in sugar, saturated fat, sodium, or energy. We aimed to
evaluate alignment between the systems.
Methods: New Zealand packaged products (n=13,868) were classified according to the two
systems. Alignment was assessed by cross-checking the number of products meeting the
criteria for warnings against star ratings. Products with no warnings but an HSR <2, or with >1
warning but an HSR of ≥3.5 were considered outliers.
Results: Two-thirds of products met the criteria for at least one warning. There was a significant
positive relationship between the number of warnings and mean HSR: 0 warnings = HSR
3.77±.0166 (p<0.001), 1 warning = HSR 2.70±.0206 (p<0.001) and >1 warning = HSR 2.00±.0160
(p<0.001). The systems were non-aligned for 1,117 products (8%).
Conclusion: HSR and the Chilean Warning Label systems are broadly aligned. Non-alignment is
due to the Chilean system restricting warnings to foods containing added ingredients and HSR
awarding points for positive components.
Implications for public health: These results could be helpful in informing improvements to
the HSR system.
Key words: nutrition labelling, food labels, Health Star Rating, Chilean Warning Labels
New Zealand developed through a public- fibre content.8 Points are awarded according
private partnership with the food industry, to the nutrient composition per 100 g or
which was implemented in 2014.7 The 100 mL and translated into an overall score
system rates products from 0.5 to 5 stars (five and HSR star rating.8 Approximately 5% of
being healthiest) depending on the product products in New Zealand displayed HSR in
nutrient profile and is intended to compare 2016, but this increased to ~21% in 2018.9,10
products within broad categories. The Five years after its original implementation,
algorithm underpinning the system is based the HSR is currently under review.10 The
on a nutrient profiling model that considers labelling system has also received criticism
the energy, saturated fat, total sugars and for allowing some discretionary products
sodium contents of foods along with positive to display high star ratings.11 Therefore,
dietary components (fruits, vegetables, nuts it is timely to investigate how the HSR
and legumes [FVNL]) and, for some categories system compares with other international
of food and beverages, protein and dietary government-endorsed FOP labelling systems,

1. Stockholm University, Sweden

2. Karolinska Institute, Sweden
3. National Institute for Health Innovation, University of Auckland, New Zealand
4. The George Institute for Global Health, New South Wales, Australia
Correspondence to: Mr Fredrik Söderlund, Stockholm University, Stockholm, Sweden; e-mail: f_soderlund@hotmail.com
Submitted: August 2019; Revision requested: October 2019; Accepted: November 2019
The authors have stated the following conflict of interest: Cliona Ni Mhurchu is a member of the New Zealand Health Star Rating Advisory Group. The Advisory Group had no
role in study design, data collection and analysis, decision to publish, or preparation of the manuscript.
This is an open access article under the terms of the Creative Commons Attribution-NonCommercial-NoDerivs License, which permits use and distribution in any medium,
provided the original work is properly cited, the use is non-commercial and no modifications or adaptations are made.
Aust NZ J Public Health. 2019; Online; doi: 10.1111/1753-6405.12959

2019 Online Australian and New Zealand Journal of Public Health 1

© 2019 The Authors
Söderlund, Eyles and Ni Mhurchu
specifically the Chilean Warning Label system,
for potential future co-existence.
In 2016, the Chilean Government
implemented a new law requiring products
high in energy, sodium, total sugars,
and saturated fat (hereby referred to as
nutrients) to display a mandatory warning
label.12 Chilean law proclaims that products
containing adverse nutrients above a certain
threshold require a warning label for that
specific nutrient, and a product can display
up to four warning labels. To be eligible for
a warning label a food must first contain
added sugars, saturated fatty acids or sodium.
Thereafter, the product is compared against
a threshold for that specific nutrient, and
if exceeding the threshold, the product
is required to display a warning label for
that nutrient. A product can be eligible for
a warning label for sugar, saturated fat or
sodium alone, but to be eligible for a warning
label for energy, a product needs to contain
added ingredients of either sugar or saturated
fat.
The overall goal of this study was to evaluate
how the application of the Chilean Warning
Label criteria would have an impact on
packaged food and beverages in New
Zealand. Therefore, two objectives were set:
i) to estimate the proportion of New Zealand
packaged food and beverages that would
receive a “High in” warning label for sugar,
saturated fat, sodium and energy by food
group; and ii) to determine the degree of
alignment between the HSR system and the
Chilean Warning Label system.
Method
2018 Nutritrack database
We used the New Zealand Nutritrack
database, which contains nutritional
composition and labelling information
for 15,193 packaged foods and beverages
available for sale in 2018. The data were
collected at four major New Zealand
supermarket stores (New World, Countdown,
PAK’nSAVE and 4Square) in the Auckland
region in 2018. Product information includes
barcode, brand, product name, pack size,
recommended serving size, gluten-free
status, HSR status (displayed labels and
estimated ratings for products that don’t
display the voluntary label), Daily Intake
Guide label, nutrition information panel (NIP)
values, and listed ingredients. Products not
displaying a NIP, alcohol, unpackaged fresh
foods, bulk buy items, seasonal products, and
2 Australian and New Zealand Journal of Public Health
dietary supplements (except sports foods) reported fibre value for similar products in the
are not included in Nutritrack. The database same food category.
contains 15 major food groups, 66 categories,
and 197 subcategories using a hierarchical Alignment of the Chilean Warning
structure.13 Quality checks are conducted on Label system with the Health Star
a random sample of 15% of all products each Rating system
year and quality reports are run to identify
The alignment of the two nutrition labelling
any extreme and missing values.
systems was evaluated by cross-tabulation
of the number of Chilean Warning Labels
Exclusion of products
a product met the criteria for against the
Products that: displayed NIP errors (e.g. product HSR score.
where the amount of saturated fat listed
for a product was greater than total fat); Statistical analysis
displayed more than one NIP (i.e. more than
A one-way ANOVA was used to detect any
one product per package); were in need
differences in the HSR score of products
of reconstitution before consumption (e.g.
meeting the criteria for either 0, 1 or >1
packaged soup); had missing information for
warning, using SPSS version 24 with a
any adverse nutrients required to estimate
significance level of p<0.05. Products were
HSR or warning labels (energy, saturated fat,
identified as ‘outliers’ when a product received
sugar or sodium); had nutrient values that
no warning label but had an HSR score of
were only reported per serving size (i.e. not
<2, or those that received >1 warning label
per 100g); were vitamins and supplements;
but had an HSR score ≥3.5. The HSR cut-offs
or were unable to be categorised were
used were based on analyses that found that
excluded prior to analysis. After initial product
core foods in Australia had a mean HSR score
exclusions, a total of 13,868 products (91%
of 3.7, while discretionary foods had a mean
of original database) were included in the
HSR score of 1.9.14 Considering that most
analysis.
discretionary foods are high in more than one
adverse nutrient, >1 warning was chosen.
Eligibility for warning labels
A product met the criteria for a warning for
sugar if it contained added sugar and had Results
a total sugar content of >10g/100g (foods)
A total of 4,591 of the 13,868 New Zealand
or >5g/100mL (beverages). A product met
packaged products (33%) met the criteria
the criteria for a warning for saturated fat
for a warning for sugar, 4,028 (29%) met
if it contained added saturated fat and
the criteria for a warning for saturated fat,
had a saturated fat content of >4g/100g or
4,690 (34%) met the criteria for a warning
>3g/100mL, and a product met the criteria
for sodium, and 5,140 products (37%) met
for a warning for sodium if it contained
the criteria for a warning for energy (Table
added sodium and had a sodium content of
1). Two-thirds (n=9,359) of products met the
>400mg/100g or >100mg/100mL. A product
criteria for at least one warning label.
met the criteria for a warning for energy if it
contained either added sugar or saturated fat Confectionery was the group with the
ingredients and had a total energy content of highest proportion of products meeting the
>1151kJ/100g or >293kJ/100mL. criteria for warnings for both sugar (91.7%)
and saturated fat (65.5%), see Table 1. Meat
and meat products was the group with the
Estimation of the Health Star Rating
highest proportion of products meeting
A total of 2,404 products (~17%) in the
the criteria for warnings for sodium (80.2%),
2018 Nutritrack database displayed the HSR
while snackfood products had the highest
voluntarily. For the remaining products, an
proportion of warnings for energy (96.6%).
estimation was made of the HSR score. In
Although confectionery also had the highest
order to calculate the HSR, standardised
absolute number of products meeting the
points were applied at food category level
criteria for a warning for sugar (n=798), dairy
for FVNL, because information on these
had the highest absolute number of products
components of the HSR algorithm is not
meeting the criteria for a warning for
mandatory on the NIP in New Zealand.
saturated fat (n=1,114). Sauces and spreads
Products missing fibre values (also voluntary
was the food group with the highest absolute
on the NIP) were allocated the median
number of products meeting the criteria for a
2019 Online
© 2019 The Authors
 Comparison of nutrition labelling: stars versus warnings

warning for sodium (n=1148), and bread and Degree of alignment between the two difference was observed in the mean HSR
bakery products had the highest absolute food labelling systems score of products according to the number of
number of products meeting the criteria for a warning labels they qualified for: 0 warnings
A total of 12,454 products were included in
warning for energy (n=1182) (Table 1). = mean HSR 3.77 ± .0166 (p<0.001); one
the analysis of alignment between the HSR
The food group with the highest average warning = mean HSR 2.70 ± .0206 (p<0.001);
and the Chilean labelling system. A significant
number of warning labels per product was
confectionery, with 2.5 warnings per product, Table 1: Number and proportion of products by food group that met the criteria for a warning label.
followed by snackfoods with 2.2 warnings Food group Sugar Saturated fat Sodium Energy Mean
n (%) n (%) n (%) n (%) warnings/
per product, and bread and bakery products
product
with 2.1 warnings per product (Table 1). The Bread and bakery products (n=1,650) 718 (43.5%) 827 (50.1%) 728 (44.1%) 1,182 (71.6%) 2.1
food groups with the least average number Cereal and cereal products (n=1,378) 486 (35.3%) 259 (18.8%) 198 (14.4%) 676 (49.1%) 1.2
of warnings per products were eggs (0.0 Confectionary (n=870) 798 (91.7%) 570 (65.5%) 11 (1.3%) 791 (90.9%) 2.5
warnings per product), and convenience Convenience foods (n=597) 15 (2.5%) 53 (8.9%) 156 (26.1%) 32 (5.4 %) 0.4
foods (0.4 warnings per product), followed Dairy (n=1,833) 700 (38.2%) 1114 (60.8%) 579 (31.6%) 377 (20.6%) 1.5
by edible oils and oil emulsions and non- Edible oils and oil emulsions (n=319) 0 (0%) 88 (27.6%) 24 (7.5%) 87 (27.3%) 0.6
alcoholic beverages (both with 0.6 warnings Eggs (n=89) 0 (0%) 0 (0%) 1 (1.1%)b 0 (0%) 0.0
per product), see Table 1. Fish and seafood products (n=422) 3 (0.7%) 26 (6.2%) 244 (57.8%) 37 (8.8%) 0.7
Fruit and vegetables (n=1,841) 398 (21.6%) 159 (8.6%) 388 (21.1%) 336 (18.3%) 0.7
Bread and bakery products was the food
Meat and meat products (n=1,026) 23 (2.2%) 230 (22.4%) 823 (80.2%) 204 (19.9%) 1.2
group eligible for both the highest proportion
Non-alcoholic beverages (n=1,056) 493 (46.7%) 21 (2.0%) 24 (2.3%) 66 (6.3%) 0.6
(5.9%) and highest absolute number of Sauces and spreads (n=1,683) 696 (41.4%) 367 (21.8%) 1148 (68.2%) 614 (36.5%) 1.7
products (n=98) that met the criteria for all Snackfoods (n=497) 64 (12.9%) 212 (42.7%) 351 (70.6%) 480 (96.6%) 2.2
four warnings (Figure 1). Snackfoods was Special foodsa (n=321) 86 (26.8%) 78 (24.3%) 8 (2.5%) 155 (48.3%) 1.0
the food group with the highest proportion Sugars, honey and related products (n=286) 111 (38.8%) 24 (8.4%) 7 (2.4%) 103 (36.0%) 0.9
of products with at least 1 warning (97.6%) Total (n=13,868) 4,591 (33%) 4,028 (29%) 4,690 (34%) 5,140 (37%) 1.3
followed by confectionery (94.5%), see Note:
a: Babyfood, breakfast beverages, diet drink mixes, meal replacements, protein bars, protein powders, and other fitness or diet products.
Figure 1.
b: Cooked salted duck eggs met the criteria for a warning for sodium.

Figure 1: Proportion of products meeting the criteria for 0, 1, 2, 3 or 4 warnings by food group.

11.0
19.0
Bread and bakery products 25.2
38.7
5.9
46.2
8.1
Cereal and cereal products 17.3
28.2
0.3
5.5
3.9
Confectionary 27.1
62.5
0.9
68.8
21.9
Convenience foods 1.8
7.0
0.3
23.1
18.8
Dairy 14.2
42.8
1.0
72.4
0.3
Edible oils and oil emulsions 7.5
19.7

98.9
1.1
Eggs
Food group

39.1
Fish and seafood products
51.2
6.9
2.8

54.8
26.1
Fruit and vegetables 4.5
14.2
0.4
16.1
51.2
Meat and meat products 8.1
24.7

51.6
41.6
Non-alcoholic beverages 2.0
4.8

16.6
29.4
Sauces and spreads 26.4
24.8
2.7
2.4
14.5
Snackfoods 37.6
43.3
2.2
45.8
13.7
Special foods* 5.9
34.0
0.6
58.0
7.0
Sugars, honey and related products 8.7
26.2

32.5
23.3
Total 18.5
24.3
1.4

0 10 20 30 40 50 60 70 80 90 100

Percentage of products
0 warnings 1 warning 2 warnings 3 warnings 4 warnings
Note:
* Babyfood, breakfast beverages, diet drink mixes, meal replacements, protein bars, protein powders, and other fitness or diet products.

2019 Online Australian and New Zealand Journal of Public Health 3

© 2019 The Authors
Söderlund, Eyles and Ni Mhurchu
and more than one warning = mean HSR 2.00
± .0160 (p<0.001), indicating broad alignment
in the expected direction between the two
nutrition labelling systems (Table 2). However,
1,117 products (8%) were identified as outliers.
There were 249 products that did not meet
the criteria for any warning label but had an
HSR of <2 (indicating an unhealthy nutritional
profile). The major food groups accounting for
these outlier products were sugars, honey and
related products with 138 products (55.4%
outliers), dairy with 35 products (14.1%),
edible oils and oil emulsions with 35 products
(14.1%), and non-alcoholic beverages with 33
products (13.3%), see Supplementary Table 1.
A further 868 products were also considered
outliers because they received >1 warning
label but had an HSR of ≥3.5 (indicating a
healthy nutritional profile). Of these products,
cereal and cereal products accounted for
27.3% (n=237), fruit and vegetables for
19.9% (n=173), sauces and spreads for 15.6%
(n=135) and dairy for 13.4% (n=116), see
Supplementary Table 2.
Outliers were predominantly due to products
meeting the criteria for energy warning labels
while also having an HSR of ≥3.5, where 692
products (62% of all outliers) met the criteria
for a warning for energy (Supplementary
Table 3). A total of 430 products (38% of all
outliers) met the criteria for a warning for
sugar; 397 (36% of all outliers) met the criteria
for a warning for sodium; and 341 (31% of
all outliers) met the criteria for a warning for
saturated fat. Energy density accounted for
warning labels on all 237 products considered
outliers within the food group of cereal and
cereal products, representing the largest
absolute number of warnings for any food
group among the outliers (Supplementary
Table 3). The second-largest absolute number
of outliers was also among cereal and cereal
products, with 209 products meeting the
criteria for a warning for sugar.
Analysis of food categories (subcategories
to the food groups) showed that breakfast
cereals, with 180 products (16% of all
outliers), was the largest food category
Table 2: Cross-tabulation of the Health Star Rating system and the Chilean Warning Label system. Products were
categorised as meeting the criteria for either 0 warnings, 1 warning or >1 warning.
Health Star Rating (HSR)
Warning labels 0.5 1 1.5 2 2.5
0 71 95 83 293 89 219 782
1 132 270 415 327 226 445 675
>1 953 627 871 897 678 420 284
Note:
CI = Confidence interval
4 Australian and New Zealand Journal of Public Health
meeting the criteria for >1 warning label
while having an HSR of ≥3.5 (Supplementary
Table 4). The second-largest subcategory was
cheese (n=102, 9% of all outliers), followed by
nuts and seeds (n=87, 8% of all outliers) and
spreads (n=78, 7% of all outliers). Breakfast
beverages had 24 products (2% of all outliers)
meeting the criteria for >1 warning but with
an HSR of ≥3.5.
Discussion
Summary of key findings
We investigated how New Zealand packaged
foods and beverages would rate under the
Chilean Warning Label system and how this
system would align with the current HSR.
The study found that a warning label for high
energy content (37% of products) would be
the most common, followed by warnings for
high sodium (34%), sugar (33%) and saturated
fat (29%) contents. The study also found
that two-thirds (n=9,359) of products would
meet the criteria for at least one warning. The
analysis indicates a broad alignment between
the HSR system and the Chilean Warning
Label system, but approximately one in 12
(8%) of products were found to be outliers
(non-aligned).
Possible reasons for the discrepancy
between systems
The two labelling systems are broadly
aligned with a significant difference in the
expected direction in HSR score between
products eligible for 0, 1 and >1 warning
label. Nonetheless, 1,117 products (8%)
were identified as outliers. Sugars, honey
and related products was the food group
with the greatest number of products with
no warnings but an unhealthy nutritional
profile according to the HSR (n=138).
These products did not meet the criteria
for any warning label, mainly because they
are single-ingredient foods without the
addition of other adverse nutrients, therefore
making them non-eligible for warning labels
according to the Chilean regulations. The
Mean HSR
3 3.5 4 4.5 5 (95% CI)
1,138 541 851 3.77 (3.74–3.81)
430 80 69 2.70 (2.66–2.74)
376 144 64 2.00 (1.97–2.03)
© 2019 The Authors
HSR, on the other hand, does not consider
additives to food (such as added sugars) and
instead scores the overall nutritional profile.
The food group cereal and cereal products
contained 237 products considered outliers
due to a healthy nutritional profile according
to the HSR but which met the criteria for
more than one warning. Of these, 180 were
breakfast cereals, corresponding to nearly
half (46%) of all breakfast cereals in the
dataset. Warnings in this category were
most common for high energy content
(204 products) and high sugar content
(195 products). The discrepancy between
systems is most likely a consequence of: i)
the HSR system awarding points for positive
components (fibre, FVNL, and protein) often
found in breakfast products, which can offset
the negative nutrient points; and ii) the HSR
using total sugars instead of added sugars.
Both of these differences could lead to some
foods displaying higher than expected HSRs.
Of note, cereal and cereal products was the
food group with the highest uptake of the
voluntary HSR label at a two-year post-
implementation review of the HSR conducted
in 2016 (216 products or 13% of 1,555 cereal
and cereal products).15 The relatively high star
ratings achieved by these products might
be a reason for widespread adoption by the
category of the voluntary HSR system.
Eligibility for a warning for high energy
density but with an HSR of ≥3.5 was the main
reason for outlier products. Since all of the
237 cereal and cereal products identified
as outliers met the criteria for a warning for
energy, there seems to be a discrepancy
between the two labelling systems with
respect to energy content. The HSR algorithm
might be too lenient towards energy-dense
products that also contain positive nutrients
in the form of FVNL, protein and dietary
fibre. Furthermore, the HSR system has
been criticised for food industry influence
on development of the product nutrient
profiling algorithm leading to some foods
with high levels of risk nutrients scoring
better than expected.16 It seems that, even
though a public–private partnership might
be considered desirable when developing
public health initiatives order to increase
participation and impact, the private sector
may have had an inappropriate influence on
p-value
the HSR, leading to a perceived advantage for
<0.001
some companies and product types.
<0.001
<0.001
2019 Online

Evidence for warning labels to date
The Chilean Warning Labels have been in
effect since June 2016 and studies examining
the effect of their implementation are
underway. So far, study methods have
focused on either virtual stores or shopping
simulations, and no studies have investigated
in-store sales. A paper published in 2017
by Cabrera et al. evaluated the influence of
the design of FOP nutrition warning labels
on perceived healthfulness and consumer
attention. The authors conducted five
different trials including variation in colour,
shapes, textual information and position of
warning labels. The authors concluded that
black octagons with the text “excess of...”
had the strongest connection to perceived
unhealthfulness.17 This is similar to the final
format of the labels implemented in Chile,
with a slight difference in wording, which
ended up with the text “High in…” for the
warning labels.
If the Chilean Warning Label system were
implemented in New Zealand, two-thirds
of supermarket products would meet
the criteria for at least one warning label
(assuming no product reformulation since
2018). Similar numbers were found for
products in Colombia, where 66.4% out of
6,708 products met the criteria for at least one
warning label.18 Another study, conducted
by Kanter et al. on Chilean products, showed
that 83% (n=6,861) of products would receive
at least one warning label.19 However, the
Chilean study focussed on food and beverage
categories most likely to be subjected to
the labelling regulations (rather than all
packaged foods), making a direct comparison
inappropriate. These results indicate that
adoption of warning labels could have
a major impact on the labelling of foods
and beverages in New Zealand, with most
available products meeting the criteria for at
least one nutrient warning.
Strengths and weaknesses of this
study
This cross-sectional study of packaged foods
and beverages included 13,868 products
sampled from four major supermarkets
in Auckland. The study product sample
is considered representative of the New
Zealand market because around 74% of
packaged foods in New Zealand are sold in
supermarkets and the data were collected
at four major stores owned by the two
retailers dominating the New Zealand market:
2019 Online Australian and New Zealand Journal of Public Health
Comparison of nutrition labelling: stars versus warnings
Progressive Enterprises Ltd (Countdown) and
Foodstuffs New Zealand Ltd (New World,
PAK’nSAVE and 4Square).20
However, the study had some limitations.
Due to the lack of products displaying the
voluntary HSR, this study used estimated HSR
scores for most (~80%) products. Because
fibre and FVNL values were estimated based
on the within-category median values,
there might be a discrepancy between
the estimations and actual HSR scores.
This could potentially lead to either more
or less products being considered outliers
depending on over- or under-estimation of
the values.
Implications for policy/practice
The findings of this study indicate that
the majority (67%) of packaged foods and
beverages sold in New Zealand supermarkets
contain high levels of adverse nutrients
such that they would meet the criteria to
display warning labels under the Chilean
labelling system. These levels of adverse
nutrients contribute to an unhealthy food
environment and are contributors to the high
levels of obesity and diet-related disease in
New Zealand. If warning labels were to be
implemented, they have the potential to
increase public awareness of unhealthy foods
and thereby aid in helping consumers choose
healthier products.
Scoring of both positive and negative
nutrients in the HSR algorithm is intended
to reflect the Australian and New Zealand
dietary guidelines. However, the points
awarded for positive nutrients may distort
the apparent healthiness of some products.
In contrast, the Chilean warning labels only
direct consumers away from products high in
critical nutrients and do not provide guidance
on healthier alternatives. Although there are
differences between the systems, the HSR
system and the Chilean Warning Label system
could potentially co-exist, which may alleviate
the limitations of each system. Warning labels
could be an aid in helping consumers identify
unhealthy foods while the HSR could be used
to guide consumers towards healthier foods.
However, changes to both the HSR algorithm
and the warning label criteria would be
necessary to improve alignment.
In terms of specific food groups,
confectionery and snack foods had the
highest proportion of products meeting the
criteria for warning labels. Products within
these food groups are often considered
© 2019 The Authors
discretionary. Consumers generally
comprehend that these products are
unhealthy, but even so, the products are
still purchased and consumed frequently.
Nonetheless, if warning labels could
encourage consumers to avoid products with
warnings and/or choose products containing
fewer warnings, it could lead to small
improvements in population dietary intake. A
qualitative study published in 2019 by Correa
et al. investigated the responses of mothers
in Santiago, Chile after the implementation of
the warning labels law and found the system
prompted some shoppers to choose products
with fewer warnings.21
Product reformulation
Front-of-pack labelling may prompt product
reformulation.9 A review published in 2019
concluded that food labelling influenced
manufacturers to reduce product content
of artificial trans-fat and sodium, while also
reducing dietary intake of selected nutrients
among consumers.22 One modelling study
conducted on food available in the French
market evaluated the health impact of
product reformulation regardless of the
reason of the reformulation.23 The study
concluded that product reformulation
would result in significant improvements in
population health outcomes even without
any changes in consumers’ behaviours,
although the authors stated that the results
should be interpreted with caution due to
uncertainties in modelling assumptions and
food composition. Consumer acceptability
of reformulated products is of importance
for manufacturers. A review published in
2017 by Jaenke et al. evaluated consumer
acceptability of salt-reduced foods. One meta-
analysis indicated that a salt reduction of up
to 37% in breads and 67% in processed meats
was acceptable to consumers.24
Two studies on product reformulation
regarding the Chilean Warning Labels were
published in 2018 by a research group in
Uruguay. One conclusion from the studies
was that consumers preferred reformulated
products without nutritional warnings
compared to their original (less healthy)
versions containing warnings.25,26 Therefore,
warning labels might be a powerful incentive
for manufacturers to reformulate their
products if they want to be market leaders.
5
Söderlund, Eyles and Ni Mhurchu
Conclusions
This study shows that should the Chilean
Warning Labels criteria be applied to
packaged foods and beverages sold in New
Zealand, more than two-thirds of products
would display at least one warning label. A
warning on foods with high energy content
would be the most common warning
label, followed by warnings for high sugar,
sodium, and saturated fat contents. The
results indicate a broad alignment between
the current HSR nutrition labelling system
and the Chilean Warning Label system, but
almost one in 10 products were found to
be outliers (non-aligned). Non-alignment
(most common among the food groups
sugars, honey and related products, and
cereal and cereal products) was largely due
to the Chilean system restricting warnings
to foods containing added ingredients (and
hence excluding single ingredient unhealthy
products such as sugar) and the HSR system
not differentiating between intrinsic and
added sugars and awarding points for
positive components, which can offset
negative nutrient content scores and lead to
some foods displaying higher than expected
HSRs.
Future perspectives
There is a need for high-quality studies
to assess the impact of food labels on
consumers’ behaviour. Such studies
should ideally use sales data to evaluate if
nutrition labels influence shopper purchase
behaviours. More research is needed to
understand the relationship between
nutrition labels and actual consumption in
order to determine if warning labels would
influence dietary intakes positively.
Acknowledgements
FS would like to thank the National Institute
for Health Innovation for hosting his
internship and Masters dissertation research.
The authors would also like to thank Dr
Lorena Rodriguez from the Chilean Ministry
of Health for kindly answering all questions
and queries regarding the Chilean law
and the implementation of the warning
labels, Yannan Jiang for estimating product
HSRs and providing statistical advice, and
all fieldworkers who collected, entered,
categorised and quality checked the data
used.
6 Australian and New Zealand Journal of Public Health
References
1. World Health Organization. Healthy Diet [Internet].
Geneva (CHE); WHO; 2018 [cited 2019 Oct 15]. Available
from: https://www.who.int/en/news-room/fact-sheets/
detail/healthy-diet
2. N Z Ministry of Health. Health Loss in New Zealand
1990-2013: A Report from the New Zealand Burden of
Diseases, Injuries and Risk Factor Study. Wellington (NZ):
Government of New Zealand; 2016.
3. NZ Ministry of Health. Annual Data Explorer 2017/18:
New Zealand Health Survey [Internet]. Wellington
(NZ): Government of New Zealand; 2018 [cited 2019
Jan 8]. Available from: https://www.health.govt.nz/
nz-health-statistics/health-statistics-and-data-sets/
obesity-statistics
4. Lal A, Moodie M, Ashton T, Siahpush M, Swinburn B.
Health care and lost productivity costs of overweight
and obesity in New Zealand. Aust N Z J Public Health.
2012;36(6):550–6.
5. World Health Organization. Global Strategy on Diet,
Physical Activity, and Health [Internet]. Geneva (CHE):
WHO; 2004 [cited 2018 Oct 1]. Available from: http://
www.who.int/dietphysicalactivity/strategy/eb11344/
en/index.html
6. World Health Organization Regional Office for Europe.
European Food and Nutrition Action Plan 2015-2020.
Copenhagen (DNK): WHO; 2015.
7. Colmar Brunton. 2018 Health Star Rating Monitoring and
Evaluation: Year 2 Follow-up Research Report. Wellington
(NZ): Health Promotion Agency; 2018.
8. Health Star Rating Advisory Committee. Guide for
Industry to the Health Star Rating Calculator (HSRC).
Version 6. Canberra (AUST): Australian Department of
Health; 2018.
9. Mhurchu C, Eyles H, Choi Y-H. Effects of a voluntary
front-of-pack nutrition labelling system on packaged
food reformulation: The Health Star Rating System in
New Zealand. Nutrients. 2017;9(8):918–34.
10. mpconsulting. Health Star Rating System - Five Year
Review Draft Report [Internet]. Melbourne (AUST):
mpconsulting; 2019 [cited 2019 May 8]. Available
from: http://www.mpconsulting.com.au/wp-content/
uploads/2019/02/Health-Star-Rating-System-Five-
Year-Review-Draft-Report-compressed.pdf
11. Lawrence M, Dickie S, Woods J. Do nutrient-based
front-of-pack labelling schemes support or undermine
food-based dietary guideline recommendations?
Lessons from the Australian Health Star Rating System.
Nutrients. 2018;10(1):32–47.
12. Reyes M, Garmendia ML, Olivares S, Aqueveque C,
Zacarías I, Corvalán C. Development of the Chilean
front-of-package food warning label. BMC Public Health.
2019;19(1):906.
13. Dunford E, Webster J, Metzler AB, Czernichow S,
Mhurchu CN, Wolmarans P, et al. International
collaborative project to compare and monitor the
nutritional composition of processed foods. Eur J Prev
Cardiolog. 2012;19(6):1326–32.
14. Dunford E, Cobcroft M, Thomas M, Jason W. Technical
Report: Alignment of NSW Healthy Food Provision Policy
with the Health Star Rating System [Internet]. Sydney
(AUST): New South Wales Ministry of Health; 2015 [cited
2019 May 8]. Available from: https://www.health.nsw.
gov.au/heal/Publications/health-star-rating-system.
pdf
15. NZ Ministry for Primary Industries. Health Star Rating:
Monitoring Implementation at Year Two. Wellington (NZ):
Government of New Zealand; 2017.
16. Australian Department of the Senate. Final Report:
Obesity Epidemic in Australia [Internet]. Canberra
(AUST): Government of Australia; 2018 [cited 2019
May 10]. p. 29. Available from: https://www.aph.gov.
au/Parliamentary_Business/Committees/Senate/
Obesity_epidemic_in_Australia/Obesity/Final_Report
17. Cabrera M, Machín L, Arrúa A, Antúnez L, Curutchet MR,
Giménez A, et al. Nutrition warnings as front-of-pack
labels: Influence of design features on healthfulness
perception and attentional capture. Public Health Nutr.
2017;20(18):3360–71.
© 2019 The Authors
18. Mora-Plazas M, Gómez LF, Miles DR, Parra DC, Taillie
LS. Nutrition quality of packaged foods in Bogotá,
Colombia: A comparison of two nutrient profile models.
Nutrients. 2019;11(5):1011–24.
19. Kanter R, Reyes M, Swinburn B, Vandevijvere S, Corvalán
C. The food supply prior to the implementation of the
Chilean Law of food labeling and advertising. Nutrients.
2018;11(1):52–61.
20. Euromonitor. Packaged Food in New Zealand [Internet].
London (UK): Euromonitor International; 2018 [cited
2019 Mar 6]. Available from: http://www.portal.
euromonitor.com.ezproxy.auckland.ac.nz/portal/
analysis/tab
21. Correa T, Fierro C, Reyes M, Dillman Carpentier FR,
Taillie LS, Corvalan C. Responses to the Chilean law of
food labeling and advertising: Exploring knowledge,
perceptions and behaviors of mothers of young
children. Int J Behav Nutr Phys Act. 2019;16(1):21.
22. Shangguan S, Afshin A, Shulkin M, Ma W, Marsden D,
Smith J, et al. A Meta-analysis of food labeling effects
on consumer diet behaviors and industry practices. Am
J Prev Med. 2019;56(2):300–14.
23. Leroy P, Réquillart V, Soler L-G, Enderli G. An assessment
of the potential health impacts of food reformulation.
Eur J Clin Nutr. 2016;70(6):694–9.
24. Jaenke R, Barzi F, McMahon E, Webster J, Brimblecombe
J. Consumer acceptance of reformulated food products:
A systematic review and meta-analysis of salt-reduced
foods. Crit Rev Food Sci. 2017;57(16):3357–72.
25. Ares G, Aschemann-Witzel J, Curutchet MR, Antúnez
L, Machín L, Vidal L, et al. Product reformulation in the
context of nutritional warning labels: Exploration of
consumer preferences towards food concepts in three
food categories. Food Res Int. 2018;107:669–74.
26. Ares G, Aschemann-Witzel J, Curutchet MR, Antúnez
L, Machín L, Vidal L, et al. Nutritional warnings
and product substitution or abandonment: Policy
implications derived from a repeated purchase
simulation. Food Qual Prefer. 2018;65:40–8.
Supporting Information
Additional supporting information may be
found in the online version of this article:
Supplementary Table 1: Products per food
group with 0 warnings and a Health Star
Rating of <2.
Supplementary Table 2: Products per food
group with >1 warning and a Health Star
Rating of >3.5.
Supplementary Table 3: Products per food
group with >1 warning and a HSR score ≥3.5
distributed among the nutrients.
Supplementary Table 4: Products per food
group and food category with >1 warning
and a Health Star Rating score of >3.5.
2019 Online
 Corrected Proof
1 © IWA Publishing 2018 Water Supply | in press | 2018

Advantages of TiO2/carbon nanotube modified

photocatalytic membranes in the purification
of oil-in-water emulsions
Gábor Veréb, Viktória Kálmán, Tamás Gyulavári, Szabolcs Kertész,
Sándor Beszédes, Gábor Kovács, Klára Hernádi, Zsolt Pap, Cecilia Hodúr
and Zsuzsanna László

ABSTRACT

For the effective purification of emulsified oil contaminated waters advanced treatment methods Gábor Veréb (corresponding author)
Viktória Kálmán
have to be applied, such as membrane filtration, which is able to eliminate macro-, and even Szabolcs Kertész
Sándor Beszédes
nanoscale oil droplets, however, membrane fouling is still a major problem, which prevents Cecilia Hodúr
Zsuzsanna László
economic utilization. Therefore, fouling mitigation is one of the most important aspects in the field of
Institute of Process Engineering, Faculty of
membrane separation developments. In the present study, solely TiO2 and TiO2/carbon nanotubes Engineering,
University of Szeged,
(CNT) composite modified PVDF membranes were prepared and used to purify oil-in-water Moszkvai Blvd. 9, Szeged H-6725,
Hungary
emulsions. Achievable fluxes, reversible and irreversible filtration resistances, fouling models, E-mail: verebg@mk.u-szeged.hu

filtration efficiencies and photocatalytic activities were compared in case of different nanomaterial
Tamás Gyulavári
covered and unmodified PVDF membranes. Applying either solely TiO2 or solely CNT coating resulted Gábor Kovács
Klára Hernádi
in the significant reduction of total filtration resistance in both cases, but the combination of the two Department of Applied and Environmental
Chemistry,
components (TiO2 with 1 wt% CNT) resulted in by far the highest flux and lowest resistance, University of Szeged,
Rerrich Sq. 1, Szeged H-6720,
meanwhile, the enhanced photocatalytic efficiency of the composite was also achieved. To the best Hungary
of our knowledge, this study demonstrates the beneficial effects of the combination of TiO2 and CNT
Zsolt Pap
nanomaterials for the first time in the field of membrane separation of oil-in-water emulsions. Cecilia Hodúr
Institute of Environmental Science and
Key words | carbon nanotube, composite, enhanced flux, membrane, oil-in-water emulsion, Technology,
University of Szeged,
titanium dioxide Tisza Lajos Blvd. 103, Szeged H-6720,
Hungary

INTRODUCTION

Purification of emulsified oil contaminated
(doil droplets < 5 μm) cannot be carried out by conventional
water treatment methods (such as gravity separation, cen-
trifugation, skimming, etc.), but membrane filtration can be
a suitable method to eliminate macro- and even nanoscale
oil droplets (Chakrabarty et al. ; Abadi et al. ; Yi
et al. ). Microfiltration (Abadi et al. ; Shokrkar
et al. ; Yang et al. ) ensures higher fluxes, meanwhile
ultrafiltration (Chakrabarty et al. , ; Masoudnia
et al. ) results in higher purification efficiency, but
waters membrane fouling is a major problem in both cases
(Padaki et al. ), which causes flux reduction and
increases the cost of these procedures, preventing the econ-
omical utilization. Therefore, the suppression of fouling is
one of the most important aspects in terms of developing
advanced membrane separation techniques.
Nanotechnology-based methods can be used to prepare
highly hydrophilic and/or low-fouling membranes (Van der
Bruggen ; Fischer et al. ; Yin & Zhou ; Islam
et al. ; Kovács et al. ), moreover, in case of the

doi: 10.2166/ws.2018.172

Downloaded from https://iwaponline.com/ws/article-pdf/doi/10.2166/ws.2018.172/497199/ws2018172.pdf

by COLUMBIA UNIVERSITY LIBRARIES user
 Corrected Proof
2 G. Veréb et al. | TiO2/CNT coated photocatalytic membranes for advanced separation of o/w emulsion Water Supply | in press | 2018

utilization of suitable semiconductor nanoparticles, con-
taminated membranes can be purified photocatalytically
by UV (or even by solar) irradiation. Titanium dioxide
(TiO2) is one of the most investigated photocatalytic nano-
material, because of its many favorable properties, such as
non-toxicity, biocompatibility, chemical- and photostability,
etc. (Vajda et al. ; Chang et al. ; Kertész et al.
). Carbon nanotubes (CNT) are also highly investigated
both in composite photocatalytic material production
(Woan et al. ; Vajda et al. ; Réti et al. ) and in
the development of novel membrane surfaces (Smajda
et al. ; Esfahani et al. ; Rashid & Ralph ).
Carbon nanotubes (as a composite component – e.g. in
TiO2/CNT) are able to enhance the photocatalytic efficiency
of a semiconductor nanoparticle, due to the following two
mechanisms (Gao et al. ; Woan et al. ): CNT can
conduct the electron from the valence band of the activated
TiO2, resulting in extended electron-hole lifetime and,
therefore, suppressed electron-hole recombination rate
(Hoffmann et al. ). Moreover, CNT can act as a photo-
sensitizer, if the photo-generated electrons of CNTs are
able to migrate to the valence band of TiO2, which can
initiate redox reactions (Wang et al. ). The authors
proved that both the physical mixture of TiO2/CNT, and
more likely, the synthesized composites had higher photoca-
talytic efficiency than pure TiO2. Different weight ratios of
CNT/TiO2 composites were also widely investigated in the
literature. Some authors (Wang et al. ; Yen et al. )
determined relatively high beneficial CNT/TiO2 ratios (20
and 8 wt%, respectively) for phenol decomposition, how-
ever, other authors determined much lower optimal CNT
contents. Gao et al. (Gao et al. ) investigated 1.5–
20 wt% CNT contents and found that even 1.5 wt% signifi-
cantly increased the activity, and no notable further
increase was determined at higher CNT contents. Yu et al.
(Yu et al. ) reported 3 wt% as optimal CNT/TiO2 ratio,
although this content was the lowest in the investigated com-
posite series. Réti et al. (Réti et al. ) investigated the
1–10 wt% interval and measured the best photocatalytic
activity in case of 1 wt% CNT content for phenol decompo-
sition (and 5 wt% for oxalic acid degradation).
Due to the enhanced photocatalytic efficiency of TiO2/
CNT nanocomposites (and some other advantageous prop-
erties, such as increased mechanical and chemical stability,
mesoporous characteristics, etc.), their utilization can be
beneficial to create photocatalytic membranes, however,
the hydrophobic surface property of CNT may cause
disadvantageous effects during the membrane filtration of
oil-in-water (o/w) emulsions. In the present study, TiO2/
CNT nanocomposites were prepared (with 1 wt% CNT
content, which was chosen for the reasons detailed
above) and used to modify the surface of a UV resistant
polyvinylidene fluoride (PVDF) ultrafilter membrane.
Self-prepared TiO2/CNT/PVDF membranes were applied
to purify 100 ppm crude oil containing o/w emulsions.
Achievable fluxes, reversible and irreversible filtration
resistances, fouling mechanisms, filtration efficiencies and
photocatalytic activities were compared in case of solely
TiO2-, CNT- and TiO2/CNT composite-covered, and unmo-
dified membranes.
MATERIALS AND METHODS
Production of the nanomaterial modified membranes
For the membrane surface modification, commercial tita-
nium dioxide (TiO2; Aeroxide P25, Germany, d¼
S 2 1
25–39 nm, aBET ¼ 50.6 m g ) and carbon nanotube
(CNT; Nanothinx NTX1 multi walled carbon nanotube,
Greece, l  10 μm; d ¼ 15–35 nm) were applied. Nanomater-
ials (TiO2 and CNT) by themselves or in composites (TiO2
with 1 wt% CNT) were suspended in 2-propanol (c ¼ 400
mg L1) by 1 min ultrasonic homogenization (Hielscher
UP200S, Germany) at 25  C (maximal amplitude and cycle
were applied). 40 mg of the given nanomaterial (suspended
in 100 mL of 2-propanol) was immobilized on a PVDF mem-
brane (New Logic Research Inc., USA, 100 kDa;
2
∼1.0 mg cm catalyst coverage) by physical deposition
method: the suspension was filtered through the membrane,
applying 0.3 MPa transmembrane pressure in a batch-stirred
membrane reactor (Millipore, XFUF07601, USA), followed
by drying in air at room temperature.
Determination of contact angles
For the description of the hydrophilicity of the membrane
surfaces, the contact angles formed between the membrane

Downloaded from https://iwaponline.com/ws/article-pdf/doi/10.2166/ws.2018.172/497199/ws2018172.pdf

by COLUMBIA UNIVERSITY LIBRARIES user
 Corrected Proof
3 G. Veréb et al. | TiO2/CNT coated photocatalytic membranes for advanced separation of o/w emulsion Water Supply | in press | 2018

and ultrapure water were measured using the sessile
drop method (Dataphysics Contact
OCA15Pro, Germany) at room temperature. 10 μL water
was carefully dropped onto the membrane surface and
contact angles were immediately measured within 5 s
(measurements were repeated 10 times and average values
were calculated).
Production of the oil-in-water (o/w) emulsion
O/w emulsions (coil ¼ 100 mg L1; ddroplets < 1.5 μm) were
prepared in two steps, using crude oil (provided by MOL
Nyrt.; Hungary), and ultrapure water (PureLab Pulse,
ELGA Labwater, UK). Intensive stirring (35,000 rpm,
1 min) of crude oil and water was followed by 10 min ultra-
sonic homogenization (Hielscher UP200S, Germany) at

25 C (using maximal amplitude and cycle). For the photo-
catalytic experiments 20 ppm oil concentration was set by
the dilution of the emulsion.
Membrane filtration experiments
Angle System
Filtration of o/w emulsions was carried out in a batch-stirred
membrane reactor (Millipore XFUF07601, USA) equipped
with the given membrane, using 0.1 MPa transmembrane
pressure and 5.83 s1 stirring speed (350 rpm). In all fil-
tration experiments, 250 mL emulsion was filled into the
reactor and filtered until the production of 200 mL permeate
(volume reduction ratio: VRR ¼ 5). Purification efficiencies
were determined by measuring the COD and the extractable
oil content of the permeates.
Filtration resistances and fouling models
The membrane resistance (RM) was calculated as:
Δp
RM ¼ [m1 ] (1)
JW × ηW

Determination of the photocatalytic efficiencies where Δp is the applied transmembrane pressure [Pa], JW is
the water flux of the clean membrane [m3 m2 s1] and ηW

Photocatalytic experiments were carried out in a modified is the viscosity of the water [Pa s]. The irreversible resistance

Millipore reactor, which was equipped with a UV-A (RIrrev) was determined by remeasuring the water flux on the

fluorescence tube (Lightech, 10 W, λmax ∼ 365 nm; UV used membrane after the filtration, followed by a purifi-

intensity: 24 mW m2 – measured by an Optix UVTEX cation step (intensive rinsing with distilled water):

radiometer), and a magnetic stirrer. Photocatalytic efficien-

Δp
cies were determined by measuring the changes of RIrrev ¼  RM [m1 ] (2)
JWA × ηW
chemical oxygen demand (COD) and extractable oil content
of a 20 ppm o/w emulsion during the irradiation of the
where JWA is the water flux after the cleaning procedure. The
photocatalytic membranes for 120 min. COD values were
reversible resistance (RRev) can be calculated as:
measured by a standard method, based on potassium
dichromate oxidation, using standard test tubes (Hanna
Δp
Instruments, USA), a Lovibond ET 108 type digester RRev ¼  RIrrev  RM [m1 ] (3)
Jc × ηWW

(t ¼ 2 h, T ¼ 150 C), and a Lovibond COD Vario type
spectrophotometer. Extractable oil content was measured
where Jc is the flux at the end of the filtration and ηww is the
by a Wilks InfraCal TOG/TPH type analyzer, using hexane
viscosity of the emulsion. The total resistance (RT) can be
as extracting solvent. Additionally, photocatalytic perform-
calculated as the sum of the previously detailed resistances:
ances of the prepared membranes were determined by
phenol decomposition. Changes in phenol concentration
RT ¼ RM þ RIrrev þ RRev [m1 ] (4)
were followed using an Agilent 1100 series HPLC system
equipped with Lichrospher RP 18 column applying metha-
nol/water (35:65 vol%) mixture as eluent (the detection Hermia’s filtration law (Hermia ; Bowen et al. ;
was carried out at λ ¼ 210 nm). Zhao et al. ) can be applied as a mathematical model to

Downloaded from https://iwaponline.com/ws/article-pdf/doi/10.2166/ws.2018.172/497199/ws2018172.pdf

by COLUMBIA UNIVERSITY LIBRARIES user
 Corrected Proof
4 G. Veréb et al. | TiO2/CNT coated photocatalytic membranes for advanced separation of o/w emulsion
characterize the fouling mechanism:
2
 n
d t dt
¼k
dV 2 dV
where t is the filtration time, V is the volume of the perme-
ate, k is the fouling constant and n is a value illustrating
the different fouling mechanism (complete pore blocking:
n ¼ 2, intermediate pore blocking: n ¼ 1, internal pore
blocking: n ¼ 1.5, cake layer formation: n ¼ 0). More details
about the calculations can be found in other publications
(Bowen et al. ; Aryanti et al. ; Veréb et al. ).
RESULTS
Description of the produced membrane surfaces
The photographs of the produced membranes are presented
in Figure 1, which also demonstrates their hydrophilicity
with the water droplets formed on the surfaces. Uncoated
PVDF membrane was slightly hydrophilic, based on the
measured 57.2 ± 0.6 contact angle. Meanwhile, both solely
TiO2-covered and TiO2/CNT composite-covered surfaces
were highly hydrophilic, since the droplets were immedi-
ately and totally spread on the surfaces. So, surprisingly,
no measurable effect on the surface hydrophilicity was
determined in case of 1 wt% carbon nanotube content.
Solely CNT-covered membrane was also prepared as a
Figure 1 | Photographs of membranes (uncoated membrane, TiO2-, TiO2/CNT-, and CNT-coated membranes, respectively) and the contact angles formed between the membrane and
water droplets.
Downloaded from https://iwaponline.com/ws/article-pdf/doi/10.2166/ws.2018.172/497199/ws2018172.pdf
by COLUMBIA UNIVERSITY LIBRARIES user
Water Supply | in press | 2018
control sample, which was highly hydrophobic as expected
by the measured 125 ± 1.2 contact angle value.
(5)
Photocatalytic activities
In the first series of experiments, the photocatalytic efficien-
cies of TiO2-, and TiO2/CNT-coated membranes were
compared to investigate the effect of the 1 wt% CNT content
on the photocatalytic activity of the composite. First, the
photocatalytic decomposition of phenol, as a widely used
(Wang et al. ; Vajda et al. ; Réti et al. ) model
organic contaminant was investigated. Phenol concen-
tration was followed by HPLC (Figure 2), and the results
proved the increased photocatalytic activity of the TiO2/
CNT composite-covered membrane.
After the increased photocatalytic activity was proven in
the case of phenol model contaminant, 20 ppm crude oil
containing o/w emulsion was treated photocatalytically for
120 min. Meanwhile, the COD and extractable oil content
of the taken samples were measured. Figure 3 demonstrates
that both COD and extractable oil content values decreased
more intensively in the case of the TiO2/CNT composite-cov-
ered membrane, compared to the solely TiO2-covered
membrane. As can be seen in Figure 3, the extractable oil
content decreased slightly more than the COD, which can
be explained by the production of water-soluble organic
compounds during the photocatalytic decomposition,
which are not extractable by hexane, but still contribute to
the COD values. The improved activity can be beneficial
 Corrected Proof
5 G. Veréb et al. | TiO2/CNT coated photocatalytic membranes for advanced separation of o/w emulsion Water Supply | in press | 2018

higher flux (Figure 4(a)), and the considerable reduction of

Figure 2 | Photocatalytic decomposition of phenol, during the UV irradiation
(λmax ∼ 365 nm; UV intensity: 24 mW m
2
) of the TiO2-, and TiO2/CNT-covered
membranes.
during the photocatalytic regeneration of the contaminated
self-cleaning photocatalytic membrane surfaces.
Membrane filtration of o/w emulsions
In the next series of experiments, the effects of different
coatings on membrane filtration of 100 ppm crude oil con-
taining o/w emulsions were investigated in detail. During
the filtration of o/w emulsions with the uncoated mem-
brane, quick and significant flux reduction (Figure 4(a))
was observed, therefore high total resistance (Figure 4(b))
was calculated, which was caused mainly by irreversible
resistance. Coating with TiO2 resulted in significantly
irreversible and total resistances (Figure 4(b)). Surprisingly,
despite the hydrophobic surface property of the carbon
nanotube, the TiO2/CNT composite modified membrane
resulted in by far the highest flux and lowest resistance.
Moreover, the ratio of reversible and irreversible resistances
(Figure 4(b)) was also the most beneficial in case of the com-
posite-covered membrane. The very low flux reduction rate
proved that this composite coating inhibited successfully
the adhesion of the oil droplets on the surface. Lower
amounts of accumulated hydrophobic contaminants resulted
lower probability for the droplets to create a hydrophobic
water barrier or to be pressed inside the composite layer
during the filtration.
Unexpectedly, highly beneficial effect of the presence of
CNT cannot be related to the surface hydrophilicity, since
there was no measurable difference between the solely
TiO2-, and the TiO2/CNT-covered membranes (both was
highly hydrophilic – see Figure 1). Additionally, 100%
CNT-covered hydrophobic membrane also resulted higher
flux than the uncoated membrane, but lower than the
solely TiO2-covered membrane. To get some explanation,
the fouling mechanisms were investigated, to determine
which fouling model (complete pore blocking, intermediate
pore blocking, internal pore blocking, or cake layer for-
mation) best describes the measured flux curves. The
linearized forms of the models (Hermia ; Aryanti et al.
; Veréb et al. ) were fitted onto the measured flux

2
Figure 3 | Decreasing chemical oxygen demand (a) and extractable oil content (b) of the o/w emulsions during the UV irradiation (λmax ∼ 365 nm; UV intensity: 24 mW m ) of the TiO2-,
and TiO2/CNT-covered membranes.

Downloaded from https://iwaponline.com/ws/article-pdf/doi/10.2166/ws.2018.172/497199/ws2018172.pdf

by COLUMBIA UNIVERSITY LIBRARIES user
 Corrected Proof
6 G. Veréb et al. | TiO2/CNT coated photocatalytic membranes for advanced separation of o/w emulsion
Figure 4 | Representative flux curves measured during the filtration of o/w emulsions with different membranes (a) and the calculated filtration resistances (b).
curves, and the correlation coefficients were determined
(Figure 5).
As can be seen in Figure 5, utilization of the uncoated
membrane resulted in the formation of a cake layer on the
surface – which was a significant barrier for water flow
due to the hydrophobicity of the oil layer – and caused the
observed intensive flux reduction during the filtration. In
all other cases, cake layer formation was not dominant,
resulting slower flux reduction, and the slightly fouled
pores of the produced photocatalyst layers can be easily pur-
ified by UV- or solar irradiation. For the confirmation, the
photocatalytic cleanability of the modified membranes
were also investigated. After 24 h of UV-A irradiation, the
original water flux was entirely recovered both in case of
TiO2-, and TiO2/CNT-covered membranes. From the point
of the retention (during the filtration), in all cases, >98%
Figure 5 | Correlation coefficients of the fitted fouling models.
Downloaded from https://iwaponline.com/ws/article-pdf/doi/10.2166/ws.2018.172/497199/ws2018172.pdf
by COLUMBIA UNIVERSITY LIBRARIES user
Water Supply | in press | 2018
purification efficiencies were measured for COD and extrac-
table oil content as well, and there was no significant
difference between the different membranes.
DISCUSSION
According to the literature, from the point of the photocata-
lytic efficiency, the optimal CNT content of TiO2/CNT
composites is determined mostly as 1–20 wt% (Wang et al.
; Yu et al. ; Yen et al. ; Gao et al. ;
Woan et al. ; Vajda et al. ; Réti et al. , ),
and is strongly dependent on the contaminants and several
surface and structural properties of the composite com-
ponents. Based on the observed significant beneficial effect
of 1 wt% CNT content on membrane filtration and the
wide literature of TiO2/CNT composite photocatalysts,
different CNT contents, surface modification of the CNTs,
or hydrothermally synthesized composites may lead to
more effective o/w emulsion separation and/or advanced
self-cleaning photocatalytic membranes. Detailed investi-
gations of the optimisation of TiO2/CNT ratio, the
utilization of modified/functionalized CNT, and the incor-
poration of the composites into membrane materials are
also highly promising in the field of o/w emulsion separ-
ation, as similar investigations already resulted improved
properties in case of other kind of water contaminants
(Bai et al. ; Esfahani et al. ; Irfan et al. ).
Additionally, it must be noted that, in long-term utilization,
 Corrected Proof
7 G. Veréb et al. | TiO2/CNT coated photocatalytic membranes for advanced separation of o/w emulsion
the widely used polymeric membrane materials (even the
UV resistant membranes) can be damaged by highly reactive
hydroxyl radicals, which are produced during photocatalytic
applications. For example, Dzinun et al. recently published
(Dzinun et al. ) that UV irradiation slightly decreased
the stability of the TiO2/PVDF membrane after 30 days’
exposure, which was mainly attributed to the formation of
surface cracks. However, there was no Ti leaching from
the membrane. On the basis of these considerations,
highly chemical resistant membranes, such as polytetrafluor-
oethylene or ceramic membranes also have potential for
future investigations.
CONCLUSIONS
Both TiO2 and CNT coatings resulted in significant
reduction of total resistances during the ultrafiltration of
oil-in-water emulsions. Surprisingly, the TiO2/CNT compo-
site modified membrane resulted in by far the highest flux
and therefore the lowest total resistance; moreover, the
ratio of reversible and irreversible resistances was also
the most beneficial in the case of the composite covered
membrane. In addition, the composite had increased
photocatalytic activity (both for oily and water-soluble
contaminants), which is beneficial from the point of regener-
ation properties of the contaminated membranes. Based on
the presented results, detailed investigations about the utiliz-
ation of TiO2/CNT modified membranes in o/w emulsion
separation are highly promising.
ACKNOWLEDGEMENTS
This project was supported by the János Bolyai Research
Scholarship of the Hungarian Academy of Sciences and by
the UNKP-18-4 New National Excellence Program of the
Ministry of Human Capacities. The authors are grateful for
the financial support provided by the Hungarian Science
and Research Foundation (NKFI-K112096, 2017-2.3.7-TÉT-
IN-2017-00016) and by the Hungarian State and the
European Union (EFOP-3.6.2-16-2017-00010).
Downloaded from https://iwaponline.com/ws/article-pdf/doi/10.2166/ws.2018.172/497199/ws2018172.pdf
by COLUMBIA UNIVERSITY LIBRARIES user
Water Supply | in press | 2018
REFERENCES
Abadi, S. R. H., Sebzari, M. R., Hemati, M., Rekabdar, F. &
Mohammadi, T.  Ceramic membrane performance in
microfiltration of oily wastewater. Desalination 265 (1–3),
222–228.
Aryanti, N., Wardhani, D. H. & Supandi, S.  Flux profiles and
mathematical modelling of fouling mechanism for
ultrafiltration of konjac glucomannan. Scientific Study and
Research: Chemistry and Chemical Engineering 17 (2),
125–137.
Bai, H., Zan, X., Zhang, L. & Sun, D. D.  Multi-functional
CNT/ZnO/TiO2 nanocomposite membrane for concurrent
filtration and photocatalytic degradation. Separation and
Purification Technology 156, 922–930.
Bowen, W. R., Calvo, J. I. & Hernández, A.  Steps of
membrane blocking in flux decline during protein
microfiltration. Journal of Membrane Science 101 (1),
153–165.
Chakrabarty, B., Ghoshal, A. K. & Purkait, M. K. 
Ultrafiltration of stable oil-in-water emulsion by
polysulfone membrane. Journal of Membrane Science 325 (1),
427–437.
Chakrabarty, B., Ghoshal, A. K. & Purkait, M. K.  Cross-flow
ultrafiltration of stable oil-in-water emulsion using
polysulfone membranes. Chemical Engineering Journal 165
(2), 447–456.
Chang, Q., Zhou, J.-e., Wang, Y., Liang, J., Zhang, X., Cerneaux, S.,
Wang, X., Zhu, Z. & Dong, Y.  Application of ceramic
microfiltration membrane modified by nano-TiO2 coating in
separation of a stable oil-in-water emulsion. Journal of
Membrane Science 456, 128–133.
Dzinun, H., Othman, M. H. D., Ismail, A. F., Puteh, M. H.,
Rahman, M. A. & Jaafar, J.  Stability study of PVDF/TiO2
dual layer hollow fibre membranes under long-term UV
irradiation exposure. Journal of Water Process Engineering
15, 78–82.
Esfahani, M. R., Tyler, J. L., Stretz, H. A. & Wells, M. J. M. 
Effects of a dual nanofiller, nano-TiO2 and MWCNT, for
polysulfone-based nanocomposite membranes for water
purification. Desalination 372, 47–56.
Fischer, K., Grimm, M., Meyers, J., Dietrich, C., Gläser, R. &
Schulze, A.  Photoactive microfiltration membranes via
directed synthesis of TiO2 nanoparticles on the polymer
surface for removal of drugs from water. Journal of
Membrane Science 478, 49–57.
Gao, B., Chen, G. Z. & Li Puma, G.  Carbon nanotubes/
titanium dioxide (CNTs/TiO2) nanocomposites prepared by
conventional and novel surfactant wrapping sol–gel methods
exhibiting enhanced photocatalytic activity. Applied
Catalysis B: Environmental 89 (3–4), 503–509.
Hermia, J.  Constant pressure blocking filtration law:
application to power law non-newtonian fluids. Transactions
of the Institution of Chemical Engineers 60, 183–187.
 Corrected Proof
8 G. Veréb et al. | TiO2/CNT coated photocatalytic membranes for advanced separation of o/w emulsion
Hoffmann, M. R., Martin, S. T., Choi, W. & Bahnemann, D. W.
 Environmental applications of semiconductor
photocatalysis. Chemical Reviews 95 (1), 69–96.
Irfan, M., Basri, H., Irfan, M. & Lau, W.-J.  An acid
functionalized MWCNT/PVP nanocomposite as a new
additive for fabrication of an ultrafiltration membrane with
improved anti-fouling resistance. RSC Advances 5 (116),
95421–95432.
Islam, M. S., McCutcheon, J. R. & Rahaman, M. S.  A high flux
polyvinyl acetate-coated electrospun nylon 6/SiO2 composite
microfiltration membrane for the separation of oil-in-water
emulsion with improved antifouling performance. Journal of
Membrane Science 537, 297–309.
Kertész, S., Cakl, J. & Jiránková, H.  Submerged hollow fiber
microfiltration as a part of hybrid photocatalytic process for
dye wastewater treatment. Desalination 343, 106–112.
Kovács, I., Veréb, G., Kertész, S., Beszédes, S., Hodúr, C. &
László, Z.  Investigation of surface and filtration
properties of TiO2 coated ultrafiltration polyacrylonitrile
membranes. Water Science & Technology 77 (4), 931–938.
Masoudnia, K., Raisi, A., Aroujalian, A. & Fathizadeh, M. 
A hybrid microfiltration/ultrafiltration membrane process for
treatment of oily wastewater. Desalination and Water
Treatment 55 (4), 901–912.
Padaki, M., Surya Murali, R., Abdullah, M. S., Misdan, N.,
Moslehyani, A., Kassim, M. A., Hilal, N. & Ismail, A. F. 
Membrane technology enhancement in oil–water separation.
A review. Desalination 357, 197–207.
Rashid, M. H. & Ralph, S. F.  Carbon nanotube membranes:
synthesis, properties, and future filtration applications.
Nanomaterials (Basel) 7 (5), 99–126.
Réti, B., Mogyorósi, K., Dombi, A. & Hernádi, K. 
Substrate dependent photocatalytic performance of TiO2/
MWCNT photocatalysts. Applied Catalysis A: General 469,
153–158.
Réti, B., Major, Z., Szarka, D., Boldizsár, T., Horváth, E., Magrez,
A., Forró, L., Dombi, A. & Hernádi, K.  Influence of TiO2
phase composition on the photocatalytic activity of TiO2/
MWCNT composites prepared by combined sol-gel/
hydrothermal method. Journal of Molecular Catalysis A:
Chemical 414, 140–147.
Shokrkar, H., Salahi, A., Kasiri, N. & Mohammadi, T. 
Prediction of permeation flux decline during MF of oily
wastewater using genetic programming. Chemical
Engineering Research and Design 90 (6), 846–853.
Smajda, R., Kukovecz, A., Hopp, B., Mohl, M., Kónya, Z. &
Kiricsi, I.  Morphology and N2 permeability of multi-wall
carbon nanotube – teflon membranes. Journal of
Nanoscience and Nanotechnology 7 (4–5), 1604–1610.
First received 26 June 2018; accepted in revised form 1 October 2018. Available online 17 October 2018
Downloaded from https://iwaponline.com/ws/article-pdf/doi/10.2166/ws.2018.172/497199/ws2018172.pdf
by COLUMBIA UNIVERSITY LIBRARIES user
Water Supply | in press | 2018
Vajda, K., Mogyorosi, K., Nemeth, Z., Hernadi, K., Forro, L.,
Magrez, A. & Dombi, A.  Photocatalytic activity of
TiO2/SWCNT and TiO2/MWCNT nanocomposites with
different carbon nanotube content. Physica Status Solidi B
248 (11), 2496–2499.
Van der Bruggen, B.  Chemical modification of
polyethersulfone nanofiltration membranes: a review.
Journal of Applied Polymer Science 114 (1), 630–642.
Veréb, G., Kovacs, I., Zakar, M., Kertész, S., Hodúr, C. & László,
Z.  Matrix effect in case of purification of oily waters by
membrane separation combined with pre-ozonation.
Environmental Science and Pollution Research Article
In Press. doi:10.1007/s11356-018-1287-9.
Wang, W., Serp, P., Kalck, P. & Faria, J. L.  Photocatalytic
degradation of phenol on MWNT and titania composite
catalysts prepared by a modified sol–gel method. Applied
Catalysis B: Environmental 56 (4), 305–312.
Woan, K., Pyrgiotakis, G. & Sigmund, W.  Photocatalytic
carbon-nanotube-TiO2 composites. Advanced Materials 21
(21), 2233–2239.
Yang, H. C., Pi, J. K., Liao, K. J., Huang, H., Wu, Q. Y., Huang, X. J.
& Xu, Z. K.  Silica-decorated polypropylene
microfiltration membranes with a mussel-inspired
intermediate layer for oil-in-water emulsion separation.
ACS Applied Materials and Interfaces 6 (15), 12566–12572.
Yen, C. Y., Lin, Y. F., Hung, C. H., Tseng, Y. H., Ma, C. C., Chang,
M. C. & Shao, H.  The effects of synthesis procedures on
the morphology and photocatalytic activity of multi-walled
carbon nanotubes/TiO2 nanocomposites. Nanotechnology
19 (4), 045604.
Yi, X. S., Yu, S. L., Shi, W. X., Sun, N., Jin, L. M., Wang, S., Zhang,
B., Ma, C. & Sun, L. P.  The influence of important factors
on ultrafiltration of oil/water emulsion using PVDF
membrane modified by nano-sized TiO2/Al2O3. Desalination
281, 179–184.
Yin, J. & Zhou, J.  Novel polyethersulfone hybrid
ultrafiltration membrane prepared with SiO2-g-(PDMAEMA-
co-PDMAPS) and its antifouling performances in oil-in-water
emulsion application. Desalination 365, 46–56.
Yu, Y., Yu, J. C., Yu, J.-G., Kwok, Y.-C., Che, Y.-K., Zhao, J.-C.,
Ding, L., Ge, W.-K. & Wong, P.-K.  Enhancement of
photocatalytic activity of mesoporous TiO2 by using carbon
nanotubes. Applied Catalysis A: General 289 (2), 186–196.
Zhao, Y., Sun, Y., Tian, C., Gao, B., Wang, Y., Shon, H. & Yang, Y.
 Titanium tetrachloride for silver nanoparticle-humic
acid composite contaminant removal in coagulation-
ultrafiltration hybrid process: floc property and membrane
fouling. Environmental Science and Pollution Research 24
(2), 1757–1768.
Sys Rev Pharm. 2017;8(1):39-47 Review Article
A multifaceted Review journal in the field of Pharmacy

Emulsion Micro Emulsion and Nano Emulsion: A Review

Santosh Nemichand Kale1,Sharada Laxman Deore2
Department of Pharmaceutical Sciences, Shri Jagdish Prasad Jhabarmal Tibrewala University, Rajasthan, INDIA.
1

Department of Pharmacognosy, Govt College of Pharmacy, Amravati, INDIA.

2

ABSTRACT Key words: Emulsion, Micro emulsion, Nano emulsion, Surface tension,
Lipid dosage forms are attractive delivery systems for hydrophobic drug Zeta potential.
molecules. Emulsion is one of the popular system since many decades.
Correspondence:
Pharmaceutical applications of emulsions widened especially after micro
and nano-emulsion emergence. This paper is an attempt to summarise Sharada Laxman Deore
comparative aspects like definition, theories, types, methods of prepara- Department of Pharmacognosy, Govt College of Pharmacy, Amravati, INDIA.
tions, advantages, disadvantages and methods of analysis of emulsion, Email: sharudeore_2@yahoo.com
micro-emulsion and nano-emulsion. DOI : 10.5530/srp.2017.1.8

INTRODUCTION
Emulsions are dispersions made up of two immiscible liquid phases
which are mixed using mechanical shear and surfactant. Amphiphilic
surface-active molecules are called as ‘surfactants’ which are responsible
to reduce naturally existing attractive forces in the form of surface ten-
sion.1 Choice of surfactant on the basis of hydrophilic-lipophilic balance
(HLB) value or critical packing parameter (CPP) helps to develop de-
sired emulsion. Surfactants with low HLB3-8 values as shown in Figure
1 are useful to form W/O emulsion and that of with high HLB values8-18
are used to form O/W emulsion.2-4 critical packing parameter (CPP) is
ratio of hydrophilic and hydrophobic parts of surfactant molecule. CPP
also gives idea of nature of aggregates.5 recently two new concepts are
emerged in emulsion that is as follows:
Micro-emulsion is clear, thermodynamically stable, isotropic liquid mix-
ture. It is prepared by using oil, water, surfactant and a co-surfactant. It
incorporates very small size particles up to nano size as compared to
conventional emulsion.6,7 IUPAC defines micro-emulsion as dispersion
made of water, oil, and surfactant(s) that is an isotropic and thermo-
dynamically stable system with dispersed domain diameter varying ap-
proximately from 1 to 100 nm, usually 10 to 50 nm.5-6 Nano-emulsions
are very similar to micro-emulsions that are dispersions of nano scale
particles but obtained by mechanical force unlike to micro-emulsions
which forms spontaneously.7,8
droplets. The film avoids the contact and subsequent coalescence of the
dispersed phase; a tougher and more pliable film will result in greater
physical stability of the emulsion.2
•• Surface tension theory- this theory assumes that, when surface tension
between two phases lessens then emulsion can be formed
•• Repulsion theory- this theory explains a phenomenon by which emul-
sifying agent forms a film containing globules on one of the immis-
cible phases with ability to repel each other. Thus immiscible globules
remain suspended in the dispersion medium due to these repulsive
forces.
•• Viscosity modification- according to this theory emulsifying agents
raises viscosity of the medium and thus miscible viscous suspension
of globules is formed.
Types3
Following are different types of emulsions
Water-in-oil (w/o)
Oil-in-water (o/w)
Water-in-oil-in-water (w/o/w)
Oil-in-water-in-oil (o/w/o)

1.4.2 Emulsion Methods of preparations4

•• Dry Gum Method: Triturate mixture of emulsifier and oil with addi-
Emulsions are dispersions made up of two immiscible liquid phases tion of water which will form primary emulsion. Further add water to
which are mixed using mechanical shear and surfactant. Particle size of
dilute and mix continuously to form emulsion.
this conventional emulsion grows continuously with time and hence fi-
•• Wet Gum Method: Initially triturate oil with water and then with
nally separation occurs at gravitational force thus these emulsions are
emulsifier to form primary emulsion. Further add water, dilute and
thermodynamically unstable.
mix to form emulsion.
Theories: According to the surface-tension theory of emulsification, the
emulsifiers or stabilizers lower the interfacial tension between the two •• In Situ Soap Method: Take oil and lime water (calcium hydroxide so-
immiscible liquids, reducing the repellent force between the two liq- lution). Mix with stirring to form emulsion.
uids and diminishing the attraction between the molecules of the same •• Mechanical Method: Take oil, water and emulsifier together, mix well
liquid2 The oriented-wedge theory assumes the formation of mono- and stir by machine to form emulsion
molecular layers of the emulsifying agent which are curved around the
droplet of the internal phase of an emulsion. This theory is based on the Advantages5
presumption that certain emulsifying agents orient themselves around a •• To solubilise hydrophobic or oil soluble drugs
liquid droplet in a manner reflective of their solubility in that particular •• To enhance drug absorption through
liquid. The plastic-or interfacial-film theory describes that the emulsify- •• To enhance topical absorption of drugs
ing agent is located at the boundary between the water and oil, form- •• To mask the disagree able taste and odour of drugs
ing a thin film by being adsorbed onto the surface of the internal phase •• To enhance palatability of nutrient oils

Systematic Reviews in Pharmacy, Vol 8, Issue 1, Jan-Dec, 2017 39

 Kale et al.: Emulsion, Micro-emulsion and Nano Emulsion
Disadvantages
•• Less stable as compared to other dosage forms
•• Possesses short shelf-life
•• Creaming, cracking (breaking), flocculation and phase inversion are
common problems observed during storage of emulsions (Figure 2)
Micro-emulsion
IUPAC defines micro-emulsion as dispersion made of water, oil, and
surfactant(s) that is an isotropic and thermodynamically stable system
with dispersed domain diameter varying approximately from 1 to 100
nm, usually 10 to 50 nm.
Theories: Interfacial theory
It is also called as mixed film or dual film theory. Surfactant and co-sur-
factant together forms complex film (Figure 3) at the oil water interface
and thus creates generation of micro emulsion droplets.6-8
Solubilization theory
This theory assumes that swollen micellar system forms in the form of
micro emulsion. Oil solubilised due to normal micelle formation and
water solubilised by reverse micelle formation. Phase diagram (Figure 4)
is generally useful to understand this theory assumption.7-9
Thermodynamic theory
When interfacial tension between two immiscible phases reduces to zero,
causes spontaneous formation of micro emulsions and formed negative
free energy helps to make emulsion thermodynamically stable.
Microemulsions are also called as transparent emulsion, swollen mi-
celle and micellar solution. self-microemulsifying drug delivery system
(SMEDDS) is also one of the popular term for microemulsion mediated
delivery of drugs. The term microemulsion is coined by T. P. Hoar and
J. H. Shulman when they used this term to describe multiphase system
consisting of water, oil, surfactant and alcohol, which forms a transpar-
ent solution in 1953. But discovery of microemulsions confirms well be-
fore use in the form white spirit and or liquid waxes.
Types
•• According to Winsor, there are four types of micro emulsion phases
exists in equilibrium, these phases are referred as Winsor phases.10-13
they are:
•• Winsor I (two phase system): upper oil layer exists in equilibrium with
lower (o/w) micro emulsion phase
•• Winsor II(two phase system): the upper(w/o) micro emulsion exists in
equilibrium with lower excess water.
•• Winsor III (three phase system): middle bi-continuous phase of o/w
and w/o called) exists in equilibria with upper phase oil and lower
phase water.
•• Winsor IV (single phase system):it forms homogenous mixture of oil,
water and surfactant
•• The R-ratio is one of the characterisation concepts which was first pro-
posed by Winsor to explain the influence of amphiphiles and solvents
on interfacial curvature. R-ratio compares the affinity for an amphi-
phile to disperse into oil, to its affinity to dissolve in water. If one phase
is favoured, the interfacial region forms a definite curvature. Thus, if R
> 1, the interface increases its area of contact with oil while decreasing
its area of contact with water. Thus oil becomes the continuous phase
and the corresponding characteristic system is type II (Winsor II).
Similarly, a balanced interfacial layer is represented by R = 1.
40
Preparation methods
•• Phase titration method: Micro emulsion was prepared by dispers-
ing required quantity of drug in appropriate quantity of oil which
is required for the solubilisation of drug.14 The mixture was homog-
enized and accurately weighed quantity of surfactant: co surfactant
blends was added in small portion with stirring to it.15-18 The blends
were mixed thoroughly using magnetic stirrer and drop wise double
distilled water added to it with continuous stirring around 10 minute
and rate of stirring was optimized as per requirement of particle size.19
•• Phase inversion temperature method (PIT): Phase inversion of mi-
cro emulsions means conversion of O/W to W/O system (Figure 5) by
adding excess of the dispersed phase or by rising temperature when
non-ionic surfactant are used to change spontaneous curvature of the
surfactant which brings system near to minimal surface tension and
to form fine dispersed oil droplets.20-22 This method shows extreme
changes in particle size which further leads to changes in in-vivo and
in-vitro drug release pattern.23-25
Advantages25-27
•• It is very easy to prepare and scale up due to spontaneous formation
ability
•• It is very good system to raise rate of absorption as well as bio avaibil-
ity by eliminating interfering variations
•• It able to improve solubility of lipophilic drugs
•• It is thermodynamically more stable system as compared to conven-
tional system and hence suitable for long term use
•• It can be preferred to develop sustained and controlled releases drug
system
•• It is best system to minimise first pass metabolism.
Disadvantages 28-29
•• Additional use of excess amount of surfactant and co-surfactant in-
creases cost
•• Excess concentration of surfactants can lead to mucosal toxicity
Composition
The major components of micro emulsion system are:
1) Oil phase
2) Surfactant (Primary surfactant)
3) Co-surfactant (Secondary surfactant)
4) Co-Solvent
Commonly used components of Micro-emulsion 5-15
Components Examples
Oils Saturated fatty acid-lauric acid, myristic acid, capric acid
Unsaturated fatty acid-oleic acid, linoleic acid, linolenic acid
Fatty acid ester-ethyl or methyl esters of lauric, myristic and
oleic acid.
Example: (GlycerylMono-anddicaprate, isopropylmyristate,
sunflower oil, soyabean oil, Labrafac ®CC), surfactant
(Cremophor ®EL, Labrasol®)
Systematic Reviews in Pharmacy, Vol 8, Issue 1, Jan-Dec, 2017
 Kale et al.: Emulsion, Micro-emulsion and Nano Emulsion
Surfactants Polyoxyethylene/Polysorbate/Tween 20,40,60,80,;
Sorbitan Monolaurate (Span),
Soybean lecithin,
egg lecithin,
lyso lecithin,
Sodium dodecyl sulphate (SDS),
Sodium bis (2–ethylhexyl) sulphosuccinate (Aerosol OT),
Dioctyl sodium sulphosuccinate,
Sodium dexoycholate,
Labrasol (Polyethylene glycol–8–caprylic acid),
TritonX–100
Co-surfactants Ethanol, propanol, Isopropanol, butanol, pentanol, hexanol,
sorbitol, n–pentanoic acid, n–hexanoic acid, n–butylamine,
sec, butylamine, 2-aminopentane, 1,2-butanediol, Propylene
glycol.
Some newly evolved cosurfactants are as follows :
Cremophor RH40 (polyoxyl 40 hydrogenated castrol oil),
Plurololeique (polyglyceryl–6–dioleate),
Plurolisostearique (isostearic acid of polyglycerol),
Distearoylphosphatidyl ethanolamine–N–poly
(ethyleneglucol)2000 (DSPE–PEG),
Poloxamer
Polyoxythylene–10–oelyl ether (Brij 96V)
Polysorbate 80 (Tween80)
Span 20
Sodium monohexyl phosphate
Sodium monooctyl phosphate
N,N–Dimethyl dodecylamine–N–oxide (DDNO)
N,N–Dimethyl octylamine–N–oxide (DONO)
Cinnamic alcohol
Cinnamic aldehyde
Oil phase
Oil phase is second most important vehicle after water due to its prop-
erties to solubilise lipophilic drug molecules and improve absorption
through lipid layer present in body.6 Oil has unique property of pen-
etrating cell wall and hence very useful for lipophilic active drug delivery.
Swelling of tail group region of the surfactant is influence by oil phase.
Such penetration is to greater extent in case of short chain alkanes as
compared to long chainalkanes. 7
Example
Saturated fatty acids: lauric, myristic and capric acid
Unsaturated fatty acids: oleic acid, linoleic acid and linolenic acid
Fatty acid esters: ethyl or methyl esters of lauric, myristic and oleic acid
Surfactants
During the preparation of the microemulsion,surfactantmustbeableto
reducetheinterfacialtensionnearest to zeroto facilitate dispersion of all
components. These surfactants can be:
Non-ionic
Anionic
Cationic
Zwitterionic,
Nature of surfactants helps in deciding stability of microemulsion.Di-
pole and hydrogen bond interactions stabilizes non-ionic surfactant and
electrical double layer stabilizes ionic surfactants.
Ionic surfactants are also affected by salt concentration. Hence ionic sur-
Systematic Reviews in Pharmacy, Vol 8, Issue 1, Jan-Dec, 2017
factants being sensitive in stability issues and due to toxicity concern, are
generally nor preferable. But non-ionic surfactants can produce nontoxic
pharmaceutical dosage forms and hence more popular.8
Surfactants with HLB values3-6 are useful in preparation of W/O micro
emulsion and surfactants with higher HLB values8-18 are useful in prepa-
ration of O/W micro emulsion. Surfactants with more than 20 HLB val-
ues are acts as co-surfactant to reduce concentrations of surfactants to a
acceptable limit and micro emulsion formation.9-10
Examples of non-ionicsurfactants:
Polyoxyl 35 castor oil (Cremophor EL)
Polyoxyl 40 hydrogenated castor oil (Cremophor RH 40)
Polysorbate20(Tween20)
Polysorbate80(Tween80)
d-α-tocopherolpolyethylene glycol1000succinate(TPGS)
SolutolHS-15
Sorbitanmonooleate(Span80)
Polyoxyl40 stearate,
PolyglycolyzedglycerideslikeLabrafilM-1944CS,LabrafilM-2125CS,
Labrasol, Gellucire 44/14, etc.
Co-surfactants
It is studied that high concentrations of single-chain surfactants are re-
quired to reduce the O/W interfacial tension to a level to enable a spon-
taneous formation of a microemulsion. However, if co-surfactants are
added then with minimum concentration of surfactants different curva-
tures of interfacial film can be formed to generate stable micro emulsion
composition. (11-16) Co surfactants raises the fluidity of the interface
due to presence of fluidizing groups like unsaturated bonds, then demol-
ishes liquid crystalline or gel structure and alters the HLB value in such
way to cause spontaneous formation of micro emulsion.23-29
Example:
Short chain alcohols like ethanol to butanol
Short chain glycols like propylene glycol
Medium chain alcohols like amines or acids
Co-solvents
Co-solvents are organic solvents like ethanol, propylene glycol (PG),
and polyethylene glycol (PEG) which helps to dissolve relatively high
concentrations of surfactants as well as lipid soluble drugs. Hence co-
solvents are also considered as co-surfactants.
Nano-emulsion
Nano-emulsions are very similar to micro-emulsions that are disper-
sions of nano scale particles but obtained by mechanical force unlike to
micro-emulsions which forms spontaneously.7-8
Theories
The combination of two theories, turbulence and cavitations, explain the
droplet size reduction during the homogenization process of nano emul-
sions.30-31
Types32-33
Oil-in-water (o/w)
Water-in-oil (w/o)
Oil-in-water-in-oil (o/w/o)
Water-in-oil-in-water (w/o/w)
41
 Kale et al.: Emulsion, Micro-emulsion and Nano Emulsion

Preparation methods
•• High energy emulsification method: ultra sonication and high pres-
sure homogenization
•• Low energy emulsification: Phase inversion temperature method,
solvent displacement method and phase inversion composition meth-
od
•• High-Pressure Homogenization: specially designed high- pressure
homogenization instrument is used to produce nano sized particles.
At very high pressure (500 to 5000 psi), oil phase and water phase are
allowed to force through small inlet orifice.34 Hence extremely small
size particles are created due to strong turbulence and hydraulic shear.
But this method requires high temperature and energy. Pressure, ho-
mogenization cycles are directly responsible for particle size.35 Higher
the pressure and higher the homogenization cycles, smallest is particle
size. This method is easy to scale up.
•• Microfluidization: In this method also specially designed device
called as micro fluidizer is used to create high-pressure (500 to
20000psi). Initially prepare coarse emulsion of by mixing oil and wa-
ter phase.36 This device consists of interaction chamber of small micro
channels through which coarse emulsion is forced to an impingement
area to form nano size fine particles followed by filteration to obtain
uniform particles.37
•• Ultrasonication: This method is based on principle that when coarse
emulsion is in ultrasonic field and external pressure is increased, cavi-
tations threshold also increases to limit where fine nano size particles
are formed.38
•• Phase inversion method: This method uses principle of phase inver-
sion temperature which is the temperature at which phase transition
occurs. Low temperature favours O/W emulsions and high tempera-
ture favours W/O emulsion. Rapid cooling and heating cycles produc-
es fine particles. Non-ionic surfactant like polyoxyethylene becomes
lipophilic at high temperature and hydrophilic at low temperature due
to dehydration of the polymer chain.
•• Spontaneous Emulsification: This method is simple and uses volatile
organic solvent composition of oil, water, lipophilic and hydrophilic
surfactant. This composition is allowed to mix homogenously by mag-
netic stirring. Then evaporate the water-miscible solvent under vac-
cum to obtain nano-emulsion.39
•• Solvent Evaporation Technique: In this technique, initially mix drug
with organic solvent using suitable surfactant and prepare O/W emul-
sion by mixing continuous phase. Then evaporate organic solvent
under vacuum or heating or at atmospheric conditions to obtain mi-
crospheres loaded with drug followed by centrifugation or filtration.40
•• Hydrogel Method: This method shares similarity with solvent evapo-
ration method. High shear forces are used to form nano-emulsion of
drug- solvent which is miscible with the drug anti-solvent.

Parameters Emulsion1-5 Microemulsion6-15 Nano emulsion35-42

Appearance (Figure 6) Turbid Clear Clear

Figure 6: Appearance comparison between emulsion, micro emulsion and nano emulsion.
Particle size 1 to 20 mm 1 and 100 nm 1 and 100 nm
Formation Mechanical shear Self assembly Mechanical shear
Stability Thermodynamically Thermodynamically Stable Kinetically stable/ metastable, thermodynamically unstable
unstable, Kinetically Long shelf life
Stable
Phases Biphasic Monophasic Monophasic
Viscosity High Low Low (about 1 cP at room temperature)
Preparation cost Higher cost Lower cost Higher cost
Interfacial Tension High Ultra Low Ultra low (less than 10 dyn cm−1)
Optical isotropy Anisotropic Isotropic Isotropic
Light scattering Less scattering Strong Strong
multiple scattering of visible multiple scattering of visible light hence white
light hence white

42 Systematic Reviews in Pharmacy, Vol 8, Issue 1, Jan-Dec, 2017

 Kale et al.: Emulsion, Micro-emulsion and Nano Emulsion

Concentration of High High (20% by weight) Low (3-10% by weight)

surfactant
Types Oil in Water (O/W) or Oil- in- water micro (a) oil in water nano emulsion in which oil is dispersed in the
direct emulsion emulsion or winsor I continuousaqueousphase,
Water in Oil (W/O) or Water – in oil micro (b)waterinoilnano emulsion in
reverse emulsion emulsion or winsor II which water droplets are dispersed in continuous oil phase,
Bi-continuous micro and (c) bi-continuous nano emulsions
emulsion or winsor III
Single phase homogeneous
mixture or winsor IV
Formulation methods Continental or Dry Phase Titration Method High energy emulsification methods
Gum Method (Water Titration Method) Low energy emulsification methods
Wet Gum Method Phase inversion method
Bottle or Forbes Bottle
Method
Theories Surface tension theory Thermodynamic theory Surface tension theory
Repulsion theory Solubilisation theory Interfacial theory
Viscosity modification Interfacial theory
theory
Oriented-Wedge Theory
Interfacial film theory
Parameters Physical appearance
Globule size determination
Conductivity test
Dye-solubility test
Refractive index measurement
Filter paper test
Dilution test
Drug content determination
Poly disperity determination
pH determination
Viscosity determination
Scattering Techniques
Percent Transmittance (Limpidity Test) determination
Zeta potential determination
In-vitro and in-vivo drug release determination
Stability studies

Advantages41-42
•• It is used to improve water solubility and ultimate bioavailability of lipophilic drugs

Systematic Reviews in Pharmacy, Vol 8, Issue 1, Jan-Dec, 2017 43

 Kale et al.: Emulsion, Micro-emulsion and Nano Emulsion

Figure 1: HLB value showing role of surfactants. Figure 3: Interfacial theory (film formation).

Figure 2: Stability issues with emulsions. Figure 4: Phase diagram based on solubilisation theory.

Figure 5: Phase inversion method approach.

44 Systematic Reviews in Pharmacy, Vol 8, Issue 1, Jan-Dec, 2017

 Kale et al.: Emulsion, Micro-emulsion and Nano Emulsion

•• It is preferred dosage form to incorporate GIT irritation causing ac- Dis-advantages43-44

tive drugs. •• The major disadvantage is cost of fabrication of nano emulsion is ex-
•• It is preferred dosage form to incorporate first pass metabolism medi- pensive. Ostwald ripening is the major issue in nano emulsions.
ated degradation prone drugs. Comparative analysis of emulsion, micro emulsion and nano-emul-
•• Stability issues like creaming, flocculation, coalescence, and sedimen- sion: and Characterisation Parameters for Various Emulsions Fol-
tation are rarely observed in nano-emulsion lowing are various parameters useful to evaluate micro emulsions:
Parameters Discussion
Visual Inspection Appearance, homogeneity, transparency, optical clarity, and fluidity.1
Cross-polarizing To exclude liquid crystalline systems it is necessary to confirm absence of birefringence by cross polarizing microscope.1
Microscope testing
Limpidity Test Limpidity is defined as an acceptable level of visible impurities. Spectrophotometeric determination of percent transmittance
directly proportional to limpidity.1-2
Globule size The globule size is very essential aspect to differentiate emulsion, micro emulsion and nano emulsion. It can be determined by
light scattering method and or photomicroscope method.3
Viscosity The rheological properties play an important role in stability as viscosity is immediately affected by storage conditions. It can be
determined by Brookfield digital viscometer.2
pH The pH of the formulation not only affects the stability of the emulsions but also alters the solubility and bioavailability of the
drug through micro emulsion at the site of permeation. PH meter is useful to determine PH of emulsions.3
Specific gravity Determine the specific gravity by a capillary gravity bottle method. Gravity settling can be used alone only to treat loose,
unstable emulsions; however, for stronger emulsions, gravity settling separates water from oil only when used with other
treating methods that increase water droplet size by destabilizing the emulsion and creating coalescence.4
Study of microstructure Electron Microscopy is the most important technique for the study of micro structures of micro-emulsions because it directly
produces images at high resolution and it can capture any co-existent structure and micro-structural transitions.5
Identification test for type of Dilutability test: emulsion can be diluted in 1:10 and 1:100 ratios with double distilled water to check if the system shows any
micro emulsions signs of separation.24
Staining test: Water soluble dye such as methylene blue or amaranth is when added to emulsion and if drop is observed under
microscope, background looks blue/redand globule appears colourless shows o/w emulsion.24
Zeta potential measurement Electrical charges on particles influence the rate of flocculation and as well as bioavailability. Negative, positive or neutral nature
depends on excipients and drug’s own charges. Zeta potential between + 30 to -30 is acceptable.5
Phase Behaviour Studies Phase behaviour studies are essential for the study of efficiency of different surfactant systems which can be determined by
phase diagram. Oil phase, water phase and surfactant/co-surfactant mixture ratios by keeping concentration of one component
or the ratio of two components constant provides useful structural organization of final emulsion. One approach to characterize
thesemulticomponentsystemsisbymeansof pseudoternary diagrams that combine more than one component in the vertices of
the ternary diagram.6
Polydispersity Size, shape and dynamics of the components can be determined by small-angle X-ray scattering (SAXS), small-angle neutron
scattering (SANS), static and dynamic light scattering techniques. Modification of the structure and the composition of the
pseudophases due to dilution can be overcome by measuring intensity of scattered light at different angles. In dynamic light
scattering (DLS) the size distribution of molecules or particles is the property of interest.Here, the distribution describes how
much material there is present of the different size “slices.” Traditionally, this overall polydispersity has also been converted into
an overall polydispersity index PDI which is the square of the light scattering polydispersity. For a perfectly uniform sample, the
PDI would be 0.0
Conductivity O/W emulsions are more conductive, whereas W/O emulsions are non-conductive.
In Vitro Skin Permeation Study For local use of emulsions, skin permeation study is conducted to find the permeation of drug through skin.The study must be
carried out under the guideline compiled by Committee for the Purpose of Control and Supervision of Experiments on Animal
(CPCSEA, Ministry of Culture, and Government of India).
Take the abdominal skins from male Wistar rats weighing 230 ± 20 g (age, 6–8 weeks).Shave hair and excise skin carefully
from the abdominal region of each sacrificed rat. Wash the excised rat skins and examine for integrity, and then store at
4°C for 24h in phosphate -buffersaline pH 6.8 (PBS) until permeation experiments. Perform permeation experiments using
Franz diffusion cells fitted with excised rat skins having epidermal surface outward. The effective diffusion area is about 3.14
cm2(20mmdiameter orifice). Fill the receptor compartment with 12 ml of PBS. The diffusion cell is to be maintained at 37
± 1°C using a re-circulating water bath and the solution inreceptor chamber is stirred continuously at 600 rpm throughout
the experiment. Place the specified amount of formulation gently in a donor chamber. At 1, 2, 4, 6, and 8 h aliquot of 2 mL,
withdraw sample from the receptor compartment for spectrophotometric determination and replace immediately with an
equal volume of fresh PBS. Calculate an average value of three readings of in-vitro permeation data and plot the average
cumulative amount of drug permeated per unit surface area of the skin versus time. Determine the permeability coefficient Kp
(centimetresper hour) by using following equation
Kp ¼ Jss = C donor
Where, Kp is the permeability coefficient, Jss is the flux, and C donor represents the applied drug concentration in the donor
compartment.

Systematic Reviews in Pharmacy, Vol 8, Issue 1, Jan-Dec, 2017 45

 Kale et al.: Emulsion, Micro-emulsion and Nano Emulsion

Nuclear Magnetic Resonance Self-diffusion measurements by Fourier transform pulsed-gradient spin-echo (FT-PGSE) technique provide information on the
Studies: structure, dynamics and mobility of the particles. Self-diffusion coefficients vary in the range of 9 to 12 m2/s.6
Stability Tests Centrifugation stress testing: Stability studies is time consuming process, so accelerated stability test is preferred. Centrifuge
micro emulsion at 5000 and 10,000 rpm for 30min to assess phase separation, phase in version, aggregation, creaming and crack
in go the formulations. Follow same procedure for previously thermally tested emulsions.(1-4)
Freeze-Thaw Cycles (FTC): Store samples at 25°C for 24 h followed by 24 h at −5°C.Repeat three times to access any change in
stability.
Determination of thermal stability: Keep 20 ml of drug-loaded emulsions in a 25 ml transparent borosil volumetric contain erat
three different temperatures, i.e.4°, 25°and40°C, 1°C in BOD for a period of 1 month.
Remove samples periodically for visual inspection to observe any physical changes like loss of clarity, coal essence and turbidity
etc. Observe the samples for the determination of loss of aqueous phase that is an essential part of the emulsion stability.
Long Term Stability: For this, store emulsion samples under ambient conditions for 6 months, and examine periodically
after 1, 3, and 6 months by visual inspection and measurement of percent transmittance, pH, specific gravity, and rheological
evaluation. Follow detail procedure as per ICH guidelines.
In vitro models for intestinal The parallel artificial membrane permeability assay (PAMPA) uses artificial membrane to predict trans-membrane diffusion.
absorption The everted sac and Ussing chamber assay techniques are more superior models than PAMPA as they provide additional
information with respect to intestinal metabolism.

CONFLICT OF INTEREST
There is no conflict of interest.
ABBREVIATIONS USED
nm: Nanometer; mm: Icrometer; GIT: Gastrointestinal tract; mg: Mil-
ligram, O/W: Oil in water; W/O: Water in oil; HLB: Hydrophilic lipo-
philic balance; CPP: Critical packing parameter; CP: Centipoise; PDI:
Polydispersity index; PBS: Phosphate buffer saline; ICH: International
Conference on Harmonisation; BOD: Biological Oxygen Demand.
REFERENCES
1. Allen LV. Ansels Pharmaceutical Dosage forms and drug delivery systems. 8th
edition.2005.
12. Vandamme TF. Microemulsions as ocular drug delivery systems: recent devel-
opments and future challenges. Prog Retin Eye Res. 2002;21(1):15-34.http://
dx.doi.org/10.1016/S1350-9462(01)00017-9.
13. Flanagan J, Singh H. Microemulsions: a potential delivery system forbioactives
in food. Crit Rev Food Sci Nutr. 2006;46(3):221-37.http://dx.doi.org/10.1080/104
08690590956710;PMid:16527754.
14. Ghosh PK, Murthy RS. Micro emulsions: a potential drug delivery system. Curr
Drug Deliv. 2006;3(2):167-80.http://dx.doi.org/10.2174/156720106776359168;P
Mid:16611003.
15. Jadhav KR, Shaikh IM, Ambade KW, Kadam VJ. Applications of micro emulsion
based drug delivery system. Curr Drug Deliv. 2006;3(3):267-73.http://dx.doi.org
/10.2174/156720106777731118;PMid:16848728.
16. Spernath A, Aserin A. Microemulsions as carriers for drugs and nutraceuti-
cals. Adv Colloid Interface Sci. 2006;128-130:47-64.http://dx.doi.org/10.1016/j.
cis.2006.11.016;PMid:17229398.

2. Alexander T Florence and JuergenSiepmann. Modern Pharmaceutics, Vol.1( 17. Boonme P. Applications of micro emulsions in cosmetics. J Cosmet Derma-
Drug and the pharmaceutical sciences vol.188) 5th ed., 2009 Informa health tol. 2007;6(4):223-8. http://dx.doi.org/10.1111/j.1473-2165.2007.00337.x;PM
care. id:18047605.

3. Aulton, Michael E. (Editor) Aulton’s Pharmaceutics: The Design and Manufac-
ture of Medicines (3rd ed.). Churchill Livingstone. 2007;384:390-405.
4. Troy DA, Remington JP, Beringer Paul. Remington: The Science and Practice of
Pharmacy (21st ed.). Philadelphia: Lippincott Williams & Wilkins. 2006;336:886-
87.
5. Khan AY, Talegaonkar S, Iqbal Z, Ahmed FJ, Khar RK. Multiple emulsions: an
overview. Curr Drug Deliv. 2006;3(4):429-43.http://dx.doi.org/10.2174/15672010
6778559056;PMid:17076645.
6. Kumar P, Mittal KL. Handbook of Micro emulsion Science and Technology; 1st
Edn; CRC Press, New York,1999.
7. Tang JL, Sun J, He ZG. Self-Emulsifying Drug Delivery Systems: Strategy
For Improving Oral Delivery of Poorly Soluble Drugs. Current Drug Therapy.
2007;2(1):85-93.http://dx.doi.org/10.2174/157488507779422400.
8. Talegaonkar S, Azeem A, Ahmad FJ, Khar RK, Pathan SA, Khan ZI. Micro-
emulsions: A Novel Approach to Enhanced Drug Delivery. Recent Pat-
ents on Drug Delivery & Formulation. 2008;2(3):238-257.http://dx.doi.
org/10.2174/187221108786241679.
9. Min DI. Neoral: a micro emulsion cyclosporine. J Transpl Coord Review. Erratum
in: J Transpl Coord. 1996;6(2):52.http://dx.doi.org/10.7182/prtr.1.6.1.f04016025h
h795up;PMid:9157923.
10. Tenjarla S. Microemulsions: an overview and pharmaceutical applications. Crit
RevTher Drug Carrier Syst.1999;16(5):461-521.http://dx.doi.org/10.1615/critrevt-
herdrugcarriersyst.v16.i5.20.
11. Lawrence MJ, Rees GD. Micro emulsion-based media as novel drug delivery
systems. Adv Drug Deliv Rev. 2000;45(1):89-121.http://dx.doi.org/10.1016/
S0169-409X(00)00103-4.
18. Narang AS, Delmarre D, Gao D. Stable drug encapsulation in micelles and mi-
croemulsions. Int J Pharm. 2007;345(1-2):9-25.http://dx.doi.org/10.1016/j.ijphar
m.2007.08.057;PMid:17945446.
19. Santos P, Watkinson AC, Had graft J, Lane ME. Application of micro emulsions in-
dermal and transdermal drug delivery. Skin Pharmacol Physiol. 2008;21(5):246-
59.http://dx.doi.org/10.1159/000140228;PMid:18562799.
20. Azeem A, Rizwan M, Ahmad FJ, Khan ZI, Khar RK, Aqil M, et al. Emerging role
of micro emulsions in cosmetics. Recent Pat Drug Deliv Formul. 2008;2(3):275-
89. Review.http://dx.doi.org/10.2174/187221108786241624;PMid:19075913.
21. Karasulu HY. Microemulsions as novel drug carriers: the formation, stability,
applications and toxicity. Expert Opin Drug Deliv. 2008;5(1):119-35.http://dx.doi.
org/10.1517/17425247.5.1.119;PMid:18095932.
22. Gasco MR, Priano L, Zara GP. Chapter 10 - Solid lipid nano particles and micro
emulsions for drug delivery The CNS. Prog Brain Res. 2009;180:181-92.http://
dx.doi.org/10.1016/S0079-6123(08)80010-6.
23. Azeem A, Khan ZI, Aqil M, Ahmad FJ, Khar RK, Talegaonkar S. Micro emul-
sions as a surrogate carrier for dermal drug delivery. Drug Dev Ind Pharm.
2009;35(5):525-47.http://dx.doi.org/10.1080/03639040802448646;PM
id:19016057.
24. Patel D, Sawant KK. Self micro-emulsifying drug delivery system: formulation
development and biopharmaceutical evaluation of lipophilic drugs. Curr Drug
Deliv. 2009;6(4):419-24. .http://dx.doi.org/10.2174/156720109789000519;PM
id:19534704.
25. Mehta SK, Kaur G. Microemulsions as carriers for therapeutic mol-
ecules. Recent Pat Drug Deliv Formul. 2010;4(1):35-48.http://dx.doi.
org/10.2174/187221110789957282.
26. Zoumpanioti M, Stamatis H, Xenakis A. Microemulsion-based organogelsas-

46 Systematic Reviews in Pharmacy, Vol 8, Issue 1, Jan-Dec, 2017

 Kale et al.: Emulsion, Micro-emulsion and Nano Emulsion

matrices for lipase immobilization. Biotechnol Adv. 2010;28(3):395-406.http://
dx.doi.org/10.1016/j.biotechadv.2010.02.004;PMid:20156546.
27. Russell-Jones G, Himes R. Water-in-oil microemulsions for effective transder-
mal delivery of proteins. Expert Opin Drug Deliv. 2011;8(4):537-46.http://dx.doi.
org/10.1517/17425247.2011.559458;PMid:21413905.
28. Furlanetto S, Cirri M, Piepel G, Mennini N, Mura P. Mixture experiment method-
sin the development and optimization of micro emulsion formulations. J Pharm
Biomed Anal. 2011;55(4):610-7.http://dx.doi.org/10.1016/j.jpba.2011.01.008;PM
id:21295935.
29. Hath out RM, Woodman TJ. Applications of NMR in the characterization of phar-
maceutical micro emulsions.J Control Release. 2012;161(1):62-72.http://dx.doi.
org/10.1016/j.jconrel.2012.04.032;PMid:22579644.
30. David Julian Mc Clements. Nano emulsions versus micro emulsions: terminol-
ogy, differences, and similarities. Soft matter. 2012;8:1719-1729;http://dx.doi.
org/10.1039/C2SM06903B.
31. Patrick F, Valerie A, Jens R, Angelika K. Nano-emulsion formation by emul-
sion phase inversion. Colloids and Surfaces A: Physico chem. Eng Aspects.
2004;251(1):53-8.http://dx.doi.org/10.1016/j.colsurfa.2004.09.029.
32. Hörmann K, Zimmer A. Drug delivery and drug targeting with parenteral lip-
idnano emulsions - A review. J Control Release. 2016;223:85-98.http://dx.doi.
org/10.1016/j.jconrel.2015.12.016;PMid:26699427.
33. Fonseca-Santos B, Gremião MP, Chorilli M. Nanotechnology-based drug de-
livery systems for the treatment of Alzheimer’s disease. Int J Nanomedicine.
2015;10:4981-5003.http://dx.doi.org/10.2147/IJN.S87148;PMid:26345528
PMCid:PMC4531021.
34. Yukuyama MN, Ghisleni DD, Pinto TJ, Bou-Chacra NA. Nano emulsion: pro-
cess selection and application in cosmetics - a review. Int J Cosmet Sci.
2016;38(1):13-24.http://dx.doi.org/10.1111/ics.12260;PMid:26171789.
35. Thukral DK, Dumoga S, Mishra AK. Solid lipid nano particles: promising thera-
peutic nano carriers for drug delivery. Curr Drug Deliv. 2014;11(6):771-91.http://
dx.doi.org/10.2174/156720181106141202122335;PMid:25469779.
36. Pawar KR, Babu RJ. Lipid materials for topical and transdermal delivery of nano
emulsions. Crit Rev Ther Drug Carrier Syst. 2014;31(5):429-58.http://dx.doi.
org/10.1615/CritRevTherDrugCarrierSyst.2014010663.
37. Ganta S, Talekar M, Singh A, Coleman TP, Amiji MM. Nano emulsions in transla-
tional research-opportunities and challenges in targeted cancer therapy. AAPS
Pharm Sci Tech. 2014;15(3):694-708.http://dx.doi.org/10.1208/s12249-014-0088-
9;PMid:24510526PMCid:PMC4037485.
38. Cerpnjak K, Zvonar A, Gašperlin M, Vrečer F. Lipid-based systems as a
promising approach for enhancing the bioavailability of poorly water-soluble
drugs. Act a Pharm. 2013;63(4):427-45.http://dx.doi.org/10.2478/acph-2013-
0040;PMid:24451070.
39. Odriozola-Serrano I, Oms-Oliu G, Martín-Belloso O. Nano emulsion-based de-
livery systems to improve functionality of lipophilic components. Front Nutr.
2014;5(1):24.
40. Mc Clements DJ. Nano emulsion-based oral delivery systems for lipophil-
ic bioactive components: nutraceuticals and pharmaceuticals. Ther Deliv.
2013;4(7):841-57.http://dx.doi.org/10.4155/tde.13.46;PMid:23883127.
41. Wu Y, Li YH, Gao XH, Chen HD. The application of nano emulsion in dermatol-
ogy: an overview. J Drug Target. 2013;21(4):321-7.http://dx.doi.org/10.3109/1061
186X.2013.765442;PMid:23600746.
42. Kotta S, Khan AW, Pramod K, Ansari SH, Sharma RK, Ali J. Exploring oral nano
emulsions for bioavailability enhancement of poorly water-soluble drugs. Expert
Opin Drug Deliv. 2012;9(5):585-98.http://dx.doi.org/10.1517/17425247.2012.668
523;PMid:22512597.
43. Rajpoot P, Pathak K, Bali V. Therapeutic applications of nano emulsion based
drug delivery systems: a review of patents in last two decades. Recent Pat
Drug Deliv Formula. 2011;5(2):163-72.http://dx.doi.org/10.2174/18722111179547
1427;PMid:21361870.
44. Sarker DK. Engineering of nano emulsions for drug delivery. Curr Drug De-
liv. 2005;2(4):297-310. http://dx.doi.org/10.2174/156720105774370267;PM
id:16305433.

GRAPHICAL ABSTRACT
SUMMARY
• Emulsions (macroemulsion) are dispersions made up of two immiscible
liquid phases which are mixed using mechanical shear and surfactant.
• Micro-emulsion is defined as dispersion made of water, oil, and
surfactant(s) that is an isotropic and thermodynamically stable system
with dispersed domain diameter varying approximately from 1 to 100 nm,
usually 10 to 50 nm.
• Nano-emulsions are very similar to micro-emulsions that are disper¬sions
of nano scale particles but obtained by mechanical force unlike to micro-
emulsions which forms spontaneously.
• Microemulsions and nanoemulsions are promising delivery for poorly wa-
ter soluble drugs.
• Microemulsion or nanoemulsion mediated topical, transdermal, muco-
adhesive and oral delivery of drugs is more promising with benefit of
AUTHOR PROFILE extended release and enhanced bioavaibility.

Dr. S. L Deore: Is working as Assistant Professor in Govt. College of Pharmacy, Amravati. She has pub-
lished 03 books and more than 50 research papers. She has grabbed Research Promotion Grant (RPS) and
awarded with Career award for Young Teacher (CAYT) by AICTE. Her areas of research are extraction and
isolation of phytochemicals, planar chromatography, intellectual property rights, structural elucidation of
phytochemicals, neutraceutical development and traditional medicine screening.

Systematic Reviews in Pharmacy, Vol 8, Issue 1, Jan-Dec, 2017 47

 Journal of Petroleum Science and Engineering 171 (2018) 974–981

Contents lists available at ScienceDirect

Journal of Petroleum Science and Engineering

journal homepage: www.elsevier.com/locate/petrol

Experimental study on a fine emulsion flooding system to enhance oil T

recovery for low permeability reservoirs
Haishun Fenga, Wanli Kanga,b,∗, Liming Zhanga, Jun Chena, Zhe Lia, Qiong Zhoua, Hairong Wua
a
Research Institute of Enhanced Oil Recovery, China University of Petroleum (Beijing), Beijing, China
b
School of Petroleum Engineering, China University of Petroleum (East China), Qingdao, Shandong, China

A R T I C LE I N FO A B S T R A C T

Keywords: Numerous studies and field application tests have shown that emulsification is an important mechanism to
Fine emulsion flooding improve oil recovery. Fine emulsion (FE) with small droplets can improve oil recovery by displacing residual oil
Low permeability reservoir after water flooding at a low cost. In this work, a series of core displacement experiments were conducted to
Enhanced oil recovery compare the effectiveness of different chemical flooding for crude oil. Then, the oil-water interfacial tension
Micromodel tests
(IFT), viscosity and rheological properties were studied thoroughly to understand the displacement mechanism
by using an interfacial tensiometer, a viscometer or a rheometer. Finally, micromodel flooding tests were per-
formed to demonstrate the suitability and effectiveness of FE flooding for oil recovery for low permeability
reservoirs. The displacement results show that the oil recovery efficiency can reach 16.8% after water flooding
by the optimum FE flooding system. The FE flooding system has viscoelastic properties, strong emulsifying
performance and stability. Such behavior can reduce the IFT value to the magnitude of 10−1 mN/m and improve
the mobility ratio. The displacement mechanism of FE enhanced oil recovery (EOR) is that emulsification can
improve the displacement efficiency and increase the swept efficiency. The micromodel tests indicate that the
emulsification mechanisms include emulsification carrying-on and the performance control of the O/W emul-
sion. The FE flooding system has powerful EOR potential for low permeability reservoirs.

1. Introduction Therefore, the formation of water-in-oil (W/O) emulsions has been

As most of oilfields enter the high water cut stage, crude oil pro-
duction is declining. Low-permeability reservoirs are the most pro-
mising development direction for improving oil production. In such
reservoirs, the water displacement efficiency is low, and the residual oil
saturation is high, which leads to low oil recovery (Zhao et al., 2015;
Shangguan et al., 2015; Yuan et al., 2014; Tian et al., 2012; Dou and
Yang, 2012). Conventional methods to improve the recovery of low-
permeability reservoirs have advantages and disadvantages, but all
have failed to enhance oil recovery. Therefore, further investigation is
required to provide theoretical guidance for the efficient development
of low-permeability reservoirs.
Researchers have investigated the details of low oil-water interfacial
tension (IFT) in low permeability reservoirs, which is similar to that of
conventional oil. Alternatively, the formation of oil-in-water (O/W)
emulsions has also been suggested as a possible recovery mechanism,
and researchers have hypothesized that O/W emulsions may plug water
channels, leading to an improved volumetric sweep of the reservoir
(Bryan and Kantzas, 2009; Dong et al., 2009; Mirchi et al., 2017).
proposed as a possible recovery mechanism (Liu et al., 2016). These
emulsions are expected to be more viscous than water, thus improving
the mobility ratio and sweep efficiency of the flood. To improve the oil
displacement efficiency, the crude oil emulsifying ability of the dis-
placement system must be improved. Liu et al. have developed an al-
kali/surfactant oil displacement technology (Dong et al., 2009; Liu
et al., 2006a; Chen et al., 2013). The natural shearing action of a porous
medium forms an O/W emulsion. The droplets are driven out of the
formation by a displacing fluid (Liu et al., 2006b, 2007). Bryan et al.
concluded that W/O and O/W emulsions are formed simultaneously
during flooding (Bryan et al., 2008). Compared with emulsification
entrainment, the Jamin effect of a W/O emulsion on a pore throat is
stronger, and the recovery is higher (Bryan and Kantzas, 2007). Kang
concluded that the synergistic effects of alkali and surfactant are ben-
eficial for the emulsification of crude oil (Kang et al., 2012). When a
number of droplets jammed a large pore throat, the displacement fluid
entered inaccessible pores to improve the sweep efficiency (Wang et al.,
2006). The oil displacement results showed that the effect of emulsion
flooding is better than the effects of alkali flooding, surfactant flooding

∗
Corresponding author. School of Petroleum Engineering, China University of Petroleum (East China), Qingdao, 266580, China.
E-mail address: kangwanli@upc.edu.cn (W. Kang).

https://doi.org/10.1016/j.petrol.2018.08.011
Received 19 March 2018; Received in revised form 3 July 2018; Accepted 6 August 2018
Available online 08 August 2018
0920-4105/ © 2018 Elsevier B.V. All rights reserved.
H. Feng et al.
and polymer flooding (Kang et al., 2009).
Most of the previously mentioned studies have focused on heavy-oil
reservoirs with medium and high permeability, and the optimization of
the surfactant flooding system has been based solely on the reduction of
IFT (Watson and Trahan, 2014; Chen and Zhao, 2015). However, there
have been few studies on optimum oil displacement agents using a fine
emulsion (FE). The evaluation criteria for a crude oil emulsifier, the
mechanism of emulsification in the oil displacement process, and the
relationships among emulsifying capacity and interfacial activity and
viscosity are still unclear. In this study, we used a FE that was pre-
viously characterized in our laboratory. The optimum compounded
system was composed of the emulsifier OP-10 and the stabilizer AP-P4.
A series of core displacement experiments was used to evaluate the
different formulations. Then, the oil-water IFT, viscosity and rheolo-
gical properties were studied using an interfacial tensiometer, a visc-
ometer or a rheometer. Finally, micromodel flooding was performed to
assess the suitability and effectiveness of FE flooding in low perme-
ability reservoirs.
2. Experimental
2.1. Materials
The oil was obtained from Changqing Oilfield, (China). The visc-
osity, density, and four components of the oil were analyzed and are
shown in Table 1. The oil had a viscosity of 3.4 mPa s and a density of
0.83 g/cm3 at 50 °C. Alkylphenol polyoxyethylene (OP-10) was an in-
dustrial product provided by Haian Petrochemical Co., Ltd. The AP-P4
polymer was purchased from Sichuan Guangya Chem Co., Ltd and its
chemical structure is shown in Fig. 1. In addition, the salinity of the
simulated formation water is 22784 mg/L (Table 2).
2.2. Oil displacement experiments
The core was 2.5 cm in diameter and 7.5 cm in length. The experi-
mental procedure was as follows: first, the water permeability of the
core was measured in the presence of the formation water, and the core
was subsequently saturated with the crude oil. The injected oil was
continued until water production almost ceased (oil saturation >
99%). Then, the core was flooded by the formation water until the oil
production became negligible (oil saturation < 1%). Followed by a 0.5
pore volume (PV) chemical slug, the chasing water was injected until no
oil produced. The injection rate of the slugs was 0.2 mL/min.
2.3. Emulsification test
Eight milliliters of the aqueous solution containing different con-
centrations of emulsifier was added to a tube, and then, 2 mL of crude
oil was carefully transferred to the top of the aqueous solution using a
syringe to minimize the mechanical disturbance. For a set of tubes, each
tube was turned very gently from a vertical to a horizontal position to
mix the oil and water phases at 50 °C. The emulsions were examined
using a XSJ-2 microscope (Chongqing Photoelectric Instrument Co.,
Ltd.). The emulsion droplet size distributions were analyzed using an
LS-13-320 laser diffraction particle sizing analyzer (Beckman Coulter,
America).
Table 1
Viscosity, density and components of the crude oil sample.
Density (g/cm3,50 °C) Viscosity (mPa·s, 50 °C) Saturate (%)
0.83 3.4 73.68
975
Journal of Petroleum Science and Engineering 171 (2018) 974–981
2.4. Rheological measurement
Viscometric measurements were carried out using an Anton Paar
MCR 302 rheometer at 50 °C with shear rate ranging from 0.1 to 1000
s−1. Dynamical shear measurements were performed with the same
rheometer and measuring system at 50 °C in order to determine the loss
(G″) and storage (G′) moduli of the FE flooding as a function of fre-
quency ranging from 0.01 to 10 Hz. It should be noted that all dyna-
mical measurements were preceded by an oscillation strain sweep to
identify the linear viscoelastic region. All of the measurements were
performed in the linear response region.
2.5. Determination of interfacial tension
Determination of the interfacial tensions between surfactants aqu-
eous solution and crude oil were measured at 50 °C using the spinning
drop interfacial tensiometer of dataphysics SVT20.
2.6. Micromodel test
A glass-etched micromodel was used as the porous medium to in-
vestigate the microscopic displacement mechanisms of FE flooding. The
steps for the micromodel test are as follows: (1) saturating micromodel
with brine; (2) displacing brine with oil; (3) flooding brine until the
water cut reaches up to 98%; (4) 0.5 PV chemical flooding at 0.003 mL/
min; (5) resuming brine injection until the water cut up to 98% again.
All the dynamic processes were videotaped.
3. Results and discussion
3.1. Performance of FE oil displacement
The optimum FE flooding system 1% OP-10 + 0.25% AP-P4 was
used in our laboratory (Feng et al., 2017). To compare the effectiveness
of different chemical flooding for crude oil, the formulations 1% OP-10,
1% OP-10 + 0.25% AP-P4, and 0.25% AP-P4 were selected and a series
of core displacement experiments (core 1 - core 3) were conducted. The
injected volume of the chemical solution was maintained at 0.5 pore
volume (PV); the other parameters of the cores, chemical formulations,
and flooding results are summarized in Table 3 and Fig. 2.
Table 3 and Fig. 2 show that the chemical flooding oil recovery of
the three formulations are 10.5%, 14.2% and 16.9% after water
flooding. The chemical oil recovery of the 1% OP-10 + 0.25% AP-P4
system reached 16.9%, which was higher than that of the others. This
indicates that the FE flooding system has a better effect on improving
oil recovery.
Fig. 3 shows the resistance factor responses as a function of che-
mical flooding injected in core flooding tests. Ding et al. indicates that
the following positive correlation exists between chemical oil recovery
and the resistance factor: the higher the resistance factor is, the greater
the swept volume and the greater the chemical oil recovery are (Ding
et al., 2010). The 0.25% AP-P4 polymer system has good viscosity,
which can effectively improve the mobility ratio. It has the highest
resistance factor and a better oil displacement effect. However, for low
permeability reservoirs, the higher the resistance factors are, the worse
the field injection performance is, and the higher the requirements for
ground injection equipment are (Wang et al., 2017). The 1% OP-10
surfactant system has moderate ability to reduce the IFT. It can reduce
the resistance factor and has the lowest chemical oil recovery. The 1%
Aromatic (%) Asphaltene (%) Resin (%)
18.51 0.32 7.48
H. Feng et al. Journal of Petroleum Science and Engineering 171 (2018) 974–981

Fig. 1. Chemical structure of AP-P4 polymer.

Table 2
The formulation of Changqing Oilfield formation water.
Na++K+ Mg2+ Ca2+ Ba2+ Cl−(mg/L) OH−(mg/L) Total
(mg/L) (mg/L) (mg/L) (mg/L) (mg/L)

7075 79 170 2606 12754 30 22784

OP-10 + 0.25% AP-P4 FE system has the advantages of both surfactant

and polymer. It has an appropriate resistance factor and the best en-
hanced oil recovery (EOR) efficiency. Therefore, considering the in-
jection performance and EOR effect, the FE flooding system has good
application potential in low permeability reservoirs.

3.2. Oil displacement mechanism of FE flooding

How does the FE flooding system affect pressure drop and chemical
oil recovery? Wang et al. (2017) indicates that EOR mechanisms in low Fig. 2. Displacement results of different chemical flooding systems.
permeability reservoirs mainly involve oil flows, oil swelling, IFT re-
duction, and emulsion formation. To thoroughly understand the me-
chanism, the emulsification, oil-water IFT, viscosity and rheological
properties of different formulations were studied as follows.

3.2.1. Emulsification properties

Previous studies have shown that adding a polymer to a chemical
formulation significantly improves the emulsion stability, and the
emulsion droplet sizes are widely distributed (Xu et al., 2017;
Pajouhandeh et al., 2017). The emulsification performances of the
different formulations used in this study are shown in Fig. 4. To
quantitatively characterize the emulsion stability, the emulsification
degree of water (RE) is introduced and calculated using the following
formula:
VOW − Vdw
RE = × 100
VOW (1)
where Vow is the initial volume of water and Vdw is the volume of water
after demulsification. In the emulsification test, the higher the RE value
is, the longer the duration of the emulsion is. Fig. 4 shows the stability Fig. 3. Resistance factor response in core displacement experiments.
of the emulsions and the variation in RE with time.
Fig. 4a and b shows photographs of each tube before and after
emulsification for the different formulations. The emulsions are dark
brown. The formulations of 1% OP-10 and 1% OP-10 + 0.25% AP-P4

Table 3
Displacement results of various chemical flooding systems.
Core Length (cm) Diameter(cm) Porosity (%) PV (cm3) Permeability (10−3μm2) Formulations Oil recovery (%)

Water flooding Chemical flooding Total

Core 1 7.5 2.54 17.5 6.65 13.7 1% OP-10 50.2 10.5 60.7
Core 2 7.5 2.54 17.9 6.80 15.3 0.25% AP-P4 50.5 14.2 64.7
Core 3 7.5 2.54 17.2 6.53 10.6 1% OP-10 + 0.25% AP-P4 49.3 16.9 66.2

976
H. Feng et al. Journal of Petroleum Science and Engineering 171 (2018) 974–981

Fig. 4. Variation in RE curves for different formulations: (a) original, (b) 0 min,
Fig. 5. Photomicrographs and droplet size distribution curves.
(c) 10 min, (d) 100 min, and (e) 240 min.

have satisfactory dispersion abilities that allow oil droplets to be

quickly dispersed into solution to form a uniform emulsion. However,
the 0.25% AP-P4 system has poor dispersibility to crude oil. After re-
peated turning up and down, a large amount of oil droplet particles
with uneven grain size can be observed in the middle of the vial and the
oil-water interface was obvious. After a short time, most of the oil se-
parated to the top of the tube, exhibiting poor emulsification ability. As
Fig. 4c shows, the emulsion exhibits demulsification in the tube of 1%
OP-10, and a clear interface between the oil and the aqueous phases is
observed after 10 min, indicating the instability of the emulsion. In the
tube of 0.25% AP-P4, the oil and water are already separated and only a
small amount of oil droplets are suspended in the water due to polymer
viscosity. Fig. 4d shows that different degrees of demulsification occur
for all formulations after standing for 100 min. Fig. 4e shows the results
after standing for 240 min, at which time the emulsions have separated,
and a relatively small amount of emulsion transition zone is present in
the test tube. Overall, 1% OP-10 + 0.25% AP-P4 has the strongest
emulsion stability, and 0.25% AP-P4 has poor emulsification ability.
Thus, only the RE variation curves with time for two formulations are Fig. 6. IFT curves for different formulations.
shown in Fig. 4. Initially, each formulation has an RE of 100%, in-
dicating that both formulations have a satisfactory ability to form an
emulsion. Over time, RE first decreases and then stabilizes. After formation and stability of an emulsion (Wei et al., 2016). The IFT be-
standing for 240 min, the RE is 3.5% for 1%OP-10 and 20.5% for 1% haviors between the crude oil and the formulations were investigated,
OP-10 + 0.25% AP-P4. Therefore, the FE flooding system has the better and the results are displayed in Fig. 6.
stability. As expected, the IFT curves exhibit a similar trend, i.e., the IFT
Emulsion stability is inversely proportional to the size of the dis- decreases with time and then remains relatively constant at a new level
persed droplets, and a sample with a smaller droplet size is considered after 25 min. The 1% OP-10 system has the lowest IFT, and the 0.25%
more kinetically stable (Kumar et al., 2017). Therefore, the particle size AP-P4 system has a higher IFT value than that of the 1% OP-10 system.
of emulsion droplets should be investigated in a comprehensive eva- When adding polymer, the IFT increases slightly and the magnitude of
luation of emulsification properties. The microscopy and laser particle change is insignificant. The IFT values are approximately 0.269 mN/m,
size analysis results are shown in Fig. 5. 0.301 mN/m and 12.303 mN/m for 1% OP-10, 1% OP-10 + 0.25% AP-
Fig. 5 shows photomicrographs of the emulsions of different for- P4, and 0.25% AP-P4, respectively. However, none of the formulations
mulations and the droplet size distribution curves. The droplet size and reduce the IFT to an ultralow level (on the order of 10−3 mN/m). This
uniformity of the emulsions are significantly varied. The size of the result indicates that the effect of improving oil recovery by reducing IFT
emulsion droplets formed by the FE decreases with the addition of is not as obvious when the IFT is reduced to a certain value. Similar
polymer, and the droplet size distribution becomes more concentrated. results have been reported by the other researchers (Liu et al., 2017).
The average diameter of the emulsion droplets of the two samples are
6.12 μm and 1.50 μm. The results show that the synergistic effect be-
3.2.3. Viscosity properties
tween the surfactant and polymer is crucial for oil emulsification in
Viscosity is another important parameter for a chemical system in
brine and can greatly improve the droplet size distribution and increase
the EOR process and is closely related to emulsion stability (Sun et al.,
the stability of the emulsion. This result is in accordance with that
2018; Zhou et al., 2017). Therefore, viscosity changes in the polymer at
obtained by Xu et al. (2017).
different concentrations before and after the addition of 1% OP-10 were
investigated.
3.2.2. IFT behavior Fig. 7 shows that AP-P4 is a hydrophobically associating polymer
The IFT between oil and water is an important parameter for a that initially has a slow increase in viscosity with increasing con-
chemical system in an EOR process and is closely related to the centration. The viscosity increases rapidly once the concentration

977
H. Feng et al.
Fig. 7. Viscosity changes of the polymer for different concentrations.
reaches the critical association concentration. When the 1% OP-10
surfactant (far greater than the critical micelle concentration) is added
to the polymer, the viscosity of the polymer system at different con-
centrations decreases significantly. When the polymer concentration is
0.25%, the viscosity reduction rate is as high as 80.1%. As the surfac-
tant forms numerous micelles in the solution, the polymer's hydro-
phobic chain is solubilized in the micelle. The network structure of the
polymer is then broken down and the viscosity sharply decreases (Pei
et al., 2017).
3.2.4. Rheological properties
The rheological properties of the formulations are comprehensively
studied in this section (Zhou et al., 2017; Li et al., 2016). Fig. 8 shows
shear viscosity as a function of shear rate for different formulations. The
viscosity of the 1% OP-10 system remained substantially constant as
shear rate increased, which indicates Newtonian fluid properties. The
viscosity curves of the other two formulations generally fall into two
distinct stages. The first stage is observed at low shear rates in which
viscosity remains constant with shear rate. As shear rate increases, a
transition occurs at the second stage, i.e., viscosity decreases linearly
with an increasing shear rate, suggesting a pronounced shear-thinning
behavior. The change in the aggregate structure of the polymer solution
depends on shear conditions. At lower shear rates, the steady-state
shear cannot destroy the aggregate structure, and the viscosity of the
system does not change. During the second stage, however, the mole-
cular chains of the polymer become deformed, and the aggregate
structure is destroyed, leading to a shear-thinning behavior.
The storage (G′) and loss (G″) moduli of the formulations as
Fig. 8. Shear viscosity changes for different formulations.
978
Journal of Petroleum Science and Engineering 171 (2018) 974–981
Fig. 9. Viscoelastic property changes as a function of frequency.
functions of frequency are shown in Fig. 9. G″ is greater than G′ over the
entire evaluated frequency range, indicating the viscous fluid behavior
of all the formulations. G′ and G″ clearly increase with increasing for-
mula viscosity.
Numerous studies have shown that the emulsions formed during the
oil displacement process have a positive effect on oil displacement ef-
ficiency (Zhou et al., 2017; Li et al., 2016). Fig. 10 and Fig. 11 examine
the viscoelastic properties of the emulsions produced by the emulsifi-
cation test.
Fig. 10 shows the variation in shear viscosity with increasing shear
rate for different emulsions. The viscosity of 0.25% AP-P4 decreases
linearly with shear rate, suggesting a pronounced shear-thinning be-
havior. The viscosity of 1% OP-10 + 0.25% AP-P4 decreases slowly
with the increase of shear rate, and then remains basically unchanged,
indicating that the emulsion of the emulsifying system is stable. Com-
pared to the behavior shown in Fig. 8, the viscosity of the emulsion has
varying degrees of reduction; thus, the O/W emulsion migrates more
easily than the FE flooding system under shear conditions. Notably, the
viscosity of the 1% OP-10 emulsion first decreases rapidly because the
stability of the emulsion is poor, and the viscosity is very low after
demulsification. When the shear rate exceeds 80 s−1, the new emulsion
is generated due to the high shear rate, and the viscosity slowly in-
creases.
Fig. 11 shows that G′ of the 1% OP-10 + 0.25% AP-P4 emulsion is
greater than its G″ over a certain frequency range, indicating viscoe-
lastic properties. Compared with Fig. 9, the elastic modulus G′ of the
emulsion is clearly increased, indicating that the emulsion maintains a
profile control performance mechanism in the oil displacement process.
G″ of the 0.25% AP-P4 system is greater than G′ over the entire
Fig. 10. Shear viscosity changes for different formulations.
H. Feng et al.
Fig. 11. Viscoelastic property changes as a function of frequency.
evaluated frequency range, which is consistent with Fig. 9. G′ and G″ of
the 1% OP-10 emulsion increase, indicating the formation of the
emulsion.
In summary, OP-10 surfactant, AP-P4 polymer and the FE flooding
system have better interface, viscosity and emulsifying properties, re-
spectively. The mechanism of EOR is primarily divided into two as-
pects: increasing swept volume and improving oil displacement effi-
ciency. The surfactant system efficiently reduces the IFT. The capillary
number increased after the surfactant was injected, which reduces the
work done by moving small oil droplets through the narrow pores and
greatly improves oil displacement efficiency. The polymer system with
good viscosity effectively improves the mobility ratio and allows the
displacing liquid to enter the residual oil pores, greatly improving the
swept volume. The FE flooding system has good emulsification prop-
erties. Emulsification improves displacement efficiency, increasing
swept volume. Additionally, the FE flooding system also benefits from
the advantages of both the polymer and surfactant to improve oil re-
covery.
3.3. Micro-displacement mechanisms of FE flooding
To thoroughly understand the emulsification mechanism of the FE
flooding system, micromodel tests were conducted, and the results are
Fig. 12. Micromodel images (a) at initial oil saturation, (b) after 0.5 PV water flooding, (c) after 10 PV water flooding, (d) after 0.5 PV FE flooding, and (e) after
extended water flooding.
979
Journal of Petroleum Science and Engineering 171 (2018) 974–981
shown in Fig. 12 (Wang et al., 2006).
Fig. 12a illustrates the micromodel with the initial oil saturation.
After 0.5 PV water flooding as shown in Fig. 12b, a significant channel
is formed along the main flow direction, leaving a large volume of
untouched oil, particularly in the diagonal region. Fig. 12c shows the
remaining oil distribution after 10 PV water flooding. The remaining oil
in the upper right section of the model has been partially swept, but the
overall sweep volume remains low. Fig. 12d shows the response of a 0.5
PV FE injected. The unswept region of the water flooding in the lower
left section of the model is displaced. Small emulsion droplets are ob-
served, and the swept volume is improved. Fig. 12e shows the re-
maining oil distribution after extended water flooding. Most of the
crude oil in the micromodel is produced, in addition to a small amount
of residual oil. Compared with the results shown in Fig. 12c and e, the
swept volume and oil displacement efficiency are greatly improved
with continued water flooding.
Based on the above results, we conclude that the emulsification
mechanism is the most important oil displacement mechanism of FE
flooding (Liu et al., 2017). Therefore, the interaction between the FE
flooding system and oil was further investigated in a microscopic dis-
placement experiment as shown in Fig. 13.
Fig. 13a shows the emulsification, drawing deformation and the
improving flow ratio when the FE is injected. Fig. 13b shows a partially
enlarged view of Fig. 13a. Emulsion droplets and oil bands of different
sizes formed by drawing are clearly observed in the figure. The emul-
sification mechanism includes predominantly emulsification carrying
and emulsion profile control. Emulsification causes the remaining oil to
detach and form an O/W emulsion that flows easily. Emulsion droplets
of a certain size and viscosity are continuously migrating and accu-
mulating to produce a specific profile control effect.
Fig. 13c and d describe the emulsification carrying property of the
oil displacement system. The mechanism of reducing the IFT causes
residual oil deformation in the pores of the rock, and the emulsification
mechanism causes the oil film to detach from the rock surface and form
tiny droplets. Emulsification carrying causes the O/W emulsion to flow
easily, without stopping or adhering to the pore surface; thus, the
emulsion can flow and improve the oil displacement efficiency.
Fig. 13e and f describe the profile control performance of emulsions.
Emulsion droplets with a certain particle size and viscosity are con-
tinuously gathered in the high water flooding seepage channel, which
has a specific plugging effect on the crude oil to the adjacent medium
and low permeability channels. As the remaining oil moves, it is
H. Feng et al.
Fig. 13. Micromodel images of one location during the FE flooding stage.
continuously deformed, stretched, peeled and emulsified into a small-
droplet emulsion. The profile control of the emulsion greatly improves
the swept volume of the displacement system.
4. Conclusions
FE displacement results show that chemical oil recovery can reach
10.5%–16.9% after water flooding. The oil recovery factor of the 1%
OP-10 + 0.25% AP-P4 system reached 16.2%. The viscoelastic FE
flooding system exhibits a strong emulsifying performance and emul-
sion stability. It reduces the IFT value to the order of 10−1 mN/m and
the good emulsification improves the mobility ratio. The displacement
mechanism of the FE flooding system suggests that emulsification can
improve the displacement efficiency and the sweep efficiency. The EOR
mechanisms in porous medium are the emulsification carrying property
and the profile control performance of the O/W emulsion. The FE
method has a promising EOR potential for low permeability reservoirs.
Acknowledgments
This work is financially supported by National Science and
Technology Major Project (2017ZX05009-004), the Science Foundation
of China University of Petroleum, Beijing (No. 2462015YJRC033), and
the National Natural Science Foundation of China (No. 51774309).
References
Bryan, J., Kantzas, A., 2007. Enhanced heavy-oil recovery by alkali-surfactant flooding.
980
Journal of Petroleum Science and Engineering 171 (2018) 974–981
In: SPE Annual Technical Conference and Exhibition, Anaheim, Califomia, USA, SPE
110738.
Bryan, J., Kantzas, A., 2009. Potential for alkali-surfactant flooding in heavy oil reservoirs
through oil-in-water emulsification. J. Can. Petrol. Technol. 48, 37–46.
Bryan, J., Mai, A., Kantzas, A., 2008. Investigation into the processes responsible for
heavy oil recovery by alkali-surfactant flooding. In: SPE/DOE Improved Oil Recovery
Symposium, Tulsa, Oklahoma, USA, SPE 113993.
Chen, Z., Zhao, X., 2015. Enhancing heavy-oil recovery by using middle carbon alcohol-
enhanced waterflooding, surfactant flooding, and foam flooding. Energy Fuels 29,
2153–2161.
Chen, L., Zhang, G., Ge, J., Jiang, P., Tang, J., Liu, Y., 2013. Research of the heavy oil
displacement mechanism by using alkaline/surfactant flooding system. Colloid.
Surface. Physicochem. Eng. Aspect. 434, 63–71.
Ding, B., Zhang, G., Ge, J., Liu, X., 2010. Research on mechanisms of alkaline flooding for
heavy oil. Energy Fuels 24, 6346–6352.
Dong, M., Ma, S., Liu, Q., 2009. Enhanced heavy oil recovery through interfacial in-
stability: a study of chemical flooding for Brintnell heavy oil. Fuel 88, 1049–1056.
Dou, H., Yang, Y., 2012. Further understanding on fluid flow through multi-porous media
in low-permeability reservoirs. Petrol. Explor. Dev. 39, 674–682.
Feng, H., Kang, W., Wu, H., Li, Z., Chen, J., Zhou, Q., 2017. Study on the relationship
between emulsion stability and droplet dynamics of a spontaneous emulsion for
chemical enhanced oil recovery. J. Dispersion Sci. Technol.
Kang, W., Liu, S., Meng, L., 2009. Microscopic mechanism of spontaneous emulsification
displacement. J. Oil Gas Technol. (J. Jianghan Petroleum Inst.) 31, 99–102.
Kang, W., Liu, Y., Meng, L., 2012. Screening of emulsified viscosity reducer on heavy oil
and effect evaluation of oil displacement. Petrol. Geol. Recovery Effic. 19, 59–61.
Kumar, N., Gaur, T., Mandal, A., 2017. Characterization of SPN Pickering emulsions for
application in enhanced oil recovery. J. Ind. Eng. Chem. 54, 304–315.
Li, K., Jing, X., He, S., Ren, H., Wei, B., 2016. Laboratory study displacement efficiency of
viscoelastic surfactant solution in enhanced oil recovery. Energy Fuels 30,
4467–4474.
Liu, Q., Dong, M., Yue, X., Hou, J., 2006a. Synergy of alkali and surfactant in emulsifi-
cation of heavy oil in brine. Colloid. Surface. Physicochem. Eng. Aspect. 273,
219–228.
Liu, Q., Dong, M., Ma, S., 2006b. Alkaline/surfactant flood potential in western canadian
heavy oil reservoirs. In: SPE/DOE Symposium on Improved Oil Recovery, Tulsa,
Oklahoma, USA, SPE 99791.
H. Feng et al.
Liu, Q., Dong, M., Ma, S., Tu, Y., 2007. Surfactant enhanced alkaline flooding for Western
Canadian heavy oil recovery. Colloid. Surface. Physicochem. Eng. Aspect. 293,
63–71.
Liu, H., Zhang, Y., Li, Y., Hou, J., Liu, Y., 2016. Influence on emulsification in binary
flooding of oil displacement effect. J. Dispersion Sci. Technol. 37, 89–96.
Liu, W., Luo, L., Liao, G., Zuo, L., Wei, Y., Jiang, W., 2017. Experimental study on the
mechanism of enhancing oil recovery by polymer – surfactant binary flooding. Petrol.
Explor. Dev. 44, 636–643.
Mirchi, V., Saraji, S., Akbarabadi, M., Goual, L., Piriet, M., 2017. A systematic study on
the impact of surfactant chain length on dynamic interfacial properties in porous
media: implications for enhanced oil recovery. Ind. Eng. Chem. Res. 56,
13677–13695 2017.
Pajouhandeh, A., Kavousi, A., Schaffie, M., Ranjbar, M., 2017. Experimental measure-
ment and modeling of nanoparticle-stabilized emulsion rheological behavior. Colloid.
Surface. Physicochem. Eng. Aspect. 520, 597–611.
Pei, H., Zhang, G., Ge, J., Jiang, P., Zhang, J., Zhong, Y., 2017. Study of polymer-en-
hanced emulsion flooding to improve viscous oil recovery in waterflooded heavy oil
reservoirs. Colloid. Surface. Physicochem. Eng. Aspect. 529, 409–416.
Shangguan, Y., Zhang, Y., Xiong, W., 2015. The effect of physical property change on the
water flooding development in Changqing oilfield Jurassic low permeability re-
servoir. Petroleum 1, 300–306.
Sun, N., Jiang, H., Wang, X., Jin, K., 2018. Research on factors affecting heavy oil-in-
water emulsion rheology and pressure drop. J. Dispersion Sci. Technol. 39, 411–422.
981
Journal of Petroleum Science and Engineering 171 (2018) 974–981
Tian, S., Lei, G., He, S., Yang, L., 2012. Dynamic effect of capillary pressure in low per-
meability reservoirs. Petrol. Explor. Dev. 39, 405–411.
Wang, F., Qu, Z., Kong, L., 2006. Experimental study on the mechanism of emulsion
flooding with micromodels. Petrol. Explor. Dev. 33, 221–224.
Wang, L., Tian, Y., Yu, X., Wang, C., Yao, B., Wang, S., Winterfeld, P., Wang, X., Yang, Z.,
Wang, Y., Cui, J., Wu, Y., 2017. Advances in improved/enhanced oil recovery tech-
nologies for tight and shale reservoirs. Fuel 210, 425–445.
Watson, A., Trahan, G.A., 2014. An interim case study of an alkaline-surfactant-polymer
flood in the Mooney Field, Alberta, Canada. In: SPE Improved Oil Recovery
Symposium, Tulsa, Oklahoma, USA.
Wei, B., Li, Q., Jin, F., Li, H., Wang, C., 2016. The potential of a novel nanofluid in
enhancing oil recovery. Energy Fuels 30, 2882–2891.
Xu, X., Ouyang, J., Wang, Y., Wang, C., 2017. Experimental investigation using an ac-
rylamide-based polymer with emulsifying capability for enhanced oil recovery: a
preliminary study. J. Ind. Eng. Chem. 55, 110–118.
Yuan, Z., Wang, J., Li, S., Ren, J., Zhou, M., 2014. A new approach to estimating recovery
factor for extra-low permeability water-flooding sandstone reservoirs. Petrol. Explor.
Dev. 41, 377–386.
Zhao, J., Fan, J., He, Y., Yang, Z., Gao, W., Gao, W., 2015. Optimization of horizontal well
injection-production parameters for ultra-low permeable–tight oil production: a case
from Changqing Oilfield, Ordos Basin, NW China. Petrol. Explor. Dev. 42, 74–82.
Zhou, Y., Cao, R., Liu, B., 2017. Mechanism for viscoelastic emulsion displacing oil film –
a numerical simulation approach. J. Dispersion Sci. Technol. 1–4.
 Kinetics of Emulsion Polymerization
Wendell V. Smith and Roswell H. Ewart

Citation: J. Chem. Phys. 16, 592 (1948); doi: 10.1063/1.1746951

View online: http://dx.doi.org/10.1063/1.1746951
View Table of Contents: http://jcp.aip.org/resource/1/JCPSA6/v16/i6
Published by the AIP Publishing LLC.

Additional information on J. Chem. Phys.

Journal Homepage: http://jcp.aip.org/
Journal Information: http://jcp.aip.org/about/about_the_journal
Top downloads: http://jcp.aip.org/features/most_downloaded
Information for Authors: http://jcp.aip.org/authors

Downloaded 15 Sep 2013 to 131.170.6.51. This article is copyrighted as indicated in the abstract. Reuse of AIP content is subject to the terms at: http://jcp.aip.org/about/rights_and_permissions
 THE JOURNAL OF CHEMICAL PHYSICS
Kinetics of Emulsion Polymerization
WENDELL V. SMITH AND ROSWELL H. EWART
General Laboratories, United States Rubber Company, Passaic, New Jersey
(Received February 12, 1948)
As a basis for understanding emulsion polymerization,
the kinetics of free radical reactions in isolated loci is dis-
cussed subject to the condition that the free radicals are
supplied to the loci from an external source. Three cases
of interest are considered: that in which the average
number of free radicals per locus is small compared with
unity, that in which this number approximates one-half,
a~d that in which the number is large. Of these three possi-
bilities, the second, in which the free radicals per locus
approximate one-half, is by far the most interesting as it
explains in a satisfactory manner the characteristic
features of styrene emulsion polymerization. For this case
the average rate of reaction per locus is independent of the
size of the locus, since this rate is simply one-half the rate
INTRO DUeTIO N
O NEof emulsion
of the most interesting characteristics
polymerization is the produc-
tion of high molecular weight polymer with
simultaneous rapid rate of reaction. The most
plausible current attempts to explain this consist
in attributing an abnormally low value to the
rate of mutual termination of growing free
radicals due to the high viscosity of the poly-
merization locus (i.e., the swollen polymer parti-
cles).l However, a more attractive explanation is
offered by a consideration of the kinetics of free
radical reactions in isolated loci when the free
radicals originate in a medium outside of the
loci of reaction, or are generated by reaction of
substances which come from the outside medium.
Harkins 2 has recently discussed the locus of
the emulsion polymerization reaction and the
function of the various phases present. His
discussion may be briefly reviewed as follows.
During emulsion polymerization there are four
phases which play an integral role in the over-all
process. The water phase normally contains the
"catalyst," or more properly, chain initiator; it
is probable that the initial formation of free
radicals takes place here. Dispersed in the water
J . H. Baxendale, M. G. Evans, and J. K. Kilham,
1
J.Pol. Sci. 1,466 (1946); W. P. Hohenstein and H. Mark,
J. Pol. Sci. 1, 549 (1946).
2 W. D. Harkins, J. Chern. Phys. 13, 381 (1945); 14, 47
(1946); and J. Am. Chern. Soc. 69,1428 (1947).
592
Downloaded 15 Sep 2013 to 131.170.6.51. This article is copyrighted as indicated in the abstract. Reuse of AIP content is subject to the terms at: http://jcp.aip.org/about/rights_and_permissions
VOLUME 16. NUMBER 6 JUNE. 1948
of polymerization of a single free radical. Thus the rate
of emulsion poiymerization. the concentration of monomer
in the lor;i, and the number of loci present provide the
information needed for calculating the chain propagation
constant for the monomer.
A simplified treatment is given for approximating the
number of reaction loci (polymer particles) produced in
emulsion polymerization when the rate of polymerization
per locus is constant (see case 2 above). The law obtained
indicates that the number of particles should increase with
the soap concentration (3/5ths power) and with the rate of
formation of free radicals (2/5ths power), but should
decrease with increasing rate of growth of the free radicals
(-2/5ths power).
phase are emulsified droplets of monomer j as
long as these remain present, they serve to keep
the other phases supplied with monomer. In the
early stages of the reaction, soap micelles con-
taining dissolved monomer are present; these
serve as "generators" of polymer particles and
they continue to serve this function until all the
soap becomes adsorbed on the polymer-water
interface produced by the polymerization. After
polymerization has started, the fourth phase
present consists of very small polymer particles
which are swollen with monomer; these serve as
the principal loci of polymerization.
Thus, the problem of the kinetics of emulsion
polymerization is twofold. There is the problem
of determining what factors govern the rate of
polymerization in a single swollen polymer
particle and also there is the problem of deter-
mining how many such polymer particles are
formed. Part I of this discussion is concerned
with the first, while Part II presents a simplified
discussion of the factors determining the number
of reaction loci produced in emulsion polymer-
ization.
In Part I the rate of polymerization is dis-
cussed for three limiting cases in terms of the
variables: rate of formation of free radicals, rate
of escape of free radicals from reaction loci, rates
of termin;:ttion of free radicals in reaction loci
and water solution, rate of polymerization of a
 KINETICS OF
free radical in a reaction locus, size, and number
of, reaction loci (polymer particles).
Case 1 is that in which the number of free
radicals per reaction locus is much less than
unity. Under these conditions, if termination is
chiefly in the water phase, the rate law obtained
is similar to the oil phase law, but the initiation
rate and termination constant are those for the
water solution, also a new factor appears which
is the ratio of free radicals in the reaction loci to
those in the water phase. The rate, therefore, is
independent of the size of the reaction loci. If
termination is in the reaction loci, the law is
identical with the oil phase law except that the
termination constant is replaced by a quantity
giving the probability of escape of a free radical
from a reaction locus. Since this latter quantity
does involve the interfacial area, the rate is
dependent on the size of the reaction loci but
not very greatly so.
Case 2 is that in which the number of free
radicals pet reaction locus approximates one-half.
This is the case of outstanding interest, since its
existence is responsible for the extraordinarily
high rates of polymerization and high molecular
weights obtainable by emulsion polymerization.
The rate law is remarkably simple since it in-
volves only the rate of polymerization of a free
radical and the number of reaction loci present.
This simplicity makes it possible to determine
the chain propagation constants of polymerizing
monomers by studying their rates of emulsion
polymerization.
Case 3 covers the situation when the number
of free radicals per reaction locus is large. The
rate law obtained is exactly equivalent to the
oil phase law, and hence does not depend on the
size of the reaction loci.
PART I. FREE RADICAL REACTION IN
ISOLATED LOCI
Consider a system consisting of 1 cc of an
external medium (water solution) having sus-
pended in it N isolated reaction loci (polymer
particles), each of which has a volume v and an
interfacial area a. Suppose that free radicals are
initiated only in the external medium, then let
the rate of entrance of free radicals into a single
locus be
dn/dt = p' / N,
Downloaded 15 Sep 2013 to 131.170.6.51. This article is copyrighted as indicated in the abstract. Reuse of AIP content is subject to the terms at: http://jcp.aip.org/about/rights_and_permissions
POLYMERIZATION 593
where p' is the over-all rate of entrance into all
the N loci.
Having once entered a locus, suppose that a
free radical continues to cause polymerization
until its activity is destroyed or transferred out
of the locus. Let the rate of transfer out of a
locus be given by
dn/dt= -koa(n/v),
where ko is a specific rate constant for the event,
n/v is the concentration of free radicals in a
locus, and a is the interfacial area through which
the transfer takes place. Suppose that destruction
of free radicals takes place only by mutual
termination so that the rate of destruction in a
given locus is given by
dn/dt= -2kin[(n-1)/v],
where the factor of 2 arises from the fact that
two free radicals are destroyed for each event of
termination, k t is the mutual termination specific
reaction rate constant, and (n -1)/v is the
concentration of free radicals with which any of
the n free radicals in a locus can react.
If these three events be the only ones which
need be considered in determining the numbers
of free radicals in the various reaction loci, then
the No, N I , N 2 •• ·Nn ··· reaction loci containing
0, 1, 2, ... n· ., free radicals, respectively, will
be related by the steady-state condition:
Nn-I(p' / N)+Nn+Ikoa((n+ 1)/v)
+Nn+2k t [(n+2)(n+ 1)/v]
= N n{(p' / N) +koa(n/v) +k t n[(n-1)/v]}. (1)
This equation states that the rate of formation
of reaction loci characterized by containing n
free radicals is just equal to the rate of disap-
pearance of these loci.
Rather tha~ obtaining a general solution of
this recursion formula, which would appear to
be difficult, a discussion is given of three limiting
cases which are of interest.
Case 1. Number of Free Radicals per Particle
Small Compared with Unity
If the free radicals have a high enough prob-
ability of being transferred out of a particle, then
at any time only a small number of the particles
will have free radicals in them. This condition
 594 W. V. SMITH AND
will be fulfilled when
p' / N«kfIL/v.
Then of the various relations given by Eq. (1),
it is only necessary to consider the first which
approaches
But since
No"'"'N, N{"p'v/koa.
The number of free radicals in polymer particles
is also very nearly equal to N I , so if the rate of
polymerization per free radical is kp(M) where
k p is the propagation constant and (M) is the
monomer concentration in the particle, then the
over-all rate of polymerization per cc of external
medium (water solution) will be
dM/dt=kp(M)(p'v/koa).
An obvious alternative form for writing this
equation is
(2a)
where Vp is the total volume of the polymer
particles in 1 cc of water solution and Cp is the
average concentration of free radicals in the
particles.
Now termination of the free radicals may take
place in either the water phase or the polymer
particles. If termination is in the water phase,
the rate law governing their disappearance may
be written
where k t is the termination constant and Cw is
the concentration of free radicals in the water
phase. When a steady state is attained, this
rate will be equal to p, the rate of formation of
free radicals per cc of water phase; thus
Under these conditions of rapid exchange of
free radicals between water phase and polymer
particles it is· useful to use a partition coefficient,
ex, defined by
. OI.=cp/cw •
Then from Eqs. (2a), (3), and (4)
dM/dt=kp(M) Vpex(p/2k t )t.
Another quantity of interest is the average
polymerizing lifetime of a free radical, which is a
Downloaded 15 Sep 2013 to 131.170.6.51. This article is copyrighted as indicated in the abstract. Reuse of AIP content is subject to the terms at: http://jcp.aip.org/about/rights_and_permissions
R. H. EWART
measure of the initiator efficiency. The average
lifetime, T p , of a free radical in polymer particles
is equal to the number oUree radicals in polymer
particles divided by the rate at which they are
terminated or
Tp= [Vpcp/2k t (cw)2J = (Vpex/2k tcw ).
From Eq. (3) this becomes
Tp = [Vpex/(2k t p)IJ. (6)
Thus under these conditions the rate of polymer-
ization and initiator effi.ciency do not depend
on the size of the polymer particles but only on
their total volume.
If termination takes place in the polymer
particles and if these particles are so small that
~ermination takes place very rapidly every time
(2) two free radicals are in the same particle, then
the rate of termination is simply two times the
rate at which free radicals enter the polymer
particles which already contain a free radical or
dn/dt= -2(p'/N)NI = -2[(p')2/NJ(v/koa). (7)
Equating this to the rate of formation of free
radicals, p, to obtain the steady state condition,
solving for p' and substituting in Eq. (2) gives
dM/dt=kp(M)(Vpp/2koa)t. (8)
The mean polymerizing lifetime is approximately
NI divided by the rate of termination; so from
Eq. (7),
Tp=N/2p' = (Vp/2koap)1. (9)
To know which of the two terminations dis-
cussed will apply, it is necessary to make an
assumption concerning the relationship between
cw and p' / N. The simplest assumption to make
is that the rate of entrance of free radicals into
(3) a particle is just that given by the rate of
diffusion of molecules from an infinite medium
of concentration cw into a particle of radius, r,
having zero concentration of the molecules,
this rate is
p' / N = 47rDrc w ,
(4)
where D is the diffusion constant of the molecules
through the water phase. Then the rate of
(5) termination in the polymer particles will be
given by Eq. (7) to be
dn/dt= -2N(411'Drcw )2(v/koa).
 KINETICS OF POLYMERIZATION
If this is small compared with the rate of termi-
nation in the water phase, Eq. (3), then the
water phase termination will apply. Thus water
phase termination predominates when
Case 2. Number of Free Radicals per Polymer
Particle Approximately Equal to 0.5
Suppose that there is no readily available
mechanism by which the activity of a free radical
in a polymer particle can be transferred again to
the water phase, then having once entered a
polymer p~rticle a free radical must remain there
until another one comes in to terminate it. If,
in addition, the probability of mutual termina-
tion of two· free radicals in the same particle is
large enough so that the average time necessary
for them to terminate is small compared with the
average time interval between successive en-
trances of free radicals into a particle, then the
very simple situation exists in which approxi-
mately one-half the particles contain a single
free radical and the other half contain none.
This is much the most interesting case and is the
one which appears to apply to the emulsion
polymerization of styrene under normal condi-
tions. The requirements for this case can be
stated as
ko(a/v)«p' / N <kt/v. (10)
In view of the importance of this case, a
solution will be given to a higher approximation
than the simple limiting law; however, this will
be done only for the condition in which ko = 0
(this is probably closely approached in many
unregulated polymerizations). Neglecting terms
involving ko, Eq. (1) becomes
Nn-1(p' /N) +Nn+2kt[(n+2) (n+ 1)/v]
=N,,{(p'/N)+k tn[(n-1)/v]}.
For convenience, the quantity /3 may be defined
as
/3=k t N /vp',
(from (10) /3> 1) then Eq. (11) may be written
+
N n- 1 N,,+2/3(n +2) (n+l)
=N.. [1+f3n(n-1)].
It is shown in Appendix I that a satisfactory
approximation for this recursion formula when
Downloaded 15 Sep 2013 to 131.170.6.51. This article is copyrighted as indicated in the abstract. Reuse of AIP content is subject to the terms at: http://jcp.aip.org/about/rights_and_permissions
595
/3> 1 is
N ..-I/Nn = 1+/3n(n-1). (13)
From Eq. (12) when n=O
N 2 =No/2/3.
When n=1
N o+3X2Na/3=N 1•
But Na can be related approximately to N2 by
Eq. (13) so
Na = [N o/2/3(1 +6/3)],
and
This could be continued to obtain any degree of
approximation desired.
So far as the rate' of polymerization is con-
cerned, the important thing is the total number
of free radicals present in polymer particles;
this is given by
nT=1N1+2N2+3Na+·· ·nN,,···,
while the total number of particles is
From these relations and those given above, the
total number of free radicals can be expressed as
the series
nT=(N/2)(1+1//3-1/3/32+ ... ). (14)
Thus, if /3 is sufficiently large, the total number
of free radicals present will be very nearly equal
to one-half the number of polymer particles.
Under these conditions, the rate of polymer-
ization per cc of water solution is given by the
remarkably simple expression
dM/dt=k p (M)N/2. (15)
The mean polymerizing lifetime, T p , will be
N /2p'. Under normal polymerization conditions,
(11) some semiquantitative considerations indicate
that practically every free radical produced will
enter polymer particles; hence p' = p and
(16)
The characteristic features of emulsion poly-
merization can now be easily interpreted. It is
seen from Eq. (14) that the number of polymer-
(12)
izing free radicals will be nearly equal to half the
number of particles. Since it is possible to have
a large number of particles present (compared
 596 W.
with the concentration of free radicals normally
present in oil phase polymerization), the fast
rate of polymerization naturally follows. Also
from Eq. (16) the average lifetime of a free
radical increases with increase in number of
particles; thus it is possible to have high rates of
polymerization with simultaneous high molecular
weights in emulsion polymerizations.
I t may be pointed out that when the conditions
characterizing this case are fulfilled, determina-
tions of the over-all rate of polymerization,
number of polymer particles, and concentration
of monomer in the particles provide the data
necessary to calculate the chain propagation
constant by Eq. (15).
Case 3. Number of Free Radicals per Polymer
Particle Large Compared With Unity
This situation will prevail when
p' / N»kt/v.
This case is not of as much interest as case 2,
but in view of its possible application to some
"bead polymerizations," a brief discussion will
be given.
For most purposes, it is not necessary to have
the detailed knowledge of the distribution of
free radicals which would be provided by a
solution of the recursion formula (1). It will
suffice to write down directly the steady-state
condition as
This assumes that the system can be approxi-
mated by one in which all the particles contain
the same number, n, of free radicals. This is,
no doubt, a good approximation if n is large
enough. Solving Eq. (17) for n gives
n = (vp' /2k t N)!.
So the over-all rate of polymerization per cc of
water solution will be
and the polymerizing lifetime of a free radical
will be
If the exposed interfacial surface is large enough
so that practically every free radical produced
Downloaded 15 Sep 2013 to 131.170.6.51. This article is copyrighted as indicated in the abstract. Reuse of AIP content is subject to the terms at: http://jcp.aip.org/about/rights_and_permissions
V. SMITH AND R. H. EWART
enters the particles, then p' = p, the rate of
production of free radicals per cc of water phase.
Then there will be no advantage in having a
large number of very small particles as the rate
and lifetime will depend only on the total volume
of polymer particles. This will simply be an oil
phase type of polymerization in suspended
particles which are supplied with free radicals
from the water phase. If a substantial fraction
of the free radicals are terminated in the water
phase, then the system is an inherently inefficient
one.
Regarding the relationships between the three
cases discussed, it is evidently possible, under
suitable conditions, to go progressively from
one case to the next by increasing the rate of
formation of free radicals. However, for case 2
two conditions must be fulfilled; i.e.,
ko(a/v) «(p' / N) < (kt/v),
so, obviously, for this case to be obtained, koa
must be much smaller than k t • If this condition
is not fulfilled, then progressive increase in the
rate of formation of free r.adicals will cause a
transition from case 1 to case 3 without ever
realizing case 2.
PART II. NUMBER OF POLYMER PARTICLES
The process considered in this development is
based on the ideas originated by Harkins 2 re-
garding the formation of polymer particles by
soap micelles. It is considered that originally
(17) most of the soap present is in the form of micelles
containing dissolved monomer. When a free
radical from the surrounding water phase enters
a micelle, it initiates polymerization of the
monomer in the micelle. When this polymeriza-
tion starts, monomer from the surrounding
medium diffuses into the polymerizing region
until shortly this region is no longer identified as
a micelle, but is now considered a growing
polymer particle and is subject to the considera-
tions given in Part 1. As the area of the polymer
particles inqeases because of growth and forma-
tion of new ones, the particles adsorb more and
more soap from the surrounding micelles until a
time is reached at which no soap remains in the
(19)
micellar form. After this time, the soap is no
longer effective in forming new particles.
To make the problem as simple as possible,
 KINETICS OF POLYMERIZATION 597

the soap dissolved in the water without forming micelles are present. So
micelles and the soap adsorbed on the emulsified
dNldt=p. (21)
monomer may be neglected; ordinarily this soap
will represent only a small fraction of the total To obtain the total number of particles
present. 2 Thus, if S is the total amount of soap formed, Eq. (21) must be integrated to the time
associated with one cc of water phase, it will t1 at which the total area of the polymer particles,
consist of Sm grams in micellar form and Sp A p , is just equal to the total area of the soap, a.S.
grams adsorbed on polymer particles so that The area of the polymer particles is the sum-
mation of the areas for all the particles produced
(20) from zero time to the time considered. To obtain
Also for simplicity, it will be assumed that the the area at time t of a particle which was formed
interfacial area, as! occupied by a gram of soap at time T, it is necessary to know the law govern-
is the same in soap micelles as on polymer ing the rate of growth of a particle. For case 2
particles, so long as micelles are present. This is discussed in Part I, the rate of polymerization of
probably not true but is a good enough approxi- a particle is a constant, independent of the size
mation for the present discussion. So if A, Am, of the particle or of the rate of entrance of free
and Ap are the total interfacial area, area of radicals. Now if the ratio of monomer to polymer
micelles, and area of polymer particles, respec- in the particle remains constant during the
tively, period in which new particles are being formed,
the rate of increase in volume of a particle will
be a constant which may be called f.1., so if v is
the volume of a particle
Now the question arises as to how effective a
given interfacial area is in collecting free radicals dvldt=f.1..
from the solution. If the ordinary laws of diffu-
Thus the volume, v T, t, at time t of a particle
sion hold, as they probably do in this case, then
formed at time T is
a given interfacial area on a very small particle
will be more effective in collecting free radicals
than the same area on a large particle (i.e., the
Assuming a spherical particle, the area, aT, t, of
number entering a particle will be proportional
this pa~ticle at time t is
to the radius; hence, the number entering a given
area will be inversely proportional to the radius). (22)
This introduces some difficult compli~ations into For convenience make the substitution
the problem. However, one can solve the problem
of the number of particles produced for two (J= [(47r)!3f.1.J!. (23)
idealized situations which should give, respec- Then Eq. (22) becomes
tively, more and fewer particles than the actual
situation. Fortunately, the results obtained do aT,t=(J(t-T)I. (24)
not differ greatly so it is thus possible to approxi- The total area, A p , of all the particles present at
mate fairly closely the actual situation, without time t is given by the integration
having to discuss the size distribution of particles.
The simplest idealized situation is that in
(25)
which the very small micelles capture all the free
radicals being generated as long as micelles are
which gives
still present. Obviously, this will give too many
particles, since actually some of the free radicals
will enter polymer particles. If p is the rate of
At time t = t 1 , when the soap micelles disappear,
formation of free radicals per cc of water solution,
Ap=a.S so
the rate of formation of new particles, dNIdt, is
assumed equal to p and constant as long as

Downloaded 15 Sep 2013 to 131.170.6.51. This article is copyrighted as indicated in the abstract. Reuse of AIP content is subject to the terms at: http://jcp.aip.org/about/rights_and_permissions
 598 W. V. SMITH AND R. H. EWART

and the total number of particles is may be expressed by the infinite series
N = ptl = p2 /5(Sa.S/30)3/5 dN y"
00

= 0.S3(p/ fJ)2/5(a.S)8/5. (26) -=p:E , (29)

dt ,,=0 r(1 +nS/3)
The other idealized situation is that in which where
(411" )1I332f3r(S /3) pfJ2/3t5/3
a given interfacial area always has the same y=
effectiveness in collecting free radicals regardless a.S
of the size of the particle on which it is situated.
This will give too few particles since a given Combination of the numerical constants gives
interfacial area on the very small micelles will be 4.36pfJ213t5/3
more effective than the same area on the larger y= (30)
polymer particles. (The diffusion current of free a.S
radicals through unit area of interface should be By using a method of successive approxima-
inversely proportional to the radius.) For this tion, the value, Yl, of y which gives dN/dt=O in
situation, the rate of formation of particles is Eq. (29) is found to be
given by
dN/dt=pAm/A, (21a) Yl= -2.13.

instead of by Eq. (21). Substituting from Eq. Thus the time tl at which the soap micelles
(20) gives disappear and after which no new particles are
dN /dt=p(l-Ap/a.S). (27) formed by them is (Eq. (30»

The number of particles formed in the interval tl = ( 2.13a.S )3/5 = 0.6S0(a.S)3/5.

d1' at time l' may be expressed as (dN /dT)dT, and 4.36p}L2/3 fJ2/5 P
the area of one of these particles at some time,
t, after T is given by Eq. (24), so the total area Now for temporary convenience let
at time t of all particles formed up to t is
~= (4.36PfJ'/a.S) ,
Ap=O i t
(t-1')J(dN/dT)dT' (2Sa) so that (Eq. 30)
y= _~t5/3.

Thus Eq. (27) may be written Then the first few terms of Eq. (29), which are

dN/dt= p- (pO/a,S) It
o
(t-1')i(dN/dT)dT. (28)
the only ones of importance, may be written
out as

This integral equation is a form of Volterra's

equation of the second kindS which may be
written
~3t15/3 +~4t20/3 _ ... ).
cfJ(x) =f(x)+}. f" K(x, z)cfJ(z)dz.
o
r(18/3) r(23/3)

The solution of this is given by the infinite series To get the total number of particles produced by
00
a given amount of soap, this may be integrated
cfJ(x) = L }.ncfJ,,(x), from 1=0 to 1=/1, the time at which the soap
"=0 micelles disappear. Carrying out term by term
where integration and substituting the limits gives
cfJo(x) =f(x) and cfJ,,(x) = f" K(x, zJcfJn-l(z)dz.
o
3 ~t1513 3 ~2tl10/3
(
Applying this to Eq. (28), the desired solution 8
N=ph 1- r(8/3)+ 13 r(13/3)

3 H. Margenau and G. M. Murphy, Mathematics oj

'physics and Chemistry (D. Van Nostrand Company, Inc.,
New York, 1943), p. 506.

Downloaded 15 Sep 2013 to 131.170.6.51. This article is copyrighted as indicated in the abstract. Reuse of AIP content is subject to the terms at: http://jcp.aip.org/about/rights_and_permissions
 KIN E TIC S 0 F POL YM E R I Z A T ION S99

or Making the substitution

N=0.6S0(~)2/5(a.S)3/5(1+ 3Y1 n'=n/2,

p. 8r(8/3) so that n' will now give the number of the term
3(Y1)2 3(Y1)3 in the series
+ 13r(13/3) +---
18r(18/3)
3(YI)4 ) The ratio expressed by (A2) now becomes
+ 23r(23/3) + ... '
= 0.370(p/ 1-') 2/5(a.Sp/5.
(26a) (n+2)N n +2
nN
1 1 [
=1- n '+n'(2n'+1) 1-~, (A4)
X-l]
n

This is identical with Eq. (26) except for the

which is the ratio of successive terms in the
value of the numerical constant, and the con-
series of Eq. (A3). This is now in the form
stants are not greatly different. The actual
situation should lie between that represented
by Eqs. (26) and (26a). Thus co

N = k(pl p.)2/5(a.S)3/5, where k> 1 and IWn I is finite. The series L an

n=r

where 0.37 <k <0.S3. The application of this to has been shown to diverge if p.~1. Therefore,
4

experimental data will be discussed in a future
paper.
APPENDIX I
Approximate Solution of Recursion Formula
For No Transfer of Free Radical from
Polymer Particle to Water Phase
For convenience, make the substitutions
X = Nn_1/Nn, Xl = Nn/N n+1, x2=Nn+1/Nn+2 ,
then the recursion formula (12) may be written
x = 1 +,8n(n-l) - (1/xlx2),8(n+2)(n+ 1).
It is immediately evident that if x remains
less than unity by a finite amount as n~oo then
co
the series L N n diverges and is therefore a
n=O
physically unsatisfactory condition.
To examine the situation wh~n x-tl as n-too
consider the ratio of the free radicals in the Nn+2
particles containing n+2 free radicals each to
those in the N n particles containing n free
radicals each. This ratio, from Eq. (Al) is
(n+2)Nn+2 n-l x-l
nNn n+l ,8n(n+ 1)
the series in Eq. (A3) diverges so the condition
x-t 1 as n-t 00 is physically unacceptable.
The one remaining possibility is for x to
remain greater than unity by a finite amount as
n-t 00. To examine this, it is convenient to
rewrite Eq. (Al) in the form
1 (n+2)(n+l)]
x=l+,8n(n-l) [ 1 - - . (AS)
X1X2 n(n-l)
Since x> 1 as n-t 00, then Xl and X2 must also
remain greater than unity. Thus the term in
(Al) brackets in Eq. (AS) must remain greater tha~
zero. But since the multiplier, ,8n(n-l), may
become indefinitely large x, Xl and X2 will all
become indefinitely large as n~ 00. Thus the
bracketed term will approach unity and the
approximation
x-tl +,8n(n-l), (A6)
will be very good for large values of n; also it
will remain a good approximation for small
values of n if ,8 is large enough.
4 Frank and v. Mises, Die Differential- und Integral-
gleichungen der Mechanik und Physik (Friedrich Vieweg
(A2) und Sohn Aktien-Gesellschaft, Braunachweig, 1930), p.
197.

Downloaded 15 Sep 2013 to 131.170.6.51. This article is copyrighted as indicated in the abstract. Reuse of AIP content is subject to the terms at: http://jcp.aip.org/about/rights_and_permissions