Chemical Engineering Research and Design 1 6 1 ( 2 0 2 0 ) 279–303

Contents lists available at ScienceDirect

Chemical Engineering Research and Design

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

Review

Integrated design of emulsified cosmetic products:

A review

Fernando Calvo a,∗ , Jorge M. Gómez a , Luis Ricardez-Sandoval b ,

Oscar Alvarez a
a Chemical Engineering Department, Universidad de Los Andes, Colombia
b Chemical Engineering Department, University of Waterloo, Canada

a r t i c l e i n f o a b s t r a c t

Article history: Chemical product design has progressively become a more critical issue since the chemi-
Received 12 May 2020 cal industry is rapidly moving toward the production of consumer-oriented products at low
Received in revised form 8 July 2020 cost. This new paradigm has boosted research and developments in this emerging field.
Accepted 14 July 2020 However, designing a new chemical product through an integrated approach is still chal-
Available online 24 July 2020 lenging. In particular, the design of emulsified cosmetic products commonly involves the
implementation of heuristics during the formulation of the product, highlighting the need
Keywords: of implementing integrated strategies in this field. This study reviews the current status of
Product design the integrated design of emulsified cosmetic products, including but not limited to, prop-
Cosmetic emulsion erty modeling, manufacturing methods, the key variables affecting final product quality,
Integrated design and the current challenges in this field. This review highlights the need to perform close
Process design integration between market parameters, engineering variables, and business models, on the
Population balance models one hand, and systematic and standardized approaches to translate consumer needs into
technical specifications on the other. Also, this study presents the requirement for better
accuracy of predictive models for emulsified product’s physical properties for the successful
integrated design of cosmetic emulsions, considering different modeling frameworks such
as population balance models that have the potential to improve the models’ prediction
capabilities.
© 2020 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 280
2. Emulsified products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 282
2.1. General classification of emulsions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 282
2.2. Product formulation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 282
2.2.1. Selecting emulsion type. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .282
2.2.2. Surfactants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 282
2.2.3. Viscosity modifying agents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 283
2.2.4. Sensory agents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 283
3. Product preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 284
3.1. Mixing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 284

∗
Corresponding author.
E-mail address: fj.calvo@uniandes.edu.co (F. Calvo).
https://doi.org/10.1016/j.cherd.2020.07.014
0263-8762/© 2020 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
280 Chemical Engineering Research and Design 1 6 1 ( 2 0 2 0 ) 279–303

3.2. Energy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 285

3.3. Temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 285
4. Product properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 285
4.1. Macroscopic scale properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 285
4.2. Microscopic scale properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 286
4.3. Molecular scale properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 288
5. Product stability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 288
6. Mathematical modeling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 289
6.1. Macroscopic modeling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 289
6.2. Microscopic modeling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 291
6.3. Molecular modeling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 292
6.4. Optimization problem formulation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 292
6.5. Dimensional analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 293
7. Design approach . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 293
8. Challenges and opportunities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 295
9. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 297
Conflicts of interest . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 297
Acknowledgement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 297
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 297

1. Introduction tured in the form of emulsions due to the advantages that this
presentation offers (Wibowo and Ng, 2001).
In recent decades, significant changes in the chemical indus- Emulsions are thermodynamically unstable colloidal sys-
try have emerged in response to an increasingly competitive tems, in which there are droplets of a liquid dispersed in a
globalized market (Cussler and Moggridge, 2011). The era of second immiscible fluid. The use of emulsions in the industry
globalization has intensified competition generating strong has a vast number of applications at different sectors, such as
market forces that play an essential role in the chemical cosmetic, food, petrochemical, pharmacy, biotechnology and
industry (Smith and Ierapepritou, 2010). Among these market nanotechnology (Masalova and Malkin, 2008; Desbrières et al.,
forces affecting new product strategies within the chemical 2017; Villena de Francisco and García-Estepa, 2018; Zhu et al.,
industry, the most commonly found are global competi- 2018) leading to a great interest to understand the relation-
tiveness, demand for product variety, and time-to-market ship between the formulation, the process variables, and the
pressure (Smith and Ierapepritou, 2010). Consequently, the properties of these systems. A multi-scale approach, whose
chemical product industry has moved from the production primary purpose is to understand the links between the dif-
of bulk commodities products toward higher value-added ferent temporal and spatial scales within a system and its
products, placing particular interest in the manufacture of overall impact on a finished product, is an appropriate way
specialty chemicals and consumer-oriented products (Cussler to study these relationships at different levels. As highlighted
and Moggridge, 2011; Edwards, 2006). Chemical products are in previous studies (Braatz et al., 2006; Derkach, 2009; Sagis,
frequently categorized into basic, industrial, and configured- 2011; Ricardez-Sandoval, 2011), these links are of significant
consumer products (Smith and Ierapepritou, 2010; Smith, importance for the design and development of new products.
2005). Basic chemical products are obtained from natural The design process could be addressed using different solution
resources (Smith, 2005), aiming to produce these products strategies, such as experiment-based (trial-and- error), model-
in large quantities at the lowest possible cost (Cussler and based, and integrated approach (Conte et al., 2011). Recent
Moggridge, 2011). Examples of basic chemical products are studies have drawn particular attention to the application of
ethylene, acetone, benzene, ammonia, and polyethylene. an integrated approach to manage the design process of chem-
These basic products are utilized to start the production of ical products (Bernardo, 2016; Rafiei and Ricardez-Sandoval,
industrial chemical products, which consists of mixtures of 2020), e.g. emulsions. Integrated chemical product and process
basic products blended and shaped into structured formu- design denote the specification of a chemical-based product
lated products (Picchioni and Broekhuis, 2012). This category along with the design of the process required to manufac-
includes a great variety of products such as films, woven ture the product (Bernardo, 2016). The integrated approach is
and nonwoven fibers, paper, creams, and pastes (Seider the most appropriate compared to classical design method-
et al., 2009). Both the basic chemical and industrial chemical ologies such as trial-and-error and model-based approaches,
products are employed to produce configured-consumer prod- as highlighted by previous reports (Conte et al., 2011) since one
ucts. Some examples of configured-consumer products are can achieve higher efficiency and reliability at manufacturing
pharmaceuticals, pesticides, drug-delivery patches, fuel cells, an emulsified product. This approach requires a combina-
detergent, and cosmetics. Among configured-consumer prod- tion of experimental techniques and computer-aided tools
ucts, consumer and pharmaceutical products are of significant (Conte et al., 2011) to achieve an optimal solution to the design
concern, since they represent the main business of about 75% problem. Hence, notable advances have been achieved in the
of the chemical industry in the United States (Wibowo and Ng, implementation of structural design principles to manufac-
2001). According to Muda et al. (2017), the global market size ture emulsions (McClements, 2012).
for the cosmetics, toiletry and fragrance industry was about Currently, there is a need for the design of emulsified
USD 382 billion for 2010. Most of these configured-consumer cosmetic products using an integrated approach, relating ele-
products, especially those related to skincare, are manufac- ments of the multi-scale approach of emulsion properties
 Chemical Engineering Research and Design 1 6 1 ( 2 0 2 0 ) 279–303 281

Nomenclature A new surface area (m2 )

p capillary pressure (Eq. (15))
A experimental proportionality coefficient (Eq. Hf heat of formation (Eq. (19))
(6)) ı parameters (Eq. (16))
Ai volumic aggregation rate (Eq. (14)) ␥0 surface tension (Eq. (19))
ai cross-sectional area covered by surfactant A new surface area (m2 )
molecules (Eq. (17)) p capillary pressure (Eq. (15))
Bi volumic breakage rate (Eq. (14)) Hf heat of formation (Eq. (19))
Bf fixed data matrices (Eq. (26)) ı Masalova and Malkin model coefficient
C concentration of polymer (Eqs. (1) and (2)) ε rate of energy dissipation (J s−1 kg−1 )
CT cost associated to the product (Eq. (20)) ε dielectric constant in the diffuse region (Eq.
Cf fixed data matrices (Eq. (26)) (18))
c2 experimental constant (Eq. (11)) εs dielectric constant in the Stern layer (Eq. (18))
c surfactant concentration (Eq. (16)) 1 experimental constant (Eq. (1))
c1/2 experimental adjustable parameters (Eq. (16)) 2 experimental constant (Eq. (2))
D0 intermolecular distance between droplets (Eq. kB Boltzmann constant (Eq. (17))
(6)) −1 Debye–Hückel screening length
d32 Sauter mean diameter ␰1 experimental constant (Eq. (1))
dmax maximum stable drop size ␰2 experimental constant (Eq. (2))
d Stern layer thickness (Eq. (18)) ˘ NI non-electrostatic contribution (Eq. (17))
e charge of a proton (Eq. (17)) ˘ elec electrostatic contributions (Eq. (17))
f(x) related to process variables (Eq. (20))  interfacial tension (N m−1 )
f1 (x,t) number density function  o/w interfacial tension between water and oil
G Gibbs free energy (J) (N m−1 )
G* complex modulus (Pa) ϕ dispersed phase volume fraction (Eq. (5))
G elastic (storage) modulus (Pa) ϕc critical volume fraction (Eq. (6))
G viscous (loss) modulus (Pa) ϕ* Masalova and Malkin model coefficient
g1 , g2 inequality constraints (Eqs. (24) and (25)) ωi weights determined from surveys (Eq. (24))
H consumer preference score (Eq. (27))
h(x,t) discrete growth of x
h1 ,h2 ,h3 equality constraints (Eqs. (21)–(23)) with the formulation and the process involved in the man-
k Masalova and Malkin model coefficient ufacturing of these systems. Emulsified products are often
KHO Kier–Hall topological descriptor (Eq. (19)) implemented as delivery vehicles in the cosmetic indus-
l1 ,l2 ,l3 constrains lower bounds (Eqs. (24)–(26)) try, since multiple components with different physical and
m Masalova and Malkin model scaling factor chemical properties can be combined in this presentation
n Masalova and Malkin model scaling factor (Wibowo and Ng, 2001). Also, the application of emulsified
ns number of surfactants used to prepare the cosmetic products is easy and convenient, while they are
emulsion (Eq. (17)) effective at delivering small dosages of active ingredients
ni discrete representation of the DSD (Wibowo and Ng, 2001). However, most of these products are
NO oxygen atoms in the hydrophilic section (Eq. still designed using heuristic or even artisanal considerations
(19)) (Arrieta-Escobar et al., 2019). Consequently, an active area of
R radius of curvature (Eq. ((15)) research in this filed is focused on the product properties, for-
Rav average drop radius (Eq. (6)) mulation, and preparation of emulsions through an integrated
R32 mean drop radius (Eq. (5)) approach. In particular, studies have used model-based tech-
Ru universal constant of gases niques to predict the properties of emulsions. Most of these
ri radius of the adsorbed surfactant molecules studies have focused on the calculation of emulsion proper-
(Eq. (17)) ties (e.g., viscosity) using an average value of the drop diameter
T system temperature (Eq. (16)) rather than considering the actual droplets size distribution.
u1 ,u2 ,u3 constrains upper bounds (Eqs. (24)–(26)) The distributions for emulsions can be predicted using pop-
x internal coordinate or distributed property ulation balance models (PBMs). PBM is a proven method and
(PBM) represents a robust modeling framework for the description of
Ẋ (x, t) continued growth of x the dynamics of properties characterized by distributions, as
y vector of integer (binary) variables (Eq. (20)) it is the case for emulsions droplets diameter (Nopens et al.,
yi consumer-related properties (Eq. (27)) 2015). Although considerable attention has been devoted to
zi valence of the surfactant molecules of type i the study and implementation of PBMs in emulsions, there
(Eq. (17)) is a lack of studies linking this modeling framework with the
integrated design approach of emulsified cosmetic products.
Greek letters The aim of this study is to provide an overview of important
i surfactant molecules concentration at the issues concerning the integrated design of emulsified cos-
interface (Eq. (17)) metic products, providing concise information on the status
∞ experimental adjustable parameters (Eq. (16)) of the application of the integrated approach, emulsified cos-
␥0 surface tension (Eq. (19)) metic product property modeling, manufacturing methods,
and principal components for product formulation. Addition-
282 Chemical Engineering Research and Design 1 6 1 ( 2 0 2 0 ) 279–303
ally, the main factors affecting final product performance, and
the challenges that these integrative strategies confront, are
discussed in this work. This study is organized as follows: Sec-
tion 2 describes the general classification of emulsions and
the main components for the product formulation. The emul-
sified product preparation is described in section 3. Section 4
describes the product properties at different scales. Informa-
tion related to the emulsified products stability are presented
in Section 5. Section 6 presents the mathematical modeling
for product properties at different scales. Section 7 describes
the main approaches for emulsified product design. Chal-
lenges and opportunities for the design of emulsified cosmetic
products are discussed in Section 8; concluding remarks are
presented in Section 9.
2. Emulsified products
2.1. General classification of emulsions
Emulsions are commonly composed of two immiscible fluids
(typically oil and water), where one of the fluids is in the form
of droplets immersed within the other, creating a continuous
and dispersed phase (Leal-Calderon et al., 2007). Emulsions
can be classified in terms of the nature of the liquid forming
the continuous phase and the drop size (Schramm, 2005).
In terms of the continuous phase, emulsions can be clas-
sified as oil-in-water emulsions (O/W), water-in-oil emulsions
(W/O), and multiple emulsions (W/O/W) (O/W/O). O/W emul-
sions, also referred to as direct emulsions, are formed by
dispersed oil droplets in a continuous aqueous phase. These
emulsions are commonly used in the cosmetic industry to
manufacture products such as creams and lotions (Lin, 2010).
In contrast, water-in-oil emulsions (W/O) consist of water
droplets in a continuous oil phase. This type of emulsion is
used to manufacture waterproof products such as sunscreen
(Lin, 2010). Concerning multiple emulsions, these consist of
droplets that contain inner smaller droplets (Silva et al.,
2016). This kind of emulsions have relevant applications in
controlling drug release (Lin, 2010), during encapsulation pro-
cesses (Vladisavljević et al., 2014), or food applications (Pagano
et al., 2018). Regarding the drop size of the dispersed phase,
emulsions can be further classified as macro-emulsions or
mini-emulsions (also referred to as nano-emulsions, Blin et al.,
2016). Macro-emulsions present drop sizes larger than 1 ␮m
(Tadros, 2013). Macro-emulsions are applied in a wide variety
of industrial purposes, from the petrochemical sector (Umar
et al., 2018) to cosmetics (Tal-Figiel, 2007) and the food industry
(Galus and Kadzińska, 2015). Mini-emulsions drop size typ-
ically is in the range between 100 and 1000 nm (Schramm,
2005). These emulsions have found multiple applications in
sectors such as cosmetics (Quintão et al., 2013), pharmaceuti-
cal (Schwarz et al., 2012), and food (Borthakur et al., 2016).
2.2. Product formulation
Emulsified products are of significant application in the
cosmetic industry since they enable the combination of
hydrophilic and hydrophobic active ingredients, which make
emulsions an ideal vehicle to include a great variety of
essential components in personal care products (Lin, 2010).
Consequently, product formulation plays a vital role in design-
ing an emulsified product; selecting the appropriate active
ingredient, as well as the base formula, is crucial for the
overall process (Farris, 2014). This procedure is not straight-
forward since commercial emulsified products own numerous
components in their formulation. For instance, food emul-
sions may contain oil, water, viscosity modifying agents,
preservatives, antioxidants, colorants, flavors (McClements,
2005), while in the cosmetic sector some components such as
emollients, humectants, thickeners, emulsifiers, stabilizers,
preservatives, and neutralizers are commonly used (Cheng
et al., 2009).
2.2.1. Selecting emulsion type
The decision of whether to select an O/W emulsion, a W/O
emulsion, or a multiple emulsion (e.g., W/O/W), should be
made by taking into account technical aspects (e.g., spread-
ability or the ability to treat a specific lesion) as well as the
perception of the consumer (Cheng et al., 2009). As an exam-
ple, in pharmaceutical applications, O/W emulsions can be
designed to be easy to spread for treating weeping lesions or
designed to stay in the skin for dry lesions. Also, for achieving
an occlusive effect, it is common to implement W/O emul-
sions (Marti-Mestres and Nielloud, 2010). Conversely, in some
cases, consumer preference is considered more critical (Cheng
et al., 2009). For instance, W/O emulsions for dermatological
purposes, provide higher hydration of the skin than O/W. How-
ever, W/O emulsions typically produce an oily sensation on
the skin (Spiess, 1992), which further enhances the presence
of O/W emulsified products in the market. O/W emulsions
represent nearly two-thirds of the total emulsified products
available on the market since their sensorial properties are
frequently preferred (Sakamoto et al., 2017).
2.2.2. Surfactants
Due to the unstable character of emulsions, these systems
require the presence of surface-active agents (surfactants) to
avoid coalescence among droplets (Leal-Calderon et al., 2007).
Surfactants are amphipathic molecules that are composed of
a hydrophilic section (polar or ionic) and a hydrophobic sec-
tion (non-polar) (Tadros, 2005). According to the characteristic
of the hydrophilic group, surfactants are often classified as
anionic (negatively charged), cationic (positive charged), non-
ionic (non-electrically charged), and amphoteric surfactants
(change between a cationic or anionic charge depending on
the pH value of the media) (Myers, 2006).
Regarding cosmetic purposes, non-ionic surfactants are
the most applied type of surfactants. Non-ionic surfac-
tants present low irritant potential, making them suitable
to manufacture cosmetic products (Tadros, 2015). During the
preparation of cosmetic emulsions, it is often common to for-
mulate these products using a combination of non-ionic and
ionic surfactants. As reported by Iwata and Shimada (2013),
non-ionic surfactants can be used in combination with anionic
surfactants or fatty acids for cosmetic applications, improving
product performance (stability or dermatological properties).
In agreement with these findings, Tian et al. (2016) studied
the destabilization phenomenon within emulsified products
in the presence of non-ionic and ionic surfactant mixtures. In
that study, the influence of these mixtures on product sta-
bility and drop size was assessed, concluding that due to
their electrosteric stabilization, the emulsion physical long-
term stability is improved, which is in agreement with the
results reached by Yang et al. (2019). That study showed that
using a combination of anionic and non-ionic surfactants
may produce a reduction in drop sizes and, consequently, a
more stable product. According to Corazza et al. (2010), the
 Chemical Engineering Research and Design 1 6 1 ( 2 0 2 0 ) 279–303
presence of surfactants in a skincare product could enhance
its dermatological properties. That study concluded that sur-
factants could improve product wetting properties, cleansing
power, bactericidal activity, or moisturizing properties. How-
ever, surfactants must be implemented correctly, since these
components may also damage or irritate consumer skin. The
irritation effects can be related to the surfactant’s critical
Micellar concentration (CMC) (Corazza et al., 2010), which is
the minimum concentration required to form micelles (Farn,
2006). Corazza et al. (2010) also indicated that once the sur-
factant concentration reaches the CMC, the free surfactant
molecules (i.e., those not forming micelles) may interact with
the skin causing damage or irritation (Corazza et al., 2010).
Moreover, Seweryn (2018) studied the surfactant irritant effect
on the skin. That study concluded that the irritant effect could
be reduced using surfactant mixtures, adding polymers, or
decreasing the concentration of free surfactant. Consequently,
it is required to formulate the product using surfactants (or a
mixture of surfactants) with the lowest possible CMC value
while designing an emulsified cosmetic product.
The CMC can be related to the structure of the surfactant
molecule. Huibers et al. (1996) presented a mathemati-
cal model for predicting the CMC of non-ionic surfactants
employing topological descriptors. That model relates the
CMC to the hydrophilic and hydrophobic groups sizes and
the structure of the hydrophobic group. That model considers
the group contribution from non-hydrogen atoms, ethylene
oxide groups, and alkane carbon groups (Huibers et al., 1996).
Similarly, Wang et al. (2005) obtained a regression model for
the prediction of the effectiveness of surface tension reduc-
tion of non-ionic surfactants at the CMC. In that model, this
reduction in surface tension is defined as a function of the
number of oxygen atoms in the hydrophilic section, a topo-
logical descriptor, and the heat of formation of a mole of
surfactant molecules (Wang et al., 2005). Those findings high-
light that the performance of an emulsified cosmetic product
is influenced, not only by surfactant nature but also by its
molecular structure. Hence, it is necessary to accurately model
these surfactant properties to address the emulsified prod-
uct design problem from an integrated approach. The effect of
the surfactant’s molecule structure could be addressed using
group contribution (GC) methods. These methods have been
extensively implemented for the representation and selection
of molecular structures to estimate substances properties (e.g.
surfactant’s molecules) (Gani, 2019). Due to their applicabil-
ity and accuracy, GC methods have been widely applied for
the design of chemical products, including emulsified prod-
ucts (Torres et al., 2020). Concerning the design of emulsions,
GC methods have been implemented to estimate surfactant
properties such as CMC, hydrophile–lipophile balance (HLB),
and Cloud Point (Mattei et al., 2013).
Another relevant property to consider at selecting a
surfactant (or mixture of surfactants), is the HLB. This
property quantitatively correlates surfactant structures with
their effectiveness as emulsifiers (Myers, 2006). Tadros (2015)
reported that HLB should be in the range 3–6 for W/O emul-
sions, while for O/W emulsions HLB range is 8–18. As reported
in the literature, HLB can also influence other product prop-
erties affecting its performance. In agreement, Paruta-Tuarez
et al. (2011) studied the effect of the HLB on the rheologi-
cal properties of W/O emulsions. According to their results,
HLB can influence the rheological properties of the emulsions,
affecting the elastic modulus as the product formulation is
changed. Hong et al. (2018) studied the effect of HLB on
283
rheology, mean drop size, and drop size distribution (DSD) uni-
formity for O/W emulsions. That study concluded that there is
an optimal HLB at which the mean drop size minimized with
a narrow drop size distribution. Those results at the micro-
scopic scale may influence the macroscopic product behavior
(rheology), while product stability is also improved. Salager
et al. (2001) introduced the hydrophilic–lipophilic deviation
(HLD) method, which is a more general approach (compared
to the HLB method) for the formulation of emulsified sys-
tems. The HLD method has been successfully implemented
to formulate emulsified systems (Salager et al., 2007) or for
emulsion destabilization (Mercado et al., 2014). This approach
takes into account the physicochemical contributions from
a wider variety of components such as surfactants, alcohols
or electrolytes through the implementation of experimen-
tal parameters (Mercado and Fuentes Pumarejo, 2016), which
could make this method more difficult to link to the integrated
design of emulsified products compared to the HLB method.
The implementation of HLD is expected to demand signif-
icant experimental efforts to determine the parameters for
each potential surfactant included in the product design pro-
cess. Since HLD considers the physicochemical contributions
for several components for emulsified systems formulation,
it may represent a breakthrough for the integrated design of
cosmetic emulsions.
2.2.3. Viscosity modifying agents
The viscosity of cosmetic products can be modified for sat-
isfying consumer preferences (sensorial properties) (Susuki
and Watanabe, 1971), preventing phase separation or improv-
ing the stability of the emulsion (Barel et al., 2010). The
use of thickening agents enables the adjustment in emul-
sified cosmetic product viscosity. Water-soluble thickeners
are often preferred for cosmetic products. Depending on
their source, these agents can be classified as organic
and inorganic. Organic compounds are classified as natu-
ral, natural-modified, and synthetic polymers (Mitsui, 1997).
Xuewu et al. (1996) reported that power or exponential rela-
tionships could describe the increase in viscosity as a function
of the polymer concentration as given by Eqs. (1) and (2).
 = 1 exp ( 1 C) (1)
 = 2 C 2 (2)
where C is the concentration of polymer while 1 , 2 , 1 , and
2 are experimental constants.
Also, some inorganic products act as water-soluble thick-
ening agents, such as bentonite, laponite, silicate powders,
and colloidal alumina (Mitsui, 1997). Additionally, some com-
pounds are used to modify the viscosity of the oily emulsion
phase, including lipophilic thickening agents such as poly-
isobutene, hydrogenated polyisobutene, stearic acid, or wax
esters (Mitsui, 1997).
2.2.4. Sensory agents
Sensory agents can provide sensorial properties to a cos-
metic product, enhancing consumer perception (Barel et al.,
2010). This effect is reached using ingredients such as viscos-
ity modifying agents, emollients, or humectants (Savary et al.,
2013). As mentioned above, viscosity modifying agents may
influence the rheological behavior of an emulsion. Since the
rheological properties of an emulsified product relates to tex-
tural properties, the effect of the viscosity modifying agents
284 Chemical Engineering Research and Design 1 6 1 ( 2 0 2 0 ) 279–303

can be related to sensorial properties (texture) (Gilbert et al.,

Table 1 – Physical methods for emulsions preparation
2013a). Regarding emollients, these components can affect (L = low, M = moderate, H = high. B = batch, C = continuous.
cosmetic product properties such as consistency and spread- V = viscous forces in laminar flow, T = turbulence,
ability (Gore et al., 2018). Emollients are substances that help to C = cavitation) (Myers, 2006).
maintain the softness, smoothness, and pliability of the skin Method Energy input Process Drop formation
(Terescenco et al., 2018). Emollients can be classified according
Shaking L B T
to their chemical composition as hydrocarbons, fatty alcohols,
Stirring
esters, and silicone derivates (Chao et al., 2018). Emollients
Simple L B/C T/V
can increase the lipid content of the upper layers of the skin, Rotor–stator M–H B/C T/V
preventing skin defatting and dry skin (Barel et al., 2010). Vibrator L B/C T/V
Regarding humectants, these compounds are ingredients that Scraper L–M B/C V
can enhance the water content of the skin (Terescenco et al., Pipe flow
2018). Humectants are hygroscopic constituents, commonly Laminar L–M C V
Turbulent L–M C T
water-soluble, which maintain an aqueous film at the skin
Colloid mill M–H C V
surface (Barel et al., 2010). Humectants, in cosmetic formula-
Ball and roller mill M B/C V
tions, treat or prevent dry, rough, scaly, itchy skin, and minor Homogenizer H B/C T/V/C
skin irritations (Cochran and Anthonavage, 2015). The most Ultrasonic M–H B/C C/T
implemented humectants in cosmetic products are glycerine, Injection L B/C T/V
propylenglicol, polyethylene glycol, sorbitol, amino acids, and Electrical M B/C –
skin natural moisturizing factors as the pyrrolidonecarbonate Condensation L–M B/C –
Aerosol to liquid L–M B/C –
and lactates (Barel et al., 2010).

mechanism (i.e. turbulence, laminar, and cavitation), and the

3. Product preparation
Three principal approaches are used to prepare emulsified
products: spontaneous emulsification, phase inversion, and
mechanical techniques. Respecting spontaneous emulsifica-
tion, emulsion formation arises from two immiscible fluids
with very low interfacial tension. Once these fluids come
into contact, the emulsion forms with no energy require-
ment (Leal-Calderon et al., 2007) due to significant chemical
potential gradients between the phases (Solans et al., 2016).
In the phase inversion method, the emulsion structure sud-
denly changes; for instance, from O/W to W/O or vice versa
(Schramm, 2005). This emulsion structure modification occurs
as a result of changes in temperature, pressure, salinity, use
of a co-surfactant, or the oil-water ratio (Leal-Calderon et al.,
2007). This method allows the preparation of emulsions at
short production times with low energy costs (Hua et al., 2019).
Phase inversion technique has been performed to achieve
stable emulsified products for cosmetic and pharmaceutical
applications. (Miller et al., 2001) proposed an approach for
phase inversion on O/W emulsions. In that study, a hydrophilic
emulsifier was added to the emulsion, changing the HLB.
This technique allowed the preparation of stable cosmetic
emulsions through the phase inversion approach, but with-
out requiring temperature-dependent emulsifier properties
(Miller et al., 2001). Quintão et al. (2013) applied the phase
inversion technique to prepare emulsions of hydroalcoholic
extract of Vellozia Squamata for pharmaceutical or cosmetic
applications (phytomedicines and topical products). Accord-
ing to their results, the emulsions were stable since no changes
in mean drop sizes emerged during an accelerated physical
stability evaluation.
Mechanical emulsification is perhaps the most popu-
lar technique. Therefore, the information going forward is
related to this technique. This emulsification process is the
classical method for emulsion preparation (Schramm, 2005).
This method requires the addition of mechanical energy for
droplets formation through high shear rate values (Kékesi
et al., 2016). These techniques can be classified depend-
ing on the amount of energy consumed (i.e. low, moderate,
or high-energy consumption methods), the drop disruption
mode of operation (batch or continuous) (Becher, 1983). Some
studies have proposed the semi-batch process as an addi-
tional mode of operation that consists of a two-step procedure.
First, the dispersed phase is incorporated into the continuous
phase, while in the second step the system is homogenized in
the same equipment (Alvarez et al., 2010). Table 1 summarizes
a list of mechanical techniques for emulsion preparation.
3.1. Mixing
Mixing is an essential factor in manufacturing emulsified cos-
metic products since this process variable can be related to the
shear experienced within the system, which is linked to the
drop breakup process (Tcholakova et al., 2011). Hence, vari-
ables such as mixing velocity or impeller geometry typically
appear as elements of significant concern. Regarding mixing
velocity, this process variable has been reported to influence
the droplet size and polydispersity of the product (Capdevila
et al., 2010). Simovic et al. (1999) evaluated the effect of process
variables, such as mixing time and velocity, on O/W emul-
sions’ viscosity and physical stability. That work found that
as the mixing time and mixing velocity increases, the prod-
uct viscosity and stability also increase. In contrast, some
studies have proposed the angular mixing velocity (tip veloc-
ity) as a more appropriate scale-up variable. Capdevila et al.
(2010) studied the influence of emulsification process vari-
ables on the droplet size and polydispersity of W/O highly
concentrated emulsions. According to their results, the main
factor affecting the drop size is the shear stress applied to the
droplets, which in turn is related to the tip velocity. Addition-
ally, Capdevila et al. (2010) also studied the effect of product
formulation. According to their results, the surfactant/oil ratio
was the most crucial formulation variable to decrease the aver-
age drop size in the emulsion. These findings also highlight the
links between product properties, emulsification process, and
product formulation.
Concerning impeller geometry, this process variable has
been reported to influence the emulsified product viscosity
and the amount of energy incorporated during the emulsifi-
cation process (Gallo-Molina et al., 2018). Torres and Zamora
(2002) studied the effect of axial (propeller), radial (Rushton),
 Chemical Engineering Research and Design 1 6 1 ( 2 0 2 0 ) 279–303
and mixed flow (Lightnin) impellers on power consump-
tion during the emulsification process. That study reported
that the propeller impeller was able to transfer more energy
than the Rushton and the Lightnin impellers, thus showing
the influence of flow characteristic on energy consumption;
though that work also reported that each of these impellers
had different diameters which can affect the results. Similarly,
El-Hamouz (2009) studied the effects of two different impeller
geometries on the DSD for silicone O/W emulsions. In that
work, the two impellers had the same diameter but differ-
ent power numbers. According to their results, the tip velocity
is a more appropriate way of predicting the mean drop size
than the energy dissipation rate for emulsified products (El-
Hamouz, 2009). Pradilla et al. (2015) reported that the energy
incorporated during the emulsion manufacturing process is
mainly a function of two process variables: the tip velocity by
which droplet formation is set through shear, and the pump-
ing capacity of the impeller, which determines the circulation
of the emulsion on the mixing tank.
3.2. Energy
The energy added during the emulsification process can be
treated as a transversal variable for the manufacture of emul-
sions, i.e. influencing the product properties at different scales
(Pradilla et al., 2015). Alvarez et al. (2010) related this process
variable for (W/O) emulsions with dispersed phase volume
fractions of 91% and 93% at the macroscopic scale to rhe-
ology, and at the microscopic scale to the average drop size
of the emulsion. According to their results, there is a rela-
tionship between average drop size (dp ) and emulsification
energy (Ev ) for highly concentrated emulsions, i.e. dp ∝ Env .
Pradilla et al. (2015) obtained a similar result for O/W emul-
sions with a dispersed phase concentration between 80% and
90% (w/w). According to their results, the dispersed phase con-
centration can influence the relationship between energy and
average drop size. Changes in the exponent (n) of the expres-
sion presented above demonstrate the influence of the energy
incorporation over drop size. For emulsions between 80% and
85% of dispersed phase concentration, n is set to −2.5, while
for emulsions with dispersed phase concentration between
85% and 90%, n is set to −1.5. Recently, Li et al. (2018) pre-
sented similar results for dilute O/W emulsions. In that work,
the same functional relationship between average drop size
and energy incorporation was established. In that case, the
value for n was found to be −0.6, following the exponential
trend between energy incorporation and the dispersed phase
concentration. These findings illustrate the existing close rela-
tionship between product formulation, process variables, and
product properties, highlighting the importance of including
this process variable as a transversal factor for the cosmetic
emulsified product design problem.
3.3. Temperature
The temperature has been found to affect product properties
such as rheology, drop size, or interfacial tension, as well as the
stability of emulsified cosmetic products. Shinoda and Saito
(1969) related the emulsification temperature to the drop size
of O/W emulsions. That study reported that the drop size of the
emulsions decreased as the temperature increased, achieving
the smallest drop size close to the phase inversion tempera-
ture. This effect of temperature on drop size can be related
to a reduction in interfacial tension as the temperature of
285
the system increases (Ye et al., 2008). On the other hand, the
reduction in drop size could also be achieved by decreasing the
temperature. The viscosity of the continuous phase increases
as the temperature decreases (Wright, 1961), which may also
increase the shear stress for a given mixing condition. Since
the shear stress experienced by the dispersed phase may pro-
duce the drop deformation and breakup (Tcholakova et al.,
2011), a higher shear stress is expected to produce smaller
drop diameters.
Regarding stability, this phenomenon is influenced by the
emulsification temperature since the adsorption of the emul-
sifying agent decreases with temperature, and in some cases,
it may be thermally decomposed (Morrison and Ross, 2002).
However, moderate temperature increments can facilitate the
emulsification since increasing temperature decreases the
interfacial tension and viscosity of the fluid (Chen and Tao,
2005). Martin-Piñero et al. (2019) investigated the effect of
the heating temperature for a mixture of thyme oil and sur-
factant on the physical stability of emulsions prepared with
this mixture as a dispersed phase. That study showed that
the heating temperature has no significant influence on the
physical stability of the emulsions prepared. Nevertheless, a
study on the physical stability of the dispersed phase mix-
ture showed an improvement in the thyme oil/surfactant
mixture stability as the temperature increases (Martin-Piñero
et al., 2019). Additionally, it also has been reported that stor-
age temperature is an essential factor for product stability.
Limthin and Phromyothin (2019) studied the stability of O/W
nano-emulsions containing Centella Asiatica, Lycopersicon Escu-
lentum Mil. and Moringa oleifera Lam. extract, which could have
key pharmacological cosmetic applications. According to their
results, the storage temperature affects product stability, with
an optimal temperature around 25 ◦ C. Moreover, the corre-
lation between process variables, formulation, and product
stability was also highlighted in that study. Process conditions
such as formulation (water:oil:surfactant ratio), and mixing
(agitation velocity and homogenization time) were manually
adjusted to improve the emulsified product stability. Accord-
ing to their results, that study established a formulation of
80:10:10 (water:oil:surfactant ratio) homogenized for 20 min at
4000 rpm.
Certainly, there is a coupled effect between the formula-
tion variables, process variables, and product properties of an
emulsified system. These effects should be considered to solve
and optimize the cosmetic emulsified product design problem,
highlighting the applicability of integrated design strategies
for emulsified cosmetic products design.
4. Product properties
From a multi-scale perspective, the properties of an emulsi-
fied product can be classified as macroscopic, microscopic,
and molecular.
4.1. Macroscopic scale properties
Rheology and sensory perception are perhaps the most
notable properties investigated at the macroscale level. The
rheological behavior of cosmetic emulsions, which is asso-
ciated with deformation and flow (Barnes et al., 2005), is
an essential factor in the design and manufacture of emul-
sions. The rheological properties of emulsified products are
linked with product stability (Gallegos and Franco, 1999) and
286 Chemical Engineering Research and Design 1 6 1 ( 2 0 2 0 ) 279–303
are useful to predict the product behavior during fabrication,
packaging, and final use (Tadros, 2004). As reported in the
literature, product formulation, composition, or process con-
ditions strongly influence these product properties (Pradilla
et al., 2015).
Regarding product formulation, (Krstonošić et al., 2019)
evaluated the interactions between Xanthan gum (anionic
polymer) and anionic (sodium lauryl sulfate, SDL) or non-ionic
(Tween 80) surfactants. That study concluded that the inter-
actions between Xanthan gum and these surfactants affect
the product’s rheological behavior. According to their results,
the Xanthan gum solution becomes more viscous as the
surfactant and polymer concentrations increase. Also, more
viscous products may be obtained using surfactant Tween
80 compared with those prepared using SDL, probably as a
consequence of electrostatic interactions between Xanthan
gum and SDL (Krstonošić et al., 2019). Product composition
(i.e., dispersed phase concentration) also has an impact on
the rheological properties of concentrated emulsified prod-
ucts (Guerrero et al., 1998). Briceño et al. (2001) evaluated the
influence of dispersed phase concentration and its viscosity
on the mixing process of concentrated O/W emulsions in the
transition flow regimen. That study stated that, for the transi-
tion flow regimen, as the concentration in the dispersed phase
increases, the emulsion viscosity dominates the formation of
the drop size. Thus, increasing the dispersed phase concen-
tration reduces the droplet sizes with no additional energy
consumption (Briceño et al., 2001). For dilute emulsified prod-
ucts, this effect is less pronounced (Kundu et al., 2015).
Concerning to process variables, the energy incorporated
through the emulsification process can affect the mean drop
size and their distribution, which influences the product rhe-
ological properties (Gallo-Molina et al., 2018). Leong et al.
(2009)) evaluated the effect of the applied shear rate (pro-
cess variables), and surfactant selection (product formulation)
on dilute O/W nano- emulsions average drop size (product
property). In that work, the drop size was minimized by ade-
quately selecting the product composition (dispersed phase
content), which in turn is associated with a minimum shear
rate or power density requirement. Furthermore, it has also
been reported that impeller geometry at a constant tip veloc-
ity during the emulsification process can affect the elasticity
of an emulsified product (Pradilla et al., 2015). These facts
demonstrate that the rheological behavior of an emulsified
cosmetic product is affected by either product composition or
formulation and process variables.
With regards to sensory perception, the textural proper-
ties that are commonly evaluated for cosmetic products are
absorbency, greasiness, smoothness, spreadability, thickness,
viscosity, and cohesiveness (Schwartz, 1975). It is common to
perform this evaluation through a panel of experts based on
the (Schwartz, 1975) approach (see Table 2), which provides
a sensory texture profile method to assess skincare prod-
ucts using panel evaluations. (Parente et al., 2008) evaluated
the textural properties of emollients commonly used in the
cosmetic industry through a panel of sensory assessors. In
that study, differences in the sensory profiles of the emollient
tested were found, which could produce a different textu-
ral performance of the emulsified cosmetic product (difficulty
of spreading, gloss, residue, stickiness, and oiliness). These
findings showed that methods based on a panel of expert cri-
teria might provide useful information for the development of
new emulsified cosmetic products. However, those methods
require time and economic resources; therefore, associating
sensory assessments to instrumental measurements offers
an excellent opportunity to improve the emulsified cosmetic
product design process (Gilbert et al., 2013b). In this regard,
some studies have considered the relationships between rhe-
ological and textural variables of cosmetic emulsions. Wittern
et al. (2001) correlated rheology measurements to sensory
evaluations for cosmetic emulsions. According to their results,
at high shear rates, the sensory skin feeling is related to the
product viscosity; at low shear rates, this is related to the prod-
uct yield stress and its viscosity as well. Gilbert et al. (2013b)
implemented the quantitative descriptive analysis and the
spectrum descriptive analysis method to investigate the pre-
diction of the textural properties of cosmetic emulsions using
instrumental measurements. In that study, the authors corre-
lated the textural properties of emulsified cosmetic products
with instrumental texture properties (using a texture ana-
lyzer) and rheological assessment (flow, creep, and oscillation
tests). Brummer and Godersky (1999) related the sensations
experienced during application on the skin of an emulsified
cosmetic product with the flow properties. That study showed
that rheology affects the textural product perception. Gilbert
et al. (2013a) investigated the relationships between rheologi-
cal and textural parameters of emulsified cosmetic products.
That work suggested that differences in shear-thinning behav-
ior cause notable variances in the textural parameters of the
product.
The textural properties of emulsified cosmetic products are
governed not only by rheology but also by product formula-
tion. Dubuisson et al. (2018) evaluated the impact of thickener
and oil phase fraction on the textural properties of cosmetic
products. Their results showed that increasing the oil phase
fraction and amounts of thickener enhance specific textural
parameters of the product (the integrity of shape, penetra-
tion force, wetness, ease of spreading, grease, stickiness, and
gloss.). Other components, e.g., emollients, have been found
to have an impact on product textural properties, such as
spreadability and greasiness (Arrieta-Escobar et al., 2019). Gore
et al. (2018) evaluated the effect of emollients and a mixture
of emollients in the spreadability and frictional effect on films
of O/W emulsions. Their results showed that the presence of
emollients in the dispersed phase enhances the spreading of
the emulsion on the skin, while the friction behavior is mainly
driven by the emollient consistency. These findings highlight
that consumer perception depends on both the formulation
and rheological behavior of the emulsified cosmetic product.
4.2. Microscopic scale properties
The microscopic structure within cosmetic emulsified product
governs the macroscopic scale behavior of these products, as
a consequence of the influence of the product microstructure
on its rheological properties. This microstructure is repre-
sented by the DSD and volume fraction of the dispersed phase
(Wibowo and Ng, 2001), which can also directly affect the inter-
actions between the droplets thus affecting the macroscopic
properties of the emulsion. These microscopic properties are
critical factors for designing emulsified products since they
relate to emulsion rheology and energy consumption during
the manufacturing process (Alvarez et al., 2010). Therefore,
the microstructure of an emulsified cosmetic product can be
affected by the product formulation or composition as well as
the manipulation of the process variables.
Regarding product formulation, viscosity modifying agents
can generate an electrostatic or steric barrier between droplets
 Chemical Engineering Research and Design 1 6 1 ( 2 0 2 0 ) 279–303 287

Table 2 – Texture profile for skincare product evaluation (Schwartz, 1975).

Stage of evaluation Skincare product attribute and definition Texture profile parameters

PICK-UP, product removed from
container, product poured or squeezed
from bottle onto fingertips, or product
lifted from jar with forefinger.
RUB-OUT (application), spread of product
over and into skin with fingertips using
gentle circular motion at a rate of two
rubs per second for a specified period of
time, depending on the product.
AFTER-FEEL (and appearance), evaluation
of skin surface with fingertips, visually
and kinesthetically immediately after
product application and possibly at
varying intervals thereafter.
THICKNESS – Perceived denseness of product. Viscosity (for lotions) hardness,
Evaluated as force required to squeeze between cohesiveness (also springiness,
thumb and forefinger. adhesiveness) for creams
Or
CONSISTENCY – Perceived structure of product.
Evaluated as resistance to deformation and
difficulty of lifting from container.
SPREADABILITY – Ease of moving product from Viscosity, cohesiveness, springiness,
point of application over rest of face. Evaluated gumminess, adhesiveness other
as resistance to pressure. characteristics – (oil and water content of
ABSORBENCY – Rate at which product is product)
perceived to be absorbed into skin. Evaluated by
noting changes in character of product and in
amount of product remaining and by changes in
skin surface.
AFTER-FEEL – Type and intensity of product Other characteristics - (oil and water
residue left on skin; changes in skin feel. Product content) geometrical characteristics–
residue is described by type. (gritty, powdery. etc.)

(Parente et al., 2008), which together with an increment in
the continuous phase viscosity, produce an improvement in
the stability of an emulsified cosmetic product since this phe-
nomenon causes a reduction of the motion of the droplets in
the system (Myers, 1999). Therefore, these viscosity-modifying
agents can affect the microscopic structure of the product,
which in turn influences the macroscopic behavior of the cos-
metic emulsion as a finished product (Gräbner and Hoffmann,
2017). Additionally, product microstructure has been reported
to be related to the dispersed phase concentration. According
to Pradilla et al. (2015), increments in dispersed phase con-
centration promote small average drop sizes for emulsified
products. That study concluded that not only product formu-
lation could affect the microscopic structure of the product,
but also process variables such as pumping capacity or tip
velocity (related to shear rate). The latter is an essential factor
for the drop formation within the emulsified cosmetic prod-
uct since this variable establishes the shear rate experienced
by the dispersed phase during emulsification (Pradilla et al.,
2015). Tip velocity also can affect the product DSD. As reported
by Cristini et al. (2003), the DSD strongly depends on the shear
rate experienced within the system.
Moreover, some studies have reported that DSD could also
affect product properties (Otsubo and Prud’homme, 1994) and
product stability (Gaukel et al., 2015), thus becoming a cru-
cial factor in designing emulsified cosmetic products. (Otsubo
and Prud’homme, 1994) studied the effect of DSD on the rhe-
ological behavior of O/W emulsions at moderate and high
concentrations of the dispersed phase. That study showed
that the flow behavior of the emulsion (especially at concen-
trations close to the critical volume fraction) strongly depends
on both, mean drop size and the width of the DSD. Likewise,
Richardson and Booth (1993) studied the effect of multiple
physical parameters, including viscosity and DSD on the per-
ceived creaminess of milk and creams. That study showed that
the width of the DSD might influence the textural properties
of emulsified products, thus affecting the final consumer per-
ception of the product. Also, Afoakwa et al. (2008) evaluated
the effects of particle size distribution on textural properties
and the appearance of dark chocolates. In that study, textural
parameters (firmness, consistency, cohesiveness, index of vis-
cosity, and hardness) were evaluated; the results showed that
interactions between product formulation and particle size
distribution can influence the texture of the product. These
findings lead to assert that the macroscopic behavior of emul-
sified products is highly influenced, not only by mean drop size
and dispersed phase concentration but also by DSD. Although
DSD has been found to play a vital role in emulsified prod-
uct performance, there is still a lack of implementation of
models that consider the DSD for the development of new
emulsified cosmetic products. Consequently, the production
of new emulsified cosmetic products with specific desired
properties makes use of a combination of extensive exper-
tise from previous product formulations and experimental
data, which causes a more challenging design process delay-
ing product development (Raikar et al., 2009). An attractive
method that can be used to address this issue consists of
the development of rigorous mathematical models for DSD at
different process conditions and for various product formu-
lations (Maindarkar et al., 2015a). PBM is an approach widely
used to describe systems characterized by particle distribu-
tions (Nopens et al., 2015), making this framework suitable for
emulsified cosmetic product characterization. PBM has been
extensively applied for modeling DSD during emulsification,
due to the possibility that this method offers to simultane-
ously model coalescence and breakup processes (Håkansson
et al., 2013). As the demands for accurate control of DSD for
process optimization and new product design is increasing
(Qin et al., 2016), the PBM framework is expected to play a
more significant role in product and process design in the
near future. Despite their significant and potential impact in
this field, few studies have been conducted coupling PBM to
emulsified product design.
PBM has been implemented to control product properties
or achieving a desired DSD in the product. Srour et al. (2007)
developed a model for process design and control of emulsion
terpolymerization, which enables the prediction and control
of product final use properties. In that study, the particle size
distribution was predicted, employing a PBM to support the
optimization and properties product control in semi-batch
emulsion terpolymerization. Crowley et al. (2000) aimed to
achieve a bimodal target distribution during styrene semi-
batch emulsion polymerization since, according to industrial
expertise, multiple latex product properties improve as a
288 Chemical Engineering Research and Design 1 6 1 ( 2 0 2 0 ) 279–303
result of a bimodal particle size distribution. In that study, a
PBM was implemented for particle size distribution estima-
tion to determine an appropriate surfactant feed to achieve
the desired distribution. Maindarkar et al. (2015a) made use of
a PBM for achieving the desired DSD for the design of emul-
sified products manufactured in high-pressure homogenizers.
In that work, the authors attained a desired normal DSD, while
simultaneously, they minimized the amounts of surfactant
used for emulsion preparation. The experimental validation
of the optimal solution showed excellent agreement with the
target DSD, demonstrating that it is feasible to couple the PBM
framework to the emulsified cosmetic product design. These
findings highlight the deciding role that the application of PBM
could play for integrated emulsified cosmetic product design.
PBM implementation may contribute to a better control of the
product properties during the manufacturing process, or for
designing emulsified cosmetic products with specific desired
properties.
4.3. Molecular scale properties
Molecular properties (including Brownian motion, diffusion,
osmotic pressure, surface tension, interfacial charge, and
many other derived interfacial and electrical properties) are
factors to be considered for the design of emulsified products
(Sharma et al., 2014). Interfacial tension is probably the most
critical property of fluid-fluid interfaces (Lyklema, 2000) since
it could potentially be used to control the emulsion’s stability
(Sharma et al., 2014) and drop formation during emulsification
(Farzad et al., 2018). Interfacial tension is the work demanded
to generate a new interface area between two immiscible flu-
ids (Schowalter, 1979); hence, this property impacts energy
consumption during the emulsification process. Both product
formulation and process variables, such as the emulsification
temperature, could influence this molecular property.
With regards to product formulation, interfacial tension is
related to the surfactant selection, i.e., this molecular prop-
erty is linked to the replacement of molecules of solvent at
the interface by molecules of the surfactant (Rosen, 2004).
Pichot et al. (2010) evaluated the effect of surfactant type
(ionic and non-ionic surfactants) and surfactant concentra-
tion on the interfacial tension of O/W emulsions. According
to their results, as the surfactant concentration increases, the
interfacial tension decreases until a stable value is reached,
with average drop sizes around 10 ␮m and 30 ␮m for the non-
ionic and ionic surfactants, respectively. Pichot et al. (2010)
concluded that this phenomenon correlates to the emulsi-
fied product stability since the average drop size decreases as
the interfacial tension is reduced, as a consequence of higher
surfactant concentrations. Additionally, some components
such as alcohol or electrolytes can absorb at the oil–water
interface according to their structural and geometric arrange-
ments affecting the interfacial tension (Sharma et al., 2014).
El-Aasser et al. (1984) studied the effect of the fatty alcohol
chain length on the interfacial tension for O/W mini emul-
sions. The interfacial tension was assessed for alcohol with
a chain length between 10 and 18 carbon atoms. The results
showed that the interfacial tension increases as the alcohol
chain length increases, from 4.1 dyn/cm (decanol) to 8.3 dyn/cm
(octadecanol). With regards to electrolytes, Kent and Saunders
(2001) investigated the effect of adding MgSO4 on the oil–water
interfacial tension. That study reported that, as the electrolyte
concentration increases, the interfacial tension decreases.
Likewise, that study also showed that a reduction in the
interfacial tension causes an increment in drop size. That
increment in drop size may be attributed to a reduction of
the surfactant adsorption rate at the oil–water interface due
to the presence of electrolytes.
As mentioned above, interfacial tension can be influenced
by process variables. Temperature plays a crucial role in reduc-
ing the interfacial tension for an emulsified cosmetic product.
An increment in the temperature could produce a reduction
in the interfacial tension of the system. This phenomenon is
a result of the mobility of molecules at fluid interfaces. As the
temperature increases, the mobility of surfactant molecules
and their total entropy also increases, thus reducing the Gibbs
free energy (G) (Myers, 1999). This reduction in G eventu-
ally causes a reduction in the interfacial tension (), since this
property can be thermodynamically defined as (Myers, 1999)
G
= (3)
A
where A represents the new surface area. Recently, atten-
tion has been placed on the role that interfacial rheological
behavior could have on the stability of emulsified prod-
ucts (Fuller and Vermant, 2012). The interface between bulk
phases can adsorb molecules (ions, electrolytes, surfactants,
and polymers), which can modify the interfacial tension,
affecting product stability. Consequently, having access to
the molecules arrangement in the interface would be cru-
cial for the design of new emulsified products with enhanced
stability (Sharma et al., 2014). Some studies reported that
these rheological properties of interfaces have a significant
impact on the stability of macroscopic systems, e.g., emul-
sions (Pepicelli et al., 2017). Georgieva et al. (2009) evaluated
the elasticity of the oil–water interface for O/W emulsions
stabilized using cationic, non-ionic, and polymeric surfac-
tants. That study determined that the nature of the surfactant
has a significant effect on surface elasticity. That study indi-
cated that non- ionic surfactants produced interfaces with
higher interfacial elastic modulus and stable emulsions. Those
results demonstrated the high impact that surface elastic-
ity has on emulsified product stability. Pal (2011) developed
mathematical models to predict the viscosity of concentrated
emulsions. That model considered the effects of interfacial
rheology through an “interfacial mobility parameter.” This
parameter varies from zero (mobile interface) to one (immo-
bile interface), enabling to model the decrease in mobility of
the interface due to the presence of a surfactant. Since the
interfacial rheological properties may influence the emulsified
product’s stability, these properties may be implemented to
relate the molecular scale behavior to the integrated design of
emulsified cosmetic products. However, more research must
be conducted to link bulk responses of the emulsified product
with interfacial rheology (Pradilla et al., 2018).
5. Product stability
Due to the unstable nature of emulsified cosmetic products,
these systems tend to destabilize over time. Five mechanisms
have been conventionally used to explain the destabilization
process in emulsified products: creaming, flocculation, coales-
cence, Ostwald ripening, and phase inversion (Pradilla et al.,
2018). These mechanisms can be related to breakdown pro-
cesses during emulsified product storage. According to Tadros
(2009), during the emulsified product storage, some destabi-
 Chemical Engineering Research and Design 1 6 1 ( 2 0 2 0 ) 279–303
lization process may occur as a consequence of the following
phenomena:
• particle size distribution and density variance within the
continuous and dispersed phase, which may cause phase
separation;
• attractive and repulsive forces, which determine floccula-
tion
• the solubility of the disperse droplets, producing Ostwald
ripening;
• the stability of the liquid film between the droplets, which
determines coalescence, and phase inversion.
Emulsified product stability is an important quality control
parameter for screening purposes during the initial phases
of the development of a new cosmetic emulsified product
(Chiari et al., 2019). Wibowo and Ng (2001) showed that an
emulsified cosmetic product should remain stable for over a
year subjected to the environmental conditions that it would
experience. Thus, it is crucial to evaluate the destabilization
process occurring within the emulsified product during this
period time. The physical stability of an emulsified cosmetic
product can be related to different variables such as product
properties, emulsification process, or product formulation.
The product stability has been typically related to the
product’s rheological properties at the macroscopic scale
and the DSD and mean drop size at the microscopic scale.
Rheology has been implemented to assess and predict the
long-term physical stability of emulsified products, including
destabilization phenomena such as creaming, flocculation, or
coalescence (Tadros, 2004). Tadros (2004) reported that rheo-
logical measurements such as steady-state shear stress, creep,
and oscillatory tests can be performed to assess the long-term
stability of emulsified products. Regarding DSD and mean drop
size, Pradilla et al. (2018) used these properties to evaluate the
long-term physical stability of W/O emulsions at the micro-
scopic scale. According to their results, the destabilization
phenomena that occurs within the system can be associated
with increments in mean drop size and changes toward larger
drop sizes in the DSD. (Aguilera-Miguel et al., 2018) assessed
the performance of modified dextrans as stabilizers for highly
O/W concentrated emulsions. In that work, the authors con-
sidered, together with other factors, drop size changes as a
parameter to evaluate dextrans performance as a stabilizer.
Rámirez et al. (2002) evaluated the effect of DSD bimodality on
O/W emulsions viscosity and stability. That study indicated
that bimodality tends to decrease the emulsion viscosity,
affecting the stability of the system. The stability of an emulsi-
fied cosmetic product can also be related to process variables
or product formulation. Simovic et al. (1999) studied the influ-
ence of mixing conditions (mixing speed and agitation time)
on the physical stability of O/W emulsions assessed through
centrifugation. The authors reported that increments in mix-
ing speed and agitation time improved the emulsions’ physical
stability. Similarly, Tal-Figiel (2007) related the stability of O/W,
W/O, and W/O/W cosmetic emulsions to the average drop sizes
and mixing conditions. That study concluded that the average
drop size mainly depends on the energy incorporated dur-
ing the emulsification process, affecting the product’s physical
stability. Process variables, such as mixing regimen, can sig-
nificantly influence the microstructure of the product as a
consequence of the dependence of the DSD on the shear rate
experienced during the manufacturing process (Cristini et al.,
2003).
289
With regards to product formulation, it has been reported
that, in addition to surfactants, the presence of viscosity mod-
ifying agents or electrolytes can modify the stability of the
product. Viscosity modifying agents may improve the physi-
cal stability of cosmetic emulsions. According to Tadros (2004),
a common practice for reducing destabilization phenomena in
an emulsified product is the utilization of viscosity modifying
agents in the continuous phase. Accordingly, if the concentra-
tion of these components were sufficiently high, then neither
creaming nor sedimentation would be present in the product
(Tadros, 2004). Krstonošić et al. (2015) studied the influence
of Xanthan gum on the physical stability of O/W emulsions.
The authors concluded that increases in the Xanthan gum
concentration reduce the average drop size, which improves
the physical stability of the product. Moreover, studies have
reported that adding electrolyte in the emulsified cosmetic
product formulation can also influence the physical stabil-
ity of the emulsion. Galindo-Alvarez et al. (2012) studied the
effect of using a mixture of a non-ionic surfactant and an
amphiphilic anionic polyelectrolyte on the physical stability
of O/W nanoemulsions. According to their results, destabi-
lization phenomena such as Otswald ripening reduces when
these emulsions are prepared using the abovementioned sur-
factant/electrolyte mixture. According to some studies, W/O
emulsions prepared with electrolytes tend to show a more
elastic behavior (i.e. higher elastic modulus values) (Pradilla
et al., 2018). The presence of electrolytes may improve the
product’s stability compared to those manufactured with no
salts (Pradilla et al., 2018; Aronson and Petko, 1993). How-
ever, the presence of electrolytes within the emulsion can also
adversely affect product stability. As surfactants may elec-
trically charge the surface of the dispersed phase particles,
the presence of electrolytes may induce an electrical neu-
tralization if these charges are opposite, which may lead to
destabilization phenomena such as flocculation (Rhein et al.,
2007).
6. Mathematical modeling
The implementation of model-based approaches for the
design of chemical products is an emerging active area in
the chemical industry (Kalakul et al., 2016). This trend is a
consequence of the time and cost reduction that integrated
approaches offer at designing a new chemical product (Gani,
2004). Therefore, the proper modeling of cosmetic emulsion
properties related to its performance as a finished product is
crucial. Accordingly, this section presents an overview of the
main emulsified cosmetic product properties using a multi-
scale modeling approach. Additionally, this section presents a
typical mathematical formulation for the optimization prob-
lem related to the integrated design of emulsified cosmetic
products, and a brief discussion of dimensional analysis.
6.1. Macroscopic modeling
At the macroscopic scale, modeling viscosity plays a vital role
in designing an emulsified cosmetic product from an inte-
grated approach, since a significant number of the product
properties such as the average drop size or energy consump-
tion are related to this rheological property. A wide variety
of mathematical models has been developed for emulsions
viscosity. The first attempt to model the viscosity of emul-
sions was the Einstein model (Einstein, 1906) developed for
290 Chemical Engineering Research and Design 1 6 1 ( 2 0 2 0 ) 279–303

Table 3 – Emulsion viscosity models.

Viscosity model Scope Authors

r = 1 + 2.5 Developed for low dispersed phase volume fraction Einstein (1906)
( < 2%)

r = exp (2.5 ) Applicable in the limiting case when: dc → ∞
  d +0.4c  Arrhenius (1917)
r = 1 + 2.5 d +c Developed for very dilute emulsions, neglecting the Ingram (1932)
interactions among droplets. Integrates the effect of
dispersed and continuous phases viscosity (d ,c )
r = 1 + 2.5 + 14.1 2
Integrated interactions among droplets. Appropriate Guth and Simha
for higher concentrations of the dispersed phase (1936)
ln r =  Modifies the Einstein Model to include the term k Richardson (1950)
which represent the relative compressibility of the
two phases
2.5
ln r = 1− M Good agreement with experimental data for a wide Mooney (1951)
range of ␾. When ␾ is larger than 50–60%, the model
is not valid. (1.35 < M < 1.91)
−2.5
r = (1 − ) Adequate to predict the emulsion viscosity for Brinkman (1952)
higher values of . Assumes rigid spherical particles
in the dispersed phase.
r =   1+  Considered the effect of properties at different Oldroyd (1955)
2
5+2 (5+2)2 1 2 NCA scales:
1+ + 2
2(+1) 10(+1)2 1+ 2 N2
1 CA
1 =
(19+16)(2+3)
 19+16
 • Macroscopic (viscosity, r ) • Microscopic (drop size,
40(+1)
1+ 5(+1)(2+3)
d) • Molecular (interfacial tension,  o/w )
2 =
(19+16)(2+3)
 3(19+16)
 This model was developed for dilute emulsions,
40(+1)
1− 10(+1)(2+3)
which limits its implementation.
c d˙
NCA = 2 ow
This model considers the maximum packing
 concentrations:
For high −2.5 m Krieger and
r = 1 − concentration ( m ) for the dispersed phase. When Dougherty (1959)
m
applied to low concentrated systems, the equations
 −2.5 m
For low concentrations:
tend to the Einstein model.
r = lim 1 − =
→∞ m

1 + 2.5 m
r = 1 +  84  4 Suitable for high dispersed phase concentrations of Yaron and Gal-Or
4 7/3 +10− 2/3 + (1− 7/3 ) slightly deformable particles. The model assumes (1972)
5.5
11
 
uniformly-sized spherical particles.
10( 1− 10/3 )−25 4/3 )+ 10 (1− )( 1− 7/3 )
(1− 1/3
−2
r = (1 − 0.5k ) Developed for highly concentrated systems. k is an Quemada (1977)
experimental phenomenological constant.
0 −0.5
r = c ˙
+ 32 ( − 0.73) NCA Developed for highly concentrated emulsions Princen and Kiss
( > 0.74).  0 is the yiel stress, ˙ is the shear rate, c is (1989)
the viscosity of the continuous phase, and NCA is the
capillary number.
 2r +5K 1.5  
r = exp 1−2.5/ m These two models were developed for concentrated Pal (2001)
 r +5K 1.5
2+5K
emulsions. Considered the effect of dispersed and
r 22+5K =
 −2.5 m continuous phases ratio (K). Accurate prediction of
1− m experimental data, but the first model
overestimates the value for m

a low volume fraction of the dispersed phase (see Table 3). In addition to viscosity, storage modulus (G ) and loss
Some popular models for describing emulsions viscosity are modulus (G ) are two decisive rheological properties of an
the power-law or Herschel–Bulkley model and the exponential emulsified cosmetic product. These two properties are related
model of Barnes (Wibowo and Ng, 2001). The latter enables to the solid-like and fluid-like behavior of the product, respec-
the estimation of viscosity as a function of time once an tively. These properties are correlated as follows:
applied shear force is removed (Wibowo and Ng, 2001). The
viscosity of emulsions strongly depends on variables such as G∗ = G + iG (4)
the volume fraction of the dispersed phase, temperature, or
viscosity of the continuous phase (Kundu et al., 2015) (see where G* is known as complex modulus (Wibowo and Ng,
Table 3). Typically, most of the mathematical models for vis- 2001). Some mathematical relationships have been developed
cosity estimation are expressed as a function of the relative to predict the G for emulsified systems. (Princen and Kiss,
viscosity. This parameter denotes the ratio between contin- 1986) presented a mathematical model for predicting the stor-
uous phase viscosity and emulsion viscosity (Kundu et al., age modulus for concentrated O/W emulsions, i.e.
2015). For predicting emulsions viscosity, it is common to
employ viscosity models developed for suspensions to infer  0.33
G = 1.769 ϕ (ϕ − 0.712) (5)
the viscosity dependence of dispersed phase concentration R32
(Pal, 2001). Table 3 presents some of the mathematical mod-
els commonly used for predicting the viscosity of emulsified where  is the interfacial tension, R32 represents the mean
products. drop radius, and ϕ is the dispersed phase volume fraction.
Paruta-Tuarez and Marchal (2013) proposed a more general
 Chemical Engineering Research and Design 1 6 1 ( 2 0 2 0 ) 279–303
model-based method on the percolation theory to estimate
the elastic modulus of highly concentrated emulsions. That
study concluded that it is possible to derive the Princen and
Kiss model from a Taylor first-order expansion, which could
be used as a general approach to model the elastic modulus in
highly concentrated emulsified systems. Mougel et al. (2006)
proposed a relationship for G as a function of the interfacial
tension (), average drop radius (Rav ), intermolecular distance
between droplets (D0 ), the critical volume fraction (ϕc ), the
dispersed phase volume fraction (ϕ), and an experimental pro-
portionality coefficient (A), i.e.
2AD0 ϕ
G =
2
Rav (ϕc − ϕ)
This model is valid for a wide range of dispersed phase vol-
ume fractions (70–95%) (Mougel et al., 2006). However, since
the model was developed using a specific nonionic surfactant
(Span 80), additional research must be conducted to determine
if the model is still accurate while using different surfactants
(Mougel et al., 2006). Additionally, Masalova and Malkin (2007)
proposed two mathematical models for G based on geomet-
rical arguments (Eq. (7)) and dimensional analysis (Eq. (8)):
ı
G = k 2
 (ϕ − ϕ∗ )
(2R)
m
ı
G = k 2
(ϕ − ϕ∗ )
n
(2R)
In these equations, k reflects the transition from the diag-
onal elongation to the simple shear, ı is the width of a thin
surface layer related to the elasticity of droplets, ϕ* is a char-
acteristic volume fraction of the dense packing, while m and n
are scaling factors (Masalova and Malkin, 2007). According to
the authors, although both approaches (energetic and dimen-
sional) lead to similar mathematical relationships, Eq. (8) is a
more general expression than Eq. (7). Also, these two models
have a limited range of application since they were developed
for highly concentrated emulsions with a dispersed phase
weight concentration between 90% and 96%.
6.2. Microscopic modeling
The microscopic scale of an emulsified cosmetic product is
typically characterized by an average drop size and the DSD.
Although DSD can influence the product properties, and con-
sequently the consumer perception, most of the available
mathematical models neglect the DSD (Wibowo and Ng, 2001).
Most of the mathematical models commonly used for predict-
ing emulsified product properties are based on a mean drop
size, such as the Sauter mean diameter (d32 ) (e.g., Oldroyd
model, Table 3). (Tcholakova et al., 2011) presented equations
for maximum stable drop size (dmax ) at the viscous (Eq. (7))
and inertial (Eq. (10)) hydrodynamic regimes of drop breakup.
These emulsification regimens were proposed by the stud-
ies performed by Kolmogorov (1949) and Hinze (1955) on the
emulsification in turbulent flow.
1/3 3/5
D ε1/3 dD −3/5 −2/5
dmax = A1 1 + A2  3/5 c
 cess (Liao and Lucas, 2009). For these models, Liao and Lucas
−1/2 −1/2 −1/2
dmax = A3 c ε c  (10)
291
From the Kolmogorov theory of isotropic turbulence, it is
possible to define models in terms of a Weber number poten-
tial factor (We0.6 ) for predicting the maximum stable drop size
(dmax ) (Zhou and Kresta, 1998). Similarly, d32 can be correlated
to the maximum stable drop size using Eq. (11), where the
constant “c2 has been reported to vary between 0.37 and 0.7
(El-Hamouz, 2009).
d32 = c2 dmax (11)
In agreement with these findings, Zhou and Kresta (1998)
presented an extensive review of available correlations for the
(6) prediction of d32 as a function of Weber’s number. Likewise,
Calabrese et al. (1986) support the assumption that the mean
drop size may be estimated as a function of Weber’s number
using experimental data for emulsified systems. On the other
hand, Pacek et al. (1998) have reported that assuming a direct
proportion relation between the mean drop size and dmax may
not be necessarily accurate. In that work, the authors demon-
strated that for lognormal and normal drop size distributions,
which is in agreement with experimental data for emulsified
systems, the Sauter mean diameter is not a linear function of
dmax . This suggests that d32 depends not only on dmax but also
on dmin and DSD. This result is a relevant conclusion since it
(7) highlights the need to account for the complete DSD to char-
acterize the microscopic structure of an emulsified cosmetic
product instead of using a mean drop size estimate. DSD could
be coupled to the design of a new cosmetic emulsified product
(8)
through the implementation of PBM. The general equation for
PBM is expressed as follows (Nopens et al., 2015):
∂f1 (x, t) ∂  
+ Ẋ (x, t) f1 (x, t) = h (x, t) (12)
∂t ∂x
where x is the internal coordinate or distributed property (e.g.
drop size), f1 (x,t) is the number density function (e.g. DSD),
Ẋ (x, t) represent the continued growth of x and h(x,t) is the
PBM reaction term or discrete growth (e.g. drop coalescence
and breakup). For aggregation-breakage processes, as it is the
case for emulsions, the population balance can be expressed
by Eq. (13), where a discrete function of ni values represent
the DSD (Vanni, 2000). The discrete growth term is described
by Eq. (14).
∂ni
= h (x, t) (13)
∂t
h (x, t) = Ai − Bi i = 1, 2, 3 (14)
where Ai and Bi represent the volumic aggregation and
breakage rates. Ai is a function of the rate at which particles
in classes i are consumed to give aggregates, whereas Bi is a
function of the rate at which particles in classes i break up to
give smaller particles (Vanni, 2000). These rates of breakage
and aggregation are expressed in terms of kinetic coefficients,
also referred to as the kernel, which can describe droplets coa-
lescence and breakup in emulsified products. With regard to
coalescence, contact and collision on droplets are the principal
mechanisms for this process (Liao and Lucas, 2010). Regard-
ing drop breakup, hydrodynamic conditions of the continuous
ε (9) phase and the characteristic of the droplet itself drive the pro-
(2009, 2010) present extensive reviews on kernel models for
breakup and coalescence processes in turbulent dispersions.
292 Chemical Engineering Research and Design 1 6 1 ( 2 0 2 0 ) 279–303

6.3. Molecular modeling
At the molecular scale, interfacial tension is perhaps the most
critical property at liquid-liquid interfaces (Lyklema, 2000).
The modeling of the interfacial tension for emulsified systems
is typically accomplished through the Young–Laplace equa-
tion, which can be simplified as follows (assuming perfect
spherical droplets formation during emulsification):
2
p=
R Wang et al. (2005) related the effectiveness of surface ten-
where R is the radius of curvature and p represents the
capillary pressure created due to the tension at the inter-
face. To consider the effects of the surfactant used to produce
the emulsified product (or mixtures of surfactants), some
mathematical models have been proposed in the literature.
Maindarkar et al. (2015b) developed a mathematical relation-
ship for the prediction of the interfacial tension for emulsified
products, i.e.
c
 = o/w − Ru T∞ ln 1+
c1/2
where  o/w represents the interfacial tension between water
and oil, Ru is the universal constant of gases, T corresponds
to the system temperature, and c is the surfactant concentra-
tion. The constants ∞ and c1/2 are experimental adjustable
parameters (Maindarkar et al., 2015b). From an integrated
perspective, the experimental adjustment of the abovemen-
tioned parameters may demand tedious work at using this
model for the design of a new cosmetic emulsified product.
Although this mathematical model has been coupled with
PBM for the design of emulsified products (Maindarkar et al.,
2015a), its implementation has been limited to a reduced num-
ber of surfactants. This limited implementation is perhaps
a consequence of the experimental effort required to adjust
the model parameters for surfactants or mixture of surfac-
tants. Similarly, Mulqueen and Blankschtein (2002) presented
a mathematical model to predict the oil-water interfacial ten-
sion for ionic and nonionic surfactant mixtures.
−1 is the Debye–Hückel screening length, e is the charge of a
proton, zi is the valence of the surfactant molecules of type i, d
is the Stern layer thickness, and εs is the dielectric constant in
the Stern layer. The implementation of that model may lead to
accurate predictions for the interfacial tension with a reduced
number of empirical parameters; however, it is not appropri-
ate when the surfactant tails and the oil phase have a different
chemical composition (e.g., unsaturated hydrocarbon compo-
nents in the oil phase and surfactant’s tails with saturated
hydrocarbons (Mulqueen and Blankschtein, 2002)).
(15)
sion reduction at the CMC for nonionic surfactants to the
surfactant molecule structures, i.e.
 0 = 11.63 + 0.675NO + 0.686KHO
− 0.013 Hf − 0.0139 NO KHO (19)
In their model, the tension is assessed considering the
number of oxygen atoms in the hydrophilic section (NO), the
(16) Kier–Hall topological descriptor (KHO), and the heat of forma-
tion (Hf ). This mathematical relationship was tested for 30
nonionic surfactants at 25 ◦ C. The model predictions where
compared to experimental values reporting an error rate below
5%. Even though this approach is limited to the list of non-ionic
surfactants tested in that work, it offers a simple approach to
estimate the interfacial tension for emulsified products. Torres
et al. (2020) used this approach to achieve the optimal formu-
lation for emulsified products, highlighting the applicability of
the Wang et al. (2005) model.
6.4. Optimization problem formulation
The chemical product design problem is typically addressed
by implementing the general mathematical formulation pro-
posed by Gani (2004):
 
FOBJ = max CT y + f (x) (20)
h1 (x) = 0 (21)

 = o/w − ˘NI − ˘elec (16 )

h2 (x) = 0 (22)
 ns  2

ns
  r
i=1 i i
˘NI = kB T i=1 i
+   (17) h3 (x) = 0 (23)
ns 2
1− a
i=1 i i 1−
ns
a
i=1 i i
l1 ≤ g1 (x) ≤ u1 (24)
⎡ ⎤
  i=1 2 l2 ≤ g2 (x) ≤ u2 (25)
 ε  k T 2   2e 2 
B ⎢ ⎥
˘elec =
 e
⎣ 1 + εk T ezi i − 1⎦
B
ns
l3 ≤ Bf y + Cf x ≤ u3 (26)

 i=1 2 where CT is the cost associated to the product, y is a vector of

2d 
− ezi i
εs
ns
where ˘ NI and ˘ elec are the non-electrostatic and electro-
static contributions, respectively. For the non-electrostatic
contribution, kB is the Boltzmann constant, ri is the radius of
the adsorbed surfactant molecules, ai is the cross-sectional
area covered by the surfactant molecules, i is the surfactant
molecules concentration at the interface, and ns is the number
of surfactants used to prepare the emulsion. For electrostatic
contribution, ε is the dielectric constant in the diffuse region,
(18) integer (binary) variables, f(x) is related to process variables,
h1 (x) symbolizes equality constraints related to the process
design specifications, h2 (x) represents equality constraints
related to process model equations, and h3 (x) represents
equality constraints related to molecular structure, or mix-
ing rules. g1 (x) represents inequality constraints associated
with specifications for the process design, and g1 (x) denotes
inequality constraints related to environmental constraints
and/or special property constraints associated with chemi-
cal product design (Gani, 2004). In Eq. (26) the terms Bf and
Cf represent fixed data matrices, while l1 , l2 , l3 , u1 , u2 , and
 Chemical Engineering Research and Design 1 6 1 ( 2 0 2 0 ) 279–303
u3 are the constrains lower and upper bounds, respectively
(Gani, 2004). This general representation has been applied to
design different chemical products. Mattei et al. (2014) imple-
mented this framework for surfactant design and selection as
part of the emulsified cosmetic product design. In that work,
the general optimization problem formulation proposed by
Gani (2004) was applied to solve the surfactant design problem
for an emulsified UV sunscreen. Lampe et al. (2015) applied a
similar formulation for the design of chemical products fea-
turing a working fluid for an Organic Rankine Cycle and a
solvent designed for the capture of CO2 by physical absorp-
tion. In that study, the integration of process and product
design was successfully implemented, simultaneously opti-
mizing process and fluid parameters to satisfy a set of required
product properties. Bagajewicz (2007) proposed a mathemat-
ical formulation for the design of chemical products that
considers pricing, and consumer preference models coupled
with the product composition, structure, and functionality. In
that work, the authors applied this approach for the design of
an insect repellent, which highlights the benefits of integrat-
ing product property models, process variables, and product
composition, along with market parameters.
6.5. Dimensional analysis
Another relevant approach for the design of emulsified prod-
ucts is the implementation of dimensional analysis. This
method allows the description of complex systems (as it might
be the case of emulsions) by simplifying a great number
of independent variables into a reduced number of dimen-
sionless groups (Bird et al., 2006). This method has been
implemented to scale up process conditions or to represent
emulsion formation and emulsions’ physical properties. (Maa
and Hsu, 1996) applied the dimensional analysis approach to
scale-up process variables for a microencapsulation process.
In that study, the authors correlated microspheres size with
process parameters achieving accurate microspheres size pre-
dictions when scaling up the process. Likewise, (Wibowo and
Ng, 2001) summarized a list of dimensionless groups that
could be implemented to coupled emulsion formation, pro-
cess variables, and final emulsified product’s properties for
emulsified systems. That study employed different dimen-
sionless numbers such as the Weber number, adsorption time,
collision time, drainage time, fragmentation number, dimen-
sionless power number, Reynolds number, Capillary number
and Deborah number. That study concluded that these dimen-
sionless numbers could be applied for the integrated design
of emulsified products since process variables (e.g. equipment
and operating conditions) as well as product properties could
be related by implementing these dimensionless groups.
7. Design approach
Chemical product design involves the specification of a group
of chemical blends that satisfy a set of target properties,
from which the most promising alternatives are selected
for final experimental validation (Conte et al., 2011). Cussler
and Moggridge (2011) proposed a four-step methodology to
address the design of chemical products: (1) identify the needs
from consumer requirements, (2) develop ideas to satisfy the
needs, (3) select among different alternatives or ideas and (4)
manufacture the product. Gani et al. (2007) presented a frame-
work for chemical product–process design. That framework
293
is proposed as a sequence of steps: (1) problem definition,
(2) selection of the application source, (3) selection of the
active ingredients, (4) selection of additives, (5) process sim-
ulation, (6) modeled-based verification or implementation of
a process–product modeling tool, and (7) development of the
selected product–process. Seider (2009) presented an inte-
grated design approach for chemical-product design. That
approach starts from a potential opportunity identification.
Starting from a “primitive problem”, the product structure
is defined and the process creation is developed. The lat-
ter approach places particular attention to process design,
considering elements such as detailed process synthesis,
plantwide controllability assessment, detailed design, and
process optimization (Seider, 2009). These design strategies
represent general frameworks that may be applied as a start-
ing point for chemical product and process design. Though
it could be convenient to expand such strategies for spe-
cific implementations (Hill, 2009). According to Ng and Gani
(2019) the design process for many chemical products (e.g., fuel
additives, refrigerants, aroma design, disinfectant, and bio-
fuel) may involve one or more elements of the general design
frameworks depending on the specific case of study.
The chemical product design problem is formulated and
solved in multiple ways, e.g., trial-and-error, model-based,
and integrated approaches (Ng et al., 2006). The trial-and-
error approach requires a high number of experimental trials,
and usually, an expert or prior knowledge may supply a list
of product candidates. This approach is performed when no
mathematical models are available for predicting the prod-
uct properties. The model-based approach is considered when
mathematical models are available for predicting the desired
properties of the product, enabling the designer to seek for
viable product formulation alternatives on the range on which
those models are valid. The integrated approach combines
the application of mathematical models and experimental
procedures for the evaluation of the product properties. This
approach decomposes the design problem into a hierarchical
sequence of levels, where the alternatives decrease from outer
to inner levels. The integrated approach enables the reduction
of time and resources required for product design (compared
to the trial and error approach), and the achievement of
more reliable results (compared to the model-based approach)
(Conte et al., 2011). However, some inefficient practices such
as product design based on a trial-and-error approach, fol-
lowed by product and process design, product design schedule,
and cost overruns are typically found in the chemical indus-
try (Smith and Ierapepritou, 2010). Fig. 1 presents a schematic
representation of the integrated approach considering the
variables involved in the design process.
Achieving a successful product design process requires
close integration between market parameters and engineer-
ing variables of the product (Deng et al., 2014). Consequently,
this integrated strategy involves variables such as the demand
of the product, product structure or formulation, pricing
models, consumer preference, supply chain, manufacturing
costs, manufacturing process, and product properties models
(Bagajewicz et al., 2011). Integrated product design strate-
gies require interdisciplinary collaboration, which must be
supported by the use of systematic approaches to generate
a suitable product solution (Hung et al., 2008). Smith and
Ierapepritou (2010) developed an industry benchmark study
where 15 chemical manufacturers participated. That study
showed that as a response to the new chemical industry
294 Chemical Engineering Research and Design 1 6 1 ( 2 0 2 0 ) 279–303

Fig. 1 – Schematic representation of the integrated approach.

trends, the execution of an integrated design strategy should
consider consumer preferences, process models, and busi-
ness decisions. However, the lack of standardized frameworks
limits the application of these strategies. As reported in that
study, consumer preference is an element commonly coupled
to the product design practices within the chemical indus-
try, while additional elements such as product–process or
business variables are coupled into emulsified product design
activities to a lesser degree. Bagajewicz et al. (2011) proposed
a consumer preference model, which allows maximizing the
consumer preference based on physical characteristics per-
ceived by the consumer (Tinjacá et al., 2018). This model
considers a weighted average of normalized scores of different
consumer-related properties (yi ) (Bagajewicz et al., 2011), i.e.
 Product–process integration can also be applied to the design
H= yi ωi (27)
where H is the consumer preference score of the emul-
sified product and ωi represents weights determined from
surveys. This model was applied in a case study of a skin
moisturizing lotion, where the design problem was solved
to obtain simultaneously the consumer’s most preferred skin
lotion and the most profitable formulation. The model allowed
to achieve different formulations for consumer- driven and
profit-driven cases, resulting in a not profitable formulation for
the consumer- driven case, while a less preferred product was
significantly more profitable (Bagajewicz et al., 2011). In this
model, the emulsified product selling price and product for-
mulation can be determined by assuming a single competitor
economic model, which considers a constant total demand for
the product and constant market size. According to Bagajewicz
(2007), the model assumes that a similar product is well estab-
lished in the market, while this economic model may conduce
to a profitable substitution of the currently available prod-
uct. Also, the process operating conditions can be related to
the product properties models, e.g., mixing conditions to vis-
cosity models. Nevertheless, the availability of mathematical
models relating consumer preference to emulsified product
properties, process operating conditions, and business vari-
ables is not currently available to perform integration to the
chemical design process. This is mostly due to the absence
of a standard approach, no association between the point of
information capture and point of application (product design),
and excessive confidence in heuristic knowledge (Smith and
Ierapepritou, 2010).
Concerning product–process integration, this practice has
emerged as a result of the paradigm change in the chemi-
cal industry toward consumer-oriented products (Smith and
Ierapepritou, 2010). Product–process integration denotes the
design of a chemical product along with the design of the pro-
cess required to produce the product (Bernardo and Saraiva,
2005). As reported by Gani (2005) , this integration between
product and process in the design problem offers attractive
advantages. For instance, in pharmaceutical product design, it
is crucial to achieve reliability in the product even if they imply
high production costs. For this high-value product design,
the product properties and process operating conditions are
firmly related, highlighting the need for this integration.
of bulk chemical products, which can lead to the specifica-
tion of economically feasible process designs (Gani, 2005).
That integrated approach has been successfully implemented
for the emulsified cosmetic product design; however, these
implementations remain limited. A summary of some stud-
ies implementing integrated design strategies for emulsified
products is presented in Table 4. Bernardo and Saraiva (2005)
applied this approach to the design of a cosmetic emulsion,
integrating product quality, product properties models, and
a process model. In that study, the authors showed that it
was possible to obtain optimal product formulation as well as
the optimal process conditions. Fung et al. (2016) integrated
process, property, quality, cost, pricing, economic models into
the design of consumer-oriented products. The authors also
considered additional elements, such as company strategy,
government policies, and regulations in their analysis. That
work considered two case studies; a die attach adhesive and
the design of an emulsified product (a hand lotion). In the
latter case, the results showed that product quality, which is
related to the product properties, can affect the global pro-
cess profit. On the other hand, product profit will depend on
the stated selling price. Accordingly, an integration of research
and development (R&D), design procedure, process operation,
and business models will lead to better satisfaction of the con-
sumer needs (Bagajewicz, 2007). Mattei et al. (2012) presented
the application of an integrated strategy for the design of
emulsified products. A conceptual case of study for the design
of a sunscreen lotion was performed. The methodology used
 Chemical Engineering Research and Design 1 6 1 ( 2 0 2 0 ) 279–303
Table 4 – Comparison of studies performing integrated design strategies.
Authors Product Property models
Molecular
Bernardo and Cosmetic emulsion Interfacial tension
Saraiva (2005) (Fixed)
Bagajewicz et al. Moisturizing lotion Surface tension
(2011) (Escobedo and
Mansoori)
Fung et al. (2016) Hand lotion Interfacial tension
(Fixed)
Kontogeorgis Hand-wash Surface tension,
et al. (2019) detergent CMC
Torres et al. Cosmetic emulsion Interfacial tension
(2020) (Wang et al.)
in that study combines a model-based stage with a further
experimental validation stage. In the first stage, consumer
needs are identified while the target properties are set. Then,
suitable product formulations are established from structured
databases and product property models, reducing the experi-
mental runs required to satisfy the target properties. The use
of this approach may reduce development costs and time-to-
market, while experimental resources can be employed for
validation purposes. Kontogeorgis et al. (2019) implemented
a similar methodology for the design of emulsified formu-
lated products that consists of three stages. In the first stage,
consumer needs are identified and translated into engineer-
ing variables. In the second stage, based on computer-aided
methods, property databases, and property models, potential
product formulations are obtained, which are then experi-
mentally validated in the last stage of the methodology. In that
work, the integrated methodology was implemented in a case
of study for a hand wash detergent, demonstrating the use-
fulness of the integrated approach for the design of emulsified
products.
Business models have been implemented within the chem-
ical product design to determine variables such as product
selling price, projected sales, or manufacturing schedule
(Bagajewicz, 2007). Bagajewicz et al. (2011) proposed a busi-
ness model for the design of a skin moisturizing lotion. In
that work, the business model was applied to predict prod-
uct demand as a function of the selling price. That model
considered a comparison between an existing product and a
newly designed product. That study also compared the con-
sumer preference for the designed product, and the consumer
preference for the product available in the market. Therefore,
business models should be related to consumer preference
models to establish the abovementioned consumer preference
ratio among the distinct products evaluated. In addition, the
business model considers the selling prices and demands for
each of the products as well. All those facts suggested that
the coupling between consumer preference models, business
models, and product-process elements into the design pro-
cess of the product is necessary to perform highly integrated
emulsified cosmetic product design
8. Challenges and opportunities
Chemical product design is an increasingly essential compo-
nent of chemical engineering, becoming even more critical
as a consequence of the new chemical industry paradigm
toward consumer-oriented products. Conversely, designing a
new chemical product through an integrated approach is still
295
Integration strategy
Microscopic Macroscopic
Max drop size Viscosity (Yaron and Process, product integration
(Shimizu et al.) Gal-Or)
Not considered Viscosity (Yaron and Product design, consumer,
Gal-Or) business model integration
Mean drop size Viscosity (Oldroyd) Process, product, consumer,
(Fixed) business model integration
Not considered Viscosity, Product, consumer model
spredeability integration
Mean drop size Viscosity (Oldroyd) Process, product, consumer,
(Tcholakova et al.) business model integration
a challenge that requires extensive research. Despite all the
research efforts and advances, the formulation of an emul-
sified product still remains as an art rather than a science
(Buffo et al., 2001). No exact formulas or systematic proce-
dures are available to formulate these products, and most
decisions during the design process are conducted under
heuristic considerations (Wibowo and Ng, 2001). While the
chemical product design research community continuously
offers advances and developments in this area, the prod-
ucts and processes designed through model-based techniques
remain limited (Zhang et al., 2016). According to Zhang et al.
(2016), this limitation is related to the absence of data and
theory to implement product properties and process models
within the product design, leading to face considerable chal-
lenges in this field.
Challenges and opportunities for chemical product design
have been extensively covered in the literature (Zhang et al.,
2016; Ng and Gani, 2018). Costa et al. (2006) presents five
generic categories in which the challenges and opportunities
of chemical product design can be classified, i.e.
• frameworks to effectively link product discovery to R&D
efforts,
• tools to convert problem representation spaces from cus-
tomer needs to technical specifications,
• predictive capabilities for physical properties,
• systematic approaches supporting chemical product
design,
• modeling and optimization approaches for chemical prod-
uct design.
In addition to those challenges and opportunities pre-
sented in the literature, there are other open issues that
require attention: (1) coupling innovative modeling frame-
works to improve the emulsified product design, (2) temporal
scale integration, and (3) “Industry 4.0” framework.
Regarding emulsified product modeling improvement, this
challenge can be addressed through a better understanding of
the product properties at different scales, as well as the inter-
connection between these scales (i.e., multi-scale modeling
approach), which could lead to the development of highly pre-
dictive models for product property estimation. For instance,
most of the viscosity models for emulsified products neglect
the DSD effect. Consequently, coupling a framework such as
Population Balance Modeling with property prediction mod-
els (e.g., viscosity) could represent a critical factor to improve
the control and quality of the emulsified cosmetic product
properties. On the other hand, as the properties of a cos-
296 Chemical Engineering Research and Design 1 6 1 ( 2 0 2 0 ) 279–303
metic emulsified product are connected at different scales
(macroscopic, microscopic and molecular scales), it is cru-
cial to address the cosmetic emulsified product design from a
multi-scale approach, coupling the effects of properties such
as the DSD on final product performance. Hence, the multi-
scale modeling approach represents a central element for the
design of emulsified cosmetic products from an integrated
approach.
Another attractive element to consider is the presence
of uncertainties within the design process, which can be
addressed through the implementation of optimization for-
mulations that take into account process uncertainty for
optimal chemical product design (Bernardo et al., 2001).
Process uncertainty is present in property estimations,
model parameters, raw material costs, or information that
could exhibit random behavior that affect the manufac-
turing process and eventually final product design quality.
Thus, optimization under uncertainty arises as a promis-
ing tool in dealing with these situations in the design of an
emulsified cosmetic product. This coupling has been suc-
cessfully applied for studying different multiscale process
systems (Rasoulian and Ricardez-Sandoval, 2015; Chaffart
et al., 2016), demonstrating that uncertainty associated with
a model parameter may impact process control and oper-
ating policies during the design of a new chemical product
(Rasoulian and Ricardez-Sandoval, 2014) such as cosmetic
emulsions.
With regards to the temporal scale integration, a compre-
hensive understanding of the phenomena occurring during
the emulsification process at the transient state may play a
significant role in the control and estimation of target prod-
uct properties. Although it is widely accepted that properties
and stability of an emulsified product are significantly depen-
dent on process conditions (Alvarez et al., 2010), most studies
related to emulsified product design neglect the effect that the
emulsification transient state may have on the final product
properties or stability. This influence of temporal scale during
emulsification for cosmetic products has not been reported.
Different emulsification paths may lead to achieving distinct
product properties. The emulsified product microstructure
could be determined by process conditions during the tran-
sient state emulsification; however, this phenomenon is not
entirely understood. Due to this lack of phenomenological
knowledge, the development of new emulsified products is
still based on expert criteria, process heuristics and empir-
ical experimentation (Maindarkar et al., 2015a). Thus, more
research needs to be conducted to assess the effect of the
transient emulsification stage on the final microscopic (i.e.,
DSD) and macroscopic (i.e., rheology and texture) properties
of the product, which may also affect consumer perception.
This influence of the transient conditions on the final prod-
uct properties could be attained through the implementation
of a PBM framework. PBMs allow predicting the DSD for cos-
metic emulsions, providing information regarding the product
microstructure during the transient emulsification. This infor-
mation, coupled with a multi- scale evaluation, may provide
the required understanding of the emulsification process to
establish the effect of the emulsification path on the final
product properties and stability.
Industry 4.0, also known as the fourth industrial revolu-
tion and digital transformation (Ghobakhloo, 2020), seeks for
the reduction of raw materials and energy consumption to
improve the production processes based on sustainable tech-
nologies (Uhlemann et al., 2020). This framework includes
elements such as Artificial Intelligence (AI), Machine Learn-
ing (ML), or Big Data (BD), which may have several potential
applications within the chemical industry (e.g., chemical
product design) (Uhlemann et al., 2019). Recently, these
elements have been coupled to the design of emulsified prod-
ucts to establish process variables, product formulation, and
for improving the emulsified product properties. Rodríguez
Dorado et al. (2018) implemented AI tools to optimize the
process operating variables for the production of core–shell
microparticles by inverse gelation based on W/O emulsion
of an aqueous calcium chloride solution in sunflower oil.
In that study, the authors set the process variables through
the implementation of Artificial Neural Networks (ANNs),
neuro-fuzzy logic, and genetic algorithms. The application
of those modeling-based methods reduced significantly the
number of experiments initially required. Concerning prod-
uct formulation, Rouco et al. (2018) coupled AI tools to the
design of nanostructured lipid carriers for controlled drug
release. Product formulation variables such as dispersed phase
concentration, surfactant concentration, and the amount of
the active ingredient were established through AI tools (i.e.
Artificial Neural Networks, Fuzzy Logic, and Genetic Algo-
rithms), highlighting the relevance that these methods could
have for the design of emulsified products. Kennedy et al.
(2020) aimed to enhance the anti-aging properties of emul-
sified cosmetic products through the implementation of AI
tools (i.e. Deep Learning). In that study, a natural peptide
with anti-aging effects was identified from natural plants
using these tools. Experimental validation was performed,
verifying that the identified peptide presented anti-aging
properties. Those results show that Industry 4.0 tools have the
potential to discover novel ingredients for cosmetic applica-
tions.
Industry 4.0 provides tools that could potentially contribute
to a better understanding of phenomena that are difficult to
explain within the framework of current theoretical models.
A relevant element to consider is the linking of mechanis-
tic modeling approaches with ML approaches such as ANNs
(Chaffart and Ricardez-Sandoval, 2018). Coupling mechanistic
modeling and data-driven approaches allows the prediction
of data and relationships in highly nonlinear and noisy sys-
tems (Chaffart and Ricardez-Sandoval, 2018), as it might be
the case with the emulsification process. In particular, drop
breakup and coalescence phenomena are suited to be cou-
pled with data-driven approaches since the available models
to describe these phenomena require reliable experimental
data and input parameters that are usually not well defined
or difficult to access (Liao and Lucas, 2009). Also, there is a
lack of applicable breakup and coalescence models for a wide
range of conditions (Liao and Lucas, 2010), which represent an
opportunity to couple data-driven approaches to integrated
design strategies for improving the design of emulsified cos-
metic products. Moreover, the implementation of AI or ML
tools may improve the understanding of consumer preference
and market behavior. For instance, ANNs might be imple-
mented as a powerful tool to provide information regarding
consumer perception about an existing emulsified cosmetic
product, which formulation can be adjusted to improve prod-
uct quality. Ramaswamy and DeClerck (2018) highlight the
applications that Deep Learning (DL) may have for consumer
perception analysis. Deng and Yu (2014) define DL as a mul-
tilayer machine learning implementation (commonly using
ANNs) that attempt to learn in multiple levels of representa-
 Chemical Engineering Research and Design 1 6 1 ( 2 0 2 0 ) 279–303
tion and abstraction to extract and process information from
data such as images, sound, and text. Since consumer per-
ception feedback is collected in multiple forms (Ramaswamy
and DeClerck, 2018) such as text messages, emails and social
media, DL may drive to a more precise perception of consumer
needs, thus emerging as a powerful tool to improve the inte-
grated design of emulsified cosmetic products.
9. Conclusions
This review presented the status of integrative strategies
implementation within the emulsified cosmetic product
design, the challenges faced in this field, and the different
design approaches currently considered for the development
of a new chemical product. This study also presents an
overview of emulsified cosmetic product property model-
ing, manufacturing methods, main components for product
formulation along with main variables affecting the final prod-
uct performance. Undoubtedly, chemical product design has
reached significant advances over the past decades as a conse-
quence of notable changes in the chemical industry. However,
more research is needed to overcome challenges that inte-
grated emulsified cosmetic product faces.
Close integration between market parameters, engineering
variables, and business models is required to achieve a suc-
cessful product design. This integration represents a major
challenge for the emulsified cosmetic product design pro-
cess since the development of many chemical products is
still based on expert criteria or a trial-and-error approaches
(Ng and Gani, 2018). Moreover, systematic and standardized
approaches that translate consumer needs into technical
specifications are needed. Consumer preference is closely
related to product properties, product composition, or process
variables. Hence, an adequate model describing consumers’
preferences is a major concern when designing a new chem-
ical product. Modeling consumer preference is particularly
relevant for emulsified products, since interactions among
process conditions, product formulation, and product prop-
erties (hence consumer preference) at different scales are
strongly correlated. Consequently, the multi-scale approach
emerges as a fundamental tool for the design of emulsified
cosmetic products from an integrated framework.
Moreover, highly predictive models for physical product
properties are still in need. It still exists an enormous gap
between current modeling tools for basic product proper-
ties and the understanding of more complex systems (Costa
et al., 2006), such as drop breakup and coalescence pro-
cesses for emulsified cosmetic products. Closing this gap for
emulsified products could be attained by considering the com-
plete DSD instead of using a mean drop size, thus improving
model prediction quality. The DSD coupled with the integrated
design of emulsified cosmetic products can be achieved using
PBMs, which would represent a significant advance for the
implementation of integrative design strategies for emulsified
products. In addition, there are still challenges for developing
model-based optimization methods to find optimal product
design solutions (Zhang et al., 2016). Optimization approaches
involving process uncertainty offer enormous advantages for
the design of emulsified products that may be immune to pro-
cess uncertainty (Costa et al., 2006).
This review also discussed the impact that integration of
the temporal scales for emulsification as well as the imple-
mentation of Industry 4.0 tools may have on the integrated
297
design of emulsified cosmetic products. Taking into account
the transient state of the emulsification process may provide
a better understanding of the phenomena occurring within
the system during operation. This may improve the estima-
tion of the product properties and therefore be able to have
better control on the final product quality. However, more
research must be conducted to evaluate the effect of the tem-
poral scales. In addition, the implementation of tools such as
AI, ML, or BD may contribute to a better understanding of con-
sumer preference and market behavior. Also, these tools may
be instrumental to model phenomena that are not accurately
captured by the current available models. Consequently, these
elements arise as powerful tools to design new economically
attractive emulsified cosmetic products.
Conflicts of interest
The authors declare no conflicts of interest.
Acknowledgement
This work was supported by Minciencias and the Gobernación
del Cesar, Colombia [grant number 766, 2016].
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