Acta Pharm.

62 (2012) 123–140 Review

DOI: 10.2478/v10007-012-0018-x

Interfacial rheology: An overview of measuring techniques

and its role in dispersions and electrospinning

JAN PELIPENKO Interfacial rheological properties have yet to be thorou-

JULIJANA KRISTL*
ghly explored. Only recently, methods have been intro-
ROMANA RO[IC
SA[A BAUMGARTNER duced that provide sufficient sensitivity to reliably deter-
PETRA KOCBEK mine viscoelastic interfacial properties. In general, inter-
facial rheology describes the relationship between the de-
University of Ljubljana, Faculty formation of an interface and the stresses exerted on it.
of Pharmacy, Ljubljana, Slovenia Due to the variety in deformations of the interfacial la-
yer (shear and expansions or compressions), the field of
interfacial rheology is divided into the subcategories of
shear and dilatational rheology. While shear rheology is
primarily linked to the long-term stability of dispersions,
dilatational rheology provides information regarding
short-term stability. Interfacial rheological characteristics
become relevant in systems with large interfacial areas,
such as emulsions and foams, and in processes that lead
to a large increase in the interfacial area, such as electro-
spinning of nanofibers.
Keywords: interfacial rheology, emulsions, foams, electro-
Accepted May 1, 2012 spinning, nanofibers, nanotechnology

Colloidal disperse systems represent the increasing number of modern delivery sys-
tems whose primary characteristic, a large interfacial area, causes thermodynamic insta-
bility. Therefore, the foremost challenge in dispersion design is the reduction of interface
instability and an understanding of the behaviour of interfaces. Interfacial rheology is
one of the most powerful tools for observing occurrences at the interphase. As previ-
ously mentioned, the stability of such systems is provided by the formation of a stable
interfacial layer of surfactants around each dispersible particle. The stability of these
systems can be improved by using more than one surfactant, but it must be kept in mind
that different surfactants can have varying mechanisms of stabilisation, some of which
can be mutually incompatible. Surfactant selection is therefore crucial and must be
based on physicochemical properties, stability of the interfacial film, mobility of the
molecules in the interfacial film, HLB, film formation kinetics, compatibility and interac-
tions between molecules on the surface, CMC, etc. (1). Interfacial characteristics do not

* Correspondence; e-mail: julijana.kristl@ffa.uni-lj.si

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Pharm. 62 (2012) 123–140.

only affect the stability of foams and emulsions but also influence a variety of technolog-
ical processes, such as electrospinning (2), mass transfer, foaming, emulsification, oil-re-
covery and high-speed coating (3). Numerous reports dealing with the effects of incor-
porated surfactants on dispersion stability in correlation with rheological parameters
can be found in the literature (4–6). However, most of the previously studied systems
were largely analysed from the perspective of rheology, which is better understood than
interfacial rheology. Rheology is a characteristic of a system and is independent of the
plane in which it is measured; hence, it can be also called three-dimensional rheology. In
contrast, interfacial rheology is restricted to the interfacial layer and therefore can be ca-
lled two-dimensional rheology. As interfacial rheology explores rheological properties di-
rectly at the interphase, which is a key to dispersion stability, we believe that it is much
better correlated to the stability of dispersions than rheology. However, the effects of in-
terfacial rheological characteristics on dispersion stability and the electrospinning pro-
cess have not been widely discussed or systematically investigated thus far.
Interfacial characteristics are generally dependent on the behaviour of both phases.
Moreover, these characteristics exhibit even greater dependency on the behaviour of the
molecules positioned at the interface, particularly on their chemical composition, con-
centration and interactions. These molecules are amphiphilic, meaning that they have an
affinity for the hydrophilic and lipophilic phase and can be called surfactants. A wide
variety of low- and high-molecular-weight surfactants are frequently used in pharma-
ceuticals, cosmetics and food products among their other applications. Complex interfa-
cial structures are present not only in these products but also in biological systems such
as cell membranes (7, 8) and the surfactant film on lung alveoli (9, 10). Furthermore, the
majority of natural biochemical reactions occur at interfaces, and only by understanding
interfacial characteristics, we are able to explain these processes and successfully mimic
biological systems. Given these facts, familiarity with the methods that allow determina-
tion of interfacial characteristics, and thus predict system behaviours, is critical. Interfa-
cial rheological measurements are challenging, not only because of the extremely low
forces that are needed to influence the interface, but primarily because of the flow of the
interface, which can cause deformation of the surrounding bulk phase. Thus, the main
objective of these measuring techniques is to examine the interface with sufficient sensi-
tivity and to minimise any alteration of the interfacial structure (11) while preventing
any change in the behaviour of deeper layers.
The aim of this paper is to highlight the impact of interfacial rheological characteris-
tics on the properties of various systems. Theory of interfacial rheology, an overview of
available measuring techniques, the role of interfacial rheology at liquid-liquid or gas-
-liquid interfaces and the electrospinning process are presented.

INTERFACIAL RHEOLOGY: THEORY AND AVAILABLE MEASURING TECHNIQUES

Rheology was defined by Bingham in 1929 as the science of deformation and flow
under controlled testing conditions. The term »rheology« originates from the Greek word
»rheos« meaning »flowing« or »streaming«, thus rheology is actually »flow science«, which
is based on the fundamental physical relationships concerning how materials respond to
applied forces or deformations (12).

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Pharm. 62 (2012) 123–140.

Interfaces were first mentioned in the 19th century, when the Paris Academy of Sci-
ences published a paper on the behaviour of the layer that occurs at the interface be-
tween an oil and an aqueous protein solution. The first experiment at an interface was
performed 25 years later by Plateau, who compared the dumping of an oscillating mag-
netic needle on bare and surfactant-laden interfaces (3). He discovered that the needle
was better immersed when a surfactant was present, but he could not explain why. This
phenomenon was later described by Marangoni, who explained that this result is due to
surface compression at the front of the needle and dilation on the opposite side, causing
a surface tension gradient that influences the movement of the needle. At the beginning
of the 20th century, Joseph Valentin Boussinesq proposed a theoretical model for the de-
formation of two-dimensional liquids, which was later improved by other scientists (13).
These early studies were the basis for developing various models and measuring tech-
niques in rheology as well as in interfacial rheology.

Basic equations and models in rheology and interfacial rheology

Interfacial rheology studies the response of mobile interfaces to shear (changes in
shape at constant area) and/or dilatational deformation (changes in surface area with
constant shape). Thus, we distinguish shear and dilatational interfacial rheological pa-
rameters. Interfacial
.
shear viscosity (hs) is the ratio. between the shear stress (s) and the
shear rate (Y) in the plane of the interface (hs = s / Y) and can be called two-dimensional
viscosity (14), while the interfacial dilatational viscosity (hd) can be defined as the uni-
form expansion of the interface at a constant rate (hd = dY/dlnAdt).
According to Boussinesq, interfacial rheology (flow in two dimensions) can be con-
sidered analogous to rheology (flow in three dimensions), and like in three-dimensional
rheology, springs and dashpots can be used to simulate rheological behaviour of the tes-
ted systems. Springs are used to simulate ideal elastic behaviour and can be described
by Hook’s law (Fig. 1A), while a dashpot is used to simulate plastic behaviour of the in-
terface (Fig. 1B).

Fig. 1. Schemes of (A) spring, simulating elastic behaviour, and (B) dashpot, simulating plastic be-
haviour with their corresponding equations, where .
s represents stress, G is spring constant and g is
deformation, while h represents viscosity and (Y) shear rate (15, 16).

Steady state is defined as a state in which the molecules at the interface are in their
thermodynamically most favoured state. When this interface is deformed, thermodyna-
mic forces tend to restore the original state; however, under ordinary circumstances, res-
toration of the interfacial film is only partial, meaning that the interface simultaneously
exhibits plastic and elastic characteristics. Consequently, various mathematical models
were proposed to approximate the viscoelastic behaviour of the samples by combining
spring and dashpot models. Among these mathematical representations, the best known

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Pharm. 62 (2012) 123–140.

Fig. 2. Schemes of (A) Maxwellian model, and (B) Kelvin-Voigt model with the corresponding equa-
tions (15).

is the Maxwellian model (Fig. 2A). Viscoelastic liquids that obey the Maxwellian model
include pitch, bees wax, ice-cream and concentrated solutions of polymers (15, 16); how-
ever, the primary disadvantage of this model is its inadequacy for predicting creep and
recovery. In contrast, the Kelvin-Voight model (Fig. 2B) is acceptable as a first approxi-
mation for creep and recovery behaviour, but it is insufficient for predicting relaxation
and, therefore, can be used only for elastic systems with weak viscosity characteristics
(15, 16). To improve the prediction of creep and recovery or to improve the prediction of re-
laxation, more complex models have been proposed (Linear and Burger models) (15, 17).
Viscoelastic characteristics of the bulk or interfaces can be determined using stress
relaxation, strain relaxation and/or oscillatory measurements. In a stress relaxation test,
a sudden strain is applied at the interface and the stress (s) is measured as a function of
time, while in the strain relaxation experiments, a small constant stress is applied to the
interfacial film.
In oscillatory experiments, the strain or stress is varied periodically with a sinusoi-
dal alteration at a chosen angular frequency (w). The complex modulus (G*) is obtained
from the amplitude ratio of stress or strain. G* consists of the elastic (G') modulus and
the plastic (G'') modulus, where G' is the real part of the complex modulus and repre-
sents the energy stored during stress, while G'' is the imaginary part of the complex mo-
dulus and represents the energy that is lost during sample loading (14).

Shear measuring techniques

In the past few decades, numerous measuring techniques have been proposed for
determination of the interfacial rheological parameters of fluids and semisolid disper-
sions, all of which have advantages and limitations with respect to the operating range,
sensitivity and suitability for measuring different interfaces (18). Shear interfacial rheo-
logical methods involve inducing shear in the adsorbed film without changing the area.
These methods provide information on the structures formed at the interface (3, 8, 19).
These techniques are most commonly used for the adsorption layers of protein or combi-
nations of protein and low-molecular-weight surfactants and can be divided into direct
and indirect methods.
Indirect techniques measure surface velocity profiles using inert visible particles, on
the basis of which shear interfacial characteristics can be determined. These methods are
primarily limited to gas-liquid interfaces. The most commonly used indirect viscometer is
the deep-channel surface viscometer, which consists of two stationary concentric cylinders
and a rotating dish filled with the test sample (Fig. 3A). The chamber is rotated at a known

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Pharm. 62 (2012) 123–140.

Fig. 3. (A) Scheme of a deep-channel surface viscometer, (B) scheme of a channel surface viscometer.

angular velocity (w0) and surface motion between the cylinders is measured using talc or
Teflon particles placed within the fluid interface. The primary advantage of the deep-
-channel viscometer is that it can be also used for exploring liquid-liquid interfaces. An-
other common indirect viscometer is the channel surface viscometer (Fig. 3B), where hs
is determined by the measurement of the flow rate of a film through a narrow channel
under an applied pressure differential, Dp (15, 20). Unfortunately, the channel surface
viscometer is limited to studies of insoluble monolayers at gas-liquid interfaces.
Direct methods, in contrast to indirect ones, determine the shear stress of the liquid
interface as it is stressed by contact with a foreign body. Most of the commonly used rhe-
ometers in this field are torsion pendulum surface viscometers, which can be further di-
vided into those with sharp-edge geometry suitable for gas-liquid interfaces and those
with biconal disk geometry, which can be also used at liquid-liquid interfaces. Although
various touching bodies can be used (Fig. 4), the principles for determining rheological
parameters are similar in most cases: a rotating or oscillating touching body is connected
to a motor that can detect torque and displacement while the sample is held in a station-
ary tempered dish (13, 15, 20).
In addition, a magnetic rod viscometer can be included among the interfacial shear
rheometers (Fig. 5). This viscometer is one of the most sensitive instruments for measur-
ing interfacial shear rheological parameters (21) and is capable of measuring surface shear

Fig. 4. Schemes of different interfacial measuring systems. From left to right: bicone system, plate-
-plate system and knife-edge torsion pendulum technique.

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Pharm. 62 (2012) 123–140.

Fig. 5. Schematic presentation of a magnetic

rod surface viscometer.

moduli in a wide range of values (22). The prime feature of this rheometer is its long
magnetic needle floating at the interface, which is moved by an external magnetic field
(15, 22, 23). Its primary advantage over torsion pendulum surface viscometers is that it
can be combined with a Langmuir trough, which enables control of the thermodynamic
state of the interfacial monolayer (13).

Dilatational measuring techniques

Dilatational measuring techniques induce a change in the interfacial area while si-
multaneously measuring the interfacial tension to provide information regarding the com-
position of interfacial layers. Thus, with interfacial dilatational rheology, we can observe
the rheological properties that arise in response to changes in the surface area. These
changes are strongly evident in the foamability, emulsion formation and electrospinning
during which an enormous increase in surface area occurs.
Dilatational measuring techniques are used to investigate the equilibrium and dy-
namic properties of simple and complex interfacial layers composed of low-molecular-
-weight surfactants (LMWS), proteins and polymers (24). Furthermore, these techniques
can be used to monitor surfactant concentration, competitive adsorption and the magni-
tude of interactions at the interface. Measurements are based on parameters that stron-
gly correlate with the equilibrium properties of the adsorption layers and the mecha-
nisms that control their formation.
Within the discipline of dilatational rheology, various techniques have been devel-
oped for use in different fields. A capillary wave damping instrument is used to investi-
gate the dynamic properties and structures of insoluble monolayers or adsorption layers
(25, 26). In the last twenty years, oscillating drop and bubble techniques have been de-
veloped and are now the most commonly used techniques for surface dilatational rheol-
ogy (3). These techniques can be used to study rheological properties at both liquid-liq-
uid and gas-liquid interfaces and are based on either the shape measurement of a drop/
bubble or on the measurement of the capillary pressure inside a drop/bubble (24).
The drop/bubble profile tensiometer, presented in Fig. 6, is widely used for the de-
termination of mechanical properties at gas-liquid and liquid-liquid interfaces, and is ap-
plicable to a great variety of liquids, from organic to molten metals, for which very small
amounts of sample are required. Major drawbacks of the method include the requisite
density difference between the two involved fluids and the requirement that the inter-

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Pharm. 62 (2012) 123–140.

Fig. 6. Scheme of drop/bubble profile tensiometry (DPT). Under the influence of external forces, a
drop/bubble of one liquid inside another assumes a shape that minimises the total energy of the
system and provides maximum stability.

face must be close to mechanical equilibrium when it is analysed (the interface must be
investigated at low frequencies) (24). The drop/bubble shape is defined by a combina-
tion of surface tension and gravitational force: surface forces prefer spherical drops/bu-
bbles, and gravity attempts to elongate or compress the drop/bubble. Surface tension
and surface curvature at each point on the surface of a drop/bubble are provided by the
Laplace equation (13, 27).
The principle of capillary pressure tensiometry (CPT) is shown in Fig. 7. CPT is a
versatile technique utilised by a variety of methods for investigating dynamic and equi-
librium systems at liquid-liquid and gas-liquid interfaces. This technique is also the only
dilatational rheological method that can be used for two liquids with a small density dif-
ference (28, 29). The principle is based on direct measurement of the pressure difference
between two phases separated by the spherical interface of a drop/bubble (15). The de-
vice required for this measurement is typically composed of two chambers connected by
a capillary tube. While one of the chambers is closed and includes a pressure sensor and
piezoelectric element, the other is used as a reference for the volume of a drop/bubble,
which is formed at the tip of the capillary. The diameter of a droplet is determined by either
taking its picture or calculating it on the basis of the volume of injected fluid (3, 24, 30).
Both shear and dilatational interfacial rheology offer diverse techniques for the de-
termination of rheological properties, which differ in sensitivity, range of measurement
and applicability to different systems.

Fig. 7. Scheme of a measurement cell in an open capillary pres-

sure tensiometer.

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Pharm. 62 (2012) 123–140.

THE ROLE OF INTERFACIAL RHEOLOGY IN DISPERSIONS

Interfacial film is necessary for dispersion stability, but it is also the source of its
thermodynamic instability. Therefore, familiarity with the factors influencing interfacial
film properties is critical for the determination of these properties.
Interfacial rheology is a sensitive tool used to observe structures that are formed at
the interface, define the interactions between the molecules and determine their concen-
tration (31). Dispersion behaviour is known to be affected by the characteristics of inter-
facial films, and shear rheology is linked to the long-term stability of dispersions, while
dilatational rheology provides information regarding short-term stability (32). However,
the relationship between interfacial rheological characteristics and dispersion stability is
not straightforward (33). Therefore, each system must be treated separately.

Dispersions stabilised with proteins, low-molecular-weight surfactants, or their

blends
Due to their biocompatibility and biodegradability, proteins are commonly used as
surfactants in dispersions. When adsorbed at an interface, their conformation is rearran-
ged in such a manner that the hydrophobic parts are exposed to the hydrophobic phase
and vice versa. Proteins form an immobile viscoelastic interfacial film with characteristics
that depend on the structure of the adsorbed protein and the strength of interactions be-
tween protein molecules (31). Interfacial rheological parameters like G’, G’’ are generally
higher near the iso-electric point, meaning that the pH also influences the characteristics
of the interface (11). Due to the polymeric and polyelectrolytic nature of proteins, the in-
terfacial protein film is assumed to be stabilised by the electrostatic and steric forces be-
tween the molecules (8). In contrast, Ventureira and collaborators (34) did not find any
correlation between electrostatic forces and the stability of an interfacial film in the case
of amaranth protein isolates. Instead, they emphasised the importance of hydrophobic
interactions and hydrogen bonding. Although there are conflicting results regarding the
mechanism of protein interfacial layer stabilisation, a correlation is believed to exist be-
tween the dilatational and shear rheological characteristics of the protein interfacial film,
on the one side, and the stability of the colloidal dispersion stabilised by that protein, on
the other side. However, due to great diversity in protein characteristics, this correlation
must be determined for each system separately.
LMWSs, in contrast to proteins, form a mobile interfacial layer with low viscoelasti-
city, which is more effective in reducing the dynamic interfacial tension (11). The pri-
mary mechanism of stabilisation is the Gibbs-Marangoni effect (31). The interfacial area
is greatly increased during emulsifying or foaming, leading to an inhomogeneous distri-
bution of the surfactant at the interface. Variations in surfactant concentration cause dif-
fusion of the surfactant molecules until a uniform film is established. During this pro-
cess, the liquid can be transported to the interface. This so-called Gibbs-Marangoni effect
is the driving force behind stabilisation of a thin fluid film between the droplets, pre-
venting their coalescence (31). Interfacial shear rheological characteristics of dispersions
stabilised with LMWSs depend on whether the surfactants are more soluble in the oil or
water phase (35). Furthermore, Bykov et al. proved that an increase in the length of the
surfactant alkyl chain leads to the formation of a more rigid film structure, which can be

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Pharm. 62 (2012) 123–140.

seen as having higher dilatational elasticity. This effect is better seen at low surfactant con-
centrations because the adsorption layer is more homogeneous at such concentrations
(36).
Each of the above-mentioned surfactant groups, when alone, is effective at stabilis-
ing a dispersion. However, in the pharmaceutical, cosmetics and food industries, blends
of both surfactants are often used. The results show that due to slow protein adsorption,
the final size of a drop in an emulsion stabilised with proteins depends on the time scale
at which the droplets are formed. To cover an oil-water interface more rapidly, LMWSs
are often added (33). Because LMWSs displace proteins from the interface and adsorb at
the interface much faster, they are often added as protein stabilisers to prevent biological
inactivation of the proteins exposed at the interface (37).
Addition of LMWSs to dispersions that are stabilised with proteins can lead to a de-
crease in dispersion stability due to conflicts between the two different stabilisation me-
chanisms. Small amounts of LMWSs adsorbed at the interfacial layer disrupt the protein
viscoelastic layer, which is then no longer able to stabilise the dispersion by the viscoela-
stic mechanism. At this stage, however, the concentration of LMWSs is not high enough
to provide dispersion stabilisation by the Gibbs-Marangoni effect. As the concentration
of LMWSs increases, they displace the proteins from the surface and ultimately stabilise
the dispersion by their own mechanism (19, 38). Molecules of LMWS at the interface squ-
eeze together more tightly than proteins; thus, in most cases, LMWSs replace proteins at
the interface, given a sufficient concentration in the bulk phase. According to the oroge-
nic mechanism, protein displacement by LMWS at a gas-liquid interface has three pha-
ses, as shown in Fig. 8. At point (A) where p < p eprotein (p is the surface pressure, p eprotein is
the equilibrium surface pressure of protein), LMWS adsorbs onto small defects in the
protein film. At point (B) in which p » p eprotein, the surfactant domains continue to grow,
while the protein film thickens in response to the decrease in area. Thus, the volume of
the adsorbed protein remains constant. In the third phase (C) in which p > p protein
e , the pro-
tein network breaks down and the LMWS forms a continuous film. This process is dri-
ven by low interactions between the LMWSs and the proteins (39, 40). However, one must
consider that the kinetics of these processes is to each LMWS/protein combination (31).
In contrast to the orogenic mechanism, Bykov et al. suggested the formation of heteroge-
neous adsorption layers in the case of a polyelectrolyte and an LMWS (41, 42).
Distribution of proteins and LMWSs at the interface is determined by the competi-
tive adsorption of both types of surfactants and by the nature of the protein-LMWS in-
teractions, both of which have a distinct impact on the rheological properties of the in-
terface (19). Furthermore, the interfacial viscosity and complex modulus values for adsor-
bed proteins have been often shown to be much higher than those for LMWSs (43). The-
refore, the interactions between surfactants, displacement of proteins by LMWSs, struc-
tures at the interface, incompatibilities of surfactants, film composition and the mecha-
nism of interfacial film formation can all be analysed using interfacial rheological meth-
ods (19, 20, 31).

Dispersions stabilised with nanoparticles

In addition to LMWSs and amphiphilic polymers, nanoparticles can be used to sta-
bilise dispersions. Pickering-Ramsden emulsions are emulsions stabilised with nanopar-

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Pharm. 62 (2012) 123–140.

Fig. 8. Protein displacement by LMWS at the liquid-

-air interface according to the orogenic mechanism.

ticles that are adsorbed at the interface. Their stability depends on the particle concen-
tration, size and shape; an increase in particle concentration suppresses coalescence, and
addition of smaller particles leads to a decrease in droplet size (44). Nanoparticles pre-
vent coalescence by forming a robust mechanical monolayer at the interface (11), which
can be characterised using interfacial rheological methods. Madivala and co-workers (45)
studied the effect of particle shape on emulsion stability in relation to interfacial rheol-
ogy and found that ellipsoidal particles form a denser structure at the interface, yielding
much higher viscoelastic moduli than spherical particles. Furthermore, interfacial rheol-
ogy can be also used to assess the efficacy of nanoparticle entrapment at the interface of
the dispersion in correlation with its stability (44).

Stability of gas-liquid and liquid-liquid interfaces: interfacial rheology as a predictive

tool
Stability of foams and emulsions depends on the stability of the corresponding in-
terfacial layer. There are two main phenomena indicating instability of the interfacial la-
yer: Ostwald ripening and coalescence.
At gas-liquid interfaces (foams), one of the major sources of instability is Ostwald
ripening, which shows as slow shrinkage of smaller bubbles, due to gas diffusion from
smaller bubbles to larger ones, forced by the Laplace pressure difference between them.
According to Henry’s law, the solubility of a gas in a liquid is higher around the bubble
than in bulk liquid. Consequently, the excess gas diffuses to areas of lower concentration
of dissolved gas (e.g., to larger bubbles and to the atmosphere) (46). Another source of
instability at liquid-liquid and gas-liquid interfaces is coalescence.
Regardless of the type of dispersion stabiliser, there is a connection between the foa-
ming capacity dynamics and the interfacial rheological characteristics. Formation of a
stable gas-liquid interface is based on the diffusion and rapid adsorption of stabilisers
on the newly formed surface (47). Optimum foaming capacity is reached with a reduced
lag period and with rapid diffusion of the emulsifier toward the interface (19). Croguen-
nec et al. studied the importance of the diffusion rate of the surfactant (48) and com-
pared the stabilisation abilities of native and heat-treated b-lactoglobulin. Their results

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Pharm. 62 (2012) 123–140.

proved the importance of the kinetic development of a viscoelastic interfacial protein la-
yer on the foam structure and therefore on its stability. The influence of adsorption ki-
netics was also demonstrated by Maldonado-Valderama et al. (49), who established a link
between interfacial viscosity and foamability in addition to highlighting the importance
of interfacial film elasticity to foam stability. According to their results, interfacial viscos-
ity is more important to foam formation, while dilatational elasticity has a greater influ-
ence on foam stability. Furthermore, Wooster et al. (50) correlated the three-dimensional
structure of whey protein with its interfacial rheological characteristics and emphasised
the influence of structure on dispersion stability. The effect of protein structure on disper-
sion stability was also emphasised by Kim and co-workers (51), who found that changes
in secondary and ternary structures resulted in increased interfacial shear elasticity and
shear viscosity, leading to enhanced dispersion stability.
Physical characteristics of hydrophilic and hydrophobic phases, surfactant charac-
teristics, steric and electrostatic interactions have a great influence on interfacial rheolog-
ical characteristics and consequently on the formation and properties of a liquid-liquid
interface. However, there is no simple connection between emulsion stability and inter-
facial rheology. Sanfeld and Steinchen concluded that within a given range of parame-
ters, a film’s elasticity gives a negligible contribution to its emulsion stability (52). On
the other hand, Maldonado-Valderama et al. demonstrated a connection between the in-
terfacial elasticity and coalescence in emulsions stabilised with b-casein (49). Thus, mea-
surements of interfacial viscosity and other interfacial rheological parameters are useful
tools for sensitive detection of structural changes in the interphase that can affect the
stability of the observed dispersion systems. However, no simple prediction or general
conclusions are possible.

THE ROLE OF INTERFACIAL RHEOLOGICAL CHARACTERISTICS

IN THE ELECTROSPINNING PROCESS

Nanofibers are very tiny, solid fibers with nanometre-scale diameters, theoretically
unlimited length, large surface area-to-volume ratio and high porosity. Given their phys-
ical characteristics, these materials are used in the chemical, textile, computing, energy,
biomedical and pharmaceutical industries (2), in which nanofibers join other, more es-
tablished drug nanocarriers (53, 54). The most commonly used method for nanofiber pro-
duction is electrospinning-a widely used modern, versatile and one-step method (Fig.
9). Although it was patented more than a hundred years ago by J. F. Cooley, intensive re-
search into the electrospinning process and its utility in the pharmaceutical and tissue
engineering fields began in the early 1990's, along with the development of nanotechno-
logy, when research groups demonstrated that many organic polymers could be electros-
pun into nanofibers (55). We believe that interfacial rheology could be employed also in
the formation of nanofibers.
Electrospinning produces nanofibers from polymer solutions using a high-voltage
supply. A polymer solution is placed in a plastic syringe with a metallic needle. The sy-
ringe is then mounted into a syringe pump to provide a constant flow of polymer solu-
tion, and the needle tip is connected to the high-voltage source. At sufficient voltage, the
electrostatic repulsion forces prevail over the forces maintaining the spherical shape of

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Pharm. 62 (2012) 123–140.

Fig. 9. Scheme of an electrospinning process.

the drop, first forming a Taylor cone, then forming a jet of polymer solution, which seeks
a path to the grounded collector (56) (Fig. 9). If the cohesion forces between polymeric
molecules are strong enough, the jet that is formed is stable and uniform fibers are ob-
tained (57).
Current state-of-the-art studies of electrospinning process claim that viscosity, surface
tension and conductivity of the polymer solution are the primary systemic parameters
influencing nanofiber morphology (55–60). However, we believe that interfacial rheolog-
ical characteristics are decisive in the electrospinning process and should be used as a
predictive tool for the success of electrospinning. In our opinion, given the area of a Tay-
lor cone, rheological characteristics still play a significant role due to the larger diameter
of the jet. During jet thinning, interfacial characteristics prevail due to the significant in-
crease in the surface-to-volume ratio (S/V = 4D–1). The jet diameter (D) is reduced from
approximately 1 mm (inner diameter of the needle used) to a few hundred nanometres or
less (diameter of the obtained nanofibers). Moreover, solvent evaporation creates a con-
centration gradient in polymer molecules, leading to a more pronounced effect of the in-
terfacial characteristics. Unfortunately, there is still no interfacial rheological method that
would allow simultaneous determination of the interfacial shear properties and the ac-
tual dilatational characteristics at expansion rates on the order of 103 s–1 (expansion ra-
tes achieved at the beginning of the thin jet region-transition zone). Thus far, the best ap-
proximation involves interfacial shear measurements (61).
Not only do the interfacial rheological properties differ from the bulk properties,
but they also have a different relationship with polymer concentration. Polymers spon-
taneously adsorb from aqueous solution at interfaces at which their free energy is lower
than it is in solution. During adsorption, polymer molecules alter their conformation;
they unfold and establish more intermolecular interactions with other molecules at, or
close to, the interface, which leads to the formation of an interfacial film. Interfacial rhe-
ological characteristics of the polymer solution depend on various factors, including in-
trinsic molecular properties and the physicochemical conditions of the solution. There-
fore, no precise prediction of interfacial rheological parameters can be achieved on the
basis of the rheological parameters determined in the bulk of the polymer solution.
Our research group (2) investigated the correlation between polymer solution com-
position and nanofiber formation with the emphasis on the predictive power of the most

134
J. Pelipenko et al.: Interfacial rheology: An overview of measuring techniques and its role in dispersions and electrospinning, Acta
Pharm. 62 (2012) 123–140.

commonly described electrospinning systemic parameters and interfacial viscosity (Fig.

10). Solutions of PEO and chitosan (3 % w/w) were prepared separately, then mixed to-
gether in varying mass ratios and finally electrospun using the same process parame-
ters. Surface tension was found to be independent of the polymer solution composition,
while the conductivity, viscosity and interfacial viscosity increased as the proportion of
chitosan increased. Based on the values of interfacial viscosity, solutions can be divided
into three regions coinciding with the morphology of the obtained nanofibers. From so-
lutions processed in the first region, smooth, uniform and bead-free nanofibers were for-
med. Solutions in the second region formed beaded nanofibers, and only droplets con-
taining a few nanofibers were formed in the solutions in the third region (2).
Based on viscosity, solutions may also be divided into three regions that coincide
with the regions of interfacial viscosity; still, the differences among these are much less
significant, suggesting higher sensitivity of interfacial rheology for the determination of
small differences between the solutions. Therefore, the primary advantage of interfacial
shear measurement is higher sensitivity for detecting small changes at the interface. In
addition, interfacial shear allows one to investigate the interface without simultaneously
influencing the behaviour of deeper layers (62).
Finally, we believe that interfacial rheology could be also employed in the prepara-
tion of nanoparticles, owing to the great increase of the interface, and it has been already
shown that characteristics of selected surfactants strongly influence nanoparticle forma-
tion (63, 64).

Fig. 10. Correlation between systemic parame-

ters of polymer solutions and the morphology
of obtained nanofibers (2).

135
J. Pelipenko et al.: Interfacial rheology: An overview of measuring techniques and its role in dispersions and electrospinning, Acta
Pharm. 62 (2012) 123–140.

CONCLUSIONS

Development of various dilatational and shear interfacial measurement techniques

enables an insight into the interfacial layers, their characteristics, their formation and their
role in various systems. So far, studies exploring the influence of interfacial rheological
characteristics have shown that the correlation is unique for each system and is far from
straightforward. Furthermore, the interface must be analysed with both the dilatational
and shear method, because these are two completely different but complementary meth-
ods. Dilatational deformation is primarily affected by the characteristics of the molecu-
lar structure at the interface, while shear deformation is primarily affected by the strength
of the interfacial film, which is related to intermolecular interactions. While dilatational
rheology plays an important role in short-term stability, interfacial shear viscosity is more
closely related to long-term stability. Only by combining the results of both methods it is
possible to gain complex information to help understand the correlation between the in-
terfacial mechanical properties and the structures formed at the interfaces. Unfortuna-
tely, comprehensive studies evaluating both measuring principles are still lacking. More-
over, even much less is known about the role of interfacial rheological characteristics in
electrospinning. We believe that due to the large increase in the interface during electro-
spinning, the correlation between the rheological characteristics of the interface and the
nanofiber morphology is far more distinct than the correlation between the rheological
characteristics in bulk and the nanofiber morphology. Therefore these relationships must
be further explored to optimise the process of electrospinning.
Acknowledgements. – This work was financially supported by the Ministry of Education, Sci-
ence, Culture and Sport of the Republic of Slovenia: P1 – 0189, J1 – 4236, 1000 – 09 – 310085 and
1000 – 11 – 310213.

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POVZETEK

Medfazna reologija: Pregled merilnih tehnik in njen pomen

v disperzijah in elekrostatskemu sukanju
JAN PELIPENKO, JULIJANA KRISTL, ROMANA RO[IC, SA[A BAUMGARTNER in PETRA KOCBEK

Medfazne reolo{ke lastnosti so {e dokaj neraziskane. [ele pred kratkim so razvili

metode, s katerimi je mogo~e z zadostno ob~utljivostjo in natan~nostjo dolo~iti viskoela-
sti~ne lastnosti medfaze. Medfazna reologija opisuje odnos med deformacijo medfaze in
silo, ki to deformacijo povzro~i. Zaradi razli~nih deformacij medfazne plasti (strig in raz-
tezanje, oziroma kr~enje) se tudi medfazna reologija deli na stri`no in dilatacijsko. Stri-
`ne reolo{ke lastnosti medfaze se odra`ajo v dolgotrajni stabilnosti disperzij, medtem ko
se dilatacijske predvsem v kratkotrajni stabilnosti. Poznavanje medfaznih reolo{kih last-
nosti je pomembno v sistemih z velikimi medfaznimi povr{inami, kot so emulzije in pe-
ne ter pri procesih, kjer pride do velikega pove~anja medfazne povr{ine, kot je elektro-
statsko sukanje nanovlaken.

Klju~ne besede: medfazna reologija, emulzije, pene, elektrostatsko sukanje, nanovlakna, nanotehno-
logija

Univerza v Ljubljani, Fakulteta za Farmacijo, Ljubljana, Slovenija

140