Microgel Particles and Their Effect on the Textural Properties of Foods

Anisa Loewen, Stefan Nobel, and Jorg Hinrichs, University of Hohenheim, Stuttgart, Germany
2017 Elsevier Inc. All rights reserved.

Introduction 1
Microgels in Food Applications 3
Polymer Systems 3
Polysaccharides 3
Proteins 3
Mixed Polymer Systems 4
Rheological and Textural Relationships 4
Polysaccharides 4
Formation and Components 4
Additional Components 4
Proteins 5
Formation and Components 5
Additional Components 6
Complex Microgel Systems 6
Conclusion 6
Outlook 6
References 7

Introduction

Gels are soft matter structures comprised of a liquid-lled and continuous colloidal or polymer network that exhibits solidlike
properties on the macroscopic scale (Jones et al., 2008). A dispersion of gel-like particles with an equivalent diameter from 0.1
to 100 mm are usually called microgels, microspheres, or microbeads (Dickinson, 2015; Fernandez-Nieves et al. 2011a,b), although
no universal length scale or denition can be expressed (Pich and Richtering, 2010). Microgels possess a dualism of a complex
microscopic structure due to the underlying polymers and the macroscopic behavior of stable colloidal dispersions (Dickinson,
2015). A unique attribute of microgels is the large amount of solvent immobilized within the gel network since the particles
contained therein occupy a signicantly higher volume fraction, f, compared to the solid mass fraction, w. As a result of this solvent
integrated into the particle network, microgels have a sensitivity to swelling or shrinkage as a function of small changes in environ-
ment and solvent condition (Dickinson, 2015).
Phase behavior of microgel dispersions is highly dependent on the particle volume fraction, f, and can be described through
relationships with the viscosity of a dispersion as shown in Fig. 1. For dilute (f < 0.05), monodispersed, spherical microgels
this relationship is expressed by Einsteins viscosity equation, in this case equal to the complex viscosity.
hd
hrel 1 2:5f (1)
hc
where hrel is the relative viscosity given as the viscosity ratio of discontinuous phase or dispersed phase hd to the continuous phase or
dispersion medium hc and 2.5 stands for a spherical particle in a shear ow. At low f, particles rotate in a laminar shear ow
resulting in an apparent effective volume corresponding to 2.5 times the actual volume of the particle. For more concentrated
dispersions (fmax  0.4) the KriegerDougherty equation adequately illustrates viscosity behavior.
 
f hfm
hd hc 1  (2)
fm
where hd and hc are the dispersed phase and dispersion medium viscosities, [h] is the intrinsic viscosity, f is the hydrodynamic
volume fraction, and fm is the maximum packing fraction.
Increasing the proportion of microgel particles further results in a crowding effect up to a particular volume fraction where
sticking, fm, with the neighboring particles occurs (Willenbacher et al., 2011). At this point, free rotation of particles is impeded,
and they are elastically deformed or even destroyed. With only weak and short-range attractive forces between particles, the disper-
sion shifts from the liquid to the glassy state (repulsive glass). If new particle bonds form due to dominant attractive forces, the
dispersion approaches the gel state (attractive glass), where existing microgels are embedded in a new gel phase because of their
high degree of concentration (Willenbacher et al., 2011; Dawson, 2002). It is clear from Fig. 1 that the main viscosity outcomes
of volume fraction only appear with f > 0.4 for typical, monodispersed, spherical microgel particles. Although the relationships
above this f are not fully understood, it is clear that apparent viscosity h 0 is a function including other factors that direct the char-
acteristics and mechanical stability of microgels.

1
2 Microgel Particles and Their Effect on the Textural Properties of Foods

Figure 1 Qualitative viscosity increase depending on volume fraction of microgel particles. Adapted from Hinrichs, J., 2000. UHT processed milk
concentrates. Lait 80 (1), 1523. Available at: http://www.scopus.com/inward/record.url?eid2-s2.0-0034404014&partnerIDtZOtx3y1.

h0 f g;
_ s; f; t; w; pH. (3)
where h0 is the apparent viscosity, g_ is the shear rate, s is the shear stress, f is the total volume fraction, t is time, and w is
temperature. The f within Eq. (3) can be thought of as the sum for the volume fraction of particles of different size and/or
composition:
f f1 f2 f3 / (4)
0
For microgels with f > 0.4, apparent viscosity h is correlated with shear viscosity as a function of shear rate g_ . There are three
main consequences of shear that lead to a decrease in microgel viscosity: (1) particles are broken down into smaller sizes, (2) solvent
is released from particles, and (3) particles are deformed.
Eq. (3) can also be postulated for other rheological and textural parameters including rmness and elasticity, where changes in
each parameter may lead to both reversible and irreversible changes in microgel characteristics. As non-Newtonian materials, the
shear stress is time dependent; specically, deformability directs the microgel response to shear because of the ability to change
shape in response to agitation, especially at high f. In conjunction, swelling and deswelling of microgel particles is typically asso-
ciated with a reduction and increase, respectively, of the individual microgel particle elastic modulus (Hashmi and Dufresne, 2009).
A variety of tailorable microgel properties, summarized in Fig. 2, are relevant for food applications, for example, interior stiffness
and deformability, variable shape, surface activity, and reversible swelling depending on temperature, pH, and ionic strength.

Figure 2 Parameters affecting microgel characteristics; degree of cross-linking: particle stiffness and deformability, particle surface charge: interpar-
ticle forces and miscibility, shape: ow and phase behavior, colloid or polymer type: responsiveness to environmental changes. Modied from She-
wan, H.M., Stokes, J.R., 2013. Review of techniques to manufacture micro-hydrogel particles for the food industry and their applications. J. Food
Eng. 119 (4), 781792. http://dx.doi.org/10.1016/j.jfoodeng.2013.06.046.
 Microgel Particles and Their Effect on the Textural Properties of Foods 3

Specic makeup and formation methodology of polymer systems can be manipulated to bring about a range of responses under
different conditions such as changes in pH, temperature, enzymatic treatment, and mechanical load during processing (Shewan and
Stokes, 2013; Weidendorfer et al., 2008; Hahn et al., 2012b; Pich and Richtering, 2010).
Microgel adaptability makes them attractive food ingredients, for instance, encapsulation systems or fat replacers (McClements,
2014; Yan and Pochan, 2010; Ching et al., 2016). The interior polymer network of microgels often exhibits an amphiphilic structure
that is capable of stabilizing emulsions in a different way than solidlike particles in the so-called Pickering emulsions (Dickinson,
2015; Murray and Phisarnchananan, 2016). However, reviews on the subject of microgels as emulsiers and delivery vehicles
are available elsewhere in the literature (Dickinson, 2015; McClements, 2014; Matalanis et al., 2011; Chen et al., 2006;
Fernandez-Nieves et al., 2011b; Heyes and Bra nka, 2009; Shewan and Stokes, 2015; Siebenbrger et al., 2012). Furthermore, owing
to their soft structure and high solvation capacity, microgels may be useful partially or completely to replace single phases,
for example, as a fat replacer or to replace starch granules (Dickinson, 2015; Schmitt et al., 2010; Wu and McClements, 2015;
Krzeminski et al., 2011). Through these applications and others, the microgel particles are building blocks in the structure of the
food product and may contribute to textural characteristics, whether unintended in the case of incapsulation systems or intended
in the case of phase replacement.

Microgels in Food Applications

Microgels in food applications can be categorized using two principal features that contribute to structure and stability: (1) polymer
makeup of the microgel particles and (2) origin or formation method of the microgel particles. The majority of food-grade micro-
gels make use of proteins and polysaccharides as polymer systems. Formation of gel and particles, which can occur simultaneously,
can be carried out using three different basic methods: (1) (natural) self-assembly of (bio)polymers, (2) induced polymerization
into a homogeneous gel; or (3) photolithographic techniques (Pich and Richtering, 2010). Particles are initially formed and subse-
quently stabilized or, alternatively, obtained by mechanical treatment of a homogeneous gel. The majority of food-grade microgels
are prepared using the rst two methods (Nbel et al., 2014; Shewan and Stokes, 2013); additionally, specics of formation
methods for microgel particles added later to foods have been summarized previously (Farjami and Madadlou, 2017; Shewan
and Stokes, 2013).

Polymer Systems
Polysaccharides
Microgel dispersions have long been used for rheological control, with likely the oldest examples being starches from ancient times
(Stokes, 2011). Gelatinized starch particles form when swollen with water and heated above a critical temperature, which results in
a soft solid texture. Especially at high f, a prevailing attractive force results in gel-like properties, which are maintained on cooling,
are useful for thickening, and provide an apparent yield stress in foods to mimic a creamy or fatty texture. From the initial
semicrystalline structure, the gelatinized particles of starch release polymer chains into the dispersion medium, allowing the starch
granules to absorb water, which increases f (Fig. 2). This whole process leads to changes in system rheology, such as increased
viscosity, that result from the existence of the swollen, deformable granules, as well as the long-chain polymeric components
incorporated into the dispersion medium (Steeneken, 1989; Lagarrigue and Alvarez, 2001; Stokes, 2011). The components released
into the dispersion medium, namely the hydrocolloids amylose and amylopectin, interact with other components, for instance
proteins and fats, added to the food system (Raphaelides and Georgiadis, 2008; Carvalho et al., 2004). A more detailed review
of starches as microgel particles can be found in Stokes (2011).
Generally, hydrocolloids are inherently suitable as polymers for intentional food-grade microgels. This is particularly owing to
their swelling and thermoresponsive properties that can be adjusted by means of modied side chains, cross-linking agents, and
environmental pH (Fernandez-Nieves et al., 2011a; Vlassopoulos and Cloitre, 2014). Microgel particle formation abilities have
been studied; however, food applications and contributions to textural properties are yet to be found in the literature.

Proteins
Food-grade microgel particles from whey protein (WP; Schmitt et al., 2010) are also described in the literature. WP refers to a group
of proteins including b-lactoglobulin, a-lactalbumin, and bovine serum albumin. These are globular and highly structured proteins
naturally occurring in bovine milk. Polymerization of WP isolate or puried WP fractions in a narrow pH range or by fast heating
forms particles considered as microgels due to their size, viscoelasticity, complex fractal structure, and surface activity (Alting et al.,
2004; Schmitt et al., 2010; Nicolai, 2016). The so-called microparticulation of proteins is an effective technique to form microgel
particles with tailored characteristics, based on the native protein and process steps such as heating, mechanical treatment, extru-
sion, and alteration of pH (Shewan and Stokes, 2013). One such example is microparticulated WP, which has been the subject
of patents (Singer et al., 1991; Konrad et al., 2013; Singer et al., 1992; Huss and Spiegel, 2004). Casein proteins are also capable
of forming microgels during processing. In milk, casein micelles exist as a dispersion and are responsive to changes in temperature,
pH, and ionic strength meeting the characteristics of a microgel. Further to this, acidication of milk results in a porous, homoge-
neous gel based on the building blocks of casein micelles and heat-induced WP aggregates (Andoyo et al., 2014; Lee and Lucey,
2006; van Marle et al., 1999; Mellema et al., 2002), and in the case of stirred dairy products, the nal gel network is destroyed during
4 Microgel Particles and Their Effect on the Textural Properties of Foods

processing by mechanical stress. A general description of acidied and fermented dairy products such as yoghurt and fresh cheese in
terms of microgel properties can be found in the literature (Nbel et al., 2016; Van Vliet et al., 2004; Lucey, 2002; Hahn et al., 2014;
van Marle et al., 1999; Nicolai and Durand, 2013).

Mixed Polymer Systems

Mixtures of polymers give rise to systems with differing characteristics based on individual particle properties. StarchWP gels are
commonly applied in foods such as puddings, breads, and yoghurts for their thickening, emulsifying, and stabilizing properties
(Carvalho et al., 2004). In addition, mixed systems such as pectingelatin microgels and pectinWP or k-carrageenanWP microgels
are proposed as replacements for food components such as starch granules and fat globules in foods to lower caloric load (Wu and
McClements, 2015; Nicolai, 2016). Microgel particles made of such polymers have potential in these applications to further tailor
exploited characteristics based on polymerparticle contributions.

Rheological and Textural Relationships

Rheological and textural relationships for microgels in foods are important because of the changes that may occur with processing,
storage, transport, and nal product state. The rheology of colloidal microgel dispersions shares characteristics of both polymer and
hard-sphere suspensions (Shewan and Stokes, 2015; Stokes, 2011), for instance, increased viscosity and shear thinning at low solids
content like polymers but as particles they are regulated by many of the same factors such as hard spheres. Despite this fact, rheo-
logical parameters depend on a variety of other factors such as composition, the physical and chemical properties of the microgel
components, and the microstructure (Steffe, 1996). An efcient modication of rheological behavior, regarding the texture and
sensorial properties of microgel dispersions, is an important issue in industrial applications, due to the fact that the physical attri-
butes and visual appearance affect the functionality and consumer acceptance of these products (Fischer and Windhab, 2011), for
example, dispersed dairy microgels (Lucey, 2002).
Food-based microgels tend to exhibit viscoelasticity. The viscoelasticity is usually characterized by the following rheological
parameters: storage G0 and loss moduli G00 reecting the elastic and viscous contribution, respectively, and the yield stress s0 , deter-
mining resistance to ow and susceptibility to break (Lucey, 2002; Norton et al., 2010; Steffe, 1996; van Vliet, 2014). It is worth-
while to note that care should be taken when comparing rheological measurements conducted using different methods, for
example, equipment, geometry, and procedure, since the resulting values are partially method dependent.

Polysaccharides
Formation and Components
Numerous sources of starch have been reviewed regarding a variety of characteristics or processes including chemical modication
(Singh et al., 2007), structure and composition (Hoover et al., 2010), and the relationship with rheology. The process of starch
microgel formation has a signicant effect on the rheology of these gels with differences arising from gelation and polymer release
(Lagarrigue and Alvarez, 2001; Tecante and Doublier, 1999). Considering factors listed in Eq. (3), it is of interest to describe modi-
cations occurring to a microgel throughout the entire process chain (i.e., microgel formation, postprocessing). Unfortunately, data
from rheological studies on process conditions of starch systems may have limited transferability to real food systems as study
parameters are often not comparable to real process conditions (Lagarrigue and Alvarez, 2001).
The connection between starch concentration and viscosity indicates that the rheology is typical of microgel systems shown in
Fig. 1 (Steeneken, 1989). For example, starches that are capable of higher swelling result in higher viscosity in the dilute regime
while lower swelling starches give rise to more viscous systems when concentrated. Deviations from this relationship at high phase
volumes are thought to be due to granule anisotropy, deformability, microphase separation, and associated osmotic equilibria
(Evans and Lips, 1992). The particle size and distribution also control starch microgel rheology, as is anticipated from ndings
in hard-sphere model systems (Farris, 1968; Ojijo and Shimoni, 2008). Multimodal mixing of different sized spheres or having
a monomodal distribution with higher polydispersity results in lower relative viscosities at the same total f since smaller particles
become trapped between larger ones and increase the overall random close packing (Dames et al., 2001; Farris, 1968). A ternary plot
(Fig. 3) shows predictive viscosity contours for a trimodal distribution of solid spheres with altered size ratios, where lower relative
viscosity is shown for mixtures of spheres centered around the middle of the diagram (Farris, 1968). Although limited work can be
found with starches, it was reported that cassava starch ow properties can be altered by applying the Farris effect, wherein the
apparent viscosity and yield stress of the pastes were reduced by over 20% at f > 0.4 and a critical particle size ratio (Ojijo and
Shimoni, 2008).

Additional Components
Polymers in the dispersion medium around starch microgels also dictate the quality of extensional viscosity observed in cooking
sauces and desserts based on starch. These components, whether originating from or added to the dispersion, can form supplemen-
tary microgel particles and result in further modication of rheological characteristics (Tecante and Doublier, 1999; Savary et al.,
2008; Carvalho et al., 2004). Additional dispersed compounds such as fatty acids can interact with starch granules and inhibit
granule swelling; long chain fatty acids have increased effectiveness (Raphaelides and Georgiadis, 2008). The impact of additional
 Microgel Particles and Their Effect on the Textural Properties of Foods 5

Figure 3 Contour plot of relative viscosity (lighter contour represents lower relative viscosity) in accordance with trimodal blend ratios for hard
spherical particles of different sizes (small, medium, large) with a constant total volume fraction (f 0.65); dotted lines are guides to the eye. Adapt-
ed from Farris, R.J., 1968. Prediction of the viscosity of multimodal suspensions from unimodal viscosity data. J. Rheol. 12 (2), 281.

dispersed compounds has been investigated for polysaccharidestarch composite systems, for instance, simulations of fruit prep-
arations used in avored dairy products (Savary et al., 2008). Although both starch and polysaccharide concentration contribute
to the viscoelastic properties, additional complications can arise because the polysaccharide may position partly inside the starch
granule and also mix with amylose in the dispersion (Savary et al., 2008; Tecante and Doublier, 1999); as such, rheology of each
polymer combination is individual and dependent on preparation conditions. Until now, no general approach is available to model
the viscoelastic behavior based on characteristic data of individual components of food and the further interactions that transpire in
food systems.

Proteins
Formation and Components
From protein microgels prepared via polymer self-assembly to those formed through polymerization into a gel, the formation route
and incorporated components of microgel particles determine the overall system rheology. Dispersions of dairy protein microgels
such as yoghurt and fresh cheese are useful examples of protein microgels since they are used as such and can be studied in different
concentration regimes with additional components.
Acidied dairy gels from dispersions of casein micelle can be formed using two possible routes dependent on pH and temper-
ature parameters, which modulate the location of certain compounds within the casein micelle and thus the casein microgel particle
(Vasbinder et al., 2003). For example, below 5 C, b-casein, calcium, and phosphorus are released from the casein micelle and result
in bridging and rmer gels due to the available serum caseins (Koutina et al., 2014; Vasbinder et al., 2003). Hence, dairy microgels
are responsive to temperature, pH, and ionic strength changes but also partially dissociate depending on these parameters, contra-
dicting the microgel principle (Dickinson, 2015; Van Vliet et al., 2004).
Initially, the water binding and effective f of dairy protein microgel particles follows the volume fractionviscosity relation
(Eqs. 1 and 2) and the temperatureviscosity relation due to the swelling characteristics (Nbel et al., 2012); however, the appli-
cation of this relationship at higher f is limited by instrumental techniques and therefore the validity is currently unknown. Since
the particleparticle interactions become dominant at f > 0.4, the rheological properties of concentrated dispersed dairy microgels,
such as fresh cheese and greek-style yoghurt, can be adjusted primarily by changing the solid content to result, for instance, in
increased viscosity (Hahn et al., 2015; Hahn et al., 2012b; Krzeminski et al., 2013; Nbel et al., 2014). However, the major drawback
of this approach is that modication of solid content may lead to the sensory deterioration as well as cause high manufacturing costs
and technical difculties.
Reducing the application of stress is particularly important for handling of dairy microgels during and postprocessing to
maintain the desired structure and has been reviewed previously (Mokoonlall et al., 2016). Dairy protein microgels follow typical
microgel behavior regarding shear, where viscosity is time dependent partly due to interactions between microgels (Fig. 1) and
partly as a consequence of stress sensitivity leading to the release of serum from microgel particles. A reduction in f follows for
nonreversible viscosity decrease and instability i.e., syneresis. Microgels of fermented milk display apparent thixotropicity and
major structural breakdown after an initial applied stress. As a result, rheological characteristics are highly dependent on the compo-
sition and processing history of these microgels. To this extent, some approaches to describe these relationships have been reviewed
(Mokoonlall et al., 2016).
6 Microgel Particles and Their Effect on the Textural Properties of Foods

Furthermore, attempts have been made to describe the relationships between particle size and distribution for dairy protein
microgels and sensory perception. Thresholds for sensory perception of creaminess or grittiness have been suggested (Hahn
et al., 2012a; Cayot et al., 2008), although it is cautioned that these are product specic. Nevertheless, larger particles are perceived
as less smooth in both fat-free yoghurt and fresh cheese. Modication of textural characteristics by modifying particle size distribu-
tion using the Farris effect, as shown in Fig. 3, has also been explored (Hahn et al., 2015). For example, tempering and subsequent
mechanical processing of fresh cheese result in multimodal particle size distribution, wherein the ow properties and gel rmness of
microgel particles in fermented dairy products can be modulated. Particle shape, width of the particle size distribution, particle
deformation, and the arrangement of particles also can contribute to the ow properties of dispersed microgels (Hahn et al.,
2015). On one hand, optimization of particle size distribution may improve the textural and sensory properties, but on the other
hand, it is an additional process step that requires sufcient equipment (Hahn et al. 2012a,b; Kealy, 2006) and may also result in
undesirable structure loss, i.e., syneresis (Mokoonlall et al., 2016).

Additional Components
Additional components in the dispersion can modify the texture of fermented dairy products through various mechanisms. The
concentration of exopolysaccharide (EPS) in the dispersion medium increases product viscosity and water-holding capacity (Lucey,
2004; van Marle et al., 1999; Kketin et al., 2009; Hahn et al., 2014). Additionally, EPS forms bridges with the casein microgel
particles and also interferes with the number and strength of bonds between casein microgel particles by locating between them.
These effects decreased the storage modulus, yield stress, and visual roughness in yoghurts (Kketin et al., 2009); however, in
fresh cheese the particle size decreased and storage modulus increased (Hahn et al., 2014). It is proposed that the effects are concen-
tration dependent for both EPS and microgel particle, wherein the EPS can locate between microgel particles to result in a stronger or
weaker network based on space availability (Hahn et al., 2014). Other components such as WP and fat modulate and help to
disguise texture by interacting with the microgel particles (Krzeminski et al., 2011). Particle size in stirred fat-free yoghurts increased
with higher WP and decreased with increasing fat. Storage modulus and apparent viscosity increased as a function of increased
interparticle interactions (from self-aggregation, or aggregated WP-coated fat globules). Additionally, resistance to shear decreased
with increasing WP concentration. Confocal laser scanning microscopy revealed large WP aggregates and fat globules that interrup-
ted and formed a coarse gel (Krzeminski et al., 2011).

Complex Microgel Systems

When microgel particles are formed and subsequently added to a system, the matrix can embody one of the two simplied forms:
(1) a single-type microgel dispersion with a complex dispersion medium or (2) a multitype microgel dispersion with a simple or
complex dispersion medium.
Microgels are added to complex systems with the aim of improving sensory characteristics, while also maintaining or improving
nutritional value, for example, replacement of food components (i.e., fat). The success of using microgels to improve product
texture is dependent on a variety of product and microgel factors, as expected from the characteristic environmental responsiveness
of microgels. Crucial to each application is the importance of particle size in relation to other product components to achieve
improved textural characteristics as is shown for WP microgels in yoghurt, concentrated fermented dairy products, cheese, ice cream
(Ipsen, 2016), and pectin microgels in mayonnaise (Liu et al., 2007). Processing conditions of the product, such as fermentation
time and temperature, and raw material composition, such as fat content, regulate the inuence of microgel particles on product
texture (Ipsen, 2016; Giroux et al., 2015). Basic differentiation of textural impact can be explained by the function of microgel parti-
cles within the food product matrix: inert or interactive (Fig. 4). Nevertheless, effective use of these microgel particles for textural
design requires further clarity on the connections between additional microgel characteristics, such as hydrophobicity and charge
density, and the role microgels take on within the product matrix.

Conclusion

Microgels for food applications can be prepared using widely available (bio)polymer systems in relatively simple preparation steps.
However, application of microgel particles for rheological and textural modication of food requires an in-depth understanding of
the polymer makeup, formation, interaction with the environment and other food components, and the processing history of the
microgel. Although general relationships for microgel rheology are understood, the complexity of food formulations and processing
conditions are still under investigation.

Outlook

Microgels are attractive for the purpose of tailored rheological properties because of their ability to be modied by environmental
conditions. Their adaptable characteristics are appealing since rheological control is available through system modication, rather
than increased material usage. Nevertheless, the links and full relationships between local particle characteristics and macroscopic
properties are not well established. A major reason for this lack of exploration is the absence of methods that are able to characterize
 Microgel Particles and Their Effect on the Textural Properties of Foods 7

Figure 4 Schematic representation of the inert and interactive roles microgels may play within a food product matrix; blue represents food compo-
nents, solid green represents an inert microgel, striped green represents an interactive microgel.

microgels on a single particle level. Future research should focus on approaches to investigate single microgel particle properties to
understand the relationships between micro- and macroscopic attributes in microgel systems.

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