Foods 07 00170
Foods 07 00170
Foods 07 00170
Review
Alginate-Based Edible Films and Coatings for Food
Packaging Applications
Tugce Senturk Parreidt 1,2, * , Kajetan Müller 2,3 and Markus Schmid 4
1 Chair of Food Packaging Technology, TUM School of Life Sciences Weihenstephan, Technical University
of Munich, Weihenstephaner Steig 22, 85354 Freising, Germany
2 Fraunhofer Institute for Process Engineering and Packaging IVV, Giggenhauser Straße 35,
85354 Freising, Germany; kajetan.mueller@hs-kempten.de
3 Faculty of Mechanical Engineering, University of Applied Science Kempten, Bahnhofstraße 61,
87435 Kempten, Germany
4 Faculty of Life Sciences, Albstadt-Sigmaringen University, Anton-Günther-Str. 51,
72488 Sigmaringen, Germany; schmid@hs-albsig.de
* Correspondence: tugce.sentuerk@ivv.fraunhofer.de; Tel.: +49-8161-491-472
Received: 14 August 2018; Accepted: 14 October 2018; Published: 17 October 2018
Abstract: Alginate is a naturally occurring polysaccharide used in the bio industry. It is mainly
derived from brown algae species. Alginate-based edible coatings and films attract interest for
improving/maintaining quality and extending the shelf-life of fruit, vegetable, meat, poultry,
seafood, and cheese by reducing dehydration (as sacrificial moisture agent), controlling respiration,
enhancing product appearance, improving mechanical properties, etc. This paper reviews the
most recent essential information about alginate-based edible coatings. The categorization of
alginate-based coatings/film in food packaging concept is formed gradually with the explanation
of the most important titles. Emphasis will be placed on active ingredients incorporated into
alginate-based formulations, edible coating/film application methods, research and development
studies of coated food products and mass transfer and barrier characteristics of the alginate-based
coatings/films. Future trends are also reviewed to identify research gaps and recommend new
research areas. The summarized information presented in this article will enable researchers to
thoroughly understand the fundamentals of the coating process and to develop alginate-based edible
films and coatings more readily.
Keywords: edible coating; edible film; food packaging; alginate; crosslinking; additives; application
method; food; transport mechanism
1. Introduction
The principal roles of food packaging are to protect food products from physical, chemical,
and biological influences by delaying food deterioration, retaining and prolonging the beneficial
effects of processing, and maintaining the quality and safety of the foods with extending shelf
life [1]. Broad external influences such as the development of international food markets, legal and
technological requirements, raw material availability, consumer demands, etc. caused the food
packaging area to change perpetually [2]. A total of 1.3 billion tonnes of municipal solid waste per
year was generated in 2012, but it is expected to increase to 2.2 billion tonnes per year by 2025 [3].
Non-renewable, non-biodegradable packaging materials have serious environmental drawbacks.
They have been considered a major source to the solid waste and environmental pollution by consumers
and environment activists [4,5]. In order to solve this problem, companies and researchers have been
working on ways to develop new packaging strategies with environmentally friendly, abundant
biodegradable packaging materials made from renewable natural polymers [4,6]. Furthermore,
the rapidly growing interest in the use of edible packaging can also be associated with a growing
interest from consumers for minimally processed fresh-like foods with an extended shelf life and trend
in improving the quality of food with edible barriers [7].
Edible films and coatings are thin layers of material (their thickness is generally less than 0.3 mm)
used for enrobing the food product to replace or fortify the natural layers and can be consumed as
a part of the product or with further removal [8,9]. Therefore, the materials used in the formulation
should conform to the general food laws and regulations [10]. Additionally, the coatings and films
should not affect the organoleptic properties of the food product negatively [6].
Edible packaging can be a superficial coating on the food or continuous layers between
compartments/ingredients of the heterogeneous products (e.g., pizza, bakery fillings, and toppings) [8].
The coating can also be applied on individual pieces of the whole product, which have not been
individually packaged due to practical arguments, such as fresh-cut melons, kiwis, strawberries, nuts,
beans, pears [11].
Edible films and coatings can be used to overcome many obstacles involved in the marketing
of foods [12]. These functions can be specified as retarding moisture, gas, solute and oil migration,
improving structural integrity, retaining volatile flavor compounds, conveying food additives [12].
In addition, they improved the aesthetic appearance by minimizing the development of physical
damage, hiding scars, and improving surface shine [13,14]. For instance, hot-melt paraffin waxes have
been used to coat citrus fruits to retard moisture, edible collagen casings have been used for sausages
to provide structural integrity and apples have been coated with wax to improve surface shine and
prevent physical damage.
The required features expected from edible films and coatings can be assigned by the specific
characteristics of the product and changes during production, transportation, and storage periods.
Despite providing a barrier, the non-edible packaging is still essential for edible coated food products
due to hygienic reasons [8]. Nevertheless, combining edible films and coatings with traditional
packaging would likely reduce the non-biodegradable packaging waste of processed foods and
environmental effluence [12,15,16].
Although edible coating and edible film terms have been used interchangeably or as synonyms in
some sources; their application on the food products constitutes their main difference [9]. Edible films
are stand-alone wrapping materials which can be cut and placed on the food product separately due
to having enough integrity; on the other hand, edible coatings form a thin layer on the product directly
subsequent to the application [8,9,17,18]. Therefore, although produced from the same gelling agent,
the characteristics of edible films and coatings can be very different [9].
Alginate-based food coatings and films attracted widespread interest. A wide range of scientific
research has been published in the literature. This overview summarizes the literature information
with dividing into categories in a layout:
Our present study can be used as a guide for researchers both in the academy and industry who
plan to work on alginate-based coatings, will select the components of their formulations, and plan
their future studies and experiments.
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2. Film-Forming Materials
Film-forming biopolymers are generally classified according to the type of film-forming material,
which form cohesive and continuous matrices [8]. These are hydrocolloids (polysaccharides and
proteins), lipids and composites (Figure 1) [12,19]. Hydrocolloids are composed of hydrophilic
polymers of microbial, vegetable, animal, or synthetic origin [15]. Mostly, they are large molecules
with many hydroxyl groups [15,20]. Hydrocolloid film applications do not target to control water
vapor migration due to their hydrophilic nature [12]. However, the continuous polysaccharide film
can be referred to as a sacrificial moisture agent. That is, moisture evaporates from the film instead of
the food surface [21–24]. Subsequent to the desiccation of the coating film, the food product would
lose its moisture [24].
Figure 1. The film-forming biomaterials that have been studied extensively for the formation of edible
coatings and films (Donhowe and Fennema [12], Embuscado and Huber [25]).
In general, polysaccharides are used as gas barriers; lipids reduce water transmission, while
proteins provide mechanical stability [9]. The main disadvantages of lipid-based films and coatings
are their opaqueness, fragility, and instability (rancidity), on the other hand, hydrocolloid films and
coatings have a more neutral taste [6]. Composites are formulated using both lipid and hydrocolloid
components, which are incorporated into the formulation in order to benefit from their advantages
together [12]. Composites can be formed as a bilayer or as a conglomerate [12].
3. Alginate
Alginates are naturally occurring, indigestible polysaccharides commonly produced by
and refined from various genera of brown algae (mainly Laminaria hyperborean, Macrocystis
pyrifera, Ascophyllum nodosum; lesser extent Laminaria digitate, Laminaria japonica, Eclonia maxima,
Lesonia negrescens, Sargassum sp.) [26–30]. Some bacteria such as Azotobacter vinelandii or mucoid strains
of Pseudomonas aeruginosa also synthesize alginate like polymers as exopolysaccharide (i.e., extracellular
polymeric substances, EPSs) [29,31]. Alginate production from Marine algae [32] and A. vinelandii [33]
are explained elsewhere.
The molecular structure of alginates is composed of unbranched, linear binary copolymers
of β-D-mannuronic acid (M) and α-L-guluronic acid (G) residues linked by 1–4 glycosidic bonds
(Figure 2a) [27,28,34,35]. An algal alginate structure could be separated into three fractions (three uronic
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acid blocks): These are homopolymeric regions of M and G blocks, and alternating MG blocks
containing both polyuronic acids [27,35,36]. Bacterial alginates have O-acetyl groups, while they
are not present in the structure of algal alginates [37]. Additionally, bacterial alginates have higher
molecular weights compared to the algal polymers [33].
Figure 2. The structural formulae of monomeric units in alginate and the schematic representation of
the egg-box model (a) Left hand side: Haworth conformation; right hand side: Chair conformation
(b) Gelation of poly L-guluronate blocks (G Blocks, ) with Ca2+ ( ) (Peteiro [32],
Lee and Rogers [38]).
The source of the alginate affects the ratio of M and G residues, which have an impact on the
physical and chemical properties of the alginate, as well as the viscosity of the coating solution and
thickness on the product [28,36,39]. Martinsen, et al. [40] characterized the relationship of physical
properties of alginate gel beads with a polymer composition, sequential structure, and molecular size
of the several different alginate sources.
Alginic acid was first discovered and isolated by Dr. E.C.C. Stanford in 1881 [35]. Alginates
(i.e., sodium alginate (E401), potassium alginate (E402), ammonium alginate (E403), and calcium
alginate (E404)) are monovalent salts of alginic acid (E400) [27,41,42]. Alginic acid and calcium
alginate are insoluble in water while sodium alginate, potassium alginate, and ammonium alginate are
water-soluble polymers [42,43]. They have a limited solubility at low pH values [44]. The solubility of
different types of alginates in numerous solvents and solutions were listed by Kimica Corporation [45].
The U.S. Food and Drug Administration (FDA) classifies food grade sodium alginate as GRAS
(generally regarded as safe) substance in Title 21 of the Code for Federal Regulations (CFR) and lists its
usage as an emulsifier, stabilizer, thickener, and gelling agent [46]. The European Commission (EC)
listed alginic acid and its salts (E400–E404) as an authorized food additive [41].
Alginate is widely used in various industries such as food, beverage, textile, printing,
and pharmaceutical as a thickening agent, stabilizer, emulsifier, chelating agent, encapsulation,
swelling, a suspending agent, or used to form gels, films, and membrane [28,47]. Sodium alginate is
the most common salt of alginate [48].
4. Crosslinking
It is widely well-known that alginate is polyuronide, a natural ion exchanger [49]. The charged
state of alginate is beneficial for film formation. In the absence of bivalent ions, alginate can be only
used to increase viscosity [38]. However, the addition of certain bivalent cation into the alginate
Foods 2018, 7, 170 5 of 38
solution leads to a gel formation through ion exchange [42,47]. The affinity of alginate for the alkaline
earth metals increases in the order Ca2+ < Sr2+ < Ba2+ [38,49]. Monovalent cations and Mg2+ ions do
not form a gel [50]. Even though divalent cations such as Pb2+, Cu2+ , Cd2+ , Co2+ , Ni2+ , Zn2+ , and Mn2+
can also induce gelation, their toxicity limits their utilization [51].
Alginate gel formation is rather a complex process. The proportion and length of the guluronic
acid block (G-blocks) in the polymeric chain, the capacity to bind the number of divalent ions, the type
of gelling ions and gelling conditions affect strongly the hydrogel properties of alginate [39,52–54].
The introduction of divalent cations (usually Ca2+ ions) to the system induces conformational changes
in alginate such as alignment of the G-blocks and the formation of the egg-box model [54] due to
bounding of calcium ions between two chains and forming divalent salt bridges (Figure 2b) [39,40].
A higher amount of G-Blocks will create rigid and dense gels, while a higher amount of M-Blocks
will build flexible, porous gels [54–57]. Therefore, the diffusional resistance of gels containing
predominantly high polyguluronic alginate content against high-molecular-weight-compounds
is high [56,57]. Besides, the study by Olivas and Barbosa-Cánovas [58] revealed that films
containing higher proportions of G-Block (in other words, lower M/G ratio) showed better moisture
barrier characteristics.
There are two types of procedures for the incorporation of gelling ions into the alginate solution to
form hydrogel (i.e., external and internal gelling modes) [59,60]. (1) For external gelation (the traditional
method), alginate solution is directly exposed to the solution of gelling ions, Ca2+ instantaneously
reacts with carboxylic groups of guluronic acid residues and hydrogel is formed irreversibly due to the
diffusion of ions [52,59,61]. (2) On the other hand, the internal gelling method consists in incorporating
an insoluble source of gelling ions with alginate solutions and afterward, the gelling ions are released
by processes that lower the pH: the addition of organic acids or slowly hydrolyzing lactones [52,59].
When these two methods are compared, internal gelation forms more homogeneous but less dense gel
matrices with larger pore sizes compared to the external gelation due to the displacement of Ca2+ by
H+ with the acid addition [60,61].
According to Mancini and McHugh [53], gel formation by cooling of the hot solution,
which contains all the components, can be evaluated as the third method to initiate the controlled
alginate gelation. Due to the thermal energy that the alginate solution possesses, a calcium-induced
hydrogel formation can only take place after cooling [53].
The source of calcium ions (i.e., calcium chloride, calcium lactate, calcium gluconate, calcium nitrate,
and calcium propionate) has an influence on gel formation. Allen et al. (as cited in Reference [62,63])
reported that crosslinking with calcium chloride generated stronger alginate gels compared to calcium
gluconate, calcium nitrate, and calcium propionate. The calcium source also affects the kinetics of
gelation; in other words, the rate of gelation and Ca2+ concentration is positively correlated [38]. Calcium
chloride has the highest solubility (75 g/100 mL) followed by calcium lactate (8 g/100 mL) and calcium
gluconate (3 g/100 mL) at 20 ◦ C [38]. The steady-state gel strength was reached fastest by calcium
chloride followed by calcium lactate and calcium gluconate [52]. On the contrary, according to the
study by Chrastil [64], the gelation kinetic constants did not depend on the calcium source. However,
the strength of the formed gel and the resistance against calcium diffusion are not dependent on the
calcium source type [38,52].
Despite its high solubility, calcium chloride is not an attractive calcium source due to imparting a
bitter taste on the food [38]. On the other hand, calcium gluconate and calcium lactate can be used in
coating applications where the taste attributes are important [38].
In situ gelation of alginate, and strongly homogeneous structure forming are also an interest
of biotechnology (e.g., tissue engineering, immobilization of cell and enzyme systems, carriers for
drug delivery system). A technique to prepare homogeneous alginate gels with a slow release of
calcium ions has been reported [65,66]. In a similar approach, Kuo and Ma [67] used calcium carbonate
D-glucono-δ-lactone (CaCO3 -GDL) or calcium sulfate dihydrate (CaSO4 .2H2 O -CaCO3 -GDL) as a
gelation agent due to their very low solubilities, which allows for a uniform distribution of the CaCO3
Foods 2018, 7, 170 6 of 38
in the alginate solution and, therefore, a more controlled and more uniform gel formation. In their
subsequent research, the dimensional stability (swelling tendency of the gel due to an increased
tendency of the carboxyl and hydroxyl groups to interact with water molecules and osmotic pressure)
was controlled by controlling the calcium ion concentration of the external aqueous environment,
crosslinking density, and polymer concentration of the gel and chemical composition of alginate [68].
It was pointed out by Pavlath, et al. [69] that two type of reactions take place when an alginate
film/coating is immersed in crosslinking calcium solution: diffusion of the multivalent ion which
induces formation of calcium linkage with the carboxyl groups for the insolubilization of the alginate
film, and the dissolution of alginate by the solution [58]. The increased concentration of the multivalent
ion diminishes the dominance of the dissolution process [69]. Rhim [70] also noticed the same
phenomena and added that the method of CaCl2 treatment affected the thickness of the film, i.e., direct
addition of the crosslinking agent lead to thicker films compared to immersing the alginate films into a
crosslinking solution.
The properties of the formed film are also dependent on the mixing temperatures; although
mixing at ~20 ◦ C caused an immediate gel formation that could not be cast, mixing at ~50 ◦ C formed a
viscous solution which could be poured into the frames [69].
The degree of crosslinking affects the swelling ability of the 3D structure of the alginate in the
solvent, and we end up with a decrease in the permeability to various solutes and being used in drug
controlled release systems [71]. In the study by Zactiti and Kieckbusch [71], the degree of swelling
decreased (in other words, the crosslinking was increased) with the increasing concentration of Ca+2
ions in the crosslinking solution and, therefore, the solubility and elongation of the alginate films
decreased, while the tensile strength increased. Similarly, Rhim [70] observed that an increase in
the CaCl2 concentration caused an increase in the tensile strength and a decrease in the percentage
elongation at break.
The literature on the effects of calcium chloride dipping alone (without coating) has shown that
CaCl2 can be used as an effective firming agent due to the ability of calcium to bind cell wall polymers,
maintain its structure, and diminish the water solubility of pectic substances with forming calcium
pectate [72–74]. Improvement in firmness increases with increasing concentration of CaCl2 , however,
this is independent from the dipping time [75].
5. Additives
The mechanical, functional, organoleptic, and nutritional characteristics of edible films and
coatings can be modified with the incorporation of various natural or chemical additives [12].
5.1. Plasticizers
The mechanical properties of biodegradable packages can be improved by the plasticization of the
polymer-network with plasticizers, which are generally non-volatile and miscible with the polymer.
The primary objectives of the plasticizers are increasing the free volume or molecular mobility of
polymers, decreasing the intermolecular forces, bestowing flexibility, reducing brittleness, improving
tear impact resistance, and regulating the flow of the coating material [26,76–79]. Furthermore,
the plasticizers should have the same solubility properties with the polymer in the solvent system
(to prevent plasticizer or polymer separation during film/coating application), possess a high boiling
point, and should be able to change the physical and mechanical properties of the substance when
incorporated into the formulation [6,76].
Water is the most common and most effective plasticizer; still, the plasticizing effect of water
in hydrophilic biopolymers is difficult due to the dependency of the environmental conditions
such as relative humidity and temperature [6,8]. Apart from water, glycerol, sorbitol, acetylated
monoglyceride, polyethylene glycol, sucrose, etc. have been used as plasticizers in food coating
studies [12]. The addition of hydrophilic plasticizers to the formulation generally promotes water
vapor permeability (WVP) and influences the mechanical properties of the coating material [12,80].
Foods 2018, 7, 170 7 of 38
Therefore, the type and the quantity of the plasticizer are very important in the designing of the
edible coating formulation. Parris, et al. [81] stated that based on the total solid content of the film,
the plasticizer amount should be determined between 10% and 25% as lower concentrations cause
brittleness whereas higher concentrations lead to stickiness.
Glycerine and sodium lactate lead to stronger and more elastic alginate-based films compared to
sorbitol, which was stiffer [81]. However, sorbitol added films exhibited better water vapor barrier
properties at the same concentration due to being less effective in reducing intermolecular hydrogen
bonding between polymer molecules [81]. Jost, Kobsik, Schmid, and Noller [80] compared the effects of
glycerol and sorbitol addition to alginate films in terms of their mechanical properties and determined
that both plasticizers decreased equilibrium moisture content and porosity. On the other hand,
the incorporation of glycerol caused higher WVP and oxygen permeability, while sorbitol did not alter
barrier properties [80]. Similarly, Olivas and Barbosa-Cánovas [58] analyzed the effects of different
plasticizers (glycerol, sorbitol, polyethylene glycol (PEG), and fructose) on WVP and the mechanical
properties of calcium alginate films in two different RH values. WVP increased in the order of fructose,
sorbitol, glycerol, and PEG incorporated films. Plasticizers induced a sharp increase in moisture
content in the moisture sorption isotherm graphs and modified the mechanical properties with an
increasing tensile strength.
In several studies, glycerol has been used as a plasticizer, particularly for alginate films and
coatings. However, the amount used is variable. Rojas-Graü, et al. [82] reported that the water vapor
resistance (WVR) of alginate coatings increases with an increasing glycerol concentration up to 1.75%
(v/v) in the formulation; however, WVR decreases at higher concentrations of glycerol. Likewise,
Azarakhsh, et al. [83] observed the same type of effect during the optimization of the alginate coating
formulation and determined the amount as 1.16% (w/v). On the other hand, Tapia, Rojas-Graü,
Carmona, Rodríguez, Soliva-Fortuny, and Martin-Belloso [39] determined that glycerol concentrations
above 1.5% (w/v) decreased the WVR.
High wettability and uniform spreading ability of the edible coating on the targeted food product
are desired characteristics of edible coatings while designing the formulations [84–86]. Therefore,
the effects of the components on the surface tension of the coating solutions are an important factor.
Yet, glycerol and sorbitol do not have a significant effect on the surface tension of the solutions due to
not being tensio-active substances [87,88].
High amounts of plasticizer (>10%) have also been incorporated in alginate-based edible coating
formulations in the literature [89–93].
Some studies combined more than one plasticizer in order to overcome the brittleness of the
alginate films and coatings. Fan, et al. [94] chose glycerol, palmitic acid, β-cyclodextrin, and glycerol
monostearate in film formulation. Su Cha, et al. [95] used a 1:1 concentration of polyethylene glycol
and glycerol combination.
5.2. Surfactants
Adhesion on hydrophobic, rough surfaces and obtaining a uniform edible coating can be very
difficult due to the low surface free energy of the surface [9]. Addition of surface active agents
(surfactants) are the key ingredients to increase the wettability of the product and improve the
adhesion of the coating material [88]. Moreover, with a reducing superficial water activity, surfactants
and emulsifiers had a decreased rate of moisture loss when they were incorporated into the coating
formulation [96].
The major characteristics of the surfactants are being present at the surface of the interfaces
(liquid-air, liquid-liquid, liquid-solid) at higher concentrations compared to the bulk of the liquid [97].
Surfactants can be classified based on two characteristics: charge type of the surface active part
and the chemical structure of the hydrophilic groups [97]. Accordingly, these groups are; anionic
(negatively charged), non-ionic (no charged group), cationic (positively charged), and amphoteric
(can be positively or negatively charged, or both, depending on the circumstances) surfactants [97].
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The uniform spreading ability of the coating on the targeted product is a very important
effectiveness indicator of an edible coating. Therefore, researchers checked the surface free energy of the
food products, the surface tension of the edible coatings, and spreading coefficient (Ws ) while designing
their coating formulations. Senturk Parreidt, Schott, Schmid, and Müller [88] characterized the
alginate-based coating formulations with various concentrations and types of surfactants (0–5% tween
40, tween 80, span 80, span 60, and soy lecithin).
5.3. Antimicrobials
The addition of antimicrobial and antioxidant agents to the edible coatings and films is beneficial
compared to their direct application to food products due to providing the opportunity of gradually
releasing the agents and maintaining a critical concentration for a prolonged period [26,71,98,99].
In contrast with the migration of antimicrobials from the coating, the direct addition of antimicrobials
to food will cause immediate microbial inhibition while the recovery of the injured cells and the later
growth of the undestroyed cells may cause quality losses and/or foodborne diseases [100].
A great variety of antimicrobial agents have been incorporated into alginate-based edible films and
coatings (Table 1). The summarized results show that alginate forms an effective base for antimicrobials
to decrease the microbial load of coated food products.
Antimicrobial properties, mode of action, and the potential uses of essential oils (EOs) have been
revealed in various studies in the literature [101–104]. These natural preservatives have also been
added into edible films and coatings to introduce antimicrobial properties [105]. The limiting factor
of their usage is their strong flavor, which originates from the phenolic compounds (i.e., abietane
diterpenes, carnosol, ursolic acid) they contain [105].
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Table 1. Cont.
5.4. Antioxidants
Antioxidants have been defined by FDA as “substances used to preserve food by retarding
deterioration, rancidity, or discoloration due to oxidation” [144]. Autoxidation comprises of a free
radical chain mechanism in which unsaturated fatty acids react with free radicals [145]. Apart from
autoxidation, lipid quality deterioration can arise from photooxidative conditions, oxidation via
lipoxygenase-assisted process or oxidation under high temperatures [145].
Coatings can also serve as carriers of antioxidative substances to protect against discoloration,
degradation and oxidative rancidity [96]. Table 2 lists antioxidant agents used in alginate-based edible
films and coatings. The application of an edible coating with incorporated antioxidants decreases the
oxidation successfully due to the gas barrier properties of alginate coating and the synergistic effect
between two factors.
Phenolic antioxidants, which have often been incorporated into alginate-based coatings and films,
do not work as oxygen absorbers but prevent the formation of fatty acid-free radicals and, therefore,
their absorbance of oxygen in autooxidation [128].
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Table 2. The incorporation of antioxidant agents in alginate-based edible films and coatings.
6. Application Methods
Film formation methods and conditions of coating processes have important impacts on the
physical properties of the formed film [26]. Uniform and defect-free (i.e., no air bubble and mechanical
damage) film forming is very crucial to optimize its functionalities [26].
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1. Simple coacervation: The precipitation or phase change of the hydrocolloid, which is dispersed in
water, is achieved following to (i) the solvent evaporation process (i.e., drying); (ii) incorporation
of hydrosoluble non-electrolyte (in which the hydrocolloid is not soluble, e.g., ethanol); (iii) the
pH adjustment with the addition of electrolyte, which impel salting out or cross-linking.
2. Complex coacervation: The precipitation of the polymer complex is achieved by mixing two
hydrocolloid solutions, which have opposite electron charges.
3. Gelation or thermal coagulation: Precipitation or gelation is accomplished by heating of the
macromolecule which causes its degradation (e.g., proteins such as ovalbumin) or the cooling of
hydrocolloid dispersion (e.g., agar, gelatin).
The production principles of shelf-standing film techniques are similar to those for thermoplastic
films: solvent casting and extrusion, although the conditions are different [26].
6.1.2. Extrusion
The extrusion technique is based on the thermoplastic properties of the polymers [167].
Subsequent to the plasticizer addition, the solution is heated above its glass transition temperature
under low water content conditions [26,167]. The extrusion method is preferred in commercial
applications due to the lack of solvent addition and evaporation steps [167].
The co-extrusion technique can be utilized to form multilayer films. However, due to the
differences in the chemical-physical characteristics of each film-forming material, mechanical, optical,
and barrier defects can come into existence [26].
6.2.1. Dipping
Food products are usually coated by a dipping or spraying technique, in which a thin film
was formed on the surface that acts as a semipermeable membrane to control moisture loss and gas
transfer [168,169].
This method consists of four steps: sample immersion into the alginate dispersions followed
by withdrawing the sample and draining the excessive film-forming solution covering the product.
Then, a second immersion of the alginate coated sample into the crosslinking bath to achieve the gel
formation and draining of the excessive solution [170]. The dipping process is generally very short,
therefore the evaporation from solvents in the coating and crosslinking solutions are neglected [171].
The duration of the dipping and draining times differ from each study, but it is generally between 30
Foods 2018, 7, 170 15 of 38
s to 5 min. The main advantage of the method is its total coating even around complex and rough
surfaces [172].
Due to the hydrophilic surface of the cut surfaces of the food products, a good adhesion cannot
be easily accomplished by the simple dipping of the food product into the coating material. Multilayer
coating or the layer-by-layer (LbL) technique has been used to minimize the sticking difficulty of
the coating on the hydrophilic surface of the cut surfaces [26,110,173,174]. The process is based
on the dipping of food product into different coating solutions that contain oppositely charged
polyelectrolytes to achieve physical and chemical bonding to each other [110,174]. Currently, the LbL
technique is applied mainly on fruits and vegetables [175].
The dipping method forms thick coatings. Additionally, Duan, Wu, Strik, and Zhao [92] pointed
out that dipping might have diminished the efficacy of the coating application due to the dilution and
dissolving effect.
6.2.2. Spraying
The spraying method is another conventional technique used to form a semi-permeable membrane
on the surface of food products [89]. The spraying system distributes the coating solution through the
formation of droplets over the targeted food surface area with the help of nozzles [172]. The spraying
technique needs less amount of coating material to achieve good coverage due to high spraying
pressure (approx. 60–80 psi) [176]. The other advantages of this method are the uniform coating,
control of thickness, possibility of multilayer applications, avoidance of coating solution contamination,
temperature control of the solution and enabling of working with large surface areas [172].
The spraying solution should not have a high viscosity. Spray-flow characteristics are dependent
on (i) liquid properties (i.e., density, viscosity, surface tension), (ii) operating conditions (flow rate, air
pressure, etc.), and (iii) system conditions (nozzle design, spray angle, etc.) [172,177].
Earle and McKee [22] sprayed the dispersion containing water-soluble algin and, later, a gelling
agent on the freshly slaughtered hanging animal carcasses. Researchers determined the viscosity of
the solution as the critical point of the vertical spraying application to have a uniform adherence to the
alginate film. Papajová, Bujdoš, Chorvát, Stach, and Lacík [59] designed a setup to prepare externally
gelled planar alginate hydrogels with the airbrushing aerosols of a gelling solution. Amanatidou,
Slump, Gorris, and Smid [148] applied a different spraying procedure. Carrot slices were initially
dipped in CaCl2 solutions and, following the drying, an alginate-based solution was sprayed on the
surface of the slices.
Table 3. Cont.
Table 4. The application of alginate coating on meat, poultry, and seafood products.
Table 4. Cont.
7.3. Cheese
The main quality losses of cheese products take place in a storage period and can be summarized
as microbial contamination, moisture loss, and the development of off-flavor and other undesirable
organoleptic properties [216]. It is very important to underline that the addition of an extra calcium
with the aim of crosslinking is not an essential step in cheese coating due to possessing calcium
itself [138].
Edible coatings and films have been applied and studied in several types of cheese as packaging
system to prevent the quality losses. Zhong, et al. [217] investigated the performance of three different
coating materials (i.e., sodium alginate, chitosan, soy protein isolate) with four various application
methods on mozzarella cheese. The results showed that alginate-coated samples possessed better
overall qualities due to its better wettability on the product surface [217]. Lucera, Mastromatteo, Conte,
Zambrini, Faccia, and Del Nobile [137] demonstrated that the antimicrobial activity of potassium
sorbate, sodium benzoate, calcium lactate, and calcium ascorbate, which were incorporated into an
alginate coating and used to coat mozzarella cheese, were similar. The main difference arose from the
sensory point of view. Kavas, Kavas, and Saygili [136] fortified the composite coating of alginate-whey
protein isolate coatings with ginger EO and obtained kashar cheese with a lower acidity and higher
fat level.
Study Source
The effects of soy isolate-sodium alginate and soy isolate-PGA 1 interactions on the functional properties of the film formation were investigated and it
Shih [219]
was found that protein-polysaccharide interactions enhanced the film-forming properties.
≈10% PGA addition to the soy protein increased the whiteness and tensile strength and decreased the yellowness, percentage elongation at break,
Rhim, et al. [220]
WVP 1 , and water solubility of the multicomponent EF 1 .
Films formed from alginate-whey protein complexes had higher tensile strength, elastic modulus, and elongation than whey protein alone. Coughlan, et al. [221]
Different protein-polysaccharide films were compared in terms of oxygen and WVP, tensile strength, transparency, etc. Yoo and Krochta [48]
1
By using a Box-Behnken experimental design and RSM (for 3 factors; sodium alginate, low acyl gellan, glycerol concentration), a biofilm formulation
González-Cuello, et al. [222]
was designed in terms of mechanical properties.
EF formulation was prepared by mixing sodium alginate with a variable quantity of cashew tree gum. However, tensile strength and water barrier
Azeredo, et al. [223]
properties were weakened due to the competition between two gel-forming polysaccharides for the interaction with calcium ions in the crosslinking step.
Gelation of calcium alginate with rice starch and/or rice flour was examined. Coarser and more rigid gel structures with an increased diffusion
Chrastil [64]
coefficient, a heterogeneous structural resistance constant, and a decreased gelation rate constant were obtained.
Incorporation of garlic oil as a natural antibacterial agent caused darker, yellowish color formation, reduced tensile strength and elongation at break Pranoto, Salokhe,
while garlic oil interfered with the calcium ion interactions due to being incorporated before crosslinking. and Rakshit [142]
Ginseng extract (white, red and extruded white extract) was inserted into the film formulation and a slight decrease in moisture content, and increase
Norajit, Kim and Ryu [154]
in water solubility, transparency, and alteration in the mechanical properties of EF was observed.
A new multilayer film, which contained chitosan in the top layer, ornidazole-incorporated polyvinyl alcohol middle and sodium alginate sublayer,
Pei, et al. [224]
with an enhanced swelling rate, water absorption capacity, control of water vapor transmission, and light transmittance, was developed.
Incorporation of pyrogallic acid into the sodium alginate-CMC 1 matrix increased the gas, vapor, and UV barrier properties of EF. Han and Wang [143]
Interactions between encapsulated n-hexanal (aroma compound) and alginate matrix affected the barrier, permeability, and surface properties of Hambleton, Debeaufort,
emulsified alginate EF. Bonnotte, and Voilley [159]
Enzyme activity of pig liver esterase with enhanced encapsulation efficiency (i.e., chitosan coating of alginate beads) was studied. Pauly, et al. [225]
With a novel approach, the alginate film was designed based on the RGB image analysis and color changes. Alginate surface concentration and surface
Acevedo, et al. [226]
color were modeled to predict the physical properties of the film with a non-destructive method.
1EF: edible film; PGA: propyleneglycol alginate, produced with the reaction of alginic acid and propylene oxide; WVP: water vapor permeability; CMC: carboxymethyl cellulose;
RSM: response surface methodology.
Foods 2018, 7, 170 24 of 38
8. Transport Mechanisms
Ideal edible coatings and films should create a barrier to impede the loss of water vapor, flavor
volatiles, and the exchange of CO2 and O2 , in other words, to control the rate of transport of the
food products’ molecular components [96]. In this way, the adverse reactions with deteriorative
effects (such as respiration and ethylene production) can be diminished or slowed down [96,227,228].
Mass transfer and barrier characteristics are one of the most important properties of edible films
and coatings due to their enormous impact on product quality [229]. Mass transport properties of
polymer films can be represented by three coefficients: the diffusion coefficient, solubility coefficient,
and permeability coefficient, which have been described in detail by Miller and Krochta [230], Donhowe
and Fennema [12], McHugh and Krochta [231].
and Saygili [136] fortified alginate-whey protein isolate coating with a 1.5% ginger EO and coated
kashar cheese.
The water vapor barrier properties of alginate films were intended to be improved with the
addition of other gel-forming biopolymers. Parris, Coffin, Joubran, and Pessen [81] developed
alginate-milk based materials (i.e., whole or non-fat milk, whey, sodium caseinate). Films containing
whole milk had decreased WVP up to 35% [81]. Likewise, Coughlan, Shaw, Kerry, and Kerry [221]
have demonstrated that films formed from alginate-whey protein complexes had lower WVP. Rhim,
Wu, Weller, and Schnepf [220] found that up to 10% PGA addition decreased the WVP of soy protein
isolate films. Han and Wang [143] evaluated the WVP of sodium alginate-CMC films containing
pyrogallic acid.
The type of film formation method also affects water barrier properties. Poverenov, Danino, Horev,
Granit, Vinokur, and Rodov [174] demonstrated that LbL-coated melons (with the alginate-chitosan
combination) had superior water vapor barrier properties compared to uncoated, only-alginate or
only-chitosan coated samples.
Mathematical models were also created to predict the water transport properties of alginate-based
edible coatings and films [234].
Han and Wang [143] analyzed the O2 permeability of a sodium alginate-CMC film containing
pyrogallic acid.
Buonocore, Conte, and Del Nobile [234] presented a mathematical model, which was fitted to the
experimental data of oxygen barrier properties of the alginate-based film.
The respiration rate of alginate coated sweet cherry fruit [90], strawberry [192], peach [197],
apples [107,166], pineapples [83], guava [146], and lettuce [200] were evaluated in the literature. Due to
being a hydrocolloid, the alginate-based films and coatings generally decreased the respiration rate
during storage and, in this way, achieve retention of the quality attributes of the food products. Sipahi,
Castell-Perez, Moreira, Gomes, and Castillo [110] stated that the LbL coating application method
inhibited the respiration process of fresh-cut watermelon.
Another important change is the amount and/or presence of some internal volatiles of anaerobic
conditions, which is created by the high gas barrier properties of the edible coating or film [188].
For instance, higher acetaldehyde and ethanol production compared to the uncoated samples indicate
the presence of a modified atmosphere in the alginate coated fruits [79].
9. Future Trends
Studies about film forming and coating food products with edible biopolymers have been
expanded recently. Edible/biodegradable films and coatings can be used to maintain the quality
during the shelf life of the product. Promising results have been achieved on fresh cut fruits, vegetables,
and meat products coated with alginate solutions with incorporated additives. However, further
improvements could be obtained by incorporating new antimicrobial, antioxidative, antibrowning
agents to enhance food safety and food quality. A better understanding of any synergistic effect among
alginate coating and active agents can be developed.
Blending of film-forming biopolymers to improve the properties of the structure is also a
promising strategy. Developing new synergistic gelling systems can be identified as another
research gap.
Diffusion properties of active substances from the alginate gel matrix and its structure can
be studied in more detailed with varying the concentrations of alginate and cross-linking agents.
Comparative studies can be conducted.
The effects of different calcium salts (e.g., calcium chloride, calcium lactate, calcium gluconate)
on the quality parameters can be identified in detail with clarified mechanisms.
Most studies on alginate coating applications have been conducted at the laboratory scale and
commercial applications are still very limited. Further research with practical applications should focus
on the industrial implementation to commercialize the alginate coated food products with increased
shelf life. Coating application methods can be readjusted so as to implement a recycle process that
does not waste too much of coating solution, decrease microbial load of the solution during recycling,
design spraying method for irregular surfaces, design industrial size vacuum tanks, etc. to prevent the
disadvantages of the application methods. Therefore, sodium alginate-based edible films and coatings
could be used to an even greater extent than they are currently.
10. Conclusions
In an ideal case, an edible coating or film should decrease the evaporation of the water content,
loss of desirable odor and flavor volatiles, prevent microorganism growth, suppress respiration,
and gas exchange; while the modified atmosphere created by the barrier should not cause anaerobic
respiration (and, therefore, anaerobic growth) and undesirable volatiles. On the basis of the
evaluation of the previous literature on alginate-based edible films and coatings, it can be concluded
that the alginate-based edible films and coatings can be efficiently used to accomplish these aims
with an enhancing shelf life of fresh-cut fruits and vegetables, meat, poultry, seafood, and cheese.
The information summarized here can lead researchers to design successful coating applications.
Author Contributions: T.S.P. conceived the focus of the review, conducted the literature search, and drafted the
manuscript. M.S. and K.M. formatted, reviewed, and edited the manuscript upon critical revision of the texts.
Funding: This research received no external funding.
Conflicts of Interest: The authors declare no conflict of interest.
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