Andersson 2008

PACKAGING TECHNOLOGY AND SCIENCE
Packag. Technol. Sci. (2008)

Published online in Wiley InterScience (www.interscience.wiley.com). DOI: 10.1002/pts.823
New Ways to Enhance the Functionality of

Paperboard by Surface Treatment – a Review
By Caisa Andersson*
Karlstad University, Faculty of Technology and Science, Department of Chemical Engineering, SE-651 88 Karlstad,
Sweden
This review summarizes recent development of functional materials to improve the

barrier properties of paperboard with emphasis on bio-based polymers. Focus is
directed to novel application techniques and water-borne, renewable coating
materials. Some aspects on substrate properties and the requirements on food
packaging are discussed as are the processability, convertability, recyclability
and biodegradability of packaging materials. The functionality, advantages and
disadvantages of several bio-based polymers are presented in detail. Among these
are starch and cellulose derivatives, chitosan, alginate, wheat gluten, whey
proteins, polycaprolactone, poly(lactic acid) and polyhydroxyalkanoates. Also
discussed is the enhancement of barrier properties by incorporation of nanosized
materials, by application of thin protective top coatings and local reinforcement
by self-healing agents. Copyright © 2008 John Wiley & Sons, Ltd.
Received 29 January 2008; Revised 10 June 2008; Accepted 20 June 2008
key words: coating; sizing; bio-based materials; barrier properties; paperboard;
functionality
INTRODUCTION war and civil disturbances in the oil-producing

countries, tightened legislation on the treatment of
Surface treatment of paperboard for the improve- packaging waste (disposal, incineration, composta-
ment of functionality has been dominated by lam- bility, recyclability), extended retailer and producer
ination with low-cost, readily available plastic responsibility, and the need to reduce the discharge
materials over the last decades. The workhorse of greenhouse gases.1
among these plastics is polyethylene (PE), accom- Market aspects such as enhanced customer ori-
panied mainly by ethyl vinyl alcohol (EVOH) and entation of products and services, changes in con-
poly(ethylene terephthalate) (PET). More recently, sumer demand towards environmentally friendly
the development of synthetic polymer dispersions materials and easy-open and re-closable packages,
has increased their attractiveness for use in the demographic aspects such as changes in house-
coating of board. In recent years, environmental hold size and lifestyle, increasing demand on
aspects have become the subject of greater atten- health and hygiene2–4 have also become more
tion, and considerable work and effort has been important for company profiling and product mar-
put into the replacement of fossil-based raw mate- keting. The challenge is to find new materials or
rials with environmentally friendly, biodegradable new uses of existing natural materials that are
or recyclable materials from natural sources. competitive with plastics with regard to both eco-
Driving forces have been the increasing oil prices, nomical and functional properties. Reduction in
* Correspondence to: C. Andersson, Karlstad University, Faculty of Technology and Science, Department of Chemical
Engineering, SE-651 88 Karlstad, Sweden.
E-mail: [email protected]
Copyright © 2008 John Wiley & Sons, Ltd.

Packaging Technology C. ANDERSSON
and Science
costs and reduced impact on the environment have changes, including any changes in flavour, odour,
also driven the trend towards less material usage texture, colour or taste of the food by interaction
in the production and design of packages. with their surrounding environment. Time, tem-
The aim with this literature survey was to gener- perature, moisture, light, gases and pressure are
ate an overview of new ways for improvement of factors that indirectly affect the shelf life and
functionality of fibre-based materials by surface quality of foods,5,6 while direct spoilage of food can
treatment. Surface treatment involves all available be caused by mechanical damage during transport
techniques except that of extrusion of (plastic) or by the attack of microorganisms.7
films. Focus is directed to paperboard, although Controlling permeation of water vapour through
some examples are also applicable on flexible the packaging material is necessary to prevent
paper substrates. Functionality refers to water growth of microorganisms in the food. A relative
vapour and oxygen barrier properties, and water humidity (RH) of 60% or higher inside the package
and grease resistance. The properties of various promotes growth of mould, while yeasts and bac-
materials with respect to processability, convert- teria require an RH of >80% to start growing.5
ability, recycling and compostability are also dis- When selecting suitable materials for food packag-
cussed as is their suitability for food contact. ing, it is necessary to consider the moisture content
of the food itself, its ability to take up or lose water
by interaction with moisture in the air, the prevail-
FUNCTIONALITY OF ing humidity of the anticipated environment and
the efficiency of the barrier material with respect
PAPERBOARD to water vapour.5 Moisture uptake in dry products
can cause loss of crispness, while moisture loss
A package should provide protection of both the from vegetables and fruits causes shrivelling.
content and the environment. It should prevent Quality impairment also occurs upon moisture
damage and spoilage of the packed goods. For loss from sensitive frozen or chilled food.6
food applications, this includes both hygienic and The water vapour transmission rate (WVTR) is
health aspects covering maintenance of nutritional defined as the amount of water vapour that is
value and avoidance of toxicological substances transmitted through a unit area in a unit time
arising within or coming into contact with the under specified conditions of temperature and
food. The functions of a package also involve the humidity. In the packaging industry, the test condi-
communication of important information about tions are often set to 23°C and 85% RH to match
the content and quality (freshness, expiry date), realistic packaging environments. Common stan-
proper design for marketing and reduction of dards for measurement of WVTR by the gravimet-
the risk of tampering or adulteration, reduction of ric method are ASTM E 96,8 DIN 53122-1,9 ISO
waste by prolongation of shelf life and convenience 2528,10 TAPPI T 44811 and T 464.12 The WVTR of
throughout the packaging chain.2,5 A functional coated paperboard materials generally decreases
package should also provide low production cost exponentially with increased coating layer or film
and should reduce energy usage by eliminating thickness.13 Permeation will mainly take place
the need for the refrigeration or freezing of the through coating defects such as cracks, voids and
product.2 Paperboard offers both mechanical pinholes or through the amorphous regions of
strength and flexibility for the production of pack- polymer films.
ages but lacks barrier properties and thus needs Water absorption of paperboard is generally
to be surface treated in order to improve the recorded as the Cobb value, defined as the amount
functionality. of water in gram per square meter that is absorbed
over the test area under a water pressure of 10 mm
Barrier properties of coated board during a specified time, usually 60 s (ISO 535).14
Packaging materials are commonly sized to reach
Packaged food products need protection against Cobb60 values of ca 20 g/m2. Hard-sized substrates
physical, biochemical and microbiological deterio- are defined as having a Cobb60 < 10 g/m2, which
ration as well as protection against organoleptic requires a combination of internal and surface
Copyright © 2008 John Wiley & Sons, Ltd. Packag. Technol. Sci. (2008)
DOI: 10.1002/pts
SURFACE TREATMENT OF PAPERBOARD TO ENHANCE Packaging Technology
and Science
sizing with hydrophobic sizing agents such as par- The European Commission lists materials either as
affin wax emulsion, polyurethanes and styrene- starting substances (monomers) or as additives.
based copolymers.15 New substances should be evaluated and autho-
Oxygen is strongly and irreversibly absorbed by rized before being added to the positive list. The
polymers naturally present in different foodstuffs,5 petition for a new substance should contain iden-
thereby causing permanent changes in food quality. tity, properties, use, and migration and toxicologi-
Exposure to oxygen can cause oxidation followed cal data. The petition process preceding addition
by rancidity of fats or enzymatic browning of fruits of a new substance to the list is both long (2 years)
and vegetables.6 Many hygroscopic materials will and costly (*500 000),26 which is a strong reason
lose their oxygen barrier at high RH due to absorp- why novel functional coating materials have not
tion of water and subsequent swelling of the ended up on the list, despite having non-harmful
polymer, resulting in a more porous structure.16 properties. Chitosan, gluten and zein are examples
The oxygen transmission rate (OTR) is defined as of bio-based coating materials (described below)
the quantity of oxygen gas passing through a unit which are not present on the positive list up to this
area per unit time under specified conditions date.
of temperature, humidity and pressure (ASTM Direct contact between food and packaging
D3985-05).17 The oxygen permeability (OP) of materials can cause undesired migration of molec-
hydrophilic bio-based polymers increases expo- ular species and ions from the packaging into the
nentially with increased RH.18 food, thereby causing both quality changes and
Several methods are available for determination health risks.6,24 Migration of substances are con-
of resistance to oil, fat and grease. Grease resis- trolled by diffusion and is driven by concentration
tance can be probed using dyed testing substances gradients.28 Species that might migrate from the
such as turpentine (TAPPI T 454),19 vegetable and packaging material are small monomer residuals
mineral oils (TAPPI T 507)20 or palm grease (DIN (styrene, acrylates, vinyl acetate, ethylene), which
53116).21 All these techniques involve evaluation of are always present as unreacted substances after
grease resistance by visual observation of the stain- completion of the polymerization process, plasti-
ing of the substrate under test. The Kit test (TAPPI cizers that are added for increase of flexibility or
UM 557)22 was developed by Rengel23 to meet the other coating additives.6,24 Other sources of migrat-
requirements for a realistic method for evaluating ing substances can be chemicals present in the
surface-treated substrates showing oil repellence. board, printing inks and their components, and
adhesives for sealing which are not in direct contact
but are in close proximity to the packaged food.6,28
Requirements on food packaging Compounds present in the environment can also
be sorbed by the packaging with subsequent migra-
Packaging materials for food products are restricted tion into the food.24 The occurrence of migration
by the need to follow the legislation limiting food can be monitored by sensory assessment or by
contact. In the USA, the Food and Drug Adminis- chemical analysis of the food. Overall migration
tration (FDA) regulates factors influencing migra- includes all the different substances released per
tion, odour and taste changes associated with unit area from the packaging material under spec-
packaging. In Europe, the German Bundesinstitut ified testing conditions, while specific migration
für Risikobewertung (BfR) (formerly named refers to an individual, identifiable compound
Bundesinstitut für gesundheitlichen Verbrauch- only.24 Standard European methods for determina-
ershutz und Veterinärmedizin) has the same function of overall migration include the use of olive
tion. There is still no common legislation in the oil and aqueous food simulants.29 EU Directive
European Union (EU), even though work is carried 2002/72/EC stipulates an overall migration limit
out to harmonize the national regulations within of 60 mg/kg food for plastics in food contact.
the EU.24–26 Substances intended to come into Microbiological contamination of packaging
contact with foodstuffs should be on the ‘positive material is most likely to happen during transpor-
list’,27 which is ‘a list of the substances the use of tation, storage or handling. Sterilization of the
which is authorized to the exclusion of all others’. package prior to filling is sometimes necessary to
DOI: 10.1002/pts
and Science
reduce the microbial load.26 Special attention has food in the case of food packaging. Defects or weak
to be focused on the use of recycled fibres which spots in the seal can provide pathways for trans-
may carry contaminants, or to bio-based packag- portation of gases or liquids in or out of the package
ing materials, which are sensitive to microbial or can cause microbial contamination.34 Poor seals
attack. In most cases, the microbial load of fresh may also result in physical damage or spoilage of
food products widely exceeds the amounts that the packaged goods. Seal failure is a more frequent
could permeate through the packaging so that the cause of product deterioration than poor pack-
latter can be practically neglected.26 ages.35 An adhesive failure of the seal in the fibre
layer, rather than a cohesive failure in the coating,
Convertability is indicative of a sufficiently strong seal.30,36
Board coated with thermoplastic polymers can
Forming a carton involves creasing, cutting and be closed by heat sealing, which involves melting
folding the paperboard into the desired shape.24,30 of the polymer by application of heat, followed by
The box can be sealed either by heat sealing or joining of the surfaces under pressure. Coating
gluing, which usually takes place after filling on film properties that govern heat sealability are low
the food manufacturer’s product line. melting point, low melt viscosity, wide seal tem-
perature range, reasonable hot tack and cohesive
Creasing and cutting. Creasing or die cutting of strength.37 Heat sealability without the need for
paperboard involves complex tensile, compres- external glues is an additional argument for the
sional and shear forces acting on the board.30,31 use of dispersion coatings or thermoplastic,
These forces, operating over a very small area, can bio-based polymers as alternatives for plastic
cause cracks in the coating, thus resulting in laminates.
decreased barrier properties. Separation of the Cartons are often glued along the length (straight
coating layer from the board or separation of side seam gluing) after filling on the packaging
adjoining board plies can also occur. This sets con- line. Typical applications are packaging for flour,
siderable demands on the mechanical properties cereals and detergents.30 Packaging of e.g. sweets
(ductility) of the coating layer. in cartons often involves gluing of the board at
Creasing and cutting lines can be reinforced by multiple points to form a tray with a lid. Water-
local surface treatment by a novel technique to based dispersions including acrylates or acetates
better withstand the mechanical stresses connected are often used as the adhesive. Efficient gluing
with these operations. The concept is to apply the then requires sufficiently high porosity of the
functional chemicals only in areas where they are paperboard for rapid penetration of water into the
required, rather than to apply the expensive prod- substrate, which promotes good film formation
ucts over the full surface area. Local treatment of and adhesion between the glued parts.31 Disper-
self-healing agents applied by ink-jet and flexogra- sion coatings are generally gluable by starch or
phy printing has been reported.32 These self-healing vinyl acetate-based glues.13 A hot-melt adhesive is
agents are composed of hydrophobic materials sometimes required for gluing of board coated
encapsulated in a biopolymer membrane. The with plastic films or dispersions to override prob-
mechanism for self-healing involves plasticization lems associated with the wetting of water-based
of the coating layer when the capsules break and glues on such surfaces.30,38 Gluing with water-
release their core material over the coated surface based glues may have deleterious effects on the
under the applied stress. The results indicate a barrier properties of water-sensitive bio-based
localized termination of the cracks formed upon coatings because interaction with water will cause
creasing. Improved cutting performance, present the polymer to swell.16 A starch adhesive did,
as a reduced tendency towards linting, has also however, result in an overall migration 1 and 10
been observed.33 orders of magnitude lower than for an ethylene
vinyl acetate (EVA) hot-melt or a polyvinyl acetate
Heat sealing and gluing. Sealing a package so as (PVAc) dispersion adhesive, respectively.39 All the
to maintain the barrier properties is of utmost adhesive types showed overall migration values
importance, especially for the safety and quality of well below the 60 mg/kg foodstuff limit.
DOI: 10.1002/pts
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Recycling, composting and dues should either be used in other industrial pro-
biodegradability cesses (e.g. as insulation material) or for energy
recovery.45 The recycling process includes separa-
The overall impact of surface-treated packaging tion of non-fibrous materials through washing,
material on the environment should be investi- flotation, cleaning and screening where the removal
gated by life cycle analysis, taking into consider- of contaminants is based on differences in size,
ation each step in manufacturing the substrate, the shape, density and surface properties.46
surface chemicals, processing, converting, use and
recycling of the products.26 An increased use of Biodegradation and compostability. According
agricultural products for non-food use will have to the 94/62 EC Directive, biodegradable packag-
an impact on the environment by increasing the ing is defined as a material that must be capable of
amount of carbon stored in plant biomass, which physical, chemical, thermal and/or biological deg-
can lead to increased amounts of carbon dioxide in radation such that this material used as compost
the atmosphere. More focus on specific cultivation ultimately decomposes completely into carbon
products might also lead to reduced biodiversity. dioxide and water.47 A rough criterion of biode-
Studies on the use of starch and starch-containing gradability is that 90% of the material should
plastics have shown efficient utilization of resources degrade in a period of 6 months.26
and considerable reductions in the emission of According to the European standard EN 13432,48
greenhouse gases as compared to conventional a package is compostable if it is formed from com-
plastics.26 However, the study has also shown ponents which have been individually qualified as
that the manufacture of starch-based plastics biodegradable. Complete disintegration of the
leads to an increase in water pollution through product during the composting process is also a
over-fertilization. criterion. The compostability is, however, strongly
dependent on the environmental and testing con-
Recycling and repulpability. Packages are consid- ditions,49 which should be taken into account
ered as recyclable if there is a widely available, when different functional surface treatments are
economically viable collection, processing and compared. Standard methods for testing of com-
marketing system for the material.1,40 The Euro- postability are ASTM D 533850 and EN 14046.51
pean Directive on Packaging and Packaging Waste, Dispersion-coated paper or board can be compos-
94/62/EC, sets the following targets for the recov- ted, resulting in visual disappearance of the mate-
ery and recycling of packaging materials: 50–65% rial, which takes 1.5–2.0 times longer than for
by weight of the packaging waste shall be recov- uncoated material of the same origin. Reference
ered (including energy recovery through incinera- testing of PE-coated board has shown that it
tion, material recycling and composting); 25–45% remains unchanged under the same composting
by weight of the packaging waste shall be recov- conditions.38,49
ered by material recycling, and a minimum of 15%
by weight of each packaging material must be pro-
cessed by material recycling.25 Requirements for
packages related to material recycling and energy SURFACE TREATMENT
recovery are given in the European standards EN OF PAPERBOARD
1343041 and EN 13431,42 respectively, while stan-
dards EN 1342843 and EN 1342944 cover source There is a vast amount of literature and scientific
reduction and reuse. papers describing the extrusion of thermoplastic
Recyclability of paper and board products is materials (covering both petroleum-based plastics
mainly affected by the amount and nature of and bio-based polymers) and the properties of
the non-fibrous materials, i.e. adhesives, plastics, extruded/laminated products. This survey does
mineral pigments and printing inks. These compo- not aim to investigate the subject of extrusion.
nents should not have a negative affect on the pro- However, thermoplastic materials normally pro-
cessing of recovered paper nor should they be cessed by extrusion techniques should, in theory,
harmful to the environment. The processing resi- also be able to coat onto paper or other substrates.24
DOI: 10.1002/pts
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Various materials for surface treatment of board
are described in the following sections.
Synthetic polymer dispersions

Barrier dispersions. Polymer dispersions or
latexes have become attractive in recent years
among both companies (e.g. Clariant, Ciba Spe-
cialty Chemicals, Dow Chemical Company and
EKA Polymer Latex) and researchers,52–55 as a
replacement for petroleum-based plastics for use
as barrier materials. Barrier dispersions can be
applied using conventional coating techniques,
both online and off-line.38 Common applications of
dispersion coatings are corrugated board, sacks,
disposables, frozen and chilled food cartons, ream
wrappings for copy paper, electronic packages and
wallpaper base.13 The most commonly used latexes
consist of polymers or copolymers of styrene, buta-
diene, acrylates, vinyl acetate and polyolefins
(Figure 1) dispersed in water to give an emulsion
of small particles, 50–300 nm in diameter.38
Several additives are used to reach the desired
level of consistency, durability and runnability,
e.g. colloidal stabilizers, thickeners, waxes, anti-
foaming agents, biocides and pesticides. Latices
used for paper coatings are often carboxylated in
order to enhance their colloidal stability, the adhe- Figure 1. Structure of commonly used monomers in
sion between latex and base substrate, the binding barrier dispersions.
power between latex and pigment, and also the
water-retention properties and runnability.
A coat weight above 10 g/m2 is required to resistance, while styrene–butadiene copolymers
achieve an appropriate level with respect to water show moderate barrier properties.56
vapour barrier for dispersion coatings. Improved Despite their many advantageous properties,
water vapour barriers are often achieved through dispersion coatings still have no wide commercial
the application of two layers,13 which not only use. Factors that need to be overcome in order to
increases the coat weight but also closes the surface grow the market share are a reduction in the costs
by elimination of pinholes. A certain coat weight for production and processing (e.g. drying capac-
is also necessary to achieve high water resistance. ity), and further increase in competitiveness with
In case of packaging materials, the Cobb value is respect to barrier properties.38 However, the appli-
often measured over 1800 s or more, to get appro- cation cost of water-based barrier coatings per ton
priate results.13 of coated substrate decreases with increased base-
Dispersion coatings also provide grease and oil stock basis weight. It is thus more economical to
resistance, and are hence suitable also for the pro- use barrier coatings on board substrates than on
duction of packages for confectionery or bakery paper since a smaller amount of dispersion is then
products. Ready meals are another application required. The coat weight can be further decreased
area since dispersion-coated paper or board often by using substrates with low roughness, low poros-
can be used in microwave ovens directly.13 Acry- ity and low absorptivity.57 Application of a pre-
lates provide hydrophobicity and good grease coating in order to optimize the surface can also
DOI: 10.1002/pts
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reduce the amount of barrier dispersion coating (DP). Heating the dispersion above 80°C is neces-
required.38 sary to fully dissolve PVOH in water.58
Several dispersion coating materials form films The PVOH polymer is linear, allowing for molec-
with low flexibility, thus invoking the risk of a ular alignment and strength.59 The –OH groups are
reduction in barrier properties upon creasing.13 capable of forming hydrogen bonds and thereby
The flexibility of barrier dispersions can be provide good adhesion between different surfaces.
increased by changing the monomer composition The –OH groups can also have a plasticizing effect
to reach a lower glass transition temperature, Tg, and can enhance the water retention of the film.
or by adding a plasticizer. Fully hydrolysed PVOH films have some water
Acrylic coatings are readily heat sealable over a resistance due to molecular association/crystalli-
wide range of sealing temperatures.37 Factors that zation through hydrogen bonding. Polymers with
may have an unfavourable effect on the heat seal- a lower degree of hydrolysis contain bulky vinyl
ability of dispersion coatings include the presence acetate groups that make the solvation easier.59
of fillers, additives or waxes.13 Enrichment of the The film strength and adhesion to cellulose sub-
surfactant by migration to the surfaces to be sealed strates also increase with an increased degree of
has been shown to result in weaker seals.54 hydrolysis.
Barrier dispersion-coated paper and board prod- PVOH has been used in the paper industry for
ucts are easily recyclable. Coated broke and long time. In recent years, some novel substituted
winding waste can be used directly in a paper or products have reached the market. Modification
board machine without removal of the dispersion via substitution with ethylene groups (Figure 2a)
coating constituents from the fibre mass.38 Prob- renders the molecule more hydrophobic, thus
lems can, however, arise with stickies, which are giving improved water resistance but also an
known to reduce the quality of the repulped enhanced barrier to oxygen. Modified grades are
products. manufactured under the trade name ExcevalTM
(Kuraray Europe GmbH), which covers a range of
Poly(vinyl alcohol) (PVOH) and derivatives. products with different degrees of hydrolysis, DP
PVOH is a water-soluble synthetic polymer with and content of substituent groups.60
good film-forming properties. The hydrophilic Another novel modification of PVOH includes
character of PVOH, however, means that the mate- the incorporation of silanol groups (Figure 2b),
rial offers a poor barrier against water vapour, and available as Kuraray R-polymers (Kuraray Europe
that the permeability increases with increasing GmbH, Frankfurt am Main, Germany). The high
RH.58 In contrast, PVOH films are practically reactivity of the silanol groups can give rise to
impermeable to gases such as O2, N2 and CO2, and cross-linking with inorganic materials such as
are resistant to oils, grease and organic solvents.24,59
The water resistance of PVOH can be improved by
cross-linking through addition of e.g. glyoxal,
urea- or melamine formaldehyde resins or ammo-
nium zirconium carbonates.59
PVOH is prepared from the radical polymeriza-
tion of vinyl acetate that gives poly(vinyl acetate)
in a first step. Hydrolysis of the product, catalysed
by NaOH, then gives PVOH. The degree of hydro-
lysis can be controlled to reach different grades of
PVOH regarding water solubility and adhesive
properties. PVOH with 98.0–99.0 mol% is denoted
fully hydrolysed. A high degree of hydrolysis
increases the crystallinity and the crystallization
tendency, making fully hydrolysed grades less Figure 2. Fully hydrolysed PVOH (containing vinyl acetate
soluble in water. The water solubility is also lower residues) modified with (a) ethylene and (b) silanol
for polymers with a high degree of polymerization groups.
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alumina present on paper surfaces, leading to gel so that the surface becomes water repellent at
formation and the formation of a film on the surface much lower material requirements than with tra-
which exhibit good barrier properties against oil ditional resins.63 These types of synthetic polymers
and improved water resistance compared to con- are derived from materials that are both inexpen-
ventional PVOH. sive and regarded as non-toxic.
PVOH is readily degraded in waste water–acti- Another PET-based material is Biomax® from
vated sludges through enzymatic oxidation fol- DuPont: this is a class of biodegradable polyester
lowed by hydrolysis, resulting in chain cleavage.61 that can be used as coating for board-based pack-
The material can also be recycled or combusted to ages, plates, cups, etc., but also as films, thermo-
carbon dioxide and water. Chemically modified formable sheets and injection/blow moulded
PVOH (Kuraray R-polymers and ExcevalTM) has a products. The PET modification involves the incor-
biodegradability of >90% measured by the Zahn– poration of aliphatic monomers, making the
Wellens test and >70% measured by the method polymer weaker and thus susceptible to degrada-
OECD 301 A, according to the manufacturer. tion by hydrolysis.64 Microbiological consumption
finally results in conversion of the residuals into
Polyesters from recycled PET. PET is manufac- carbon dioxide and water.65
tured by the condensation reaction of terephthalic Paper and paperboard coated with polyester
acid and ethylene glycol. PET films have good resins from recycled PET are easily recyclable and
resistance to oils and different solvents.62 Waste repulpable66 because the resins can be removed
products of PET including bottles and sheet mate- from the paper or board substrate by alkaline water
rial can be recycled via consumer collecting systems washing. Recyclability testing of board coated with
and then can be used for production of new barrier recycled PET has shown a low tendency for the
materials. Water-soluble hydrophobic polyester formation of stickies.67
resins formed from such waste, which can be The most commonly used monomers in the pro-
applied on paper or board substrates by conven- duction of barrier dispersions are safe for food
tional coating techniques, have recently been contact and are present on the EU positive list.
developed. They are now manufactured by the However, the final products must also undergo
company EvCo Research LLC. testing and must fulfil the requirements set by the
Through condensation polymerization of the FDA and BfR.38 Conventional PVOH is compliant
recycled plastics, a polyester backbone is formed with FDA regulations concerning contact with
which is then further modified to give water- and both dry and aqueous/fatty foods.59 Polyester
oil-repellent properties to the product. The linear resins derived from recycled PET are both FDA
or branched polyester backbone makes up about and BfR approved.68
30–70% of the total weight of the resin and is typ- Polyolefins, polystyrene, styrene–butadiene
ically derived by reacting recycled PET with a copolymers and polyacrylates are resistant to bio-
hydroxyl-functionalized compound (e.g. mono-, degradation.61 However, biodegradable polymer
di- or tri-ethylene glycol or glycerol) at a level of units can be combined with non-biodegradable
5–40% by weight, which imparts additional units by block copolymerization or grafting, thus
hydroxyl functionality. Ionic groups are introduced giving a polymer that is partially degradable.61
on the polyester backbone to provide water dis-
persibility, e.g. carboxylic acids from polyacid
monomers, with the weight percent typically Biomaterials
ranging between 1 and 20. Aliphatic groups con-
sisting of straight-chain or branched fatty acids or Several studies have been undertaken in recent
triglycerides with 6–24 carbon atoms, e.g. stearic, years to investigate the potential of bio-based
oleic or palmitic acid originating from animal or materials for packaging applications. Bio-based
vegetable oils, are also introduced at a weight polymers including polysaccharides and proteins
percent of 10–60, in order to enhance the hydro- have the ability to form crystalline films with low
phobicity. When films of these types of polymer permeability to oxygen, thus making them inter-
are dried, the hydrophobic parts orient themselves esting for use in packaging applications. Biode-
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gradable films for use in food packages based on mechanical properties of starch films obtained
starch,16,69,70 chitosan,71–74 wheat gluten,75 whey pro- from non-conventional starch sources such as
teins76 or zein77 are described in detail in the litera- banana or mango have been published.83 High
ture. Bio-based materials have also been used in amylose starch and hydroxypropylated starch
composite formulations, e.g. starch–low-density have been used in food packaging and for the
polyethylene (LDPE) blends.78,79 Starch–PVOH coating of edible films.18 Starch can be used as a
blends have shown properties competitive with thermoplastic film in the presence of plasticizers
those of conventional LDPE and polystyrene (PS) or as fillers in the form of fine fractions of starch
films.18 granules.
The use of biodegradable materials with respect Starch is a naturally abundant plant polymer the
to food packaging requirements is discussed by function of which is to serve the plant with carbo-
Krochta and de Mulder-Johnston18 and by Petersen hydrates. The starch polymer consists of a-D-anhy-
et al.80 Starch-based products that can replace con- droglucose units built up of the components
ventional plastics are commercially available.81 amylose and amylopectin. Amylose has histori-
Examples are Paragon, manufactured by Avebe, cally been regarded as linear with the glucose units
Mater-Bi® produced by Novamont, and Bioflex®, linked together by a-1,4-glucosidic bonds. Amylo-
produced by BIOTEC Biologische Naturverpack- pectin is a highly branched molecule in which the
ungen GmbH. branches are bound to the main chain through a-
Bio-based film-forming materials can also be 1,6-glucosidic linkages. Later evidence of an inter-
used in the surface treatment of cellulose-based mediate fraction present in natural starches either
substrates, either by coating or by extrusion/lami- as a slightly branched amylose or as a less branched
nation. There is, however, a lack of literature in the amylopectin has been reported.84 The amylose
field concerning the improvement of functional fraction contains about 500–3000 anhydroglucose
properties of paperboard via coating with bioma- units, while amylopectin is built up of several
terials. In contrast, the use of biomaterials for the thousand units.85
production of edible films or thin coatings applied Starch in its native form exists as semi-crystal-
directly on the food, e.g. on fruits for mechanical line granules which vary in size and shape depend-
protection or barrier purposes has received consid- ing on the plant source. Crystallites are formed
erable attention.18,24,82 In the following sections, when linear amylose and linear segments of amy-
some special features of different types of bioma- lopectin orient parallel to each other, facilitating
terials are discussed. Out of these, one can identify the formation of hydrogen bonds between adjacent
that starch, cellulose, chitosan and alginate can be segments.86 A significant portion of amylose is
classified as belonging to the group of natural present in the amorphous phase because of its high
polysaccharides, while wheat gluten, whey and mobility and ease of association.87 It is therefore
zein are clearly proteins. Polycaprolactone, poly- primarily the amylopectin fraction that is respon-
hydroxyalkanoates (PHA) and poly(lactic acid) sible for the crystalline order in the native
(PLA) are classified as polyesters. granule.88,89 Potato starch consists of 21% amylose
and 79% amylopectin with an average granule size
Starch derivatives. Starch is widely used for pack- within the range 15–100 mm and a degree of crys-
aging applications, in the sizing and coating of tallinity of 20–28%.90 Potato starch amylose has a
paper and board, as a thickener or adhesive, as molecular weight, Mw, of 1.0–1.5 · 106 g/mol, which
well as an additive in many types of food. Several is low compared with the amylopectin Mw ∼ 50–
companies offer starch derivatives from various 500 · 106, and high compared with cellulose (Mw ~
plant sources. Examples are Lyckeby Stärkelsen 90 000–150 000).85
Industrial Starches AB and Emsland Stärke GmbH The starch molecule forms a helical structure
(potato), Roquette (maize, wheat and potato), due to intramolecular hydrogen bonding. In the
National Starch & Chemical (maize, potato) and native granules, potato starch shows an X-ray dif-
Avebe (potato and tapioca). Potato is the major fraction pattern that is denoted as the B-type crys-
source of starch for use in the paper industry in talline form. From a dilute solution, both the
Europe. In recent years, studies on the barrier and amylose and the amylopectin fractions of potato
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starch can re-crystallize in this B-type crystalline pylated starches have a DS of ca 0.1. The reaction
form.70 The crystallinity is dependent on the ability can be carried out with the starch in its native
of the chains to organize and to form crystals and granular form, which has the advantage that
hence on the chain mobility during crystallization. unwanted by-products can be removed by washing
The amylose fraction crystallizes rapidly, while the and filtering, and moreover, that the starch can be
amylopectin fraction needs several days to develop further modified by e.g. cross-linking.
a crystalline pattern in the X-ray diffraction trace. Incorporation of the hydrophilic hydroxypropyl
The presence of water or the addition of a plasti- groups lowers the gelatinization temperature,91
cizer facilitates the mobility of amylopectin chains and the substitution also prevents association
and thus facilitates the onset of crystallization. of the amylose chains after cooking (retrograda-
The hydroxyl groups on the starch glucose units tion). Hydroxypropylation improves the low-
can undergo substitution reactions, thus forming temperature stability, the stability of the dispersion
different types of starch ethers or esters. The viscosity and the flexibility of the resultant films.
number of substituent groups affects the proper- Hydroxypropylated starch has found use in both
ties of the resulting starch derivative and is reported food and non-food applications, and shows excel-
as the degree of substitution (DS). The maximum lent film-forming properties along with high
theoretical DS value is 3, which is equal to the binding power, high adhesive strength and benefi-
number of –OH groups on each glucose unit. Since cial rheological properties. Furthermore, non-ionic
starch is readily soluble in water, a high degree of starch ethers are not sensitive to changes in elec-
substitution is not required to improve the solubil- trolyte concentration and pH. Hydroxypropylation
ity as is the case with cellulose,91 and commercial reduces the tensile strength of the film but increases
starches seldom have a DS value above 0.2. the elongation and burst strength and the resis-
Oxidation of starch is carried out to reduce the tance to folding. Films have also been shown to be
chain length and thus to lower the viscosity of the impermeable to oxygen.91
starch solution. Sodium hypochlorite (NaClO) or Temperature-responsive starches can be pre-
hydrogen peroxide (H2O2) is used as the oxidizing pared by the incorporation of cationic/hydropho-
agent. Reaction with sodium hypochlorite under bic substituents. So-called QUAB reagents carry
alkaline conditions introduces carboxylic and car- a positively charged quaternary amine and can
bonyl groups on the glucose hydroxyl sites which also have alkyl chains of varying lengths. Reaction
act to stabilize the starch by sterically hindering with 3-chloro-2-hydroxypropyl dimethyl dodecyl
the retrogradation process.91 Carboxyl group for- ammonium chloride gives substituent groups with
mation is favoured at high pH, and the anionic a C12 chain94 (Figure 3b). Using pre-oxidized starch
charge on these groups further facilitates disper- leads to a zwitterionic starch ether which is com-
sion by electrostatic repulsion. The oxidation pletely insoluble in water below a critical tem-
causes depolymerisation, and the resulting molec- perature at a DS as low as 0.01.95 These
ular weight after oxidation determines the starch temperature-responsive starch particles could act
viscosity. Commercial starches for paper coating as hydrophobic filler materials in coatings.
are usually highly oxidized and contain 0.4–1.2 wt% However, intermediate products formed in the
carboxyl groups,92 corresponding to a DS of 0.015– reaction chain are suspected to be carcinogenic,
0.044. Oxidation also reduces the gelatinization which means that extensive safety precautions
temperature of the starch. must be taken in the preparation and handling of
The hydroxypropyl substitution involves reac- these starch derivatives.
tion of starch with propylene oxide under alkaline The linear amylose fractions in starch are able to
conditions. Figure 3a shows the structure of an form continuous, strong and flexible films through
oxidized, hydroxypropylated starch with the sub- hydrogen bonding, while the branched amylopec-
stituent groups arbitrarily placed. The reactivity is tin structure prevents the molecules from coming
highest for the attachment of the –OH group in the close enough to form hydrogen bonds.86 Amylo-
C2 position. Consequently, the location of the sub- pectin films are thus hard and brittle.88 The film-
stituent group is favoured here over location at the forming behaviour depends on the molecular
C3 or C6 positions.93 Commercial hydroxypro- weight of the amylose and the amylopectin frac-
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Figure 3. Molecular structures of natural/chemically modified polysaccharides.
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tions, the water-holding properties and the ization varies between a few hundred to several
colloidal stability of the starch dispersion. The thousand glucose units for cellulose from various
amylose fraction strongly influences the bonding origins. The chain adopts an extended, helical con-
properties when applied on paper, while the amy- formation with the adjacent anhydroglucose units
lopectin fraction controls the water retention and twisted around the axis, a structure that can be
rheology. The addition of a plasticizer such as glyc- likened to a twisted belt.102 This conformation
erol can improve the mechanical properties, but at makes the cellulose chain relatively rigid. The stiff-
high levels, the plasticizer can increase the mobil- ness of the chain is dependent on steric interac-
ity of amylose chains at a degree which leads to tions as well as on intrachain hydrogen bonding
increased crystallinity.88 The effect of the formation between C(3′)OH–O(5) and C(6′)OH–O(2)OH.
of a close-packed structure with linear amylose on Introduction of substituent groups on the hydroxyl
the barrier properties was illustrated by Jansson sites changes the hydrogen bonding but leads to
and Järnström,96 who showed that the water vapour new steric interactions between the substituent
permeability of a high amylose starch film was groups. Hence, an extended chain conformation is
about 10 times lower than for that of a normal also retained in derivatized celluloses.
potato starch. Hydroxypropyl cellulose (HPC) is a non-ionic
Starch films are moisture sensitive due to their cellulose ether formed by the base-catalysed reac-
hydrophilic character and are therefore poor barri- tion of cellulose with propylene oxide. An idealized
ers against water vapour,80 but can provide moder- structure is given in Figure 3c. The addition of a
ate oil barriers.18 The crystallinity of starch films strong base is necessary to break up the intermo-
facilitates the barrier properties towards gases. The lecular hydrogen bonds and makes the –OH groups
effect is more pronounced for amylose films than available for reaction with the propylene oxide.
for amylopectin films.70 Gas permeability and The properties of HPC depend on the number of
water vapour permeability can also take place hydroxypropyl substituents per anhydroglucose
through pores present in the films, which can be unit. Once again, as in starch, the maximum degree
20–100 nm in size.70 of substitution, DS, is 3.0. The reactivity is, in con-
Water transport through a coated surface is trast to that for the starch hydroxyl groups, largest
mainly driven by capillary forces and is affected for the –OH group in the C6 position. The location
by surface roughness, surface chemical properties of the substituent groups will affect the properties
and pore structure.97 In general, starch increases of the derivatized molecule. However, the possibil-
both the roughness and the hydrophilicity of the ity of further reaction of the –OH groups of the
coated surface. The water resistance of starches can newly incorporated substituents leads to a theo-
be enhanced by incorporation of hydrophobic retically unlimited number of hydroxypropyl
groups95 or by cross-linking. groups per anhydroglucose unit. It is therefore
Native starch and many starch derivatives such more appropriate to refer to the molar substitution
as hydroxypropylated potato starch fulfil the (MS), which is defined as the average number of
requirements of easily biodegradable materials. hydroxyalkyl groups per anhydroglucose unit. For
Experiments have also been carried out with blends commercial types of cellulose ethers, MS lies in the
of granular (modified) starch (up to 30% vol) and range 3.5–4.5 with a DS of 2.2–2.8.103 To ensure
some bioinert plastics made from mineral oil, e.g. water solubility in cold water, MS should be around
PE.98–101 When the starch granules undergo enzy- 4.0.104
matic degradation, the sample loses its strength HPC has the ability to form ordered, anisotropic
and continuity and thus disintegrates, leaving phases [liquid crystalline phases (LCPs)] in con-
small particles of PE.101 More recently, PE has been centrated solutions. The rigid polymer molecules
replaced with PVOH to give a fully compostable can orient parallel to each other in various layered
product.80 structures, referred to as nematic, cholesteric and
smectic phases, each leading to improvement of
Cellulose derivatives. A cellulose chain consists of the barrier properties to different extents. The
a number of anhydroglucose units linked together permselectivity has been shown to be improved in
by b-1,4-glucosidic bonds. The degree of polymer- films with cholesteric structure compared to amor-
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phous HPC films.105 Materials that form liquid mol. The viscosity of a cellulose derivate solution
crystals by interaction with a solvent (i.e. by increases with increasing polymer concentration
increasing or lowering the concentration) are due to entanglements between polymer chains.
denoted lyotropic. If the same phenomenon occurs Above a critical concentration, the viscosity
when the temperature is changed, the material is decreases as a result of the orientational ordering
denoted thermotropic.106 HPC is both lyotropic of the rigid polymer segments (formation of an
and thermotropic. anisotropic phase). The viscosity is composed of
In order to form LCPs, the intramolecular forces the viscosities of the two coexisting phases. The
must be weak enough to allow the chain backbone viscosity passes through a minimum and rises
groups to move and achieve an orientational order. again with a further increase in the concentration
The critical concentration for phase separation of to the fully anisotropic phase.106 For an isotropic
derivatized celluloses is thus determined by the solution, the viscosity decreases exponentially at
stiffness of the chain – the stiffer the chain, the higher temperatures.113 The viscosity of the choles-
higher the tendency to form LCPs.107 At higher teric solution initially decreases with increasing
temperatures, higher critical concentration for temperature, but rises at the phase transition and
mesophase formation is often observed simply passes through a viscosity maximum. At the cloud
due to the decreased chain stiffness. The critical point, the viscosity rapidly decreases and becomes
concentration for the formation of anisotropic similar to that of water.103
phases is also affected by the polymer–solvent Since HPC contains hydroxyl groups, it is
interaction, the relative distribution of substituent extremely difficult to completely dry the films and
groups and, to some extent, the molecular weight the remaining, tightly bound water may affect e.g.
of the polymer. For molecules such as HPC, the the mechanical properties. Finally, HPC films are
rigid units, mesogens, which are capable of forming assumed to be flexible, transparent, odourless,
LCPs, reside on the main chain. This type of tasteless, biodegradable, edible and thermoplastic.
polymer molecule is called persistently flexible Furthermore, they show moderate mechanical
and is often modelled using worm-like chains.107 strength and are moderate barriers to moisture and
LCPs of HPC in water are reversibly formed oxygen, while they are resistant to oils and fats.18
above 40% w/w polymer.108,109 Critical concentra- Non-ionic HPC also provides water retention,
tions for the formation of a lyotropic mesophase at surface activity, electrolyte stability and binder
room temperature in the range 19–40% have been properties.114 The use of HPC in food packaging
reported.110 Furthermore, LCPs of HPC can be is mentioned in the literature.18,26,80
formed at constant polymer concentration below More rigid LCP chains often display favourable
40% w/w upon heating, leading to a phase separa- mechanical and thermal properties compared to
tion at 44 ± 2°C.109 Above 40°C, the formation of a their more flexible counterparts.115 In general, LCPs
precipitate with cholesteric order is observed as show high modulus and strength along the shear
the solution becomes white.109 At higher concentra- direction and low strength in the transverse direc-
tions, the appearance of the precipitate changes tion as a result of the molecular orientation. In the
from a white suspension to a semi-transparent transverse direction, the strength can be as low as
gel.111 Gel formation is favoured in cellulose deriv- one-tenth of that in the shear direction.115 The
atives rich in –OH groups, i.e. at low degrees of problem with different mechanical properties in
substitution, due to the strong hydrogen bonding different directions can be overcome by producing
between cellulose chains.102 A variation in cloud a biaxially oriented film, e.g. by using a counter-
points between 37 and 44°C has been reported for rotating circular extrusion die.116
commercial grades of HPC,108 depending on the Commercial, synthetic LCPs such as Vectra®
degree of substitution. (Ticona/Celanese Corp.) provide good barrier
The rheological properties of cellulose deriva- properties for both gases and water vapour even
tives are related to the degree of polymerization in very thin layers.115 In fact, the water vapour
(DP), i.e. the number of anhydroglucose units. permeability of a 25 mm thick LCP film is around
Commercial grades vary between DP 300 and 100 times lower than that for EVOH, PET and
1500112 and have an average Mw of 8 · 104−1 · 106 g/ high-density polyethylene (HDPE) films of the
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same thickness.117 The OP is one, two and three Hemicelluloses such as arabinoxylans extracted
orders of magnitude lower for LCP than for the from cereal cell walls (e.g. barley husks) have also
three named polymers. Even though The LCP been investigated for the production of polymer
prices are too high for bulk coating, the LCPs may films or coatings with oxygen barrier properties.121
be put to effective use as thin top coatings or in The hydrophobicity of films from arabinoxylan
blends with other barrier polymers.118 Thus, liquid extracted from maize was increased by grafting
crystalline polymers such as bio-based HCP are functional aliphatic acrylates.122 The study showed
interesting for the enhancement of paperboard a significant improvement in the water vapour
functionality even though the barrier properties barrier properties.
for these water-soluble polymers are not as high as
those of the synthetic, water-insoluble materials. Chitosan. Chitosan is a polysaccharide derived
Besides HPC, ethyl cellulose, methyl cellulose from chitin, acting as a load-bearing component
(MC), carboxymethyl cellulose (CMC) and in the shells of shellfishes. Chitin is the second most
hydroxypropyl methyl cellulose (HPMC) are abundant natural polysaccharide after cellulose
further examples of cellulose ethers that can be cast and is extracted from by-products of the seafood
as films or coated from water and/or ethanol solu- industry in a multi-step process. The molecular
tions. In contrast to HPC, these derivatives are not structure of chitin is 2-acetamide-2-deoxy-b-D-
thermoplastic and hence do not give heat-sealable glucose joined by b-1,4-glycosidic linkages. By
coatings.18 All these ethers offer poor moisture deacetylation of the acetamido group to amine,
barrier properties, but they have found use as oil chitin can be derivatized to chitosan, 2-amino-2-
and fat barriers. The moisture barrier performance deoxy-D-glucose (Figure 3d), which is water soluble
of HPMC has been significantly improved by intro- under acidic conditions. Dissolving chitosan in a
duction of fatty acids.82 Cellulose ethers are weak acid causes protonation of the NH2 groups
regarded as slowly biodegradable. The biodegrad- to NH3+, thus rendering the molecule cationic.
ability decreases with increased degree of substitu- Commercial grades of chitosan have a deacety-
tion since this makes the ether linkages more lation degree of 80–90%.123 Chitosan forms a highly
resistant to microbial attack.101 viscous, shear-thinning solution that can be coated
The major factor that has prevented large-scale on cellulose substrates or cast into transparent,
commercial use of cellulose ethers as coating mate- free-standing films.123 The amino- and hydroxyl
rials is, however, the high costs associated with the groups are readily undergoing chemical reactions,
derivatization processes. The highly crystalline thus offering a wide spectrum of possible
structure of cellulose makes it less accessible for modifications.
the derivatization reaction compared with starch.26 Chitosan shows good film-forming properties.
One manufacturer of cellulose derivatives is The films are transparent, flexible and semi-
Aqualon (Hercules Inc. Wilmington, DE). crystalline, thus giving low OP. Due to its cationic
character, chitosan will bind strongly to anionic
Xylan. Xylan is one of the most abundant biopoly- cellulose fibres. This cationic property also pro-
mers since it is one of the major constituents of vides numerous possibilities for further derivatiza-
wood and plants. It is also available in large quan- tion and favourable interactions with coating or
tities from agricultural waste. Xylan consists of a food components. Chitosan also exhibits natural
1,4-b-D-xylopyranosyl main chain with various antibacterial and fungicidal properties, thus
side chains or substitutent groups depending on making it attractive for use in the coating of paper
its origin. A novel bio-based material for coating and paperboard for food or medical applications.73–75,124
applications has been developed from glucuronox- Chitosan has e.g. been incorporated into starch to
ylan, which comes from hardwood. Water-based give antimicrobial functionality to the edible coat-
solutions of glucuronoxylan plasticized with sor- ings.124 For surface treatment of paper and board,
bitol have been found to give films with an OP chitosan with Mw of 400 000 g/mol has been
comparable to that of PVOH or EVOH plastics.119 used.74,75 Chitosan is commercially available in a
Xylan-based barrier materials are now commer- range of different grades. Manufacturers are e.g.
cially available under the name Xylophane®.120 France Chitine and Aqua Premier Co., Ltd.
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Chitin is enzymatically degraded by chitinase.101 into an alcohol-soluble group (gliadins) and an
Chitosan degradation by the action of bacteria has alcohol-insoluble group (glutenins). Dissolving the
been found to occur more rapidly than cellulose protein requires a complex solvent system and
enzymatic degradation by cellulase, which sug- either high or low pH to break up the hydrogen
gests that a chitosan coating makes cellulose resis- and disulphide bonds.123
tant to enzyme attack.125 Wheat gluten products on the market typically
contain 80–90% protein. Solutions of wheat gluten
Alginate. Alginates are salts of the polysaccharide in ethanol may be used as coatings or as oxygen
alginic acid naturally present in brown algae. Its barrier films for packaging applications.123
molecular structure is a linear block copolymer
built up of b-D-mannuronic acid and a-L-guluronic Whey proteins. Whey is a by-product from the
acid joined through 1,4-linkages126 (Figure 3e). cheese-making process and is thus widely avail-
Alginates in the form of monovalent cation salts able. Once considered as merely a waste product,
are water soluble. They form gels through cross- whey has gained interest in recent years due to its
linking and become water insoluble when divalent high protein content. The main component of whey
or polyvalent cations such as Ca2+ or Al3+ are is b-lactoglobulin, but the proteins a-lactalbumin,
added.101 Different forms of alginate are used as immunoglobulin(s) and bovine serum albumin are
food additives and thus, alginate-based coatings also included as are some specific polypeptides
should be regarded as safe for food contact. in a complex mixture.129 Protein from whey can be
Like all other bio-based polysaccharides, algi- divided into two quality types: whey protein con-
nates provide poor moisture barrier but have been centrate (WPC) and whey protein isolate (WPI).
shown to give coatings with low OP and good WPI contains a higher level of protein but is more
grease and fat resistance. Board coated with algi- expensive due to the higher costs associated with
nate or alginate-montmorillonite composites the purification process.123
showed higher water absorptivity than uncoated Water-based whey protein solutions form excel-
board.127 This was explained by absorption and lent oxygen barrier films due to the high content
swelling behaviour in the coatings, thus accelerat- of intermolecular hydrogen bonds. The barrier
ing the water uptake. Commercial, water-soluble properties are generally enhanced by cross-linking;
sodium alginate products for paper coating in a intermolecular disulphide bonds are formed when
number of viscosity grades are available from Syn- the protein is heated to the denaturation tempera-
thetic Natural Polymers, Inc. The products provide ture. WPI-coated paperboard exhibits grease and
excellent runnability and water-holding proper- oxygen barrier properties in the same range as
ties, thus finding application also as additives to those for PVOH and fluorocarbon polymers.130 The
starch in surface sizing by conventional and meter- water vapour permeability of WPI and WPC films
ing size press (MSP) applicators.128 containing MC has been found to decrease with
increasing concentration of MC.131 The authors sug-
Wheat gluten. Gluten is the main storage mode gested that these polysaccharide–protein blends
of protein in wheat and corn and is thus highly could be used for the packaging of heterogeneous
abundant in nature at a low price.26 Starch is sepa- foodstuffs such as pizza and breakfast cereals.
rated from wheat for further fermentation to Gällstedt et al.132 studied the effects of creasing
ethanol for use in fuel production, for example. on a paperboard coated with chitosan or whey
The remaining wheat gluten (8–16% by weight, protein onto which a nitrocellulose lacquer had
depending on the quality of the growth environ- been applied to improve the moisture resistance.
ment) can be isolated after washing and filtration. The lacquer layer on top of the chitosan fractured
Wheat gluten is composed of more than 50 differ- upon creasing, whereas the whey-treated substrate
ent proteins of different classes which vary in could withstand the creasing forces, probably due
viscous and elastic properties. The proteins contain to the penetration of the lacquer into the protein
high levels of non-polar amino acids and thus layer. In contrast, when a low coat weight of lacquer
exhibit low hydrophilicity. Wheat gluten is insolu- was used, chitosan-treated paperboard showed
ble in water. The gluten proteins can be divided potential to withstand 90° folding.
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Zein. Zein is a group of proteins present in corn with high crystallinity (50%) and hydrophobicity
and is commercially available as a by-product from that is prepared from the ring-opening polymer-
the corn wet milling industry.26 Parris et al.77 found ization of e-caprolactone, a starting material that is
that Kraft paper coated with corn zein isolate derived from petroleum. One reaction process uses
(composition 80–85% protein, 15–20% lipid and cyclohexanone that is allowed to react with perace-
<0.25% starch) showed significant improvement in tic acid formed through the reaction between acetic
grease resistance and water vapour barrier proper- acid and hydrogen peroxide.137 Even though it is
ties. The zein–lipid coating could be easily sepa- synthetic, this polyester is slowly biodegradable
rated from the Kraft paper, using enzymatic through hydrolysis. PCL resembles LDPE with
hydrolysis, thus providing advantageous proper- regard to glass and melting temperatures and
ties with respect to repulping and recycling as appearance.138 PCL is highly compatible with other
compared to wax-treated paper. polymers and is used for direct coating but has
Zein-coated paper has properties equal to PE- also found use in composite barrier films based on
laminated paper for the packaging of fatty foods. starch.78,139 PCL is insoluble in water, alcohol and
It is also attractive due to its heat-sealable proper- acetone, and the most commonly used solvent is
ties.133,134 Coating of sandwich wrapping paper chloroform.76,140 The use of PCL particles in chito-
with corn zein has also led to a reduction in WVTR san or WPI films has been found to substantially
and OTR, but demonstrated the need for high coat decrease water vapour permeability.76 Even though
weights and uniform coating layers.135 Due to the the OP is high for pure PCL films,76,139 blends of
freeze–thaw stability of zein films, the material is small amounts of PCL in chitosan films have shown
also suitable for use in frozen food packaging.136 OP values that are even lower than for pure chito-
The hygroscopic character of polysaccharide san.76 PCL is also used in commercial packaging
and protein coatings means that, in order to be materials such as Mater-Bi® and Bioflex®. PCL is
useful as barriers for packaging applications, they manufactured by Union Carbide Corporation and
need protection through a hydrophobic top layer Solvay under the trade names TONETM and CAPA®,
such as beeswax.18,72 respectively.
Polycaprolactone. Poly(e-caprolactone) (PCL) is PLA. Lactic acid is produced by fermentation of

a synthetic, linear aliphatic polyester (Figure 4a) natural carbohydrates, e.g. maize or wheat or
waste products from the agricultural or food indus-
try. PLA is a thermoplastic, biodegradable polymer
produced synthetically by polymerization of lactic
acid monomers or cyclic lactide dimers (Figure 4b).
Lactic acid contains an asymmetrical carbon atom
giving rise to the two optically active, L and D
isomers. Lactide dimers are formed by the conden-
sation of two lactic acid molecules, resulting in L-
D- or LD (meso) lactide.141,142 Commercial quantities
of PLA for packaging applications are produced
through ring-opening polymerization of lactide,142
because this reaction favours the formation of
higher-molecular-weight PLA.143 The final crystal-
linity and mechanical properties of the polymer
depends on the stereochemistry of the polymer
backbone, i.e. the relative amounts of the L and D
isomers. The L-form gives a polymer with very
high crystallinity, whereas copolymers of D and L
isomers become amorphous.26
Figure 4. (a) Polycaprolactone, (b) PLA and (c) PHA PLA can be used for paper and board coat-
monomers. ings,18,65 for use as drinking cups and containers.142
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Extrusion coating is the commonly used method respect to flexibility, tensile strength and melting
for packaging applications even though solution point.18,138
coating using chloroform as solvent is also possi- Commercially available PHA products include
ble.143,144 The major drawback with PLA is its BiopolTM from Metabolix Inc. PHAs possess excel-
insolubility in water, thus making it less attractive lent film-forming and coating properties and are
for use in industrial dispersion coating for paper- water resistant due to their high hydrophobicity.80
board. PLA shows moderate moisture barrier PHB-coated paperboard has been used for packag-
properties but produces poor oxygen barrier ing of ready meals, while PHB/V or PLA-coated
films. The increased surface hydrophobicity of board has been used for dry products, dairy prod-
board coated with PLA has been demonstrated ucts and beverages.26 The water vapour barrier of
through a tremendous decrease in the water paper or board coated with PHB/V can be further
absorptiveness.144 Recycling of PLA can be carried lowered by incorporation of wax or tall oil rosin.147
out by simply hydrolysis through water action. The drawbacks with PHAs are poor gas barrier
PLA fulfils the requirements for direct food properties and high production costs.
contact with aqueous, acidic and fatty foods.47 Krook et al.148 investigated the creasability of PCL
Cargill Dow is the largest producer of PLA and and PHB/V compression moulded onto paper-
offers the product by the trade name NatureWork- board. A low-molecular-weight PCL coating was
sTM PLA. The use of PLA is, however, limited by more prone to crack and delaminated from the
the brittleness of the coatings. The DuPont paperboard upon application of creasing and
Company has therefore developed a petroche- bending stresses, while a high-molecular-weight
mical additive, Biomax® Strong, which, by low PCL could withstand such forces due to its higher
levels of addition (1–5% by weight), confers the toughness. The PHB/V coating showed no evi-
required toughness to the material while still dence of cracks, and the delamination was observed
being compostable.145 to decrease with increased moulding temperature
PLA-coated paperboard biodegrades rapidly due to improved paperboard-coating adhesion.
upon composting,47,49 whereas PCL can be slowly Paper coated with poly(hydroxybutyrate) and
degraded by hydrolysis. This process can be cata- PHB/V has been demonstrated to biodegrade
lysed by enzymes, or by the activity of bacteria or rapidly. The biodegradation mechanism of these
fungi.101,146 Both PLA and PLA–PCL copolymer bacterially produced polyesters involves hydroly-
films have been shown to be fully biodegradable sis in water followed by chain scission.101
according to the 90% criteria.143 Polycaprolactone Favourable heat-sealing properties have been
and PLA are both FDA approved and are on the observed with HPC149 and corn zein134 coatings.
EU positive list. Kuusipalo147 investigated the heat sealability of
PHB/V extrusion coated onto a series of paper and
PHAs. PHAs are biopolymers produced by micro- board substrates. The results show that the sealing
organisms for energy or for carbon reserves.26 temperature increased with increased substrate
Examples are polyhydroxybutyrate (PHB) and basis weight. The coating could be heat sealed both
copolymers of hydroxybutyrate (HB) and against itself and against the substrate, at tempera-
hydroxyvalerate (HV), poly(hydroxybutyrate-co- tures ranging from 190 to 230°C, with ca 25°C
valerate) (PHB/V), or more precisely 3-hydroxy- higher temperatures for the latter case.
butanoic acid-3-hydroxypentanoic acid (Figure
4c). The polymers are insoluble in water. PHB Other biopolymer aspects. Besides the bio-based
forms highly crystalline films which are thus stiff materials for functional treatment of paper and
and very brittle, whereas films from copolymers board mentioned above, there are several others
containing the longer alkyl chain of HV give films that have been investigated. Among these are
with excellent toughness and strength.101 By adding polysaccharides (carrageenan), plant proteins
propionic acid to the growth medium, the ratio of (soy, potato) and animal proteins (casein, collagen,
HB and HV in the copolymer can be changed. gelatin and keratin). The limitation for the practical
Copolymers rich in HB resemble polypropylene, use of these biopolymers is their hydrophilic
while copolymers rich in HV resemble PE with nature.
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Natural macromolecules must contain molecu- gels by the interaction with counter-ions. The
lar groups that can undergo chemical, biological degree of cross-linking depends on pH, the type of
and/or photochemical degradation146 to degrade counter-ion (mono-, di- or trivalent) and the charge
in nature. When the macromolecules contain density of the polymer.101 The level of crystalliza-
hydrolyzable functional groups, the degradation tion is reduced upon cross-linking of thermoplastic
generally occurs by hydrolysis followed by oxida- polymers because close packing of molecules is
tion driven by enzymes.101,146 The hydrolysis reac- prevented,24 thus resulting in lower hardness and
tion requires wetting of the material, which means yield strength of the polymer. Cross-linking of
that a material with poor water resistance such as charged latex particles has been found to increase
starch is more easily degraded than polymers with the mechanical strength and barrier properties of
higher barriers to water vapour transmission. The the film.153
enzymatically catalysed degradation requires that The –OH groups in starch are capable of under-
the polymer chain is flexible enough to fit into the going cross-linking reactions that give a network
active site of the enzyme. Hence, amorphous structure with increased viscosity, decreased water
regions of a semi-crystalline polymer will degrade retention and increased film strength.101 Cross-
faster than crystalline regions.101 In case of cellu- linking can give insoluble solutions or films which
lose and starch derivatives, steric hindrance from have numerous industrial applications, e.g. wet-
the substituent groups can prevent the enzymes strength paper. Derivatization with reagents that
from attacking the polymer.61 The environmental have more than one functional group can promote
conditions that promote efficient biodegradation cross-linking within or between molecules and
after disposal must, however, be avoided during increases the resistance to gelatinization and dis-
storage in order to maintain the performance of the persion.154 In the cross-linking reaction, the hydro-
packaging material and to prevent deterioration of gen bonds are replaced by covalent bonds between
the packaged food.26 starch and the cross-linking agent which keeps the
A trend towards an increasing demand for trans- granule together. Thus, the granule is more resis-
parency, i.e. visibility of the content of the packag- tant to fragmentation under the influence of shear,
ing, has been identified among consumers.150 This high-temperature and acidic conditions.91
demand can be met by using a small see-through Cross-linking of starch in its granular state will
window that displays the packaged items. Besides lead to about one cross link every 100–3000 anhy-
the use of biomaterials for direct coating or surface droglucose unit.86 Nevertheless, cross-linking has
treatment of board, film-forming materials with a very strong effect on the starch properties and at
appropriate barrier properties (e.g. starch or PLA the highest levels of cross-linking, granule swell-
films) may be used for such transparent windows ing in hot water is almost completely prevented.
on cartons, or as covering lids for ready-meal Cross-linking also has a positive effect on the
trays.26 Bio-based packaging materials may also, tensile strength of starch films since the amylopec-
despite their lack of moisture barrier properties, be tin is kept in the swollen granules upon cooking,
of use in packaging for food products with rela- while the flexible amylose chains that are emerging
tively short shelf life such as vegetables and bakery out of the granules will be solely responsible for
products.151 The poor water vapour barrier of the mechanical properties.86 Cross-linking can be
starch makes a package breathable, which can be achieved by reaction with phosphoric acid salts,155
advantageous in the storage of certain types of with vegetable oils,156 by reaction with glyoxal,
food.152 Other possible applications are food with urea- or melamine formaldehyde, epichlorohydrin
low moisture content and short-term use products and a wide variety of other reagents.86,91
such as fast-food containers, cups and plates.18 Solid HPC films with cholesteric order may be
prepared by solvent evaporation from lyotropic
Enhancement of barrier properties by mesophases or by slow precipitation from solu-
chemical treatment tions.157 The liquid crystalline structure can be pre-
served in the solid state by cross-linking. Several
Polysaccharides bearing positive or negative techniques for cross-linking are available: irradia-
charges can undergo cross-linking and forming tion byg–rays, photo-initiated cross-linking (ther-
DOI: 10.1002/pts
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motropic mesophases) in N,N-dimethylacetamide the surrounding humidity.16,163 Addition of a (syn-
and chiral cross-linking of lyotropic mesophases thetic) plasticizer can have a similar effect by
by addition of a chemical cross-linking agent such increasing the polymer chain mobility and thus
as p-formaldehyde.158 The occurrence of cross- decreasing the crystallinity in films. However, anti-
linking in a polymer can be observed as the forma- plasticizing effects have been observed at interme-
tion of a swollen gel. The right-handed helical diate concentrations of plasticizers.160,164 An
structure (cholesteric) has been shown to be main- optimized plasticizer addition has been found to
tained after cross-linking byg-irradiation of both give low water vapour permeability of a starch-
HPC mesophase and solid films, whereas no cross- glycerol film while maintaining the OP at an
linking has been observed when HPC powder is acceptable level.165 Thus, finding appropriate con-
irradiated.157 Studies of the change in surface centrations of the included materials can lead to
tension of aqueous solutions of HPC have shown conditions where the positive and negative effects
the formation of an ordered monolayer at the are nicely balanced.
solution surface that is driven by diffusion and PVOH coatings can be heat sealable after plasti-
crystallization.108 cization of the polymer with glycol or glycerol.60 A
Mechanical and barrier properties of protein plasticizer is usually required to impart thermo-
films can be improved by cross-linking through plastic properties to biopolymers. Glycerol addi-
enzymatic, chemical or thermal treatment or by tions will e.g. lower the Tg of a starch film,166 thus
UV- or g-irradiation.159 making the coating heat sealable at lower tem-
peratures. The thermoplastic properties in starch–
PVOH blends are also superior to that of starch
Plasticizers and plastisol coatings alone.18
Several different types of additives may be
In order to achieve polymer films with appropriate required to attain the desired properties of coating
mechanical properties, a plasticizer might be nec- formulations with respect to rheology, runnability,
essary. The plasticizer molecules (often short-chain, dispersion stability, etc. Among these, the surfac-
low-molecular-weight polymers or oligomers) tants and plasticizers are most likely to reduce the
arrange themselves between the polymer chains barrier properties due to their tendency to migrate
such that the intermolecular hydrogen bonding is to the coating–air interface.
disrupted, hence giving films with less stiffness. A novel technique for surface treatment of fibre-
The most commonly used plasticizer for starch and based substrates is the use of plastisol coatings. A
proteins is glycerol.16,70,129,160 Other plasticizers are plastisol is defined as a suspension of fine polymer
sorbitol, PE- and polypropylene glycol, PVOH, particles dispersed in a liquid plasticizer, to which
amino acids, amides, di- and triethanolamine.26,161,162 additives such as pigments and dyes may be
PVOH increases the elongation and tear strength added. The advantageous properties of this water-
of amylose films. High molecular weight, fully free coating are that the substrate fibre swelling
hydrolysed grades of PVOH are compatible with upon water contact is avoided, and that the coating
starch films and improve the film properties by technique does not involve extensive on-machine
lowering the intermolecular attraction and by drying. Starch–PVOH-based plastisol coatings
interfering with the packing of the amylose mole- have been shown to give a significant reduction of
cules.88 Both the toughness (area under the tensile WVTR when applied on board and greaseproof
stress–strain curves) and the flex-fold resistance paper. Overcoming the presence of pinholes should
of starch films increase with increased levels of also give promising OTR values.166
PVOH.
Absorption of moisture from the air or of water
from e.g. wet foodstuffs may cause swelling and/ Wax treatment
or may exert a plasticizing effect on polar poly-
mers. This will lead to reduced barrier properties. Wax coating enhances the hydrophobicity of paper
Thus, the OP of coated substrates or films of hygro- or board substrates. Wax impregnation means that
scopic polymers are often increased by increases in the wax penetrates into the fibre structure to give
DOI: 10.1002/pts
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a matte surface. A glossy, hydrophobic surface can The critical pigment volume concentration
be formed through rapid cooling of the hot-melted (CPVC) is an important factor concerning filler
wax using a chill roll, in which case the wax freezes addition. The CPVC concept refers to the point
and thus remains on the surface.167 Wax-treated where the binder concentration is just large enough
paperboard is used for packaging of frozen food, to fill in the interstitial voids between pigment par-
ice cream and confectionery.168 Incorporation of ticles (Figure 6). For conventional paper coating,
wax in barrier dispersions is one way to enhance the addition of fillers is usually done at concentra-
the water resistance of such coatings.56,169 In recent tions considerably higher than the CPVC. In barrier
years, natural waxes such as candelilla, carnauba dispersions, on the other hand, pigments are added
or beeswax have received some interest. These at a concentration well below the CPVC. The reason
waxes can be applied as thin top coatings to render is that an increased number of filler particles will
the surface more water resistant or to protect the lead to an increase in voids, thus leading to an
underlying moisture-sensitive coating.72 The main increase in permeability (Figure 6). A higher binder
disadvantage with wax treatment involves diffi- concentration gives a more flexible coating, and
culties associated with recycling since separation the optimum pigment volume concentration
of wax from the fibrous material includes both becomes a compromise between barrier properties
large costs and severe processing problems.1,46 and flexibility.
The CPVC of dispersions is affected by the
immobilization volumes (i.e. the packing volume
Filler reinforcement of the wet coating, which is dependent on particle
shape, size, size distribution of pigment and
Fillers can be added to a barrier polymer to reduce binders, colloidal, chemical and rheological prop-
the price of the coating, to enhance the opacity or erties), the consolidation power of the binders, the
for mechanical reinforcement. The addition of type of substrate and the drying conditions.170 The
fillers to polymer matrices can either increase or most important factors concerning filler addition
decrease the permeability, depending on the com- to barrier dispersions are the adhesion of the binder
patibility and adhesive properties between the to the pigment particles, the particle shape and the
polymer and the filler and also on their relative chemical nature of the pigments. The CPVC value
concentrations. Dispersion polymers are readily of a polymer/pigment system depends on the
compatible with conventional coating pigments latex particle size and its size distribution. Increased
such as clay, talc, calcium carbonate or titanium particle size decreases the CPVC as does an
dioxide. The barrier properties are improved by increased value of the glass transition temperature.
increasing the diffusion path length of the perme- In contrast, in dispersions where strong deforma-
ating species (Figure 5). tion of the latex particles occurs, a higher CPVC
is obtained due to the more dense packing of
polymer.171
Figure 5. Mechanism of barrier improvement by fillers or

nanocomposites. Figure 6. CPVC.
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Schuman et al.172 reported a 50% reduction in component mixture.175 Nanoparticles are generally
WVTR for styrene–butadiene latex filled with defined as having a size below 100 nm and can be
either talc or delaminated kaolin clay (60% by either inorganic (silicates, metal oxides) or organic
weight). Addition of wax (5% by weight) to the (polymers, dyes). Examples of nanoporous materi-
latex-filler dispersions led to a further halving of als are zeolites and gels.174
the WVTR value. Cellulose fibrils for mechanical reinforcement of
Fillers also make the coating process more eco- synthetic polymers and biopolymers have been
nomic since they are cheaper than synthesized derived from e.g. sugar beets, potato tuber cells or
polymers. Mineral or plastic pigments also have wheat straw, although wood provides a more
positive effects on dispersion stability, coating run- appropriate base material for the extraction of cel-
nability, printability and the glueability of coated lulose fibrils due to high availability and low
products and last, but not least, they are an impor- costs.176 Nanofibres based on cellulose with a diam-
tant factor in the prevention of blocking.38 The eter below 100 nm derived from sulphite pulp by
blocking tendency is further affected by the parti- a combined chemical/mechanical process have
cle orientation and the adhesion between pigment been found to increase the tensile strength of HPC
and polymer. A pigment volume concentration of or PVOH films by up to five times.176 The use of
about 40–50% has been shown to give low block- natural fibres as nanofillers offers both high flexi-
ing tendency.171 bility and biodegradability of the material. The dif-
Commercial ready-for-use filled barrier disper- ficulties lie in the poor dispersion characteristics
sions are RebarcoTM from Ciba Specialty Chemicals and the hydrophilic nature of the fibres. The cationic–
(containing talc) and VaporCoat® from Michelman anionic interaction between chitosan and cellulose
Inc. Products containing nanosized silicates are has been utilized to form reinforced composite
manufactured by InMat Inc. under the name materials for packaging with improved barrier
NanolokTM. and mechanical properties.123 Hosokawa et al.125
reported OP for chitosan–cellulose fibre composite
films that were comparable to PET films.
Nanoparticulate materials Montmorillonite is a naturally abundant clay
material with a layered aluminosilicate structure
Nanotechnology is one of the fastest growing that is often used in nanocomposite technology
research fields in the world. The concept of using due to its high surface area and large aspect ratio.
nanosized materials to enhance the functionality of Dispersion of layered silicates in a polymer matrix
paper and board covers the whole range of appli- can result in a number of different states, leading
cations from improvement of optical properties to to microcomposites, intercalated or exfoliated
abrasion and scratch resistance to barrier or nanocomposites (Figure 7). It is believed that com-
mechanical reinforcement,173 and is believed to be plete and homogeneous dispersion in which the
one of the most important strategic development clay platelets are arranged in a non-parallel manner
lines in the coming years.174 (exfoliation) will give the highest performance
Many of the characteristic properties of nano- improvements in coatings.177 The aluminosilicates
sized materials lie in their small size, which give a can be dispersed into individual layers only 10 Å
very large total surface area due to the very large thick.178 The distance between the platelets, the
number of particles present per unit volume. basal spacing, is defined as the distance from a
Nanosized materials can be classified in different certain plane in one layer to the corresponding
ways. Nanofillers have at least one dimension in plane in a parallel layer. Montmorillonite is hydro-
the nanometer scale. Two-dimensional nanofillers philic but can be made organophilic by exchanging
can be long or short fibres based on cellulose. the naturally occurring Na+ ions in the galleries of
Three-dimensional nanofillers are nanoparticles, the clay with organic cations, e.g. alkylammonium
nanostructured or nanoporous materials. The surfactants,179 making them more compatible with
fillers are dispersed in a polymer matrix to give a organic polymers.
composite material, either with particles or fibres The relationship between surface diameter and
or with both types of nanofillers in a three- thickness of the nanoclay particles is defined as the
DOI: 10.1002/pts
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mechanism of barrier improvement relies on
increasing the path length that the molecules have
to traverse while diffusing through the film, i.e.
forcing them to take a tortuous path, which leads
to significantly prolonged transmission rates
(Figure 5). The barrier properties of a nanocompos-
ite material depend on the relative orientation of
the silicate layers and on the state of aggregation
and dispersion. The plate-like structure of clay
increases the path for diffusing molecules, thus
decreasing the permeability of molecules through
the material.47,179 Porous nanoparticles into which
the diffusing molecules can penetrate are also effi-
cient in this respect.173 Improvement of barrier
properties by up to four orders of magnitude upon
incorporation of nanoclays in a polymer coating
has been reported. The lack of a completely exfoli-
ated structure has been used to explain why an
efficient reduction in WVTR could not be observed
when montmorillonite clays were dispersed in a
barrier latex.172
The incorporated clay particles can inhibit crys-
tallization of the polymer matrix by restricted
chain mobility through the association with the
Figure 7. Dispersion of nanoclay in a polymer matrix clay plates.178 This has led to an increase in the
(drawn after Alexandre and Dubois177). tensile strength of starch/polyester blends with
increased montmorillonite content.
Fischer et al.181 reported the blend of a thermo-
aspect ratio. Typically, commercial nanoclays have plastic starch with clay particles using a modifier
aspect ratios between 50 and 1000, which is much (e.g. cationized starch) which is compatible with
larger than for typical clay pigments (10–30) used both the clay and the matrix. The results observed
in paperboard coating. The large aspect ratio of were a homogeneous incorporation of clay parti-
nanoclays makes them effective for barrier improve- cles in the starch matrix, followed by an easier
ment even at very low (≤5% by weight) concen- processing and a strong decrease in hydrophilicity.
trations.159,172,177 Higher weight additions may be The stiffness, strength and toughness of the film
difficult from a processing perspective, because the could also be changed by changing the water
viscosity of the dispersions increases significantly content. Homogeneous dispersion of nanoparticles
at increased loads of clay. The use of nanoparticles in nematic crystal matrices of liquid crystalline
in paper and board coating is thus advantageous, polymers has also been observed.179 Nanoclays
particularly given that less material is required have been demonstrated to reduce both the water
(thinner coating layers) to reach the desired barrier vapour and the OP of PLA and PLA–PCL films.143
or mechanical properties. Less material use leads Organic nanoparticles based on modified starch
to reduced costs and reduced amounts of waste.174 can be prepared e.g. by cross-linking and hydroly-
Southern Clay Products and Nanocor are among sis of starch granules with subsequent release of
the biggest suppliers of montmorillonite clays for the crystalline growth rings. Recent studies have
nanocomposite applications. also shown the opportunity of forming nanopar-
The addition of a nanofiller is made to reinforce ticles from hydrophobically modified biomaterials
the polymer, i.e. to increase the strength and tough- by sonification.182 The principle is that the hydro-
ness of the material.180 Other issues are to enhance phobically modified polymer can self-aggregate
the optical, thermal or barrier properties.177 The due to inter- and intramolecular hydropbobic
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interaction, leading to nanoparticles with a hydro-
philic shell and a hydrophobic core.183 Commercial
bio-based nanoparticles from chemically modified
starch granules are produced by Ecosynthetix Inc.
under the trade name ECOSPHERE®. These mate-
rials offer cost-competitive, biodegradable and
recyclable substitutes to conventional coating
binders and adhesives.184
The use of nanosized materials in food packag-
ing should be approached so as to minimize the
potential risks with inhalation or ingestion of small
particles that can have unhealthy effects on the
human body.173 However, overall migration tests
and analysis of specific metals (Fe, Mg and Si) have Figure 8. Inorganic–organic polymers (drawn after Haas
shown no change in the quantity of these species et al.187).
in food that has been in contact with a potato
starch/clay nanocomposite film.185
WVTR and OTR was also achieved by applying an
ORMOCER® coating on paperboard pre-coated
Thin top coatings with hydroxypropylated starch.189
The water vapour and oxygen barrier properties

of a starch-based film have been improved by the
application of a thin glass-like SiOx coating by BARRIER PROPERTIES OF
plasma deposition.186 Such SiOx coatings are trans- FUNCTIONAL COATINGS
parent, water-resistant and provide barriers com-
parable to metallization. The problems involved The water vapour and gas permeability of polymer
with poor mechanical resistance of the SiOx coat- films depends strongly on the temperature and the
ings can be solved by varnishing or lamination.150 RH on either side of the barrier film, which is why
A class of hybrid inorganic–organic polymers adequate references to the test conditions are nec-
was developed some decades ago and is now avail- essary. Strong cohesion within the film reduces the
able under the trademark ORMOCER® (Fraun- flexibility and the permeability of gases and solutes
hofer-Gesellschaft zur Förderung der angewandten through the film.190 The mechanical and barrier
Forschung e.V.). These functional composites properties of amorphous materials are also strongly
combine hardness through the inorganic network affected by the glass transition temperature of the
and flexibility through the organic cross-linking.187 material.
A schematic sketch of the structural units of Direct comparison of reported barrier properties
ORMOCER®s is given in Figure 8. of various materials from literature values is not
Thin coatings of these hybrid materials give readily carried out because of the strong influence
scratch and abrasion resistance, corrosion resis- of the substrate structure, presence of sizing or
tance, anti-static or anti-fogging properties to pre-coatings, etc. The final barrier properties on a
various surfaces. In recent years, they have found surface-treated paperboard depend on the thick-
use as barrier coatings for food packaging.187,188 ness of the functional polymer layer. Without
Hybrid polymers have been shown to be effective directly contributing to the barrier properties, a
as flavour barriers and as protective coatings on board substrate can act as a supporting material to
top of SiOx layers. ORMOCER® coatings on SiOx- render the functional barrier more effective than in
treated polypropylene (PP) or PET films lead to a the case of a free-standing film. Some examples of
dramatic reduction in the OP of such laminates.187 barrier properties (WVTR, OTR, Cobb and grease
Similar effects have been seen regarding water resistance) of coated paperboard are given in Table
vapour permeability.188 A significant reduction in 1. The barrier improvement factor, defined as the
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Table 1. Literature data on WVTR, OTR, water absorption and grease resistance for some barrier-coated substrates
and Science
Coat wt WVTR OTR Cobb60 Grease resistance

Ref Coating/substrate Application (g/m2) (g/m2 · d) (cm3/m2 · d) BIFWVTR (g/m2) (%)/test method
54 Styrene/acrylate Roll coater 4.8 144 – 2.4 – –

Kraft paper, 90 g/m2
36 Styrene/acrylate + 25 wt% clay TWIN-HSM 6.5 89 26 000 3.3 3.6 –
Pre-coated, hard sized board,
Copyright © 2008 John Wiley & Sons, Ltd.

200 g/m2
Packaging Technology
169 Styrene/butadiene Blade 3.1 103 – 3.2 – –

White top kraftliner, 160 g/m2
169 Styrene/butadiene + 5 wt% wax Blade 4.3 29 – 11.5 – –
White top kraftliner, 160 g/m2
189 Starch Curtain coating 10 220 1 105 3.7 – 0 (no. 12)
Pre-coated, unsized board,
Kit test
255 g/m2
75 Chitosan Curtain coating 5 – 0.3 – – –
73, 74 Chitosan Rod coating 6 120 5 1.7 ca 30 0 (>1800 s)
Greaseproof paper, 45 g/m2 TAPPI T 454
75 Wheat gluten Compression mould – – 6.8 – – –
130 WPI Bird applicator 24.5 – 918 – – 0 (16 h)
Solid bleached sulphate TAPPT T 507
77 Zein Spray coating 10 881 – 1.7 – 1.4 (4 h)
Kraft paper TAPPT T 507
144 PLA Wire bar coating ca 50 9.7 – 24 ca 10 –
SC manila board, 180 g/m2
147 PHB/V Extrusion 20 30 – – – –
166 Plastisol (starch/PVOH/glycerol) Rod coating 112 50 – 5.5 – –
Cartonboard, 425 g/m2
The values are recalculated from literature data to the given units (with reservation for errors).
DOI: 10.1002/pts
Packag. Technol. Sci. (2008)
C. ANDERSSON
and Science
ratio of WVTR for the uncoated substrate to that
of the coated substrate, gives an indication regard-
ing the effectiveness of the functional coating.
APPLICATION OF
FUNCTIONAL COATINGS
Board for packaging purposes is generally surface
sized on one or both sides to improve stiffness and
surface strength before application of the func-
tional coating. Surface sizing is usually performed
Figure 9. Coating structures with (a) an even surface and
in a metered size press, MSP.191 Paperboard for
(b) contour coating following the substrate irregularities.
packaging of liquids, frozen or chilled food is hard-
sized.168 Common chemicals for surface sizing are
chemically modified starches, CMC, PVOH, poly-
urethanes and fluorochemical emulsion sizing from a barrier point of view.52,193 Blade coating, on
agents.24 All these sizes provide oil- and grease- the other hand, acts in order to level out the irreg-
repellent properties to various extents, besides ular substrate surface,194 with large variations in
enhancing the water resistance. It has been dem- barrier layer thickness as a result (Figure 9). Bar,
onstrated that the penetration of sizing compo- size press or film press coaters often give coating
nents into the substrate can be adjusted by control layer structures between these two extremes.
of the colloidal stability in starch-hydrophobic In general, the maximum achievable coat weight
sizing agent formulations,192 thereby providing by blade coating is 15 g/m2.191 Increasing the solids
wide possibilities to reach the desired surface func- content of the surface size or coating colour by 1%
tionality of paper or board. will increase the final dry coat weight by 1 g/m2.194
Size press applicators only give coat weights of
3–4 g/m2, which is far too thin for efficient barrier
Application techniques layers to form. Film press or MSP applicators are
often more appropriate for this purpose.57 Rod
Sufficient barrier properties of a functional coating coaters are capable of giving coat weights around
require a surface-located layer13 with minimized 7–11 g/m2.194 The final coat weight can be increased
penetration of the chemicals into the substrate. by increasing the rod diameter and by decreasing
This task can be difficult to achieve with the limita- the rod loading pressure. Curtain coating gives
tions set on maximum solids content of barrier excellent holdout and provides the possibility of
dispersions due to viscosity and colloidal stability simultaneous application of multiple coating
considerations. Too low a solids content and/or layers,57 thus extending the range of achievable
too low a formulation viscosity of the formulation coat weights. Schlichtling195 reported coat weights
will lead to excess penetration into the paper or up to 21 g/m2 for pigment coating of board by a
board substrate, especially in the case of substrates direct fountain coater. Table 2 gives values for the
with high porosity. The final location of the coating operating range of speed and viscosity for various
layer can also be partly controlled by the applica- coating applicators.
tion technique. In recent years, new non-contact
coating techniques such as curtain coating and
spray coating have gained interest. Curtain coating Processability of coating materials
has, like the air knife method,13,57 the advantage of
giving a contour coating layer that follows the Thermoplastic bio-based materials such as starch
irregularities of the substrate and hence forms a and PLA are readily processable by conventional
layer with even thickness, which offers advantages extrusion techniques and thus have an existing
DOI: 10.1002/pts
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Table 2. Ranges of speed and coating colour viscosity for coating
of paperboard with different coating applicators
Applicator Speed (m/min) Viscosity range (mPas)
Blade 250–2000 500–1500

Rod 200–1000 100–300
Roll 500–1500 80–1000
Air knife 120–500 50–500
Curtain 300–1000 100–300
Data from various machine suppliers and/or literature.
Table 3. Brookfield viscosity values (100 rpm, 25°C unless

otherwise stated)
Dispersion Concentration (wt%) Viscosity (mPas)
Barrier dispersions 50 50–500

PVOH 10 100–1000
Starch derivatives (50°C) 20 50–300
Cellulose derivatives 10 250–800
Chitosan (water/acetic acid) 1 200
Mainly product data.
potential for large-scale industrial surface treat- temperature. The resulting viscosity is strongly
ment of paperboard. Water-based polymer disper- dependent on the concentration. The dispersions
sions have the advantage of being able to be applied can be applied by standard coating techniques
in online coating processes.38,56 Materials that such as blade or roll coaters.60
cannot be applied as water dispersions directly, Most biopolymers are, like PVOH, supplied in
due to insolubility in water, may still be useful in powder form and have to be dispersed in water at
sophisticated composite formulations when dis- the coating unit before application. The maximum
persed in water-soluble polymer matrices. Exam- concentration for dissolution in water depends on
ples are PCL–starch139 composite films and PCL– the solubility of the biopolymers, a parameter that
chitosan76 films. is strongly affected by the type and degree of
Commercial barrier dispersions are supplied chemical substitution. Viscosity is also a factor that
with solids content typically around 50% by sets an upper limit for concentration in aqueous
weight. Increasing the polymer concentration solution. The viscosity is strongly dependent
above 50% is not practically possible since this will on polymer molecular weight; chain shortening
result in a very dramatic increase in dispersion results in lower viscosity, while an increased
viscosity.38 The dispersions are, however, highly number of bulky substituent groups increases it.
shear thinning. Thus, to meet the specific demands Table 3 shows typical viscosity values (Brookfield,
regarding type of coating applicator (Table 2), the 100 rpm) for some water-based dispersions.
viscosity can be increased by the addition of Strong hydrogen bonds between glucose chains
conventional viscosity regulators (CMC, starch, make the granules insoluble in cold water. High
PVOH). energy is therefore needed in order to disperse the
PVOH and its derivatives are dissolved in water chains and to obtain a starch solution that can be
at 95°C and then are cooled down to the processing used in coating applications. Heating a starch solu-
DOI: 10.1002/pts
and Science
tion to the gelatinization temperature causes the ments can associate in networks forming a gel with
bonds to break, allowing water to penetrate and to a subsequent increase in the viscosity. The retro-
swell the starch granules. As cooking proceeds, the gradation process depends on the starch concen-
swollen granules are ruptured and separate chains tration, its molecular weight, the time, the
disperse in the water solution. The gelatinization temperature, the pH and the presence of salt.88 A
temperature for potato starch is in the range 56– starch dispersion is regarded as stable over the
66°C.85 Swelling of granules leads to the formation temperature range 60–70°C.89 Because of its
of gel particles and to a highly increased viscosity branched structure, the amylopectin fraction is
of the solution. As the granules are fragmented, the more resistant to aggregation.199
viscosity gradually decreases. Temperature, pres- Cooling of cooked starch dispersions with high
sure and time are important factors in the cooking amylose content can give irreversible gels or crys-
process. Simultaneous mechanical stirring facili- talline particulate matter. The formation of crystal-
tates the granule fragmentation and chain disper- line amylose precipitates is favoured at low solids,
sion. The gelatinization process implies a transition low viscosity and severe cooking conditions.197 The
from an ordered to a disordered phase which amylose crystals can be of type I (small) or type II
includes loss of crystallinity, an uptake of heat and (large). The second type of crystallites can give rise
hydration of the starch.196 Higher temperature, to scratching in the coating processes.154 Crystalli-
longer cooking time and stirring lead to a lower zation will occur in the critical temperature range
viscosity of the cooked starch.154 A minimum of about 67–89°C.198 The amylose fraction is more
cooking time of 20 min at a temperature of 93–95°C prone to undergo gel formation or precipitation
under strong agitation is required to fully swell than the amylopectin fraction.94 Once a gel or pre-
and disperse the starch.197 In papermaking, starch cipitate has formed, heating to >120°C is necessary
dispersions free of any residue from swollen gran- to redissolve the amylose.89 The amylopectin frac-
ules are preferred. This is achieved by so-called tion has higher storage stability even at lower
overcooking of the starch,89 which leads to a drastic temperatures.
decrease in the viscosity of the dispersion. At this The maximum concentration for the dissolution
stage, it is the amylopectin fraction that forms the of chitosan in water is about 1–10% by weight,
continuous phase and thus determines the rheo- depending on the chitosan molecular weight. The
logical properties. The presence of swollen or frag- viscosity increases very rapidly with increased
mented granules can give problems with picking, concentration, thus limiting the processability on
decreased strength and retention.198 some coating applicators. The low concentration
The viscosity of starch dispersions will strongly makes chitosan less useful in large industrial
decrease with increased temperature. Application coating processes since it is hard to achieve a
of warm solutions can be a way to overcome prob- coating layer thick enough for appropriate barrier
lems with overly high viscosities in some coating properties. The coating process is also expensive
applicators. A decrease in viscosity with increas- due to the large amounts of water that have to be
ing temperature is also seen with dispersion removed by evaporation in the drying sections.
polymers.38 HPC films can be applied as paper and board
Cooked starch can undergo retrogradation, coatings, in extrusion coating and in injection,
when the dissolved amylose molecules reorient compression and blow mouldings. HPC can act
themselves in a linear fashion and then associate both as a film-forming material and as a thickener,
through hydrogen bonding, thus forming aggre- binder or suspending agent in both coatings and
gates in the solution. In dilute solutions, precipi- in printing inks. Its thermoplasticity makes it suit-
tates are formed that result to a decrease in the able for heat sealing. HPC solutions have low
viscosity.86,154 Precipitation can also be observed as surface and interfacial tensions and are compatible
the dispersion changes from transparent to opaque. with e.g. latices.
An indication of retrogradation can be found in the PLA is readily processable by extrusion in the
viscosity changes of the dispersion. In concentrated temperature range 60–125°C, depending on the
solutions, steric hindrance prevents the molecules ratio of D and L isomers. The Tg can be decreased
from orienting parallel to each other, but short seg- by the addition of plasticizers, which can be lactic
DOI: 10.1002/pts
and Science
acid monomers or oligomers.26 The limiting value dispersion polymers should be much desired from
for dissolution of PLA in chloroform for solution an environmental viewpoint.
coating should be ca 5% by weight.144
Bacterial growth and polymer

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PACKAGING TECHNOLOGY AND SCIENCE

Packag. Technol. Sci. (2008)

New Ways to Enhance the Functionality of

This review summarizes recent development of functional materials to improve the

INTRODUCTION war and civil disturbances in the oil-producing

Copyright © 2008 John Wiley & Sons, Ltd.

Synthetic polymer dispersions

Figure 3. Molecular structures of natural/chemically modified polysaccharides.

Polycaprolactone. Poly(e-caprolactone) (PCL) is PLA. Lactic acid is produced by fermentation of

Figure 5. Mechanism of barrier improvement by fillers or

The water vapour and oxygen barrier properties

Coat wt WVTR OTR Cobb60 Grease resistance

54 Styrene/acrylate Roll coater 4.8 144 – 2.4 – –

Copyright © 2008 John Wiley & Sons, Ltd.

169 Styrene/butadiene Blade 3.1 103 – 3.2 – –

Applicator Speed (m/min) Viscosity range (mPas)

Blade 250–2000 500–1500

Table 3. Brookfield viscosity values (100 rpm, 25°C unless

Dispersion Concentration (wt%) Viscosity (mPas)

Barrier dispersions 50 50–500

Bacterial growth and polymer

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