Article

pubs.acs.org/IECR

Multilayered Alkyd Resin/Nanocellulose Coatings for Use in

Renewable Packaging Solutions with a High Level of Moisture
Resistance
Christian Aulin*,†,‡ and Göran Ström†
†
Innventia AB, Box 5604, SE-11486 Stockholm, Sweden
‡
Wallenberg Wood Science Center, Royal Institute of Technology, SE-10044 Stockholm, Sweden

ABSTRACT: A surprisingly simple and rapid methodology for large-area, lightweight, and thin laminate coatings with
remarkable moisture barrier properties is introduced. Commercially available paperboards are coated with thin layers of
nanocellulose. The nanocellulose coating induces a surface smoothening effect on the coated sheets as characterized by
environmental scanning electron microscopy and white light interferometry. A moisture-protective layer of renewable alkyd
resins is deposited on the nanocellulose precoated sheets using a water-borne dispersion coating process or lithographic printing.
Through an auto-oxidation process, the applied alkyd resins are transformed into moisture sealant layers. The moisture barrier
properties are characterized in detail by water vapor permeability measurements at different levels of relative humidity. The water
vapor barrier properties of the nanocellulose precoated substrates were significantly improved by thin layers of renewable alkyd
resins. The effect of the alkyd resin properties, coating technologies, and base paper substrates on the final barrier performance of
the sheets were studied. It was found that the nanocellulose coating had a notable effect on the homogeneity and barrier
performance of the alkyd resin layers and in particular those alkyd resin layers that were applied by printing. The concept is
environmentally friendly, energy-efficient, and economic and is ready for scaling-up via continuous roll-to-roll processes. Large-
scale renewable coatings applicable for sustainable packaging solutions are foreseen.

■ INTRODUCTION
There is growing interest in using agriculture and food industry
intermolecular hydrogen bonds.14 Nanocellulose materials can
be isolated by chemical/enzymatic and homogenization
byproducts to develop biodegradable materials to replace treatments from the cell walls of wood and plants,15−19
petroleum-based polymers in packaging applications. Further- where they are responsible for structural strength. NFC forms a
more, the use of nanotechnology in food packaging is expected remarkable emerging class of nature-derived nanomaterials
to grow rapidly over the next few years as further globalization because of its extraordinary mechanical properties, combining
increases demand for shelf life-enhancing packaging. Applica- high stiffness of up to ca. 140 GPa and its expected strength in
tions of nanotechnology include improved barrier, mechanical, the GPa range with a lightweight character (density ca. 1.5 g/
and antimicrobial properties as well as the incorporation of cm3).20 Since NFC is derived from wood or plant sources, it is
nanosensors for traceability and the monitoring of the globally abundant and renewable and represents a resource that
condition of foodstuffs during transport.1 In recent years, a does not interfere with the food chain or require petrochemical
lot of effort has been aimed at developing new biobased components. Consequently, NFC is emerging as one of the
polymer containing films and nanocomposites which can act as most promising sustainable building blocks for future advanced
barrier materials in packaging.2−10 materials.
Unlike synthetic plastics, under dry conditions the films of So far the main interest in NFC has been to generate strong
natural polymers exhibit good barrier properties against oxygen and tough nanopapers and nanocomposites by adding small
and grease due to their high cohesive energy density. However, amounts to polymeric matrices or robust foams and
natural polymers are hydrophilic in nature, and films produced aerogels.21−24 Flexible and transparent NFC sheets with low
from these materials are often hygroscopic, resulting in the thermal expansion have been used as substrates for organic
partial loss of their barrier properties at high humidity levels.4,11 light-emitting diode displays, highlighting the possibilities of
The gas permeability of polysaccharide materials can increase developing new forms of electronics based on degradable and
by orders of magnitude as humidity increases. Since most food renewable materials.25
applications demand materials that are resistant to moisture as In order to expand the use of nanocellulose as a gas barrier in
well, the major challenge is to overcome the inherent large-volume packaging applications in high-moisture environ-
hydrophilic behavior of these biomaterials.12,13 ments, the hydrophilicity of the nanofibers must be decreased.
Nanocellulose, also referred to as nanofibrillated cellulose Recently, the use of surfactants has enabled the production of
(NFC) or microfibrillated cellulose (MFC), exhibits diameters
in the nanometer range and lengths reaching several micro- Received: July 6, 2012
meters. These nanofibers are composed of aligned β-D-(1→ Revised: January 29, 2013
4)glucopyranose polysaccharide chains, which form native Accepted: January 31, 2013
cellulose I crystals in which the parallel chains form strong Published: January 31, 2013

© 2013 American Chemical Society 2582 dx.doi.org/10.1021/ie301785a | Ind. Eng. Chem. Res. 2013, 52, 2582−2589
Industrial & Engineering Chemistry Research

■
Article

stable cellulose whisker suspensions in toluene and cyclo- EXPERIMENTAL SECTION

hexane.26,27 Alternatively, chemical modifications to the surface Materials. In order to study the impact of the surface
hydroxyl groups have also been studied using silane structure of the substrate formation on the resulting barrier
reagents,28,29 fluorination,30 and acetylation.31 Furthermore, properties of the alkyd resin layer, two cellulose-based
frequently used methods to improve the strength and water packaging materials were used. A highly open surface structure
resistance as well as barrier properties of natural polymers are was represented by the uncoated side (bleached sulfate pulp) of
to blend them with inorganic fillers, such as montmorillon- a commercial one-side coated paperboard from Stora Enso
ite.12,13,32 Despite a large amount of work on the modification (Fors Mill, Sweden) with a grammage of 204 g/m2 and a
of nanocellulose fibrils and substrates and corresponding thickness of 312 μm. This substrate is named substrate O (as in
oxygen permeability measurements, few studies report on the open) hereinafter. The other substrate had a more closed
water vapor permeability of nanocellulose and the use of surface structure and was represented by a surface-treated side
moisture protective layers on nanocellulose films and coat- of an unbleached kraft paper with a grammage of 191 g/m2 and
ings.33,34 a thickness of 263 μm. This substrate is named substrate C (as
Alkyd resins have been widely used in coating applications, in closed) hereinafter. A commercial low-density polyethylene
such as paint, coating, adhesives, binder for composites, etc. (LDPE) film was used as a reference substrate.
Alkyd resins are polyesters whose principal building blocks are Nanocellulose was prepared by a carboxymethylation16
fatty acids derived from vegetable oils (e.g., linseed oil, soybean pretreatment of the fibers. In brief, the dissolving pulp
oil, and tall oil), polyhydric alcohols (e.g., glycerol) and a (Domsjö Dissolving Plus, Domsjö Mills, Sweden) was first
dicarboxylic acid (e.g., phthalic acid).35 They can be dissolved dispersed in deionized water at 10 000 revolutions in an
in organic solvents, such as white spirit, and cast from the ordinary laboratory reslusher. The fibers were then solvent-
solution to create glossy coatings or emulsified in water and exchanged to ethanol by washing in ethanol four times with an
used to create waterborne coatings.35,36 intermediate filtration step. The fibers were thereafter
The alkyd molecule has pendant unsaturated hydrocarbon impregnated with a solution of monochloroacetic acid in
chains which originate from the vegetable oils used during isopropanol. This carboxymethylation reaction was allowed to
production. Alkyd resins are referred to as drying oils since they continue for 1 h. Following this carboxymethylation step, the
polymerize and solidify under exposure to oxygen in a process fibers were filtered and washed in three steps: first with
of auto-oxidation followed by polymerization.37 The rate of this deionized water, then with acetic acid (0.1 M), and finally with
curing process depends on the unsaturation of the fatty acids, deionized water. The fibers were then impregnated with a
access to oxygen, temperature, and added catalytic driers such NaHCO3 solution (4 wt % solution) to convert the carboxyl
as soaps of cobalt and magnesia.38,39 Under the right groups to their sodium form. Finally, the fibers were washed
conditions, the hardening process can be completed within a with deionized water and drained on a Buchner funnel. After
few hours. these treatments, the anionic fibers were homogenized using
Although alkyd resins typically have a low molecular weight the high-pressure fluidizer (Microfluidics Ind., U.S.). Cellulose
and a glass transition temperature far below ambient slurries containing a 2% pulp fiber suspension in deionized
conditions, the auto-oxidative cross-linking reactions result in water were processed through the homogenizer. The thus
excellent film formation, transparency, a sharp increase in prepared nanocellulose dispersion was further diluted through
hardness over time, and notable hydrophobic layer character- homogenization to a final concentration of 0.85%. The density
of a dry nanocellulose film has previously been determined to
istics. The protective or architectural coating properties of the
be 1.57 g/cm3.4
alkyd resins can be correlated with material morphology and
Four commercially available alkyd resins (DSM, Nether-
the individual components in the resin.
lands) were used in the coating trials (Table 1). The alkyd
Accordingly, alkyd resins based on tall oil and linseed oil
were applied as moisture protective layers on top of
Table 1. Chemical Components and Characteristics of the
nanocellulose precoated paper substrates. The alkyd resins
Alkyd Resins According to the Supplier
were applied using a single-step water-based coating or printed
directly onto the precoated papers. Their hydrophobicity, commercial name code origin of fatty acid oil length (%)
biodegradability, and renewability characteristics make them water based
very promising candidates in combination with nanocellulose Uradil AZ514 Z-60 wLO73 linseed oil 73
for commercial use and up-scaling. Uradil AZ515 Z-60 wTO73 tall oil 73
The effect of the alkyd resin components, e.g., type of oil and Uradil AZ516 Z-60 wTO63 tall oil 63
oil length, on the water vapor barrier properties of the oil based
unmodified nanocellulose precoated papers was studied. Uradil AD14 W-75 oLO68 linseed oil 68
Furthermore, the improved surface smoothness of the paper
substrates generated by the nanocellulose coating was found to resins had an oil length, i.e., weight percent of fatty acid to
be beneficial to the formation of the moisture protective alkyd resin, of 63−73%. The water-based dispersion consisted of
resin layer. The surface morphology and roughness of the alkyd resin emulsified in water to a solid content of 60 ± 1 wt
coated and uncoated sheets was characterized in detail by %. The oil-based dispersion consisted of an alkyd resin
environmental scanning electron microscopy (E-SEM) and dissolved in white spirit to a solid content of 75 ± 1 wt %.
white light interferometry. The alkyds resins were used as received. According to the
We report on multilayer-structured barrier coatings on paper supplier, the density of cured alkyd resins is 1.08 g/cm3.
that can be obtained by using simple, quick, and scalable Methods. Dynamic Light Scattering (DLS) Measurements.
concepts including printing and water-based dispersion coat- The size of the particles in the aqueous alkyd resin emulsions
ings. was determined using a Zetasizer ZEN3600 particle character-
2583 dx.doi.org/10.1021/ie301785a | Ind. Eng. Chem. Res. 2013, 52, 2582−2589
Industrial & Engineering Chemistry Research Article

ization system (Malvern Instruments Ltd., U.K.) with a 633-nm Environmental Scanning Electron Microscopy (E-SEM)
red laser collecting the scattered light at an angle of 173°. The and Energy Dispersive X-ray Analysis (EDAX). A Philips XL30
particle diameter was measured as the z-average size. E-SEM-FEG (environmental scanning electron microscope-
Aqueous Nanocellulose/Alkyd Resin Dispersion Coating. field emission gun) electron microscope was used to analyze
Each substrate was single- or double-coated with an aqueous the surface texture of the coated and uncoated substrates. The
nanocellulose dispersion (Na-form) with a concentration of surfaces of the paper substrates were coated with a thin
0.85 wt %, using a rod coater (K101 Control Coater, RK Print conducting layer of gold and imaged in the high vacuum mode
Coat Instruments Ltd., U.K.) and dried under ambient using an SE detector (secondary electrons). The acceleration
conditions. Immediately before the coating procedures, the voltage was 5 kV and working distance was approximately 7
nanocellulose dispersion was mechanically stirred at 1000 rpm mm.
using a four-blade propeller stirrer (RW 20, IKA, Germany). A X-ray analyses were carried out using the Philips XL30
coat weight of 3 ± 0.1 g/m2 was applied in each coating. The ESEM-FEG unit in low vacuum mode with a pressure of 0.3
wet coat weight of nanocellulose was measured and the dry mbar in the sample chamber. The instrument is equipped with
coat weight was calculated based on the nanocellulose a BSE detector (backscattered electrons), EDS (energy
dispersion concentration. Based on the density of nano- dispersive spectrometer), X-ray detector, and INCA X-ray
cellulose, the average coating thicknesses of nanocellulose analysis system from Oxford Instruments. Working conditions
were calculated to be 2 μm (3 g/m2) and 4 μm (6 g/m2), were as follows: acceleration voltage 15 kV and working
respectively. The papers were stored at 23 °C and 50% RH for distance 10 mm. No conductive coating was used for analyzed
at least 24 h before further alkyd resin coating or testing. Some samples.
of the nanocellulose precoated sheets were further coated with The energy dispersive spectrometer detects the energy of all
aqueous alkyd resin dispersions. A coat weight of 20 ± 0.3 g/m2 of the elements occurring in the analyzed materials/compounds
was applied in each coating. Based on the density of the cured simultaneously and, together with the INCA X-ray analysis
alkyd resin films, the coating thickness of alkyd resin was system, gives semiquantitative results for the chemical
calculated to be 19 μm. composition of all of the elements present in the analyzed
Transfer of an Oil-Based Alkyd Resin through Laboratory material.
Printing, Drying, and Curing. The oil-based alkyd was Water Vapor Permeability. The water vapor transmission
transferred to the substrate using an instrument referred to as rate (WVTR) tests were performed with a Mocon Permatran
the ink surface interaction tester (ISIT).40 This technique is 3/33 apparatus (Mocon, Minneapolis, U.S.A.) in accordance
widely used to study interactions between a paper surface and a with ASTM F 1249-05; the test conditions were 23 °C at 50%
printing ink. It requires the fluid to have a certain tackiness. and 80% relative humidity (RH) and 37.8 °C at 90% RH,
Thus oil-based alkyd resins can be used but not water-based respectively. The sample area was 5 cm2 and the partial
alkyd resins. The technique enables the transfer of thin layers, pressures of the water vapor were 0.01387, 0.02219, and
and the amount of the fluid transferred is determined 0.05826 atm at 50, 80, and 90% RH, respectively.
gravimetrically. The fluid (in our case the oil-based alkyd
resin) is first evenly distributed over the surfaces of a set of
metallic rollers. The mass of the metallic roller with the film of
■ RESULTS AND DISCUSSION
Analysis of Material. The surface treatment of substrate C
the fluid is determined. This roller is then placed in the ISIT, was not revealed by the supplier but subjected to standard
and the fluid is transferred to the paper in a “printing” nip. The analysis at our laboratory. The E-SEM surface-image (Figure
mass of the roller is measured again and the transferred amount 1b) showed a relatively closed, nonporous fiber structure. The
is calculated. X-ray analysis showed that the main elements were carbon (9.4
Coat weights of 1.4−14 g/m2 were applied in each printing at. %), oxygen (62.6 at. %), alumina (12.6 at. %), and silica
step. The alkyd resin coated boards were dried at 60 °C for at (14.6 at. %). Traces of sodium, potassium, calcium, titanium,
least 2 weeks before performing the water vapor permeability and sulfur were found but with a content less than 0.3 at. %. No
evaluation. This was to ensure that complete hardening was magnesia was detected. The surface analysis suggests that the
reached without using catalytic driers, although the hardening pretreatment was a thin coating of a polymer containing platy
process of the alkyd layer is most probably completed within a kaolinite clay. Most other minerals contain significant amounts
few hours under optimal conditions. Based on the density of of magnesia, potassium and/or calcium.
the cured alkyd resin films, coating thicknesses of 1−13 μm The average particle diameter and polydispersity index (PDI)
were applied in each printing step. of the alkyd resins was determined using DLS. The size
Topography. Topography/surface roughness of the un- distribution of the alkyd resins was found to be monomodal
coated and coated substrates was characterized in detail using a and the corresponding PDI very low, indicating a high level of
white light interferometry instrument, MicroProf (Fries monodispersity (Table 2). The particles size and PDI were
Research Technology, Germany). White light is focused slightly higher for Uradil AZ514 Z-60 compared with Uradil
through a lens with chromatic aberration generating different AZ515 Z-60 and Uradil AZ516 Z-60.
colors which focus at different distances. The color composition Influence of the Nanocellulose Coating on the
of the reflected light is analyzed and translated into height Resulting Paperboard Surface Texture and Surface
positions. Twenty profiles with a length of 40 mm in the CD Topography. The surface structures of the uncoated and
direction were measured on each of the samples. The profiles nanocellulose-coated substrates were studied using E-SEM. The
were placed 2 mm apart in the MD direction. Resolution was results of this study are summarized in Figure 1, which show
2.2 μm in the CD direction and 5 nm in the z-direction. The micrographs of the paperboards with different coat weights of
height variations (μm standard deviation) which represent the nanocellulose and alkyd resin.
roughness were divided into six wavelength bands, ranging Substrate O (Figure 1a) shows a very open, porous network
from 0.016 to 1 mm. of randomly crossed fibers. A nanocellulose coat weight of 3 g/
2584 dx.doi.org/10.1021/ie301785a | Ind. Eng. Chem. Res. 2013, 52, 2582−2589
Industrial & Engineering Chemistry Research Article

< 1 μm), which is not possible using air-leak techniques such as

Bendtsen and PPS. Figure 2 shows the surface roughness at

Figure 2. Topography spectrum of substrates O and C coated with 3

and 6 g/m2 of nanocellulose, respectively. Substrate O (▲) with 3
(◆) and 6 g/m2 (■) of nanocellulose precoating and substrate C (Δ)
with 3 (◇) and 6 g/m2 (□) of nanocellulose precoating.

different wavelength bands for uncoated substrates and

Figure 1. Top view E-SEM micrographs (magnification ×500) of (a) substrates coated with 3 and 6 g/m2, respectively. The
substrate O, (b) substrate C, (c) nanocellulose-coated substrate O nanocellulose coating is accompanied by a significant decrease
(coat weight 3 g/m2), (d) nanocellulose-coated substrate C (coat in surface roughness at all wavelengths, e.g., the smoothness of
weight 3 g/m2), (e) alkyd resin/nanocellulose-coated substrate O the paperboards was significantly improved by the nano-
(coat weight 20 g/m2), and (f) alkyd resin/nanocellulose-coated
substrate C (coat weight 20 g/m2). The scale bar is 50 μm.
cellulose coating already at very low coat weights (3 g/m2). A
further increase in coat weight (6 g/m2) resulted in minor
Table 2. Chemical Components and Characteristics of the improvements in surface smoothness. This is in agreement with
Alkyd Resins the surface texture analysis with E-SEM, indicating unchanged
surface texture associated with the double-coating. The surface
commercial name particle diameter (nm) polydispersity index (PDI) smoothing effect of nanocellulose allows for the material to be
Uradil AZ514 Z-60 446 0.205 used as a general primer; a first layer coating, which is
Uradil AZ515 Z-60 403 0.155 important in technical applications such as paper pigment-
Uradil AZ516 Z-60 398 0.179 coating. Surface smoothness is also essential for various printing
operations, where printability is dependent on the topography
of the underlying substrate.
m2 resulted in a continuous film formation of the coating layer The open substrate had a higher surface roughness than the
(Figure 1c) and a hardly visible fiber structure in the base closed substrate but after nanocellulose coating, both substrates
paper. As expected, substrate C (Figure 1b) revealed a closer exhibited rather similar surface roughness profiles. The open
and less porous structure than substrate O. As for substrate O, substrate actually became slightly smoother in the fine scale
when a coat-weight of 3 g/m2 was applied to substrate C, the region. Nanocellulose coating thus has a high potential to
network structure became more diffuse and a continuous smooth and densify the quite rough and open structure of an
nanocellulose film was formed. An additional nanocellulose uncoated paper surface already at very low coat weights.
coating, 3 g/m2, was applied on both single-coated substrates Water Vapor Permeability of the Alkyd Resin/Nano-
and resulted in unchanged surface textures (not shown). E- cellulose Coated Paperboards. The applicability of
SEM images reveal highly uniform and featureless alkyd resin biobased polymer films in packaging may be enhanced when
coatings on top of the nanocellulose precoated paperboards they are applied as coatings on a backing material, thereby
(Figure 1e,f). The perfect uniformity of the applied alkyd resin serving as a layer improving the gas barrier properties of the
layers is a result of the rod coating technique in combination layered packaging. Coatings of nanocellulose and renewable
with the auto-oxidation of the alkyd resin emulsions. The rod alkyd resin were accordingly applied onto commercially used
coating technique seems to be most suitable for spreading the packaging board in a multilayer structure. Coating techniques,
viscous dispersion onto the paper surfaces with adjustable alkyd resin properties and nanocellulose precoating affected the
coating thickness. The alkyd resin film formation on the paper water vapor permeability results.
surface is not limited to the alkyd resin water-borne emulsion, Oil-based alkyd resins are tacky which make it possible to
as printing also allows for very homogeneous alkyd resin films deposit thin and uniform films through lithographic printing. A
with identical surface textures as for the alkyd resin dispersion linseed oil-based alkyd resin (named oLO63) was applied at coat
surfaces (not shown). weights of 1.4 to 14 g/m2 to the open substrate (substrate O)
In order to fully study the influence of nanocellulose coating before and after the substrate had been precoated with
on the resulting paperboard surface roughness, a technique nanocellulose. As shown in Figure 3, there was a decrease in
based on white light interferometry was used. The instrument WVTR at 23 °C and 50% RH with an increased alkyd resin
allows the measurement of small-scale roughness (wavelengths coat weight and also from nanocellulose coating only. The
2585 dx.doi.org/10.1021/ie301785a | Ind. Eng. Chem. Res. 2013, 52, 2582−2589
Industrial & Engineering Chemistry Research Article

for more homogeneous deposition and a further reduction in

WVTR. This clearly shows the importance of rendering the
surface smooth and nonporous in order to maximize the hold
out of the alkyd resin layer.
In order to obtain a more optimal situation, the substrate was
changed to one that originally had a more closed surface (i.e.,
substrate C). The surface of the substrate was further improved
by nanocellulose precoating and the alkyd resin used was now
water-based in order to render the system more environ-
mentally friendly.
The WVTR of substrate C decreased with single (3 g/m2)
Figure 3. Water vapor transmission rate at 23 °C and 50% RH vs coat and double (6 g/m2) layered coatings of nanocellulose (Table
weight for an alkyd resin-coated substrate O. (■) Nanocellulose 3). At 23 °C and 50% RH, the WVTR was decreased from 90
precoated substrate O and (□) substrate O. to 29.4 g/m2 day by 3 g/m2 nanocellulose and to 30.7 g/m2 day
by 6 g/m2 nanocellulose. A similar reduction in WVTR was
WVTR decreased from 517 to 73 g/m2 day with the application obtained with the nanocellulose coating at 23 °C and 80% RH.
of 3 g/m2 of nanocellulose followed by 14 g/m2 of alkyd resin. Thus it appears that a dense nanocellulose film is achieved
It is somewhat unexpected that nanocellulose alone improves already at a low coat weight.
water vapor barrier properties of the paperboard. Nanocellulose Substrate C was further coated with alkyd resin dispersion
is highly hygroscopic and associated with an increased moisture before and after it had been precoated with nanocellulose, and
uptake with increasing RH.4 Water molecules adsorbed to the the ability of the alkyd resin to act as a moisture protective layer
surface or in the amorphous zones of the fibrils may disrupt was again studied by measuring the WVTR. An alkyd resin coat
hydrogen bonding and weaken the fibril/fibril joint formation, weight of 20 g/m2 was used in order to create a dense alkyd
resulting in increased mobility of the fibril network. This could resin layer and to avoid the formation of pinholes in the layer.
create additional sites for the permeation of, e.g., oxygen and Remarkable increases in moisture barrier properties were
water vapor and increased mobility of penetrating molecules observed for all of the alkyd resin coated samples (Table 3).
within the polymer network. The reduction in WVTR is At 23 °C and 50% RH, the WVTR of the nanocellulose
probably due to surface densification and the partial closure of precoated substrates was reduced by approximately 1 order of
the surface pores by the nanocellulose. Water molecules might magnitude by top-coating with wTO73 and even more with
be strongly adsorbed to the surface or in the amorphous zones wLO73, whereas the reduction in WVTR was approximately
of the nanofibrils which could result in lower water vapor 50% using wTO63. The WVTR of bare substrate C was reduced
transmission through the nanocellulose film. by approximately 2 orders of magnitude by nanocellulose
It is clear that pretreatment by nanocellulose has a strong precoating followed by wLO73 top-coating. Similar trends can
impact on WVTR for thin alkyd resin layers, but the effect is be observed at 23 °C and 80% RH. Coating with alkyd resins
reduced as the thickness of the alkyd resin layer increases. A only, without nanocellulose precoating also gave significant
precoated nanocellulose layer of 3 g/m2 efficiently creates a improvements, but not to as large extent as when the substrate
dense, smooth layer for the alkyd resin printing step that allows had been precoated.

Table 3. Water Vapor Transmission Rate (WVTR, g/m2 day) and Water Vapor Permeability (WVPcoating, g mm/m2 day atm) of
Nanocellulose (NFC)/Alkyd Resin Coatings on Substrate C at 23°C and 50% RH, 23°C and 80% RH and 37.8°C and 90%,
Respectively
WVTR WVPcoating
base substrate and coatings 23 °C, 50% RH 23 °C, 80% RH 37.8 °C, 90% RH 23 °C, 50% RH 23 °C, 80% RH 37.8 °C, 90% RH
substrate C before treatment 90.0 224 603 1707a 2655a 2722a
wLO73, 20 g/m2 9.4 28.9 202 14.0 27.7 64.2
wTO73, 20 g/m2 12.6 34.1 19.6 33.6
wTO63, 20 g/m2 11.9 36.0 18.3 35.8
NFC, 3 g/m2 29.4 104 >1200 6.2 17.1 >40
NFC, 3 g/m2 and wLO73, 20 g/m2 2.0 17.2 104 3.0 18.8 36.6
NFC, 3 g/m2 and wTO73, 20 g/m2 4.2 17.1 6.5 18.3
NFC, 3 g/m2 and wTO63, 20 g/m2 13.2 19.2 22.8 21.2
NFC, 6 g/m2 30.7 107 13.2 36.2
NFC, 6 g/m2 and wLO73, 20 g/m2 0.8 12.7 1.3 13.6
NFC, 6 g/m2 and wTO73, 20 g/m2 3.1 16.3 5.2 17.8
NFC, 6 g/m2 and wTO63, 20 g/m2 12.5 17.9 23.5 19.7
PLA7 117
arbinoxylan41 201
cellophane42 2326
polystyrene42 68
LD-PE 7.3 7.2 6.9

a
WVPcoating based on a substrate thickness of 263 μm

2586 dx.doi.org/10.1021/ie301785a | Ind. Eng. Chem. Res. 2013, 52, 2582−2589

Industrial & Engineering Chemistry Research Article

The improvement using nanocellulose is due to at least two thickness of the alkyd resin/nanocellulose multilayer is less than
effects. First, the layer of nanocellulose seals the surface and 25 μm, the results imply that high moisture barrier properties,
creates a surface layer with low porosity, and thus reduces the especially related to the wLO73 nanocellulose and wTO73
WVTR compared to the bare substrate. Second the layer nanocellulose coatings, were achieved and that this application
smoothes the surface and thus allows for a more homogeneous can be an effective solution to extend the application of paper
alkyd resin deposition with high hold out. The second based materials in e.g. the food packaging area, thus avoiding
conclusion is also supported by the fact that WVTR became the use of oil-derived products.
slightly lower when the coat weight of nanocellulose was Due to different WVTR measuring methods, bare substrate
increased from 3 to 6 g/m2. This increase in coat weight did thickness and permeability, it is difficult to compare the WVTR
not result in lower WVTR in absence of alkyd resin deposition presented here with previously published data. Therefore, to
but it made the surface smoother as is evident from Figure 2 assist comparability and to further evaluate the effect of alkyd
and thus a more optimal deposition of the alkyd resin layer. resin/nanocellulose coating on the moisture barrier properties,
Additional WVTR measurements on bare substrate C, the water vapor transmission rate (WVTRcoating) and hence the
nanocellulose precoated, alkyd resin-coated (wLO73) and water vapor permeability of the coating layers (WVPcoating) were
wLO73/nanocellulose-coated substrates were performed at determined (Table 3). The WVTR of the alkyd resin/
37.8 °C and 90% RH. Major improvements in moisture barrier nanocellulose coating, WVTRcoating, and base substrate,
properties were observed, especially associated with the WVTRsubstrate, was calculated from the WVTR of the multi-
substrate that had been nanocellulose precoated. The WVTR layer-coated substrates, WVTRtot, according to eq 147
of substrate C decreased from 603 to 104 g/m2 day by
nanocellulose precoating (3 g/m2) followed by wLO73 top- 1 1 1
coating. Nanocellulose precoating (3 g/m2) resulted in a + =
WVTR coating WVTR substrate WVTR tot (1)
WVTR of >1200 g/m2 day, above the detection limit of the
instrument. The high WVTR value for the nanocellulose Equation 1 is based on the assumption of well-defined and
precoated substrate is probably related to a significant moisture uniform coating layers with no defects and interpenetrating
uptake and corresponding swelling of the nanocellulose film.
layers, thus the WVPs presented here are presumably slightly
Nanocellulose films are associated with an exponential moisture
overestimated.
uptake as a function of RH.4 Alkyd resin coating alone resulted
The coated layers of substrate C (6 g/m2 of nanocellulose
in a WVTR of 202 g/m2 day.
precoating followed by wLO73 top-coating) exhibited a WVP of
The WVTR at 23 °C and 50% RH for substrate O precoated
1.3 and 13.6 g mm/m2 day atm at 23 °C and 50% RH and 23
with 3 g/m2 of nanocellulose followed by wLO73 was measured
°C and 80% RH, respectively. Under tropical conditions, 37.8
as 9.1 g/m2 day. A similar coating procedure on substrate C
resulted in a WVTR of 2 g/m2 day (Table 3), indicating that a °C and 90% RH, the coated layers of substrate C (3 g/m2 of
dense, nonporous surface is indeed essential for optimal barrier nanocellulose precoating followed by wLO73 top-coating)
performance. exhibited a WVP of 36.6 g mm/m2 day atm. The WVP of
Substrate C coated with wLO73/nanocellulose (0.8 g/m2 LDPE was determined to be 7.3, 7.2 and 6.9 at 23 °C and 50%
day) and wTO73/nanocellulose (3.1 g/m2 day), respectively, is RH, 23 °C and 80% RH and 37.8 °C and 90% RH, respectively.
shown to exhibit one of the lowest WVTR reported for Thus, at 23 °C and 50% and 23 °C and 80%, respectively, the
biobased coatings and laminations at 23 °C and 50% RH. Hult WVP of the wLO73/nanocellulose coated layers are in the same
et al. demonstrated a WVTR at 25 °C and 50% RH of 7 g/m2 range as LDPE, whereas at tropical conditions, the WVP of the
day when laminating nanocellulose precoated greaseproof alkyd resin/nanocellulose coated layers are higher, but in the
papers with shellac.33 Edlund et al. coated polyethylene same region as LDPE. At tropical conditions, the WVP of the
terephthalate (PET) with wood hydrolysate containing 50% wLO73/nanocellulose coated layers are lower than that reported
of chitosan and showed a WVTR at 23 °C and 50% RH as low for polystyrene (68 g·mm/m2·day·atm) 42 and cellophane
as 0.16 g/m2 day.43 However, the authors used a rather thick (2326 g mm/m2 day atm).42 At 23 °C and 50% RH, the WVP
PET film (38 μm). Previously published data on petroleum- of the wLO73/nanocellulose coated layers are much lower than
based latex barrier coatings is very extensive. Earlier studies for that reported for other biobased packaging materials, including
example include cross-linked and carboxylated styrene- arbinoxylan (201 g mm/m2 day atm) 41 and polylactic acid
butadiene latex coating on commercial paperboard. The (PLA) (117 g mm/m2 day atm).7
authors achieved a WVTR of < 10 g/m2 day at 23 °C and Surprisingly, the WVPcoating of nanocellulose at 23 °C and
50% RH with a coating thickness of ca. 150 μm.44 Earlier 50% RH is low; 6.2 and 13.2 g mm/m2 day atm at coat weights
studies also include water-based coatings of commercial of 3 and 6 g/m2, respectively. As discussed earlier, nano-
linerboard using coating formulations with different ratio of cellulose seals the pores of the base substrate already at very
styrene-butadiene latex and kaolin clay.45 A clay/latex solid low coat weights which might contribute to the low WVPcoating
ratio of 1:1 and a coat weight of 15 g/m2 resulted in a WVTR values. At 37.8 °C and 90% RH, the WVPcoating of nanocellulose
of 18 g/m2 day at 23 °C and 50% RH. Another widely used is considerably higher; > 40 g·mm/m2·day·atm due to
method for creating a barrier layer is lamination or coextrusion moisture-induced swelling of the nanocellulose layer.
with high-barrier polymers, such as PET in combination with It is possible to draw conclusions regarding the impact of the
polyethylene (PE). Common flexible packaging films based on chemistry of the alkyd resins on the barrier properties of the
coextrusion of PET/PE exhibit a WVTR of 4−6 g/m2 day at 23 material. As expected, increased oil length (increased fatty acid
°C and 80% RH.46 content) improved the WVTR. An alkyd resin with a higher oil
As far as WVTR is concerned, a material can be considered a length has a higher density of fatty acid chains which will
“high moisture barrier” if values are lower than 5 g/m2 day (at facilitate efficient polymerization and the formation of a highly
25 °C, 50% RH) for a 25 μm thick film).33 Given that the cross-linked hydrophobic polymer layer.
2587 dx.doi.org/10.1021/ie301785a | Ind. Eng. Chem. Res. 2013, 52, 2582−2589
Industrial & Engineering Chemistry Research

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Article

Comparisons could also be made between alkyd resin based ACKNOWLEDGMENTS

on tall oil and linseed oil at the same oil length, i.e., 73. The
The authors thank the Wallenberg Wood Science Centre for
results showed that the alkyd resin based on linseed oil was the
financial support. Joanna Hornatowska is gratefully acknowl-
most efficient one in terms of reducing WVTR. This is also
edged for her assistance with the E-SEM measurements. Anni
expected and can be explained by the fatty acid composition
Hagberg and Lucyna Lason are acknowledged for their
and the degree of unsaturation in the two vegetable oils. About
50% of the fatty acid of linseed oil is linolenic acid, which laboratory assistance. Dr. Göran Flodberg is acknowledged
contains three double bonds. The content of linolenic acid in for his valuable discussions.
tall oil is low, typically around 10% 35 or below.48 The content
of oleic acid (one double bond) on the other hand is around
50% and that of linolic acid (two double bonds) is around 35%.
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