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The Improvement of Water Resistance Property of Paperboard by SF6 Plasma

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 PACKAGING TECHNOLOGY AND SCIENCE
Packag. Technol. Sci. 2012; 25: 19–30
Published online 27 June 2011 in Wiley Online Library (wileyonlinelibrary.com) DOI: 10.1002/pts.953

PAPER PRESENTED AT IAPRI SYMPOSIUM 2011, BERLIN

Effects of Treatment Time by Sulphur Hexafluoride (SF6) Plasma
on Barrier and Mechanical Properties of Paperboard

By T. Jinkarn,1* S. Thawornwiriyanan,1 D. Boonyawan,2 P. Rachtanapun3 and S. Sane1

1
Department of Packaging and Materials Technology, Faculty of Agro‐Industry, Center of Advanced Studies for
Agriculture and Food, KU Institute for Advanced Studies, Kasetsart University, Bangkok 10900, Thailand
2
Fast Neutron Research Facility, Department of Physics, Faculty of Science, Chiang Mai University, Chiang Mai 50200, Thailand
3
Department of Packaging Technology, Faculty of Agro‐Industry, Chiang Mai University, Chiang Mai 50100, Thailand

Sulphur hexafluoride (SF6) plasma, using inductively coupled plasma technique, was applied on paperboard
surfaces. Effects of different treatment times on water and oil resistances, mechanical properties (through tensile,
compression and folding endurance tests) and barrier properties [through water vapor transmission rate (WVTR)
and oxygen transmission rate (OTR)] were determined. Results showed that SF6 plasma treatment can improve
water resistance properties of paperboard significantly, beginning with only a 2 s treatment time (p ≤ 0.05),
whereas oil resistance properties can be improved over a longer time period. Plasma treatment had no effect on
tensile strength of treated paperboard; however, machine direction (MD) compression strength, as well as MD and
CD folding endurance, of treated paperboard was significantly lower than that for an untreated sample (p ≤ 0.05).
WVTR and OTR of treated paperboard were higher with increasing treatment time, because of fluorine atoms and
electron bombardment causing etching of cellulose fibres. Copyright © 2011 John Wiley & Sons, Ltd.

Received 7 December 2010; Revised 30 March 2011; Accepted 4 April 2011

KEY WORDS: sulphur hexafluoride (SF6); plasma treatment; paperboard; barrier properties; mechanical properties

INTRODUCTION

Paperboards are cellulose polymers and are considered one of the most practical packaging materials.
However, one critical drawback of paperboard is its hydrophilic nature. Paperboards are prone to absorb
water from the environment, especially when stored under high humidity conditions or when coming into
contact with high‐moisture products such as fresh agricultural produce. Absorption of moisture reduces the
physical and mechanical strengths of paperboard, causing corruption of packages during storage and
distribution. Surface treatments such as sizing, coating and laminating are usually used to improve
physical strength as well as water barrier properties.1,2
A water barrier can be formed by changing paper surface characteristics with sizing agents, or through
coating with hydrophobic materials. The main purpose of sizing is to reduce water wettability, whereas
paraffin wax applied in a molten form and polyethylene (PE) applied by extrusion on paper or paperboard
are commonly used to reduce water vapour penetration. However, the PE and paraffin content of
packaging materials make it difficult to separate, recycle or compost them after use, because wax particles
cannot be cleanly separated from paper fibre during mechanical pulping.3,4
A wide range of conservation and protection techniques have been developed to prevent paper
deterioration. Most of these methods are based on chemical and mechanical principles.5–10 When applying

* Correspondence to: T. Jinkarn, Department of Packaging and Materials Technology, Faculty of Agro‐Industry, Center of
Advanced Studies for Agriculture and Food, KU Institute for Advanced Studies, Kasetsart University, Bangkok 10900, Thailand.
E‐mail: [email protected]

Copyright © 2011 John Wiley & Sons, Ltd.

20 T. JINKARN ET AL.

chemical methods, the influence of chemicals on paper properties, as well as environmental impact, must
be taken into account. A new conservation method may be a plasma treatment, which is a well‐established
technique in a number of other processes (e.g. plasma coating, etching, cleaning). In recent years, the
influence of low‐temperature plasma on paper, textile and biopolymers has been extensively studied.11–18
Various gases and vapours of liquids can be used as starting plasma for discharging ions, depending on
the purposes of the study.19,20 For cellulose‐based materials, if a fluorine‐containing compound is used as
the treating gas, it is possible to obtain a water‐resistant surface owing to the fluoro‐functional groups
created on the surface that lowers the surface energy. The fluoro‐compound can be selected from such
compounds as tetrafluoride (CF4), hexafluoroethane (C2F6), hexafluoropropylene (CF3CFCF2),
octafluorocyclobutane (C4F8), monochlorotrifluorocarbon (CCLF3) and sulphur hexafluoride (SF6), as
well as other fluoro‐sulphur compounds.21 Some published studies in recent years have also shown that
water resistance improvement can be imparted to cellulose fibres through low‐temperature plasma
treatment employing fluorine‐based gases.22–26 However, different liquids and gases as plasma ion
sources, as well as different plasma conditions, can result in different surface characteristics.19
Paper and cellulose materials treated with fluorochemicals by a plasma treatment method offer some
advantages over polymer‐coated paper or laminates. For example, paper treated with fluorochemicals
provides the flexibility of being able to vary the amount of fluorochemicals used, to control the degree
of water repellency required for a particular application.3 In general, plasma treatment methods do not
produce chemical wastes and waste disposal problems, and they can be fully automated. The treatment
methods demonstrate a high efficiency of surface activation for various materials through the actions
of ultraviolet photons, radicals and charged particles (electrons and ions).27 Also, paper treated with
fluorochemicals can be easily recycled, whereas polymer extrusion coatings and waxes must be
separated from the paper during the recycling process.1,3,28
Water resistance, which is a typical characteristic of fluorinated polymers, can be imparted to
natural fibres through the application of fluorine‐containing resins, thus creating outstanding water
resistance properties. On the other hand, low‐temperature plasma treatments are known to induce
physical and chemical surface changes in polymers through etching, grafting, polymerization and/or
cross‐linking processes, without changing their bulk properties.29–33 Plasma species do not penetrate
below about 10 nm of the surface; therefore, the rest of the paperboard’s chemical structure remains
totally unmodified during the plasma treatment.31,34,35
Because demand for environmentally friendly packaging using renewable resources with high water
resistance and oil barrier properties is increasing, further investigation on the effect of plasma
technology on biodegradable packaging materials such as paperboard is needed. In the present work,
the paperboard selected was a single‐side coated duplex board for packaging applications, with a basis
weight of 300 g/m2. An SF6 radio frequency (RF) plasma reactor was used to generate fluorine ions.
The main objective of this research is to determine the effects of treatment time on water and oil
resistances as well as on the mechanical and barrier properties of paperboard.

EXPERIMENTAL

Materials
Single‐side coated duplex board with a basis weight of 300 g/m2 was used for the plasma treatment. The
paperboard was supplied by Thai Union Paper Industry Co., Ltd., Bangkok, Thailand. The front or top
surface of the paperboard was pre‐coated with CaCo3 and starch‐based compounds, resulting in a clean,
white‐coloured surface, whereas the back surface was left uncoated and had the colour of unbleached
recycled pulp. Sulphur hexafluoride (SF6) gas was obtained from Thai Industrial Gases Co., Ltd. A low‐
temperature plasma system was provided by the Fast Neutron Research Facility, Department of Physics,
Faculty of Science, Chiang Mai University, Thailand.

Plasma treatment
The vacuum chamber consists of a series of cylindrical glass tubes with a diameter of 9 cm and a
height of 16 cm, with several ports for diagnostics. The chamber was evacuated to a residual pressure

Copyright © 2011 John Wiley & Sons, Ltd. Packag. Technol. Sci. 2012; 25: 19–30
DOI: 10.1002/pts
 EFFECTS OF SF6 PLASMA ON PROPERTIES OF PAPERBOARD 21

of 10−3 Torr by a rotary pumping system. A system similar to that used in this study can be found in
previous research.35
Actual operating gas pressure in the reactor was manually controlled by a needle valve connected to
the SF6 gas feeding system. The gas pressure was kept constant at 100 mTorr. During the operation,
pressure inside the plasma chamber was monitored by a Pirani vacuum gauge. Inductively coupled
plasma discharge (ICP) technique was applied to generate the plasma by utilizing an RF power supply
(CESAR® 1310; Advanced Energy, Fort Collins, CO, USA) with a frequency of 13.56 MHz. The
operating power of the RF was kept constant at 50 W. During plasma treatment, a single piece of
paperboard sample cut to a size of 6 × 16 cm was suspended in the middle of the vacuum chamber,
allowing excited fluorine ions to attach to carbon atoms on both surfaces.

Characterization of plasma‐treated paperboard

After exposure to SF6 plasma at specific treatment times (2, 10, 60 and 600 s), the physical properties
of the paperboard samples – basis weight, thickness and moisture content – were investigated. Basis
weight measurement procedure was modified from ASTM D646 (sample size is smaller at 6 × 16 cm),
thickness measurement was evaluated according to ASTM D645 and moisture content was evaluated
following ASTM D644.
The water resistance property of paperboard samples was investigated by contact angle, absorption
time and Cobb test method. The contact angle of pure water on each paperboard sample was measured
by a comparatively simple method previously performed by Selli et al.36 Photographs of the 40 µl
water droplets on the paperboard were transferred to a personal computer, and the contact angles were
calculated manually using the AutoCAD 2006 program. Absorption time is the time in minute for a
droplet of water to be fully absorbed into the paper surface. The absorption times of 40 µl water
droplets on different samples were also determined following similar studies.36,39 The amount of water
absorption for a specific time period was measured by Cobb test method (modified from ASTM
D3285 by using a smaller sample size of 6 × 6 cm).
The barrier properties of paperboard samples, including oil resistance as well as water vapour
(WVTR) and oxygen permeability (OTR) were also investigated using a Permatran‐W model 398
(Mocon, Minneapolis, MN, USA) and a model 8500 oxygen permeation analyzer (Illinois
Instruments, Johnsburg, IL, USA), respectively. Oil resistance property was measured using the
same techniques as that for water resistance property. The testing oil selected was a general vegetable
oil commercially found on the market. WVTR measurement was modified from ASTM E96 standard
procedure (smaller sample size with a total test area of 0.28 m2), and OTR evaluation was performed
according to ASTM D3985.
Mechanical properties of paperboard samples – tensile strength, ring crush resistance and folding
endurance – were investigated according to ASTM D828, TAPPI T818 and ASTM D2176, respectively.
Tensile strength and ring crush resistance were measured using a Testometric M350 (Testometric, Co.,
Ltd, Rochdale, England), and folding endurance was tested using a Toyoseiki model 530 (Toyoseiki
Co., Ltd, Tokyo, Japan).
The surface of each paperboard sample was analysed using scanning electron microscopy (SEM) and
X‐ray photoelectron spectrometry (XPS). SEM measurements were conducted using a Philips XL30
(Philips, Eindhoven, the Netherlands), and XPS results were analysed by a Perkin Elmer (Waltham, MA,
USA) PHI 5400 ESCA system (MG anode, 200 W, 10 kV).

RESULTS AND DISCUSSION

Hydrophobicity improvement of paperboard

Plasma treatment can significantly improve the hydrophobicity property of paperboard (p ≤ 0.05). The
results can be observed from water contact angle and water absorption characteristics on the paperboard
surface (Figures 1 and 2).
Figure 2 shows water contact angle, absorption time and amount of water absorbed (Cobb test) of
the treated samples. According to the results, the water resistance property of treated paperboard is

Copyright © 2011 John Wiley & Sons, Ltd. Packag. Technol. Sci. 2012; 25: 19–30
DOI: 10.1002/pts
22 T. JINKARN ET AL.

(a) (b)

Figure 1. Images of water droplets on paperboards: (a) front surfaces and (b) back surfaces.

(a)

(b)

(c)

Figure 2. Water resistance of paperboard samples: (a) contact angle, (b) absorption time and (c) Cobb
test (amount of oil absorption).

significantly improved, as can be observed from the increase of contact angle and absorption time and
from the decrease of water absorption.
As shown in Figure 2a, the water contact angle increases up to approximately 110° to 145° for all
treatment times (2, 10, 60 and 600 s), whereas the contact angle of untreated paperboard is
approximately 25° for the back surface and 70° for the front surface. The contact angles observed in this

Copyright © 2011 John Wiley & Sons, Ltd. Packag. Technol. Sci. 2012; 25: 19–30
DOI: 10.1002/pts
 EFFECTS OF SF6 PLASMA ON PROPERTIES OF PAPERBOARD 23

study are considered higher than the contact angles found for most hydrophobic papers coated with
conventional biodegrading or sizing substances.37,38 The results also clearly show the effect of treatment
time; it can generally be concluded that the longer the treatment time, the higher the contact angle.
However, after 60 s treatment time, only a slight improvement is detected, and no significant
improvement is found between the 60 and 600 s treatment times. In comparison with similar studies, the
contact angles of treated paperboards in this research are approximately the same as the hydrophobicity
improvement measured in plasma‐treated Thai silk (Grazie™) in previous studies.35,39
Higher contact angles found with increasing treatment time can be explained by the fact that with a
longer treatment time, fluorine atoms derived from SF6 plasma ionization are able to replace more
oxygen and hydrogen atoms within the cellulose structure; therefore, more CF–CF groups are
distributed on the paper surface (Figure 3). In comparing the front and back surfaces, contact angles
are rapidly improved for the back surface. Water resistance could be derived from synergistic effects
of the plasma treatment and surface roughness. Rough surfaces of hydrophilic materials on the back
surface of the paperboard were first modified to become more hydrophobic; hydrophobicity was then
further strengthened by surface roughness of the paperboard’s back surface, according to the Cassie
law.40,41 After this process, significant water resistance improvement can be observed. Fewer fluorine
atoms were detected on the front surface. This is because the coating substances on the front side
might obstruct the attachment of fluorine atoms, whereas the cellulose fibres of the back surface are
directly exposed to discharged ions. This claim can further be proved through XPS characterization,
which will be discussed in a later section. In addition, the front surface of the paperboard was coated
with starch‐based compounds and CaCO3 to achieve a smoother surface; therefore, hydrophobicity
cannot be further strengthened by surface roughness.
According to the results, water absorption time of treated back surfaces is an average of 13 min for
2 s treatment time and approximately 140 to 170 min for longer treatment times. However, the water
absorption time of an untreated back surface is only 1 min. For front surfaces, water absorption times
of both untreated and treated samples are longer than 200 min. In general, the front surface of a
paperboard is usually coated with modified starches, CaCO3, sizing agents, and so on, because of the
need for surface smoothness, good printing ability and improvement of water resistance properties.42
Thus, water absorption can take several minutes without any plasma treatment.
For the Cobb test, the average amount of water absorbed when testing the untreated front surface is
1.53 g/m2; this can be reduced to 0.16 g/m2 for a plasma‐treated surface. In addition, the amount of
water absorbed on the back side of the untreated sample is 15.16 g/m2, which can be reduced to
approximately 2.97 to 3.63 g/m2 (Figure 2b) when treatment time is longer than 10 min.
Contact angles of water droplets on paper surfaces are reduced with longer contact time between
treated surface and the water droplet (Figure 4). A gradual reduction of contact angles is found for the
front surfaces of both treated and untreated samples. This could also be due to water absorption by
coating substances on the front surface. On the other hand, for the back surfaces, contact angles

Figure 3. Schematic diagram of SF6 plasma treatment on a paperboard surface.

Copyright © 2011 John Wiley & Sons, Ltd. Packag. Technol. Sci. 2012; 25: 19–30
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24 T. JINKARN ET AL.

(a)

(b)

Figure 4. Dynamic contact angles of paperboard samples: (a) front surfaces and (b) back surfaces.

decrease rapidly over time for 2 s treatment. However, with a longer treatment time, especially for 60
and 600 s treatments, contact angles appear to remain unchanged. Because more CF–CF groups are
found on the back surface at longer treatment times, the hydrophobicity property of the back surface of
the paperboard can be improved when treatment time is longer, which in this study was found to be
approximately 60 s. For 2 s treatment time, although CF–CF groups are present, fewer fluorine atoms
are detected on the surface; therefore, water can easily enter the porous structure of the paperboard and
penetrate the cellulose fibres.

Mechanical properties of paperboard

Effects of SF6 plasma treatment on mechanical properties of treated samples are shown in Figure 5.
Plasma treatment had no effect on tensile strength of treated paperboard; however, machine direction
(MD) compression strength, as well as MD and cross direction folding endurance, of treated
paperboard was significantly lower than for the untreated sample ( p ≤ 0.05). The results show that
plasma treatment can decrease the strength of paperboard, which conforms to other research.16 This is
because broken cellulose chains are produced under the influence of particle bombardment.16,33

Barrier properties of paperboard

To evaluate barrier properties of paperboard in terms of lipophobic property, the oil resistance of
treated samples was studied. Figure 6 shows the results of oil contact angle, oil absorption time and
Cobb test for the treated samples. According to the results, plasma treatment significantly improves
the oil resistance property of treated paperboard ( p ≤ 0.05). This finding is in accordance with
previous studies.3,13

Copyright © 2011 John Wiley & Sons, Ltd. Packag. Technol. Sci. 2012; 25: 19–30
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 EFFECTS OF SF6 PLASMA ON PROPERTIES OF PAPERBOARD 25

(a)

(b)

(c)

Figure 5. Mechanical properties of paperboard samples: (a) tensile strength, (b) ring crush resistance
and (c) folding endurance. MD, machine direction; CD, cross direction.

As shown in Figure 6a, the oil contact angles of treated front surfaces of paperboard increase up to
approximately 66° at above 60 s treatment time. However, for the untreated front surface, the
measurement could not be performed, as the oil droplet immediately flattened out with 0° contact angle.
The oil contact angles of treated back surfaces also increase up to approximately 71° at above 60 s
treatment time; the oil contact angle of the untreated surface is approximately 13°. For both surfaces,
oil absorption time is over 200 min for all treatments.
Cobb test results show that the average amount of oil absorbed over time for all treatments is
not significantly different. However, for back surfaces, oil absorption of treated samples at 600 s
treatment time decreases from 5 to 2 g/m2 (Figure 6b). It can be concluded that to enhance the oil
resistance property of SF6 plasma‐treated paperboard, the treatment time must be maintained for
at least 60 s or longer.
In this study, water vapour and oxygen permeability were evaluated through WVTR and OTR.
Barrier properties are important parameters for packaging materials, especially for plastic film
intended for primary packages. However, WVTR and OTR assessments are rarely performed for
paper materials because the materials themselves show no barrier to such factors. Furthermore,
paperboards are usually employed as secondary packages. However, in some cases, such as for ready‐
to‐eat foods, the application of paperboards as primary packages is increasing, and OTR as well as

Copyright © 2011 John Wiley & Sons, Ltd. Packag. Technol. Sci. 2012; 25: 19–30
DOI: 10.1002/pts
26 T. JINKARN ET AL.

(a)

(b)

(c)

Figure 6. Oil resistance of paperboard samples: (a) contact angle, (b) absorption time and (c) Cobb test.

WVTR is of primary concern.43 Further assessments of WVTR and OTR of plasma‐treated

paperboard can reveal the future possibilities of replacing petrochemical plastic materials with barrier
paperboard.
Figure 7 shows WVTR and OTR of treated paperboard. During the test, both surfaces of all
paperboard samples were subjected to direct contact with water vapour (typically at 95% relative
humidity) for the WVTR test and oxygen gas for the OTR test. The results show that water vapour
permeability of both surfaces of treated paperboard samples increases slightly with an increase in
treatment time. For OTR, at 10 s treatment time (or less), there were no significant differences between
treated and untreated samples for both front and back surfaces. In this study, a high increment of OTR
and significant differences between front and back surfaces were only found at treatment times longer
than 10 s.
According to other studies, fluorine atom and ion bombardment can etch the polymer surface.44,45
Therefore, beyond a critical threshold of treatment time, the SF6 plasma will begin to etch or degrade
the surface of paperboard. The etching found is typically in the 500–1000 Å range.46,47 Moreover,
longer treatment time not only can cause an unsmooth appearance of the surface but also might further
deteriorate the entire material structure, causing a ‘spongelike’ matrix of the paperboard, which in turn

Copyright © 2011 John Wiley & Sons, Ltd. Packag. Technol. Sci. 2012; 25: 19–30
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 EFFECTS OF SF6 PLASMA ON PROPERTIES OF PAPERBOARD 27

(a)

(b)

Figure 7. Permeability of paperboard samples: (a) water vapour transmission rates and (b) oxygen
transmission rates.

increases the water vapour and oxygen or gas permeability.45 Thus, although SF6 plasma applications
can increase water resistance properties, the treatment time must be controlled at an optimal level to
prevent deterioration of materials under high‐moisture conditions during long‐term storage.

Surface morphology
Figure 8 displays SEM images of cellulose fibres of paperboard. The images show that SF6 plasma
treatment had no effect on the surface morphology of paperboard samples; this is because plasma
species usually do not penetrate below 10 nm of the surface.28,31,32 However, at a longer treatment
time, such as 600 s for this study, cellulose fibres seem to show a rough surface, which is mainly due
to plasma etching.
Further surface analysis was conducted by XPS to investigate the number of fluorine atoms on the
paper surface as a function of treatment time. The results confirm that with an increase in treatment
time (Table 1), more fluorine atoms are present on both front and back surfaces. In addition, more
fluorine atoms are detected on the back surfaces than on the front. This is due to more carbon atoms at
the surface being exposed to the SF6 plasma treatment without any blocking from coating substances.

CONCLUSIONS

SF6 plasma‐treated paperboard exhibits different water and oil resistances at certain plasma treatment
times, whereas the basis weight and thickness of the paperboard were not affected. In this study,
significant hydrophobicity improvement can be found beginning with only a 2 s treatment time. A
hydrophobic paper surface can be obtained by fluorine ions creating C―F bonding, which strongly
resists polar molecules such as H2O. At present, this technique can be effectively applied for water
droplet resistance. However, for water vapour resistance, it may be necessary to modify the paper
sample to achieve a denser structure prior to plasma treatment.

Copyright © 2011 John Wiley & Sons, Ltd. Packag. Technol. Sci. 2012; 25: 19–30
DOI: 10.1002/pts
28 T. JINKARN ET AL.

Figure 8. Scanning electron microscopy micrographs of cellulose fibres of paperboard samples at

×5000: (a) front surface of an untreated sample; (b) front surface of a treated sample at 600 s, (c) back
surface of an untreated sample and (d) back surface of a treated sample at 600 s.

Table 1. Atomic percentage (%) of the samples.

Sample F O N Ca C S Si Al
Front side 10 s treated 1.4 23.9 0.4 6.3 62.9 – 2.8 2.4
Back side 10 s treated 17.8 20.4 1.0 1.1 58.2 – 0.7 0.9
Front side 60 s treated 13.4 17.0 0.9 2.5 61.0 2.9 1.2 1.0
Back side 60 s treated 18.7 20.8 1.0 1.7 56.5 0.8 0.5 –
Front side 600 s treated 28.1 11.4 – 10.4 45.5 – 2.3 2.3
Back side 600 s treated 30.9 17.4 0.4 1.7 48.2 – 0.5 1.0
Note: Residual pressure about 10−8 Pa.

Drawbacks that were found were significantly lower compression strength as well as lower folding
endurance of treated paperboard due to particle bombardment that caused etching of cellulose fibres,
especially at longer treatment times. OTR and WVTR of treated paperboard were also higher, which
may be due to particle bombardment as well.
Results of surface characterization confirmed that SF6 plasma treatment for hydrophobicity
improvement was more effective on the uncoated paperboard surface because carbon atoms were
freely exposed to fluorine ions without any blocking from coating substances; hydrophobicity was
also further strengthened by surface roughness of the paperboard’s back surface.

ACKNOWLEDGEMENTS

The authors would like to thank Thai Union Paper Industry Co., Ltd., Thailand, for supplying duplex board
and the Neutron Research Facility, Department of Physics, Faculty of Science, Chiang Mai University,
Thailand, for the use of an inductively coupled plasma discharge unit. Finally, Kasetsart University,
Thailand, is gratefully acknowledged for financial support through the NRU project (Bio‐based and Smart
Materials for Packaging Industry).

Copyright © 2011 John Wiley & Sons, Ltd. Packag. Technol. Sci. 2012; 25: 19–30
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 EFFECTS OF SF6 PLASMA ON PROPERTIES OF PAPERBOARD 29

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