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A new potential paper resource; Recyclability of paper cups coated with water-
soluble polyacrylate-based polymer

Article  in  Nordic Pulp and Paper Research Journal · March 2017


DOI: 10.3183/NPPRJ-2017-32-01-p155-161

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A New Potential Paper Resource;
Recyclability of Paper Cups coated with
Water-soluble Polyacrylate-based Polymer
Tai Ju Lee, Cheol Yoon and Jeong Yong Ryu

KEYWORDS: paper cups, polyacrylate, paper substrate with synthetic films to compensate
recyclability, flake, kneading, beating the defects of paper. Such synthetic films as a water
SUMMARY: Paper cups are typically made by barrier have several advantages. They can be easily
laminating PE or PLA onto the surface of paper. PE handled and formed with heat. In addition, water or
and PLA are hydrophobic and easy for film formation. beverages cannot directly contact the paper surface
However, recycling of PE- or PLA-coated paper cups due to the synthetic resin laminating layer. Various
is difficult. Polyacrylate (PA)-based polymers may be barrier materials have been investigated by many
an alternative to PE and PLA, and recycling of researchers. Among these barrier materials,
polyacrylate-coated paper cups may be considered polyethylene (PE) and polylactic acid (PLA) were
if the barrier film can be disintegrated. The chosen in this study. PE is the most common plastic;
recyclability of paper cups coated with PE-, PLA-, it has low strength, hardness, and rigidity, and is very
and PA-based polymers was investigated by pilot hydrophobic and non-biodegradable. Owing to these
pulper and screen. Furthermore, mechanical properties, PE has been used in the manufacture of
treatments were investigated for the removal of packaging materials in various fields including those
remaining polyacrylate flakes (RPF). The pulping of food packaging (Palma, et al., 2015; Hannon, et
yield of PA-coated paper cups was higher than that al., 2015), antioxidant coatings (Mahiyan et al. 2015),
of PE- or PLA-coated paper cups, since PE or PLA anti-bacterial coatings (Xu et al. 2015), and other
films were discarded as hole screen rejects. In the barriers (Ge, et al., 2015; Nakaya, et al., 2015) PLA,
case of PA-coated paper cups, RPF could not be on the other hand, is biodegradable, versatile, and
separated by slot screening due to its deformability. hydrophobic. According to previous research, PLA
However, RPF must be treated properly since it can could be coated onto the surface of white duplex
result in specks on the surface of paper. RPF could board by simple heating to give it water resistance
be fragmented effectively, with over 95 % (ECOIN Inc., 2009). Cheng et al. (2015), on the other
disappearing after one pass of kneading and 10 min hand, focused on the coating performance of PLA.
of beating. Consequently, it may be possible to use In their study, they improved the properties of PLA
PA-coated paper cups as a raw material in the paper as a paper coating material by the addition of
recycling process. modified gelatin. A new PLA-based hybrid coating
ADDRESSES OF THE AUTHORS: Tai Ju Lee was also studied as a barrier material, which was
(assorrow@kangwon.ac.kr): Senior researcher transparent and showed good barrier properties
Changgang Institute of Paper Science and against oxygen and water. However, paper cups
Technology, 1, Kangwondaehak-gil, Chuncheon-si, laminated by synthetic resins are very difficult to be
Gangwon-do, Republic of Korea, Cheol Yoon recycled with other recovered papers, since the
(cheolyoon@repaper.kr): Director, RePaper Inc., 1, laminating layer does not disintegrate by water and
Dongtanjungsimsangga-gil, Hwaseong-si, shearing forces in the paper recycling process.
Gyeonggi-do, Republic of Korea, Jeong Yong Ryu Moreover, with the increase in consumption of
(jyryu@kangwon.ac.kr): Professor, Dept. of Paper instant food and beverages, the demand of paper
Science & Engineering and 1, Kangwondaehak-gil, cups is increasing. In the light of the above, and
Chuncheon-si, Gangwon-do, Republic of Korea since the fibers in paper cups are valuable to use as
Corresponding author: Jeong Yong Ryu a raw material in papermaking, it is therefore
Paper, made of cellulose that is formed by 1-4 necessary to investigate recycling technologies of
linkage between glucoses, is typically very sensitive paper cups.
to water. Glucose has three free hydroxyl groups Recently, water-based coating agents as a water
that are attached to the number 2, 3, and 6 carbons. barrier was invented by Ahn, et al. (2003) They
Water can easily penetrate into a paper structure laminated the inner surface of paper cups with a
through pores, after which breaking of hydrogen hydrophilic coating agent that could possibly be
bonding can occur. A hydrophilic character and applied to food packaging. Those paper cups could
porous structure as a water barrier is therefore then be easily recycled compared to PE-laminated
inappropriate for paper cups. Therefore, paper cups paper cups. In addition, Yoon, et al. (2015) invented
are typically produced by laminating the surface of a an eco-friendly coating material for paper cups.
Silicone- and acrylate-based coating materials (b)
provided paper cups with good water and oil Fig 1 Monomer of PA-based polymer cited from
resistance, as well as biodegradability, and it was Yoon et al. (2015). (Rn = alkyl or arly group)
demonstrated that the paper cups coated with these Apparatus
materials could be easily recycled. Pilot pulper
Slushing or pulping can separate pulp into individual A pilot pulper as shown in Fig 2 was used for the
fibers and make a pumpable slurry. This stage is the slushing process of paper cups. This pulper was a
primary unit in the papermaking process and occurs low consistency pulper. The vat of the pulper was
in a pulper. In brief, pulp or recovered paper and comprised of cylindrical stainless steel. Slushing
processing water are introduced into a pulper; occurred by rotation of the rotor at the bottom of the
hydrogen bonding between the fibrous raw materials pulper. The inside of the pulper was equipped with
can then be broken by wetting, and shear forces baffles. After slushing, a slurry could be obtained
generated by a rotor promote the defibration. When through the gateway valve. The total volume of the
slushing is finished, a pumpable slurry is fed to a pilot pulper was 20 L (Amend, et al., 1997).
high-density cleaner and screening stages through
a perforated plate at the bottom of the pulper.
Therefore, the screening and cleaning efficiency will
be dependent on the initial stage. If slushing is poor,
the process runnability and the properties of the final
products will also be poor.
As mentioned above, a PA-based coating could be
a new method to produce eco-friendly paper cups in
terms of improved recyclability. In order to confirm
Fig 2 - Pilot pulper cited from Lee et al. (2015)
whether poly acrylate-based coating materials would
be a good alternative to PE or PLA, the recyclability
of the newly-developed paper cups must be verified.
Pilot screen
The purpose of screening is to remove debris and
In this study, the recyclability of paper cups using
flakes present in the slurry after slushing. This
different coating materials (PE, PLA, PA) was
screening process is an essential stage to evaluate
therefore evaluated by comparing the efficiency of
the recyclability of paper cups. As shown in Fig 3, a
slushing, screening, and flotation. Furthermore,
pilot screen was used for separation of the
mechanical treatments to improve the recyclability of
components in the slurry. This pilot screen has holes
PA-coated paper cups were also investigated.
with a diameter of 3 mm and slots with a width of 0.3
mm. Therefore, the screen can be separated
Materials and Methods sequentially according to particle size. Slurry could
Materials be pumped into the screen basket through the 3 mm
Three types of paper cups were investigated. Paper holes at the bottom of the screen. When particles are
cups were obtained from rePAPER Inc. (Gyeonggi- larger than these holes, that fraction was separated
do, Republic of Korea). PE, PLA, and PA-based as hole rejects. The slurry that passed through the
coating materials were coated onto the surface of holes was then separated by the slots. Fibers would
the same base paper with grammage of 300 g/m2. pass through the slots due to centripetal forces
Chemical structure of PA-based polymer can be generated by the rotatory power of the foils.
described in Fig 1. As shown in Fig 1, the monomer Simultaneously, flakes or debris with a size larger
of the polymer are silicone and polyacrylate. than the slot width was discarded as slot rejects.
Finally, three kinds of fraction were obtained from
the pilot screen.

.
(a)

Fig 3 - Pilot screen.

Somerville screen and flotation


After slushing and screening, the ratios of flakes,
fibers and fines in the slurry were analyzed using a
Somerville screen with 0.15 mm slots. Flotation
using a modified version of DeltaCell of Voith
(Germany) was performed in order to remove the
hydrophobic particles of the paper cups.

Kneader and beater


Remaining flakes during paper cup recycling can Fig 4 - Experimental flow for the evaluation of
become defects of recycled paper. Therefore, recyclability of paper cups.
unsegregated flakes must be broken down to fine
particles. A lab-scale twin-shaft kneader and valley
Investigation of mechanical treatments for
beater were used for the removal of residual
polyacrylate flakes (RPF). control of RPF
Undesired problems in terms of papermaking
efficiency and quality can be caused by RPF.
Experimental methods for evaluation of
Therefore, it is necessary to develop methods for the
slushing and screening efficiency control of RPF. Experimental conditions were set up
Fig 4 shows the experimental scheme for as shown in Fig 5 in order to control RPF by
recyclability evaluation of the three kinds of paper kneading and beating. Slushing conditions were
cups. First, slushing was performed using the pilot identical to those in Fig 4. At that stage, the effects
pulper. The slushing consistency was maintained at of slushing energy on the removal of RPF were
5% by using 1 kg paper cups with 19 L of water in investigated using variable pulping times. Kneading
the pulper. The hardness and temperature of the and beating were also performed in order to
water were set to 300 ppm and 45°C, respectively, fragment RPF that remained after slushing. The
and 0.05% non-ionic surfactant was added for slurry obtained after 10 min slushing was treated
removal hydrophobic residual substance, equal to with the kneader and beater, using a passing time of
the oven-dried weight of the paper cups. Slushing the kneader of 1-3 min and a beating time of 0-30
was performed at a rotor speed of 450 rpm for 20 min. Ratios of flakes, fibers, and fines of the slurry
min. After slushing, screening was performed using obtained after kneading or beating were analyzed by
the pilot screen. Accept, hole reject and slot reject Somerville screen. Finally, specks in the handsheets
fractions were obtained individually, and the mass were observed by image analysis. Images of the
balance after the screening stage was analyzed by handsheets were taken with transmittance light and
measurement of the oven-dried weight of each converted into binary images. After conversion, the
fraction. The “accept” fraction was then subjected to presence of black spots using different mechanical
flotation in order to segregate the hydrophobic treatments was compared.
contaminants. For this flotation stage, the
consistency of the slurry was adjusted to 1% and the
temperature set to 45°C. Flotation was implemented
at a rotor speed of 1,000 rpm for 8 min, with the air
flow rate set at 7 L/min. After the flotation stage, the
ratios of flakes, fibers, and fines of the flotation Fig 5 - Experimental scheme for control of residual
accept fraction were analyzed using the Somerville polyacrylate flakes (RPF).
screen and a 200 mesh screen. Handsheets were
subsequently fabricated of the flotation accept
fraction using a retention and drainage analyzer Results and discussion
(RDA, GIST Co. Ltd., Republic of Korea), a lab-scale Analysis of pilot screen and flotation
apparatus for making handsheets. Retention and rejects
drainage were analyzed simultaneously at vacuum Fig 6 shows the pilot screen and flotation rejects of
dewatering conditions. Therefore, the RDA could the three kinds of paper cups. As shown, hole screen
simulate the actual wet-end process in a paper rejects of PE- and PLA-laminated paper cups were
machine (Jeon, et al., 2010). The mean grammage 10.26 and 17.63%, respectively. The hole screen
of the handsheets was 60±3 g/m2. Paper properties reject of PA-coated paper cups was extremely low.
including density, strength and optical properties As shown in Fig 7, most of the rejects from PE- and
were measured. PLA-laminated paper cups were fragmented PE and
PLA films. All slot screen rejects were below 0.5%.
In terms of flotation reject fractions, those of PE- and
PLA-laminated paper cups were 0.21 and 0.42%,
respectively. The flotation reject fraction of PA-
coated paper cup was 1.52%. The much lower hole
reject fraction of PA-coated cups compared to that of
PE- and PLA-laminated paper cups indicated that
their slushing efficiency was better than that of PE-
and PLA-laminated paper cups. Moreover, the yield
and screening efficiency of PA-coated paper cups
was good. On the other hand, the flotation reject
fraction of PA-coated paper cups was higher than
that of PE- and PLA-laminated paper cups. The
green-colored flotation reject fraction is shown in Fig
8. Flotation is a separation process of debris based Fig 8 - Flotation reject from PA-coated paper cups.
on the introduction of air bubbles that attach
themselves to hydrophobic particles and carry them Analysis results of flakes, fibers and fines
to the surface of the slurry (Redlinger-Pohn, et al., Ratios of flakes, fibers and fines in the flotation
2016). According to theory, sources of the reject accepts were analyzed by Somerville screen. As
would be considered hydrophobic particles or shown in Fig 9, the flake contents of PE- and PLA-
printing ink present in paper cups. laminated paper cups were below 1%. However,
flakes of PA-coated paper cups were as much as
30
2.4%. The fiber contents of PE- and PLA-laminated
25
Hole reject
Slot reject paper cups were 90.5 and 91.5%, respectively, while
Flotation reject that of PA-coated paper cups was 89.6%. The
content of fines in all three types of paper cups was
Reject ratio, %

20
about 8%. According to these results, small or soft
15
flakes of PA-coated paper cups could pass through
10
the slots in the pilot screen. We consider that these
flakes had an effect on the decrease in fiber content.
5 Accordingly, a decrease in strength and optical
properties of the paper can be caused by the flakes
0
PE PLA PA
since they may be separated into the accept fraction
by the centripetal forces in the screen. The fiber
properties after flotation are shown in Table 1. The
Fig 6 - Hole, slot and flotation reject fractions from fiber length and width of PA-coated paper cups were
the three kinds of paper cups. (PE: polyethylene; lower than those of PE- and PLA-laminated cups.
PLA: polylactic acid; PA: polyacrylate) However, the fibril perimeter and freeness were
similar.

140
Flake
Ratio of flake, fiber and fines, %

120 Fiber
Fines

100

80

60

(a) PE-laminated paper cup 40

20

0
PE PLA PA

Fig 9 - Ratios of flakes, fibers, and fines of the


three types of flotation accepts.

Table 1 - Fiber analysis results of flotation accepts


Mean
Mean Mean
Origin of fibril Freeness,
(b) PLA-laminated paper cup fiber
length, width
perimeter, mL CSF
Fig 7 - Hole rejects of PE- (a) and PLA-laminated mm , μm
%
paper cups (b) from pilot screening. PE-
laminated 0.9 22.3 9.8 616
paper cups
PLA- 0.8 20.2 7.1 657
laminated
paper cups
60

PA-coated 50
0.7 19.6 8.8 636
paper cups

Tear index, mNm2/g


40

Analysis of handsheet properties


30

Handsheets made from the flotation accepts were 20

made by RDA, after which their bulk mass, tensile, 10


tear, and burst strengths, as well as optical
properties were analyzed. Fig 10 shows the bulk of
0
PE PLA PA
handsheets, indicating that the bulk masses of Fig 12 - Tear strength of sheets based on flotation
handsheets obtained from PE- and PLA-laminated accept fractions.
paper cups were lower than that of sheets made of
fibers obtained from PA-coated paper cups. As 2.5

shown in Figs 11-13, all the strength properties of


handsheets obtained from PA-coated paper cups
2.0

Burst index, kPam2/g


were lower than other handsheets. On the other 1.5
hand, from Fig 14 we can see that the opacity and
light scattering coefficients of handsheets obtained 1.0

from PA-coated paper cups were much better than


those of sheets made of fibers obtained from PE-
0.5

and PLA-laminated paper cups. The strength 0.0

properties of handsheets obtained from PA-coated PE PLA PA

paper cups were poor since their fibers had a shorter Fig 13 - Burst strength of sheets based on flotation
length than other fibers, as shown in Table 1. accept fractions.
Additionally, the residual flakes of PA-coated paper
cups can be considered a bad influence on paper
50
Light scattering coefficient, m2/kg

strength and optical properties. Therefore, it is


necessary to study mechanical treatments to
48

improve or enhance paper properties.


46

3.0

44 PLA
2.5
PE
PA
2.0
Bulk, cm3/g

42
78 80 82 84 86
1.5
Opacity, %
1.0 Fig 14 - Opacity vs. light scattering coefficients of
0.5 sheets based on flotation accept fractions.
0.0
PE PLA PA Effects of mechanical treatments on
Fig 10 - Bulk of sheets based on flotation accept. control of RPF
Fig 15 shows the ratios of flakes, fibers, and fines of
PA-coated paper cups corresponding to various
40
pulping time. Flake contents decreased with an
increase in pulping time, while fiber contents
30
increased. The content of fines however remained
Tensile index, Nm/g

constant. The pulping time had no effect on freeness.


20
The results from Fig 15 and Table 2 taken together
suggest that an increase in pulping time contributed
10 to the reduction in RPF without changing the fiber
properties. However, an increase in pulping time to
0 reduce RPF was not efficient, since as much as 30%
of flakes remained after pulping for 40 min. Naturally,
PE PLA PA

Fig 11 - Tensile strength of sheets based on RPF decreased with an increase in pulping time
flotation accept fractions. because the flake content depends on the pulping
energy. However, pulping could not break RPF
completely, while excessive pulping energy
consumption can be caused by the increase in confirmed as suitable methods to control RPF.
pulping time. Accordingly, an increase in pulping Eventually, the amount of RPF is related to specks
time over 10 min is not efficient. Therefore, other in the paper. If RPF remains as a residue during
mechanical treatments were investigated for stock preparation, the appearance of paper will be
improved control of RPF. Fig 16 shows the results of poor. However, RPF can be well-controlled, since
flake, fiber and fines contents of kneaded stock. The paper recycling mills have mostly kneaders and
consistency was 18%, while 97.5% of RPF was beaters (refiners). Consequently, RPF can be
removed by kneading, even in just one pass. broken down by the beating and kneading actions
Generally, kneading is used in the paper recycling during the papermaking process.
process. Kneading can fragment dirt specks below
the visibility limit and break down large particles. In 140

addition, it can improve strength and flexibility by


Flake

Ratio of flake, fiber and fines, %


120 Fiber
Fines

mechanical treatment as a result of the abrasion of 100

fibers (Fabry, 2013). Therefore, the moderate 80


shearing action of kneading could break down RPF 60
to very fine particles that cannot be seen. Fig 17
shows the change in freeness with an increase in
40

pass number of the kneading process. The freeness 20

was constant up to 2 passes of kneading, but 0

decreased evidently after 3 or more passes, related


10 20 30 40
Pulping time, min
to the change in fines content. As shown in Fig 16, Fig 15 - Ratios of flakes, fibers, and fines after
the fines contents increased rapidly at 3 passes of various pulping times.
the kneading process. It is considered that
excessive friction could affect the generation of fines. 140

Consequently, freeness was low after 3 passes of Flake


Ratio of flake, fiber and fines, %

120 Fiber

kneading due to poor drainage because of increased 100


Fines

fines content.
Flake, fiber, and fines contents after beating are
80

shown in Fig 18. The initial RPF content of 47.42% 60

decreased remarkably to less than 1% by beating for 40

10 min. The general purpose of beating, an 20


important mechanical treatment in papermaking 0
process, is to improve fiber properties such as 0 1 2 3

flexibility, swelling, and fiber bonding potential. Passage of kneader, number

Fibers can be bruised between the rotor and stator Fig 16 - Ratios of flakes, fibers, and fines after
by mechanical actions. At this time, fiber shortening kneading.
and internal or external fibrillation can be caused, 700
while RPF can be fragmented.
Fig 19 shows that freeness decreased with an 650

increase in beating time. As mentioned above, fines


Freeness, mL CSF

600
and fibrillation can be generated by beating. This
can be confirmed with the results in Table 3, showing 550

that fiber length decreased gradually up till 20 min. 500

However, at more than 30 min, the length decreased 450


rapidly. Simultaneously, the mean fibril perimeter
increased with an increase in beating time. The 400
0 1 2 3
decrease in length indicates the generation of fines Passage of kneader, number
due to fiber shortening, whereas the increase in fibril Fig 17 - Freeness after kneading.
perimeter can be explained by delamination of the
primary and S1 layer of the secondary wall of
cellulose fibers. Consequently, we can consider that
the beating time must be controlled to less than 20
min in order to fragment RPF but avoid the
generation of excessive fines. Figs 19-20 show
specks in the handsheets after kneading and
beating. Specks, shown as black spots, disappeared
as a result of these mechanical treatments. From the
above results, both kneading and beating were
Table 3 - Characteristics of fibers after various
140
Flake
beating times
Beating Mean Mean
Ratio of flake, fiber and fines, %
120 Fiber
Fines
Mean Mean fibril
time, length, width,
shape, % perimeter, %
100

80 min mm µm
60 5 0.89 19.1 87.9 5.4
40
10 0.88 19.2 89.4 6.0
20 0.87 19.6 89.8 8.6
20

0
0 5 10 15 20 25 30
30 0.82 20.2 89.6 13.5
Beating time, min

Fig 18 - Ratios of flakes, fibers, and fines after


various beating times. Conclusions
Paper cups are generally made of paper coated by
1000 synthetic resins. However, such synthetic resins can
complicate the recycling of used paper cups. PA-
800 based polymers may be easier to recycle compared
to PE- and PLA-based ones, since PA is hydrophilic.
Freeness, mL CSF

Therefore, the recyclability of paper cups coated


600

400 with PE, PLA, and PA was investigated. The fraction


of hole rejects of PA-coated paper cups was much
200 lower than that of other cups. However, small or soft
flakes originating from the coating layer could not be
removed by screening and flotation. The RPF had a
0
0 10 20 30 40
Beating time, min negative effect on paper properties and the recycling
Fig 19 - Freeness after various beating times. process. Accordingly, mechanical treatments were
investigated in order to remove RPF. An increase in
pulping time was not suitable because RPF could
not be efficiently removed and excessive energy
was consumed. Kneading and beating, on the other
hand, were very efficient for the removal of RPF to
less than the visible limit. Over 95% of RPF could be
removed by one pass of kneading and 10 min of
beating. Consequently, this method can be
considered for application to the paper recycling
Fig 20 - Specks in the handsheets after kneading. process.
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