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International Journal of Biobased Plastics

ISSN: (Print) (Online) Journal homepage: https://www.tandfonline.com/loi/tbbp20

Suitability of poly(butylene succinate) as a coating


for paperboard convenience food packaging

Henry Thurber & Greg W. Curtzwiler

To cite this article: Henry Thurber & Greg W. Curtzwiler (2020) Suitability of poly(butylene
succinate) as a coating for paperboard convenience food packaging, International Journal of
Biobased Plastics, 2:1, 1-12, DOI: 10.1080/24759651.2020.1785094

To link to this article: https://doi.org/10.1080/24759651.2020.1785094

© 2020 The Author(s). Published by Informa


UK Limited, trading as Taylor & Francis
Group.

Published online: 10 Jul 2020.

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INTERNATIONAL JOURNAL OF BIOBASED PLASTICS
2020, VOL. 2, NO. 1, 1–12
https://doi.org/10.1080/24759651.2020.1785094

Suitability of poly(butylene succinate) as a coating for


paperboard convenience food packaging
Henry Thurbera,b and Greg W. Curtzwiler a,c

a
Polymer and Food Protection Consortium, Iowa State University, Ames, Iowa, USA; bDepartment of
Materials Science and Engineering, Iowa State University, Ames, Iowa, USA; cDepartment of Food Science
and Human Nutrition, Iowa State University, Ames, Iowa, USA

ABSTRACT ARTICLE HISTORY


Take out and convenience food packaging has seen rapid growth in Received 19 May 2020
recent years, particularly in the last few months due to restrictions Accepted 16 June 2020
of in-restaurant dining. Paper-based packaging is often thought to KEYWORDS
be a more sustainable option to plastics. However, paper-based Sustainable; compostable;
food packaging materials generally require supplemental treat­ microwave; poly(butylene
ments, such as applications of perfluorinated chemicals and petro­ succinate); packaging
leum-based plastics to improve performance. These are effective
but limit sustainable end-of-life options (e.g., recycling and com­
posting). Landfill diversion strategies are needed to divert food
packaging waste as consumer demand for ready-to-eat (RTE) con­
venience meal kits and single-use packaging continues to increase
municipal solid waste accumulation. This investigation evaluated
the suitability of poly(butylene succinate; PBS) as a direct-melt
coating on recycled paperboard for grease resistance in microwave
rapid reheat and heat and hold convenience food packaging appli­
cations. This research demonstrates PBS as a viable alternative to
perfluorinated chemicals and petroleum polymers with a more
sustainable end-of-life option due to its oil migration resistance at
elevated temperatures and compostability properties.

Introduction
As global demand for packaged food expands, the production of non-degradable and
non-renewable sourced materials will escalate the strain on Earth’s environmental
resources. Packaging comprises the largest market of plastics and is one of the major
contributors to solid waste in landfills and marine environments in the United States [1].
In 2017, 80 million tons (29.9% of the total MSW) consisted of containers and packages
[2]. Traditional petroleum-based convenience food packaging structures have very
a short service lifetime and food contamination reduces recyclability which increases
landfill accumulation potential. Therefore, utilizing sustainably sourced, degradable
packaging, and diverting plastic waste from landfills and marine environments is crucial.
With the anticipated and continuous growth of the paper packaging sector at 4.82%
CAGR ($321 billion by 2024) [3], the ability to compost post-consumer waste instead of

CONTACT Greg W. Curtzwiler gregc@iastate.edu Polymer and Food Protection Consortium, Iowa State
University, Ames, Iowa, USA
© 2020 The Author(s). Published by Informa UK Limited, trading as Taylor & Francis Group.
This is an Open Access article distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/
by/4.0/), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
2 H. THURBER AND G. W. CURTZWILER

landfilling is expected to increase environmental health by reducing accumulation


potential. However, paper-based products generally do not have sufficient physical
properties to function appropriately alone in all food packaging applications as listed
in the Code of Federal Regulations (21 CFR 176.170) [4]. This is particularly true for
high-temperature applications which generally requires supplemental treatments for
performance such as toxic perfluorinated chemicals [5] and petroleum -based polymers
[6]. While effective, these treatments limit recycling and composting potential leading to
increased landfill accumulation.
Since the 1940s, perfluoroalkyl substances (PFAS) have been used in the food industry
as barriers to moisture and oil penetration in paper packaging. These PFAS have been
under intense scrutiny because of their connection to high toxicity which may induce
cancer and other health concerns [7,8] which has led to regulations and bans in food
packaging driving the increased demand for bio-based alternatives in paper-based packa­
ging. These alternatives would be recyclable or compostable reducing waste in landfills
thereby avoiding increased PFAS accumulation from treated paper products. Recently,
both the European Union and the United States (H. R. 2827 and H.R. 5845) have proposed
or passed PFAS and single-use packaging bans [9–14]. As a result, there is an urgent need
for high performance bio-based alternatives to PFAS and petroleum-based feedstocks.
Potential alternatives for paper coatings are bio-based and degradable polymers such
as poly(lactic acid) and poly(butylene succinate). For example, Rhim et al. coated paper
with poly(lactide) coatings via the solvent cast method [15]. PLA was dissolved in
chloroform at different concentrations and applied to paperboard via the drawdown
method followed by water contact angle, water vapor permeability (WVP) and mechan­
ical properties analysis. It was determined that water contact angle increased ~10 degrees
indicating increased hydrophobicity but plateaued at 3 w/v % up to 5 w/v %. The WVP
decreased dramatically from 4.08 to 0.16 (×10−9 g·m/m2·s·Pa) and plateaued again from
3–5 w/v %. The increase in contact angle and reduced water vapor permeability shows
that coated paperboard, at 3 w/v %, is the most effective for water protection. Critically,
these solutions were prepared using chloroform which presents significant problems in
commercial production due to use of toxic solvents. Furthermore, the polymer morphol­
ogy is anticipated to change when scaling from solvent casting to the more commercially
relevant direct-melt method which may alter physical properties.
PBS is another degradable, biobased aliphatic polyester [16] with limited information
for use as a paperboard coating for elevated temperature food packaging applications.
Poly(butylene succinate) is produced through a poly condensation reaction of succinic
acid and 1,4-butanediol (Figure 1). PBS biodegradation studies have determined gradual

Figure 1. Molecular structure of poly(butylene succinate; PBS).


INTERNATIONAL JOURNAL OF BIOBASED PLASTICS 3

weight loss over a four-month period while buried in soil [16]. The degradation rate was
determined to be nearly constant throughout the degradation study with an average of
13 mg/cm2 of weight loss per month. Furthermore, PBS grades have been listed as
certified compostable according to the Biodegradable Products Institute and are available
in direct food contact grades [17]. The biodegradability of PBS is an attractive attribute
for single-use food packaging since it is able to degrade at high rates over short periods of
time [16]. This would decrease landfill accumulation through industrial and home
compostable end-of-life options.
Thermal and mechanical properties of PBS and PBS-corn starch blends have been
previously reported [18]. Lai et al. determined that PBS melts at around 114°C with
a glass transition temperature around −32.5°C. This work blended corn starch with PBS
between 4 and 18.5 wt% and determined that these thermal properties did not practically
vary (Tm: 113°C, Tg −35°C) suggesting that cellulosic fillers can be used to reduce cost
without detrimentally altering important properties for convenience food packaging [18].
However, both the tensile and tear strength decreased when more starch was added
indicating that property-cost optimization is required depending on the application.
Thermogravimetric analysis identified increased mass loss at elevated temperatures
which was attributed to excess water trapped in the starch blend. Since PBS is
a polyester, this could present an issue at elevated temperatures due to hydrolysis
reactions leading to additional performance degradation.
Our research reports the ability of poly(butylene succinate) to be used as a direct-melt
coating for paperboard in two different ready-to-eat convenience food packaging scenarios:
microwave rapid reheat and heat and hold (hot case convenience). Our goal was to evaluate
the material’s performance capabilities in simulated retail environments. We assume that all
federal safety considerations, such as compliance with the Code of Federal Regulations, are
met for the specific conditions of use. These packaging scenarios correspond to how PFAS
treatments and polymer coatings have been used to resist moisture and grease in convenience
food packaging applications. The microwave rapid reheat procedure represents heating up
food from room temperature in a commercial microwave. The heat and hold procedure
simulates food being heated/cooked, placed in a package, then left at a warm temperature (e.g.,
under a heat lamp or in a hot display case) for an extended period of time. Both of these
scenarios are often used in convenience ready-to-eat food packaging applications. The results
presented herein will enable packaging manufactures and commercial retailers to source
biobased food packaging with more sustainable end-of-life options without compromising
performance. Replacement of traditional paper treatments with a compostable, degradable
polymer for paper-based convenience food packaging will enable more sustainable structures
which, when collected and composted, will reduce landfill accumulation and global
contamination.

Methods and materials


Sample preparation
Poly(butylene succinate) (PBS; BioPBS FZ79AC, Mitsubishi Chemical, MI, USA) was
melted directly onto kraft paperboard at 190.5°C at a speed of 380 cm/min (Figure S1)
using a Cheminstruments laboratory melt coater model HLCL-1000 (OH, USA). Three
4 H. THURBER AND G. W. CURTZWILER

unique coating trials using the same parameters were performed to determine the repro­
ducibility of the coating technique. According to the manufacturer’s specifications, the
BioPBS possesses a melt flow rate of 22 g/10 min at 190°C, a flexural modulus of 630 MPa,
flexural strength of 40 MPa, and a yield stress of 40 MPa [19]. The coated paperboard was
cut into 50 mm x 50 mm squares then attached to glass slides with double-sided tape. The
edges were sealed with single-sided tape, and finally sealed with a 30-minute delayed
setting two-part epoxy to prevent oil from saturating the paperboard via the edges. The
utilized samples possessed a PBS coating thickness between 3.6 µm – 5.1 µm (1.4–2.0 mil).

Poly(butylene succinate) thermal characterization


Thermal transitions of poly(butylene succinate) were measured between −70°C and 200°C
utilizing a modulated heating protocol (modulating ± 1.00°C every 60 s) at a rate of 3°C/
minute with a TA Instruments Q2000 differential scanning calorimeter (New Castle, DE) in
a nitrogen atmosphere. Specimens (3–6 mg) were singularly loaded into a hermetically sealed
T-zero DSC pan and crimped prior to analysis. Total volatile content and thermal degradation
properties were quantified via thermogravimetric analysis using a TA Instruments Q5000IR
thermogravimetric analyzer (New Castle, DE) [20]. Samples (5–10 mg) were loaded into
a platinum pan then heated at 10°C/min from room temperature to 700°C under a nitrogen
atmosphere.

Surface morphology investigations


Scanning laser confocal microscopy was used to determine morphological changes in the
poly(butylene succinate) direct-melt coatings before and after convenience food packa­
ging simulations at 20 x magnification using a Keyence (IL, USA) VK-X1000 confocal
laser scanning microscope equipped with a 661 nm laser.

Contact angle measurements


A Ramé-Hart 250 automatic goniometer (NJ, USA) was used to measure the contact angle
of deionized water and avocado oil; these liquids were chosen to provide an understanding
of water and oil resistance performance, respectively. The software triggered a video
recording then a 20 µL drop of deionized water or avocado oil was manually delivered
via 22-gauge or 30-gauge needle, respectively. The contact angle was measured using
DROPImage Advanced software in accordance with ASTM D7334-08(2013) [21].

Convenience food packaging simulations


In the microwave rapid reheat procedure, a fiber-optic probe attached to Optocon
FOTEMP1-4, Fiber optic temperature monitoring system was taped atop each sample
along with an ambient-temperature avocado oil-soaked sponge (see Figure S2). The
sample was placed in a Sharp (1000 W/R-21LT; Thailand) 1000 W commercial microwave
oven and heated from ambient temperature to 100°C, after which the oven was turned off.
The sample was maintained in the unopened microwave for 2 min then removed and
INTERNATIONAL JOURNAL OF BIOBASED PLASTICS 5

Figure 2. Representative temperature profile at the food simulant/packaging surface interface in the
microwave rapid reheat procedure.

cooled to room temperature, after which the surface morphology was investigated via
scanning laser confocal microscopy. A typical heat profile can be found in Figure 2.
In the heat and hold procedure, the sample and optical temperature probe were
arranged in the same manner as the microwave rapid reheat procedure. An avocado oil-
soaked sponge was placed in an oven and heated to 94°C (201°F). Each sample was placed
in a Fisherbrand Isotemp oven at 60°C (140°F) and the heated sponge placed on top.
These temperatures were selected as they were above the Food and Drug Administration
Food Code (Chapter 3) for reheat temperature and equivalent to the minimum storage
temperature for serving hot food [22,23], similar to what would be expected in conve­
nience food bars. The samples were heated for a total of 4 hours, after which the oven was
turned off and the samples slow cooled to room temperature in the oven. After cooling to
room temperature, the sample surface morphology was investigated via scanning laser
confocal microscopy. A typical heat profile can be found in Figure 3.

Results and discussion


The thermal properties of poly(butylene succinate) were determined using differential
scanning calorimetry (DSC) and thermogravimetric analysis (TGA). These were used to
evaluate potential upper limits of temperature abuse for PBS coated paperboard conve­
nience food packaging. The DSC data in Figure 4 show that PBS cold crystallizes at 93.5°C,
with a standard deviation of 0.5°C, indicated by an exothermic peak. The endothermic
event at 114.7°C, with a standard deviation of 0.8°C, shows the melting temperature of PBS.
The onset of melting commences around 100°C and the glass transition temperature was
measured to be −33.1°C, with a standard deviation of 2.2°C. Indeed, with an onset of
melting ~100°C, the coating system likely cannot be used for applications requiring higher
temperatures for extended periods of time. Furthermore, cold crystallization temperatures
6 H. THURBER AND G. W. CURTZWILER

Figure 3. Representative temperature profile at the food simulant/packaging surface interface of the
heat and hold procedure.

Figure 4. Representative thermogravimetric analysis thermograms (left) and differential scanning


calorimetry thermograms (right) of food-grade poly(butylene succinate) in pellet and coated paper
forms.

slightly above 90°C are expected to exhibit whitening which may detrimentally influence
consumer perception that the packaging is “bad” or “over cooked” from heating.
There was no measurable volatile content from the PBS pellet up to the onset of degrada­
tion temperature indicating no likely adulteration of food from the evolution of small
molecules from the polymer. However, a 2.5% additional mass loss was determined at 100°
C for the coated paper sample compared to the pellet which is anticipated to be absorbed
water in the paper structures (Figure 4 and S3). Values of melting and glass transition differ
slightly from that of the PBS pellet. Interestingly, the cold crystallization temperature and
melting temperature decreased ~6°C after application to the paper. This may be attributed to
water absorption of the polymer during application which would be mitigated during
commercial manufacturing with a nitrogen blanket and closed hopper system. These results
INTERNATIONAL JOURNAL OF BIOBASED PLASTICS 7

were consistent across all three lots (see Figure S4). A second endothermic event was detected
above the melting point of the PBS pellet ~147°C. This is likely attributed to melting
temperature of the paperboard’s binders. This hypothesis is supported in Figure S5 where
the paperboard alone possessed two endothermic events near 134°C and 183°C.
Convenience single-use packaging is often used for fatty or oily foods at elevated
temperatures. A paperboard coating is therefore required to resist oil penetration (i.e.,
“bleeding”) to avoid oily contents from reaching consumers and to maintain structural
integrity. The contact angle of water and avocado oil was determined to be 85 degrees and
80 degrees with standard deviations of 7.7 and 12.3 degrees, respectively, indicating
a slight wetting of the surface for both liquids. This suggests a relatively balanced surface
for the protection of both oil and water liquids. The effect of oil on coated and uncoated
paperboard at ambient temperature is shown in Figure S6. On uncoated paperboard, the
avocado oil bleeds through immediately which presents as a rapid color change of the
paperboard. This provides a rapid and visual inspection method for determining oil
bleed-through of polymer coatings for the convenience food packaging simulations.
All samples tested exhibited similar behavior under all convenience packaging simulations.
Dimpling on the coating surfaces of 2–14 microns were observed after microwave treatments
via scanning laser confocal microscopy (Figures 5 and 6). Multiple coating trials were
completed and similar dimpling was observed for each trial and can be found in Figures S7

Figure 5. Representative confocal images of the first trial poly(butylene succinate) coated paperboard
surfaces after microwave rapid reheat convenience food packaging simulation (upper left) and line
scan of observed dimpling (upper right). Optical images front (lower left) and back (lower right) after
the microwave rapid reheat procedure.
8 H. THURBER AND G. W. CURTZWILER

Figure 6. Representative confocal images of the second trial of poly(butylene succinate) coated.

and S8. This is consistent with the localized temperatures exceeding the onset of PBS melting
(~100°C) from concentrated microwave energy absorption by oil droplets at the coating
surface. Therefore, we attribute the dimpling to localized heating of the oil above the melting
temperature of PBS (Figures 5 and 6) that was not captured by the temperature probe. The
dimpling did not result in oil bleed through for all samples tested except for one where
confocal microscopy identified defects in the coating prior to testing (Figure S9) resulting in
inconsistent coverage of the paper substrate. This oil bleed through was not seen on other
coatings since, through confocal images, defects were not observed to be deep enough to
provide insufficient coverage of paperboard. Presumably, these defects would be minimized
during commercial manufacturing. The dimpling did not significantly affect the coating
performance against the oil penetration but after the oil-soaked sponges were removed,
surface whitening was observed (Figure 5, 6, S7, and S8). This can be attributed to the surface
reaching the cold crystallization temperature of PBS. Although dimpling was observed in all
microwaved samples, their depth was insufficient to generate direct access of the oil to the
paper substrates and still provided protection from oil bleed through. These results are
INTERNATIONAL JOURNAL OF BIOBASED PLASTICS 9

Figure 7. Representative confocal images of poly(butylene succinate) coated paperboard surfaces


after heat and hold convenience food packaging simulation (upper left) and line scan (upper right).
Optical images of front and back images after the heat and hold procedure.

expected to translate to an industry targeted thickness of 25 microns. It is anticipated that the


localized rise in temperature-induced dimpling could result in oil bleed through if tempera­
tures increased or were sustained for longer periods of time.
Paperboard surfaces after microwave rapid reheat convenience food packaging simu­
lation (upper left) and line scan of observed dimpling (upper right). Optical images
before (lower left) and after (lower right) the microwave rapid reheat procedure.
Unlike the microwave rapid reheat test, there was no change in the surface morphol­
ogy according to the confocal imaging before and after the heat and hold simulation
procedure (Figure 7). No dimpling was observed since the temperature did not reach the
melting temperature of PBS. This also explains the absence of surface whitening observed
in the microwave rapid reheat simulation. None of the PBS coated paperboard samples
exhibited oil bleed through the coating because no melting in the PBS occurred and no
major surface defects in the paperboard were observed.

Conclusions
Poly(butylene succinate) is a degradable-biobased thermoplastic polyester with
grades available for direct food contact. With more scrutiny over end-of-life con­
siderations and impending legislation for more sustainable single-use packaging, the
identification and availability of compliant alternatives are critical. We coated paper­
board with PBS via direct-melt application and subjected samples to simulated
10 H. THURBER AND G. W. CURTZWILER

convenience packaging scenarios. Some surface dimpling and whitening were


observed under microwave rapid reheat conditions which may detrimentally affect
consumer perception although this was not observed for the heat and hold scenario.
This study demonstrated that poly(butylene succinate) is a suitable replacement for
perfluoroalkyl substances and petroleum-based chemicals in convenience ready-to-
eat food packaging using the simulation parameters employed here. Replacement of
PFAS and petroleum polymer coatings with a compostable, biobased polymer for
paper-based convenience food packaging will enable the manufacturing of more
sustainable and fully compostable structures which, when collected and composted,
will reduce landfill accumulation and global contamination. Future work includes
determination of compliance for direct food contact in the convenience food
packaging conditions of use and investigation of performance in similar scenarios
with more complex chemistries, such as blends of oil, acetic acid, and water.

Acknowledgments
The authors would like to thank Alexandra Ivey and Dr. William Colona of Iowa State University
for their valuable input into this work and guidance for testing.

Disclosure statement
The authors declare no conflict of interest. The funding sponsors had no role in the design of the
study; in the collection, analyses, or interpretation of data; in the writing of the manuscript, and in
the decision to publish the results.

Funding
This study was supported by the Polymer and Food Protection Consortium at Iowa State
University and the Iowa Agriculture and Home Economics Experiment Station, Ames, Iowa and
Project No. IOW04202 Accession # 1021300 by the Hatch Act and State of Iowa. The authors
would like to thank InnoPak, LLC., Thermo Fisher Scientific, GC Innovations America, and
Mitsubishi Chemical for their generous support;U.S. Department of Agriculture [IOW04202]

Notes on contributors
Henry Thurber is an undergraduate student studying Materials Science and Engineering at Iowa
State University. He is an undergraduate research assistant in the Polymer and Food Protection
Consortium at Iowa State University.
Dr. Greg W. Curtzwiler is an Assistant Professor in the Polymer and Food Protection Consortium
at Iowa State University. His research is focused on commercially viable sustainable materials for
adhesives and coatings in the packaging and automotive industries including bio-based, compo­
stable, and recycled polymers. He is currently working on understanding the structure–property
relationships between renewably sourced biobased polymers, hydroplasticization, and compatibi­
lization of biobased waste diverted fillers for adhesives and coatings.
INTERNATIONAL JOURNAL OF BIOBASED PLASTICS 11

ORCID
Greg W. Curtzwiler http://orcid.org/0000-0002-4300-7937

Data availability statement


Data will be made available upon request to the corresponding author at gregc@iastate.edu.

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