Accepted Manuscript

Extrusion blow molding of environmentally friendly bottles in biodegradable polyesters

blends

M. Barletta, C. Aversa, M. Puopolo, S. Vesco

PII: S0142-9418(19)30050-9
DOI: https://doi.org/10.1016/j.polymertesting.2019.05.001
Reference: POTE 5885

To appear in: Polymer Testing

Received Date: 6 January 2019

Revised Date: 10 March 2019
Accepted Date: 4 May 2019

Please cite this article as: M. Barletta, C. Aversa, M. Puopolo, S. Vesco, Extrusion blow molding of
environmentally friendly bottles in biodegradable polyesters blends, Polymer Testing (2019), doi: https://
doi.org/10.1016/j.polymertesting.2019.05.001.

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 ACCEPTED MANUSCRIPT
Extrusion blow molding of environmentally friendly bottles in biodegradable polyesters blends

M. Barletta1,*, C. Aversa2, M. Puopolo1, S. Vesco2

1 Dipartimento di Ingegneria, Università degli Studi Roma Tre, Via Vito Volterra 62, 00146 Roma
(Italy)
2 Dipartimento di Ingegneria dell’Impresa, Università degli Studi di Roma Tor Vergata, Via del

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Politecnico 1, 00133 Roma (Italy)
* Corresponding author’s e-mail: massimiliano.barletta@uniroma3.it

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tel: + 39 (0)6 57333477

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Abstract. Increasing awareness of the environmental impact of oil-relying plastic materials is
prompting Academia and manufacturing industry to develop eco-friendly materials and alternative
technological solutions. Blown bottles and containers represent a significant share of the

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worldwide plastic market and great environmental concern is arising about their disposal.
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Generally, blown plastic bottles are made of three different materials: (i) a cap manufactured from
High Density Polyethylene (HDPE), (ii) a bottle body manufactured from Polyethylene
Terephthalate (PET), (iii) a label manufactured from printed Low Density Polyethylene (LDPE). The
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disposal of blown bottles requires, therefore, the separation of the different materials and, then,
their individual recovery. An eco-friendly alternative to multi-material blown bottles is the
development of a bottle entirely made from a biodegradable polymeric blend, designed to be
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suitable for manufacturing both the cap, the bottle body and the label. In this framework, the
present manuscript deals with the design and development of novel biodegradable blends based
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on bio-based polyesters. The blends are herewith specialized for extrusion blow molding of the
bottle body, although they could be further customized for both the cap and the label. Twin-screw
co-rotating extrusion of the compounds, extrusion blow molding of the compounds for bottle
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manufacturing and the evaluation of the thermo-physical and mechanical properties of the bottles
are hereinafter reported. The novel polymeric blends are found to be suitable for extrusion blow
molding of the bottle body, also exhibiting valuable performances in terms of mechanical strength
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and impact resistance as well as protection against gas permeation and light transmission.
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Key words: Biodegradable Polyesters; Blending; Compounding Extrusion; Extrusion Blow Molding;
Bottle.
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Introduction
Two decades ago, most (approximately 70 %) of the packaging waste produced in European Union
(EU) was landfilled. Nowadays, the numbers are completely different, with almost two-thirds of
the packaging waste being recovered. In 1998, recovered plastic packaging waste averaged 11 %.
After 20 years, the amount of plastic packaging being recycled is almost four times higher (43%).
Despite the considerable progress already made, the road to a near-zero Circular Economy is still
long and tortuous. In the last years, the pressure of the environmental impact of packaging waste,
in particular of plastic packaging, is deeply influencing legislators, media and public opinion

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(Dauvergne, 2018). This pressure is favoring the definition of always more restrictive measures on
the management of packaging waste. In addition, criteria of economy based on circularity, on the

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minimization of waste and on the creation of value from waste, are increasingly imposing in the
political and entrepreneurial scenario. In 2011, the European Commission diffused a first
communication (COM 2011/571 entitled “Table of march to an efficient Europe in the use of

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resources”) on the conversion of the European Union economy according to the paradigms of
Circular Economy. The document indicates the pillars of the new growth model, introducing the
terms “Reduce, Reuse, Replace, Protect, Value” with reference to resources. In 2014, the European

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Commission promoted another document (COM 2014/398 entitled “Towards a circular economy:
program for a Europe with zero waste”) that, transposing the details of COM 2011/571, triggered
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ambitious targets on waste management (80% of the packaging waste to be recycled within the
2030 and prohibition of landfill within the 2025). However, in 2015 (COM 2015/614 entitled “The
missing ring. European action plan for the circular economy”), the proposals of COM 2011/517
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were mitigated, posing a more realistic 75% as threshold of packaging materials to be recycled and
adding severe initiatives for the regulation of waste disposal. COM 2015/614 sets a twofold
objective, namely: (i) to ensure recycling and improve the use of secondary raw materials, also
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favoring the cross-border circulation of secondary raw materials and (ii) to replace problematic
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substances (or difficult to recycle or high impact on environment) and, if not possible, reduce their
presence and improve traceability. In 2018, the European Commission released a new document
(COM 2018/32 entitled “On the implementation of the package of circular economy: possible
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solutions to the interaction between the regulations in matter of chemical substances, products
and waste”), opening the debate on the research of novel solutions, also valid at local level, to
simplify the recycling of raw materials, sometimes difficult or impossible to operate for the
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presence of multi-materials among them or of potentially harmful substances.

Every minute, about 1 million plastic bottles are sold worldwide. In 2018, about 500 billion plastic
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bottles were sold, whereas, ten years ago, the number of plastic bottles sold on the market was
only 300 billion, boosting sales. By the end of 2021, the number of plastic bottles sold on the
market will reach 600 billion, doubling the units sold less than 15 years. The disposal of plastic
bottles is therefore a huge environmental problem. Replacing oil-relying plastics with bio-based,
biodegradable and compostable plastics can be a viable alternative to reduce the environmental
impact (Bos, Meesters, Conijn, Corrè, & Patel, 2012). In 2007, Kale et al. showed the degradation
of poly(lactide) packages in composting and ambient exposure conditions (Kale, Auras, & Singh,
2007), showing the role of temperature, relative humidity and pH of the compost pile in the rate
of degradation of a bottle (Kale, Auras, Singh, & Narayan, Biodegradability of polylactide bottles in
real and simulated composting conditions, 2007). In 2012, Gironi and Piemonte highlighted the
environmental advantage of polylactic acid (PLA) bottles for drinking water with respect to
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polyethylene terephthalate (PET) bottles for the same use (Gironi & Piemonte, 2011). The
environmental advantage of PLA bottles stems from the use of renewable resources, despite the
impact on human health and ecosystem quality should be strictly monitored due to the use of
pesticides and the consumption of land and water used for the production of raw materials.
Recently, Chen et al. evaluated, on a comparative base, the environmental impact of fossil and
bio-based PET bottles (Chen, Pelton, & Smith, 2016). They showed that, depending on the biomass
feedstock, extraction and pre-processing of bio-based PET were likely more emission-intensive
than the corresponding fossil refinery processes due to the significant upstream emissions

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embodied in the application of fertilizers, and the significant chemical and energy inputs required
to break recalcitrant lignocellulosic bonds. However, mixed results were found across impact
categories when comparing the environmental performances of partially and fully bio-based PET

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bottles versus fossil-based ones.
Despite the environmental advantages of PLA compared with PET and bio-PET in the fabrication of

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bottles, the market demand of PLA is, however, still very limited. PLA is difficult to process (Nofar,
Sacligil, Carreau, Kamal, & Heuzey, 2019), rather expensive (~2100-2300 Euro/ton for PLA vs.
~1100-1300 Euro/ton for PET), with limited availability on the market (Nature Works and Corbion,

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the biggest players, can only produce ~200’000 tons/year). In addition, PLA boasts limited barrier
properties (Goncalves, et al., 2013) and it is slow to crystallize (Picard, Espusche, & Fulchiron,
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2011), which makes it not suitable for packaging of oxygen or light sensitive beverages like wine or
milk, if not adequately designed. Nassar et al. observed the crystalline morphology of PLA has a
negligible impact on the oxygen diffusion coefficient (Nassar, et al., 2017). In contrast, they found
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that the occurrence of a rigid amorphous fraction (RAF) in the amorphous phase, caused by its
insufficient decoupling from the crystalline phase, provides an accelerated pathway for diffusion.
Welle showed the higher migration and sorption of PLA beverage bottles compared to PET (Welle,
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2008), stating that the lower inertness of PLA is in agreement with its worse oxygen transmission
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rate, which is a factor 10 times higher than for PET. Pati et al. showed PLA containers caused a
faster wine quality loss compared to both PET and glass (Pati, Mentana, Notte, & Nobile, 2010),
despite PLA was judged able to replace glass for up to three months storage with the advantage of
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being biodegradable. For the above-mentioned reasons, the use of PLA in manufacturing of
beverage bottles has been marginal so far and little efforts have been paid by Academia and
Industry to reverse such trends. PLA-based bottles are today only in use for drinking water of few
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premium brands (i.e. https://www.santanna.it/en/bio-bottle/). PLA-based bottles are used for wine
bottling, only if coated with barrier layers (https://www.aimplas.net/blog/bioplastics-first-pla-wine-
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bottle/), which make the bottle stiffer and the cost of the packaging solution often unreasonable.
PET still is, by far, the leading material in the market of drinking water, milk and juice bottles.
Multi-layer materials, often based on PET itself, are, instead, used for bottling extended shelf life
milk or other products, which require a high shield against light or oxygen. PET is recyclable, but it
cannot be used to manufacture the bottle cap (too brittle to manage the ejection of the caps from
the mold in injection molding, without breaking the cap undercuts). PET bottles for milk, juice,
wine must be thoroughly washed before recycling, this significantly increases the cost of the
recycled material (i.e., recycled PET is commonly 100/150 Euro/ton more expensive than virgin
PET). This is, therefore, the general context in which the present manuscript moves to explore
novel solutions for the manufacturing of single-material bioplastic bottles with low environmental
impacts, suitable for packaging of light and oxygen sensitive beverages (like wine and milk). The
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investigation concerns an eco-friendly alternative to multi-material blown bottles, that is, a blown
bottle entirely made from a biodegradable polymeric blend, designed to be suitable for
manufacturing both the cap, the bottle body and the label and, accordingly, to simplify
significantly the composting step of the whole packaging solution. Specifically, the present
manuscript deals with the design and development of novel biodegradable blends based on bio-
based polyesters. The blends are herewith specialized for extrusion blow molding of the bottle
body, although they could be further customized for both the cap and label. The novel polymeric
blends are hereinafter found to be suitable for extrusion blow molding of the bottle body, also

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exhibiting valuable performances in terms of mechanical strength and impact resistance as well as
of protection against gas permeation and light transmission. For this reason, the newly developed
bottles might be a viable alternative to self-protected bottles in multi-layer materials, to glass

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bottles and carton packages for bottling of light and oxygen sensitive liquids like alcoholic
beverages or milk-based beverages.

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Experimental
Materials
Four polymeric blends based on biodegradable polyesters and specifically designed for extrusion
blow molding of a 200 ml and ~11 g bottle were investigated. High molecular weight PLA grades
with low (~1 mol. %) and medium (~ mol. 4%) D-isomer content are the main constituents (~62 to
75 %) of the blends. The chosen PLA grades feature a glass transition temperature of ~60°C and a
melting temperature of ~ 180 °C (the PLA grade with the lower D-isomer content) and of ~ 160 °C

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(the PLA grade with the higher D-isomer content), respectively. The two PLA grades feature similar
processability, but they differ for their crystallization kinetic, being the low D-isomer content grade
the fastest to crystallize and the high D-isomer content grade the slowest. Another polyester, a

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polymer of succinic acid, specifically polybutylene succinate (PBS), with a lower and sub-zero
softening point constitutes the secondary polymeric phase (~ 15 to 18 %) of the blends, designed

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to confer ductility to the blends. The two polymers are substantially immiscible and they disperse
and distribute each other in the resulting blend, where the minor constituent (that is, the polymer
of the succinic acid) generates a secondary phase in the form of discontinuous droplets inside a
primary semi-continuous phase constituted by PLA. Shielding against light is promoted by adding

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loose micrometric TiO2 (5 to 15 wt. %, if any) and an anti-UV additive (0.6 %, if any), a high
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molecular weight ultraviolet light absorber (UVA) of the hydroxyphenyl benzotriazole class, to the
polymeric blends. A commercially available micro-lamellar talc (Luzenac HAR W92, Imerys S.A.,
Paris, France) is used as nucleating agent (1%, if any). Processing additives (melt strength
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enhancer, impact modifiers and compatibilizers, with a maximum concentration < 1% each) and a
vegetable wax (for lubrication purposes, with maximum concentration < 1%) complete the
formulation of the biodegradable blends. The compatibilizer allows to increase the compatibility
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between the two polymeric phases, facilitating the distribution and the dispersion of the
secondary polymeric phase, which forms droplets of progressively smaller dimension by increasing
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the effectiveness of the compatibilizing additive. Processing adjuvants, specifically the melt
strength enhancer, retard the typical hydrolytic degradation of the polyesters blend during melt
processing, thus allowing to keep high the viscosity of the molten material for a longer time range.
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The impact modifier promotes the entanglement of the polymeric chains, favoring the impact
resistance of the material and increasing its toughness and ductility. Lastly, the lubricants facilitate
the extraction of the blown bottle from the mold, minimizing the interfacial adhesion between the
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semi-molten material and the mold wall at the end of the blowing process. Table 1 summarizes
the four blends investigated.
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Table 1. The formulation of the blends.

BB1, wt. % BB2, wt. % BB3, wt. % BB4, wt. %
PLA (1% D-Isomer) 71.6 - - -
PLA (4% D-Isomer) - 63.6 71.6 76
PBS 17.6 15.6 17.6 18.8
TiO2 5.0 15.0 5.0 -
Talc 1.0 - - -
Anti-UV 0.6 0.6 0.6 -
Wax 1.0 1.0 1.0 1.0
Other additives 4.2 4.2 4.2 4.2
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Processing
Processing of the blends of the biodegradable polyesters and additives was two-fold: (i) during the
first stage, all the constituents in Table 1 were compounded by reactive extrusion using a 28.3
mm, 40 diameters and 304 Nm torque twin-screw co-rotating extruder (ZSE 27 MAXX, Leistritz
Extrusionstechnik GmbH, Nuremberg Germany); (ii) during the second stage, the compounds are,
then, reprocessed by extrusion blow molding (EBM 20/33, Teknomast, Legnano (MI), Italy) to

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fabricate the bottles with the different materials. Sizes of the bottles are the following: height of
the bottle = 95 mm; base diameter of the bottle = 33 mm; neck diameter = 20 mm; volume of the
bottle = 200 ml; average thickness = ~1 mm.

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The twin-screw co-rotating extruder is split in 10 zones, also named barrels. It is equipped with a
volumetric metering feeder with paddle-massaged flexible hopper for pellets (Flexwall Plus Feeder

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FW 40/5, Brabender Technologie GMBH & Co, Duisburg, Germany) in zone (barrel) 1 and two
gravimetric single-screw feeders for packing powders (EC30M, BHT Srl, Camposanto (MO), Italy),
each with the corresponding side feeder located in zone (barrel) 4. The extruder is equipped with

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a vent position in zone (barrel) 6 and a liquid ring vacuum pump in zone (barrel) 9. Filtering section
is in zone (barrel) 10, immediately before the die head of the extruder. The twin-screw co-rotating
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extruder is also equipped with: (i) a temperature controlled strand die head flange mounted to the
last barrel of the extruder (LSA 27-5, Leistritz Extrusionstechnik GmbH, Nuremberg Germany) with
3 bores 3 mm in diameter; (ii) a cooling bath (LKB 160/17, Leistritz Extrusionstechnik GmbH,
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Nuremberg Germany) fitted with several strand guide rolls to guide the strands in the water for
cooling purposes; (iii) a strand blowing unit (LSAE 80, Leistritz Extrusionstechnik GmbH, Nuremberg
Germany) for strand pre-drying and (iv) a speed controlled strand pelletizer with frequency
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converter and range adjustment of pellets length (LSGK 25 E-F, Leistritz Extrusionstechnik GmbH,
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Nuremberg Germany) for pellet cutting.

Table 2 summarizes the process parameters used during the extrusion compounding of the four
biodegradable polyesters blends.
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The equipment for extrusion blow molding is constituted by a 30 mm single screw, 33 diameters,
temperature controlled extruder (EBM 20/33, Teknomast, Legnano (MI), Italy) with a not metered
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feeding hopper. The die head is equipped with an annular die, 20 mm in diameter, for the parison
manufacturing (i.e., parison formation stage). The parison is extruded at 90° direction with respect
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to the die head of the single-screw extruder. The equipment operates in semi-continuous mode,
with the parison extruded and cut off by a heated knife (surface temperature of the knife is set at
300 °C and the clearance between mold and knife is set at 0.1 mm). The blown zone is equipped
with a calibrated mandrel that is inserted inside the parison during the blowing process to form
the neck of the bottle and two cooled metal semi-molds, where the parison is pinched (i.e. pinch
off stage) and air is, then, blown into the parison, inflating it into the shape of the hollow bottle
(i.e., blow-up stage). After cooling down, the bottle is finally extracted from the mold and stored
for further evaluation tests.
Table 3 summarize the operational parameters set during the extrusion blow molding of the four
biodegradable polyesters blends.
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Table 2. Process parameters during extrusion compounding of the biodegradable blends

Screw Volumetric Head
T1 T2 T3 T4 T5 T6 T7 T8 T9 T10 Torque
speed Feeder Pressure
°C °C °C °C °C °C °C °C °C °C (Nm)
(rpm) (%) (bar)
BB1 160 170 175 180 185 180 180 175 175 170 150 19 19.6 75.8
BB2 160 170 175 180 180 180 180 175 170 170 250 47 45.2 114.7
BB3 160 170 175 180 185 180 180 175 175 170 250 47 45.0 105.7

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BB4 160 170 175 180 185 180 180 175 175 170 250 47 44.7 106.4

Table 3. Process parameters during extrusion blow molding of the biodegradable blends

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T1 T2 T3 T4 T5
Screw speed (rpm) Cutting blade temperature (°C)
°C °C °C °C °C

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BB1 150 180 190 185 185 150 300
BB2 140 165 185 180 180 150 300
BB3 140 165 175 170 165 150 300
BB4 140 165 175 170 165 150 300

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Characterization
The Melt Flow Index (MFI) of the polymeric blends was evaluated in gravimetric mode (190 °C, 2.16 kg) by a
metered apparatus (MFI-1221 XNR-400B, AMSE Srl, Torino, Italy) equipped with an encoder that measures
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the piston displacement and an automatic extrudate cutting device.

Thermal analysis of the polymeric blends after extrusion compounding and extrusion blow molding was
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performed by Differential Scanning Calorimetry (DSC) (DSC 200 PC Phox, Netzsch, Selb, Germany).
Approximately 25 mg of material were placed in a hermetic aluminum pan under 40 ml/min nitrogen flow.
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The samples were submitted to a heating scan from 20 °C to 220 °C at a heating rate of 10 °C/min. The
weight crystallinity degree (Xc, %) of PLA was calculated according to the following equation:
∆ −∆
% = ∗ 100
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∆ ∗

where ∆Hm and ∆Hcc (J/g) are the experimental melt enthalpy and cold crystallization enthalpy,
respectively. The experimental melt enthalpy is calculated as the area under the melting peak and the
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experimental cold crystallization enthalpy is the area of the cold-crystallization peak, which appear in the
thermogram. The theoretical melt enthalpy of PLA is ∆H0m is 93.1 J/g (Lim, Auras, & Rubino, 2008). Φ is the
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actual weight fraction of polymer in the formulation.

Attenuated Total Reflection Fourier Transform-Infrared analysis (ATR FT-IR), using an IR spectrophotometer
(Jasco 6600, Jasco Inc., Easton, Maryland, USA) equipped with an ATR device (PRO ONE, Jasco Inc., Easton,
Maryland, USA), were performed on the polymeric blends after extrusion compounding. FT-IR spectra were
recorded in transmittance mode by co-adding 32 scans in the 4000-600 cm-1 spectral range with a 4 cm-1
resolution. The FT-IR spectra were submitted to ATR and baseline correction, normalized with respect to
the ester carbonyl stretching band at 1749 cm-1 belonging to the PLA matrix and displayed in absorbance
mode. Each FT-IR analysis was preceded by a drying phase of the materials in a thermostatic oven (VD
series 23, Binder Gmbh, Tuttlingen, Germany) at 60 °C.

The mechanical strength of the bottle was tested by compression tests using a static test machine (Insight
5, MTS System Corporation, Eden Praire, MN, USA) equipped with a 10 kN load cell (100 Hz, acquisition
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rate) and according to the ASTM D695 regulation. The tests were performed at ambient temperature and
at 4 °C to simulate the typical conditions of use of bottles when stored in the fridge. The approaching speed
was set at 5 mm/min with a pre-load of 1.5 N. The head speed was set at 10 mm/min.

Impact resistance of the bottles was tested by a lab-built apparatus. The bottle was located inside a
cylinder, in which a weight of 500 g was dropped from 0.75 and 1.5 m on the bottle itself. The evaluation of
the impact strength was assessed by visual examination of the resulting damage.

Light transmission spectra of the bottles were tested by UV-VIS spectrophotometry (V670, Jasco, Easton,
MD, USA). The optical system includes a Rowland off-circle arrangement, a single monochromator, with

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double beam type. The spectral bandwidth is 1 nm. The range of wavelength investigated was from 190 to
1000 nm, with a scan speed of 1000 nm/min, a slew speed of 24000 nm/min and a step of 0.5 nm.

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Lastly, oxygen permeability was tested with a three sensors measurement apparatus suitable for O2, H20 e
CO2 sequential analysis (TotalPerm, PermTech Srl, Pieve Fosciana (LU), Italy) according to the ASTM D3985
regulation.

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Results and Discussion
Characterization of the biodegradable polymeric blends
Melt Flow Index (MFI) of the biodegradable polymeric blends was measured in gravimetric mode
at 190 °C and under a weight of 2.16 kg. The biodegradable blends were designed to feature MFI
falling in a low range of values to control the undesired sagging and swelling effect during the
parison formation according to the indications provided in (Rosato & Rosato, 1989). Table 4
summarizes the results.

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Table 4. Melt flow index of the polymeric blends

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MFI, g/10 min
BB1 2.60

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BB2 4.56
BB3 5.51
BB4 6.57

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The MFI of the first polymeric blend (BB1) is the lowest (2.6 g/10 min), being the PLA in the
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formulation characterized by a lower D-isomer content, that is quicker to crystallize. The MFI of
the other blends (BB2, BB3 and BB4) was higher (from 4.56 to 6.57 g/10 min). The increase in the
MFI can be related to the different grade of PLA used in the formulations (the higher D-isomer
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content PLA is less viscous and crystallizes slowly, keeping viscosity low for a longer time). In
addition, decreasing the amount of TiO2 inside the blend causes a progressive increase of the MFI,
making the material flow more easily (i.e., characterized by a lower viscosity). The mineral filler,
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i.e., TiO2 in this case, refrains the polymer to flow too fast, keeping the MFI of the material low.
Consequently, the blend BB4 that does not involve TiO2 features the highest MFI and, therefore,
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the lowest viscosity. However, all the MFI values fall in the range from 2 to 7, such values are still
suitable for the extrusion blow molding process. For example, in extrusion blow molding of
polyolefins, MFI as low as 0.2-0.3 g/10 min for High Density Polyethylene (HDPE) and as low as 1.5
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g/10 min for Low Density Polyethylene (LDPE) are not uncommon (Fukuzawa, Tanoue, Iemoto,
Kawachi, & Tomiyama, 2010), (Huan & Liao, 2003). Accordingly, in the extrusion blow molding
process of bottles, the polymeric material must feature a relatively high viscosity and sufficient
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melt strength to control the parison formation and the subsequent blowing step inside the cold
wall mold. This is in agreement with the findings reported in (Rodriguez-Castellanos, Martinez-
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Bustos, Rodrigue, & Trujillo-Barragan, 2015), where low temperature was crucial to process the
low viscosity starch-gelatin polymer reinforced with cellulose. Low viscosity of the polymer melt
would, in fact, quickly trigger a sagging effect in the parison material and a concurrent typical
deformation of the parison in agreement with previous studies (Huan & Liao, 2003). In the present
work, the parison is located at 90° with respect to the die head of the extruder. A material with
high MFI and low viscosity would be difficult to process in such configuration, as it would lose
stability (i.e., for sagging and swelling effect (Yousefi, Doelder, Rainville, & Koppi, 2009)) and
would flow down during the second stage of the forming process, which involves the clamping of
the parison with the shaped mandrel and its inflation by blown compressed air. A parison made
with a low viscosity polymer would, therefore, flow down stretched under its own weight, not
featuring adequate melt strength. Accordingly, this would result in thinning of the parison, most
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marked closer to the die exit (i.e., sagging effect). This would also result in a progressive increase
of the cross-sectional area of the parison itself (i.e., swelling of the parison due to small Newtonian
swelling and elastic recovery of the material once out of the extruder die head and further
swelling due to stress-relaxation) (Yousefi, Doelder, Rainville, & Koppi, 2009). Conversely, being
the biodegradable polymeric blends under investigation designed to boast low MFI (2.6 to 6.6 g/10
min) and sufficient melt strength, the formation and the blowing step of the parisons are highly
favored, without significant sagging/swelling effects being expected.

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Figure 1. DSC trends for the biodegradable polymeric blends

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Figure 1 reports the trends of the DSC tests performed on the four biodegradable polymeric
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blends under investigation. The trends show the softening points of both the PLA grades at ~59-62
°C, with no significant differences arising between the two different PLA grades and the four
formulations. The slightly lower Tg of the polymeric blends (BB2, BB3 and BB4) that involve the
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higher D-isomer content PLA is common for the three formulations and can be ascribed to the
increase in the minor unit concentration (namely, the D-lactate in the L-rich PLA herewith
investigated) (Saeidlou, Huneault, Li, & Park, 2012), although the effect of the D-lactate
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concentration in the PLA is known to be much bigger on melting temperature. Blend BB4 shows
the lowest Tg equal to 59.2 °C. The lowest Tg can be ascribed to the absence of TiO2 in this
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formulation. TiO2 can fill the free volume of the semi-crystalline PLA, slightly increasing the Tg in
agreement with similar observations reported in (Pitet, Hait, Lanyk, & Knauss, 2007) that, instead,
attributed the decrease of Tg in hyperbranched PLA to increase of the free volume. A
crystallization peak is found at ~90°C for formulation BB1 that involves the PLA grade with low D-
isomer content, while the other blends (BB2, BB3 and BB4) exhibit a crystallization peak at
approximately 99 – 100 °C. It is well known (Saeidlou, Huneault, Li, & Park, 2012) that PLA with low
D-isomer content (in this case, 1 mol. %) is much more prone to crystallize quickly and at lower
temperature, while PLA with higher D-isomer content (in this case, 4 mol. %) is definitely slower to
crystallize and displays a higher crystallization temperature. Accordingly, the melting temperature
of blend BB1 is 180 °C, while the melting temperature of blends BB2, BB3 and BB4 is lower,
averaging 160 – 161 °C, in agreement with (Bigg, 2005), (Hartmann, 1998), (Kolstad, 1996).
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Table 5. Thermal transitions for the biodegradable blends

ΔHm,PLA ΔHcc,PLA ΔHhc,PLA Wt. % PLA Xc% PLA Tg Tc Tm
BB1 30 16.2 6.7 70.6 18.7 62.2 90.6 180.4
BB2 20.8 14.6 / 62.6 10.7 61.3 100 160.8
BB3 20.4 17 / 70.6 5.2 61.5 99.1 160.6
BB4 22.1 20.2 / 75 2.7 59.2 99.6 161.0

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The aforementioned difference in Tm of the PLA phase in the blends is only attributable to the

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content of D-lactate in the PLA that decreases the equilibrium melting temperature of the polymer
(Tsuji & Ikada, 1996), being the molecular weight of the PLA grades herewith investigated
approximately the same. Blend BB1 also shows a small exothermic peak immediately before the

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melting peak that can be ascribed to the transformation of disordered α’ crystals (crystals with a
looser and less ordered chain packing that is generated for PLA which crystallized below 120 °C
and, more specifically, below 100 °C (Zhang, et al., 2005)) to the ordered α form (that is generated

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at temperatures higher than 100 °C and, specifically, higher than 120 °C) (Saeidlou, Huneault, Li, &
Park, 2012). The presence of α’ crystals in blend BB1 is not surprising, as most of the crystallization
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of this blend occurs at temperatures lower than 100 °C. The other blends do not feature the small
exothermic peak immediately before the melting peak, probably because of the scarce amount of
α’ crystals formed. Blends BB2, BB3 and BB4 feature a crystallization peak at above 100 °C and
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most of the crystallization occurs at temperatures above 100 °C that, as said, do not favor the
onset of α’ crystals.
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Similarly, the maximum degree of crystallization, 18.7 %, is achieved for the biodegradable blend
BB1, while the other blends exhibited a crystallization degree ranging from 2.7 to 10.7 %. Blend
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BB1 crystallizes more efficiently because it involves the PLA grade with the lower D-isomer content
and talc that acts as effective nucleant (Li & Huneault, 2007). In addition, blend BB1 boasts the
highest degree of undercooling (Tm – Tc), driving the crystallization and primary nucleation process
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(Saeidlou, Huneault, Li, & Park, 2012). The blends that involve the higher D-isomer content show a
lower crystallinity, since the increase in D-lactate content is known to cause crystal disruption
(Saeidlou, Huneault, Li, & Park, 2012). Blend BB4 shows the lowest crystallization degree because
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it is based on the higher D-isomer content PLA and it does not contain talc and/or TiO2, both
minerals that could speed up and improve the crystallization process. Anyhow, all the designed
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biodegradable blends are based on high molecular weight PLA (that crystallizes less effectively
because of the intrinsic big steric hindrance of the molecules) and are designed to maintain a low
or moderate crystallinity, as the material should be as much flexible as possible and highly viscous
to be processed effectively in extrusion blow molding, where good ductility and high viscosity are
required. Figure 1 also shows the melting point of the secondary polymeric phase, that is, the
plasticizer based on a polymer of succinic acid that presents a melting temperature of ~115°C. PBS
is known to form a secondary polymeric phase inside PLA (Aversa, Barletta, Pizzi, Puopolo, &
Vesco, 2017), almost completely immiscible with the PLA itself at the investigated concentrations.
This means that the expected influence of PBS on the thermal transition of PLA is minimum (if
any), whatever the formulation considered.
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Figure 2 reports the trend of the FTIR analysis performed on the biodegradable blends of
polyesters BB1, BB2, and BB3 to understand the effect of blending and adjuvants on PLA
morphological structure. Blend BB4 does not involve fillers and, therefore, was not considered
further in this analysis, being all the pertinent information already included in the other blends.
The base pattern of the spectra reveals the presence of PLA, the main component of the blends.
The most significant absorption peaks are reported in Table 6.

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Figure 2. FTIR Spectra of the biodegradable blends

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The presence of the polymer of succinic/adipic acid in the blends is visible from specific
absorptions that overlap to the as-is PLA profile in the spectra. In Figure 3 the spectrum of the
ester of succinic acid is reported. An enlargement of the spectra can be also observed. In
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particular, Figure 3a evidences the absorption peak at 2961 cm-1 belonging to the spectrum of the
succinic derivate. The peak is still visible in the spectra of blends BB1, BB2, BB3, appearing as a
shoulder of the absorption peak centered at 2946 cm-1. The sharp and intense signal of the
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carbonyl group of the ester of succinic acid, occurring at 1721 cm-1, is responsible for the strong
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enlargement of the peak of the carbonyl group of PLA, originally centered at 1747 cm-1 (Figure 3
b). The appearance of an additional shoulder on the base of the absorption peak centered at 1182
cm-1 in the spectra of all the formulations analyzed states the presence of the blended ester of
succinic acid that gives an intense peak at 1164 cm-1 (Figure 3 c). Lastly, a fainter influence of the
polymer of succinic/adipic acid signals is detectable as an increase in the relative intensity of peaks
occurring at 919 cm-1 compared to the spectrum of the as-is PLA [5] and the appearance of a weak
signal at 800 cm-1 (Figure 3 d).
The comparison of some specific absorption peaks emphasizes the difference in the crystalline
content among the formulations in agreement with (Barletta, Pizzi, Puopolo, & Vesco, Design and
manufacture of degradable polymers: Biocomposites of micro-lamellar talc and poly(lactic acid),
2017). In particular, band occurring at 955 cm-1 (Figure 4 a) and related to the vibration in the
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amorphous phase of PLA features different intensity in the spectra of the blends BB1, BB2 and
BB3. The decrease of the signal in BB2 and, even more, in blend BB1 clearly indicates the decrease
in the relative content of the amorphous phase (i.e., increase in crystalline fraction in BB1 and
BB2). The intensity of the band occurring at 1212 cm-1 related to the structural organization of the
molecule (coupling between CH3 rocking vibrations), and, thus, to the presence of crystalline chain
pack of the molecules, is higher with the increasing content of crystalline phase of the blends
(BB1>BB2>BB3 (Figure 4 b)). Similarly, the intensity of the peak related to the presence of crystals
in the α-configuration occurring at 921 cm-1 (Figure 4 c) is higher with the increase of crystalline

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content. The results achieved from FTIR spectroscopy perfectly match the results obtained from
DSC. As described in the experimental section, the crystalline content of blends is strictly related
to the enantiomeric composition of the polymeric matrix. In particular, the introduction of higher

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content of D-isomer is responsible of a slower crystallization. According to this, blend BB1 that is
obtained from 100 % PLA of (1 mol. % D-Isomer) grade is the formulation featuring the highest
content of crystalline phase. Blends BB2 and BB3, obtained from 100 % of PLA (4 mol. % D-Isomer)

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exhibited a crystalline content, accordingly. The presence of mineral filler can also be noted from
the analysis of the FTIR spectra of the biodegradable blends. The presence of talc (as little as 1 %)
is visible in some regions of the blend BB1 spectrum. Figure 5 shows the appearance of a shoulder

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at the base of peak centered at 1018 cm-1. This shoulder was attributed to the overlapping of the
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PLA band with the most intense peak of talc, occurring at about 974 cm-1 as reported in (Barletta,
Pizzi, Puopolo, & Vesco, Design and manufacture of degradable polymers: Biocomposites of micro-
lamellar talc and poly(lactic acid), 2017). In contrast, none of the absorption peaks of TiO2 caused
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any alteration in the FTIR spectrum despite the higher concentration of the mineral introduced in
blends BB1, BB2, and BB3. This phenomenon was ascribed to the overlapping of the most intense
signals of TiO2 and some absorption peaks in the formulations, specifically the peak occurring at
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1084 cm-1 (Sarker, 2014), that perfectly overlaps with the intense peak of PLA at 1081 cm-1.
Instead, the maximum peak in rutile, occurring at 704 cm-1, is hidden by the presence of the peaks
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at 754 and 686 cm-1, generated by the vibrations of C-C bonds of the polymer skeleton.
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Table 6. Absorption peaks occurring in FTIR of blend samples that are attributable to the base
polymer, PLA.

Absorption band
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-1 Intensity Vibration
(cm )
Range 4000-3481 weak Overtones of water adsorbed on the sample (M. Barletta, 2015)
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2995, 2946 medium C-H stretching on CH3 (M. Barletta, 2015)

2916 medium C-H stretching (M. Barletta, 2015)
2885 C-H stretching on tertiary carbon (V. Krikorian, 2005)
1747 strong Carbonyl stretching vibration
1454 medium Bending of CH3
1378, 1358 weak Deformation of C-H
1266 weak Stretching of ester
Medium, Coupling of -CH3 rocking vibration with asymmetric (Kister, Cassanas, &
1212, 1182
weak rocking of –CH3 groups Vert, 1998)
1126 shoulder Asymmetric rocking of CH3
1081 strong Symmetric stretching of esters
1035 strong C-CH3 deformation
(Meaurio, López-
955 weak Amorphous band
Rodríguez, &
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Sarasua, 2006)
921 weak Α-crystals [4]
754, 686 weak C-C bonds

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Figure 3. FTIR Spectra of the biodegradable blends: (a) band at 2961 cm-1; (b) range of 1770 to
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1710 cm-1; (c) range of 1200 to 1100 cm-1; (d) bands at 919 and 800 cm-1
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Figure 4. FTIR Spectra of the biodegradable blends: (a) band at 955 cm-1; (b) band at 1212 cm-1; (c)
band at 921 cm-1

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Figure 5. FTIR Spectra of the biodegradable blends: range of 1050 to 900 cm-1

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Thermo-physical characterization of the blown bottle
Figure 6 reports the DSC trends of some fragments of the bottles after extrusion blow molding.
Table 7 summarizes the thermal transitions and crystallinity of the blends. The second thermal
processing of the biodegradable blends causes a decrease in glass transition temperature Tg,
crystallization temperature Tc and melting temperature Tm. This result is ascribable to the
thermohydrolytic degradation (Piemonte & Gironi, 2013), typical of the biodegradable polyesters,
that takes place according to a third-order kinetics as proposed in (Pitt, Chasalow, Hibionada,
Klimas, & Schindler, 1981) (Pitt & Shah, Manipulation of the rate of hydrolysis of polymer-drug

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conjugates: the secondary structure of the polymer, 1996). The hydrolytic degradation of
polyester blends causes a significant decrease in the average molecular weight of the polymer,

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which is the primary reason for the decrease of Tg, Tc and Tm. A slight secondary peak can be seen
on the shoulder of the melting peak of formulations BB2, BB3 and BB4. This secondary peak can
be, probably, ascribed to the increase in the presence of α’ crystals in the material. The onset of

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the α’ crystal melting peak in formulations BB2, BB3 and BB4 can be possibly ascribed to the left
shift of the crystallization peak, whose maximum is, this time, at temperature below 100 °C,
temperature suitable to the formation of α’ crystals. Besides, the DSC trends of blends BB2, BB3,

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BB4 do not feature the typical small exothermic peak before the melting peak, typical of the
earlier mentioned rearrangement of the α’ crystals in α crystals at high temperature. For this
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reason, the α’ crystals could persist in the material and be detected in the melting peak, in the
form a small double peak arising on the shoulder of the main melting peak. Blend BB1 keeps on
showing the lowest crystallization peak temperature, which, as previously mentioned, favors the
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development of the α’ crystals. However, the same blend shows an apparent small exothermic
peak before the melting peak that states, unequivocally, the rearrangement of the α’ crystals in α
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crystals during heating. Accordingly, the blend BB1 does not feature a second melting peak on the
shoulder of the main melting peak, because all the α’ crystals formed are converted in α crystals
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during heating, immediately before the melting occurs. The crystallization degree of the polymeric
blends undergoes minimum changes after extrusion blow molding, varying from 4.6 to 16.8 %,
that is, very close to the range of crystallinity degree found on compounds after twin-screw co-
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rotating extrusion.
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Figure 6. DSC trends for the bottles manufactured with the four biodegradable polymeric blends
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Table 7. Thermal transitions for the bottles manufactured with the four biodegradable polymeric
blends
ΔHm,PLA ΔHcc,PLA ΔHhc,PLA Wt. % PLA Xc% PLA Tg Tc Tm
BB1 31.5 17.2 3.3 70.6 16.8 55.0 92.7 175.5
BB2 19.6 12.7 / 62.6 11.8 52.1 96 156.1
BB3 20.5 14.8 / 70.6 8.6 52.5 94.5 156.7
BB4 20.2 17 / 75 4.6 53.8 95.9 158.4

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Light transmission and oxygen permeation through the bottle wall are important factors to assess
the performance of bottles for beverages that are sensitive to both oxidation and photo-oxidation.

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Fresh milk can, for example, stay in a transparent, unprotected, PET bottle for maximum 6 days on
shelves of dairy stores under Light-Emitting Diode (LED) or fluorescence (FL) light (Brothersen,
Mcmahon, Legako, & Martini, 2016), after which it decays as a result of massive photo-oxidation

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of methionine and fatty acids that generates flavors as cabbage, mushroom, plastic-like, medicinal,
and burnt (Brothersen, Mcmahon, Legako, & Martini, 2016). Milk oxidation is ascribed to the
photo-excitation of riboflavin (vitamin B2) at wavelengths of 200 to 500 nm (Intawiwat, Wold,

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Skaret, Rukke, & Pettersen, 2013) that causes the formation of a variety of free radicals that not
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only result in loss of riboflavin, but can further react to degrade other compounds (Choe, Huag, &
Min, 2005). Extended Shelf Life (ESL) milk has a shelf life of 21 days maximum, if the bottle is
partially opaque, thus limiting the light transmission through the bottle wall (Johnson, et al.,
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2015). Lastly, Ultra - Heat Treated (UHT) milk can last up to 6 months on shelves, but the bottle
cannot allow any light transmission through its wall. Total blocking of all visible light transmission
at wavelength < 450 nm and > 650 nm is, in this case, recommended to protect the milk
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adequately (Intawiwat, Wold, Skaret, Rukke, & Pettersen, 2013). Similarly, oxidation is a severe
problem for wine production and storage unless large amount of sulfites are used, this being one
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of the main reason why wine is generally packed in glass bottles or in high-barrier multi-layer
carton packages (Pati, Mentana, Notte, & Nobile, 2010), (Escudero, Asensio, Cacho, & Ferreira,
2002).
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Figure 7. UV-VIS spectra for the bottles manufactured with the four biodegradable polymeric
blends
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Figure 7 shows the UV-VIS spectra of the bottles fabricated with the four biodegradable blends
investigated. The unprotected blend BB4 allows significant light transmission from 250 nm
wavelength. Starting from 360 nm, the percentage of light transmitted through the bottle wall
increases quickly to reach ~50% for larger wavelength. Blends BB1 and BB2 boast the best
response to light transmission. They do not allow light transmission through the bottle wall for
wavelength < 420 nm, after that the transmitted light percentage increases linearly up to a
maximum threshold of ~5 %. The best result, registered for bottles manufactured of blend BB1 is
ascribable to the concurrent effect of the higher crystallinity of the material (Xc of 16.8 %), to the

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screening effect of the lamellar talc that hinders the light transmission and increases its reflection
and to the 5 wt. % of the notorious shielding effect of the crystalline and whitish TiO2 inside the
formulation. For the BB2 blend, the good response to light transmission of the bottle can be

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ascribed to the major content (15 wt. %) of the shielding crystalline and whitish TiO2 inside the
formulation as well as to the rather higher crystallinity of this blend (Xc of 11.8 % compared with Xc
of 8.6 and 4.6 for the bottles fabricated with blends BB3 and BB4 that exhibit a worse UV-Vis

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spectra). These results are of particular interest, as, recently, most dairy stores use LED in place of
FL for illuminating the shelves. LED features a different light emission if compared with the
traditional FL, with low energy being emitted at higher wavelength (500 nm and above)

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(Brothersen, Mcmahon, Legako, & Martini, 2016). For this reason, the bottles manufactured with
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blends BB1 and BB2 are extremely promising as they protect milk more, where the LED energy
emission is stronger (that is, for wavelength < 500 nm).
Figure 8 reports the oxygen permeability of the biodegradable bottles and a comparison with the
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same bottle manufactured of High Density Polyethylene (HDPE), while experimental data on virgin
and recycled PET bottles are, however, largely available in the scientific literature (Dombre, Rigou,
Wirth, & Chalier, 2015). Table 8 summarizes the resulting oxygen permeability for each material,
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normalized on the single packaging item and per m2. As earlier mentioned, oxygen permeability
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through the bottle wall is crucial for oxygen sensitive foodstuffs. The presence of oxygen facilitates
microbial growth, increases oxidative reactions and induces the development of off-flavor and
color changes (Brody, Bugusu, Han, Sand, & McHugh, 2008). Keeping oxygen low is therefore of
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vital importance to preserve oxygen sensitive foodstuffs. Oxygen permeability in packaging has
often been reported in scientific literature (Michiels, Puyvelde, & Sels, 2017). PET oxygen
permeability is reported in the range of 1 to 5 (cm3·mm)/(m2·day·atm) (Lange & Wyser, 2003). PLA
oxygen permeability is, instead, approximately 10 (cm3·mm)/(m2·day·atm) (Lagaron, et al., 2005).
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PLA is therefore more sensitive to oxygen permeation and actions should be taken to reduce its
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gas permeability.

Table 8. Oxygen permeability of the biodegradable and HDPE bottles

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∙ ∙
BB1 2.82
BB2 5.94
BB3 10.76
BB4 9.4
HDPE 14.8
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Figure 8. Oxygen permeability trends for the bottles manufactured with the four biodegradable

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polymeric blends

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The bottle manufactured of BB1 polyblend boasts the lowest Oxygen Transmission Rate (OTR) of ~
2.82 (cm3)/(packaging·day·atm). As earlier mentioned, the BB1 biodegradable blend boasts the
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best response thanks to the concurrent effect of the higher crystallinity of the polymeric material
(Xc of 16.8 %) (Picard, Espusche, & Fulchiron, 2011) and to the screening effect of the micro-
lamellar talc that hinders the oxygen permeation through the bottle wall by creating a tortuous
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path in agreement with the experimental results reported in (Zeppa, Gouanvé, & Espuche, 2009),
(Ghassemi, Duchesne, & Rodrigue, 2017). In addition, the biodegradable blend BB1 crystallizes at
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the highest temperature (around 100°C) as it involves the low D-isomer (1 mol. %) PLA grade, thus
causing the formation of prevalently a crystals (Zhang, et al., 2005). As earlier mentioned,
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geometrical shape of a crystals and their better packing attitude in space is expected to reduce the
gas permeability through the bottle wall, creating a denser polymeric matrix with less free volume
available for gas to permeate. In contrast, the bottle manufactured of the BB2 biodegradable
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polyblend shows an OTR of 5.94 (cm3)/(packaging·day·atm). It benefits from the major content of
TiO2 that, filling the gaps in the free volume of the PLA molecules, is somewhat expected to reduce
the oxygen transmission. However, role of TiO2 on gas permeation of polymer is still poorly
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investigated. The bottles manufactured with polyblends BB3 and BB4 exhibit the highest oxygen
permeability (OTR of ~10.76 and 9.40 (cm3)/(packaging·day·atm) for polyblends BB3 and BB4,
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respectively), which can be ascribed to the lowest crystallinity of the corresponding materials and
to low or no mineral content that is involved in both formulations. In addition, polyblends BB2,
BB3 and BB4 are based on the PLA grade with the highest D-isomer (4 mol. %) content. This PLA
grade crystallizes at temperature well below 100 °C, generating also α’ crystals during the
crystallization (Zhang, et al., 2005), (Saeidlou, Huneault, Li, & Park, 2012). As said before, α’
crystals are a distorted form of α crystals and they do not pack in the space as tidily as α crystals
do. This is an additional reason to why the bottles manufactured with polyblends BB2, BB3 and
BB4, based on the PLA with higher D-isomer (4 mol. %) content, exhibit a worse response to
oxygen permeability.
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The comparison between the bottle manufactured of blend BB1 and of a conventional polyolefin
(i.e., High Density Polyethylene (HDPE)) shows a reduction of 7 times in oxygen permeation
through the bottle wall by switching from HDPE to the biodegradable blend BB1. HDPE, as all
polyolefins, is notoriously a material with medium-high gas permeability. However, the
biodegradable blend BB1 exhibits a significantly better response to oxygen permeation. Similarly,
the biodegradable blend BB1, nucleated by 1 wt. % micro-lamellar talc, boasts oxygen permeation
that is 4 times lower than the corresponding blend without talc as nucleating agent (i.e., polyblend
BB4), confirming the crucial role of talc itself and of the polymer crystallinity on the reduction in

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gas permeation through PLA- based materials. Although the biodegradable polyblends herewith
investigated were not specifically designed to ensure low gas permeability through the bottle wall,
the experimental results available trace the road to how progressively reduce oxygen permeation

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through packaging items. This result can be pursued by controlling crystallinity and polymeric
structure of the polymeric material as well as by posing physical obstacles (i.e., mineral fillers with
lamellar geometry) to the transmission of gases through the polymeric material itself.

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Mechanical characterization of the blown bottles
The mechanical characterization of the blown bottles was carried out by implementing both static
(i.e., compression test) and dynamic (i.e., impact test) experimental tests. Figure 9 reports the
sequence of steps during the compression test of the bottle, showing a typical deformation mode
of the bottle. Figures 10-11 summarize the corresponding load – displacement trends for the
blown bottles manufactured with the four biodegradable blends by performing the compression
tests both at ambient temperature (~25 °C) and at typical fridge temperature (~4 °C). The last test
was performed at lower temperature in order to the evaluate the mechanical strength of the

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blown bottles in real conditions, being this kind of bottles often stored in fridge or in refrigerated
shelves at temperature of ~4 °C or below.

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Figure 9. Compression test of the extrusion blow molded bottles fabricated with the four different
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biodegradable blends
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During the compression tests, the load – displacement curves were recorded. The curves present a
typical trend for all the investigated bottles. The trends are very similar with minimum difference
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arising between the bottles manufactured from the different biodegradable materials. The trend
consists in a first phase, where a linear increase of the load and a gradual shortening of the bottle
is observed (i.e., the elastic range – Figure 9A, 10). The linear trend ends up with a first peak that
corresponds to the load of maximum resistance of the bottle, without causing too much
deformation (~ 2 mm) of the bottle itself (Figure 9B, 10). Afterwards, there is a decrease in the
load due to a first failure of the structure of the bottle, taking place at the base of the bottle. That
zone can be considered a weak point for the bottle because the thickness of the wall is
substantially higher as a result of the combination of the earlier mentioned sagging and swelling
effect that, respectively, cause the material to accumulate in the lower portion of the bottle and
increases its cross-sectional area (Yousefi, Doelder, Rainville, & Koppi, 2009). The base of the
bottle is also an area where stresses of the extrusion blow molding process concentrate (Huan &
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Liao, 2003). After the first failure that occurs at the base of the bottles, there is a reconfiguration
of the bottles’ structure, which responds again to the compression offering a new stage of
increasing resistance. Therefore, a new peak in the load – displacement trend is recorded (Figure
9C, 10). After that, the load decreases again because of a second failure of the structure in the
upper portion of the bottle, at the end of the bottle neck. A gradual decrease of the load
characterizes the last part of the load-displacement trend till the complete deformation of the
bottle (Figure 9D, 10).

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Figure 10. Load-displacement trend of the extrusion blow molded bottles manufactured with the
four biodegradable blends at ambient temperature
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Figure 11. Load-displacement trend of the extrusion blow molded bottles manufactured with the
four biodegradable blends at typical fridge temperature (~4 °C)

The results of the compression tests performed at 4°C, that is, in conditions very close to those
that take place when the bottle is stored in a fridge or on a refrigerated shelf, are very similar.
Accordingly, minimum differences arose in the individual trends of the load – displacement curves
of the bottles fabricated with the four biodegradable blends under investigation when tested both
at ambient and fridge temperature.
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Table 9. Characteristic parameters of the load – displacement curves for the bottles manufactured
with the four biodegradable blends: m is a measure of the bottle stiffness, the area below the load
–displacement curve is a measure of the deformation energy during the compression test of the
bottle and, lastly, Lmax is a measure of the maximum load of the bottle during the test

T =25 °C T = 4 °C
m (Stiffness) Area (Deformation Energy) Lmax m (Stiffness) Area (Deformation Energy) Lmax

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N/mm mJ N N/mm mJ N
BB1 601.9 6388 1389 512 5580 917
BB2 433.4 4600 844 498.5 6993 937

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BB3 548.3 6647 1159 533 6735 1195
BB4 553.8 6187 1138 622 8806 1360

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Table 9 summarizes the characteristic parameters extracted from the experimental load –
displacement trends of the compression tests performed on the bottles fabricated with the four

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different biodegradable blends. The parameter m in Table 9 is the angular coefficient of the linear
branch of the load – displacement curve. The parameter m is, therefore, a measure of the stiffness
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of the investigated bottles. It is noteworthy that the bottle fabricated with the biodegradable
blend BB1 is the stiffer (601.9 N/mm) at ambient temperature (~25 °C), while, at fridge
temperature (~4 °C), the stiffer bottle (622 N/mm) is the one fabricated with the biodegradable
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blend BB4. These results can be attributed to the higher crystallinity of blend BB1, which is stiffer
at room temperature in agreement with (Aversa, Barletta, Pizzi, Puopolo, & Vesco, 2017),
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(Barletta, Pizzi, Puopolo, Vesco, & Daneshvar-Fatah, 2017). Nonetheless, at the lower temperature
of 4 °C, the crystalline blend BB1 exhibits its brittleness, with a significant decrease of its
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mechanical properties. In contrast, the bottle fabricated with blend BB4 behaves better at 4 °C. As
seen before, blend BB4 is characterized by a very low crystallinity. The cooler temperature makes
the material stiffer, without inducing too much brittleness in it as in the case of the bottle
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fabricated with blend BB1, that is much more prone to crystallize and therefore to embrittle at
cooler temperatures.
The aforementioned considerations are supported by the values of the deformation energy and of
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the maximum load of the bottles fabricated with blends BB1 and BB4. Blend BB1 boasts one of
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the highest deformation energy (6388 mJ) and the highest maximum load (1389 N) at 25 °C under
compression test, while there is a complete inversion of the trend at 4 °C, where the bottle
fabricated with blend BB1 shows the worst energy of deformation (only 5580 mJ) and the
minimum value of maximum load (917 N) among the bottles investigated. In contrast, the bottle
fabricated with blend BB4 boasts a deformation energy of 8806 mJ and a maximum load of 1360 N
when tested at 4 °C, confirming the better behaviour of blend BB4 at cooler temperature.
Anyhow, it is not possible to identify a precise trend for the stiffness, energy of deformation and
maximum load of the bottles investigated as other crucial factors, including material processing
and mold accuracy as well as the resulting swelling and sagging effect on bottle structure, can
affect, at a greater extent, the performance of the bottles and influence the final results (Yousefi,
Doelder, Rainville, & Koppi, 2009).
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Figure 12. Impact tests of the extrusion blow molded bottles fabricated with the four different
biodegradable blends
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Figure 12 shows the bottles after the impact tests with the weight of 0.5 kg that is dropped on the
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bottle from the heights of 0.75 and 1.5 m, respectively. The impact of the weight from the height
of 0.75 m did not impair the bottles, whatever the starting material. The impact of the weight
dropped from the height of 1.5 m caused the rupture of the bottles at the base, where, as said
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before, there is an abrupt increase of thickness due to the combined sagging and swelling effect
during the extrusion blow molding process (Yousefi, Doelder, Rainville, & Koppi, 2009) and there is
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also concentration of stresses inside the polymeric material (Huan & Liao, 2003). However, no
significant difference in the performance of the bottles manufactured with the four different
biodegradable blends arose.
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Conclusions
The present manuscript deals with the design and development of novel biodegradable blends
based on bio-based polyesters. The blends are herewith specialized for extrusion blow molding of
the bottle body. The following pointwise conclusions can be drawn:

• the biodegradable polymeric blends under investigation are designed to boast low MFI (2.6
to 6.6 g/10 min) and sufficient melt strength, therefore the formation and the blowing step
of the parisons during extrusion blow molding of the bottles are highly favored;

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• the biodegradable blends are based on high molecular weight PLA (that crystallizes less
effectively because of the intrinsic big steric hindrance of the molecules) and are designed
to keep low or moderate the crystallinity, as the material should be as much flexible as

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possible and highly viscous to be processed effectively in extrusion blow molding, where
good ductility and high viscosity are both required;
•

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difference in thermal transitions of the different biodegradable blends and in their
crystalline structure (crystallization degree, ratio of α to α’ crystals) can be ascribed to the
different D-isomer content of the PLA primary phase used;
•

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extrusion blow molding process of the biodegradable materials influences the thermal
transitions of the investigated materials, yielding to different proportions of α to α’ crystals
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in the bottles; the bottles fabricated with blends that involve the PLA grade with the
highest D-isomer content are, indeed, characterized by the distinctive presence of α’
crystals;
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• The bottles manufactured of blend BB1 boasts the lowest light transmission especially for
wavelength < 420 nm because of the concurrent effect of the higher crystallinity of the
material, the screening of the lamellar talc and of the crystalline and whitish TiO2; this
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result is of great practical interest because the bottles are nowadays stored under LED that
emits low energy at higher wavelength (500 nm and above);
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• Although the biodegradable polyblends herewith investigated were not specifically

designed to ensure low gas permeability, the experimental results trace the road to reduce
oxygen permeation through packaging items; for such scope it is sufficient to control
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crystallinity and polymeric structure of the material as well as posing physical obstacles
(i.e., mineral fillers with lamellar geometry) to the transmission of gases (as in the BB1
blend);
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• Static and dynamic tests showed acceptable mechanical strength and impact resistance of
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the bottles, with minimum differences arising among the variety of materials investigated;
however, blend BB1 that shows the highest crystallinity better behaves at ambient
temperature, while the blend BB4 that displays the lowest crystallinity better behaves at
fridge temperature.
In conclusions, the novel polymeric blends are found to be suitable for extrusion blow molding of
the bottle body, also exhibiting valuable performances in terms of mechanical strength and impact
resistance as well as in terms of protection against gas and light permeation. Blend BB1 featured
the best results, ensuring limited light and oxygen permeation, as it combines good crystallinity
and the physical obstacle to transmission posed by micro-lamellar talc. This class of biodegradable
blends is therefore extremely promising in replacing oil-relying plastic in the manufacturing of
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blown bottles that can also be suitable for oxygen and, especially, light sensitive foodstuffs,
strongly decreasing the resulting environmental impact.

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Acknowledgments

The authors wish to thank Teknomast Srl (Legnano (MI), Italy) for their support in the extrusion blow
molding process. The authors wish to thank Mr. Alessandro Donninelli for the useful insights and
suggestions in the development of the present investigation. The authors wish to thank the Department of
Enterprise Engineering of the University of Rome Tor Vergata and, specifically, Prof. Vincenzo Tagliaferri,
full professor in Manufacturing Engineering, for making available part of the testing equipments necessary
for the development of this work. Ms. Flavia Maffei is also warmly acknowledged for her support during the
development of the experimental tests.

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Data Availability

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The raw/processed data required to reproduce these findings cannot be shared at this time due to legal or
ethical reasons.

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HIGHLIGHTS

Extrusion blow molding of environmentally friendly bottles in biodegradable polyesters blends

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M. Barletta1,*, C. Aversa2, M. Puopolo1, S. Vesco2
1 Dipartimento di Ingegneria, Università degli Studi Roma Tre, Via Vito Volterra 62, 00146 Roma (Italy)

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2 Dipartimento di Ingegneria dell’Impresa, Università degli Studi di Roma Tor Vergata, Via del
Politecnico 1, 00133 Roma (Italy)

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* Corresponding author’s e-mail: massimiliano.barletta@uniroma3.it
tel: + 39 (0)6 57333477

List of highlights:
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1) great environmental concern is arising about disposal of plastic bottles;
2) multi-material bottles can be replaced by bottle made from a biodegradable polymeric blend;
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3) biodegradable blends designed to be suitable for manufacturing both the cap, bottle body and
label;
4) design and development of novel biodegradable blends based on bio-based polyesters;
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5) the bottles exhibit good strength and impact resistance, protection against gas permeation
and light transmission.
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