Additive Manufacturing 25 (2019) 122–130

Contents lists available at ScienceDirect

Additive Manufacturing
journal homepage: www.elsevier.com/locate/addma

Full Length Article

Recycled polypropylene blends as novel 3D printing materials T

a,⁎ a b c
Nicole E. Zander , Margaret Gillan , Zachary Burckhard , Frank Gardea
a
United States Army Research Laboratory, Weapons and Materials Research Directorate, Aberdeen Proving Ground, Aberdeen, MD, 21005, United States
b
Montana Tech, Department of Mechanical Engineering, Butte, MT, 59701, United States
c
United States Army Research Laboratory, Vehicle Technology Directorate, Aberdeen Proving Ground, Aberdeen, MD, 21005, United States

ARTICLE INFO ABSTRACT

Keywords: Consumer-grade plastics can be considered a low-cost and sustainable feedstock for fused filament fabrication
Polymer additive manufacturing (FFF) additive manufacturing processes. Such materials are excellent candidates for distributed manufacturing,
3D printing in which parts are printed from local materials at the point of need. Most plastic waste streams contain a mixture
Fused filament fabrication of polymers, such as water bottles and caps comprised of polyethylene terephthalate (PET) and polypropylene
Recycled plastics
(PP), and complete separation is rarely implemented. In this work, blends of waste PET, PP and polystyrene (PS)
Polymer blends
were processed into filaments for 3D printing. The effect of blend composition and styrene ethylene butylene
Polypropylene
styrene (SEBS) compatibilizer on the resulting mechanical and thermal properties were probed. Recycled PET
had the highest tensile strength at 35 ± 8 MPa. Blends of PP/PET compatibilized with SEBS and maleic an-
hydride functionalized SEBS had tensile strengths of 23 ± 1 MPa and 24 ± 1 MPa, respectively. The non-
compatibilized PP/PS blend had a tensile strength of 22 ± 1 MPa. PP/PS blends exhibited reduced tensile
strength to ca. 19 ± 1–3 MPa with the addition of SEBS. Elongation to failure was generally improved for the
blended materials compared to neat recycled PET and PS. The glass transition was shifted to higher temperatures
for all of the blends except the 50–50 wt. % PP/PET blend. Crystallinity was decreased for the blends, but was
highest in the 75–25 wt. % PP/PS and the 50-50 wt. % PP/PET blend with SEBS-maleic anhydride. Solvent
extraction of the dispersed phase revealed polypropylene was the matrix phase in both the 50–50 wt. % PP/PET
and PP/PS blends.

1. Introduction
Plastics consumption for consumer products and packaging is con-
tinuing to grow despite environmental and sustainability concerns. In
the United States alone, almost 32 million tons are generated annually,
yet recycling rates are typically only at 5% [1,2]. More efficient re-
processing techniques and value-added applications are likely needed
to change these recycling trends. One of the complications of plastic
recycling is the need for sorting of different types after collection since
single-stream recycling is common. In addition, some packaging con-
tains more than one type of plastic, such as water bottles with poly-
ethylene terephthalate (PET) bodies and polypropylene (PP) caps ac-
counting for ca. 5% of the waste or yogurt tubs with PP bodies and
high-density polyethylene (HDPE) lids accounting for ca. 5–10% of the
total waste.
The preparation of polymer blends of such recycled materials is
potentially an attractive way to reuse mixed waste streams at a lower
cost. In addition, polymer blending is a facile way to tailor mechanical
properties of polymers or improve certain properties while maintaining
others. Polypropylene has comparable toughness to ABS, but does not
have sufficient strength to be classified as an engineering plastic [3].
Reinforcement with a rigid polymer such as polystyrene (PS) or PET can
improve mechanical properties. However, most polymers suffer from
incompatibility, leading to poor phase morphology and mechanical
properties. There have been a number of studies evaluating the effect of
different compatibilizers to improve the stability of the blends [4–6]. Of
particular interest are studies of PP/PET and PP/PS blends, commonly
found in many consumer waste streams. PP is considered immiscible
and incompatible with both PS and PET. Many researchers have de-
scribed such blend optimization through the use of compatibilizing
copolymers such as SEBS or grafted PP in which one component can
interact with each phase [7]. Wang et al. utilized supercritical CO2 to
generate block and graft copolymer interfacial modifiers in-situ via
reactive extrusion. Supercritical CO2 facilitated the grafting reaction
due to its plasticizing effect [8]. Impact strength was improved most for
the samples with the highest supercritical CO2 concentration [9]. Ma-
caúbas et al. investigated PP/PS blends compatibilized with the triblock
copolymers styrene butadiene styrene (SBS) and styrene ethylene

⁎
Corresponding author.
E-mail address: nicole.e.zander.civ@mail.mil (N.E. Zander).

https://doi.org/10.1016/j.addma.2018.11.009
Received 1 October 2018; Received in revised form 5 November 2018; Accepted 6 November 2018
Available online 08 November 2018
2214-8604/ © 2018 Elsevier B.V. All rights reserved.
N.E. Zander et al.
butylene styrene (SEBS) and the effect on interfacial tension. SEBS was
found to be more efficient, but both copolymers served to reduce the
size of the dispersed phase and the interfacial tension [10]. Brostow
et al. found 5 wt. % SEBS to be optimal for improving PP/PS blend
morphology, generating polystyrene-styrene and polypropylene-ethy-
lene/butylene microphases and a significant size reduction of the dis-
persed phase in the matrix [11]. Huo et al. compounded PP/PS blends
with a maleic anhydride grafted PP and amino terminated PS to im-
prove miscibility [12]. PP/PET blend morphology can also be improved
with the addition of SEBS. Inoya et al. found significant size reduction
in the PP dispersed phase in recycled PP/PET blends with 5 phr com-
patibilizer [13]. Heino et al. observed improved stabilization and im-
pact strength of PP/PET blends with functionalized SEBS containing
maleic anhydride or glycidyl methacrylate likely due to the PET car-
boxylate end group reaction with the grafted SEBS midblocks. Average
particle size was significantly reduced with the functionalized SEBS
blends and the interfacial adhesion was improved [14]. Another ap-
proach to compatibilize PP/PET blends is with maleic anhydride
grafted PP [15,16]. Silane coupling agents, which change interfacial
adhesion typically between a polymer and inorganic substrate, can also
serve as compatibilizers for PP/PET blends. The alkoxy silane groups
react with PET end group hydroxyls, strengthening its interaction with
PP [17]. Impact properties of PP/PET blends were particularly im-
proved by the addition of a silane terminated polybutadiene (POLYV-
EST 25 by HÜLS-A VEBA Group Co). Singh et al. investigated the me-
chanical properties of ABS/high impact polystyrene (HIPS) blends [18].
In addition to the work by Inoya et al., there has been other work into
blends and composites of recycled polymers. Mangat et al. embedded
silk and sheep wool fibers into PLA to generate a bio-degradable
composite for biological applications [19]. Mantia et al. investigated
recycled PET/PLA blends and found that adding a small amount of PLA
increased the thermal stability without compromising the mechanical
properties [20]. Remili improved the recyclability of PS by adding an
organophilic clay which served to increase the effective molecular
weight due to crosslinking [21]. Bourmaud increased the properties of
recycled PP by adding vegetal fiber [22].
Recently, Zander et al. and others have shown that recycled poly-
mers can effectively be used to make fibrous membranes for use in a
variety of applications such as filtration and tissue engineering [23–31].
Shin and Chase formed nanofibers from styrofoam using a solution-
based electrospinning technique [28], and Rajabinejad et al. made fi-
bers from bottle-grade PET using melt-electrospinning [32]. Fibers were
also successfully prepared from blends of PET, PP and PS. Blends with
recycled PET showed improved properties compared to the neat PP, PS
and PP/PS blends [30]. Recycled materials have also been used in ad-
ditive manufacturing (AM). In this process, parts are made by the
consecutive deposition of layers of material as directed by a three di-
mensional (3D) computer aided design (CAD) model. The process
known as material extrusion or fused filament fabrication (FFF) is the
most common polymer AM technique. Solid polymer filaments are
melted in a liquefier and deposited on a temperature-controlled bed.
ABS is a widely used polymer in FFF due to its amorphous nature and
limited shrinkage and warpage upon cooling. While a few of other
polymers such as PLA, polyamide, HIPS and polycarbonate are com-
monly used, FFF feedstocks are generally limited. Commodity polymers
used in packaging and consumer products- polyolefins, PET and poly-
styrene- are rarely used in FFF. A few companies have commercialized
filaments from recycled polymers such as ABS (Kickfly®) and PLA
(Maker Geeks®). Refil® and B-PET® make filament from recycled PET. In
addition, FFF printing using recycled HDPE, PLA, and low density
polyethylene (LDPE) derived from meals-ready-to-eat (MRE) bags has
been reported [33–35]. In previous work, we have demonstrated the
use of 100% recycled and unmodified PET in the FFF of long-lead time
military parts, and found parts printed from recycled PET had com-
parable properties to those made from ABS and polycarbonate-ABS
[36]. To the best of our knowledge, we are the first to report 3D
123
Additive Manufacturing 25 (2019) 122–130
printing of recycled blends from consumer-grade plastics.
Here we report the use of recycled PP/PET and PP/PS blends,
compounded with or without a SEBS compatibilizer for the purpose of
fabricating feedstocks for FFF. While these polymers are commonly
used in many applications, they are not widely utilized as feedstocks for
FFF due to a variety of reasons including water absorption leading to
molecular weight reduction (in PET), lack of control of crystallinity,
and shrinkage/warpage, which can make printing difficult. Recycled
polymers may contain contaminants and processing aids, and have
likely been subjected to several thermal and mechanical stresses during
processing cycles, potentially leading to lower performance than a
virgin part due to deterioration of the polymer chains. However, the
tensile strength of injection molded recycled PET (rPET) is similar to
virgin PET and compares favorably to ABS (68 vs 55 MPa) [37,38].
Thus, it was predicted that the mechanical properties of printed blends
of rPET with other recycled polymers could be at least comparable to
prints made with commercial filament. Blends of rPP and rPET formed a
consistent, flexible filament that was easily 3D printed. Blends of rPS
and rPET were attempted, but yielded a brittle material that broke in
the print head. In addition, recycled PS was quite brittle and could not
spooled. Thus blends of PS with PP were pursued to improve the flex-
ibility of the filament. Although tensile properties were reduced com-
pared to recycled PET, elongation to failure was improved for PET and
PS blended with PP, and tensile strengths were comparable to com-
mercial filaments such as HIPS [39].
2. Materials and methods
2.1. Preparation of polymer filament
To fabricate the filament, feedstock was obtained from recycle bins,
cleaned by rinsing with water and then ethanol and dried. The labels
were removed before cutting in to pieces that could be fed into the
paper shredder (Compucessory model CCS60075). Sources of polymer
included clear polyethylene terephthalate plastic salad containers
(rPET), opaque polypropylene yogurt containers (rPP), and clear
polystyrene petri dishes (rPS). Different brands of each material were
used to introduce realistic variation in the data. In addition, some of the
yogurt containers had polyethylene in the lids, and this contamination
was included in the dataset. The cleaning, removing of labels and glue,
sorting and drying of the plastic was carefully controlled. However,
some of the plastics contained a certain percentage of recycled content
which was not controlled. Thus, the full thermal history of all feedstock
was unknown, and this could potentially affect the material properties
of the prints. Source and age or heat/light exposure of the plastics could
also have an effect.
Drying of PET and materials to be blended with PET is critical to
prevent melt hydrolysis of PET. PET shreds were then dried under va-
cuum overnight at 120 °C, while the PP was dried overnight under
vacuum at RT. The rPS was ground into powder in a blender, and was
maintained under ambient conditions prior to use. SEBS (G1652) and
SEBS grafted with maleic anhydride (1.4–2 wt. %, SEBS-MA, FG1901
Kraton®) were also dried overnight under vacuum at RT before use.
Blends were prepared by weighing polymer in ratios of 25/75, 50/50,
75/25 and hand mixing before feeding into the extruder.
Compatibilized blend ratios were fixed with equal weights of each
polymer and 5 wt % SEBS or SEBS-MA (final ratio 47.5/47.5/5).
A Thermo Scientific Process 11 Parallel Twin-Screw Extruder with 8
temperature zones and a conveying or non-mixing screw design was
used for extrusion. The parameters were determined based on previous
work [36]. The feed port was fixed at 140 °C and the adjacent zone to
170 °C to prevent clumping of the material while feeding. The following
5 zones were fixed at 260 °C. The die (2.5 mm) was set at 245 °C. Screw
speed was held constant at 100 rpm. A conveyor belt (at RT) with speed
set to 2 or ca. 1 m/min collected the filament (Pharma 11, Thermo
Scientific). Shredded polymer was first extruded, pelletized (Varicut
N.E. Zander et al.
Pelletizer, Thermo Scientific), and then extruded a second time to im-
proved uniformity of the filament diameter and blend mixing. The ex-
truder speed for the second extrusion was set to 25 rpm. A combination
of the conveyor belt and spooler (Filabot, speed set to 1.5 turns) was
used for the rPP/rPS filament.
2.2. 3D printing of recycled plastics
Before printing, filament was dried under vacuum overnight to re-
move any excess moisture. Both Type V tensile bars (ASTM D638) and
DMA bars (35 mm × 12.5 mm × 2 mm) were printed for character-
ization on a Lulzbot Taz 6® FFF printer. Recycled PP/PET blends were
printed on a PET tape surface. Recycled PP/PS blends were printed on a
polyetherimide surface. Simplify 3D was used to edit the STL files. For
all samples, a100 °C bed temperature and a 260 °C nozzle temperature
was used. A Y or flat on the bed build orientation was used, with
0.2 mm layer height, 2 shell layers and 100% infill [40]. 45/−45° or-
ientation for the infill was used for tensile bars, and 0° for DMA bars.
Tensile and DMA bar print speeds was 50 mm/s and 20 mm/s respec-
tively.
2.3. Fabrication of control tensile bars
Feedstock materials were cleaned as detailed above. Tensile bars
from PET bottles and yogurt containers were cut using a punch press
(Type C, ASTM D412). Injection molded tensile bars were made from
clean, dry rPET, PP and PS shreds on an Xplore® Microcompounder
(MC15) [36]. The polymer was compounded at 260 °C for 5 min and
maintained in the transfer line at 260 °C prior to injection into a mold
(Type V, ASTM D638) (temperature = 65 °C, pressure = 6 bar).
2.4. Chemical characterization
Chemical information was obtained via analysis by Fourier trans-
form infrared-attenuated total reflectance (FTIR-ATR) (Thermo Nicolet
Nexus 870 ESP) using 256 scans and 4 cm−1 resolution over a range of
4000–400 cm−1.
2.5. Thermal characterization
Differential scanning calorimetry (DSC) with a heat/cool program
(Discovery DSC, TA Instruments) was used to evaluate thermal prop-
erties. Samples were heated at 20 °C per min to 300 °C and cooled at the
same rate to −50 °C. TRIOS software (TA Instruments) was used to
analyze the data. Crystallinity for the semi-crystalline PET and PP
polymers was calculated as previously described (PET: 140 J/g, PP:
207 J/g) [36,41]. Crystallinity for each semi-crystalline polymer in the
blends was calculated by multiplying the above equation by the mass
fraction of each polymer.
Dynamic mechanical analysis (DMA, Q800 TA Instruments) enabled
characterization of the thermal mechanical properties using the single
cantilever mode. The temperature was ramped from −50 °C to 200 °C
at a rate of 2 °C per min and frequency of 1.0 Hz. The amplitude set-
point was 200 μm. The dimensions of the printed DMA bars were
35 mm x 12.5 mm x 2 mm with a span of 17.5 mm. Three replicates
were tested for each blend composition.
2.6. Rheology
Melt viscosity at 270 °C was measured using an AR2000 rheometer
(TA Instruments) with 25 mm parallel aluminum plates. The gap was
fixed at 1000 μm with the shear rate ramped from 0.1 to 10 s−1.
2.7. Uniaxial tensile measurements
Uniaxial tensile experiments were performed at a displacement rate
124
Additive Manufacturing 25 (2019) 122–130
of 2 mm/min on a servohydraulic test frame with 2 kN grips and 5 kN
load cell (Instron model 5000R). Four replicates were evaluated for
each blend composition. Strain was determined from a digital image
correlation (DIC) system consisting of one 1 megapixel monochrome
digital camera (Point Grey) which streamed images (2–10 frames per
second) to an attached computer. Camera recording settings were en-
tered using Correlated Solutions Vic-SnapC software. Post-processing
was done with Correlated Solutions Vic-2D software program, as has
been described previously [36]. Before testing, the samples were spray
painted to create a speckle pattern for DIC. The morphology of frac-
tured tensile bars were imaged using a field-emission scanning electron
microscope (SEM, Hitachi S-4700) after sputter coating with gold-pal-
ladium. Solvent extraction on fracture surfaces was conducted with
hexafluoroisopropanol to remove the PET phase in the rPP/rPET 50-50
blend and chloroform to remove the PS phase in the rPP/rPS 50-50
blend.
3. Results and discussion
3.1. Chemical analysis
Qualitative chemical characterization was performed using FTIR to
verify extruded feedstock compositions (Fig. 1). Non-overlapping peaks
were identified for each polymer and are denoted with dashed lines of
matching color. The CH3 bending at 1376 cm−1 was utilized for PP,
while the ester carbonyl C]O stretch at 1720 cm−1 and CH bending at
690 cm−1 was used to identify PET and PS, respectively. The PP iden-
tifier was present in all of the samples except the pure PET and PS,
while the PS and PET identifiers were only present in the pure PET or
PS and their blends with PP.
3.2. Rheology
The melt viscosity of the recycled polymer blends was measured to
obtain information about the interaction of the polymers in the blend
and effect of compatibilizers (Fig. 2). At low shear rates, the neat
polymers had lower viscosities compared to the blends. Recycled PET
and PS had lower viscosity than PP. For the PP/PET blends, the addition
of SEBS reduced the viscosity relative to the blend without SEBS,
however the viscosity of the blends remained higher than PP or PET
alone. However, the addition of 5% SEBS-MA led to a marked increase
in the viscosity. This is likely due to the hydrogen bonding interaction
of the maleic anhydride with the PET chain ends and effective
Fig. 1. Chemical characterization of recycled polymer blends using FTIR.
Dashed lines with matching color denote marker peaks for each polymer. All
blends were 50-50 by weight. Select blends were compatibilized with 5 wt. %
unfunctionalized (SEBS) or maleic anhydride functionalized SEBS (SEBS-MA).
N.E. Zander et al. Additive Manufacturing 25 (2019) 122–130

Fig. 2. Rheological behavior of recycled polymer blends. (A) Polyethylene terephthalate (rPET) and polypropylene (rPP), (B) polystyrene (rPS) and polypropylene
(rPP). All blends were 50-50 by weight. Select blends were compatibilized with 5 wt. % unfunctionalized (SEBS) or maleic anhydride functionalized SEBS (SEBS-MA).

molecular weight increase, in addition to the SEBS interaction with PP
and interfacial tension reduction, which has been documented by
others [42]. This trend is not observed for the PP/PS blends; instead
SEBS-MA addition leads to a sharp decline in viscosity with shear rate.
Unfunctionalized SEBS, however, increases the viscosity due to its
ability to interact with both the alkyl chains on PP and phase mix with
PS. The viscosity of the uncompatibilized blend appears only slightly
higher than neat rPP, suggesting minimal interaction. SEBS-MA was not
expected to interact more strongly than SEBS with rPS phase due to the
polarity mismatch, but it was thought there would be some improve-
ment in interaction over the uncompatibilized blend. In addition, the
viscosity of the rPP/rPS blend with SEBS-MA decreased with shear rate.
It is possible that the domain sizes increased due to coalescence which
served to reduce viscosity, although this was not studied in this work
[43]. It is notable that the viscosities of the recycled polymers and
blends were lower than that of polymers typically used in FFF processes
such as ABS (zero-shear viscosity 18,000–75,000 Pa s) [44].
3.3. Thermal analysis
The thermal behavior of the recycled polymers was probed via
differential scanning calorimetery (DSC) to determine the effect of the
immiscible blends on crystallization and melting (Fig. 3, Table 1). Re-
cycled PET has a melting peak at ca. 252 °C, which rPP melts at ca.
170 °C. Two distinct melting peaks are present in the rPP/rPET blends,
as expected, confirming immiscibilty of the blends. The addition of the
SEBS and SEBS-MA compatibilizer did not appear to improve mis-
cibility. However, the melting temperatures of rPP and rPET were
slightly decreased in the rPP/rPET and rPP/PS blends, with or without
compatibilizer (except rPP/rPET SEBS). Cold crystalization peaks for
rPET at ca. 120 °C are observed in all samples with PET except the blend
with 25% rPET. The enthalpy increase of the cold crystallization peak
corresponded nicely as expected with the increase in rPET concentra-
tion for the uncompatibilized blends and neat rPET, but the addition of
SEBS and particularly SEBS-MA served to reduce the enthapy of the PET
cold crystallization peak. The PET cold crystallization peak was reduced
by half from the 75% rPET blend to the 50% blend, was non-apparent in
the 25% rPET blend, and further reduced when SEBS and particularly
SEBS-MA was added. Possibly chain movement for recrystallization was
restricted by the PP phase, but the crystallization temperatures were
largely unchanged for these rPP/rPET blends. It should be noted that
the recycled polypropylene source had an additional melting peak at ca.
125 °C, attributed to low density polyethelene (LDPE) contamination,
potentially masking rPET’s cold crystallization peak and complicating
interpretation of the results. In most cases this peak was quite small and
the recrystallization peak of rPET could be clearly seen with the ex-
ception of the 75-25 rPP/rPET blend, as discussed above.
Upon cooling the sample, rPET and rPP crystallize at ca. 199 °C and
122 °C, respectively. Recycled PET’s crystallization temperature was
largely unaffected by blending with rPP except for the 75% rPET blend
and the SEBS-MA compatibilized blend. The Tc for the former was
shifted up 9 °C possibly due to rPP nucleation reducing the free energy
for crystal consolidation [45]. The Tc of the SEBS-MA blend was de-
creased by 5 °C potentially due to a plasticizing effect of the compati-
bilizer [46]. Chen et al. has reported this plasticization phenomenon in
similar systems, leading to a facilitation of crystallization and better

Fig. 3. Representative differential scanning calorimetry curves for FFF printed recycled polymer blends. (A) Heating showing recrystallization and melting peaks, (B)
cooling showing crystallization peaks. rPET (recycled polyethylene terephthalate), rPP (recycled polypropylene), rPS (recycled polystyrene). Select blends were
compatibilized with 5 wt. % unfunctionalized (SEBS) or maleic anhydride functionalized SEBS (SEBS-MA).

125
N.E. Zander et al. Additive Manufacturing 25 (2019) 122–130

Table 1
Thermal analysis of FFF printed recycled polymer blends.
Sample Melting Crystallization % Crystallinity

Tm (ºC) ΔHm (J/g) Tc (°C) ΔHc (J/g) ΔHcc(J/g) rPET rPP

rPET bulk 248.5 47.8 188.2 46.5 —— 23.0 ——

rPP bulk 169.9 94.6 110.7 92.0 —— —— 45.7
rPET 252.3 45.9 198.8 43.8 27.9 12.9 ——
rPP 167.9 67.6 121.8 81.7 —— —— 32.7
rPP/rPS 25-75 161.5 7.1 107.1 4.4 —— —— 0.9
rPP/rPS 50-50 163.5 21.2 117.1 29.3 —— —— 5.1
rPP/rPS 75-25 165.6 37.2 119.4 58.6 —— —— 13.5
rPP/rPS SEBS 162.4 27.5 113.1 42.7 —— —— 6.6
rPP/rPS SEBS-MA 161.4 34.9 114.4 43.7 —— —— 8.4
rPP/rPET 25-75 164.1/249.3 8.9/36.3 113.1/207.9 25.4/32.0 20.4 8.5 4.4
rPP/rPET 50-50 164.6/250.5 33.4/24.3 116.3/200.1 41.4/19.9 10.6 4.9 8.1
rPP/rPET 75-25 164.7/250.4 23.3/11.3 118.3/199.1 82.6/10.9 —— 2.0 8.4
rPP/rPET SEBS 165.5/253.3 19.4/19.3 112.2/198.3 24.9/15.8 5.2 5.0 4.7
rPP/rPET SEBS-MA 162.3/247.9 33.5/19.8 112.8/194.2 39.8/16.1 0.8 6.8 8.1

chain mobility [46]. The Tc of rPP in the rPP/rPS blends exhibited Table 2
significantly more response to the blend formulation, resulting in a Glass transition temperatures of FFF printed recycled polymers.
2.4 °C decrease in the 75% PP blend to a 15 °C drop in the 25% rPP Sample Glass Transition (ºC)
blend. Tc was lower with the compatibilizers compared to the 50–50
blend, and crystallinity was increased possibly due to plasticization DSC Tan δ
from the copolymers, as discussed above. The crystallization tempera-
rPET 72.5 83.5
ture of rPP was also reduced by ca. 7–10 °C in the 25–75 rPP/rPET rPS 94.8 104.0
blend and all blends with either compatibilizer. The rPP crystallization rPP/rPSa 25-75 100.2 110.6
peak had a small shoulder in most cases due to the contribution of rPP/rPSa 50-50 103.4 114.5
crystallization from the LDPE impurity. Relative crystallinity for each rPP/rPSa 75-25 106.2 114.1
rPP/rPS SEBSa 103.4 110.9
polymer was reduced in the blends, particularly when the polymer was
rPP/rPS SEBS-MAa 104.7 111.3
the minor component (25%). In general, the crystallinity of recycled rPP/rPET 25-75 68.1 87.9
polymers increases due to the reduction in molecular weight and chain rPP/rPET 50-50 73.2 83.7
entanglements from the repeated thermal processing cycles [47,48]. rPP/rPET 75-25 69.9 84.7
However for polymer blends, Itim et al. found a similar trend of de- rPP/rPET SEBS 77.8 92.5
rPP/rPET SEBS-MA 80.0 92.5
creased PET crystallinity in multiple extrusion cycles of PET bottles
contaminated with PP caps [49]. The PP acted like a nucleation agent, a
Tg reported for rPS.
reducing the interfacial free energy required for crystallization. Relative
crystallinity tracks well with relative mass fractions for the blends, with
the exception of the 75-25 rPP/rPET blend in which only the rPET Generally high values correspond to viscous behavior while low values
crystallinity tracked well. The addition of SEBS appears to increase to elastic behavior. The value of the neat rPET peak and blend with 25%
crystallinity over the uncompatibilized 50-50 blends, and compatibili- rPP was nearly identical at 0.36 and 0.37, respectively. The height of
zation with SEBS-MA led to a further increase. Kuzmanović et al. found the peak dropped to 0.20 in the 50-50 blend and further to ca. 0.11 for
that PP crystallite size was reduced in PET blends due to a nucleation the 75% rPP and blends with compatibilizer. Thus, the tan delta values
effect of PET, although this nucleation effect was not observed in our decreased with increasing rPP content, reflecting the viscous nature of
studies [50]. It is possible that the isolated or unreacted SEBS particles the PET and elastic behavior of blend [42]. The value of the neat rPS
acted as nucleation sites increasing crystallinity [46,50]. tan delta peak was significantly higher than rPET at 1.73 due to the
The glass transition temperature (Tg) was determined using DSC and amorphous nature of the polymer. The 25–75 rPP/rPS blend had a si-
the apex of the tan delta peak from dynamic mechanical analysis milar tan delta value (1.69), but the value was reduced to 0.93 for the
(DMA). As expected, DMA results show higher glass transition tem- 50-50 blend. Further addition of rPP (75-25 blend) or compatibilizer
perature values compared to DSC, although the trends are generally reduced the value to 0.33.
similar. Results for the Tgs of rPET and rPS are reported in Table 2. (The The addition of rPET, rPS and SEBS compatibilizers changed the
Tg of polypropylene was nearly imperceptible and therefore was not ability of rPP to store energy, which is reflected by changes in the
included in the results). The Tg of rPET calculated from the tan delta storage modulus (Fig. 5). Neat rPET had a storage modulus of 1433 MPa
peak was minimally impacted for the 50-50 and 75-25 rPP/rPET blends, at 40 °C, while neat rPP’s storage modulus was much lower (798 MPa).
but increased by 9 °C for the blends with SEBS and SEBS-MA. Trends in There was little change in the storage modulus with the addition of 50%
the Tg change for the 25–75 rPP/rPET blends are in disagreement be- rPET (747 MPa), while 75% rPET served to slightly reduce the modulus
tween the DSC and DMA results, with DSC indicating a ca. 4 °C de- (667 MPa). This reduction in the modulus with 75% PET seems coun-
crease, and DMA a ca. 4 °C increase. The Tg of rPS increased for all the terintuitive particularly since the crystallinity is increased, but Yoon
blends with rPP by ca. 6–12 °C. This increase could be attributed to et al. found similar results in blend systems with 50–90% PET and at-
molecular confinement of PS’s amorphous domains by PP’s crystalline tributed it to poor adhesion between PET and PP. The largest changes
domains since rPS’s Tg is near rPP’s crystallization temperature [51]. came from the addition of 25% rPET (870 MPa) and for the rPP/rPET
The 75-25 rPP/rPS blend appeared to have the greatest effect on the Tg blend with SEBs-MA (980 MPa). In the former system, the Tc for rPP
of rPS, which agrees with the above rationale. and rPET were closest together of all the blends and the Tg of rPET was
DMA was also used to investigate the viscoelastic properties and lower than most of the blends, potentially an indication of increased
relaxations in the polymers. Plots of the tan delta, or the relationship miscibility. For the rPP/rPET SEBS-MA, the total crystallinity was
between the elastic and viscous response, are displayed in Fig. 4. highest compared to the other rPP/rPET blends, which served to

126
N.E. Zander et al. Additive Manufacturing 25 (2019) 122–130

Fig. 4. Tan delta of FFF printed recycled polymer blends determined by dynamic mechanical analysis. (A) Recycled polypropylene/polyethylene terephthalate
blends, (B) recycled polypropylene/polystyrene blends. Select blends were compatibilized with 5 wt. % unfunctionalized (SEBS) or maleic anhydride functionalized
SEBS (SEBS-MA).

increase the stiffness. However, all values are significantly less than
neat rPET. This is due to the ductile nature of rPP and the SEBS co-
polymers, which led to a reduced stiffness in the blends and weak
mechanical interlocking between the immiscible phases. The reduction
in modulus could also be related to the phase connectivity, in which PP
domains are connected forming the matrix phase and hence modulus is
closer to that of PP. The storage modulus behavior for the rPP/rPS
blends generally followed the rule of mixtures law, with modulus re-
duced in proportion to amount of rPP added. The addition of 25% rPP
to rPS reduced the storage modulus from 1739 MPa to 1459 MPa.
Further additions of 50 and 75% rPP reduced the modulus to 1245 and
1040 MPa, respectively. SEBS and SEBS-MA additions in the 50-50
blend yielded the lowest storage moduli of ca. 830 MPa, similar to neat
rPP. This may be due to the rubbery nature of the SEBS elastomers or PP
phase connectivity as discussed above.
3.4. Mechanical testing
To get a better understanding of different recycled polymer feed-
stocks and the best properties to expect from such materials, mechan-
ical testing was performed. Tensile dogbones were cut using a die out of
soda bottles (rPET) and yogurt containers (rPP), and the shredded
polymers were injection molded. (Polystyrene materials were too brittle
to punch out). Representative stress-strain curves are displayed in
Fig. 6A. Table 3 reports the peak stress and strain for the die-cut, in-
jection molded and 3D printed materials. The soda bottles (die-cut) had
the highest tensile strength, nearly 5 times that of polypropylene and
polystyrene materials. The rPET bottles had yielding followed by strain
hardening, with substantial strain before failure. In comparison, the
injection molded rPET failed at much lower strain value. This may be
due to the additional extrusion cycle and molecular weight reduction
due to moisture uptake or loss of chain orientation from the blow
molding process. Fig. 6B displays representative stress-strain curves for
3D printed tensile bars. Average values for the ultimate tensile strength
of each material are displayed in Fig. 7. The tensile strength of printed
rPET was nearly twice that of rPS and rPP (35.1 ± 8 vs. 19.9 ± 3.9
and 20.1 ± 2.3 MPa, n = 4). All of the blends had reduced tensile
strengths compared to the neat rPET, which was expected due to the
weaker mechanical properties of rPP and immiscibility of the blends.
The differences between the neat rPP and rPS and the blends were not
significant except for the rPP/rPET SEBS-MA which was significantly
higher than neat rPP. SEBS-MA likely can interact with the PET chains,
accounting for the increased tensile strength. But SEBS copolymers are
elastomers with low tensile strength, and are typically used to improve
impact rather than tensile strength. The rPP/rPET 50-50 blend had the
lowest tensile strength of all the blend formulations evaluated at
17.2 ± 3.6 MPa, significantly lower than the compatibilized rPP/rPET
blends (23.1 ± 1.1 MPa rPP/rPET SEBS, 24.2 ± 1.3 rPP/rPET SEBS-
MA). Based on the fracture surfaces (Fig. 8), the 50-50 blend had the
weakest interfacial adhesion. Inoyen et al. attributed the weak tensile
properties of a 50-50 virgin PP/PET blend to the phase separation, with
the voids acting as stress concentration regions. The tensile strength of

Fig. 5. Storage moduli of FFF printed recycled polymer blends determined by dynamic mechanical analysis of recycled polymers. (A) Recycled polypropylene/
polyethylene terephthalate blends, (B) recycled polypropylene/polystyrene blends. Select blends were compatibilized with 5 wt. % unfunctionalized (SEBS) or maleic
anhydride functionalized SEBS (SEBS-MA).

127
N.E. Zander et al. Additive Manufacturing 25 (2019) 122–130

Fig. 6. Representative stress-strain curves of recycled polymers. (A) Die-cut and injection molded, (B) FFF printed. All blends were 50-50 by weight. Select blends
were compatibilized with 5 wt. % unfunctionalized (SEBS) or maleic anhydride functionalized SEBS (SEBS-MA).

Table 3 elongation to failure compared to injection molded samples (60 and 18%
Peak stress and strain of recycled polymers. compared to 14 and 10%, respectively). Printed rPS was extremely brittle
Sample Peak Stress (MPa) Peak Strain (mm/mm)
with elongation to failure less than 1% compared to 14% for injection
molded. Interestingly, the elongation to failure was significantly increased
rPP Die-cut 25.9 ± 6 0.09 ± 0.04 for the uncompatibilized rPP/rPET blend (47%), potentially due to the
rPET Die-cut 103.2 ± 23 0.5 ± 0.06 weak interface and the ability of the rPET tubes to pull out from the
rPP Injection Molded 34.5 ± 1 0.07 ± 0.01
rPS Injection Molded 32.2 ± 9 0.008 ± 0.002
matrix (Fig. 8). The elongation to failure was reduced to 3–4% with the
rPET Injection Molded 67.8 ± 2 0.03 ± 0.002 addition of the SEBS copolymers, which served to increase interfacial
rPP 3D Printed 20.1 ± 2 0.2 ± 0.02 bonding but also reduce pull out of the PET tubes or spheres. All of the
rPS 3D Printed 19.9 ± 4 0.007 ± 0.003 rPS blends exhibited an increase in elongation to failure due to the ad-
rPET 3D Printed 35.1 ± 8 0.02 ± 0.009
dition of the ductile rPP phase (9–21%). The largest increase was ob-
rPP-rPET 17.2 ± 4 0.4 ± 0.2
rPP-rPET SEBS 23.1 ± 1 0.03 ± 0.008 served for the rPP/rPS SEBS blend, likely due to the improved interaction
rPP-rPET SEBS-MA 24.2 ± 1 0.04 ± 0.0006 between polymer phases. As discussed above, the rPS is brittle and doesn’t
rPP-rPS 23.0 ± 1 0.1 ± 0.05 undergo any significant elongation before breaking. Thus unlike in the
rPP-rPS SEBS 19.0 ± 3 0.2 ± 0.09 case for the more ductile rPET, strong interfacial adhesion with rPP im-
rPP-rPS SEBS-MA 22.9 ± 1 0.1 ± 0.1
proves the elongation for rPP/rPS blends.
Fractured 3D printed tensile bar cross-sections are displayed in
Fig. 8. Recycled polypropylene exhibited ductile fracture, and there was
evidence of fibril deformation and stretching (Fig. 8A). Recycled
polystyrene and PET cross-sections showed generally brittle fracture,
although some tear fractures generated during deformation of the
polymer are visible (Fig. 8B, C). The rPP/rPET 50-50 blend has a cy-
linder or fractured sphere in matrix morphology with the fracture
generally brittle in nature, but there is evidence of cylinder/sphere pull-
out and regions of ductile failure like those seen in neat rPP (Fig. 8D).
Macroscopically, this sample showed ductile behavior with incomplete
breakage in the tensile test. The adhesion of the two phases is generally
poor, with some regions of gaps between the cylinders/spheres and the
matrix. Cylinder/sphere diameters were not uniform in size and ranged
from 2 to 5 μm. To determine composition of the dispersed and matrix
phases, solvent extraction in which the rPET and rPS phases were re-
moved from the rPP/rPET and rPP/rPS 50-50 blends was done (Fig. 9).
After extraction and rinsing, the matrix for both materials is intact with
Fig. 7. Ultimate tensile strength of FFF printed recycled polymers. All blends holes where the rPET and rPS once were. Thus, for these compositions,
were 50-50 by weight. Select blends were compatibilized with 5 wt. % un- the rPET and rPS are represented in the dispersed or cylinder/sphere
functionalized (SEBS) or maleic anhydride functionalized SEBS (SEBS-MA). phase while the matrix is composed of rPP, corroborating moduli values
discussed above. The volume fraction for the rPP/rPS 50-50 blend was
the rPS/rPP blends were all fairly similar, ranging from 19.0 ± 3.4 to 1.1, and thus well matched to the feed weight fraction. However, the
22.9 ± 1.4 MPa for the SEBS and SEBS-MA compatibilized to the un- rPP/rPET 50-50 blend volume fraction was 1.4, which agrees well with
compatibilized. Based on the rheological data, there was less of an in- Fig. 9A showing a greater percentage of the volume in the matrix or PP
teraction between the phases even with the addition of the SEBS co- phase. The rPP/rPET 50-50 blend compatibilized with 5 wt. % SEBS
polymers. While the SEBS-MA was not expected to interact strongly had larger cylinders/spheres on the order of 10 μm in addition to
with the PS, the unfunctionalized SEBS with its styrene groups should 1–2 μm sized cylinders/spheres (Fig. 8E). There is evidence of the SEBS
have formed a close interaction. Potentially, the effect on the impact particles at the interface between phases and matrix adhesion is
strength would be more apparent. somewhat improved. The presence of phase-separated SEBS particles
Recycled polypropylene and PET printed samples had a longer could indicate that 5 wt. % SEBS exceeds the useful threshold, and

128
N.E. Zander et al. Additive Manufacturing 25 (2019) 122–130

Fig. 8. Scanning electron microscopy images of FFF printed recycled polymer fracture surfaces. (A) Recycled PP, (B) recycled PS, (C) recycled PET, (D) rPP/rPET 50-
50, (E) rPP/rPET SEBS, (F) rPP/rPET SEBS-MA, (G) rPP/rPS 50-50, (H) rPP/rPS SEBS, (I) rPP/rPS SEBS-MA. Scale bar denotes 10 μm.

lower amounts may be more effective. The rPP/rPET 50-50 blend
compatibilized with 5 wt. % SEBS-MA has similar cylinder/sphere sizes
to the uncompatibilized blend, but there is a marked improvement in
the matrix adhesion, with almost no gaps between phases perceptible
(Fig. 8F). The rPP/rPS blends have smaller cylinders/spheres compared
to the rPP/rPET blends, which are in the size range of 0.5 to 1.5 μm
(Fig. 8G). There are many voids present in the sample and the gaps
between the matrix and dispersed phase due to the poor adhesion. The
size of the dispersed phase is significantly reduced with the addition of
SEBS (0.37 ± 0.1, n = 40) and further with SEBS-MA (0.30 ± 0.1,
n = 40). Neither appear to have the same sized voids as in the un-
compatibilized blend, but there is still evidence of gaps between the
dispersed phase and the matrix (Fig. 8H, I).
4. Summary and conclusions
Blending of polymers can be a cost-effective way to reduce plastic
waste and increase re-use of these materials. Blends of recycled poly-
propylene with PET or polystyrene represent novel and viable feed-
stocks for FFF 3D printing, with tensile strengths comparable to some
lower-end common commercial filaments such as HIPS. While compa-
tibilization with SEBS elastomers did not greatly increase tensile
strength, morphological analysis showed improved bonding between
phases. In addition, compatibilization led to an increase in the glass
transition temperature, increasing the performance window of the
materials. Recycled polypropylene blend filaments could be used in
distributed manufacturing, in which 3D printed parts are made at or

Fig. 9. Scanning electron microscopy images of FFF printed recycled polymer fracture surfaces with disperse phase extracted with solvent. (A) rPP/rPET 50-50, (B)
rPP/rPS 50-50. Scale bar denotes 50 μm.

129
N.E. Zander et al.
near the point of need using locally available materials. In addition to
reduction in cost and carbon footprint, the ability to manufacture parts
as needed could be life-changing chiefly for those in rural and isolated
locations. Future work will involve optimization of the compatibiliza-
tion of the polymers through alternative processing methods such as
solid state shear pulverization to improve miscibility in the blend. In
addition, research will be conducted into the incorporation of a re-
inforcing agent such as glass or cellulose fibers to increase mechanical
properties to match or exceed mid-grade polymers used in additive
manufacturing such as ABS.
References
[1] R.A.W.S. Khan, S. Davuluri, V.K. Dandin, Improving the economic values of the
recycled plastics using, nanotechnology associated studies, J. Mater. Sci. Technol.
30 (2014) 854–859.
[2] Q.W.I.N. Strain, A.M. Pourrahimi, M.S. Hedenqvist, R.T. Olsson, R.L. Andersson,
Electrospinning of recycled PET to generate tough mesomorphic fibre membranes
for smoke filtration, J. Mater. Chem. A 3 (2015) 1632–1640.
[3] Material and Process Selection Charts, Granta Degisn, Cambridge, UK, 2010.
[4] H.X. Li, G.H. Hu, The early stage of the morphology development of immiscible
polymer blends during melt blending: compatibilized vs. uncompatibilized blends,
J. Polym. Sci. B Polym. Phys. 39 (5) (2001) 601–610.
[5] T.S. Omonov, C. Harrats, G. Groeninckx, P. Moldenaers, Anisotropy and instability
of the co-continuous phase morphology in uncompatibilized and reactively com-
patibilized polypropylene/polystyrene blends, Polymer 48 (18) (2007) 5289–5302.
[6] J.H. Park, Y.T. Sung, W.N. Kim, J.H. Hong, B.K. Hong, T.W. Yoo, H.G. Yoon, Effects
of blend composition and compatibilizer on the mechanical properties of poly-
propylene/acrylonitrile-butadiene-styrene blends, Polymer (Korea) 29 (1) (2005)
19–24.
[7] A.H.S.A. Samsudin, M. Mokhtar, S.M.S. Jamaluddin, Chemical resistance evaluation
of polystyrene/polypropylene blends: effect of blend compositions and SEBS con-
tent, Malaysian Polym. J. 1 (2006) 11–24.
[8] Z.M.L.Z.X. Dong, B.X. Han, X.W. Pei, L.L. Liu, G.Y. Yang, Modification ofisotactic
polypropylene films by grafting methyl acrylate using supercritical CO2 as a swel-
ling agent, J. Supercrit. Fluids 31 (2001) 67–74.
[9] K. Wang, Y.Y. Pang, W. Liu, F. Wu, W.G. Zheng, A new approach designed for
improving in situ compatibilization of polypropylene/polystyrene blends via re-
active extrusion with supercritical CO2 as the processing medium, J. Supercrit.
Fluids 118 (2016) 203–209.
[10] P.H.P. Macaubas, N.R. Demarquette, Morphologies and interfacial tensions of im-
miscible polypropylene/polystyrene blends modified with triblock copolymers,
Polymer 42 (6) (2001) 2543–2554.
[11] W. Brostow, T.H. Grguric, O. Olea-Mejia, V. Rek, J. Unni, Polypropylene plus
polystyrene blends with a compatibilizer. Part. I. Morphology thermophysical
properties, e-Polymers (2008) 9.
[12] Y.L. Huo, G. Groeninckx, P. Moldenaers, Rheology and morphology of polystyrene/
polypropylene blends with in situ compatibilization, Rheol. Acta 46 (4) (2007)
507–520.
[13] H. Inoya, Y.W. Leong, W. Klinklai, S. Thumsorn, Y. Makata, H. Hamada,
Compatibilization of recycled poly(ethylene terephthalate) and polypropylene
blends: effect of polypropylene molecular weight on homogeneity and compat-
ibility, J. Appl. Polym. Sci. 124 (5) (2012) 3947–3955.
[14] M. Heino, J. Kirjava, P. Hietaoja, J. Seppala, Compatibilization of polyethylene
terephthalate/polypropylene blends with styrene-ethylene/butylene-styrene (SEBS)
block copolymers, J. Appl. Polym. Sci. 65 (2) (1997) 241–249.
[15] K.H. Yoon, H.W. Lee, O.K. Park, Properties of poly(ethylene terephthalate) and
maleic anhydride-grafted polypropylene blends by reactive processing, J. Appl.
Polym. Sci. 70 (2) (1998) 389–395.
[16] N. Zdrazilova, B. Hausnerova, T. Kitano, P. Saha, Rheological behaviour of PP/PET
and modified PP/PET blends. II. Dynamic viscoelastic properties, Polym. Polym.
Compos. 12 (5) (2004) 433–447.
[17] Z.O. Oyman, T. Tincer, Melt blending of poly(ethylene terephthalate) with poly-
propylene in the presence of silane coupling agent, J. Appl. Polym. Sci. 89 (4)
(2003) 1039–1048.
[18] S. Singh, N. Singh, M. Gupta, C. Prakash, R. Singh, Mechanical feasibility of ABS/
HIPS-based multi-material structures primed by low-cost polymer printer, Rapid
Prototyp. J. (2018), https://doi.org/10.1108/RPJ-01-2018-0028I.
[19] A.S. Mangat, S. Singh, M. Gupta, R. Sharma, Experimental investigations on natural
fiber embedded additive manufacturing-based biodegradable structures for bio-
medical applications, Rapid Prototyp. J. 24 (7) (2018) 1221–1234.
[20] F.P. Mantia, L. Botta, M. Morreale, R. Scaffaro, Effect of small amounts of poly
(-lactic acid) on the recycling of poly(ethylene terephthalate) bottles, Polym.
Degrad. Stab. 97 (2012) 21–24.
130
Additive Manufacturing 25 (2019) 122–130
[21] C. Remili, M. Kaci, A. Benhamid, S. Bruzaud, Y. Grohens, The effects of reprocessing
cycles on the structure and properties of polystyrene/Cloisite15A nanocomposites,
Polym. Degrad. Stab. 96 (2011) 1489–1496.
[22] A. Bourmaud, C. Baley, Rigidity analysis of polypropylene/vegetal fibre composites
after recycling, Polym. Degrad. Stab. 94 (2009) 297–305.
[23] N.E. Zander, M. Gillan, D. Sweetser, Recycled PET nanofibers for water filtration
applications, Materials 9 (2016) 247–257.
[24] R.P.O. Santos, B.V.M. Rodrigues, E.C. Ramires, A.C. Ruvolo, E. Frollini, Bio-based
materials from the electrospinning of lignocellulosic sisal fibers and recycled PET,
Ind. Crops Prod. 72 (2015) 69–76.
[25] C. Shin, A new recycling method for expanded polystyrene, Packag. Technol. Sci. 18
(6) (2005) 331–335.
[26] C. Shin, Filtration application from recycled expanded polystyrene, J. Colloid
Interface Sci. 302 (1) (2006) 267–271.
[27] C. Shin, G.G. Chase, D.H. Reneker, Recycled expanded polystyrene nanofibers ap-
plied in filter media, Colloids Surf. a-Physicochem. Eng. Aspects 262 (1–3) (2005)
211–215.
[28] C.Y. Shin, G.G. Chase, Nanofibers from recycle waste expanded polystyrene using
natural solvent, Polym. Bull. 55 (3) (2005) 209–215.
[29] E. Svinterikos, I. Zuburtikudis, Carbon nanofibers from renewable bioresources
(lignin) and a recycled commodity polymer poly(ethylene terephthalate), J. Appl.
Polym. Sci. 133 (37) (2016).
[30] N.E. Zander, M. Gillan, D. Sweetser, Composite fibers from recycled plastics using
melt centrifugal spinning, Materials 10 (9) (2017) 13.
[31] N.E. Zander, D. Sweetser, D.P. Cole, M. Gillan, Formation of nanofibers from pure
and mixed waste streams using electrospinning, Ind. Eng. Chem. Res. 54 (37)
(2015) 9057–9063.
[32] H. Rajabinejad, R. Khajavi, A. Rashidi, N. Mansouri, M.E. Yazdanshenas, Recycling
of used bottle grade poly ethyleneterephthalate to nanofibers by melt-electrospin-
ning method, Int. J. Environ. Res. 3 (4) (2009) 663–670.
[33] G.T.P.S.H. Chong, M. Khalid, T.C.K. Yang, S.T. Hung, C.M. Huang, Physical char-
acterization and pre-assessment of recycled high-density polyethylene as 3D
printing material, J. Polym. Environ. 25 (2017) 136–145.
[34] J. Pakkanen, D. Manfredi, P. Minetola, L. Iuliano, About the use of recycled or
biodegradable filaments for sustainability of 3D printing state of the art and re-
search opportunities, Sustain. Des. Manuf. 68 (2017) (2017) 776–785.
[35] J.B.F.K.R. Hart, J.R. Brown, Recycling meal-ready-to-eat (MRE) pouches into
polymer filament for material extrusion additive manufacturing, Addit. Manuf. 21
(2018) 536–543.
[36] M.G.N.E. Zander, R.H. Lambeth, Recycled polyethylene terephthalate as a new FFF
feedstock material, Addit. Manuf. 21 (2018) 174–182.
[37] R.W.D.W.C. Smith, Structural characteristics of fused deposition modeling poly-
carbonate material, Polym. Test. 32 (2013) 1306–1312.
[38] B.W.N. Tanikella, J.M. Pearce, Tensile strength of commercial polymer materials for
fused filament fabrication 3D printing, Addit. Manuf. 15 (2017) 40–47.
[39] P. Keane, What Is Design for Additive Manufacturing, (2016) Accessed 30
November, 2017 https://www.engineersrule.com/design-additive-manufacturing/.
[40] W.J. Sichina, http://www.perkinelmer.com/Content/applicationnotes/app_
thermalcrystallinitythermoplastics.pdf, 2000 (Accessed 30 November, 2017).
[41] L.M.G. Araujo, A.R. Morales, Compatibilization of recycled polypropylene and re-
cycled poly (ethylene terephthalate) blends with SEBS-g-MA, Polimeros 28 (1)
(2018) 84–91.
[42] Y.Y. Li, Z.Q. Chen, Y. Huang, J. Sheng, Morphology development in polypropylene/
polystyrene blends during coalescence under shear, J. Appl. Polym. Sci. 104 (2007)
666–671.
[43] M.H. Khaliq, R. Gomes, C. Fernandes, J. Nobrega, O.S. Carneiro, L.L. Ferras, On the
use of high viscosity polymers in the fused filament fabrication process, Rapid
Prototyp. J. 23 (4) (2017) 727–735.
[44] M. Rabello, Additivation of Polymers, Artliber Editora Ltda., São Paulo, Brasil,
2007.
[45] L.A. Baldenegro-Perez, D. Navarro-Rodriguez, F.J. Medellin-Rodriguez, B. Hsiao,
C.A. Avila-Orta, I. Sics, Molecular weight and crystallization temperature effects on
poly(ethylene terephthalate) (PET) homopolymers, an isothermal crystallization
analysis, Polymers 6 (2) (2014) 583–600.
[46] A. Oromiehie, A. Mamizadeh, Recycling PET beverage bottles and improving
properties, Polym. Int. 53 (6) (2004) 728–732.
[47] N. Torres, J.J. Robin, B. Boutevin, Study of thermal and mechanical properties of
virgin and recycled poly(ethylene terephthalate) before and after injection molding,
Eur. Polym. J. 36 (10) (2000) 2075–2080.
[48] B. Itim, M. Philip, Effect of multiple extrusions and influence of PP contamination
on the thermal characteristics of bottle grade recycled PET, Polym. Degrad. Stab.
117 (2015) 84–89.
[49] L.D.M. Kuzmanovi´c, D. Mi, C.I. Martins, L. Cardon, K. Ragaert, Development of
crystalline morphology and its relationship with mechanical properties of PP/PET
microfibrillar composites containing POE and POE-g-MA, Polymers 10 (2018)
291–308.
[50] R.L.V. Thirtha, T. Nosker, Glass transition phenomena in melt-processed
Polystyrene/Polypropylene blends, Polym. Eng. Sci. 45 (2005) 1187–1193.