Article

Effect of Crystallinity on the Printability of Poly(ethylene

Terephthalate)/Poly(butylene Terephthalate) Blends
Francesca Aliberti 1,*, Maria Oliviero 2, Raffaele Longo 1, Liberata Guadagno 1,* and Andrea Sorrentino 3

1 Department of Industrial Engineering, University of Salerno, Via Giovanni Paolo II, 132,
84084 Fisciano, Italy; rlongo@unisa.it
2 Institute of Polymers, Composites and Biomaterials, National Research Council, P.le E. Fermi, 1,

80055 Portici, Italy; maria.oliviero@cnr.it

3 Institute of Polymers, Composites and Biomaterials, National Research Council, Via Previati n.1/E,

23900 Lecco, Italy; andrea.sorrentino@cnr.it

* Correspondence: faliberti@unisa.it (F.A.); lguadagno@unisa.it (L.G.)

Abstract: This study explores the impact of blending polyethylene terephthalate (PET)
with polybutylene terephthalate (PBT) on the thermal, structural, and mechanical proper-
ties of 3D-printed materials. Comprehensive analyses, including Fourier-transform infra-
red spectroscopy (FT-IR), thermogravimetric analysis (TGA), X-ray diffraction (XRD), dif-
ferential scanning calorimetry (DSC), and mechanical testing, were conducted to assess
the influence of blend composition. FT-IR confirmed that PET and PBT blend physically
without transesterification, while TGA showed enhanced thermal stability with increas-
ing PET content. XRD revealed that PET and PBT crystallize separately, with the crystal-
linity decreasing sharply for blends with more than 50% PET. The DSC results indicated
that PET effectively slows down the crystallization kinetics of PBT, promoting cold crys-
tallization. Mechanical tests demonstrated that the elastic modulus remains relatively un-
changed, but the strain at break decreases with a higher PET content, indicating increased
stiffness and reduced ductility. Overall, incorporating PET into PBT improves 3D-printa-
bility and dimensional stability, reducing warpage and enhancing print precision, making
Academic Editor: José António these blends advantageous for 3D-printing applications.
Covas

Received: 20 November 2024 Keywords: additive manufacturing; PET–PBT blends; crystallinity; dimensional stability
Revised: 29 December 2024
Accepted: 8 January 2025
Published: 9 January 2025

Citation: Aliberti, F.; Oliviero, M.; 1. Introduction

Longo, R.; Guadagno, L.;
Extrusion-based Additive Manufacturing (EAM) has emerged for its simplicity, cost-
Sorrentino, A. Effect of Crystallinity
on the Printability of Poly(ethylene
effectiveness, and reliability [1]. By depositing a molten thermoplastic material layer-by-
Terephthalate)/Poly(butylene layer according to a CAD model, complex geometries can be created without material
Terephthalate) Blends. waste [2]. Currently, a wide range of materials can be involved in the EAM process, such
Polymers 2025, 17, 156. as PLA (polylactic acid), PETG (polyethylene terephthalate glycol), ABS (acrylonitrile bu-
https://doi.org/10.3390/ tadiene styrene), ASA (acrylonitrile styrene acrylate), and PA (polyamide) [3]. The tech-
polym17020156
nological flexibility of the EAM also allows for the processing of recycled plastics [4],
Copyright: © 2025 by the authors. nanocomposites [5], composite [6], and smart materials [7,8]. In this way, EAM responds
Submitted for possible open access to the increasing demand for the complexity and multifunctionality of the final 3D-printed
publication under the terms and
product [7]. However, challenges remain, particularly in addressing the requests of com-
conditions of the Creative Commons
Attribution (CC BY) license
plex industrial applications where high mechanical strength at elevated temperatures,
(https://creativecommons.org/license barrier properties, and chemical and wear resistance are required [9,10]. Crystallinity is
s/by/4.0/). critical for different fields of application such as for the polymeric membranes to retain

Polymers 2025, 17, 156 https://doi.org/10.3390/polym17020156

Polymers 2025, 17, 156 2 of 19

sufficient mechanical strength in lithium battery applications, for the polymer’s biodegra-
dation and biocompatibility in biomedical applications [9], or, in the case of high-barrier
polymers in gas separation membranes, the packaging of healthcare and pharmaceutical
goods and chemicals and the housing of fuels (including oxygenated fuels) in tanks and
lines in the automotive sector [11]. Semicrystalline thermoplastic polymers such as PP
(polypropylene), PE (polyethylene), PEEK (polyether ether ketone), PEN (polyethylene
naphthalate), and PBT (polybutylene terephthalate) in the EAM process could be the right
solution for many of these applications. However, their use is still limited due to their
tendency for thermal shrinkage and warpage, which are more pronounced than in amor-
phous polymers [12,13]. In fact, during the processing of these materials, severe cooling-
induced shrinkage results in the development of large thermomechanical stresses that are
relieved by the out-of-plane warpage of the part [14]. In extreme cases, detachment from
the build plate, delamination, or part cracking can occur, leading to issues with dimen-
sional accuracy and stability [15]. To address this problem, it is necessary that we highlight
the correlation between the EAM parameters and the phenomena that occur during the
cooling phase [16]. Many works in literature have tried to model the temperature variation
during the EAM process to predict the deformation of the specimen, the mechanical prop-
erties, and residual stresses [17–20]. The effect of the ambient temperature, the printing
speed [21], the bed temperature, the layer thickness [12], the part geometry, and the type
of toolpath [22] have been considered. Results have shown that it is possible to improve
the part quality by optimizing the previous parameters and limiting the increase in both
processing time and cost. Another proposed approach to avoid the warpage is based on
the incorporation of fillers in pristine polymers such as CaCO3 [23], wood powder [24],
perlite [23], glass and talcum [25], and natural fibers [26]. These fillers reduce the coeffi-
cient of thermal expansion of the polymer matrix and minimize shrinkage. Moreover, in
the case of conductive filler, the higher thermal conductivity of composite polymer allows
it to converge much faster toward a thermal equilibrium than the neat matrix; conse-
quently, the internal/residual stresses of the material are expected to be reduced [13,27,28].
However, especially at higher concentrations, extrusion issues due to the filler agglomer-
ation can occur [15]. Using fillers with a high aspect ratio, such as carbon fibers, can pre-
vent warp deformations at lower concentrations. However, these fillers significantly in-
crease the anisotropy of the printed and hinder interlayer polymer chain diffusion. Due
to all the presented reasons, blending polymers is a promising alternative for reducing
warpage and increasing interlayer adhesion [29]. Ho et al. blended PP with 20–40 wt% of
elastomeric ethylene-octene copolymers (EOC) to improve the flow properties and inter-
facial fusion during printing. The authors demonstrated that, owing to its amorphous
structure and low melting point, the EOC dispersed phase facilitated the material extru-
sion process, reduced warpage, and promoted fusion between the printed strands, im-
proving the mechanical properties [30]. Chatham et al. [10] showed that a blend of two
polymers with significantly different melting temperatures, like PP and PET, is beneficial
for the EAM process since the high melting phase (PET) of the blend start to crystallize at
a higher temperature, allowing the low melting phase (PP) to retain molecular mobility
until the deposited materials cool down, gaining time to relax internal stresses and mini-
mizing warpage.
Polybutylene terephthalate (PBT) is a semi-crystalline engineering thermoplastic ma-
terial that has gained commercial interest due to its wide range of applications. Its key
features make it an ideal choice in automotive, electrical and electronics, medical, and
home appliances [31]. PBT has progressively supplanted nylon materials as the primary
option for vehicle electrical connectors as the automotive industry has grown [32]. Reduc-
ing defects due to the poor dimensional stability at high temperatures and warp during
the sample preparation process would further widen its applicability.
Polymers 2025, 17, 156 3 of 19

Fundamentally, the chemical structures of PET and PBT are very similar. The main
differences involve the ability of the polymer to crystallize under cooling. Under normal
processing conditions, the PBT crystallizes efficiently enough to always achieve a high
level of organization in its structure. On the opposite, PET, with its more rigid structure,
can be obtained both amorphous or semi-crystalline depending on the cooling rate expe-
rienced. Contrarily to PET, PBT shows dimensional instability and evident shrinkage, due
to the high crystallization rate and crystallinity degree not only when processed by EAM
[33] but also in the case of other processes. With high crystallinity, even injection-molded
PBT products are easily distorted by anisotropic shrinkage or residual stress [34,35]. This
paper aims to explore the potential of blending PBT with PET to enhance the processabil-
ity of PBT in EAM. Specifically, the study seeks to clarify the impact of the crystallization
behavior on warpage and shrinkage in 3D-printed parts, thereby addressing key chal-
lenges in the additive manufacturing of semicrystalline polymers.

2. Materials and Methods

Polybutylene terephthalate (PBT) was supplied by LANXESS Performance Materials
GmbH, Cologne, Germany (Grade: Pocan B1300 000000). It is a high-viscosity PBT resin
with a 1.31 g/cm3 density. Polyethylene terephthalate (PET) granules were supplied by the
Saudi Basic Industries Corporation (Al-Jubail, Saudi Arabia) (SABIC) (Bottle Grade PET
BC 212). It is a semi-crystalline amorphous grade with an intrinsic viscosity of 0.84 dL/g.
PBT and PET pellets were blended in varying proportions (i.e., 20%, 30%, 50%, 70%, and
80%) using a single-screw extruder (Filament Maker Composer 350 by 3Devo Filament
Maker Composer 350, Utrecht, The Netherlands). The extrusion process was conducted
with a temperature profile of 230 °C, 250 °C, 240 °C, and 235 °C along the extruder, and
the screw was rotated at 5.5 rpm. The resulting spooled filaments, with a diameter of ap-
proximately 1.75 mm, were immediately used as input for 3D printing.
The 3D-printing tests were carried out on an Original Prusa i3 MK3S with a 0.4 mm
nozzle and a constant layer height of 0.20 mm. The Prusa Slicing Software (Slic3r Prusa
Edition 2.8.1) was used to generate the G-code files for printing. Table 1 outlines the key
test parameters.

Table 1. 3D-printing parameters.

Parameters Specifics
Nozzle diameter 0.4 mm
Layer thickness 0.2 mm
Infill density 100%
Platform temperature 80 °C
Extrusion temperature 250 °C
Printing speed 80 mm/s

Uniaxial tensile dog-bone specimens (ISO 527-2-1BA [36]) were printed with their
longitudinal axes aligned in the building platform. In this case, various printing condi-
tions were optimized to enhance the adhesion between the first layer and the build plat-
form and prevent any potential distortion. Specifically, the effects of bed adhesive, surface
area coverage, and part thickness were studied to establish the optimal printing condi-
tions. A brim design was also introduced to ensure strong adhesion and minimize warp-
ing. The brims consisted of two layers of material surrounding the specimens, increasing
the surface area in contact with the platform (Figure 1a).
Polymers 2025, 17, 156 4 of 19

Figure 1. Preview of CAD model of printed samples: (a) uniaxial tensile dog-bone specimens; and
(b) hollow box-shaped specimen.

For direct characterization of shrinkage and warpage in the most demanding print-
ing conditions, hollow box-shaped specimens (50 mm side length, 2 mm base thickness,
and 40 mm height) were printed with a wall thickness equivalent to a single extruded
filament (Figure 1b). In this case, no brim or adhesive was used to increase the adhesion
of the part with the building plate.
FT-IR analyses were performed using a Nicolet apparatus (Thermo Fisher Scientific,
Waltham, MA, USA) at ambient temperature on extruded filaments of PBT/PET blends.
The samples were analyzed in ATR spectra mode from 4000 to 650 cm−1, with a wave-
number resolution of 4 cm−1 for 64 scans.
The thermal stability of blends in the form of extruded filaments has been investi-
gated using a TGA Q600 (TA Instruments, 159 Lukens Drive, New Castle, DE 19720, USA).
Samples were heated from 30 to 800 °C at a heating rate of 10 °C min−1 in a nitrogen at-
mosphere.
A thermal analyzer Mettler DSC 822/400 (Mettler-Toledo, Columbus, OH, USA)
equipped with DSC cell purged with nitrogen (50 mL/min) and chilled with liquid nitro-
gen. Film samples of about 10 mg were subsequently heated, cooled, and reheated at a
rate of 10 °C/min from 20 to 280 °C. The glass transition, crystallization, and melting tem-
perature were evaluated from the resulting enthalpic curves.
Wide-angle X-ray diffraction (WAXD) patterns in reflection mode were obtained by
an automatic Bruker, Billerica, MA, USA D8 QUEST Advance diffractometer operating at
35 kV and 40 mA (CuKα radiation X-ray source, λ = 0.15418 nm). The increment of theta
has been set at 0.0081°, while the time step was 0.200 s. The degree of crystallinity of
printed samples was evaluated from X-ray diffraction data, applying the standard proce-
dure of resolving the diffraction pattern into two areas, Ac and Aa, that can be taken as
proportional to the crystalline and the amorphous fraction of the polymer, respectively,
and calculated, for the 2θ range 10–35°, using the following equation—
Ac
𝑥𝑐 = × 100
Ac + Aa
—according to the classical Hermans–Weidinger method [37]. X-ray analysis was per-
formed on PBT/PET blend samples taken from the wall of printed boxes. For comparison,
films made with either neat PBT or PET were obtained by, first, hot pressing the relative
extruded filaments and, then, cooling them in two different conditions: quenching and
slow cooling rate. The quenching procedure consisted of directly putting the melt samples
into a bath of liquid nitrogen while the slowly cooled samples were obtained, leaving
them after melting via compression molding between the hot plates until the entire setup
reached the ambient temperature.
Polymers 2025, 17, 156 5 of 19

Tensile tests have been performed on printed dog-bone-shaped samples according

to the specifics of ISO-527-2-1BA [36], using a Dual-Column Tabletop Testing Systems
(INSTRON, series 5967-INSTRON, Norwood, MA, USA) set with a crosshead speed of 1
mm/min. Each stress–strain test was repeated three times.
Dynamic mechanical analysis (DMA) was performed using a DMA 2980 (TA Instru-
ments). Test specimens measuring 40 × 10 mm were cut horizontally (0° direction) and
vertically (90° direction) from the box walls to evaluate the morphology of the extruded
filaments and bond strength. The samples were subjected to a variable tensile strain, with
the displacement amplitude set at 0.1% and the frequency at 1 Hz. The temperature range
examined extended from 30 °C to 180 °C, with a constant heating rate of 3 °C per minute.
Microscopic images were taken using a Leica MZ6 (Leica Microsystems, Wetzlar,
Germany) stereo microscope equipped with two eyepieces to combine images taken from
two different points of view. This gives the final image three-dimensionality and depth.
This instrument has a rotating focusing arm for better image visibility and can use polar-
ized lenses. Microscopic images were performed on the printed samples after the break
occurred during the tensile mechanical test.

3. Results
3.1. Characterization of the Extruded Filaments
3.1.1. FT-IR Analysis
An FT-IR analysis was conducted on the extruded filament to examine the possible
interaction between PBT and PET after the melt blending process. Several studies in the
literature have explored the possibility of transesterification reactions in polyester blends
like PET and PBT under specific processing conditions or heat treatment [38–42]. The ab-
sence of copolymers due to possible transesterification reactions has been verified via
NMR spectroscopy on the printed samples. The NMR results are shown in Figure S1 and
commented on in Section S1 of the Supplementary Materials. The ATR spectra have been
interpreted in light of the NMR results, which demonstrate the absence of transesterifica-
tion reactions.
Figure 2c shows the ATR spectra of the characteristic peaks of the pristine PBT [43]
and the pristine PET [44] compared with various blends. Given that PBT and PET have
similar chemical structures (as shown in Figure 2a,b), with the primary difference being
the length of the aliphatic segment between ester groups [31], their ATR spectra exhibit
minimal differences in transmission peaks [45,46]. Specifically, PBT contains four CH2
groups, while PET has only two. Consequently, the ATR spectra do not show significant
differences in terms of transmission peaks. However, two peaks, at 1321 cm⁻1 and 1387
cm⁻1, correspond to CH2 twisting vibrations and CH2 scissoring and wagging vibrations,
respectively [47]. These peaks are characteristic of PBT and are absent in the PET IR spec-
trum, revealing that the spectra of the blends are a superposition of contributions from
the individual components [48]. As seen in Figure 2d, with an increasing PET content, the
characteristic PBT peaks at 1321 cm⁻1 and 1387 cm⁻1 gradually disappear.
A quantitative analysis using the deconvolution method shows a good correlation
between the area of these peaks and the blend composition (Figure 2e). Specifically, the
peak at 1321 cm⁻1 exhibits a linear correlation across all concentrations, while the peak at
1387 cm⁻1 shows a deviation when PET concentration exceeds 50%. This deviation may
result from a different structural configuration that inhibits CH2 scissoring and wagging
vibrations. Moreover, the absence of any significant shifts in peak positions or the appear-
ance of new peaks indicates that no chemical interactions occurred during the extrusion
phase. Additionally, no degradation phenomena were observed since the extrusion tem-
perature was kept below the degradation point of the materials.
Polymers 2025, 17, 156 6 of 19

Figure 2. (a) Chemical structure of PET; (b) chemical structure of PBT; (c) ATR spectra of PBT, PET,
and their blends; (d) enlargement of ATR spectra on the characteristic bands of -CH2 groups; and
(e) ratio between the area of 1321 cm−1 and 1387 cm−1 peaks of blends and the area of the same peaks
of PBT spectrum.

3.1.2. Thermogravimetric Analysis

The key results of the thermogravimetric analysis, including the maximum degrada-
tion temperature (Tmax), the initial degradation temperature corresponding to a 5% weight
loss (Td), and the residue at 800 °C (R), are summarized in Table 2. As shown in Figure 3,
all TGA curves exhibited a single-step degradation process. The TGA analysis confirms
that PET has better thermal stability than PBT [49]. Specifically, PET begins to degrade at
392 °C, while PBT starts to lose weight significantly at 359 °C. This difference in thermal
stability is likely due to the longer aliphatic segments between the ester groups in PBT
chains. The methylene units (-CH2-) in PBT represent weaker points in the polymer chain
than the segments containing double bonds and aromatic rings. As a result, the increased
number of methylene units in PBT, compared to the ethylene groups in PET, facilitates
thermal decomposition [50]. Furthermore, the Td values for the PBT/PET blends fall be-
tween the initial degradation temperatures of the two pure polymers, with Td increasing
as the PET content rises (see Table 2). This trend suggests that PBT and PET are physically
compatible after blending, with the two polymers mixing without undergoing any chem-
ical reaction, such as transesterification, as indicated by the NMR results reported in Sec-
tion S1 of the Supplementary Materials Studies by P.R. Rajakumar et al. [51], and B. Ucpi-
nar Durmaz et al. [49] have shown that transesterification in PBT/PET blends leads to a
reduction in thermal stability compared to the original polymers. This reduction is due to
the formation of block copolymers in the initial stages and, eventually, random copoly-
mers, which are less thermally stable than the pristine polymers. However, it is well-es-
tablished that transesterified random copolymers typically form only after prolonged melt
mixing at high temperatures [52,53]. Based on the TGA and NMR results, it can be con-
cluded that the PBT/PET blends prepared in this study did not undergo transesterification
due to the limited extrusion time and moderate extrusion temperature [52,54].
Polymers 2025, 17, 156 7 of 19

Figure 3. TGA results of PBT, PET, and their blends: (a) thermogravimetric curves; and (b) relative
residue vs. PET content (experimental data (dots) and linear trend (red line)).

The TGA curves also reveal the formation of residue or char at higher temperatures.
This char, which consists of the organic coking residue, is higher for PET than for PBT [55–
57]. Specifically, the residue accounts for 4.55 wt% in PBT and 10 wt% in PET. Notably,
when considering a relative residue (Red) value, where PBT is zero and PET is 100%, all
blends show intermediate values that correlate well with their composition (Figure 3b).
This additive behavior further supports the absence of chemical interactions or degrada-
tion phenomena between the two polymers. However, a slight deviation from perfect lin-
earity is observed in blends with high PET content (70% and 80%). As found with the FT-
IR analysis, this deviation suggests that, in these compositions, some physical interactions
between the two polymers might slightly alter the behavior of these blends.

Table 2. Results of thermogravimetric analysis.

Sample Tmax [°C] Td [°C] R [%]

PBT 394 359 4.55
20%PET 397 361 6.08
30% PET 400 361 6.11
50% PET 419 377 8.38
70% PET 422 382 9.45
80% PET 427 382 10.0
PET 424 392 12.4

3.1.3. DSC Results

Differential scanning calorimetry was carried out of the extruded filament to charac-
terize the crystallization behavior of the blends. Figure 4a,b present the DSC heating and
cooling scans for the PET/PBT blends. During the first heating scan (solid curves in Figure
4a), two distinct melting peaks are observed for all blends: one around 225 °C, correspond-
ing to the PBT phase, and another around 250 °C, associated with the PET phase. Interest-
ingly, the melting temperature for PET in the blends is higher than in pure PET, while the
melting peak for PBT is lower than that of pure PBT. A detailed explanation of this aspect
is given in the Supplementary Materials. Additionally, the 70% and 80% PET blends show
a cold crystallization peak during the first heating cycle, indicating that these blends do
not crystallize completely during the filament extrusion process. In Section S2 of the Sup-
plementary Materials, the differences emerging from the comparison between the first
and the second heating scan of Figure 4a are extensively discussed.
Polymers 2025, 17, 156 8 of 19

Figure 4. DSC results on spooled filaments: (a) first (continuous curves) and second (dotted curves)
heating; (b) cooling scan; (c) Tg values (dots) compared to the mixing rule (red line); and (d) melting
enthalpy (of both first and second heating) and crystallization enthalpy for all the experimented
blends.

The cooling curves (Figure 4b) reveal a single crystallization peak for all blends in the
temperature range between 190 °C and 130 °C. The crystallization temperatures are 165
°C for PET and 181 °C for PBT, while the blends show a crystallization peak temperature
lower than pure PBT. This suggests that the miscible PBT phase may act as a nucleating
agent for PET, altering its crystallization behavior, as supported by Aravinthan, and Kale
[52].
Regarding the glass transition temperature (Tg), a single Tg is observed for each blend,
and its value increases as the PET content rises, closely following the linear trend pre-
dicted by the rule of mixtures (Figure 4c). This behavior confirms the good miscibility
between PET and PBT in the amorphous phase. These findings align with previous DSC
studies reported by Avramova [58].
The melting enthalpy (∆Hm) values, both in the first and second heating scan and the
crystallization enthalpy (∆Hc) during cooling, display a clear trend. For the 50%, 70%, and
80% PET blends, these values are consistently lower than expected, indicating a reduced
degree of crystallinity compared to blends with a lower PET content. This trend highlights
the impact of PET on the crystallization kinetics and degree of crystallinity of the blends.
Polymers 2025, 17, 156 9 of 19

Numerical values of glass transition temperature (Tg), crystallization temperature (Tc),

melting enthalpy (∆Hm) of the first (I) and second (II) heating, and the crystallization en-
thalpy (∆Hc) for PET, PBT, and their blends have been summarized in Table 3.

Table 3. DSC results on spooled filaments of experimented blends.

∆Hm [J/g] ∆Hm [J/g] ∆Hc [J/g]

Sample Tg [°C] Tc [°C]
I Heating II Heating Cooling
PBT 49.06 180.6 50.76 46.51 51.73
20%PET 56.91 169.1 54.77 39.48 44.12
30%PET 54.28 174.9 58.01 40.02 46.36
50%PET 61.79 148.0 46.68 30.53 35.45
70%PET 66.92 166.9 44.48 27.16 33.07
80%PET 74.28 180.4 45.78 35.18 39.71
PET 80.61 164.3 60.00 47.61 25.82

3.2. Characterization of the 3D-Printed Samples

3.2.1. Mechanical Properties of the Dog-Bone Specimens
The impact of the PET concentration on the mechanical properties of printed samples
was evaluated through tensile testing at a strain rate of 25 mm/min. Figure 5 presents the
representative stress–strain curves for the various blends considered. The average values
and distribution of the elastic modulus and strain at break for all blends are summarized
in Figure 5b. Specifically, Young’s moduli were derived from the slope of the linear region
of the stress–strain response.

Figure 5. Tensile test results: (a) stress–strain curves of PBT, PET, and PBT/PET blends, and (b)
Young modulus and strain at break variation with PET content.

The elastic modulus does not show a clear trend with varying PET content, as all
blends exhibit similar values, suggesting that the PET concentration has a limited effect.
However, the strain at break is significantly affected by the blend composition. Samples
with 70% and 80% PET show the lowest strain at break values, indicating increased rigid-
ity. This rigidity likely results from enhanced chain interactions in these samples, poten-
tially due to physical crosslinking such as crystal nuclei or reversible distance-dependent
interactions between polymer chains. These properties vary widely with composition due
to two competing morphological factors: the deterioration of properties from incompati-
bility and a resulting two-phase structure and improvement from forming more inter-
crystalline structures. Thus, differences in the interaction between blend components can
lead to mechanical behavior that deviates from the additivity rule.
Figure 6 shows typical fracture morphologies of the samples, revealing a brittle frac-
ture type for all compositions. The PBT/PET blend surfaces are rough without an
Polymers 2025, 17, 156 10 of 19

observable phase separation, indicating a good compatibility between the polymers. The
rough fracture surface suggests that the failure was mainly due to the rupture of deposited
filaments rather than interlayer bonds. The quality of interfacial bonding is crucial for the
microstructure and mechanical properties of the printed parts. This bonding quality de-
pends on the growth of the neck between adjacent filaments and the molecular diffusion
and randomization of polymer chains across the interface. Specimens with a lower PET
concentration likely had better adhesion among deposited filaments and layers, display-
ing improved polymer chain diffusion between layers, resulting in denser parts with
smaller interlayer voids.

Figure 6. Micrographs of break surfaces for tensile test samples for PBT, PET, and their blends.

3.2.2. Morphological Characterization of the Hollow Box-Shaped Specimens

Figure 7 shows photographs of the best-printed samples for each blend. As expected,
the PET content significantly influences the morphological characteristics of the samples.
Only those with more than 70% PET demonstrated warpage-free and dimensionally stable
prints. Blends with less PET content experienced issues with layer adhesion and warpage.
Specifically, samples with less than 50% PET could not be fully printed as per the CAD
model, due to the severe warpage of the initial layers, causing the detachment from the
build plate. Although the box could be fully printed with the 50% PET blend, it still ex-
hibited notable shrinkage, detachment from the build plate, and cracks on the walls. In
contrast, the sample with 70% PET showed complete dimensional stability and accuracy.
Polymers 2025, 17, 156 11 of 19

Figure 7. Images of 3D-printed boxes made of different concentrations of PBT/PET blend.

3.2.3. Thermal Analysis of the Hollow Box-Shaped Specimens

A DSC analysis was performed to investigate the effect of the PET addition to PBT
on the degree of crystallinity of the final blends after the 3D-printing process. Since PBT
has an elevated crystallization rate, PET has been added to slow down the crystallization
rate during the cooling phase of the 3D-printing process, reducing internal stresses and
minimizing warpage. Figure 8 reports the DSC curves obtained on a small piece of 3D-
printed box wall for each prepared blend. Moreover, PBT shows a lower Tg value (55 °C)
than PET, whose Tg is 76 °C. For PBT/PET blends, the Tg value tends to increase by in-
creasing the PET content. Regarding the melting region, DSC curves of PBT/PET blends
exhibit two melting peaks, each associated with one of the two components of the blends.
In fact, the melting peak of PBT at lower temperatures tends to disappear by increasing
the PET percentage, while the PET melting peak becomes more evident. This means that
PBT/PET blends form separate crystals rather than cocrystals [48,52,58]. For this work, the
most interesting region in Figure 8 is the temperature interval between 100 °C and 140 °C
where cold crystallization peaks emerge. It can be noted that, by increasing the PET con-
tent in the blends, the area of cold crystallization peak tends to increase. This area is pro-
portional to the number of polymer chains that did not crystallize during the cooling
phase of the 3D-printing process and then underwent cold crystallization during the heat-
ing scan of DSC analysis. Since both PET and PBT are semicrystalline polymers able to
crystallize beyond 30% [59], the reason to explain the reduction in crystallinity in the 3D-
printed part made of a PBT/PET blend by increasing the PET content is the fact that PET
is effectively able to reduce the crystallization kinetic of neat PBT. The cold crystallization
peak becomes more evident from the sample composed of 50% of PET, meaning that the
crystallinity of 3D-printing PBT/PET blends starts to decrease substantially when the PET
percentage exceeds 50%. It confirms the previous results as the increase in PET content in
PBT/PET blends leads to an improvement in dimension stability due to a lowering in the
degree of crystallinity and, consequently, an increase in the amorphous phase, which
causes a small volume reduction during the cooling phase of the 3D-printing process.
DSC curves of printed samples (Figure 8) have been compared to the first heating curves
of the DSC analysis performed on the spooled filaments before printing (I heating in Figure
4a) in Figure S2 and commented on in Section S3 of the Supplementary Materials.

3.2.4. X-Ray Diffraction Analysis of the Hollow Box-Shaped Specimens

Figure 9a reports the X-ray investigation performed on printed blends, and quenched
and slowly cooled neat PBT and neat PET. The 3D-printed samples were taken from the
wall of the printed boxes for all experimented blends and the neat PET to consider the
crystallization phenomenon when the materials exchange heat only with the surrounding
air without considering the heat transfer with the heated printing bed. However, for the
neat printed PBT, it was not possible to take a piece of the box wall, since, in this case, the
3D-printing process stopped before building the walls. The X-ray spectra of Figure 9a
were used to calculate the degree of crystallinity of the samples to compare these results
with those obtained by the DSC analysis. By exploiting the deconvolution method, it could
Polymers 2025, 17, 156 12 of 19

be possible to quantify the PET and PBT crystallinity [48,59]. However, it would be quite
difficult due to the close positions of the most intense peaks and lie out of the scope of this
work whose aim is to understand the effects of blending PET with PBT on the crystallinity
degree to improve PBT printability and not to study the crystalline phase of the two pol-
ymers in blends. The degree of crystallinity evaluated on the X-ray spectra of Figure 9a
according to the procedure described in Section 2 is reported in the form of spot data in
the graph of Figure 9b to compare them with the literature data. In fact, in Figure 9b, the
continuous lines define the degree of crystallinity of the pristine PBT and PET as well as
their blends at different cooling rates taken from Ref. [59]. The circle-shaped points and
the triangles represent the crystallinity of the neat PBT and PET obtained in this work
under slow and high cooling rates, respectively. According to the experimental conditions
in which the samples were obtained, the quenched samples are positioned at a cooling
rate of 100 °C/s, while the slow-cooled samples are reported corresponding to about 1
°C/s. The degree of crystallinity of 3D-printed blends is reported in the form of stars at a
cooling rate of the order of 10 °C/s. It is worth underlining the differences between pristine
PBT and pristine PET. By comparing the X-ray spectra obtained at the two extreme cooling
conditions (quenching and slow cooling rate), in the case of PBT, although the contribu-
tion of the amorphous phase becomes predominant in the quenched PBT spectrum, some
peaks remain, meaning that the cooling rate at which the sample was quenched was not
enough to make the PBT amorphous completely. On the other hand, the spectra of the
quenched PET and slow-cooled PET are completely different, and it is very evident that
the quenching procedure was effective in making the PET amorphous, while the slow-
cooled PET is highly crystalline. The fact that, by quenching PBT, it remained semicrys-
talline while PET became completely amorphous during the same quenching process con-
firms that these two polymers have two different crystallization rates. The crystallinity of
PBT is higher than that of PET over the entire cooling rate conditions investigated. More
in detail, between 1 °C/s and 10 °C/s, the neat PET undergoes a rapid change in crystallin-
ity while, for PBT, a substantial variation in the crystallinity degree happens more gradu-
ally and for cooling rates more than one order of magnitude larger. The experimental data
obtained for PET and PBT in the two extreme cooling conditions are perfectly in line with
the literature evidence. As regards the 3D-printed samples, the X-ray spectra of blends in
Figure 9a show widened peaks for concentrations lower than 70% of PET and these peaks
become less defined by increasing the PET content from 20% to 50%. Moreover, beyond
50% of PET, the 3D-printed samples made of 70% and 80% of PET are prevalently amor-
phous. This result suggests that, at the cooling condition of the 3D-printing process by
increasing the PET content, the degree of crystallinity lowers, as already demonstrated
from the DSC analysis. Furthermore, the 3D-printed neat PET is also completely amor-
phous. Reporting the degree of crystallinity calculated for printed samples on the graph
in Figure 9b (stars), the obtained values are quite close to the lines obtained by the mixing
rule, especially for the samples 20% PET, 30% PET, and 50% PET. For the 3D-printed
blends at 70% and 80% of PET, the degree of crystallinity is much lower than the values
predicted by the mixing rule. However, the strong lowering of the crystallinity degree of
PBT/PET blends for a PET concentration higher than 50% during the cooling phase of the
FFF process allows us to improve the printability of PBT, reducing the cost of the final 3D-
printed artifact (due to the lower cost of PET) without making the printing condition and
the printer setup more complicated (e.g., printing in controlled temperature atmosphere,
using brim, adding filler, etc.) [14].
Polymers 2025, 17, 156 13 of 19

Figure 8. DSC curves of 3D-printed PBT/PET blends.

Figure 9. X-ray results: (a) X-ray spectra of the 3D-printed sample (stars), of quenched PBT and PET
(triangles) and of slowly cooled PBT and PET (circles), and (b) comparison between experimental
data obtained from graph (a) and literature data [59].

3.3. Mechanical Characterization of the Hollow Box-Shaped Specimens

Figure 10a,b show the elastic modulus measured by DMA in both the filament direc-
tion (0°) and the orthogonal direction (90°), respectively. As expected, the samples exhibit
superior performance in the filament direction. At lower temperatures (below 50 °C), the
blend composition has a limited effect on the elastic modulus. However, as the tempera-
ture increases, differences between the samples become more pronounced. The PET sam-
ple shows a rapid reduction in the elastic modulus, reaching a minimum at about 110 °C,
after which the modulus increases again due to the recrystallization of the amorphous
phase. Other blends show a similar trend, with the reduction in elastic modulus propor-
tional to the PET content.
Interestingly, the glass transition temperature (Tg), determined from the peaks in the
loss tangent (tan δ) spectrum (Figure 10c,d), does not follow a monotonic trend with the
changing PET content. The Tg is the highest for the pure PET sample, decreases to the
minimum for the 80% PET blend, and then increases again with decreasing PET content.
This behavior is due to the combined effects of the degree of crystallinity in the printed
samples and the Tg values of the individual components.
In the orthogonal direction, the blend composition significantly affects the modulus,
even at lower temperatures. As the PBT content increases, the modulus decreases sharply.
Polymers 2025, 17, 156 14 of 19

This is because layer adhesion, which is crucial for sample strength in this direction, is
compromised by a higher PBT content. An increased PBT content accelerates crystalliza-
tion, leading to greater warpage and instability. At higher temperatures, after complete
recrystallization, all blends exhibit similar modulus values. This indicates that, at these
temperatures, interlayer adhesion is complete, and all internal stresses are fully relaxed.

Figure 10. DMA analysis results: (a) elastic modulus in the filament direction (0°); (b) elastic modu-
lus in the direction orthogonal to the printed filaments (90°); (c) loss tangent (tan δ) in the filament
direction (0°); and (d) loss tangent (tan δ) in the direction orthogonal to the printed filaments (90°).

4. Conclusions
Comprehensive analyses of PBT/PET blends using FT-IR, TGA, X-ray diffraction,
DSC, and mechanical testing have provided valuable insights into the effects of PET ad-
dition on the properties of PBT. Blend composition optimization enhances the printability
and dimensional stability of the Poly(polyethylene terephthalate)/Poly(butylene tereph-
thalate) blends.
The FT-IR analysis revealed that the PBT and PET polymers exhibit distinct spectral
features despite their similar chemical structures. The absence of significant peak shifts or
new peaks in the blend FT-IR spectra indicates that no substantial chemical interactions,
such as transesterification, occurred during the extrusion process, which aligns with the
TGA findings.
Thermogravimetric analysis (TGA) demonstrated that PET possesses better thermal
stability than PBT, with degradation temperatures for PET being higher than those for
PBT. The study confirmed that the blends do not undergo transesterification reactions,
which supports the FT-IR findings. The increase in residue with a higher PET content re-
flects the higher char formation associated with PET, while PBT’s lower residue indicates
its lesser char-forming tendency.
The X-ray diffraction (XRD) analysis showed that PBT and PET crystallize separately
within the blends, forming distinct crystalline phases rather than cocrystals. The degree
of crystallinity decreased with increasing PET content, particularly beyond 50%. The XRD
Polymers 2025, 17, 156 15 of 19

results also indicated that PET reduces the crystallization rate of PBT, leading to a more
amorphous structure in blends with a higher PET content. This observation was consistent
with the DSC findings.
The differential scanning calorimetry (DSC) analysis revealed that the addition of
PET to PBT leads to an increase in the glass transition temperature (Tg) of the blends. The
presence of cold crystallization peaks in the DSC curves suggests that a higher PET con-
tent slows down the crystallization rate of PBT during the cooling phase of 3D printing.
This phenomenon explains the observed reduction in crystallinity and the improved di-
mensional stability of the printed parts.
Mechanical testing showed that, while the elastic modulus remained relatively stable
across different blends, the PET content significantly influenced the strain at break. Blends
with a higher PET content exhibited increased the rigidity and lower strain at break, indi-
cating enhanced chain interactions and physical cross-linking. Notably, reducing crystal-
linity with an increasing PET content improved printability and reduced warpage,
demonstrating the practical benefits of blending PET with PBT in 3D-printing applica-
tions.
In summary, the study confirms that PET effectively modifies the crystallization be-
havior and mechanical properties of PBT, leading to the enhanced dimensional stability
and printability of the final 3D-printed artifacts. The findings highlight the potential for
optimizing blend compositions to achieve the desired material properties for specific ap-
plications.

Supplementary Materials: The following supporting information can be downloaded at:

www.mdpi.com/xxx/s1, Figure S1: (a) 13C NMR spectrum of 50%PET blend, (b) scheme of quater-
nary aromatic carbon in the case of copolymer (Z1 and Z2 positions), PET (X1 position), and PBT
(X2 position) and the carbon atom in the CH2 group of PET (a position) and PBT (b position), Figure
S2: DSC curves of first heating scan of PBT/PET blends in the form of spooled filament before print-
ing (solid lines) and of 3D printed PBT/PET blends (dotted lines).

Author Contributions: Conceptualization, L.G.; methodology, F.A., M.O., and A.S.; software, R.L.;
validation, L.G. and A.S.; formal analysis, F.A., M.O., and R.L.; investigation, F.A. and A.S.; re-
sources, L.G.; data curation, F.A., M.O., and R.L.; writing—original draft preparation, F.A.; writ-
ing—review and editing, F.A., L.G., and A.S.; visualization, M.O.; supervision, L.G.; project admin-
istration, A.S.; funding acquisition, L.G. and A.S. All authors have read and agreed to the published
version of the manuscript.

Funding: This research was funded under the National Recovery and Resilience Plan (NRRP), Mis-
sion 4, Component 2, Investment 1.1, Call for tender No. 104 published on 2.2.2022 by the Italian
Ministry of University and Research (MUR), funded by the European Union–NextGenerationEU–
Project Title Integration of Continuous Fibers and Self-healing agents in 3D-printed thermoplastic
composites (INFINITE)-CUP B53D23008690006-Grant Assignment Decree No. 966 adopted on
30/06/2023 by the Italian Ministry of Ministry of University and Research (MUR).

Institutional Review Board Statement: Not applicable.

Data Availability Statement: The data presented in this study are available upon request from the
corresponding author due to privacy reasons.

Acknowledgments: The authors kindly thank Pasquale Longo for the useful discussions on NMR
analysis on the blend systems.

Conflicts of Interest: The authors declare no conflicts of interest.

Polymers 2025, 17, 156 16 of 19

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