polymers

Article
Fused-Deposition Modeling 3D Printing of Short-Cut
Carbon-Fiber-Reinforced PA6 Composites for Strengthening,
Toughening, and Light Weighting
Bin Sun 1,2,3 , Suhail Mubarak 4 , Guocun Zhang 5 , Kangming Peng 1,6 , Xueling Hu 1,7 , Qia Zhang 8 , Lixin Wu 1,2, *
and Jianlei Wang 1,2,3, *

1 CAS Key Laboratory of Design and Assembly of Functional Nanostructures, Fujian Key Laboratory of
Nanomaterials, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences,
Fuzhou 350002, China; loney_bin@[Link] (B.S.)
2 University of Chinese Academy of Sciences, Beijing 100049, China
3 CAS Haixi Industrial Technology Innovation Center in Beilun, Ningbo 315830, China
4 State Key Laboratory of Fluid Power & Mechatronic System, Key Laboratory of Soft Machines and Smart
Devices of Zhejiang Province, Center for X-Mechanics, Department of Engineering Mechanics,
Zhejiang University, Hangzhou 310027, China
5 School of Automotive Engineering, Dalian University of Technology, Dalian 116024, China
6 College of Chemistry and Materials Science, Fujian Normal University, Fuzhou 350007, China
7 College of Chemistry, Fuzhou University, Fuzhou 350116, China
8 Chunhui Technology Group Co., Ltd., Fuzhou 350019, China
* Correspondence: lxwu@[Link] (L.W.); jlwang@[Link] (J.W.)

Abstract: Additive manufacturing of carbon-fiber-reinforced polymer (CFRP) has been widely used
in many fields. However, issues such as inconsistent fiber orientation distribution and void formation
during the layer stacking process have hindered the further optimization of the composite material’s
performance. This study aimed to address these challenges by conducting a comprehensive investi-
gation into the influence of carbon fiber content and printing parameters on the micro-morphology,
thermal properties, and mechanical properties of PA6-CF composites. Additionally, a heat treatment
Citation: Sun, B.; Mubarak, S.; Zhang, process was proposed to enhance the interlayer bonding and tensile properties of the printed com-
G.; Peng, K.; Hu, X.; Zhang, Q.; Wu, posites in the printing direction. The experimental results demonstrate that the PA6-CF25 composite
L.; Wang, J. Fused-Deposition achieved the highest tensile strength of 163 MPa under optimal heat treatment conditions: 120 ◦ C
Modeling 3D Printing of Short-Cut for 7.5 h. This corresponds to a significant tensile strength enhancement of 406% compared to the
Carbon-Fiber-Reinforced PA6
unreinforced composites, which represents the highest reported improvement in the current field of
Composites for Strengthening,
CFRP-fused deposition 3D printing. Additionally, we have innovatively developed a single-layer
Toughening, and Light Weighting.
monofilament CF-OD model to quantitatively analyze the influence of fiber orientation distribution
Polymers 2023, 15, 3722. https://
on the properties of the composite material. Under specific heat treatment conditions, the sample
[Link]/10.3390/polym15183722
exhibits an average orientation angle µ of 0.43 and an orientation angle variance of 8.02. The peak
Academic Editor: Chenliang Gong frequency of fiber orientation closely aligns with 0◦ , which corresponds to the printing direction.
Received: 23 August 2023 Finally, the study explored the lightweight applications of the composite material, showcasing the
Revised: 5 September 2023 impressive specific energy absorption (SEA) value of 17,800 J/kg when implementing 3D-printed
Accepted: 6 September 2023 PA6-CF composites as fillers in automobile crash boxes.
Published: 11 September 2023
Keywords: polyamide; fiber reinforced composites; fused deposition 3D printing; heat treatment
process; orientation distribution; crash box; honeycomb structure

Copyright: © 2023 by the authors.

Licensee MDPI, Basel, Switzerland.
This article is an open access article
1. Introduction
distributed under the terms and
conditions of the Creative Commons Fiber-reinforced composites (FRP) are derived from the modification of polymers with
Attribution (CC BY) license (https:// either continuous or short fibers [1–6]. By combining stiff and strong fibers with lightweight
[Link]/licenses/by/ polymer matrices, fiber-reinforced composites offer a high strength-to-weight ratio, excel-
4.0/). lent processability, and resistance to wear [7–9]. Polyamide 6 (PA6), as a semi-crystalline

Polymers 2023, 15, 3722. [Link] [Link]

Polymers 2023, 15, 3722 2 of 20

polymer, possesses excellent processability and shape ability, along with outstanding
wear and corrosion resistance, rendering it an ideal choice for a polymer matrix [10].
For instance, Beom et al. [11] enhanced the carbon fiber/PA6 composite via interfacial
reinforcement using a mixture of adhesive and reduced-graphene oxide coating. The
modified composite mixture exhibited a 73% increase in flexural strength and an 84%
increase in modulus. Federico et al. [12] processed carbon fiber-reinforced PA6 composites
using Fused-Deposition Modeling (FDM) and varied the raster angle in the layer sequence
according to different printing architectures. Laser writing was then performed to ob-
tain conductive tracks on the surface of the printed parts. Furthermore, reducing fiber
content or incorporating plasticizers enhanced the toughness of the composite material.
Elena et al. [13] demonstrated that increasing the fiber content in carbon fiber-reinforced
PA6 composites (10–30%) resulted in an increase in internal porosity and improved me-
chanical properties.
Composites can be reshaped through molding or extrusion processes, which offer
advantages in mass production [14]. Material extrusion-based fused-deposition modeling
(FDM) has emerged as a popular additive manufacturing technology, owing to its extensive
design flexibility and a wide range of material options [12,15–22]. Consequently, volume
contraction occurs, resulting in diminished interlayer adhesion and an increased porosity
in the printed parts [23,24]. Researchers have sought to address the inherent limitations of
fused-deposition 3D printing by optimizing printing parameters [25,26]. However, these
efforts have not yielded significant improvements in the mechanical performance of printed
materials [27,28]. In this study, we effectively addressed the inherent issues of FDM by
adjusting fiber content, optimizing printing parameters, and optimizing the heat treatment
process, significantly improving the mechanical performance of the composite materials.
On the other hand, composite materials manufactured through fused-deposition 3D
printing often lack precise control over the fiber orientation of the parts [7,29,30]. It is
crucial to control the distribution of fiber orientation to enhance the performance of com-
posites [31]. Existing fiber alignment techniques primarily involve adjusting printing
parameters, applying external forces, and developing predictive models [32–35].For in-
stance, Yan et al. [36] quantified the impact of printing parameters on the fiber orientation
distribution of carbon-fiber-reinforced ABS/PLA composites, demonstrating the significant
influence of filament line width and nozzle height on the orientation distribution of the
composite fibers. Pasita et al. [37] developed an anisotropic viscous flow model to predict
fiber orientation, microbead geometry, and inter-bead contact interface geometry. However,
there is limited research on characterizing fiber orientation within a single filament. To
address this research gap, we designed a simplified model of a single-layer monofilament
CF-OD structure to mitigate the effects of other parameters and external conditions on the
fiber orientation of composites. To accurately assess the fiber distribution in 3D-printed
PA6-CF composites, we performed a meticulous process involving the careful removal
of the upper and lower surfaces of the obtained monofilament samples. Subsequently,
milling and polishing techniques were employed on the exposed specimens to determine
the orientation distribution of the internal structural fibers.
In summary, the layer-by-layer nature of FDM printing inevitably leads to weak inter-
layer bonding in printed composites. Moreover, the incorporation of fibers increases the
material’s porosity, while the distribution of fiber orientation limits further improvement
in material properties. This study explores the potential of carbon-fiber-reinforced PA6
composites under FDM printing conditions. We prepared PA6-CF-printed samples by ad-
justing the fiber content, optimizing printing parameters, and optimizing the heat treatment
process. The fiber orientation distribution was quantified using a single-layer monofilament
CF-OD model, and the mechanism underlying the improvement in mechanical properties
with variations in microstructure and thermal properties was analyzed. Additionally, this
study explored the lightweight applications of the composite material.
 Polymers 2023, 15, x FOR PEER REVIEW 3 of 21

Polymers 2023, 15, 3722 3 of 20

analyzed. Additionally, this study explored the lightweight applications of the composite
material.

2. Materials and Methods

2. Methods
2.1.
2.1. Materials
density 1.151
Polyamide 6 (PA6 J-2400, density g/cm3),3 ),manufactured
1.151 g/cm manufacturedbybyPolymer
PolymerShun
ShunNew
New
Material
Material [Link]. Ltd.,
Ltd., (Hangzhou,
(Hangzhou,Zhejiang,
Zhejiang,China)
China)waswasutilized
utilizedas
asthe
thepolymer
polymermatrix
matrixmaterial.
mate-
Short-cut carbon
rial. Short-cut fibersfibers
carbon were were
procured from Tokuyama
procured from Tokuyama Carbon Fiber Co.
Carbon (Tokuyama,
Fiber Japan).
Co. The charac-
The characteristics of the carbon fibers are as follows: a fiber diameter of 7 µm,
teristics of the carbon fibers are as follows: a fiber diameter of 7 µm, a fiber density of 1.502 a fiber
density 3
g/cm , aof
3 1.502 strength
tensile g/cm , aoftensile strength
3550 MPa, andof 3550 MPa,
a tensile and aoftensile
modulus modulus
230 GPa. Silaneof 230 GPa.
coupling
Silane couplingWanhua
agent (KH-550, agent (KH-550,
ChemicalWanhua
Company, Chemical Company,
Yantai, China) and Yantai, China)
95% ethanol and
were 95%
used
ethanol
withoutwere used
further without further purification.
purification.

2.2.
2.2. Preparation
Preparation of of PA6-CF
PA6-CF Composite
Composite Filaments
Filaments
PA6 raw
PA6 raw pellets
pellets were
were soaked
soakedovernight
overnightwith withshort
shortcarbon
carbonfibers
fibersinina amixture
mixtureofof95%95%
alcohol and a silane coupling agent to enhance the interfacial adhesion
alcohol and a silane coupling agent to enhance the interfacial adhesion between the poly-between the polymer
matrix and and
mer matrix the the
carbon
carbonfibers [10].
fibers [10]. The
Theresulting
resultingsilanized
silanized masterbatch
masterbatch was wasco-blended
co-blended
using
using the
the HAAKE twin-screw extruder
HAAKE twin-screw extruder to to extrude
extrudefilaments,
filaments,which
whichwere
werethen thencollected
collected
and
and pelletized by the downstream winder. This process was repeated twice to achieve a a
pelletized by the downstream winder. This process was repeated twice to achieve
uniform
uniform dispersion
dispersion of of carbon
carbon fibers
fibers ininthe
thePA6
PA6matrix,
matrix,asasshown
shownininFigure
Figure1Ab. [Link]
Three PA6-
PA6-
CF composites with varying carbon fiber contents were prepared by
CF composites with varying carbon fiber contents were prepared by adjusting the rota- adjusting the rotational
speed of the of
tional speed extruder screwscrew
the extruder and the andPA6 the feed rate [38].
PA6 feed The The
rate [38]. carbon fiber
carbon mass
fiber fractions
mass frac-
of these composites were determined through thermogravimetric
tions of these composites were determined through thermogravimetric analysis experi- analysis experiments
(30–900 ◦ C, 10 ◦ C/min, N2). In this study, the composites were designated as PA6-CF10,
ments (30–900 °C, 10 °C/min, N2). In this study, the composites were designated as PA6-
PA6-CF20,
CF10, PA6-CF20, and PA6-CF25.
and PA6-CF25. The PA6-CF
The PA6-CF filaments werewere
filaments extruded usingusing
extruded a single-screw
a single-
extruder after further blending, with the filament diameter controlled
screw extruder after further blending, with the filament diameter controlled at 1.75 at 1.75 ± 0.05 mm.
± 0.05
During the extrusion process, the barrel and die head temperatures were set at 240 ◦ C and
mm. During the extrusion process, the barrel and die head temperatures were set at 240
250 ◦ C, respectively, while the screw speed remained constant at 50 rpm [13,39].
°C and 250 °C, respectively, while the screw speed remained constant at 50 rpm [13,39].

Figure 1.
Figure 1. (A)
(A) Composite
Composite PA6-CF
PA6-CF filament
filamentpreparation
preparationprocess;
process;(a)
(a)Schematic
Schematicdiagram
diagramofofcomposite
composite
material fabrication; (B) schematic diagram of a dual-nozzle composite printerfor
material fabrication; (B) schematic diagram of a dual-nozzle composite printer forthe
thepreparation
preparation
of PA6-CF specimens; (b) SEM micrographs of PA6-CF particles; (c) enlarged view of the internal
of PA6-CF specimens; (b) SEM micrographs of PA6-CF particles; (c) enlarged view of the internal
structure of the printer head; (d) printed samples of PA6-CF composite material.
structure of the printer head; (d) printed samples of PA6-CF composite material.

2.3. 3D Printing and Heat Treatment Process of PA6-CF Composites

Composite filaments need to be dried in an oven at 75 ◦ C for 12 h to remove moisture
before printing or characterization. The custom-built 3D printer (E2CF, Raised 3D) is
specifically designed for FDM printing of fiber-reinforced composites because of several
Polymers 2023, 15, 3722 4 of 20

distinct advantages: (1) Dual gear feeding system. Smoother printing for the lack of fluidity
of carbon fiber composites. (2) Highly durable nozzle. The nozzle hardness is increased
from hrc30 to 60 to withstand the wear and tear of carbon fiber on the nozzle. In this work,
the temperature and time of heat treatment are considered as two basic variables. The
heat treatment process is conducted in a vacuum drying oven, and the vacuum pressure is
maintained at 10 MPa throughout the entire experimental process. The heat-treated samples
are not allowed to contact with metal or each other. The variation interval of the heat
treatment temperature is determined by the glass transition temperature Tg of the printed
composite PA6-CF, while the variation interval of the heat treatment time is determined by
the pre-experiment. The trends of changes in mechanical properties, micro-morphology,
fiber orientation division and crystallinity of the printed composites were analyzed under
5 h of heat treatment. Finally, the heat treatment temperature parameters were optimized to
be room temperature, 90 ◦ C, 120 ◦ C, and 150 ◦ C, and the heat treatment time was optimized
to be 0 h, 5 h, 7.5 h, and 10 h. The 100 mm× 30 mm× 5 mm sample printed from PA6-CF
composite material is used as the standard specimen. The dimensional changes of the
standard specimen after heat treatment are measured precisely using a vernier caliper, with
a measurement precision of 0.01 mm. The printing parameters of the E2CF printer and heat
treatment parameters are shown in Table 1.

Table 1. Printing parameters of the E2CF printer and heat treatment parameters.

Parameters Value Parameters Value

Materials PA6, PA6-CF10, PA6-CF20, PA6-CF25 Build plate temperature 60 ◦ C, 90 ◦ C
Infill structure Triangular, Hexagonal, Kagome, Re-entrant Layer thickness 0.15 mm
Printing speed 20 mm/s infill density 100%
X/Y axis movement speed 150 mm/s Nozzle temperature 275 ◦ C
Extrusion line width 0.4 mm Heat treatment temperature rt, 90 ◦ C, 120 ◦ C, 150 ◦ C
Raster angle 0◦ , 45◦ , 60◦ , 90◦ , 135◦ Heat treatment time 0 h, 5 h, 7.5 h, 10 h

2.4. Single-Layer Monofilament CF-OD Model and Fiber Orientation Testing Methods
We utilized an optical microscope (Leica DM750) at 20× magnification to observe the
distribution of planar fibers. The orientation angle θ and the number of individual fibers
were recorded using ImageJ and subjected to statistical analysis.

2.5. Characterization of Material Micromorphology

The dispersion of carbon fibers (CF) in the composites and the microstructure of the
fractured tensile members were characterized using a scanning electron microscope (SU3,
Hitachi, Tokyo, Japan, 15 kV). The fiber orientation distribution in the CF-OD model was
also characterized using an optical microscope (T2-HD206, AOSVI, Suzhou, China). For
specimens with fiber orientation distribution on the surface, acetone treatment was applied
to expose the carbon fibers. Meanwhile, specimens with fiber orientation inside the CF-OD
were ground and polished. Grinding was performed using 1000-mesh sandpaper, followed
by polishing with a 3 µm polycrystalline diamond suspension (S01-1104D1, Ningbo, China).
To determine the length distribution of the fibers in the composite prints, the composites
were burned in a muffle furnace, and the residual CF was observed under a microscope.
The density and porosity of the composites were calculated using Archimedes’ law and
ASTM D3171-15 standard test method.

2.6. Characterization of Thermal Properties of Materials

The stability of the composites was assessed using the STA4493F3 thermogravimetric
analyzer, with the mass fraction of CF calibrated. The temperature was incrementally in-
creased at a rate of 10 ◦ C/min within the test temperature range of rt-900 ◦ C. In addition, the
composites’ crystallization behavior during the heat treatment process and the variations in
their melting temperature (Tm) and glass transition temperature (Tg) were analyzed using
a differential scanning calorimeter (TA Instruments Q2000). Under a nitrogen atmosphere,
 Polymers 2023, 15, 3722 5 of 20

approximately 10 mg of dried samples were cycled between 30 ◦ C–360 ◦ C–90 ◦ C, with a

temperature ramp rate of 10 ◦ C/min for both heating and cooling stages.

2.7. Characterization of Mechanical Properties of Materials

The tensile and flexural strengths of the composites were evaluated using a universal
testing machine (CMT6104, China) with loading rates of 5 mm/min and 2 mm/min,
respectively. The interlaminar shear strength (ILLS) was determined with reference to the
literature test methods [28]. The impact strength of the materials was determined using a
cantilever beam impact test performed with a Charpy pendulum impact tester (HST-800,
China) equipped with a 50.7 J pendulum.

3. Results
3.1. Effect of CF Content and Printing Parameters on the Properties of PA6-CF Composites
3.1.1. CF Content
To explore the potential of fused-deposition 3D printing for short-cut carbon-fiber-
reinforced composites, we conducted a study on the influence of carbon fiber mass fraction
on the properties of the composites. The thermal stability of PA6-CF was characterized
using thermogravimetric analysis (TGA), revealing an initial degradation temperature (Td)
of 389.1 ◦ C for pure PA6 material, as illustrated in Figure 2a. The mass fraction of short-cut
carbon fibers exhibited a positive correlation with the Td temperature of the composites,
increasing to 391.2 ◦ C, 399.3 ◦ C, and 405 ◦ C, respectively, accompanied by varying degrees
of elevation in the temperature corresponding to the maximum weight loss rate. The ob-
served phenomenon can be ascribed to the significantly higher decomposition temperature
of the fibers in comparison to the matrix [40]. Furthermore, the robust interfacial interaction
between the fiber and the matrix impedes the mobility and degradation of the polymer
chains during the thermal decomposition phase [41]. The fiber content in the three compos-
ites was determined by calculating the difference in weight percentage of residue at 900 ◦ C
compared to pure PA6. These composites were approximately denoted as PA6-10, PA6-20,
and PA6-25 in this study. Figure 2b,c illustrates the DSC melting and crystallization curves
of PA6-CF composites with varying fiber mass fractions. These curves provide valuable
thermal parameters, including the melting temperature (Tm), crystallization temperature
(Tc), and percent crystallization (Xc ). Xc can be calculated using the following equation:

∆Hm
Xc = × 100% (1)
(1 − w)∆Hm,PA6
0

Polymers 2023, 15, x FOR PEER REVIEW ∆Hm is the enthalpy of melting, w denotes the weight fraction of fibers, and ∆H
where 6 of
0 21
m,PA6
denotes the theoretical enthalpy of melting for 100% pure crystallization.

Figure
Figure2.2.(a)(a)
TGATGAcurves of PA6-CF
curves composite,
of PA6-CF the the
composite, boxed section
boxed has been
section magnified
has been for closer
magnified for closer
examination; (b) and (c) DSC curves of PA6-CF composite.
examination; (b,c) DSC curves of PA6-CF composite.

Theaddition
The additionofofcarbon
carbonfibers
fibersenhances
enhancesthe
themechanical
mechanicalstrength
strengthand
andstiffness
stiffnessofofthe
the
composite [42]. At elevated temperatures, this reinforcement effect effectively
composite [42]. At elevated temperatures, this reinforcement effect effectively withstands withstands
themelting
the melting of of
PA6PA6 polymer
polymer molecules,
molecules, requiring
requiring higher
higher temperatures
temperatures for achieving
for achieving a mol- a
molten ◦ C, whereas PA6-CF20 and
ten state. state. The melting
The melting temperature
temperature Tm ofTm of PA6-CF10
PA6-CF10 is 245
is 245 °C, whereas PA6-CF20 and PA6-
25 exhibit a respective increase in melting temperature by 2 °C and 5 °C. Furthermore, the
surfaces of carbon fibers possess high surface energy and reactive groups, thus augment-
ing the heterogeneous nucleation capacity of the composites. These fibers can serve as
crystallization nuclei, promoting the crystallization of polymer molecules. Based on the
Polymers 2023, 15, 3722 6 of 20

PA6-25 exhibit a respective increase in melting temperature by 2 ◦ C and 5 ◦ C. Furthermore,

the surfaces of carbon fibers possess high surface energy and reactive groups, thus aug-
menting the heterogeneous nucleation capacity of the composites. These fibers can serve as
crystallization nuclei, promoting the crystallization of polymer molecules. Based on the
calculated Xc (crystallinity) results, the crystallinity of the composites initially increases and
then decreases with the escalating content of carbon fibers: Xc values of 27.89%, 31.21%,
and 30.36% were obtained for the respective composites. This phenomenon can be ascribed
to the robust interfacial interactions between the silanized fibers and the matrix when
the mass fraction of carbon fibers reaches 25%. These interactions hinder the mobility
of polymer chains. As a semi-crystalline polymer, a portion of the PA6 polymer chain
segments align into ordered crystalline regions through the crystallization process, while
the presence of carbon fibers impacts the distribution of the remaining disordered polymer
chain segments.
Figure 3f illustrates the stress–strain curves depicting the tensile properties of CF com-
posite prints with varying contents. The tensile strength of pure PA6 is 33 MPa, whereas
PA6-CF10 prints exhibit an elevated tensile strength of 58 MPa. PA6-CF25 prints achieve a
tensile strength of 93 MPa, resulting in a 1.82-fold increase in strength, albeit with a reduc-
tion in elongation at break to 9.2%. To elucidate the pattern of tensile strength variation in
the composite prints, scanning electron microscopy (SEM) was employed to observe the
fiber dispersion in the composites, as shown in Figure 3a–c. At low CF content, carbon
fibers were disorderedly arranged. However, higher CF content leads to a more ordered
arrangement of carbon fibers, enhancing the rigidity and strength of the composites. More-
over, with an increase in carbon fiber content, the interfacial region between the carbon
fibers and the polymer matrix expands. This enlarged interfacial bonding region facili-
tates improved stress transfer and the ability to impede crack propagation, consequently
enhancing the mechanical properties of the composite [32]. SEM images of the tensile
fracture provide a clearer visualization of this phenomenon, as shown in Figure 4. In the
composite with 10 wt% CF content, only small voids and holes pulled out by carbon fibers
are observed. However, in composites with 15 wt% CF content, the number of carbon
fiber distributions and the amount of carbon fibers pulled out along the tensile direction
significantly increase. When the CF content reaches 20 wt%, the entire cross-section exhibits
Polymers 2023, 15, x FOR PEER REVIEW
a denser structure with tighter interfacial bonding, although some unimpregnated carbon 7 of 21
fibers are also present.

Figure 3.
Figure 3. SEM
SEM microscopy
microscopy ofof composite
composite materials
materials (a) PA6; (b)
(a) PA6; (b) PA6-CF10;
PA6-CF10; (c)
(c) PA6-CF20;
PA6-CF20; (d)
(d) optical
optical
microscope image of residual CF after complete burnout of the composite material; (e) fiber length
microscope image of residual CF after complete burnout of the composite material; (e) fiber length dis-
distribution frequency histogram and fiber length distribution cumulative frequency line plot; (f)
tribution frequency histogram and fiber length distribution cumulative frequency line plot; (f) tensile
tensile stress–strain curves of composite prints with different short-cut CF contents.
stress–strain curves of composite prints with different short-cut CF contents.
 Figure 3. SEM microscopy of composite materials (a) PA6; (b) PA6-CF10; (c) PA6-CF20; (d) optical
Polymers 2023, 15, 3722 microscope image of residual CF after complete burnout of the composite material; (e) fiber length
7 of 20
distribution frequency histogram and fiber length distribution cumulative frequency line plot; (f)
tensile stress–strain curves of composite prints with different short-cut CF contents.

[Link]
Figure SEMimages
imagesofoftensile
tensilefracture
fracture surfaces
surfaces of of 3D-printed
3D-printed composites
composites with
with different
different CF con-
CF contents;
tents; (a) PA6-CF10; (b) PA6-CF15; (c) PA6-CF20; (d–f) magnified image of the rectangular area in
(a) PA6-CF10; (b) PA6-CF15; (c) PA6-CF20; (d–f) magnified image of the rectangular area in each
each test sample.
test sample.

Thecomposites
The composites were were burned
burned in in aa muffle
muffle furnace
furnace toto obtain
obtain the
the length
length distribution
distribution ofof
the fibers in the composite prints. The residual carbon fibers
the fibers in the composite prints. The residual carbon fibers (CF) were observed (CF) were observed under
under a
microscope, as depicted in Figure 3d. Following the burning process,
a microscope, as depicted in Figure 3d. Following the burning process, the majority of the majority of car-
bon fibers
carbon fibersin in
thethe
matrix
matrix retained
retainedtheirtheiroriginal
originalmorphology,
morphology,with withonly
onlyaafew
few transitioning
transitioning
into powder form. The carbon fibers that preserved their morphology were quantitatively
into powder form. The carbon fibers that preserved their morphology were quantitatively
evaluatedby
evaluated byrecording
recordingtheirtheir length
length andand quantity.
quantity. The The length
length distribution
distribution of approxi-
of approximately
mately 1200 residual CFs is illustrated in Figure 3e, wherein
1200 residual CFs is illustrated in Figure 3e, wherein the majority of fibers fell the majority of fibers fell
within
within the range of 200–500 µm, aligning with microscopy and
the range of 200–500 µm, aligning with microscopy and scanning electron microscopy scanning electron micros-
copy (SEM)
(SEM) [Link]. The average
The average value value
of the of thelength
fiber fiber length distribution
distribution was 345was 345with
µm, µm,fibers
with
fibers ranging
ranging from 340 from µm 340
toµm350to µm 350accounting
µm accounting for 19%for of
19%theoftotal
the total count.
count. Moreover,
Moreover, the
the cumulative frequency curve of the fiber length distribution exhibited
cumulative frequency curve of the fiber length distribution exhibited an S-shape, indicating an S-shape, in-
dicating that carbon fibers with this length distribution contribute to
that carbon fibers with this length distribution contribute to enhanced mechanical strength enhanced mechanical
strength
in in the material.
the material.

3.1.2. Printing Parameters

In addition, to further enhance the mechanical properties of the composites, we inves-
tigated the impact of printing parameters, such as grating angle and substrate temperature,
on the properties of PA6-CF-printed parts. During the printing process, variations in the
grating angle influence the relationship between fiber orientation and tensile direction.
By enlarging the images of the stretched sample surface under a microscope (refer to
Figure 5a–c), it is evident that distinct grating angles result in different deposition direc-
tions of adjacent beads. However, there is a close arrangement between adjacent beads
and individual fibers, with no presence of voids. As presented in Figure S1 and Table 2,
the outcomes for PA6-CF samples at different grating angles align with the stretching
direction. Notably, samples printed with a grating angle of 0◦ demonstrated the highest
tensile strength and elongation at break, followed by those at 60◦ , 45◦ , 135◦ , and 90◦ . For
instance, when all other conditions were held constant, the sample with a grating angle
of 0◦ exhibited a tensile strength of 97.7 MPa and a tensile modulus of 1021.8 MPa, while
the sample with a grating angle of 90◦ showed a tensile strength of 77.7 MPa and a tensile
modulus of 711.5 MPa. Moreover, elevating the base plate temperature resulted in an
improvement in the mechanical properties of the samples. Taking the PA6-CF25 composite
as an example, for samples with all grating angles set to 0◦ , the flexural strength was
111.2 MPa and the impact strength was 17.3 kJ/m2 at a base plate temperature of 60 ◦ C.
However, at a base plate temperature of 90 ◦ C, the flexural and impact strengths underwent
an increase of 11% and 45%, respectively, reaching 123.1 MPa and 25.1 kJ/m2 .
 sample with a grating angle of 90° showed a tensile strength of 77.7 MPa and a tensile
modulus of 711.5 MPa. Moreover, elevating the base plate temperature resulted in an im-
provement in the mechanical properties of the samples. Taking the PA6-CF25 composite
as an example, for samples with all grating angles set to 0°, the flexural strength was 111.2
MPa and the impact strength was 17.3 kJ/m2 at a base plate temperature of 60 °C. However,
Polymers 2023, 15, 3722 8 of 20
at a base plate temperature of 90 °C, the flexural and impact strengths underwent an in-
crease of 11% and 45%, respectively, reaching 123.1 MPa and 25.1 kJ/m2.

Figure
Figure5.5.(a)
(a)Three
Threedeposition
depositionmodes
modesofofPA6-CF;
PA6-CF;(b) (b)3D-printed
3D-printedtensile
tensilespecimens
specimenswith
withdifferent
different
raster angles; (c) images of printed samples at different grating angles under an optical microscope.
raster angles; (c) images of printed samples at different grating angles under an optical microscope.

Table 2 presents the values of mechanical properties for the 3D-printed composite
Table 2. Mechanical test results of printed samples with varying parameters.
PA6-CF, considering three variables: CF content, raster angle, and print substrate temper-
Sample (Fiber ature. The table encompasses the results of 16 cross combinations and six categories of
Contents/Raster mechanical properties tested.
Tensile Strength Notably, a raster
Young’s angle of 90°
Flexural leadsStrength
Impact to a significant increase
Elongation at
Angle/Build-Up 2)
in the flexural strength of the 3D-printed material, with the highest value reaching(%)
(MPa) Modulus (MPa) Strength (MPa) (kJ/m Break 145.2
Temperature) MPa. Furthermore, impact strength shows a positive correlation with CF content and print
10 wt%CF angle 135◦ T90 ◦ C substrate ± 1.9
55.9 temperature, 489.3 ± the
where 108.2 ±
4.5 results from testing 11.8 ± 1.1composite
1.3 the PA6-CF25 at±a 0.2
13.4 print
10 wt%CF angle 90◦ T90 ◦ C substrate ± 2.8
46.8 temperature 424.5
of ± 7.6
90 °C 115.2
and a raster ± 1.9of 90° demonstrate
angle 9.2 ± 0.4 the highest
13.2 ± 0.2
impact
10 wt%CF angle 45◦ T90 ◦ C strength ± 26.1
57.3of 1.8 kJ/m2. 492.3 ± 4.1to provide
In order 109.3 ± 0.9 explanation
a clearer 11.1 ± of 13.2 ±of
0.3 the influence 0.1the
10 wt%CF angle 0◦ T90 ◦ C 59.1 ± 2.0 513.5 ± 3.1 117.2 ± 2.1 13.1 ± 0.1 14.3 ± 0.5
20 wt%CF angle 135◦ T90 ◦ C
three factors on the mechanical
60.3 ± 2.3
performance
582.8 ± 5.6
of the composite
124.2 ± 1.3
material, we have
15.1 ± 1.4
included
10.6 ± 0.2
20 wt%CF angle 90◦ T90 ◦ C 57.3 ± 2.5 551.2 ± 4.5 129.1 ± 1.7 12.1 ± 2.5 10.1 ± 0.1
20 wt%CF angle 45◦ T90 ◦ C 61.2 ± 1.8 560.2 ± 3.9 121.2 ± 2.3 15.2 ± 0.3 11.2 ± 0.4
20 wt%CF angle 0◦ T90 ◦ C 65.6 ± 2.0 604.2 ± 3.9 110.2 ± 1.1 14.1 ± 0.8 11.8 ± 0.5
25 wt%CF angle 135◦ T60 ◦ C 64.1 ± 2.5 614.0 ± 5.1 114.1 ± 1.2 17.2 ± 0.2 11.2 ± 0.3
25 wt%CF angle 90◦ T60 ◦ C 61.1 ± 1.2 568.9 ± 4.9 132.2 ± 2.1 15.1 ± 0.7 11.6 ± 0.4
25 wt%CF angle 45◦ T60 ◦ C 65.2 ± 1.9 616.1 ± 4.5 113.5 ± 0.7 15.4 ± 0.5 11.2 ± 0.7
25 wt%CF angle 0◦ T60 ◦ C 71.0 ± 2.3 641.2 ± 5.9 111.2 ± 1.5 17.3 ± 0.4 12.0 ± 0.2
25 wt%CF angle 135◦ T90 ◦ C 81.3 ± 1.7 791.01 ± 4.5 124.3 ± 2.4 24.0 ± 0.8 9.3 ± 1.0
25 wt%CF angle 90◦ T90 ◦ C 77.7 ± 2.1 711.48 ± 4.1 145.2 ± 2.3 26.1 ± 0.6 10.55 ± 0.9
25 wt%CF angle 60◦ T90 ◦ C 86.2 ± 1.1 877.2 ± 3.7 126.4 ± 3.1 23.1 ± 1.1 9.8 ± 1.1
25 wt%CF angle 45◦ T90 ◦ C 85.3 ± 1.0 862.38 ± 3.3 135.1 ± 1.3 21.1 ± 0.3 9.3 ± 0.4
25 wt%CF angle 0◦ T90 ◦ C 97.7 ± 2.1 1021.8 ± 9.1 123.1 ± 0.7 25.1 ± 0.2 11.7 ± 1.3

Table 2 presents the values of mechanical properties for the 3D-printed composite PA6-
CF, considering three variables: CF content, raster angle, and print substrate temperature.
The table encompasses the results of 16 cross combinations and six categories of mechanical
properties tested. Notably, a raster angle of 90◦ leads to a significant increase in the flexural
strength of the 3D-printed material, with the highest value reaching 145.2 MPa. Further-
more, impact strength shows a positive correlation with CF content and print substrate
temperature, where the results from testing the PA6-CF25 composite at a print substrate
temperature of 90 ◦ C and a raster angle of 90◦ demonstrate the highest impact strength of
26.1 kJ/m2 . In order to provide a clearer explanation of the influence of the three factors
on the mechanical performance of the composite material, we have included the results
Polymers 2023, 15, 3722 9 of 20

of the three-factor orthogonal experiment in Table S1 of the Supplementary Materials. The

results indicate that fiber content is the key factor affecting the tensile strength and impact
strength of the composite material, while print substrate temperature is the key factor
affecting the flexural strength of the composite material. The mechanical properties of
PA6-CF composites were effectively improved by altering the carbon fiber content and
adjusting the printing parameters. However, electron micrographs revealed the presence
of inconsistent fiber distribution and interlayer voids within the material, which acted as
obstacles to further enhancing the composite properties.

3.2. Analysis of the Effect of Heat Treatment Process on Mechanical Properties

3.2.1. Effect of Heat Treatment Process on Fiber Orientation of 3D-Printed Composites
3D-printed fiber-reinforced composites often exhibit microstructural anisotropy and
mechanical property anisotropy [1]. To mitigate the negative effects of anisotropy, we
developed a CF-OD model with a single layer of monofilaments for testing fiber orientation.
The CF-OD model was created by printing four monofilaments along a square wave path,
with each monofilament having a line width of 0.4 mm, a height of 0.15 mm, and a length
of 50 mm, ensuring no gaps theoretically.
Figure 6 illustrates the microscopic images of single-fiber CF-OD models printed under
various heat treatment conditions. To aid observation and analysis, white dashed lines
highlight the carbon fibers. In Figure 7a, the printed composite with a raster angle of 0◦
exhibited well-defined boundaries for individual fibers after undergoing a 5-h treatment
at 120 ◦ C. The black areas in the image represent voids. Although the quantity of carbon
fibers at the fiber edges was relatively lower compared to the interior, their orientation
distribution did not significantly differ. This can be attributed to the corrective effect of
the heat treatment process on fiber orientation at the boundaries, ultimately enhancing
the distribution of carbon fibers at the edges and improving the mechanical properties of
the composite material. Conversely, the printed model with a raster angle of 45◦ showed
reduced consistency in carbon fiber distribution at the edges. In fiber-reinforced composites
Polymers 2023, 15, x FOR PEER REVIEW 10 of 21
produced through FDM printing, fiber alignment at the edges generally surpasses that in
the interior [37]. However, heat treatment caused wetting between adjacent fiber materials,
resulting in changes in fiber orientation distribution. Furthermore, the temperature of
temperature of the also
the heat treatment heat influenced
treatment also
fiberinfluenced
orientationfiber orientation
distribution. distribution.
When the heat When the
treatment
heat treatment
temperature was set at 90 ◦ C,was
temperature set at
below the90glass
°C, below the temperature
transition glass transition
(Tg)temperature (Tg)
of the composite
of the composite
material, material,
black voids black voids
significantly significantly
increased at the increased
edges of theat the edges
single of theand
fibers, single
the
fibers, and the
consistency consistency
of carbon fiber of carbon fiber
orientation orientation
distribution distribution
at the at the
fiber edges wasfiber edgespoor.
relatively was
relatively poor.
Overall, the Overall,
analysis theimages
of the analysishighlights
of the images highlights
how heat howaffects
treatment heat treatment affects
the distribution
the
anddistribution
orientation and orientation
of carbon fibersof
atcarbon
the edgesfibers at the
of the edgesmodels,
printed of the printed models,
indicating indi-
potential
improvements
cating potentialinimprovements
the compositeinmaterial’s
the compositemechanical properties.
material’s mechanical properties.

Figure 6. Schematic diagram:

Figure diagram: preparation
preparationand
andfiber
fiberdistribution
distributionofof
single-layer monofilament
single-layer monofilamentcarbon
car-
bon
fiberfiber 3D-printed
3D-printed composite
composite sample
sample under under microscope,
microscope, thedashed
the red red dashed
box isbox is an enlarged
an enlarged imageimage
of the
of theline
solid solid line box.
box.
Polymers 2023, 15, 3722 Figure 6. Schematic diagram: preparation and fiber distribution of single-layer monofilament
10 ofcar-
20
bon fiber 3D-printed composite sample under microscope, the red dashed box is an enlarged image
of the solid line box.

[Link]
Figure Opticalmicroscopy
microscopyimages
imagesof of3D-printed
3D-printedmonofilament
monofilamentCF-OD
CF-ODmodels:
models:(a)
(a)raster
rasterangle
angle
0°
◦ printed sample heat treated at 120◦°C for 5 h; (b) raster angle 45°
◦ printed sample heat treated
0 printed sample heat treated at 120 C for 5 h; (b) raster angle 45 printed sample heat treated at at
120◦°C for 5 h; (c) raster angle 0°
◦ printed sample heat treated at 90◦°C for 5 h; carbon fibers on the
120 C for 5 h; (c) raster angle 0 printed sample heat treated at 90 C for 5 h; carbon fibers on the
surface are marked with short white lines.
surface are marked with short white lines.

3.2.2. Stereoscopic Fiber Orientation Distribution and Quantitative Analysis

In 3D-printed fiber-reinforced composites, the distribution of fibers on the surface is
generally not directly comparable to the orientation distribution of fibers inside. This dis-
crepancy arises due to various factors influencing fiber orientation and distribution during
the layer-by-layer printing process. For instance, fibers intertwine between layers, forming
a continuous network in both the transverse and longitudinal directions. Additionally, heat
treatment can induce changes in fiber orientation, leading to inconsistent distributions be-
tween the internal and surface fibers. To accurately assess the fiber distribution in 3D-printed
PA6-CF composites, we performed a meticulous process involving the careful removal of the
upper and lower surfaces of the obtained monofilament samples. Subsequently, milling and
polishing techniques were employed on the exposed specimens to determine the orientation
distribution of the internal structural fibers. The polishing process resulted in a remarkably
clear orientation distribution of the internal structural fibers, eliminating the need for further
treatment. To investigate the effects of heat treatment, the monofilament models printed from
the PA6-CF25 composite were subjected to different durations of heat treatment at 120 ◦ C:
2.5 h, 5 h, and 7.5 h. The outcomes of this experiment are presented in Figure 8a–c. It is evident
from the results that the number of pores among the monofilaments gradually decreases
with increasing heat treatment time, with Figure 8c showing almost no visible pores. This
suggests that the process of heat treatment effectively reduces the presence of internal pores
in 3D-printed materials, consequently enhancing the mechanical properties of the compos-
ite. Similarly, the three-dimensional fiber orientation angles θi can be measured, similar to
the measurement of planar fiber orientation angles. Using ImageJ 1.53t, we quantified and
recorded the angles at which the fibers deviated from the printing direction, along with their
Polymers 2023, 15, 3722 11 of 20

respective quantities. This analysis encompassed a total of 1452 visible carbon fibers. The
resulting distribution of fiber orientations within the three-dimensional structure is depicted in
Figure 9, utilizing a statistical histogram format. The fiber orientation coefficient is expressed
using Equation (2) [27].
∑n cos θi
η0 = i = 1 (2)
n
where θi is the fiber orientation angle and n is the number of visible carbon fibers. In
the analysis of fiber orientation distribution, we have also introduced the concept of the
fiber orientation distribution fraction ψ( x ), which can be expressed using Equation (3). By
calculating this fraction, we are able to quantitatively measure the extent of fiber orientation
in the composites. This enables us to conduct a more comprehensive and detailed study
and analysis of the properties and structures of fiber-reinforced composites [36].
Z +∞ ( x − µ )2
1 −
ψ( x ) = √ e 2σ2 (3)
σ 2π −∞

where µ represents the average orientation angle, and σ2 denotes the orientation angle vari-
ance, these two parameters can quantitatively describe the distribution of fibers. The three-
dimensional fiber orientation distribution function obtained through Gaussian fitting is illus-
trated in Figure 8. The orientation distribution of fibers varies under different heat treatment
conditions, resulting in changes in the fitted distribution function. Experimental results demon-
strate that the average orientation angle of the 3D-printed PA6-CF25 composite is 0.51 under
treatment condition a. This suggests that, under this specific heat treatment condition, the peak
frequency of fiber orientation closely aligns with 0◦ (consistent with the printing direction).
Comparatively, the average orientation angle α obtained from fitting under other treatment
conditions does not exhibit significant differences, indicating the statistical significance of this
one-way analysis method. As the duration of heat treatment increases, the average orienta-
tion angle decreases from 0.51 to 0.47 and 0.43, revealing a positive correlation between heat
treatment time and the degree of fiber alignment. Longer heat treatment durations result in
more uniform fiber alignment, thereby enhancing the tensile strength of the printed composites
along the printing direction (i.e., the direction of fiber alignment). Additionally, the variance of
Polymers 2023, 15, x FOR PEER REVIEW
the orientation angle signifies differences in fiber orientation distribution among the three12heat of 21

treatment conditions. Smaller variance values indicate a higher degree of fiber alignment, with
the fitted normal distribution curve more concentrated around a fiber orientation angle of 0◦ .
Notably, ◦ C for a duration of 7.5 h
thereby the sample subjected
enhancing tostrength
the tensile a heat treatment temperature
of the printed of 120 along
composites the printing direc-
exhibited
tion (i.e.,the
thehighest degree
direction of fiber
of fiber alignment,Additionally,
alignment). with an α2 value
the of 8.02. of the orientation
variance
angleInsignifies
summary, the results
differences in demonstrate thatdistribution
fiber orientation increasing the heat the
among treatment temperature
three heat treatment
and durationSmaller
conditions. has a positive
varianceeffect
valuesonindicate
fiber alignment, leading
a higher degree of to improved
fiber mechanical
alignment, with the
properties of the 3D-printed composite PA6-CF. In the subsequent sections,
fitted normal distribution curve more concentrated around a fiber orientation angle of this study will
0°.
further investigate the impact of the heat treatment process on the thermal,
Notably, the sample subjected to a heat treatment temperature of 120 °C for a duration of mechanical,
and
7.5 hmicro-morphological
exhibited the highestproperties
degree ofof the alignment,
fiber printed composites.
with an α2 value of 8.02.

[Link]
Figure Micrographsofoffiber
fiberorientation
orientation distribution
distribution in in
thethe internal
internal structure
structure of 3D-printed
of 3D-printed PA6-
PA6-CF
CF composites; (a) heat treatment at 120 °C for 2.5 h; (b) heat treatment at 120 °C for 5
composites; (a) heat treatment at 120 ◦ C for 2.5 h; (b) heat treatment at 120 ◦ C for 5 h; (c) heat h; (c) heat
treatment at 120◦°C for 7.5 h.
treatment at 120 C for 7.5 h.
Polymers 2023, 15, 3722 Figure 8. Micrographs of fiber orientation distribution in the internal structure of 3D-printed 12
PA6-
of 20
CF composites; (a) heat treatment at 120 °C for 2.5 h; (b) heat treatment at 120 °C for 5 h; (c) heat
treatment at 120 °C for 7.5 h.

Figure 9. Statistical histogram of fiber orientation distribution and Gaussian-fit normal distribution curve;
Figure
(a–c) 9. Statistical
represent histogram
the fiber of fiber
orientation orientation
distribution distributioncurves
and distribution and Gaussian-fit normal
for three different distribution
modes; (d) sum-
curve; (a–c) represent the fiber orientation distribution and distribution curves for three different
marizes the fitted curves of fiber orientation distribution under three different processing techniques.
modes; (d) summarizes the fitted curves of fiber orientation distribution under three different pro-
cessing
3.3. techniques.
Effect of Heat Treatment Process on Other Properties of 3D-Printed PA6-CF Composites
Based on standardized parts with uniform dimensions of 100 mm × 30 mm × 5 mm,
In summary, the results demonstrate that increasing the heat treatment temperature
we utilized PA6-CF25 composites for 3D printing and subjected them to various heat
and duration has a positive effect on fiber alignment, leading to improved mechanical
treatment processes. The density of the composites was measured before and after treatment
properties of the 3D-printed composite PA6-CF. In the subsequent sections, this study will
using Archimedes’ law. Notably, during shearing and extrusion, short-cut carbon fibers
tend to create voids, which consequently impact the mechanical properties of the printed
samples. To quantify the porosity, we employed Equations (4) and (5), and the porosity
was calculated as follows:
Va − Vt
P= (4)
Va
M × mf M × mM
Vt = + (5)
ρCF ρ PA
Theoretical volume (Vt ), actual volume (Va ), and actual weight (M) are used to repre-
sent the printed specimen’s dimensions and mass. The densities of the carbon fibers (ρCF )
and the PA matrix (ρ PA ) are intrinsic properties of the materials investigated in this study.
The composite densities with various carbon fiber contents are displayed in Figure S2. The
mass fractions of carbon fibers (m f ) and the matrix (m M ) are also considered.
Figure 10b,c illustrates the impact of heat treatment temperature and time on the dimen-
sional change rate and porosity of standard-sized prints. At the heat treatment temperature of
60 ◦ C, the porosity in the printed standard parts showed minimal change (<5%) compared to
the untreated samples. As the treatment temperature increased, the porosity in the printed
standards decreased significantly. For instance, at 120 ◦ C, the porosity reduced to 6.0%,
marking a 15.5% decrease compared to the untreated sample’s 7.1%. However, as the tem-
perature continued to increase to 150 ◦ C, the porosity in the samples began to increase. This
phenomenon could be attributed to polymer aging and the introduction of additional defects
resulting from excessive temperatures. Additionally, it is worth noting that 120 ◦ C is close
 Polymers 2023, 15, 3722 13 of 20

to the glass transition temperature of the composites (Figure 10d), at which the movement
of polymer chain segments reduces the number of defects. Moreover, increasing the heat
treatment time further contributed to reducing the porosity of the printed standards. After
10 h of treatment at 120 ◦ C, the porosity decreased to 5.9%. It is important to mention that
the rate of dimensional change in the printed standards, both horizontally and vertically,
aligned with the corresponding changes in porosity. The rate of dimensional change in the
printed standards decreased from 0% in the untreated samples to 0.6% as the heat treatment
temperature and duration increased. Similarly, the porosity of the printed standards also
decreased from 7% in the untreated samples to 6%. However, the magnitude of change was
more pronounced in the vertical direction, which can be attributed to the increased interlayer
porosity resulting from layer-by-layer printing, along with the significant thermal expansion
effect observed in the vertical direction during heat treatment. Finally, based on the data
presented in Figure 10d, the enthalpy of crystallization of the printed composites increased to
35.23 J/g after undergoing a heat treatment at 120 ◦ C for 10 h, compared to the untreated sam-
ples’ 32.24 J/g. The degree of crystallinity also increased from 17.9% to 19.6% when compared
to pure PA6 samples. This improvement is attributed to the increased thermal motion energy
of the polymer chains due to the higher temperature, resulting in reduced obstruction of chain
segment movement and the formation of cross-linked networks. However, excessively
Polymers 2023, 15, x FOR PEER REVIEW high
14 of 21
temperatures can also lead to the formation of oxidized networks between the PA6 polymer
chain segments, thereby reducing the crystallinity of the composite.

Figure10.
Figure (a)PA6-CF
10.(a) PA6-CF composite
composite material
material 3D
3Dprinting
printing100 mm × 30 mm × 5 mm
100mm×30mm×5mm standard
standard specimen;
specimen;
(b,c)dimensional
(b,c) dimensionalchange
changerate
rateand
andporosity
porosityofofstandardized
standardizedprints
printsunder
underdifferent
differentheat
heattreatment
treatment
temperature
temperatureand andtime
timeconditions; (d)(d)
conditions; DSC curves
DSC of the
curves of effect of heat
the effect treatment
of heat on theonthermal
treatment per-
the thermal
formance of printed
performance composites.
of printed composites.

Figure11
Figure 11displays
displays SEM
SEM micrographs
micrographs of 3D-printed
3D-printedPA6-CF
PA6-CFcomposites
compositesunder
undervarious
vari-
heat treatment conditions: untreated, and heat treated at at ◦ C for 7.5 h and 120 ◦ C for
120120
ous heat treatment conditions: untreated, and heat treated °C for 7.5 h and 120 °C
10 10
for h. h.
The untreated
The untreated 3D3Dprints exhibit
prints a relatively
exhibit large
a relatively number
large number of voids, whereas
of voids, whereasthethe
b–c
micrographs depict a significant reduction in void quantity. This reduction
b-c micrographs depict a significant reduction in void quantity. This reduction is at- is attributed
to the heat
tributed treatment
to the process,
heat treatment whichwhich
process, promotes the movement
promotes the movement of PA6 chainchain
of PA6 segments.
seg-
Macroscopically,
ments. this movement
Macroscopically, is manifested
this movement as theaspenetration
is manifested and diffusion
the penetration between
and diffusion be-
neighboring filaments, resulting in reduced void formation between layers
tween neighboring filaments, resulting in reduced void formation between layers and and neighboring
neighboring filaments. The reduction in voids leads to a more uniform stress distribution
when the composite is loaded, thereby decreasing the degree of stress concentration and
ultimately improving the mechanical properties of the printed composite.
 Figure 11 displays SEM micrographs of 3D-printed PA6-CF composites under vari-
ous heat treatment conditions: untreated, and heat treated at 120 °C for 7.5 h and 120 °C
for 10 h. The untreated 3D prints exhibit a relatively large number of voids, whereas the
b-c micrographs depict a significant reduction in void quantity. This reduction is at-
Polymers 2023, 15, 3722 14 of 20
tributed to the heat treatment process, which promotes the movement of PA6 chain seg-
ments. Macroscopically, this movement is manifested as the penetration and diffusion be-
tween neighboring filaments, resulting in reduced void formation between layers and
filaments.
neighboringThe reduction
filaments. inreduction
The voids leads to a more
in voids leadsuniform
to a morestress distribution
uniform when the
stress distribution
composite is loaded, thereby
when the composite decreasing
is loaded, the degree the
thereby decreasing of stress
degreeconcentration and ultimately
of stress concentration and
improving the mechanical properties of the printed composite.
ultimately improving the mechanical properties of the printed composite.

Figure 11.
Figure 11. SEM
SEM micrographs
micrographs of of void
void distribution
distribution in
in 3D-printed
3D-printed composites
composites under
under heat
heat treatment
treatment
process; (a) untreated; (b) heat treated at 120◦°C for 7.5 h; (c) heat treated at 120◦°C for 10
process; (a) untreated; (b) heat treated at 120 C for 7.5 h; (c) heat treated at 120 C for 10 h. h.

3.4.
3.4. Exploration
Exploration of
of Optimal
Optimal Mechanical
Mechanical Properties
Propertiesofof3D-Printed
3D-PrintedPA6-CF
PA6-CFComposites
Composites
After
Afteraadetailed
detaileddiscussion
discussionofofthethe
effects of different
effects heatheat
of different treatment process
treatment conditions
process condi-
on theon
tions parameters of fiberoforientation
the parameters distribution,
fiber orientation thermalthermal
distribution, properties, and microstructure
properties, and micro-
of the composites,
structure we conducted
of the composites, a systematic
we conducted investigation.
a systematic This investigation
investigation. focused
This investigation
on
focused on determining the highest mechanical strength achieved by the 3D-printed com-
determining the highest mechanical strength achieved by the 3D-printed PA6-CF PA6-
posites under theunder
CF composites heat treatment process, inprocess,
the heat treatment both theininterfacial
both the and horizontal
interfacial and directions.
horizontal
Based on the results presented in Figure 12, it was observed that under the optimal treat-
ment conditions (i.e., 120 ◦ C for 7.5 h), the printed composites exhibited a tensile strength
of 162 MPa and a flexural strength of 175 MPa. In comparison to the untreated samples, the
tensile strength showed a remarkable increase of 69%, while the flexural strength increased
by 58%. Notably, this tensile strength value for the printed composites is 406% higher than
that of the pure PA6 print material. In order to explain how we achieved such high tensile
strength values, we used the classical fiber composite material’s tensile strength analysis
model to validate our findings. In this model, the tensile strength σc can be expressed using
the following formula:
σc = η0 Vf σ f + σM (1 − Vf ) (6)
where η0 is the same as in Equation (2), representing the fiber orientation angle, Vf is the
fiber volume fraction, and σM represents the ultimate stress of the PA6 matrix. The fiber
volume fraction can be calculated using the following formula:
m
(1 − P) ρ ff
Vf = 1
(7)
ρc

where ρ f and ρc are the densities of the fiber and the composite material, and P is the
porosity. The calculated fiber volume fraction for our PA6-CF25 composite material is 18.4%.
By applying the tensile strength analysis model, we obtained a value of approximately
167 MPa for σc and a value of 0.985 for η0 , which was calculated using our previous CF-OD
model. The simulated results closely matched the actual test results, thus explaining why
our experimental results significantly exceeded the values reported in the literature. This
analysis also demonstrates the significant impact of fiber orientation distribution and fiber
content on the mechanical properties of the composite material.
Furthermore, under the same treatment condition, the interlaminar shear strength
(ILSS) of the printed composites reached 42 MPa, indicating a 16.7% improvement when
compared to the untreated samples. However, when the temperature exceeds 120 ◦ C,
further increasing the temperature causes a decrease in the interlayer adhesion strength
of the composite material. This may be due to oxidation cross-linking between molecular
chains at high temperatures, resulting in a decline in interlayer mechanical properties.
Similarly, increasing the heat treatment duration also enhances the interlayer adhesion
strength of the composite material. Figure 13 presents the mechanical performance data
of 3D-printed fiber-reinforced polymer composites in recent years. It is evident that the
 Polymers 2023, 15, 3722 15 of 20

mechanical properties of the printed composites achieved in this study, through process
optimization and fine-tuning of printing parameters, greatly surpass the reported average
level. The most direct example is from [12], which also uses PA6-CF25 composite material
for FDM printing. The reported tensile strength in that study is the highest among all
Polymers
Polymers 2023,
2023, 15,15, x FOR
x FOR PEER
PEER REVIEW
REVIEW 1616ofof2121
previously reported literature, reaching 105.8 MPa. In this study, further improvement in
the strength of the composite material was achieved through process optimization. As a
result, we intend to conduct broader research on the potential applications of this material.

Figure 12. (a) Stress–strain curve of flexural test after heat treatment of 3D-printed PA6-CF25; (b)
(a) Stress–strain
Figure 12. curve
Stress–strain of 3D-printedcurve of flexural test
PA6-CF25 after heattreatment;
treatment(c,d)
of 3D-printed PA6-CF25;
Figure 12. (a) Stress–strain curve of flexural tensile testheat
test after aftertreatment
heat ILSSPA6-CF25;
of 3D-printed and dimen-(b)
(b) Stress–strain
sional changes
Stress–strain curve
of printed
curve of 3D-printed
PA6-CF25
of 3D-printed PA6-CF25
under different
PA6-CF25 tensile
heatafter
tensile test test
treatment after heat treatment; (c,d) ILSS and
conditions.(c,d) ILSS and dimen-
heat treatment;
dimensional
sional changes ofchanges
printed of printed PA6-CF25
PA6-CF25 underheat
under different different heat treatment
treatment conditions.
conditions.

Figure 13. Summary of mechanical performance data for 3D-printed fiber-reinforced polymer com-
Figure 13. Summary of mechanical performance data for 3D-printed fiber-reinforced polymer com-
posites. The references in order of citation are as follows: [4–6,9,12,13,15,16,19,24,29,32,34,36].
posites. The references in order of citation are as follows: [4–6,9,12,13,15,16,19,24,29,32,34,36].
Figure 13. Summary of mechanical performance data for 3D-printed fiber-reinforced polymer com-
posites. The references
3.5. Experiments in order of citation
on Lightweighting are as follows:
of 3D-Printed [4–6,9,12,13,15,16,19,24,29,32,34,36].
PA6-CF Composites
In our previous section, we provided a detailed account of the progressive enhance-
3.5. Experiments on Lightweighting of 3D-Printed PA6-CF Composites
ment in the mechanical properties of 3D-printed PA6-CF composites. This involved ad-
Polymers 2023, 15, 3722 16 of 20

3.5. Experiments on Lightweighting of 3D-Printed PA6-CF Composites

In our previous section, we provided a detailed account of the progressive enhance-
ment in the mechanical properties of 3D-printed PA6-CF composites. This involved adjust-
ing the carbon fiber content, optimizing printing parameters, and refining heat treatment
conditions. Under optimal printing conditions, the composites exhibited highly consistent
fiber orientation, a significant reduction in interlaminar and internal voids, and improved
material crystallinity. These findings directly correspond to the improved mechanical
performance
Polymers 2023, 15, x FOR PEER REVIEW of 3D-printed composites. Building on this existing research foundation, we
17 of 21
will now discuss the lightweighting of PA6-CF composites for practical production and
real-life applications.
The fiber-reinforced composite material PA6-CF that we have obtained possesses
treatment conditions. Under optimal printing conditions, the composites exhibited highly
numerous advantages, including high specific strength, good toughness, and low density.
consistent fiber orientation, a significant reduction in interlaminar and internal voids, and
Combined with the advantages of additive manufacturing, these materials can be used
improved material crystallinity. These findings directly correspond to the improved me-
as support materials for manufacturing automobile crash boxes [43]. In this study, we
chanical performance of 3D-printed composites. Building on this existing research foun-
have referenced the existing literature and designed four honeycomb structures for use
dation, we will now discuss the lightweighting of PA6-CF composites for practical pro-
as fillers in automobile crash boxes. As shown in Figure 14, we designed Triangular,
duction and real-life applications.
Hexagonal, Kagome, and Re-entrant as the minimum lattice unit shapes [44]. Using the
The fiber-reinforced
parameterization method composite material
in SolidWorks, PA6-CFthat
we ensured thatthese
we have
fourobtained
differentpossesses
honeycomb nu-
merous advantages, including high specific strength,
3 good toughness,
structures had the same density (ρ = 0.126 g/cm ). We printed them using two different and low density.
Combinedmaterials,
composite with the advantages
PA6-CF20 and of PA6-CF25,
additive manufacturing,
and processed these materials can
them according beoptimal
to the used as
support materials for manufacturing automobile crash boxes [43]. In
heat treatment conditions to obtain samples. We used durability parameters to evaluate this study, we have
referenced the existing literature and designed four honeycomb structures
the printed honeycomb structures, including mass (m), initial peak force (Fmax ), energy for use as fillers
in automobile
absorption (EA),crash
andboxes.
specificAs energy
shown absorption
in Figure 14, we designed
(SEA). Here, FmaxTriangular, Hexagonal,
is defined as the
Kagome, and Re-entrant as the minimum lattice unit shapes [44]. Using
maximum force reached during the initial plastic deformation stage, and total energy the parameteriza-
tion method
absorption is in SolidWorks,
calculated we area
by the ensured
under that
thethese four different honeycomb
force-displacement structures
curve, as shown in
had the same density (𝜌
Equations (6) and (7) [45,46]. = 0.126 g/cm 3). We printed them using two different composite

materials, PA6-CF20 and PA6-CF25, and Zprocessed d them according to the optimal heat
treatment conditions to obtain samples. We EA = P ( δ ) dδ (8)
0 used durability parameters to evaluate the
printed honeycomb structures, including mass (𝑚), initial peak force (𝐹 ), energy ab-
sorption (𝐸𝐴), and specific energy absorption EA
SEA = (𝑆𝐸𝐴). Here, Fmax is defined as the maxi- (9)
mum force reached during the initial plastic deformation m stage, and total energy absorp-
tion isdcalculated
where is the totalby
squeezing under thePforce-displacement
the area distance, is the squeezing force, andas
curve, δ is the instantaneous
shown in Equations
squeezing
(6) and (7)displacement.
[45,46]. SEA as an indicator of energy absorbed per unit of mass.

Figure 14. Unit

Figure14. Unit cell
cell structure,
structure, relative
relative density,
density, and
and printing
printing results
results of
offour
fourdifferent
differenthoneycomb
honeycomb
structures.
structures.

𝐸𝐴 = 𝑃(𝛿) 𝑑𝛿 (8)

𝐸𝐴
𝑆𝐸𝐴 = (9)
Polymers 2023, 15, 3722 17 of 20

Polymers 2023, 15, x FOR PEER REVIEW 18 of 21

The test results, as shown in Figure 15, demonstrate that the Kagome honeycomb
structure exhibits the highest specific energy absorption capability among structures with
the same relative density. At a nominal strain of 0.9, the specific energy absorption (SEA)
of the
of the Kagome
Kagome structure
structure reaches
reaches 17,800
17,800 J/kg.
J/kg. This
This value
valueisis comparable
comparableto tothat
thatof
of metals,
metals,
despite
despite the
the PA6-CF
PA6-CF composite
composite material having
having only
only one-fourth
one-fourth the the density
density of
of metals.
metals.
Lightweight,
Lightweight, fiber-reinforced
fiber-reinforced nylon
nylon materials can effectively
effectively absorb and dispersedisperse collision
collision
energy
energy while reducing
reducing the
the weight
weightofofautomobile
automobilecrashcrashboxes.
boxes. Additionally,
Additionally, compared
compared to
to metals,
metals, high-performance
high-performance polymer
polymer composites
composites are less
are less susceptible
susceptible to corrosion
to corrosion and
and oxi-
oxidation, enabling
dation, enabling them
them to to maintain
maintain a longerservice
a longer servicelife
lifeininharsh
harshenvironments.
[Link],
Moreover,
fiber-reinforced
fiber-reinforced nylon
nylon has
has lower
lower manufacturing
manufacturing costs. Therefore, manufacturing
manufacturing PA6-CF
PA6-CF
composite
compositematerials
materialsunder
underoptimized
optimizedconditions for for
conditions use useas fillers in automobile
as fillers crash crash
in automobile boxes
is feasible.
boxes is feasible.

Figure 15. Examples

Figure 15. Examplesof ofrepresentative
representativelattices;
lattices;(a)
(a)compression
compression experimental
experimental plots of of
plots printed samples
printed sam-
of PA6-CF25
ples Hexagonal
of PA6-CF25 lattice;
Hexagonal (b) compression
lattice; (b) compressionexperimental plotsplots
experimental of printed samples
of printed of PA6-CF25
samples of PA6-
CF25 re-entrant
re-entrant lattice;lattice; (c) compression
(c) compression force-displacement
force-displacement curvescurves of several
of several typical
typical honeycomb
honeycomb lat-
lattices;
tices;
(d) (d) images
images of SEAofvalues
SEA values
of fouroflattice
four lattice structures
structures as a function
as a function of nominal
of nominal [Link].

4.
4. Conclusions
Conclusions
The
The inherent layerstacking
inherent layer stackingnature
natureofof FDMFDM leads
leads to inconsistent
to inconsistent fiberfiber orientation
orientation dis-
distribution and void formation during the 3D printing process,
tribution and void formation during the 3D printing process, which hinders further opti- which hinders further
optimization
mization of the of the composite
composite material’s
material’s performance.
performance. This This
studystudy
aimed aimed to enhance
to enhance the
the per-
performance of 3D-printed PA6-CF composite materials by altering
formance of 3D-printed PA6-CF composite materials by altering the carbon fiber content, the carbon fiber content,
optimizing printing parameters,
optimizing printing parameters,and andrefining
refiningheat
heat treatment
treatment conditions.
conditions. Through
Through the
the de-
design
sign of of a CF-OD
a CF-OD model
model and
and microscopic
microscopic observation
observation of of printed
printed composite
composite materials,
materials, it
itwas
wasconfirmed
confirmedthat thatheat
heattreatment
treatmentprocesses
processesensure
ensurehighly
highly consistent
consistent fiber
fiber orientation
orientation
within
within the
the composite.
composite. SEM SEM characterization further confirmed
characterization further confirmed the the reduction
reduction of of interlayer
interlayer
and internal voids, while DSC analysis validated improved crystallinity
and internal voids, while DSC analysis validated improved crystallinity of the composite of the composite
material. Comprehensiveevaluations
material. Comprehensive evaluations of of thermal
thermal properties,
properties, mechanical
mechanical performance,
performance, and
and microstructural characteristics indicated that under optimal
microstructural characteristics indicated that under optimal processing conditions, processing conditions,
the
the highest
highest tensile
tensile strength
strength of PA6-CF
of PA6-CF composite
composite material
material reached
reached 162162 MPa,
MPa, representing
representing a
a406%
406%increase
increase compared to pure PA6 material. This represents the
compared to pure PA6 material. This represents the greatest reported im- greatest reported
improvement
provement in in thethe fieldofofCFRP
field CFRPfused-deposition
fused-deposition3D 3Dprinting
printingto todate.
[Link],
Additionally, the the
study has explored the lightweight applications of the composite material.
study has explored the lightweight applications of the composite material. By implement- By implementing
3D-printed
ing 3D-printed PA6-CF composites
PA6-CF as fillers
composites in automobile
as fillers crash boxes,
in automobile the Kagome
crash boxes, the Kagomehoneycomb
hon-
structure exhibited a specific energy absorption (SEA) value of 17,800
eycomb structure exhibited a specific energy absorption (SEA) value of 17,800 J/kg. In J/kg. In comparison
to metallic fillers,
comparison fiber-reinforced
to metallic nylon offers
fillers, fiber-reinforced advantages
nylon such as lightweight
offers advantages design,
such as lightweight
corrosion resistance, and cost-effectiveness, making it a promising
design, corrosion resistance, and cost-effectiveness, making it a promising alternative ma-alternative material.
terial.
Polymers 2023, 15, 3722 18 of 20

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

//[Link]/article/10.3390/polym15183722/s1, Figure S1: Mechanical properties of 3D-
printed composites with different raster angles; Figure S2: Density and porosity of 3D-printed
composites with different fiber contents; Table S1: Results of Three-Factor Orthogonal Experiment on
Print Parameter Impact on Mechanical Performance.
Author Contributions: Conceptualization, B.S., L.W. and J.W.; methodology, B.S.; software, B.S.,
G.Z., K.P. and X.H.; validation, L.W. and J.W.; formal analysis, B.S.; investigation, B.S., S.M., L.W.
and J.W.; resources, B.S. and L.W.; data curation, B.S.; writing—original draft preparation, B.S.;
writing—review and editing, B.S. and Q.Z.; visualization, L.W. and J.W.; supervision, L.W. and J.W.;
project administration, L.W. and J.W.; funding acquisition, L.W. and J.W. All authors have read and
agreed to the published version of the manuscript.
Funding: This work is supported by Ningbo public welfare science and technology planning project
(Grant No.: 2022S099), the regional development project of Fujian (Grant No.: 2022H4020, 2023H4023),
Beilun District Key Core Technology Research Project (Grant No: 2022BLG011), the Major Project
of Science and Technology in Fuzhou (Grant No.: 2021-ZD-281), and Fuzhou Foreign Science and
Technology Cooperation Project (Grant No.: 2022-Y-008).
Institutional Review Board Statement: Not applicable.
Data Availability Statement: Not applicable.
Conflicts of Interest: Author Qia Zhang was employed by the company Chunhui Technology Group
Co., Ltd. The remaining authors declare that the research was conducted in the absence of any
commercial or financial relationships that could be construed as a potential conflict of interest.

Abbreviations

PA6 Polyamide 6
TGA Thermogravimetric Analysis
PA-CF25 Polyamide with 25% Carbon Fiber
PA12 Polyamide 12
FDM Fused-Deposition Modeling
ABS Acrylonitrile Butadiene Styrene
CFRP Carbon-Fiber-Reinforced Polymer
Tg Glass Transition Temperature
DSC Differential Scanning Calorimetry
Tc Crystallization Temperature
ILSS Interlaminar Shear Strength
CF-OD Carbon Fiber Orientation Distribution
Td Decomposition Temperature
CF Carbon Fiber
SEA Specific Energy Absorption
EM Elasticity modulus
FRP Fiber Reinforced Polymer
Xc Crystallinity
GF Glass Fiber
EA Energy Absorption
PP Polypropylene
PLA Polylactic Acid
PEEK Polyether Ether Ketone

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