Received: 3 July 2023 Revised: 31 August 2023 Accepted: 22 September 2023

DOI: 10.1002/pc.27805

RESEARCH ARTICLE

Additive manufacturing of high-strength polyamide

6 composites reinforced with continuous
carbon fiber prepreg

Wei Chen |Zhonglue Hu | Xiping Li | Jiawen He | Sisi Wang |

Yuan Zhao | Mengjia Li | Jiazhen Zhang

Key Laboratory of Urban Rail Transit

Intelligent Operation and Maintenance
Technology & Equipment of Zhejiang
Province, Zhejiang Normal University,
Jinhua, China
Correspondence
Xiping Li, Key Laboratory of Urban Rail
Transit Intelligent Operation and
Maintenance Technology & Equipment of
Zhejiang Province, Zhejiang Normal
University, Jinhua 321004, China.
Email: lxp2010@zjnu.edu.cn
Funding information
Natural Science Foundation of Zhejiang
Province, China, Grant/Award Number:
LQ22E010001; Science and Technology
Program Project of Jinhua, Grant/Award
Numbers: 2021-1-016, 2022-1-044
Abstract
The additive manufacturing of continuous fiber reinforced thermoplastics
(CFRTPs) paves way for the high-strength, light-weight components for variety of
load-bearing applications. In this work, the continuous carbon fiber reinforced
PA6 (CCF-PA6) composites was successfully printed from the prepreg filament.
The prepreg filament was prepared in-house by impregnating the heat-and-acid
treated 1 K carbon fiber bundle with the molten PA6. The tensile strength of the
prepreg filament, which contained with 40 vol% CF, reached 984 MPa. The unidi-
rectional CCF-PA6 specimens were subsequently 3D-printed with the prepreg fil-
ament, and the mechanical strength of those 3D-printed specimens were tunable
by adjusting a set of printing parameters, such as layer thickness, hatch spacing
and printing temperatures. The highest tensile strength of the specimen reached
555 MPa. Those specimens also exhibited outstanding mechanical strength at ele-
vated temperatures, still reaching 184 MPa at 150
C. The mechanical strength of
those specimens was dependent on the content of the fiber. This study can hope-
fully provide new insights for feedstock design and spur novel ideas in tailoring
the mechanical properties of the 3D-printed CFRTPs.

KEYWORDS
additive manufacturing, composites, fibers, mechanical properties, polyamide

1 | INTRODUCTION of CFRTPs are typically more than one order of

Continuous fiber reinforced thermoplastics (CFRTPs)
possess a suite of favorable attributes, such as high-
specific strength, high-impact toughness, ease in proces-
sing and recycling and excellent corrosion resistance,
which are ideal for a plethora of engineering applica-
tions, such as aerospace, automobiles, wind turbines,
and so forth.1 From an engineering perspective,
the mechanical strength (i.e., tensile and flexural)
Wei Chen and Zhonglue Hu contributed equally in this article.
magnitude higher than the unfilled or the short-fiber
reinforced thermoplastic counterpart.2,3 However, the
conventional manufacturing approaches for the
CFRTPs, such as the vacuum bagging, compression
molding, and stamping, typically require expensive
molds and demands intensive labor, thus hurdles the
wide application of CFRTPs. Therefore, developing a
cost-effective, automated manufacturing process tai-
lored for CFRTPs is highly desirable.
In contrast, the recently emerged 3D-printing
(or additive manufacturing [AM]) technologies allow

668 © 2023 Society of Plastics Engineers. wileyonlinelibrary.com/journal/pc Polymer Composites. 2024;45:668–679.


CHEN ET AL.
precise material deposition and manufacturing geometri-
cally complex parts free of mold, which significantly
reduces the manufacturing cost while improves the mate-
rial utilization. As a result, 3D-printing has quickly gained
tractions in manufacturing high-performance composite
components, including the CFRTPs. The exciting prospect
of mold-free manufacturing of the high-strength CFRTPs
have incented substantial research efforts to explore new
approaches, new printers, new materials for 3D-printing
CFRTPs.2 As of now, the 3D-printing of CFRTPs is domi-
nantly achieved via either in-nozzle impregnation or
directly print the preimpregnated filament. In the in-nozzle
impregnation process, the dry reinforcement fibers, such as
carbon fiber (CF),4–9 Kevlar fiber (KF),10–12 glass fiber
(GF),13 or other natural fibers,4,14 were fed into the hot end
and impregnated with the molten plastics that were fed
separately into the hot end. Matsuzaki et al.4 and Tian
et al.6 were among the earliest to report the 3D-printing of
continuous CF reinforced polylactic acid (CCF-PLA)
through in-nozzle impregnation, the tensile strength of the
3D-printed CCF-PLA reached 185.2 MPa, which is 435% of
the neat PLA specimen.4 In contrast, the latter process
directly fed the preimpregnated filament into the nozzle,
which is typically results in higher fiber content and conse-
quently higher overall strength.15–18 For instance, Usun
et al.16 preimpregnated the 3 K CF bundle with the PLA,
and subsequently 3D-printed the prepreg filament. The
resultant tensile strength reached 543.8 MPa.
The advancement in the printing technique have
unlocked a rich library of thermoplastics that can be 3D-
printed with continuous fibers. So far, a variety of thermo-
plastics have been used as matrix materials, such as
acrylonitrile-butadiene-styrene (ABS),4 PLA,5–7,16,19,20
polycarbonate,20 polyether-ether-ketone (PEEK),21,22 polyi-
mide (PI)23 and polyamide (PA).15,17,24,25 Among those
materials, PA offers highly competitive mechanical
strength and is stronger than a number of common plas-
tics, such as PLA and ABS. Meanwhile, PA is much more
affordable and cost-effective than the rest of advanced
engineering plastics, such as PEEK and PI. As a result, PA
becomes an ideal candidate for the plastic matrix in the
3D-printing of CFRPs. Currently, most of the continuous
CF reinforced PA (CCF-PA) is 3D-printed by directly feed-
ing the prepreg filament. For instance, Dickson et al.24
compared the tensile strength of the specimens 3D-printed
with different PA-based prepreg filaments, including GF,
KF and CF. The highest tensile strength reached 444 MPa
when the specimen reinforced with 33 vol% GF. Goh
et al.15 3D-printed a unidirectional specimen using only
the preimpregnated CCF-PA filament. The specimen's ten-
sile strength reached 600 MPa, where the estimated fiber
volume fraction reached 41 vol%. He et al.25 hot-pressed a
specimen 3D-printed with the preimpregnated CCF-PA
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669
filament. The hot compression has greatly elevated the
tensile strength of the specimen, increasing from
767.3 MPa (not pressed) to 939.7 MPa (hot compressed).
Recently, Liu et al.17 prepared CCF-PA12 prepreg filament
with 3 K CF bundle assisted by the in-situ micro-screw
extrusion. The resultant tensile strength reached
737.5 MPa as the volume fraction of CF exceeding 50%.
Despite the recent progress, however, the majority of
previous researches on the 3D-printed CCF-PA composites
used the proprietary CCF-PA filaments supplied by
Markforged,15,24–28 which obscured the key information on
the preparation process of the CCF-PA prepreg
filament, placing major hurdles to further optimize the pre-
preg feedstocks for developing high-performance CCF-PA
composites. In contrast, the preparation of CCF-PLA and
CCF-PEEK prepreg filaments have been well documented
in several recent studies.16,21,29 Therefore, to fully leverage
the favorable attributes of CCF-PA and expand their appli-
cations, there is a need to bridge this knowledge gap by
investigating the details on the preparation of the CCF-PA
prepreg filament and unveiling the performance relation-
ship between the prepreg and 3D-printed specimens, so that
future researchers can better allocate their efforts and
resources in pursuing higher-performance CCF-PA compos-
ite components.
Here in this study, the CCF-PA6 prepreg filaments are
first prepared by a custom-designed impregnation mold
before 3D-printed into unidirectional specimens. The 1 K
CF bundle is first heat-treated and rinsed in acid to
remove the sizing before impregnated with the molten
PA6 into the prepreg filament. The microstructures and
mechanical strengths of the prepreg filament are charac-
terized in detail. This study further investigates the effect
of several key printing parameters, namely layer thickness,
hatch space and printing speed, on the mechanical perfor-
mance of the 3D-printed specimens. The 3D-printed
CCF-PA6 specimens are also tested under elevated tem-
peratures, exhibiting outstanding mechanical strength up
to 150
C. Detailed microstructural characterization on the
cross-sections of the prepreg filament and the 3D-printed
specimens captures the relationship between the printing
parameters and impregnation conditions, which is consis-
tent with the result revealed by the fracture mode analysis
on the tensile-fractured specimens.
2 | EXPERIMENTAL
2.1 | Materials
In this study, the 1 K CF bundle (T300) was acquired
from TORAY Corp, Japan. The average diameter of a sin-
gle fiber is approximately 7 μm and the density of the

670
fiber is 1.76 g/cm3. The tensile strength and elastic modu-
lus of the CF are 3530 MPa and 230 GPa, respectively.
PA6 pellets (PA6 J-2400), purchased from Hangzhou
Juheshun New Material Co., Ltd. (China), was chosen as
matrix material. The density of the neat PA6 is
1.15 g/cm3, and the melting temperature is 221.5
C. The
silane coupling agent (KH792) was purchased from
Dongguan Kangjin New Material Technology Co. Ltd.
(China), and nitric acid (HNO3) was purchased from
Sinopharm Chemical Reagent Co., Ltd., (China).
To enhance the interfacial bonding between the PA6
and CF, the PA6 pellets were first treated with silane by
mechanically mixing the pellets with the 0.5 wt% KH792
solution. Then the treated PA6 pellets were dried in the
dehumidifier at 90
C for 6 h and subsequently used to pre-
pare CCF-PA6 prepreg filament and PA6 filament
(1.75 mm).
2.2 | Preparation of CCF-PA6 prepreg
filament
Figure 1 illustrates the process to prepare the CCF-PA6 pre-
preg filament. As shown in Figure 1A, the raw CF bundle
first passed through the 400
C oven to remove the sizing
agent on the surface and to disperse the fibers. This
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CHEN ET AL.
heat treatment significantly increases the width, or the
dispersity, of the fiber from 1.1 mm (prior treatment) to
1.8 mm (post-treatment), as shown in the Figure 1B,C.
Then, the dispersed CF bundles were treated with HNO3
(10 wt%) to introduce the active functional groups on the
surface of CF and subsequently enhance the interfacial
bonding between CF and PA6 matrix. Then, the acid-
treated CF was rinsed in the water and dried with hot-air,
before drawn into the impregnation mold, and impregnated
with the molten PA6, which was fed continuously into the
impregnation mold by a single-screw extruder, as shown in
Figure 1D. After impregnation, the CCF-PA6 prepreg fila-
ment was drawn from the nozzle (Figure 1E) and rolled
into a spool. The diameter of the CCF-PA6 prepreg filament
was tailorable by adjusting the nozzle diameter and the
drawing speed, and was monitored in real-time with a laser
micrometer.
2.3 | AM of CCF-PA6
Figure 2 shows the AM process of the CCF-PA6. In this
study, the CCF-PA6 prepreg filament and the PA6 fila-
ment were fed simultaneously into the copper heating
block, where the prepreg CCF was impregnated with the
PA6 matrix for the second time before extruded through
F I G U R E 1 Schematic illustration
on the preparation of CCF-PA6 prepreg
filaments: (A) schematic of the
preimpregnation process; (B) width of
raw carbon fiber bundle; (C) width of
the carbon fiber bundle after removing
the sizing agent; (D) picture of the
impregnation mold; (E) nozzle and the
filament.
F I G U R E 2 (A) Schematic of the
CCF-PA6 additive manufacturing
process; (B) schematic of printing
dimensions and direction of the printed
specimen; (C) printed tensile specimen.
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CHEN ET AL. 671

T A B L E 1 Printing process
Process parameters PA6 CCF-PA6
parameters for PA6 specimen and
CCF-PA6 specimen Nozzle diameter (mm) 0.4 1.0


Nozzle temperature ( C) 260 270


Bed temperature ( C) 100 100
Printing direction ±45
Along the tensile direction
Filling rate (%) 100% 100%
Layer thickness L (mm) 0.1 0.2, 0.3, 0.4, 0.5
Hatch spacing H (mm) 0.4 0.6, 0.8, 1.0, 1.2
Printing speed (mm/min) 3600 200, 300, 400, 500

T A B L E 2 Experimental groups for the 3D-printed CCF-PA6 2.4 | Characterization and tests
specimens with different parameters, the numbers in the parathesis
are the denotations for different printing conditions In order to investigate the impregnation effect of
Layer Hatch Printing Environment
the CCF-PA6 prepreg and the 3D-printed specimens, both
Group thickness spacing speed temperature the prepreg filament and the specimens were embedded in
No. L (mm) H (mm) (mm/min) (
C) epoxy resin, sanded, polished and observed with an optical
#1 0.2, 0.3, 1.0 300 25
microscope (Leica DMI3000M, Germany).
0.4, 0.5 To quantify the porosity of the 3D-printed CCF-PA6
#2 0.3 0.6, 0.8, 300 25
specimens, a digital balance (Sartorius, BAS224S-CW,
1.0, 1.2 Germany) was used to measure the density of raw PA6
pellets and printed specimens according to Archime-
#3 0.3 1.0 200, 300, 25
400, 500 des' principle. To validate the porosity level, the micro-
scopic porosity in the printed specimens was also
#4 0.3 1.0 300 25, 50, 100, 150
characterized with a μCT (Vtomex, Sievers, USA),
which was scanning at 80 kV and 100 μA. The spatial
the nozzle, as shown schematically in Figure 2A. This resolution of the μCT was approximately 7 μm. In addi-
custom-designed extruder was installed on a desktop tion, the mass fraction of the CF in the CCF-PA6 pre-
FDM 3D printer (Flashforge Aquila, Zhejiang, China) preg was determined by a thermogravimetric analyzer
to allow precise motions along the XYZ-axis. To evalu- (Netzsch STA 449C, Germany).
ate the mechanical properties of the 3D-printed The tensile strength of the 3D-printed CCF-PA6
CCF-PA6 specimens, a unidirectional, rectangular bar specimens, both at room temperature and high temper-
(125  12.5  1.25 mm3) was printed following the atures, were tested on a universal testing machine
ASTM D3039 standard (scale down to 0.5) as shown in equipped with a 20 kN load cell and a high-
Figure 2B. The printing direction is parallel to the tensile temperature chamber (SUNS, UTM4204, China). The
direction, and the picture of the printed tensile specimen cross-head speed was set at 2 mm/min. To ensure the
is shown in Figure 2C. To further quantify the reinforce- accuracy of the experimental results, five specimens
ment effect of CCF, tensile strength of the nonreinforced were tested in each group. In the high-temperature ten-
PA6 was evaluated following the ASTM D638-V standard, sile tests, each specimen was heated to the set tempera-
the tensile strength of which is approximately 58.4 MPa. ture and held for 5 min before the test. In addition, the
To reveal the effect of printing parameters on the tensile strength of the CCF-PA6 prepreg filament was
mechanical properties of the 3D-pritned CCF-PA6 compos- tested following the ASTM D4018 standard, which was
ites, three different parameters, namely the layer thickness carried out on a benchtop universal testing machine
(L), hatch spacing (H), printing speed, are considered. (ZwickRoell, Z1.0TH, Germany) equipped with a 1 kN
Table 1 lists the parameters employed for 3D-printing the load cell. At least five filaments were tested to mini-
raw PA6 specimen and CCF-PA6 specimen. In addition, mize the measurement errors. All the specimens were
this study further explored the mechanical strength of the sputter-coated (BRIGHT KAS-2000F) with pure plati-
3D-printed CCF-PA6 composites under elevated temper- num (Pt) for 180 s before SEM characterization. The
atures (up to 150
C). Table 2 summarizes the combina- microstructures of the fractured tensile specimens were
tions for the CCF-PA6 composites printed with different characterized by a scanning electron microscope (SEM,
parameters. EM-30PLUS, Coxem, South Korea).

672
3 | R ES U L T S A N D D I S C U S S I O N
3.1 | Characterization of the prepreg
filament
To evaluate the impregnation effect of the CF with the
PA, the cross-sections of the CCF-PA6 prepreg fila-
ments were characterized with optical microscope, as
shown in Figure 3A. As can be seen from the
Figure 3A, the average cross-section area of the pre-
preg filament is around 0.096 mm2, and the diameter
of the prepreg is about 0.35 mm. On the other hand,
the CFs, which appeared as bright dots within the PA
matrix, are overwhelmingly uniformly distributed
across the entire PA cross-section. Figure 3B shows a
magnified image of an individual prepreg filament. In
general, the CFs are well-impregnated by the PA,
where little to no pore can be identified from the
cross-section. Such impregnation level is mainly
attributed to the intrinsically fluidic nature of the PA6
melt, which facilitates the impregnation the CF bun-
dles in a short period of time. By estimating the pro-
portion of CF area to the entire cross-section of PA6,
the volume fraction of the CF in the prepreg filament
is around 40 vol%. This value is consistent with the
value obtained with the TG analysis, which reveals the
mass fraction of the CF in the CCF-PA6 prepreg is
50 wt%, or equivalently 39.5 vol% in volume fraction.
The consistency between the microstructural observa-
tion and TG analysis implies the prepared CCF-PA6
prepreg filament is fully dense and almost free of the
porosities.
In additional to the microstructural features, the
mechanical strength of the CCF-PA6 prepreg is also
investigated. Figure 3C compares the tensile strength
of the CCF-PA6 prepreg with CF treated with differ-
ent conditions. While all three filaments exhibited
very high-tensile strength (≥750 MPa), the CF treated
with both heat and nitric acid exhibited the highest
strength, reaching 984 MPa in average. This strength
value is also superior to the CF prepreg filament
supplied by Markforged (800 MPa)30 and Desktop
Metal (800 MPa).31 The root for such high strength is
likely attributed with the highly dispersed CFs after
the combined treatment of heat and acid, as shown
in the Figure 3D–F. High dispersity in the CFs are
conducive for the subsequent impregnation process.
In addition, the acid treatment also tunes the surface
properties of the CFs, making those CFs easier to
form strong chemical bonds with silane-treated PA6.
In contrast, the raw CFs appear both smooth and
well-aligned (Figure 3D), whereas the heat-treated
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CHEN ET AL.
CFs are bit more dispersed but remain smooth
(Figure 3E).
3.2 | Microstructures on the 3D-printed
CCF-PA6
To characterize the CF distribution in the 3D-printed
CCF-PA6 specimens, the specimen was also similarly cut
from the center to expose the cross-sections, as shown
schematically in Figure 4A. Figure 4B–E shows the cross-
sections of the 3D-printed CCF-PA6 specimens with vary-
ing layer thickness, ranging between 0.2 and 0.5 mm. The
PA6 matrix are the dark gray area, and the embedded CFs
appeared as light gray ellipses, orderly distributed over the
cross-sections of the PA6. It is clear from the Figure 4B–E,
that as the layer thickness increases, the number of ellipti-
cal CF bundles decreases significantly, which implies the
overall volume fraction of CFs within the 3D-printed PA
matrix decreases with the increasing layer thickness. Simi-
lar to the prepreg filament, the voids are not identified
over the cross-section of the 3D-printed specimens. A
closer look on the CF bundles (Figure 4F,G) reveals that
the CFs are well impregnated within the PA6 matrix,
which are essential to achieve good mechanical properties.
To quantify the volume fraction of the CF (V CF Þ in the
3D-printed CCF-PA6 specimens with different printing
parameters, a phenomenological model was proposed
that accounts the ratio of the CF fed into the nozzle to
the overall volume of the print, as shown in the
Equation (1):
D2filament
Lf  π   V CFfilament
V CF ¼ 4
, ð1Þ
V print
where Lf and Dfilament denotes the total length and diame-
ter of the prepreg filament, respectively. V CFfilament rep-
resents the volume fraction of CF within the prepreg
filament (40 vol%). Here, the Lf can then be estimated by
the total moving distance of the tool path, which can be
acquired with the slicing software. The V print is the actual
volume of the 3D-printed specimens with different print-
ing parameters. Figure 5 compares the CF content with
respect to the different combinations of layer thickness
and hatch spacing. As the value of L  H gradually
increases, the CF content in the 3D-printed CCF-PA6
specimens gradually decreases. For instance, the CF con-
tent in the 3D-printed CCF-PA6 specimens decreases
from 30.7 to 15.3 vol% as the L  H value increases from
0.18 (H0.6) to 0.36 (H1.2), a trend that is consistent with
earlier studies.32
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CHEN ET AL. 673

F I G U R E 3 Microstructures and
tensile properties of the CCF-PA6
prepreg filament: (A) microstructures of
the CCF-PA6 prepreg filaments
embedded with epoxy resin;
(B) magnified image of a single CCF-
PA6 prepreg filament; (C) tensile
strength of the prepreg filament treated
with different conditions; (D–F) SEM
images of the CF bundle with different
treatment and the inset are the
magnified images of the CF.

F I G U R E 4 Cross-sections of the
3D-printed CCF-PA6 specimens:
(A) schematic illustration on the cross-
section; (B–E) cross section of the 3D-
printed specimens with layer thickness
ranging from 0.2 to 0.5 mm; (F–G) local
microscopic images on the CF embedded
in the PA6 matrix.

3.3 | Density and porosity of the

3D-printed CCF-PA6

Porosity is another known factor that affects the mechan-

ical properties of the 3D-printed CFRTPs.7 To evaluate
the porosity of the 3D-printed specimens, the density and
weight of each specimen was measured with a high-
precision scale. The porosity of the 3D-printed CCF-PA6
specimens can be determined by Equations (2) and(3)33:

Va  Vt
P¼ , ð2Þ
Va

M  mf M  mm
Vt ¼ þ , ð3Þ
ρf ρm

where Va and Vt stand for the actual volume and theoret- F I G U R E 5 The CF content of the 3D-printed CCF-PA6
ical volume of the 3D-printed specimen. The actual specimens with different values of L  H.

674
volume can be directly measured; whereas the theoretical
volume can be calculated by summing the volumes of CF
and PA matrix (Equation (3)), where M stands for the
weight of the printed specimens, and mf , ρf , mm , and ρm
are the mass fraction and density of the fiber and PA6
resin, respectively.
Figure 6A compares the density and porosity of
3D-printed specimens with respective printing parameters.
As shown earlier, with the concurrent decreasing of the
layer thickness and hatch spacing, the CF content gradu-
ally increases, leading to a steady increase of the density in
the printed specimens, from 1.11 to 1.18 g/cm3, as the CF
has a higher density than PA6 resin. In the meantime, the
overall porosities of the specimens remain largely stable,
fluctuating between 8.7% and 12.2%. However, as the CF
content reaches its maximum when printed with 0.6 mm
hatch spacing (H0.6), the density of the printed specimen
actually dropped to 1.12 g/cm3, the resultant porosity
jumped to 16.3%. This is likely associated with the abruptly
increased printing defects, such as pores and voids, when
printed with very narrow hatch spacing. While such level
of porosity is comparable to a few earlier researches in 3D-
printed CCF-PA6 composites (10.3%–14.3% in Ref25), it is
nonetheless unfavorable for the integrity of the structure
and limits the application of such CCF-PA6 composites in
load-bearing structures. To validate the porosity level, a
small section of the printed CCF-PA6 (L0.3) specimen
(7.5 mm  12.5 mm  1.25 mm) was further characterized
with μCT, as shown in Figure 6B. It is clear that the micro-
scopic voids are mostly aligned with the printing direction,
which is likely due to the layer-wise printing process,
which results in the elongated pores along the printing
path. Such distribution of micropores is also consistent
with earlier studies on the 3D-printed CFRTPs.7,34 As can
be seen in Figure 6C, The majority of the voids are less
than 100 μm. It is interesting to note though, that the μCT
characterization yields a porosity level of 2.16%, which is
significantly lower than the microscopic porosity level
(10.36%) reported in Figure 6A. Such difference is mainly
attributed to the limited resolution of μCT employed in this
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CHEN ET AL.
F I G U R E 6 (A) The density and
porosity of the 3D-printed CCF-PA6
specimens with different printing
parameters; (B) μCT-scan image of
printed specimen; (C) the size and
distribution of voids in the printed
specimen.
study (approximately 7 μm), where microscopic pores that
are smaller than the given resolution cannot be identified.
Nevertheless, the presence of such micropores, which is
likely associated with the lacking of consolidation during
the 3D-printing process, can be effectively addressed by hot
pressing25,35 or roller compaction,34 and merits in-depth
studies in the future.
3.4 | Mechanical properties of the 3D-
printed CCF-PA6
Figure 7 summarizes the tensile strength of the 3D-
printed CCF-PA6 specimens with varying processing
parameters, including the layer thickness, hatch spacing
and printing speed. As shown in the Figure 7A, as the
layer thickness of the printed specimens increasing from
0.2 to 0.5 mm, the average tensile strength decreases
from 555.3 to 190.2 MPa, with a decrease over 65%. Such
dramatic decrease is expected as the increased layer
thickness greatly reduces the content of the load-bearing
CF within the matrix (see also Figure 4B–E), decreasing
from 25.7 to 10.9 vol% in the same span. In addition, the
increased layer thickness also lowers the interlayer pres-
sure during the print, and thus deteriorates the interlayer
bonding.15 The concurrent drop in the tensile strength
and CF content is also observed when the hatch spacing
increases from 0.6 to 1.2 mm, as shown in Figure 7B,
where the tensile strength of the specimens decreases
from 452.5 to 284.9 MPa. A wider hatching spacing
allows fewer CF bundles placed along the lateral direc-
tion, thus decreasing the content of the CF and overall
load-bearing capability. Figure 7C highlights the effect of
printing speed on the strength of the 3D-printed CCF-
PA6 specimens. As the printing speed increases from
200 to 500 mm/min, the tensile strength drops from 408.7
to 310.7 MPa. While the printing speed does not affect
the fiber content, it poses direct impact on the secondary
impregnation between the CF and PA6. Typically, a
smaller printing speed allows longer time for the molten

CHEN ET AL.
F I G U R E 7 The tensile
strength of the 3D-printed
CCF-PA6 specimens with
different printing parameters
and testing conditions:
(A) layer thickness; (B) hatch
spacing; (C) printing speed;
(D) environment temperature.
PA6 infiltrate and impregnate the CFs, and hence reduces
the possible imperfections induced by inadequate impreg-
nation, such as voids and cracks. Such adversary effect of
printing speed on the tensile strength is consistent with sev-
eral recent studies.6,21,32 As a result, it is a common practice
to limit the printing speed below 10 mm/s, or equivalently
600 mm/min when 3D printing CCF reinforced thermo-
plastics.10,17 Such printing speed is significantly lower than
printing with the conventional thermoplastics, and is thus
detrimental for the printing efficiency. Therefore, there is
still much room to explore, to retain the strength of the
3D-printed continuous fiber reinforced composites without
compromising the efficiency.
When compared PA6 with other commonly used
plastics, such as PP, PLA and ABS, PA6 is superior in
mechanical strength as well as thermal stability. There-
fore, it is of great interest to explore the mechanical prop-
erties of the 3D-printed CCF-PA6 composites at elevated
temperatures, as summarized in the Figure 7D. As the
environmental temperature increases from 25 to 150
C,
the tensile strength of the printed specimens decreased
monotonically, dropping from 356.6 to 184.4 MPa. Such
drop is understandable due to the intrinsic thermoplastic
nature of PA6, which softens considerably upon heating.
Nonetheless, while the tensile strength of the CCF-PA6
specimen at 150
C only amounts to 50.8% of the room
temperature counterpart, it is still among the highest
compared with other 3D-printed thermoplastics rein-
forced by short fibers.3,33 At 100
C, tensile strength of the
printed specimen reached 294.1 MPa, which is
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675
comparable to the strength of 6061-T6 aluminum alloy at
room temperature (310 MPa).36 It is also worth noticing
that, the mechanical performance of the 3D-printed CCF-
PA6 specimens at elevated temperatures can be further
improved by fine-tuning the printing parameters, such
reducing the layer thickness and hatch spacing. Overall,
the mechanical testing results attest promising potential
to employ 3D-printed CCF-PA6 composites in the exten-
sive load-bearing applications.
The tensile strength illustrated in Figure 7A,B also
indicate a strong correlation between the CF content
and ultimate mechanical strength. Figure 8 summa-
rizes the tensile strength of the 3D-printed CCF-PA6
composites with varying CF content.15,24–28,30,35
Clearly, in the present study, the tensile strength
increases almost monotonically with the increasing
CF content. As the CF content reaches the 25.7 vol%,
the tensile strength reaches maximum at 555.3 MPa,
which is almost 9.5 times higher than the unfilled PA6
matrix (58.4 MPa). The only exception appears when
the CF content reaches 30.7 vol%, the tensile strength
is reduced (452.7 MPa) compared with the previous
counterpart. This is probably due to the defects, such
as pores or void, introduced in the printing process. It
is also worth noting that this specimen also exhibited
the highest porosities among all the tested parts
(Figure 6A), which may partially explain the overall
reduced strength.
For the CCF reinforced thermoplastic composites, the
theoretical strength limit (σ c ) can be estimated with the

676
F I G U R E 8 Comparisons on the tensile strength of the 3D-
printed CCF-PA6 specimens and the prepreg filament with respect
to the volume content of CF.15,17,25–28,30,35
classic rule of mixture law, as described in the
Equation (4):


σc ¼ σf V f þ σm 1  V f , ð4Þ
where σ f and σ m are the tensile strength of CF and
matrix, respectively. Vf is the volume fraction of CF in
the composite. The theoretical limit for the CCF-PA6
composites is shown as the dashed line in the Figure 8.
Overall, there is a considerable gap between the theoreti-
cal limit and experimental results. For instance, at
25.6 vol% CF content, the tensile strength of the 3D-
pritned CCF-PA6 composites only accounts to 58.5% of
the theoretical limit, which indicates there is still plenty
of room for improvement. While higher tensile strength
in the 3D-printed CCF-PA6 composites has been reported
by other studies,15,17,25,26,28,35 our study appears to achieve
the highest strength in the prepreg filament, while attaining
the smallest gap between the theoretical limit and experi-
mental strength result. Nonetheless, there is still plenty of
room for improvement, such as increasing the overall CF
content, and consolidating the printed specimen via either
hot pressing35,37 or roller compaction.34
3.5 | Analysis of failure mechanism
To reveal the underlying failure mechanism of the 3D-
printed CCF-PA6 composites, Figure 9 shows the picture
of the tensile-fractured specimens with different printing
parameters. Four distinctly different failure modes have
been identified, namely the filament fracture, filament
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CHEN ET AL.
pull out, horizontal crack and interlayer delamination.21
The filament fracture is the most ideal failure mode, which
indicates the reinforcing fibers are well-bonded to the ther-
moplastic resin. Both the horizontal crack and interlayer
lamination are caused by inadequate bonding between the
adjacent layers, and the filament pull out is due to the weak
matrix-fiber bonding. From Figure 9A–D, there is a clear
transition in the failure mode from filament fracture to
interlayer lamination as the layer thickness increases from
0.2 mm to 0.5 mm. A similar failure mode transition, more
specifically from filament fracture to horizontal cracks, has
been observed in the specimens with increasing hatch spac-
ings (Figure 9E–H). In both cases, either through increasing
the layer thickness or the hatch spacings, reduce the overall
CF content within the PA6 matrix. As a result, the tension-
induced cracks are more likely to emerge and spread within
the polymeric matrix and ultimately lead to premature fail-
ure. Increasing the printing speed (Figure 9I–L), on the
other hand, reduces the overall interfacial bonding between
the PA6 matrix and CF by shortening the impregnation
time, and result in failure in both horizontal and lateral
directions. Overall, the failure modes are consistent with
the mechanical performance of the 3D-printed CCF-PA6
specimens.
To corroborate the failure mechanism revealed by the
macro-scale observation, the tensile-fractured specimens
were also characterized by SEM, as shown in the
Figure 10. The microscopic observations provide ample
evidence to support the previously analyzed failure mode
transitions. For instance, Figure 10A,B compares the frac-
tured CCF-PA6 specimens with 0.2 and 0.5 mm layer
thickness. For the specimen printed with 0.2 mm layer
thickness, the cross-section appears fully packed, absent
of noticeable cracks. The magnified image shows the
fractured CF, indicating good load-bearing capability. In
contrast, when printing with 0.5 mm layer thickness, the
cross-section exhibits large interlayer cracks, as observed
earlier in the macroscopic image. The majority of CFs
were also pulled out from the embedded matrix instead
of fractured, indicating a weak interfacial bonding and
reduced load-bearing capability. Similar transitions in the
failure mode were also easily recognized in the specimens
printed with the increasing hatch spacing (Figure 10C,D)
and printing speed (Figure 10E,F).
3.6 | Demonstration of 3D-printed
CCF-PA6 composites parts
To demonstrate the versatility and functionalities of the
3D-printed CCF-PA6 composites, we also prepared an ellip-
tical ring (length  width  height: 50  80  7.2 mm)
and tested its weight-bearing capability in the real-world
scenario, as shown in the Figure 11. This ring, printed with
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CHEN ET AL. 677

F I G U R E 9 Macroscopic
failure mechanism of the 3D-
printed CCF-PA6 specimens
with different printing
parameters: (A–D) layer
thickness; (E–H) hatch spacing;
(I–L) printing speed. Here,
image (B), (G), and (J) are the
same specimen.

F I G U R E 1 0 SEM images
on the tensile-fractured CCF-
PA6 specimens with different
printing parameters: (A and B)
layer thickness; (C and D) hatch
spacing; (E and F) printing
speed.

F I G U R E 1 1 The demonstration of
3D-printed CCF-PA6 ring for heavy-
lifting applications: (A) image of lifting a
150 kg injection-mold; (B) image of
lifting an 80 kg adult; (C and D) the size
and mass of the ring.

0.3 mm layer thickness and 0.8 mm hatch spacing, has a than 150 kg, Figure 11A) or an adult (weighs approximately
cross-section area of 7.2  7.2 mm2 and weighs only around 80 kg, Figure 11B) without fracture. This application dem-
10 g (Figure 11C,D). Despite being light weight in nature, onstrates the appealing potential of using the 3D-printed
this ring can steadily hold an injection-mold (weighs more CFRTPs for load-bearing, weight-sensitive applications.

678
4 | C ON C L U S I ON
In this study, high-strength CCF-PA6 composites compo-
nents were directly 3D-printed by in-nozzle impregnation
of the PA6 and CCF-PA6 prepreg. Microstructural charac-
terization on the prepreg reveals the CFs are homogenously
distributed within the PA6 matrix, while the volume frac-
tion of CFs reaches 40 vol%. Microscopic observations on
the cross-sections of the 3D-printed CCF-PA6 specimens
indicates the CFs are well-impregnated with the PA6
matrix, and the fiber content of the 3D-printed specimens
can be actively tailored by tuning the printing parameters,
including the layer thickness and hatch spacing. The
3D-printed CCF-PA6 specimens also exhibit outstanding
mechanical strength, reaching 555 MPa at room tempera-
ture and exceeding 180 MPa at 150
C. Parametric study
reveals that both increasing the hatch spacing or the
layer thickness decrease the overall fiber content and
consequently the mechanical strength of the 3D-printed
CCF-PA6 composites. Increasing the printing speed also
poses adversary effect in the mechanical strength of the
3D-printed CCF-PA6 composites. Beyond the microscopic
and mechanical characterizations, this study further dem-
onstrates the scalability and functionality of the 3D-printed
CCF-PA6 components by showcasing its load-bearing capa-
bility in a real-world scenario.
Overall, this present study indicates an intriguing poten-
tial for preparing the light-weight, high-performance
CCF-PA6 components with 3D printing. This study can
hopefully spur new ideas on the composite feedstocks
design and incentive new strategies on the perfor-
mance optimization for the 3D-printed thermoplastic
composites.
A C K N O WL E D G M E N T S
The research work was supported by Natural Science
Foundation of Zhejiang Province, China (LQ22E010001),
Science and Technology Program Project of Jinhua
(2021-1-016, 2022-1-044), the “Pioneer” and “Leading
Goose” R&D Program of Zhejiang Province
(2022c01163), Project of Key Laboratory of Urban Rail
Transit Intelligent Operation and Maintenance Technol-
ogy & Equipment of Zhejiang Province, China
(ZSDRTZZ2020003), and Self-Topic Fund of Zhejiang
Normal University (2020ZS04).
DATA AVAILABILITY STATEMENT
The data that support the findings of this study are available
from the corresponding author upon reasonable request.
ORCID
Wei Chen https://orcid.org/0009-0009-8994-4385
Zhonglue Hu https://orcid.org/0000-0001-7529-8751
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CHEN ET AL.
Xiping Li https://orcid.org/0000-0003-3311-4613
Mengjia Li https://orcid.org/0000-0003-2124-500X
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How to cite this article: Chen W, Hu Z, Li X,
et al. Additive manufacturing of high-strength
polyamide 6 composites reinforced with
continuous carbon fiber prepreg. Polym Compos.
2024;45(1):668‐679. doi:10.1002/pc.27805