Materials and Design 116 (2017) 253–260

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Materials and Design

journal homepage: www.elsevier.com/locate/matdes

Surface modification of carbon fibers and the selective laser sintering of

modified carbon fiber/nylon 12 composite powder
Wu Jing a, Chen Hui a,b,⁎, Wu Qiong a, Liu Hongbo a,⁎, Luo Zhanjun a
a
College of Material Science and Engineering, Hunan University, Hunan, Changsha, 410082, PR China
b
Key Laboratory of Spray Deposition Technology and Application in Hunan Province, 410082, PR China

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• Modified CFs were firstly used as rein-

forcement phases of composites made
by selective laser sintering (SLS).
• The interfacial adhesion between fillers
and matrix in SLS were firstly discussed.
• The oxygenic groups on the surface of
CFs were thermally decomposed during
the sintering process.
• Treating CFs at 400 °C after HNO3 mod-
ification can decrease the porosity of
sintered composites.
• The practical application problems of
modified CF/PA12 composite powder
in SLS were resolved.

a r t i c l e i n f o a b s t r a c t

Article history: This work aims to study the surface modification and reinforcing effect in carbon fiber (CF)/nylon 12 (PA12) com-
Received 7 August 2016 posites of CFs, and more importantly, resolves the practical application problems of modified CF/PA12 composite
Received in revised form 11 December 2016 powder in selective laser sintering (SLS). CFs were surface modified by nitric acid (HNO3), the surface changes of
Accepted 13 December 2016
CFs were characterized by SEM, FT-IR and XPS. Initially, the effects of the experimental factors on the properties of
Available online 15 December 2016
composites were investigated, and the CF/PA12 composite powder prepared with optimized technological pa-
Keywords:
rameters was subsequently adopted in SLS experiments. The sintering behavior and relationship between me-
Carbon fiber chanical properties and porosity of sintered specimens were also discussed. The results indicated that the
Surface modification oxygen functional groups on HNO3 modified CFs were partly thermally decomposed and released as gas in the
Modified carbon fiber/nylon 12 composite process of laser sintering, which caused high porosity and poor mechanical properties of sintered specimens.
powder Treating CFs at 400 °C (approximately the laser sintering temperature) after HNO3 modification was proposed
Selective laser sintering as a solution. This treatment preserved part of the modified effect and reduced the porosity of the composites
Porosity at the same time. Compared with the unmodified CF/PA12 sintered specimens, the tensile strength, tensile mod-
ulus, flexural strength, and flexural modulus were all increased to different degrees.
© 2016 Elsevier Ltd. All rights reserved.

1. Introduction

⁎ Corresponding authors at: College of Material Science and Engineering, Hunan

Selective laser sintering (SLS) is a rapid prototyping technology that
University, Hunan, Changsha 410082, PR China. creates 3D objects by sintering powder materials layer-by-layer using
E-mail addresses: hnuchh@163.com (C. Hui), hndxlhb@163.com (L. Hongbo). infrared laser beams [1]. The principal advantage of SLS is the ability

http://dx.doi.org/10.1016/j.matdes.2016.12.037
0264-1275/© 2016 Elsevier Ltd. All rights reserved.
254 W. Jing et al. / Materials and Design 116 (2017) 253–260
to manufacture complex and low-volume parts more rapidly and cost-
effectively compared with traditional techniques [2]. Many types of ma-
terials, such as metal, ceramics and polymers, can be used in the SLS
process. Among these materials, polymers were the first and are still
the most widely used materials in this field. Polyamide 12 (PA12) is
very suitable for SLS owing to its low processing temperatures, low
laser power requirement and high accuracy. Currently, many re-
searchers are focused on improving polyamide's mechanical, thermal
or electrical properties by adding micron-sized or nano-sized fillers to
further meet the requirements of different functional parts [3].
Micron-sized fillers such as glass beads [4], aluminum powder [5],
silicon carbide [6], carbon fibers (CFs) [2], potassium titanium whisker
[7] or nano-sized fillers such as clay [3], nanosilica [8], carbon nanofibers
[9], and nanosized carbon black [10] have been used to reinforce poly-
amide for the SLS process. Similar to powder production for convention-
al processing techniques, uniform particle dispersion is very important
for successful production of composites with improved properties [9].
At present, there are three main ways to prepare polymer-based com-
posite powder for SLS: mechanical mixing, cryogenic fracture and coat-
ing the fillers with the base polymer [11]. Mechanical mixing is simple
and convenient, but when the particle sizes or densities of the two pow-
ders are significantly different, this method will lead to poor dispersion.
Powders prepared by cryogenic fracture can disperse homogeneously
but with irregular morphology and a wide particle size distribution,
which is bad for the processing ability and the final characteristics of
the parts. Coating the fillers with the base polymer is often used to pro-
duce metal or ceramic parts by indirect laser sintering. In the area of
polymer based composites, Yan et al. have used the dissolution-precip-
itation method to coat many fillers with polyamide, including alumi-
num powder [12], carbon fibers [2], potassium titanium whisker [7]
and nanosilica [13], and good results were achieved.
As noted in the previous presentations [4–10], most published work
has focused on the uniform dispersion of fillers and neglected the inter-
facial adhesion between fillers and polymer matrix in the SLS process.
Although these composite powders are prepared for SLS, they still
need to follow the general principles of composites. As is known, if the
interfacial bonding strength between fillers and polymer matrix is
low, good mechanical performance of composites can't be ensured, so
surface treatment of the fillers is necessary [14].
Carbon fiber-reinforced polymer composites have been used widely
in aerospace, marine, and automobile industries, and considerable re-
search has been performed in the area of carbon fiber surface modifica-
tions. Xu et al. [15] modified carbon fibers by graft polymerization with
acrylic acid (AA) using a KMnO4/H2SO4 redox-induced system. It was
found that the carbonyl and carboxyl or ester functional groups in-
creased and the graphitic carbon and hydroxyl or ether functional
groups decreased after treatment. The InterLaminar Shear Strength
(ILSS) for composites reinforced by grafted fibers was 17.3% greater
than the ILSS for composites reinforced by untreated fibers. Kim et al.
[16] used coupling agents (CA) combined with plasma treatment to in-
crease the interfacial strength between the carbon fibers and the
Propene Polymer (PP) matrix. These researchers observed that the sin-
gle filament tensile strength of the CF decreased as plasma treatment
time increased (30 s, 1 min, 3 min) because the surface damage of CFs
increased, but the wettability of the CFs and introduction of functional
groups increased, which resulted in a 29.7% increase of the ILSS of CF/
PP composite specimens. When the plasma treatment was 1 min, the
density of the hydroxyl groups was highest, and the ILSS of the compos-
ite specimens with CFs modified by CA after 1 min of plasma treatment
increased 48.7% compared to that of the untreated specimen, which was
the highest. The reason was that the hydroxyl group on the CFs reacted
with the CA, strengthening the interface between the CFs and the PP
matrix. Li [17] oxidized CFs with nitric acid (HNO3) treatment to im-
prove the interfacial adhesion with the polyimide (PI) matrix. XPS anal-
ysis showed the number of oxygen functional groups, including the
C\\O and O\\C_O groups, were increased after treatment, but the
C_C group decreased. This result means that the HNO3 treatment
breaks the C_C bond and binds oxygen functional groups on the fiber
surface. The tensile strength and tensile modulus of HNO3 treated CF/PI
composites were improved by approximately 28% and 10% respectively,
compared with the untreated composite.
The HNO3 treatment method is widely used because it is highly ef-
fective. This method can introduce oxygen functional groups on the sur-
face of CFs and cause corrosion, thus improving the chemical bonding
and physical interlocking between the CFs and the matrix [14]. Al-
though CFs have been used for several decades to reinforce polymers,
composites were always made by traditional molding methods, such
as injection molding. Currently, it is necessary to study the treatment
processes to apply CFs to the new molding method of SLS. In this
work, CFs were oxidized by HNO3 and CF/PA12 composite specimens
were initially made by injection molding. The effects of treating temper-
ature and time on tensile strength of the composites and the chemical
composition changes of the fiber surface were investigated. Next, the
CF/PA12 composite specimens were prepared by selective laser
sintering. The sintering behavior of the composite powder and the rela-
tionship between mechanical properties and porosity of the sintered
components were also discussed.
2. Methods
2.1. Materials
PA12 powder (average particle diameter 30–40 μm, density 1.02 g-
/cm3,melting point 178 °C) and additives (antioxidant and calcium stea-
rate used for improving power flowability) were supplied by Hunan
Farsoon High-Technology Co., Ltd. Polyacrylonitrile (PAN)-based
chopped carbon fibers (tensile strength ≥ 3500 MPa, elastic modulus
230 GPa, density 1760 kg/m3, diameter 7 μm, length 150–250 μm)
were supplied by Hangzhou Gaoke Composite Co., Ltd. Analytical
grade concentrated nitric acid (HNO3 67%) reagent was used.
2.2. Carbon fiber surface modification
Carbon fibers were treated with 67% HNO3 at different temperatures
for different times. Afterwards, the fibers were washed thoroughly with
distilled water to neutral the pH and were dried in the oven.
A portion of the oxidized CFs were thermally treated at 400 °C for 2 h
under N2 protection for the selective laser sintering of modified CF/PA12
composite powder.
2.3. Composite preparation
Firstly the dried PA12 powder was mixed with the CFs using a V-
mixer for an hour. Next, the composite specimens of PA12 reinforced
with 30 wt% CFs were made by injection molding (dimension of
20 × 5 × 1 mm) or selective laser sintering (dimension of
80 × 10 × 4 mm). The parameters of the injection molding experiments
were as follows: melt temperature 210 °C; injection pressure 125 MPa;
holding pressure 40 MPa; holding time 10 s; cooling time 15 s. The
sintering experiments were carried out using an FS251P SLS system
made in Hunan Farsoon High-Technology Co., Ltd. The SLS system was
equipped with a continuous wave CO2 laser. The sintering parameters
were as follows: laser power 28 W; beam diameter 200 μm; laser scan
speed 7.6 m/s; powder layer thickness 0.1 mm.
2.4. Characterization
The tensile and flexural properties of the composites were measured
using a universal testing machine (INSTRON 3382, USA) based on the
Chinese standard GB/T1040-2006 and GB/T9341-2008, and a crosshead
speed of 5 mm/min and 2 mm/min was used, respectively. Five samples
 W. Jing et al. / Materials and Design 116 (2017) 253–260
were tested at room temperature, and the obtained quantities were
averaged.
Investigations of the surface changes of the CFs were performed with
a scanning electron microscope (SEM) (FEI Quanta 200), Fourier trans-
form infrared analysis (FT-IR) (IRAffinity-1) and an X-ray photoelectron
spectroscope (XPS) (ESCALAB 250 Xi). The XPS spectra were collected
using a 200-W Al Ka line. The C1s electron binding energy was refer-
enced at 284.6 eV. The tensile fracture surfaces of the composites were
also analyzed using the SEM. The surface area (m2/g) was determined
by nitrogen adsorption/desorption at − 196 °C (BET method) using a
Micromeritics TriStar II 3020 surface analyzer.
Measurement of the porosity of the sintered specimens was per-
formed as follows. The specimen was fully dried and weighed as m1 in
an air atmosphere. Next, it was boiled and absorbed full water, then
weighed as m2 after water on the surface was blotted with absorbent
cotton. Then a glass beaker with some water was placed in an electronic
balance and the balance was reset. Finally, the boiled specimen was
soaked in the water without touching the cup wall and weighed as
m3. The porosity р of the specimen was calculated according to the fol-
lowing equation:
p ¼ ðm2 −m1 Þ=m3  100%
3. Results and discussion
3.1. Surface analysis of the CF morphology, functional groups, and elements
The morphologies of the CFs before and after modification were ob-
tained by SEM and are shown in Fig. 1. The surface of the untreated CFs
in Fig. 1(a) is smooth with many irregularly shaped chippings, which
may come from the ball milling process. The surface of the CFs treated
with HNO3 in Fig. 1(b) is cleaner and rougher in comparison with the
untreated CFs. There are many deep, parallel grooves distributed along
Fig. 1. Surface morphologies of carbon fibers (a) untreated, (b) HNO3 treated.
255
the longitudinal direction of the treated CFs and the chippings were
removed.
FT-IR is a sensitive technique for surface functional group analysis of
CFs. All of the samples were dried before testing. The comparison of CFs
before and after treatment is shown in Fig. 2. Fig. 2(a) shows the FT-IR
spectra of the original untreated CFs. Almost no obvious peaks are de-
tected on the original CFs, which could be attributed to the low amount
of functional groups, low transmittance of black materials and low con-
tent of sizing agent. Fig. 2(c) shows that after the HNO3 treatment, some
characteristic absorption peaks can be observed. The peak at 3450 cm−1
is assigned to intra and intermolecular hydrogen bonded \\OH
stretching vibration. A pair of absorption bands at 2918 cm−1 and
2850 cm−1 are all observed in the FT-IR spectra of the 3 samples, due
to symmetrical and asymmetrical C\\H stretching vibrations of methy-
lene groups. The peak at 1720 cm−1 is assigned to C_O stretching vi-
bration, and the peak at 1150 cm−1 is assigned to asymmetric
stretching vibration of C\\O bond [18], indicating that the CFs have
been etched and oxidized by the oxidized treatment. After the oxidized
CFs are thermally treated at 400 °C for 2 h under N2 protection, shown in
Fig. 2(b), these characteristic peaks disappear and the spectrogram is
similar to the untreated CFs in Fig. 2(a). This finding means that the
ð1Þ HNO3 treatment can introduce oxygen functional groups on the surface
of CFs, while thermal treatment removes many of the oxygen functional
groups, which is significant in the SLS process.
XPS is a highly useful technique in the determination of the chemical
composition and functional groups of the fiber surface [19–22]. Fig. 3
shows the typical wide-scan survey of XPS spectra of the CFs that
were (a) untreated, (b) HNO3 treated, and (c) thermally treated at
400 °C after HNO3 treatment. It can be found that the CFs (treated and
untreated) are mainly composed of carbon, oxygen and a small amount
of nitrogen elements. The C, O and N atomic contents were 94.02%,
5.10%, and 0.88%, respectively, for the untreated CFs, 91.25%, 7.08%,
and 1.67%, respectively, for HNO3 treated CFs, and 92.99%, 5.41%, 1.6%,
respectively, for the CFs thermally treated after HNO3 treatment. The
chemical functional groups on the surfaces of CFs that were (a) untreat-
ed, (b) HNO3 treated, (c) thermally treated at 400 °C after HNO3 treat-
ment were further analyzed by curve-fitting the C1s spectra, as
illustrated in Fig. 4. The C1s peak of the untreated CF is separated into
three peaks: C_C (284.7 eV), C\\O (286.5 eV) and C_O (287.2–
287.9 eV). The C1s peak of HNO3 treated CFs and CFs thermally treated
after HNO3 treatment are separated into four peaks: C_C, C\\O, C_O
and O\\C_O (288.7–289.0 eV). These results indicated that the HNO3
treatment induced a decrease in the surface concentrations of the C el-
ement and an increase in the surface concentrations of the O element
and generate new oxygen functional groups on the fiber surface,
which corresponds to the results of the FT-IR analysis. The thermal
treatment at 400 °C caused a decrease in the surface concentration of
Fig. 2. FT-IR of carbon fibers (a) untreated, (b) thermally treated at 400 °C after HNO3
treatment and (c) HNO3 treated.
256 W. Jing et al. / Materials and Design 116 (2017) 253–260

Fig. 3. Wide-scan survey XPS spectra of carbon fibers (a) untreated, (b) HNO3 treated and (c) thermally treated at 400 °C after HNO3 treatment.

Fig. 4. Curve fit of the C1s photoelectron peak of carbon fibers (a) untreated, (b) HNO3 treated and (c) thermally treated at 400 °C after HNO3 treatment.
 W. Jing et al. / Materials and Design 116 (2017) 253–260 257

Table 1 the C_C group decreases with increasing treating temperature and
Surface element and functional group compositions of CFs treated at different time, but the oxygen functional groups (including the C\\O, C_O and
temperatures.
O\\C_O) increase after treatment. When the CFs were treated at
Treat Elementary Atom Functional group composition 100 °C (treating temperature changes), for 4 h (treating time changes),
temperature composition (%) ratio (%) (%) the relative percentages of C_C bond were the lowest. This result
C O N O/C N/C C_C C\
\O C_O O\
\C_O means that HNO3 treatment breaks the C_C bond and binds oxygen
OCFs 94.02 5.10 0.88 5.42 0.93 87.34 7.79 4.87 – functional groups on the fiber surface [24]. Furthermore, the C\\O
60 °C 90.67 7.94 1.38 8.75 1.52 78.09 9.04 5.87 6.99 group is initially increased and later it decreases as the C_O and
80 °C 91.25 7.08 1.67 7.75 1.83 78.79 9.94 4.82 6.46 O\\C_O groups increase, which illustrates that the hydroxyl-type
100 °C 91.79 7.03 1.18 7.65 1.28 75.66 8.19 5.01 11.14 groups tend to convert to carboxyl-type groups with higher treating
temperature or longer treating time.
The influences of treating temperature and time on tensile strength
are shown in Fig. 5. The tensile strength of the composite with untreated
Table 2
CFs is 53.30 MPa. After treating the CFs at 60 °C, 80 °C, and 100 °C (with a
Surface element and functional group compositions of CFs treated for different times.
treating time of 2 h), the tensile strength of the composites increased to
Treat time Elementary Atom ratio Functional group composition 60.05 MPa, 60.70 MPa, and 61.39 MPa, respectively. Similarly, after
composition (%) (%) (%)
treating the CFs with HNO3 for 1 h, 2 h, 3 h, and 4 h (with a treating tem-
C O N O/C N/C C_C C\
\O C_O O\
\C_O perature of 80 °C), the tensile strength of the composites were
OCFs 94.02 5.10 0.88 5.42 0.93 87.34 7.79 4.87 – 59.33 MPa, 60.70 MPa, 61.02 MPa, and 61.45 MPa, respectively. These
1h 91.91 6.95 1.14 7.56 1.24 79.26 8.60 5.19 6.94 results indicate that the HNO3 treatment of CFs can improve the interfa-
2h 91.25 7.08 1.67 7.75 1.83 78.79 9.94 4.82 6.46 cial adhesion between CFs and PA12 matrix, and this is mostly due to
3h 91.30 7.30 1.40 7.99 1.53 78.64 7.98 5.99 7.39
4h 89.35 9.60 1.05 10.74 1.17 75.57 6.67 – 17.76
the important contribution of physical and chemical force between ox-
ygen functional groups (C\\O, C_O and O\\C_O) on CFs and the
amide bonds in PA12. This effect can effectively transfer the stress
from the matrix to the fiber, so the fiber provide bring more reinforce-
the O element compared with the HNO3 treated CFs, but it was still ment. Based on an overall consideration of various factors, the HNO3
higher than the untreated CFs, which means that a portion of the oxygen treatment technological parameters in the future work were chosen to
functional groups were thermal decomposed. This finding is also signif- be a treating temperature of 100 °C and a treating time of 4 h.
icant for the subsequent SLS process.
From Figs. 1, 2, 3, and 4, the effect of HNO3 treatment can be summed 3.3. Selective laser sintering behavior of CF/PA12 composite powder
up in three aspects. Firstly, it removes impurities on surface of the car-
bon fiber, which prevents the formation of a weak interface between Fig. 6 shows the SEM micrographs of PA12, CFs and CF/PA12 com-
CFs and PA12. Secondly, it corrodes the fiber surface and makes the posite powder, Fig. 6(a) reveals that PA12 powders are constituted by
number and the depth grooves increase, so the surface area and rough- white spherical particles with a mean diameter of 30-40 μm. As
ness of the CFs is increased. As a result, the physical interlocking be- shown in Fig. 6(b), the CFs are about 7 μm in diameter, and 150-
tween the CFs and polyamide matrix PA12 is improved. Thirdly, it 250 μm in length. From Fig. 6(c) for the mixture of original CFs and
introduces polar functional groups, improves the concentrations of the PA12, it can be found that, the dispersion of the two-phase with a
O element on the surface, and thus the total surface energy and polarity mixing time of 1 h are uniform to some extent, only a few PA12 particles
of the CFs are increased, which improves the wettability and interfacial and CFs aggregate together.
adhesion between the fibers and the PA12 matrix. The CF/PA12 composite powder prepared by the best HNO3 treat-
ment technological parameters were adopted in the SLS experiments.
3.2. Effects of treating temperature and time In this section, three abbreviations are used, OCF/PA12 refers to com-
posites of PA12 reinforced by untreated CFs, CFO/PA12 refers to com-
The elementary and functional group composition changes on the posites of PA12 reinforced by HNO3 treated CFs, CFOH/PA12 refers to
surface of CFs caused by surface modification at different temperatures composites of PA12 reinforced by thermally treated CFs after the
and for different times are shown in Tables 1 and 2 (OCF is the abbrevi- HNO3 treatment. In the selective laser sintering experiments, a large
ation of original CF). When the CFs were treated with HNO3 at 60 °C, amount of bubbles were generated when the CFO/PA12 powder was
80 °C, and 100 °C (with a treating time of 2 h), for 1 h, 2 h, 3 h, and scanned by the laser. However, this phenomenon did not appear in
4 h (with a treating temperature of 80 °C), the O/C ratios and N/C ratios the selective laser sintering experiments of CF/PA12 and CFOH/PA12.
were all increased compared to the unmodified fibers. It was found that Fig. 7 is the photograph of the three composite powder sintered

Fig. 5. Tensile strength of composites reinforced by CFs treated (a) for different times and (b) at different temperatures.
258 W. Jing et al. / Materials and Design 116 (2017) 253–260
Fig. 6. SEM micrographs of powder (a) PA12, (b) CFs and (c) CF/PA12.
specimens. A2 corresponds to the CFO/PA12, which has an uneven sur-
face. Furthermore, the marks on the surface are fuzzy, which means the
precision of the specimen is poor. A1 and A3 correspond to CF/PA12 and
CFOH/PA12, respectively. Their surfaces are smooth and the marks are
clearer; therefore, the precision of the specimens is high. Moreover,
the weight of the CFO/PA12 specimen is much less than the CF/PA12
and CFOH/PA12 specimens.
The mechanical properties of the sintered specimens are shown in
Table 3. The tensile strength and tensile modulus of CF/PA12 sintered
specimens were increased by 60% and 323%, respectively, and the bend-
ing strength and bending modulus were enhanced by 108% and 298%,
respectively, compared with the pure PA12 specimens. However, the
mechanical properties of CFO/PA12 sintered specimens were decreased
and even lower than the pure PA12, after the HNO3 treated CFs were
thermal treated, the tensile strength and tensile modulus of the CFOH/
PA12 specimens were increased by 11% and 5%, respectively, and the
bending strength and bending modulus were enhanced by 7% and
11%, respectively, compared with the CF/PA12 specimens.
To further study the reasons for the change of mechanical properties,
the cross-section of sintered samples were polished and shown in Fig. 8,
from the optical micrographs, (a) refers to OCF/PA12 sintered sample,
(b) refers to CFO/PA12 sintered sample and (c) refers to CFOH/PA12
sintered sample, it can be found that the CFs can distribute uniformly
in PA12 matrix, and there is only a few small pores in the samples rein-
forced by untreated CFs, quite differently the pores in the samples rein-
forced by HNO3 treated CFs are higher in amount and much larger in
size. In the samples reinforced by CFs thermally treated after HNO3
modification, the pores are slightly more than OCF/PA12 sintered sam-
ple, but the mechanical performance are better than OCF/PA12, because
the interfacial adhesion and mechanical interlocking effect is stronger
than OCF/PA12. From the fractured surface SEM micrographs of the
sintered specimens, shown in Fig. 9, it was found that the untreated
Fig. 7. Photograph of sintered specimens.
CFs were debonded from the matrix and there were many pores caused
by fiber pullout, as shown in Fig. 9(a). However, in Fig. 9(b) for HNO3
treated CFs and (c) for thermal treated CFs, most of the CFs were encap-
sulated in the PA12 matrix, and the pores in Fig. 9(b) are more abundant
than in (a) and (c), and they are the largest in size.
The porosities of the sintered specimens are shown in Table 4. The
relationship between bending strength σ and porosity p is σ = σ0 -
exp (− np) [25], where n is a constant, σ0 is the bending strength of
the sintered specimens without pores. Based on this relationship, the
bending strength decreases rapidly with the increase of porosity. The
porosity of the CFO/PA12 sintered specimen is 38.12%. After thermal
treatment of the HNO3 treated CFs, the porosity of the CFOH/PA12
sintered specimen is only 4.68%, although this is still higher than that
of CF/PA12. However, the tensile strength and bending strength are all
higher. The results are in accordance with the mechanical properties.
It was observed from the surface areas shown in Table 5 that the sur-
face area of the untreated CFs is too low and is only 0.021 m2/g. After
HNO3 treatment, the surface area of the CFs was 0.1605 m2/g, and
after thermal treatment, the surface area of the CFs increased to
0.212 m2/g, which is the 10 times that of untreated CFs and 1.32 times
that of HNO3 treated CFs.
In previous studies [26], oxygen groups on the surface of carbon ma-
terials decomposed upon heating by releasing CO and CO2 at different
temperatures has been mentioned, combined with the results of FT-IR
and XPS in our work, which characterize the changes of oxygen groups
on CFs, it can be speculated that some oxygen groups were thermal
decomposed during the progress of sintering and released as gas in
composite powder, there were a great deal of CFs in the samples,
when the gas can't be expelled without external pressure, they would
spread in materials and get together to form large pores, which made
the mechanical properties poorer. The reference also mentioned that
heating under inert atmosphere is a good method used to selectively re-
move some of these functions, that's the reason of much less porosity in
CFOH/PA12 samples. On the whole, although thermal treatment
removes many oxygen functional groups on the surface of CFs, few ox-
ygen functional groups were left, which can improve the interface com-
patibility, at the same time the surface area of the CFs were higher than
the HNO3 treated CFs, which increases the interface contacting area and
the mechanical interlocking effect between CFs and PA12. The results all
demonstrated that thermal treatment after HNO3 treatment is an
Table 3
Mechanical properties of sintered specimens.
Sintered Tensile Tensile Bending Bending
specimens strength modulus strength modulus
(MPa) (MPa) (MPa) (MPa)
PA12 45 1300 51 1330
OCF/PA12 72 5500 106 5300
CFO/PA12 28 2200 43 1530
CFOH/PA12 80 5800 114 5900
 W. Jing et al. / Materials and Design 116 (2017) 253–260 259

Fig. 8. Optical micrographs of cross-sections of composites (a) OCF/PA12, (b) CFO/PA12 and (c) CFOH/PA12.

Fig. 9. SEM micrographs of tensile fractured surfaces of composites (a) OCF/PA12, (b) CFO/PA12 and (c) CFOH/PA12.

effective method to resolve the practical application problems of modi- and O\\C_O groups increased, which means that with higher
fied CFs in selective laser sintering (SLS). Most importantly, the reason treating temperature or longer treating time, the hydroxyl-type
for the pores in the samples made by SLS is that there is no molding groups tend to convert to carboxyl-type groups.
pressure in SLS, which is different from traditional molding methods, 3. The oxygen functional groups on the surface of HNO3 modified CFs
and the design ideas in this research can be used to address similar were partly thermally decomposed and released as gas in the process
problems in SLS process. of laser sintering, which caused a high porosity and poor mechanical
properties of the sintered specimens. When the HNO3 treated CFs
4. Conclusions were further treated at 400 °C under N2 protection, it preserved
part of the modified effect and reduced the porosity of sintered com-
posites at the same time. Compared with the unmodified CF/PA12
1. HNO3 treatment removes impurities on the surface of the carbon
sintered specimens, the tensile strength and tensile modulus were
fiber, increases roughness, introduces oxygen functional groups,
increased by 11% and 5%, respectively, and the bending strength
and improves the concentrations of the O element on the surface,
and bending modulus were enhanced by 7% and 11%, respectively.
thereby enhancing the physical interlocking and interfacial adhesion
between the fibers and the PA matrix. The tensile strength of the Acknowledgments
composites made by injection molding with HNO3 treated CFs was
increased by 15% compared to that without treatment. The authors gratefully acknowledge the financial support for this
work provided by the Hunan Province Science and Technology Major
2. The amount of C_C group decreases with increasing treating tem-
Projects (2013FJ1001-2), the Science and Technology Planning Project
perature and time, but the amount of oxygen functional groups, in-
of Hunan Province, China (No. 2015TP1035) and the Laboratory Open
cluding the C\\O, C_O and O\\C_O, increase after treatment. This
Fund of Key Laboratory of Spray Deposition Technology and Application
result means that HNO3 treatment breaks the C_C bond and binds
in Hunan Province (2015KF0012).
oxygen functional groups on the fiber surface. Furthermore, the
C\\O group is initially increased, then later it decreased as the C_O
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