Journal of Materials Processing Tech.

288 (2021) 116882

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Journal of Materials Processing Tech.

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

Comparative study on 3D printing of polyamide 12 by selective laser T

sintering and multi jet fusion
Chao Caia,1, Wei Shian Teya,1, Jiayao Chena, Wei Zhub, Xingjian Liuc, Tong Liud, Lihua Zhaoa,e,
Kun Zhoua,b,*
a
HP-NTU Digital Manufacturing Corporate Lab, School of Mechanical and Aerospace Engineering, Nanyang Technological University, 50 Nanyang Avenue, 639798,
Singapore
b
Singapore Centre for 3D Printing, School of Mechanical and Aerospace Engineering, Nanyang Technological University, 50 Nanyang Avenue, 639798, Singapore
c
Department of Mechanical and Industrial Engineering, University of Toronto, Toronto, Ontario M5S 3G8, Canada
d
Singapore Institute of Manufacturing Technology, Agency for Science, Technology and Research, 73 Nanyang Drive, 637662, Singapore
e
3D Lab, HP Labs, HP Inc., Palo Alto, California 94304, USA

ARTICLE INFO ABSTRACT

Associate Editor: A Clare Selective laser sintering (SLS) and Multi Jet Fusion (MJF) are two of the most developed powder bed fusion
additive manufacturing techniques for the manufacture of polymeric components. In this work, a systematic
Keywords:
benchmark and comparison of polyamide 12 (PA12) parts printed by SLS and MJF was conducted on the
Powder bed fusion
Selective laser sintering physicochemical characterization of raw powder materials (EOS PA2200 and HP 3D HR PA12) and their printed
Multi Jet Fusion specimens, as well as the mechanical performance and printing characteristics of printed objects. Both desig-
PA12 nated-supply PA12 powders for each technique possessed almost identical thermal features, phase constitutions,
Mechanical properties functional groups, and chemical states. The mechanical strength of the MJF-printed specimens was slightly
stronger than that of SLS-printed counterparts due to the synergistic effect of an area fusion mode and carbon
black additive in the MJF process. The SLS-printed specimens had a better surface finish on the top surface, but
the MJF-printed specimens showed much smoother front and side surfaces. Scaled-down merlions were printed
by both processes for the printing accuracy assessment. The results show that the SLS-printed merlion presented
higher profile deviations than those of the MJF-printed counterpart, especially in areas with sharp contours.
These fundamental experimental results can provide a comprehensive understanding of SLS and MJF processes
and serve as a valuable guideline for their industrial applications.

1. Introduction
Additive manufacturing (AM), commonly known as 3D printing, is a
group of emerging innovative techniques that create objects based on
digital models through a layer-by-layer accumulation approach (Ngo
et al., 2018; Tan et al., 2020a). Powder bed fusion (PBF), as one of the
seven categories of AM techniques classified by ISO/ASTM, has at-
tracted considerable attention from industrial and academic organiza-
tions because of its ability to print products with geometrical com-
plexity and its versatility to use any powder that can be sintered or
melted (Tofail et al., 2018).
Selective laser sintering (SLS) and Multi Jet Fusion (MJF) are two
mature industrial PBF processes for the fabrication of polymeric com-
ponents (Tan et al., 2020b). SLS was initially developed in the 1980s by
Beaman and Deckard (1990) from the University of Texas at Austin,
where a CO2 laser was used to scan and sinter each cross-section of
targeted objects to fabricate polymeric products (Fig. 1(a)). MJF,
emerging in 2014, is a proprietary technology of Hewlett-Packard (HP)
Inc. In contrast to SLS using a laser as the heat source, MJF utilizes an
array of infrared lamps as the energy source to fuse the area of interest
jetted with a fusing agent that can absorb infrared radiation energy. The
fusing agent is deposited by inkjet nozzles installed in a carriage to the
designated regions of the powder bed on the voxel level. Meanwhile, a
water-based detailing agent is jetted around contours of the printed
parts to inhibit the fusion of powder near the part edges and to improve
part resolution, as illustrated in Fig. 1(b). When printing large parts, the
detailing agent is also jetted into specific areas within the large parts to
prevent partially excessive thermal accumulation.

⁎
Corresponding author.
E-mail address: kzhou@ntu.edu.sg (K. Zhou).
1
The authors contributed equally to the work.

https://doi.org/10.1016/j.jmatprotec.2020.116882
Received 21 May 2020; Received in revised form 12 August 2020; Accepted 17 August 2020
Available online 19 August 2020
0924-0136/ © 2020 Elsevier B.V. All rights reserved.
C. Cai, et al.
Fig. 1. Schematic illustration of the two PBF processes: (a) SLS and (b) MJF.
Polyamide 12 (PA12) is the most widely used polymer for both PBF
processes because of a broad temperature range between its onset
melting temperature (during heating) and its onset crystallization
temperature (during cooling). The temperature ranges are named sin-
tering windows in SLS. A broad sintering window is able to lessen the
crystallization of printed parts during the printing processes (Wang
et al., 2015). The restraint of crystallization during build processes can
protect the printed parts from residual stress accumulation, warpage,
and distortions, endowing PA12 powder with excellent printability for
both PBF processes.
Nowadays, extensive research has been conducted on the chemical,
physical, and mechanical properties of PA12 parts printed using both
PBF techniques. For SLS, Caulfield et al. (2007) studied the effect of
energy density on the density and mechanical properties of printed
PA12 specimens by adjusting the laser power, hatch spacing, and
scanning speed. According to experimental results, a correlation be-
tween the energy density and tensile property was described via a non-
linear equation for predicting the tensile properties of SLS-printed PA12
parts. Ajoku et al. (2006) assessed the influence of build orientation on
tensile, flexural, and compression properties of SLS-printed PA12 spe-
cimens. The testing results showed distinct anisotropy in specimens
printed along three different orientations, which arose from the dif-
ferent thermal distributions within the parts during the SLS process.
Dadbakhsh et al. (2017) revealed the underlying mechanisms for the
effect of used PA12 powder on the coalescence fusing behavior, crys-
tallinity, microstructure, and mechanical properties of SLS-printed
specimens. Specimens made from used powders presented inferior
tensile strength compared to those printed from virgin powder parti-
cles, owing to the lower crystallinity and coarse spherulitic micro-
structure of the SLS specimens manufactured from used powders.
Although the MJF printer was commercialized about 3 years ago,
many scientific studies have been conducted on MJF to date. O’Connor
et al. (2018) evaluated the chemical and mechanical properties of MJF-
printed PA12 parts built along three different orientations. It was ob-
served that the samples built along the Z orientation possessed the
highest tensile strength but the anisotropy in the tensile strength of
samples printed along the X, Y, and Z orientations was weaker when
compared with the SLS production of PA12. Riedelbauch et al. (2019)
analyzed the respective impact of powders with different mix ratios of
virgin/used powders and powders with different reusing numbers (0–5
cycles) on the chemical, rheological, thermal and mechanical behavior
of MJF-printed PA12 parts. It was found that different mix ratios of
virgin/used powders, as well as powders reprocessing cycles (up to 5
cycles), had no significant impact on the printed parts in terms of me-
chanical properties. The modulus, crush strength, and energy absorbing
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Journal of Materials Processing Tech. 288 (2021) 116882
of Octagonal lattice specimens printed by fused deposition modeling
(FDM) and MJF were compared by Habib et al. (2018). The MJF-
printed lattice structures exhibited much better printing accuracy and
surface finish, as well as more robust compressive properties than the
FDM-printed ones.
Despite a number of fundamental researches providing extensive
information to understand both PBF techniques, these two similar
techniques were studied independently and many inconsistent phe-
nomena that occurred in both techniques have not been clarified to
date. For example, components printed along the Z-build orientation
showed the strongest strength in MJF, but it was the weakest direction
in SLS-printed counterparts (Ajoku et al., 2006; O’Connor et al., 2018);
thermally induced aging in used powder did not seem to degrade the
mechanical performance of MJF-printed specimens, while this factor
would dramatically decrease the mechanical properties of SLS-printed
ones (Dadbakhsh et al., 2017; Riedelbauch et al., 2019). It is essential to
distinguish the processing differences between MJF and SLS to de-
termine which technique is more favorable for specific requirements.
Therefore, this work attempts to compare and assess MJF and SLS
techniques through a systematic physicochemical characterization of
the manufacturer-specified raw powder materials and printed speci-
mens using recommended parameters, as well as a comprehensive
evaluation of the mechanical performance and printing characteristics
of printed components. It aims to serve as a guideline towards the se-
lection of a more suitable technique and printing components with
optimal performance based on their customized requirements.
2. Methodology
2.1. Printing equipment
An SLS machine, EOS P 396, Germany, was used for the printing of
EOS PA2200 powder (regarded as EOS powder hereafter). Specimens
were printed using the feedstock powder with a virgin/used mixture
ratio of 50:50 and the printing parameters recommended by the EOS P
396 manufacturer. During the exposure of each build layer, the laser
beam fused the contours of all parts before hatching their internal
areas.
An HP MJF 4200 commercial printer was used for the printing of the
HP 3D HR PA12 (defined as HP powder hereafter) specimens. The
‘Balanced’ print mode was selected for the printing of specimens using a
recommended virgin/used powder mixture ratio of 20:80. The pro-
prietary fusing agent used for the MJF process contained carbon black
of lower than 7.5% amongst other components.
The specimen layout for both printing processes is shown in
C. Cai, et al.
Fig. 2. Printing CAD model and printed specimens: (a) specimen layout for both printing processes, (b) build orientation axes according to ISO/ASTM 52921, and (c)
tensile and (d) flexural specimens printed by MJF and SLS.
Fig. 2(a). For each PBF process, the tensile and flexural bars with gauge
sizes of 33 × 6 × 4 mm3 and 80 × 10 × 4 mm3 were printed following
the ASTM D638-10 and ISO178 standards, respectively. Six tensile and
flexural specimens were printed in the X, Y, and Z-build orientations,
respectively, according to the ISO/ASTM 52921 standard (Fig. 2(b)).
Five rectangular block specimens (20 × 16 × 10 mm3) were printed to
evaluate their respective surface roughness on the top, front, and side
surfaces. A scaled-down merlion (118 × 168 × 190 mm3) was also
printed for the printing accuracy comparison. All specimens were
subjected to a sandblasting treatment (the size distribution of sand fo-
cusing on 83 μm) after the printing processes.
2.2. Powder feedstock and printed specimen characterization
The granulometric distributions of both PA12 powders were quan-
titatively detected using a laser diffraction particle analyzer
(Mastersizer 3000, Malvern Panalytical, UK). The morphologies of both
powders were observed using a scanning electron microscope (JSM-
5600 LV, JEOL, Japan) at an acceleration voltage of 15 kV. Differential-
scanning calorimetry (DSC) tests were performed using a DSC-Q200
machine (TA Instruments, UK) to determine the thermal features of
both powders. DSC specimens with weights of 10 ± 1 mg were tested
under an increasing temperature ramp from 25 °C to 250 °C at a rate of
10 °C/min before cooling down from 250 °C to 25 °C at a rate of 10 °C/
min. DSC measurements were carried out with a nitrogen flow rate of
40 mL/min and repeated 3 times for each specimen. X-ray diffraction
(XRD) measurements (Shimadzu XRD-6000, Japan) were performed on
both powders to identify phase constitutions in each powder using Cu
Kα radiation in a 2θ range of 10°–35° at a scan speed of 2°/min. The IR
Prestige 21 Fourier transform infrared (FT-IR, Shimadzu, Japan) spectra
of both powders were recorded for the identification of functional
groups. X-ray photoelectron spectrometry (XPS) scans were performed
using the Kratos AXIS Supra, UK, on both powders to analyze their
surface chemical states. A wide scan was first performed to determine
the surface elemental compositions of each powder. Thereafter, high-
resolution scans were adopted to observe the chemical bond types at
specific regions of element-binding energy.
The pore morphologies, size distributions, and porosity of both
printed blocks were analyzed by a micro-computed tomography ma-
chine (micro-CT) (GE Phoenix v|tome|xm, UK). The scans were per-
formed using a diamond target, a voltage of 80 kV, a current of 120 µ A,
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Journal of Materials Processing Tech. 288 (2021) 116882
and 2000 projection images. A magnification of x13.2 was selected with
a voxel size of 7.5 µ m. The projection images were then reconstructed
using VGStudio 3.3, where a 5 × 5 × 5 voxel filter was applied to
smoothen the reconstructed images. DSC specimens were acquired by
cutting the corner portion of each printed block to determine the
thermal properties of both printed specimens. XRD and FT-IR mea-
surements were also performed on both blocks to detect their phase
constitutions and functional groups.
2.3. Mechanical performance and printing characteristics
Tensile testing was carried out using a Shimadzu AGX 10 kN uni-
versal tester with a strain speed of 10 mm/min. Fracture morphologies
of the tensile bars were observed using the SEM. Flexural tests were
performed on a universal tester (Instron 5569 50 kN, USA) with a
testing speed of 2 mm/min to a maximum deflection of 20 mm, and the
distance between the two supports was 64 mm.
The surface morphologies and topographies of both blocks were
measured using a laser confocal scanning microscope (VK X200,
KEYENCE, Japan). Laser and optical scans were implemented on a 4.3
× 3.2 mm2 area in the middle portion of each surface of the blocks to
generate a surface profile for the measurements of their surface
roughness Ra. The scanning measurements were repeated across 4
blocks to calculate the average Ra of each surface. The dimensional
measurement of the printed scaled-down merlions was conducted using
a 3D scanner (FARO Edge Scan Arm, USA) with an accuracy of 25 µ m
and a scan rate of 560,000 points per second for the printing accuracy
assessment. The 3D mesh data acquired from the scans were then
compared to the original design file to determine the profile deviations
using the Geomagic deviation analysis tool. The deviation of each point
on the profile was measured with respect to the vector normal to the
nominal surface.
3. Results and discussion
3.1. Feedstock characterization
The powder morphologies and size distributions of EOS and HP
PA12 powders are compared in Fig. 3. Both powders showed near-
spherical morphologies with smooth surfaces, which were mainly at-
tributed to the dissolution-precipitation preparation process in an
C. Cai, et al.
Fig. 3. Morphologies and size distributions of the powder particles supplied by companies: (a–b) EOS and (c–d) HP.
ethanol solvent under an elevated temperature (Verbelen et al., 2016).
The particle size range of EOS powder focused on around 30–80 μm
with a median size Dv(50) of 52.6 μm, which was in line with published
reports by Amado et al. (2011). In contrast, the HP powder had a
broader size range and a higher fraction of coarse particles with sizes
beyond 80 μm, and its average size reached ˜ 66.2 μm.
DSC curves and quantitative thermal properties regarding the onset
melting temperature Tom, peak melting temperature Tpm, onset crys-
tallization temperature Toc, peak crystallization temperature Tpc,
melting enthalpy Hm, crystallization enthalpy Hc, and crystalline
fraction Xc for both powders are shown in Fig. 4 and Table 1, respec-
tively.
The heating curves of both powders presented a sharp single en-
dothermic peak at 188.9 and 188.4 °C, respectively. The crystallinity of
the EOS and HP powders was calculated to be 48.2% and 47.4% based
on the melting enthalpy of 100.8 J/g and 99.2 J/g, respectively. For the
cooling behavior, the Tom and Tpc of the EOS powder were ˜1 °C lower
Fig. 4. DSC curves of both powders.
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Journal of Materials Processing Tech. 288 (2021) 116882
than those of the HP powder. These results showed that both powders
exhibited similar thermal properties, which indicated that the similarity
in parameters, e.g., heating temperature, load pressure, and cooling
rate, were employed during both dissolution-precipitation powder
preparation processes.
Almost identical diffraction curves with two diffraction peaks at
21.2° and 22.1° could be found in the XRD patterns of both powders
(Fig. 5(a)). PA12 is a semi-crystalline polymer with two crystal struc-
tures, i.e., α and γ phases. Hui et al. (2018) proved that these two
distinct peaks at 21.2° and 22.1° with a d spacing of 0.419 and 0.401 nm
were assigned to the unstable monoclinic α-crystal form (010) and
(110), respectively. This was attributed to the specific powder pre-
paration conditions in the dissolution-precipitation process; the high
pressure and PA12 powder crystallizing from an aqueous solution were
in favor of the metastable α-structure formation (Dadbakhsh et al.,
2017). The fusing agent used in the MJF process showed one broad
reflection with a maximum intensity at 20.1° that corresponded to the
crystallographic plane (002) of carbon black, which was consistent with
the guideline specified for MJF 4200. The infrared spectra of both
powders (Fig. 5(b)) demonstrated the same vibrational peaks. These
spectra peaks are identified and summarized in Table 2, which showed
good consistency with PA12 powders in publications reported by
O’Connor et al. (2018) and Chen et al. (2018).
Three main XPS peaks at 532.2 eV, 399.2 eV, and 285.2 eV in both
powders were respectively indexed to O 1s, N 1s, and C 1s, and some
minor elements (i.e., Si and Ca) were also detected (Fig. 6(a)). The
elements Si and Ca derived from inorganic substances, such as glassy
oxides, silicas, and metallic stearates that were added to enhance
powder flowability, whiteness, and oxidation resistance during the
dissolution-precipitation process (Goodridge et al., 2012). To reveal the
chemical state of the main elements C and O, high-resolution XPS
spectra carried out in the corresponding element binding energy re-
gions are shown in Fig. 6(b–c). The chemical bond types and fractions
for C 1s and O 1s were nearly the same for both powders, and the
proportion of each chemical bond for C and O elements is listed in
C. Cai, et al. Journal of Materials Processing Tech. 288 (2021) 116882

Table 1
Thermal properties of both powders and their printed specimens.
Tom (°C) Tpm (°C) Toc (°C) Tpc (°C) Hm (J/g) Hc (J/g) Xc (%)

EOS powder 180.9 188.9 148.2 142.9 100.8 45.0 48.2

HP powder 181.4 188.4 149.4 143.6 99.2 47.0 47.4
SLS-printed specimen 173.0 179.4 147.4 141.4 61.2 44.3 29.2
MJF-printed specimen 172.7 179.6 153.5 149.1 55.4 46.8 26.5

Table 3. Table 2
Functional group assignments for both powders and their printed parts.
FT-IR peak (cm-1) Assignment
3.2. Printed specimen characterization
Powder Printed part
The porosity of the SLS-printed and MJF-printed blocks was re-
3292 3292 N–H stretching
spectively calculated to be 5.72% and 5.07% from the reconstructed 3D
2916 2916 CH2 asymmetric stretching
perspective images (Fig. 7), which fitted well with the published results 2846 2849 CH2 symmetric stretching
studied by Van Hooreweder et al. (2013) and Stichel et al. (2018). To 1637 1636 C = O stretching
better observe the pore morphology, the visualization of pores in the 1558 1541 C–N stretching and C = O in plane bending
1458 1466 CH2 reference band
cross section (Fig. 7) and the 100 largest pores in the 3D perspective
1367 1362 CH bend and CH2 twisting
images (Fig. S1) for each printed block were highlighted. An even 1269 1269 C–N stretching and C = O in plane bending
distribution of enclosed near-spherical pores could be seen in the SLS- 1159 1157 Skeletal motion involving CONH (am, γ)
printed block, while the MJF-printed block showed irregular inter- 1120 1119 C–C stretching
connected pores that were mainly concentrated in the middle portion of 949 943 CONH in plane
710 719 CH2 rock
the block. The formation of the uncommon interconnected pores in the
MJF-printed block was likely due to the evaporation of the aqueous
solvent in the fusing agent deposited within the printed block. Fur- endothermic peak increased as more used powder particles were mixed
thermore, the water-based detailing agent was jetted onto the middle into fresh feedstock. A polycondensation reaction that occurred during
portion of the block during the printing process to reduce thermal ac- the repeated printing processes raised the molecular weight in the used
cumulation, which could explain the concentration of interconnected powder particles, causing the used powder particles to have a higher
pores in the middle portion of the block. The pore volume distributions melting temperature than the virgin powder particles. As a result, the
of both printed blocks are shown in Fig. S2. The SLS-printed block volume of unmolten particle cores in the used powder particles was
showed a higher amount of small pores (0.001–0.006 mm3 ) as com- larger than that of the virgin powder particles under the same energy
pared to the MJF-printed block, which mainly contained large pores input, causing the shoulder peak intensity in the printed specimen to
with sizes up to 0.156 mm3 . increase proportionally with the increment in the mix ratio of used
The SLS-printed specimen exhibited a bimodal melting signal, while powders in the feedstock. However, this phenomenon contradicted our
the MJF-printed specimen retained a single endothermic peak in the findings, where there was an absence of shoulder endothermic peak in
DSC curves (Fig. 8). The small shoulder endothermic peak in the SLS- the MJF-printed specimen even though the used powder ratio in the
printed parts resulted from spherulite nuclei that had a higher melting MJF process (80% used powder particles) was much higher than that in
temperature than surrounding spherulitic crystalline structures the SLS process (50% used powder particles). This unexpected result
(Zarringhalam et al., 2006). These spherulite nuclei were generated was mainly associated with the fusing agent used in the MJF process.
from the unmolten central regions of PA12 powder particles when the The high thermal absorption capability of the fusing agent caused the
particles did not absorb sufficient heat to melt completely powder layer to be nearly fully melted, thus limiting the amount and
(Zarringhalam et al., 2019). Hence, the shoulder endothermic peak volume of spherulite nuclei formed in the printed part.
temperature (187.2 °C) was close to the peak melting temperature of It could also be observed that the MJF specimens showed a higher
the EOS powder (188.9 °C), as shown in Figs. 4 and 8. Toc and Tpc than the SLS counterparts. This was mainly attributed to the
Dadbakhsh et al. (2017) discovered that the height of the shoulder

Fig. 5. Phase constitution and chemical group identification of both feedstock: (a) XRD and (b) FT-IR.

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C. Cai, et al. Journal of Materials Processing Tech. 288 (2021) 116882

Fig. 6. XPS spectra of both powders in different modes: (a) wide scan, (b) high-resolution scan of C 1s, and (c) high-resolution scan of O 1s.

Table 3 3.3. Mechanical properties

Chemical compositions of C 1s and O 1s from high-resolution XPS spectra for
both powders. The stress-strain curves of the SLS and MJF specimens built along
C 1 s (%) O 1 s (%) the three different orientations are shown in Fig. 10. Noticeable ani-
sotropy in tensile properties could be readily seen in both specimens.
C=C C‒N C=O C‒O C=O Si‒O The SLS tensile specimens built along the X and Y orientations pos-
sessed almost the same ultimate tensile strength (UTS) and elongation
EOS powder 83.2 10.1 6.7 33.0 53.2 13.8
HP powder 78.1 14.5 7.4 52.5 38.4 9.1 at break (εab), and the Z orientation presented the weakest tensile
strength and ductility. For MJF parts, the tensile strength increased in
the sequence of Y, X, and Z orientations. It suggested that the Z or-
carbon black in the MJF-printed specimen, which could act as nuclea- ientation was the most robust direction in MJF parts, which was the
tion sites and accelerate the crystallization of the parts during the opposite of SLS parts. From the fracture morphologies of both speci-
cooling process in DSC. mens printed along the Z orientation, it was found that the fracture
Compared to the powders, both printed parts only had a single surface of the SLS-printed specimen was covered with many sintering
characteristic diffraction peak at 21.4° corresponding to a stable γ- defects (such as pores), but the MJF-printed specimen’s fracture surface
crystal form (001), as shown in Fig. 9. During both printing processes, showed ductile deformation with few defects (Fig. S3), which was in-
preheating temperatures above Tic were utilized to prevent the warpage dicative of a better sintering quality. The better sintering quality and
of the printed products until the entire printing process was completed. stronger bonding strength between layers in MJF-printed specimens
Subsequently, the printed products were cooled down and crystallized derive from the following potential reasons. Firstly, while a new layer
within the powder bed under atmospheric pressure with a slow cooling was melting, the presence of carbon black within the specimen created
rate. These conditions could induce the transformation of the molten a continuous transmission of energy into the previous layers, and the
PA12 from the crystalline chains to the stable γ-crystal form rather than depth of energy penetration was deeper and more thorough than the
the metastable α phase (Dadbakhsh et al., 2017). The metastable α one generated by the laser beam in SLS, hence promoting better mixing
phase has higher crystallinity than the γ phase, which explains the and integrity of interlayers. Secondly, the fusing agent jetted into the
sharp decrease in crystallinity from powder particles to printed parts, as designated area increased the weight of powder particles in the area,
shown in Table 1. which boosted to obtain denser printed parts with less porosity along
the Z orientation (Riedelbauch et al., 2019).
The tensile strength of the MJF-printed specimens was slightly
higher than that of SLS-printed ones in each orientation (Table 4), even

6
C. Cai, et al.
Fig. 7. 3D perspective and cross-sectional images of printed blocks: (a–b) SLS and (c–d) MJF.
Fig. 8. DSC curves of both printed specimens.
though thermal and chemical properties of both PA12 feedstock, the
porosity of both printed specimens, and the tensile strength of both
PA12 parts processed by injection molding (Fig. S4) were nearly the
same. The intrinsic distinctions between the SLS and MJF processes are
the scanning approach and the energy source. Therefore, it is reason-
able to speculate that the stronger tensile strength of MJF specimens is
correlated to the efficient area fusion approach and unique fusing
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Journal of Materials Processing Tech. 288 (2021) 116882
agent.
In the SLS process, there are three different fusion stages, i.e., single-
track fusion, fusion between tracks, and fusion between layers (Stichel
et al., 2018). When the laser scanned a single track on the powder bed,
scanned powder particles were fused, and then sintering necks between
particles were generated in the first stage. The sintering necks formed
between neighboring particles were dense and compact in this stage as
a result of the simultaneous melting and coalescence of these powder
particles. In the second stage, a next parallel track was fused similar to
the former track, but the area of sintering necks between the two tracks
was lessened compared to that of the previous single track. This was
because the previous track had cooled somewhat during the fusion of
the new track. The area of sintering necks between layers continued to
decrease, as the previous layer was cooled further after experiencing
the process of spreading a new layer. The weak layer-layer bonding
strength resulted in the most inferior strength along the Z-build direc-
tion in the SLS specimens.
In the MJF process, there are only two fusion stages, i.e., fusion
between areas and fusion between layers. The time interval required to
fuse an area or a layer in MJF with an area fusion mode was sig-
nificantly shortened in contrast with SLS adopting a point fusion mode.
This implied that the temperature differences between the adjacent
areas or layers reduced dramatically. In this case, the size of sintering
necks between the areas or layers in MJF-printed specimens was greater
than that of SLS-printed ones, resulting in a better sinter quality.
Moreover, the carbon black in the fusing agent could act as a re-
inforcement within the PA12 matrix after deposition into the powder
C. Cai, et al. Journal of Materials Processing Tech. 288 (2021) 116882

Fig. 9. Phase constitution and chemical group identification of both printed specimens: (a) XRD and (b) FT-IR.

Fig. 10. Tensile curves of both specimens printed along the three orientations: (a) SLS and (b) MJF.

Table 4 three orientations, and this tendency was ascribed to the porosity var-
Tensile properties of the printed specimens. iation within samples of different orientations. The porosities of the
Orientation Process UTS (MPa) Elongation at break Elastic Modulus
samples were gradually raised in the order of Z, Y, and X orientations,
(%) (MPa) which was inverse to the flexural strength tendency. By comparing the
measured results of tensile and flexural properties, there was an in-
X SLS 44.0 ± 0.1 27.6 ± 2.6 1394.5 ± 26.8 dication that the flexural strength was more susceptible to the porosity
MJF 48.7 ± 0.8 27.4 ± 2.2 1369.0 ± 25.0
Y SLS 43.9 ± 0.7 26.6 ± 2.9 1605.4 ± 97.6
in contrast with the tensile strength. As a whole, the average flexural
MJF 44.5 ± 0.7 15.9 ± 1.1 1368.8 ± 68.9 strength and modulus of MJF-printed specimens built in the three or-
Z SLS 39.6 ± 0.2 14.7 ± 1.1 1222.8 ± 26.8 ientations were superior to those of SLS-printed ones, which was the
MJF 49.6 ± 1.2 14.8 ± 0.3 1669.2 ± 66.7 result of a more effective fusion strategy and the addition of carbon
black reinforcements from the fusing agent.

bed. These carbon black reinforcements could help to impede crack

propagation, resulting in an improvement in the mechanical properties.
This was validated by Hong et al. (2019) who reported an improvement
in the tensile properties of PA12 with the addition of a small weight
fraction of carbon black (0–4 wt.%). Hence, it can be concluded that the
higher tensile strength of the MJF-printed parts compared to that of the
SLS-printed ones in each orientation originates from the synergistic
effect of the area fusion mode and the reinforcement of carbon black in
the PA12 matrix through the fusing agent.
The flexural properties of both specimens built in the three different
orientations are shown in Fig. 11 and Table 5. The flexural strength
tendency in the build orientations was the same as the tensile strength
tendency for the SLS-printed specimens. Unexpectedly, the flexural
strength tendency, with an increased sequence of X < Y < Z, was not in
agreement with the Y < X < Z tendency in tensile strength for the MJF-
printed specimens. O’Connor and Dowling (2020) reported a consistent
tendency in the flexural strength of MJF-printed samples built along the
3.4. Printing characteristics
The surface profiles for the top, front, and side surfaces of both
printed specimens after sandblasting are displayed in Fig. 12. Overall,
the MJF-printed specimens showed a better surface finish in compar-
ison with SLS-printed specimens, especially on the front and side sur-
faces. In the SLS process, the laser beam fused the contours of all parts
in each layer firstly and then hatched their internal area in a raster scan
mode. There was an overlap between contour and hatching scan lines,
which increased the energy density along the boundary of the speci-
mens, causing the surrounding powder particles to fuse onto their side
surfaces. In contrast, the MJF process jetted a detailing agent with voxel
resolution onto the outer edges of specimens, resulting in lesser ad-
herence of powder particles adhered onto their side surfaces.
There was a slight curvature on the top surface of the MJF-printed
specimens, accounting for their top surface roughness to be higher than

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C. Cai, et al. Journal of Materials Processing Tech. 288 (2021) 116882

Fig. 11. Flexural curves of both specimens printed along the three orientations: (a) SLS and (b) MJF.

Table 5 deviations on both merlions resulted from the adherence of surrounding

Flexural properties of the printed specimens. powder particles on the surface of merlions, which could be difficult to
Orientation Process Flexural Strength (MPa) Flexural Modulus (MPa)
remove during the sandblasting process.
For the SLS-printed merlion, the merlion and the adherent powder
X SLS 55.5 ± 1.7 956.7 ± 23.0 particles were white in colour, which made them difficult to distinguish
MJF 47.8 ± 0.3 883.7 ± 14.8 during sandblasting. This might be the cause of the high positive profile
Y SLS 50.6 ± 1.5 964.5 ± 44.5
MJF 52.2 ± 1.2 977.5 ± 23.6
deviations observed in the SLS-printed merlion. Inversely, the addition
Z SLS 46.3 ± 2.3 872.4 ± 50.1 of fusing agent onto the MJF-printed merlion changed the colour of
MJF 56.7 ± 4.1 1068.8 ± 108.2 PA12 from white to dark grey, allowing for easier identification be-
tween the adherent powder and the merlion during sandblasting. Also,
the detailing agent lowered the temperature of the powder surrounding
that of the SLS-printed specimen (Fig. S5). This curvature topography the printed merlion, weakening its adhesion strength to the merlion and
could be stimulated by capillarity effects present at the interface be- ensuring the easier removal of surrounding powder during sand-
tween the printed molten block and the surrounding solid powder blasting.
particles, which essentially originated from the interaction between the
detailing and the fusing agents. The presence of surfactants in both the
4. Conclusions
fusing agent and detailing agent could change the wetting conditions at
the outer contour of the molten block, thereby distorting the liquid
In the study, two polymeric powder bed fusion techniques, SLS and
meniscus and creating a deviation at the contour of the molten block,
MJF, were compared systematically through an investigation of the raw
resulting in a curved top surface with higher contours after solidifica-
powder materials and printed specimens, and an evaluation of me-
tion (Mele et al., 2019).
chanical properties and printing characteristics of both printed PA12
The deviation degrees (perpendicular to the nominal surface) of
parts. The conclusions can be drawn as follows.
both scanned merlions with respect to the merlion CAD model are de-
Both manufacturer-designated PA12 powders showed near-sphe-
monstrated in Fig. 13. The MJF-printed merlion exhibited lower profile
rical morphologies, whereas the mean particle size of the HP powder
deviations, ranging from 1.1344 mm to 0.668 mm. The profile de-
was coarser than that of the EOS powder. The thermal features, phase
viations of the SLS-printed merlion were up to 3 mm, especially in areas
constitutions, functional groups, and chemical states of both powders
with sharp contours (such as the corner of the eyes and the edges of the
were nearly identical.
hair). Negative profile deviations on both merlions arose from the
Both printed specimens had similar porosity of ˜ 5.0% but different
shrinkage of the merlions during the cooling process. Positive profile
pore morphologies and volume distributions. The DSC curve of the SLS-

Fig. 12. Surface profiles of the top, front, and side surfaces of both printed specimens.

9
C. Cai, et al.
Fig. 13. Profile deviation colour maps of merlions printed by both processes: (a) SLS and (b) MJF.
printed specimen exhibited a bimodal endothermic signal, while the
MJF-printed specimen still retained a single endothermic peak. Both
printed specimens showed a single diffraction peak of the γ-crystal form
(001).
An obvious anisotropy in tensile and flexural properties was dis-
covered in both printed specimens. The mechanical strength tendency
in the build orientations for both printed specimens was quite different,
especially in the Z orientation. The tensile strength of the MJF- and SLS-
printed samples in the X and Y orientations was almost the same, but
the tensile strength of the MJF-printed specimens in the Z orientation
was ˜ 25% higher than that of SLS-printed counterparts.
MJF-printed specimens had a better surface finish than the SLS-
printed ones, except for the top surface. The MJF-printed scaled-down
merlion, with relatively lower profile deviations from 1.1344 mm to
0.668 mm, was more accurate than the SLS-printed counterpart, which
demonstrated high profile deviations of up to 3 mm in areas with sharp
contours.
CRediT authorship contribution statement
Chao Cai: Conceptualization, Methodology. Wei Shian Tey:
Investigation, Writing - original draft. Jiayao Chen: Investigation. Wei
Zhu: Methodology. Xingjian Liu: Visualization. Tong Liu:
Visualization. Lihua Zhao: Writing - review & editing, Funding acqui-
sition. Kun Zhou: Writing - review & editing, Funding acquisition.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgments
This research was conducted in collaboration with HP Inc. and
supported by Nanyang Technological University and the Singapore
Government through the Industry Alignment Fund-Industry
Collaboration Projects Grant.
10
Journal of Materials Processing Tech. 288 (2021) 116882
Appendix A. Supplementary data
Supplementary material related to this article can be found, in the
online version, at doi:https://doi.org/10.1016/j.jmatprotec.2020.
116882.
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