Effects of styrene–acrylonitrile contents on the properties

of ABS/SAN blends for fused deposition modeling

Jin Zhu, Yufei Hu, Yijing Tang, Biao Wang
State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, College of Material Science and Engineering,
Donghua University, Shanghai 201620, People’s Republic of China
Correspondence to: B. Wang (E-mail: wbiao2000@dhu.edu.cn)

ABSTRACT: This paper was to assess the effects of styrene–acrylonitrile (SAN) contents on the glass transition temperature (Tg), melt
flow index (MFI), and mechanical properties of acrylonitrile–butadiene–styrene (ABS)/SAN blends for fused deposition modeling
(FDM) process. The addition of SAN had little effects on Tg but could decrease the MFI and elongation at break while improving the
tensile strength and modulus of ABS/SAN blends. For both longitudinal direction and transverse direction FDM printed specimens,
the incorporation of SAN improved mechanical properties without sacrificing dimensional stability. This result was mainly attributed
to the increasing content of continuous phase (SAN phase) and improvement in adhesion quality. V C 2016 Wiley Periodicals, Inc. J. Appl.

Polym. Sci. 2017, 134, 44477.

KEYWORDS: blends; extrusion; polystyrene; synthesis and processing techniques; thermoplastics

Received 5 July 2016; accepted 19 September 2016

DOI: 10.1002/app.44477

INTRODUCTION Modeling (FFM), is one of the most widely implemented method

Acrylonitrile–butadiene–styrene (ABS) resin is one of the most
commercially important rubber toughened plastics due to their
high impact resistance, sufficient thermal stability, satisfactory
tensile strength, excellent processibility, and good dimensional
stability.1–3 Molded ABS products are widely used in both pro-
tective and decorative applications in many industrial and con-
sumer products.4,5
ABS resin is usually composed of a binary phase system: the dis-
persed phase is grafted polybutadiene (PB) rubbery particles and
the continuous phase is styrene–acrylonitrile (SAN) copolymer.
The physical and mechanical properties, and rheological behavior
of ABS are greatly influenced by the rubbery particle size and
content, grafting degree, molecular weight of SAN resin etc.6–11
Therefore, varying of these parameters allows the ABS producers
to tailor their products according to the end-use applications.
Three-dimensional printing (3-DP) is a technology in which 3D
object can be built layer by layer to a desired geometry based upon
a computer aided design (CAD) model.12,13 In contrast to tradi-
tional manufacturing techniques, such as injection or compression
molding, the advantages of 3-DP include increased customizability,
tool-less fabrication, decreased product development time.13–15
Own to these advantages, 3-DP has gained acceptance and popular-
ity in manufacturing, educational and home-use settings.16 Fused
deposition modeling (FDM), also referred to as Fused Filament
for printing of 3D objects. The process uses a polymer filament
(typically with a diameter of 1.75 mm) as an “ink” and passes it
through a heated nozzle where it is heated to a semi-molten state.
The software-controlled nozzle extrudes semi-molten material onto
a built platform or the previously deposited layers to build up a sol-
id 3D object. Compared to traditional manufacturing techniques,
the requirements of raw material needed for FDM process are dif-
ferent. The materials to be used in the FDM process should have a
relatively low glass transition temperature (Tg), melting point (Tm),
a low tendency to shrink upon solidification, appropriate viscosity,
strength, stiffness, ductility and flexibility.16,17 Currently, the expan-
sion of the applicability of parts fabricated from this technology is
limited by the lack of printable materials. ABS resin has become
one of the most widely used materials for FDM process due to its
large processing window. A great deal of work has been studied the
mechanical properties of FDM printed ABS parts.18–24 Most of
research has been focused on the effects of FDM printing parameter
on the mechanical properties of the final parts. Based on these
research, the air gap and raster angle are more significant than layer
thickness, bead width, and model temperature. Besides the printing
parameters, the physical properties of bulk materials (i.e., mechani-
cal properties, Tg, and melting viscosity) play an important role on
the adhesion formation between the printed filaments and the
adhesion quality is very important to the mechanical properties of
the final parts. However, to the best of our knowledge, the research
on modification of ABS resin for FDM process is very limited, and

C 2016 Wiley Periodicals, Inc.

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Table I. Showing the Composition of the Blends

Sample ABS (wt %) SAN (wt %)

S1 100 0
S2 95 5
S3 90 10
S4 80 20
S5 0 100

the effect of SAN (continuous phase) content on the adhesion qual-

ity and eventually its effect on the mechanical properties of the final
printed parts has not been reported.
Here, the ABS/SAN blends were prepared by melt blending, and
the effects of SAN contents on the Tg, melt flow index (MFI),
and mechanical properties of ABS/SAN blends for FDM process
were investigated. Furthermore, these materials for FDM process
were also evaluated.

EXPERIMENTAL
Preparation of ABS/SAN Blends
The ABS resin (Chi Mei PA-747S) and SAN copolymer (Chi
Mei PN-128) were obtained from Chi Mei Corporation
(Tai nan, Taiwan). Before melt blending, ABS and SAN pellets
were dried in a vacuum oven at 80 8C for 4 h. The ABS/SAN
blends were obtained by using a KS36 corotating twin screw
extruder with a length-to-diameter ratio (L/D) of 36. The tem-
perature profile during extrusion was 200, 210, 220, 220, 220,
220, and 210 8C. The extruded strands of the blends were cooled
in a water bath, granulated, and dried before further processing.
The compositions of the blends prepared are given in Table I.
Injection Molding (IM)
The as-prepared granules were molded in an UN120SM injec-
tion molding machine to obtain a set of standard ASTM D638
type-I specimens. The temperature profile during injection
molding was 210, 215, 225, and 230 8C.
Filaments Extrusion and FDM Printed Specimens Preparation
The filaments for FDM process (diameter: 1.75 6 0.05 mm)
were prepared with the as-prepared granules and a proper die
at 220 8C by a Wellzoom-B single screw extruder. Furthermore,
a Flashforge Creator dual-head desktop FDM unit was utilized
to print the specimens. Table II shows the parameters utilized
in the FDM printer.
Table II. Printing Parameters Used for FDM Process
Object infill (%)
Print temperature (8C)
Build platform temperature (8C)
Print speed (mm/s)
Layer height (mm)
Number of shells
Nozzle diameter (mm)
Raft material
Figure 1. Schematic of FDM printed specimens for tensile test: (a) longi-
tudinal direction and (b) transverse direction. [Color figure can be viewed
at wileyonlinelibrary.com]
In order to study the impact of SAN on the mechanical proper-
ties of FDM printed specimens, two geometries of tensile speci-
mens were prepared for each sample. Rectangular specimens
were printed while changing the deposition direction:
1. 80 mm 3 10 mm 3 1 mm, in which the filaments were
deposited in the longitudinal direction as seen in Figure 1a.
The specimens were identified as LD.
2. 80 mm 3 15 mm 3 1 mm, in which the filaments were deposit-
ed in the transverse direction as seen in Figure 1b. The speci-
mens were identified as TD. Before tensile testing, the resulting
objects were cut into 80 mm 3 10 mm 3 1 mm with scissors.
Characterization
The Tg of ABS, SAN, and ABS/SAN blends was determined
through differential scanning calorimetry (Q20; TA Instruments,
USA) analysis under nitrogen flow of 50 mL/min. The samples
were first heated from 40 to 220 8C, kept at 220 8C for 3 min for
removing the thermal history and then cooled to 40 8C. The sam-
100
ples were reheated to 220 8C, and the second heating scans were
220 taken for determination of Tg. The heating and cooling rate of the
80 samples during DSC analysis was 10 8C/min. Melt flow index
40 (MFI) were determined by a Melt Flow Indexer with a loading of
0.2 10 kg at 220 8C. The fracture surfaces were observed through a
JSM-6700F scanning electron microscopy (SEM). The samples
2
were immersed in liquid nitrogen and broken in a brittle manner.
0.4
Tensile properties of the injection molded and FDM printed speci-
No
mens were measured using an Instron 5969 mechanical testing

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Figure 2. Effects of SAN contents on (a) Tg and (b) MFI of ABS/SAN blends. [Color figure can be viewed at wileyonlinelibrary.com]

Figure 3. Effects of SAN contents on the mechanical properties of injection

molded specimens. [Color figure can be viewed at wileyonlinelibrary.com] Figure 4. Effects of SAN contents on the mechanical properties of LD
specimens. [Color figure can be viewed at wileyonlinelibrary.com]

machine with a crosshead speed of 5 mm/min. The results reported
are the average of five specimens. The end deflection of printed speci-
mens was measured by clamping at 5 mm from the end of the speci-
mens and measuring the warping at the opposite end. The porosity
(P) of FDM printed specimens was calculated by the equation below:
Vt 2Va
P5 3100 (1)
Vt
where Vt is the total volume of FDM printed specimen (determined
from vernier caliper measurements of length, width, and thickness)
and Va is the actual volume of the specimens. Since there is no reac-
tion between ABS and SAN, Va could be calculated as follows:
M3ABS wt % M3SAN wt %
Va 5 1 (2)
qABS qSAN
where M is the actual mass of the specimen, qABS and qSAN are the
densities of ABS and SAN resin (1.03 and 1.06 g/cm3), respectively.
RESULTS AND DISCUSSION
Effects of SAN Contents on the Properties
of ABS/SAN Blends
Figure 2 shows the effects of SAN contents on Tg and MFI of
ABS/SAN blends. Tg of ABS (sample S1) and SAN (sample S5)
was about 108.6 and 106.2 8C, respectively, and the difference was
only 2.4 8C (Figure 2a). Therefore, the changes of Tg for ABS/SAN
blends were very little. However, the MFI of ABS/SAN blends was
increased with the SAN contents (Figure 2b). The MFI value of
ABS was 4.5 g/10 min, whereas that of ABS/SAN blends contain-
ing 20 wt % SAN was 10.4 g/10 min, which was attributed to the
higher MFI value of SAN (33.6 g/10 min) and good miscibility
between ABS and SAN. This result indicated that the flow proper-
ties of ABS could be improved by addition of SAN. During FDM
processing, the filament acts as a piston at the entrance of the
liquefier head in FDM machine, forcing the molten material out

Figure 5. Fracture surface SEM micrographs of LD specimens: (a) S1 and (b) S4.

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Figure 6. Effects of SAN contents on the mechanical properties of TD
specimens. [Color figure can be viewed at wileyonlinelibrary.com]
of the nozzle. Higher MFI benefits the forming efficiency and
processing property improvement for FDM.
In order to study the effect of SAN contents on mechanical
properties of ABS/SAN blends, the tensile properties of the
injection molded specimens are given in Figure 3. As can be
seen, the tensile strength and modulus of ABS/SAN blends
increased with the SAN content. The tensile strength and mod-
ulus of the ABS/SAN blend with 20 wt % SAN (Sample S4)
reached 46.6 and 2223.7 MPa, 15.6 and 24.8% higher than those
of the ABS sample (Sample S1), respectively. However, the
elongation at break of different injection molded specimens
decreased with the increase in SAN content. Actually the com-
mercial ABS resin contains the following two phases: PB rubber
phase and SAN phase. The PB rubber phase is surrounded by
the SAN phase and the mechanical properties of ABS mainly
depend on the nature of continuous phase (SAN phase), which
is much stiffer than the PB rubber phase. Therefore, the more
SAN introduced into the blends, the higher tensile strength and
modulus and the lower elongation can be exhibited.
Effects of SAN Contents on the Properties
of FDM Printed Specimens
The mechanical properties of the LD specimens prepared by FDM
process are shown in Figure 4. The results showed that the tensile
strength and modulus increased with SAN content. The addition of
20 wt % SAN (Sample S4) promoted a 24.7 and 36.8% increase in
tensile strength and modulus of the blend in comparison to the
ABS. However, the elongation decreased when the SAN content was
not more than 10 wt % (Sample S3). Interestingly, the elongation
slightly increased when SAN content was 20 wt % (Sample S4). For
LD specimens, the applied load was mainly taken by the deposited
Figure 7. Fracture surface SEM micrographs of TD specimens: (a) S1 and (b) S4.
WWW.MATERIALSVIEWS.COM 44477 (4 of 5)
Figure 8. The real images of different samples. [Color figure can be
viewed at wileyonlinelibrary.com]
filaments. The addition of SAN increased the content of continuous
phase (SAN phase) and therefore increased the tensile strength and
modulus and decreased the elongation of the ABS/SAN blends.
Besides this, the adhesion between the filaments also contributed to
the mechanical properties of the ABS/SAN blends. Figure 5 shows
SEM images of fracture surfaces for ABS and ABS/SAN blend LD
specimens. As can be seen, the specimens were composed of fila-
ments which were adherent together and many holes between the
filaments. Compared to the ABS (Sample S1), the blend with 20 wt
% SAN (Sample S4) had larger adhesion area and smaller hole size.
Here, porosity was used to reflect the adhesion quality. For ABS
FDM printed LD specimen, the porosity was about 13.8%.
However, for ABS/SAN blend with 20 wt % SAN specimen, it was
about 10.1%, 27% lower than that of the ABS. The lower porosity
indicated larger adhesion area and better adhesion quality which
led to better tensile strength and modulus of the samples. The
improvement of adhesion could be attributed to the high MFI (low
viscosity) of ABS/SAN blends.25,26 The slightly increasing of elonga-
tion for Sample 4 (20 wt % SAN) could be attributed to the
improvement of the load transfer between the filaments.
The variation of the mechanical properties of the TD specimens with
different content of SAN is illustrated in Figure 6. As depicted in
Figure 6, the tensile strength and modulus of TD specimens increased
J. APPL. POLYM. SCI. 2017, DOI: 10.1002/APP.44477
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Table III. Values of End Deflection for Different Samples
End deflection End deflection
(LD specimens) (TD specimens)
Sample End 1 (mm) End 2 (mm) End 1 (mm) End 2 (mm)
S1 3.45 6 0.18 2.16 6 0.21 2.03 6 0.17 1.66 6 0.11
S2 3.52 6 0.12 2.24 6 0.19 1.98 6 0.18 1.58 6 0.14
S3 3.50 6 0.20 2.38 6 0.29 2.05 6 0.14 1.60 6 0.12
S4 3.61 6 0.29 2.30 6 0.32 2.11 6 0.11 1.68 6 0.17
with SAN content. Compared to ABS (Sample S1), the ABS/SAN
blend containing 20 wt % SAN (Sample S4) exhibited an improve-
ment of 13.3% in tensile strength and 30.6% in tensile modulus.
Simultaneously, the elongation at break of different TD specimens
also increased with SAN content. For TD specimens, the applied load
was perpendicular to the deposited filaments and the mechanical
properties mainly depended on the adhesion quality. Figure 7 shows
the fracture surface of the TD specimens. Although both of ABS and
ABS/SAN blend possessed similar interlayer and intralayer fusions,
the porosity of sample S4 was about 5.9%, approximately 16.9% less
than that of ABS at the same printing condition, which indicated
that ABS/SAN blends had better adhesion quality than ABS.
Figure 8 shows the real images of different samples. It was observed
that both LD and TD specimens had good dimensional accuracy.
Table III shows the values of warping for different samples. As can
be seen, the SAN has little effect on warping for both LD and TD
specimens. The reason may be that the addition of SAN has little
effect on Tg of ABS/SAN blends which results in similar tempera-
ture gradient during the deposition process. In addition, the speci-
mens are thin-plate parts, and the heated platform can be beneficial
to the release of internal stress in the specimen.
CONCLUSIONS
ABS/SAN blends with different SAN contents were prepared by
melt blending. The addition of SAN had little effects on Tg but
could decrease the MFI and elongation at break while improving
the tensile strength and modulus of ABS/SAN blends. For both LD
and TD FDM printed specimens, the incorporation of SAN
improved mechanical properties without sacrificing dimensional
stability. This result was mainly attributed to the increasing content
of continuous phase (SAN phase) and improvement in adhesion
quality. The properties of ABS can be modified with SAN, and the
prepared ABS/SAN blends could be used for FDM forming process.
ACKNOWLEDGMENTS
This work is financially supported by Shanghai Leading Academic
Discipline Project (no. B603) and the Program of Introducing Tal-
ents of Discipline to Universities (no. 111-2-04).
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J. APPL. POLYM. SCI. 2017, DOI: 10.1002/APP.44477