Engineering Fracture Mechanics 203 (2018) 66–80

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Engineering Fracture Mechanics

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

Effect of temperature on the fracture behavior of polyamide 12 and

T
glass-filled polyamide 12 processed by selective laser sintering
⁎
A.J. Cano, A. Salazar , J. Rodríguez
DIMME, Grupo de Durabilidad e Integridad Mecánica de Materiales Estructurales, Universidad Rey Juan Carlos, C/ Tulipán, s/n, 28933 Móstoles,
Madrid, Spain

A R T IC LE I N F O ABS TRA CT

Keywords: The influence of the orientation and of the temperature on the mechanical properties of the
Selective laser sintering polyamide 12 (PA12) and the polyamide 12 reinforced with glass beads processed via Selective
Polyamide 12 Laser Sintering was analyzed. Tensile and fracture tests were performed at −50 °C, 23 °C and
Fracture toughness 50 °C with applied load perpendicular and parallel to the layered structure. The fracture re-
sistance of PA12 was higher than that of the composite due to the poor adhesion of the glass
beads to the matrix. The fracture behavior of the composite was unaffected by the temperature
and the orientation. JIC values of PA12 were similar at −50 °C and at 23 °C and much lower than
at 50 °C. The anisotropy was relevant during the stable crack growth.

1. Introduction

According to ASTM F2792-12a standard definition, Additive Manufacturing (AM) technologies are “a set of processes of joining
materials to make objects from 3D model data, usually layer upon layer, as opposed to subtractive manufacturing fabrication
methodologies” [1]. Over the last 25 years AM has grown at a rate of 25% per year and in 2020 the AM industry is expected to exceed
$21.1B in products and services [2,3]. Among these techniques, Selective Laser Sintering (SLS) of polymers is one of the most
promising due to its ability to produce geometrically complex, dimensionally accurate parts with good mechanical properties [2]. It
has been deemed suitable for end-use parts production in a great number of applications in healthcare, automotive, household,
electronics, aerospace and aviation sectors [4,5]. In fact, laser sintering (LS) end-use parts were first introduced in the late 1990s by
Boeing and NavAir to supply low pressure ducting for the Boeing FA-18 aircraft [6,7]. Since then, plastic printed parts made by
Boeing have been in flight operation for years for both the defense and commercial side.
SLS process starts from a computational solid model of the part, which is mathematically sliced at discrete intervals by a computer
controller and stored in a build file. These cross-sectional areas or slices are represented by a field of x-y vectors. Next, a laser beam
scans selectively the x-y vector field on a preheated powder bed to fuse the targeted areas. Each time a slice is finished, the build
chamber is lowered by the thickness of one layer and new powder is spread to fuse the newly sintered layer, producing a vertical
build along the z-axis direction [4]. These steps are repeated the part is completed.
Materials successfully applicable to Laser Sintering are limited by the combination of properties that have to be met. The fea-
sibility for powder production with controlled geometry and size distribution of the particles, together with a broad sintering window
(range of temperature between the crystallization temperature, TC, and the melting temperature, Tm) and a high absorption capacity
of the laser energy are crucial factors to apply SLS successfully. Polyamide 12 (PA12), polyamide 11 (PA11), polystyrene (PS),

⁎
Corresponding author.
E-mail address: alicia.salazar@urjc.es (A. Salazar).

https://doi.org/10.1016/j.engfracmech.2018.07.035
Received 2 November 2017; Received in revised form 17 July 2018; Accepted 23 July 2018
Available online 26 July 2018
0013-7944/ © 2018 Elsevier Ltd. All rights reserved.
A.J. Cano et al. Engineering Fracture Mechanics 203 (2018) 66–80

z PERP

x
y

PARA

6 ± 0.5 mm
22 mm

33 ± 0.5 mm

65 ± 5 mm

115 mm

Fig. 1. Dog bone tensile test specimen where lines show layer orientation (z-axis perpendicular to the material layers).

Acryonitrile Butadiene Styrene (ABS), Polycarbonate (PC), Polylactic Acid (PLA), Polyetherimide (PEI), Polypropylene (PP),
Polyester, Polyetheretherkeytone (PEEK) and Thermoplastic polyurethane are the technical thermoplastics for LS treatment
[3,4,7–10]. These materials cannot completely meet the needs of different functional end use parts. That is the reason of adding
inorganic filler (glass beads [11,12], short glass fibers [11] or short carbon fibers [13], carbon nanotubes [14] graphite nanoplatelets
[15]) or blending with other resins [16].
The major limitation of SLS is the inherent anisotropic nature of this stratified process. The properties within the layer are rather
consistent but the bond between layers may be weak and highly sensitive to varying process conditions or parameters [4,5,7,17,18].
Therefore, the mechanical properties of LS parts are often inconsistent compared to their injection molded (IM) equivalent coun-
terparts [7]. Both LS and IM materials exhibit similar modulus and yield strengths, though the ductility of LS products is general an
order of magnitude lower than that of IM parts [7,19] (typical values of elongation at break of IM tensile specimens at room
temperature is around 100%). Shear stresses during injection moulding produce aligned lamellar crystalline regions and inter-twined
molecular chains. This together with rapid cooling results in reduced crystallinity [7,20]. These processing phenomena in IM parts
lead to fundamentally different microstructure than LS parts. Actually, the primary reason of the lower values of elongation at break
and strength in the z-axis can be attributed to the lack of a good layer-to-layer adhesion. There are several factors causing this: firstly,
the formation of porosity between powder layers resulting in weak planar interfaces [5,7,18]; secondly, the plausible presence of
residual particles and particle “cores” of a different crystallographic nature than the surrounding crystal structure. These particles act
as short binding necks between layers with high stiffness and little elongation, resulting in a brittle macroscopic mechanical behavior

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A.J. Cano et al. Engineering Fracture Mechanics 203 (2018) 66–80

PARA
PERP
z

x
y

B= 10 mm

10 + 0.2 mm
11 ± 0.2 mm

48 ± 0.4 mm
2 mm

an= 16 mm

W= 40 ± 0.2 mm

50 ± 0.2 mm

Fig. 2. Compact tension (CT) sample where lines show layer orientation (z-axis perpendicular to the material layers).

Table 1
Density, ρ, and porosity percentage, and thermal properties of the SLS materials obtained from DSC and DMA analysis.
DSC DMA

ρ (g/cm )
3
Porosity (%) Tg (°C) Tc (°C) Tm (°C) χC (%) χm (%) Tβ (°C) Tg (°C)

PA12 0.985 ± 0.005 3.4 54.6 140.2 184.0 34.9 37.8 −63.3 54.7
PA12-R 1.3003 ± 0.0004 2.8 56.1 140.3 183.3 21.9 21.6 −61.6 56.5

[7,18].
There is extensive literature evaluating the effect of the processing parameters on the mechanical, normally evaluated through
tensile tests, and thermo-mechanical properties of SLS polyamide 12, but there are few works evaluating the fracture behavior using
the Fracture Mechanics approach. One of them is due to Hitt et al. [21], who compared the fracture behavior of SLS and injection
moulding PA12 parts as a function of the specimen thickness. The results were somewhat anomalous as different trends in the energy
at crack growth initiation versus the thickness were obtained. While for IM specimens, there is a decrease in energy as the specimen
thickness increases, the opposite trend occurs for LS samples. The reason of this anomaly is not clear and its origin could be in the
computation of the fracture parameters. While IM specimens presented a semibrittle behavior and the requirements of Linear Elastic
Fracture Mechanics (LEFM) were fulfilled, SLS samples showed a well-defined non-linear behavior where no LEFM approach could be
justified. Even though for the latter, the energy at crack growth initiation was computed using an approximation, that is, using the

68
A.J. Cano et al. Engineering Fracture Mechanics 203 (2018) 66–80

4 80

73,2
(a) (c)
PA12-PARA PA12-PARA
PA12-PERP 70 PA12-PERP
3,5

3,3
PA12-R-PARA PA12-R-PARA

64
3,2

63
62
PA12-R-PERP PA12-R-PERP

Tensile strength (MPa)

60
Young´s modulus (GPa)

2,43
2,5
50

47
2,5

44
2,02

1,96

40
2

33,2
1,64

33
1,58

29,3

29
30
1,5

1,16
1,14

20,8
20
20
1

0,64
0,55 10
0,5

0
0
-50 23 50
-50 23 50
T (ºC)
T (ºC)

0,5 60

53,8
PA12-PARA (b) PA12-PARA (d)
0,46

PA12-PERP PA12-PERP
0,45

PA12-R-PARA PA12-R-PARA
0,45 PA12-R-PERP 50
0,43

PA12-R-PERP

47
0,42
0,407

Elongation at break (%)

0,41
0,4

0,39
Poisson´s ratio

0,4 40
0,35

0,35

0,35

31
0,34

27,2
0,35 30

20
0,3 20
15,2
10
7,6

0,25 10
4,5
3,27
3,4
4

0,2 0
-50 23 50 -50 23 50

T (ºC) T (ºC)

Fig. 3. Evolution of the tensile parameters of PA12 and PA12-R as a function of the temperature and the orientation: (a) Young’s modulus, (b)
Poisson’s ratio, (c) Tensile strength and (d) Elongation at break.

energy under the force-displacement curve up to the end of the elastic response. Seltzer et al. [11] analyzed the effect of water
conditioning on the fracture behavior of neat PA12 and PA12 composites reinforced with glass beads and short glass fibers. Fracture
toughness of the composites was hardly higher than that of the neat polyamide but water conditioning affected more drastically to the
unreinforced material than to the composites. Finally, Brugo et al. [22] evaluated the effect of the orientation of the crack of the
fracture specimens respect to the building direction and the notch sharpening method on the fracture behavior of SLS PA12. Re-
garding the orientation, the fracture toughness of the specimens loaded perpendicularly to the layers was lower. Additionally, two
notching techniques were evaluated: in the first one, a crack of 0.3 mm in thickness was directly manufactured during the SLS
process; the other procedure consisted in pressing the razor blade into the notch. No relevant differences were observed in the
fracture toughness values obtained from specimens notch-sharpened via these two methodologies. That is why the authors proposed
the cracks directly manufactured from the SLS process as “good” cracks for fracture toughness evaluation. Unfortunately, the plastic
deformation area ahead of the crack tip produced during notch sharpening via the pressing contact technique was not taken into
account and, thus, the similarity in the fracture toughness results provided by the different notching technique was not ensured [23].
As previously mentioned, one major niche the SLS process is used is aeronautics. Significant efforts have been made researching
airfoil morphing structures and SLS PA12 is a suitable candidate for these structures because it assembles a series of properties that
make it ideal [3,24]. PA12 has a very high toughness and fatigue resistance compared to other thermoplastics, good tribological

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A.J. Cano et al. Engineering Fracture Mechanics 203 (2018) 66–80

1000
(a)
800

600

Force (N)
400

-50 ºC
200 PA12-PARA
PA12-PERP
PA12-R-PARA
PA12-R-PERP

0
0 0,5 1 1,5 2 2,5
Displacement (mm)
1000
(b)

800

600
Force (N)

400

23 ºC
200 PA12-PARA
PA12-PERP
PA12-R-PARA
PA12-R-PERP

0
0 0,5 1 1,5 2 2,5 3
Displacement (mm)

700
(c)
600

500

400
Force (N)

300

200 50 ºC
PA12-PARA
PA12-PERP
100 PA12-R-PARA
PA12-R-PERP

0
0 1 2 3 4 5 6 7
Displacement (mm)

Fig. 4. Representative load-displacement diagrams obtained from fracture tests of PA12 and PA12-R at PARA and PERP orientations and (a) at
−50 °C, (b) at 23 °C and (c) at 50 °C.

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A.J. Cano et al. Engineering Fracture Mechanics 203 (2018) 66–80

Table 2
Fitting values of the experimental J-R curves to the power law equation J = C ΔaN of PA12 and PA12-R tested at parallel and perpendicular
orientations and at 23 °C and 50 °C.
23 °C 50 °C

PA12- C N PA12- C N PA12- C N PA12- C N

PARA PERP PARA PERP

3 9.53 0.01 3 8.56 0.14 1 20.1 0.26 1 11 0.03

5 10.3 0.13 6 8.61 0.06 2 21.7 0.31 3 15 0.10
6 10.2 0.18 8 8.66 0.06 3 18.8 0.40 4 14 0.14
5 17 0.25

Average 10.0 ± 0.4 0.14 ± 0.04 Average 8.61 ± 0.05 0.08 ± 0.05 Average 20.2 ± 1.5 0.32 ± 0.07 Average 14 ± 3 0.13 ± 0.09

PA12-R- C N PA12-R- C N PA12-R- C N PA12-R- C N

PA- PERP PARA PERP
RA

5 6.8 0.04 4 6.8 0.11 1 8.06 0.04 1 8.7 0.10

6 7.1 0.10 5 7.3 0.05 3 8.12 0.08 2 7.0 0.22
3 8.8 0.07

Average 7.0 ± 0.2 0.07 ± 0.04 Average 7.0 ± 0.3 0.08 ± 0.05 Average 8.09 ± 0.05 0.06 ± 0.03 Average 8±1 0.13 ± 0.09

performance and high chemical resistance [10,24]. These structures are to withstand in service temperatures that range from −50 °C
to 50 °C and for design, it is essential to know the damage tolerance behavior of the materials in this temperature range. Fracture
Mechanics parameters may help to evaluate the mechanical integrity. That is the reason why the present work analyzes the effect of
the temperature on the fracture behavior of SLS PA12 and SLS PA12 reinforced with glass beads specimens built in different di-
rections. The mechanical characterization comprised fracture tests and tensile tests carried out at −50 °C, 23 °C and 50 °C to cover the
whole range of in service temperatures. Special attention has been paid to the influence of the orientation of the layers with respect to
the loading direction.

2. Experimental procedure

2.1. Materials

Two PA12 based materials suitable for SLS fabrication were used. The PA12 powder, supplied by the EOS Group, has the
commercial names PA2200 for the neat PA12 and PA3200 for the reinforced PA12 with 40%wt of glass beads with an average size of
60 µm. The SLS samples for the present study were manufactured by Prodintec, Spain.
Density measurements were performed following the Archimedes methodology using water as the submersion liquid. Five replica
were carried out for each material.

2.2. Thermal characterization

Differential Scanning Calorimetry (DSC) measurements were performed using Mettler 822e equipment and software. Sample
masses were of 12.0 ± 0.5 mg and were heated from 25 °C to 250 °C at a rate of 10 °C/min, followed by a cooling ramp at 10 °C/min
from 250 °C to 25 °C. Two heating/cooling scans were undertaken subsequently.
The melting and crystallization temperatures, Tm and Tc, respectively, were extracted from the thermograms. The crystallinity
degree, χ, was obtained from the heats of fusion and crystallization determined by integrating the heat flow under the melting and
crystallization peaks, respectively. Thus, χ was calculated as the ratio between the heat of fusion or crystallization, ΔH , and the
known heat of melting for a 100% crystalline specimen, ΔH0 :
|ΔH|
χ= × 100
ΔH0 (1)
with ΔH0 taken as 209.3 J/g [25]. Specifically, the crystallinity degrees obtained from the heat of fusion and crystallization are
named as χm and χc , respectively.
Dynamic Mechanical Analysis (DMA) was performed on a DMA Q800 (TA Instruments) analyzer in single cantilever mode on
specimens with nominal dimensions of 4 × 1 × 13 mm3. Thermograms were obtained heating from −100 °C to 150 °C at a fixed
frequency of 1 Hz with a heating rate of 3 °C/min.

2.3. Mechanical characterization

The directions in the build chamber were designated as follows: the x-axis and the y-axis are within the slice and the z-axis is
perpendicular to the x-y plane showing the vertical building direction. Therefore, in a first approach, the samples could be assumed to

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A.J. Cano et al. Engineering Fracture Mechanics 203 (2018) 66–80

14
(a)

12

10

J (kJ/m )
2
8
PA-PARA-3
PA-PARA-5
PA-PARA-6
6 PA-PERP-3
PA-PERP-6
23 ºC PA-PERP-8
PA-R-PARA-5
PA-R-PARA-6
4 PA-R-PERP-4
PA-R-PERP-5

0 1 2 3 4
Δa (mm)

30
(b) PA-PARA-1
PA-PARA-2
PA-PARA-3
25 PA-PERP-1
PA-PERP-3
50 ºC PA-PERP-4
PA-PERP-5
PA-R-PARA-1
20 PA-R-PARA-3
PA-R-PERP-1
J (kJ/m )

PA-R-PERP-2
2

PA-R-PERP-3
15

10

0
0 1 2 3 4
Δa (mm)

Fig. 5. J-R curves of PA12 and PA12-R tested at PARA and PERP orientations and (a) at 23 °C and (b) at 50 °C.

be a multi-layered orthotropic material, but in fact, no differences are considered within the x-y plane, so the material can be treated
as transversely isotropic. The batch of the tensile and fracture specimens was divided into two groups. The samples in the group
called PARA were orientated in such a way that the tensile force direction belongs to the layer plane (x-y plane in Figs. 1 and 2). In
the group called PERP, the tensile force direction is coincident with the z-axis and thus, perpendicular to the slice.
The mechanical properties were determined via tensile tests according to ASTM D638 Standard. The nominal dimensions of the
specimens are shown in Fig. 1. The tests were carried out at −50 °C, 23 °C and 50 °C in a universal electromechanical testing machine
(MTS Alliance RF/100) with a load cell of ± 5 kN and at a crosshead speed of 5 mm/min. The axial deformation was measured with a
contact MTS extensometer Model 634.12F as well as with a videoxtensometer VIC 2D. The latter was also used for the determination
of the transverse deformation and the Poisson’s ratio. Besides, the Young’s modulus, the tensile strength and the elongation at break
were obtained from the engineering stress-engineering strain diagrams.
Fracture tests were conducted on Compact Tension (CT) samples with dimensions shown in Fig. 2. The sharp crack was introduced
by tapping on a razor blade placed into the root of the notch attaining an initial crack length, a0, to width, W, ratio of 0.5. The tests
were performed at −50 °C, 23 °C and 50 °C and at a crosshead speed of 5 mm/min in a universal servohydraulic testing machine (MTS
810 Materials Testing) with a load cell of ± 5 kN and a crack opening displacement (COD) extensometer MTS 632.02F-20 with a
displacement range of +3.9 mm/−2 mm.
For the low and high temperature tests, the load train (hinges, grips, sample and extensometer) was placed inside an environ-
mental chamber (MTS 651.06E−03). The cooling/heating process was conducted till the load frame ceased to move to balance the
thermal contractions and maintain a constant load of +50 N on the specimen. Once the target temperature (−50 °C or +50 °C) was

72
A.J. Cano et al. Engineering Fracture Mechanics 203 (2018) 66–80

G PA-PARA
IC

14 G PA-PERP

13,2
IC

G PA-R-PARA
IC

G PA-R-PERP
12 IC

11,1
J PA-PARA
IC

J PA-PERP
IC
10 J PA-R-PARA
IC

8,7
8,7
J PA-R-PERP
IC

7,9
J (kJ/m )
8

7,3
6,7

6,7
7

7
6,4

6,4
6,2

6,2

5,9
6
6
IC

0
-50 23 50
T (ºC)

Fig. 6. Energy at crack growth initiation as a function of the testing temperature and orientation.

reached and before starting the test, conditioning was held 25 min more to guarantee that the specimen was in thermal equilibrium.
Among three and five replicas were tested for each condition.
For the determination of the fracture parameters, different approaches were applied depending on the mechanical response of the
material at each experimental condition. When the mechanical response was linear and semi-brittle with fulfillment of the LEFM
requirements, the recommendations of ISO13856 standard [26] were followed to determine the GIC parameter. In case of non-linear
mechanical response, the normalization method described in ASTM E1820 standard [27] was followed to determine the J-R curve.
The energy at crack growth initiation, JIC, was computed as the lower value of a J0.2 parameter (i.e. J measured at 0.2 mm of total
crack growth) or a JBL value (specified as the intersection of the blunting line with the J-Δa curve) [28].
The fracture surfaces of the SLS fracture specimens were inspected using scanning electron microscopy (SEM) to determine the
micromechanisms of failure as a function of the testing temperature, the orientation and the reinforcement. The fracture surfaces
were gold coated to enhance their conductivity and were examined using a SEM HITACHI S3400N.

3. Results and discussion

3.1. Thermal characterization

Table 1 gathers the density measured via the Archimedes method and porosity percentage of the neat PA12, and the composite of
PA12 reinforced with 40 wt% glass beads, PA12-R. Taking into account that the full dense values of PA-12 and PA12-R are 1.02 g/
cm3 and 1.34 g/cm3, respectively, the porosity percentage was of 3.4% and 2.8%, respectively. This porosity is only attributable to
the processing procedure. Regarding the thermal information obtained from DSC analysis, Table 1 shows a single melting peak, Tm,
around 183 °C belonging to the γ – crystal phase of PA12 [29] for both the unreinforced and reinforced polymer. Similarly, the
crystallization peak, Tc, coincided at ∼140 °C for both materials. The sintering window, defined as the difference between en-
dothermic and exothermic peak temperatures, ranged around 40 °C for both materials, asseverating the suitability of PA12 and PA12-
R for the SLS process. The crystalline degree was smaller in the composite than in the neat PA12 because hard particles induce
heterogeneous nucleation and more imperfections acting in detriment of crystallinity [11]. Apart from the crystallization and melting
peaks, DMA analysis confirmed the existence of another peak at low temperatures, around −60 °C, related to another relaxation
mode, specifically known as the β transition temperature, Tβ [14,15,30]. The relaxation phenomena occur at the very same tem-
perature for both the neat PA12 and the composite.

3.2. Tensile results

Fig. 3 shows the evolution of the Young’s modulus, the Poisson’s ratio, the tensile strength and the elongation at break of the neat
PA12 and the composite with glass beads, PA12-R, with the temperature and the orientation. Firstly, it is necessary to say that the
values of the tensile quantities at 23 °C are in accordance with those reported by other authors for both the neat PA12 [4,8,11,18,31]
and the reinforced polymer, PA12-R [11,12]. When analyzing the orientation, the only really affected quantity is the elongation at
break (Fig. 3d) for both materials. For the PARA specimens it is between 2 and 3 times higher than for the PERP orientation. The rest
of properties did not experience important differences between both orientations. These results seem to indicate that despite the

73
A.J. Cano et al. Engineering Fracture Mechanics 203 (2018) 66–80

-50 °C PARA

100 μm

23 °C PARA

100 μm

50 °C PARA

100 μm

Fig. 7. Fracture surfaces of neat PA12 tested at PARA orientation at −50 °C, 23 °C and 50 °C. The arrow shows the crack growth direction.

intrinsically anisotropic nature of the processing technique, the material finally resulted is mainly isotropic, at least from the uniaxial
tensile properties point of view. The significant differences observed in the elongation at break are related to the final stages of the
tensile tests, where the material inhomogeneities play a critical role.
Concerning the effect of the reinforcement, it seems to be beneficial for the elastic properties, with an increase in the Young’s
modulus and a consistent decrease in Poisson ratio too. Nevertheless, other properties such as the tensile strength and the elongation
at break are negatively affected. These results may indicate that the adhesion of the glass beads to the matrix is only maintained in the
first stages of deformation. Probably the compatibility between the coatings of the reinforcement and the PA matrix requires further
optimization [12].

3.3. Fracture characterization

For the determination of the fracture parameters, LEFM or Non Linear Fracture Mechanics (NLFM) approaches can be applied
depending on the mechanical response of the materials. That is why Fig. 4 shows the representative force-displacement records
obtained from the fracture tests of the neat PA12 and the composite PA12-R tested at the parallel (PARA) and perpendicular (PERP)
orientations at −50 °C, at 23 °C and at 50 °C. Although the response observed as a whole was basically non-linear, at −50 °C, all the

74
A.J. Cano et al. Engineering Fracture Mechanics 203 (2018) 66–80

-50 °C PERP

100 μm

23 °C PERP

100 μm

50 °C PERP

100 μm

Fig. 8. Fracture surfaces of neat PA12 tested at PERP orientation at −50 °C, 23 °C and 50 °C. The arrow shows the crack growth direction.

requirements of the LEFM were fulfilled and, thus, the ISO 13,586 standard [26] was strictly followed for the determination of GIC.
On the contrary, at 50 °C the non-linearity represented by the ratio between the maximum load, Pmax, and the load taken at crack
initiation, PQ, was so high that the application of NLFM was needed [27]. Between these two extreme cases is the mechanical
response at 23 °C, which cannot be strictly considered linear-elastic because the non-linearity given by the Pmax ratio exceeded 10%
PQ
narrowly, the maximum limit allowed for the application of the LEFM approach. Because of this, the normalization method was
applied to determine the J-R curves and the J integral value at crack growth initiation, JIC, at 23 °C and 50 °C. However, as the non-
linearity was not far away, the apparent GIC values provided by LEFM were also calculated at 23 °C. Special attention is paid in the
comparison of the JIC and apparent GIC values at this temperature. This non-linear behavior was not expected, in principle, at 23 °C as
this temperature is well below the Tg of the materials (Tables 1 and 2). However, the role played by the β relaxation may be relevant,
but this issue is beyond the scope of this work (Table 1).
Fig. 5 displays the J-R curves at 23 °C and 50 °C and as it can be observed, the curves of PA12 are well above those of the
composite for both orientations and temperatures, so the glass beads reinforcement is not playing the expected toughening role.
Secondly, the stable crack growth, represented by the slope of the J-R curves, is clearly higher in the neat PA12 oriented parallel to
the applied load. The J-R curves in this case are steeper than the others and this can be quantified by evaluating the exponent after
fitting to the power law J = C ΔaN (Table 2). This orientation effect is not observed in the case of PA12-R, regardless of the tem-
perature. As previously, in the tensile results, the role of reinforcement is scarce if any in the fracture behavior. The J-R curves reflect
the material tolerance to the fracture propagation. Any heterogeneity that is present in the material microstructure will have its

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A.J. Cano et al. Engineering Fracture Mechanics 203 (2018) 66–80

(a)

20 μm

(b)

20 μm

Fig. 9. Detail of the micromechanism of failure consisting mainly on crazes (a) at −50 °C and (b) at 23 °C.

influence in the fracture resistance curve. This is valid both for a weak matrix-reinforcement interface and for adhesion faults
between the layers of the material deposited during the laser sintering process. The only case not affected by these defects is the PA12
with parallel orientation, which are precisely associated with steeper curves.
Fig. 6 shows the energy at crack growth initiation as a function of temperature and orientation. Firstly, there are not appreciable
differences between the apparent GIC and the JIC values determined at 23 °C independently of the material and the testing orientation.
In addition, the values of the fracture toughness obtained at 23 °C were similar to those obtained by Hitt et al. [21], but lower than
those measured by Brugo et al. [22]. Secondly, regarding the effect of the testing temperature, different trends can be observed for the
neat polyamide and the composite. For the unreinforced material, there is an important increase in the JIC values obtained at 50 °C,
reaching in some cases values twice those attained at −50 °C or at 23 °C. This behavior can be explained taking into account that
50 °C is close to the Tg of the material (Table 1) and therefore, the viscous state plays an important role in determining the fracture
behavior. Curiously, the composite PA12-R is almost unaffected by the temperature, an additional signal of a fracture behavior
controlled by the microstructural heterogeneities. Finally, the general trend is not to observe an orientation effect in either PA12 or
PA12-R, with the exception of PA12 at 50 °C, showing differences higher than 20% between orientations. Once again, it seems that
close to the Tg of the material, the anisotropic fracture behavior is dictated by the viscous state.
The analysis of the fracture surfaces complemented the quantitative analysis obtained from the fracture data. In case of the neat
PA12, Figs. 7 and 8 show the fracture surfaces obtained from the tests at −50 °C, at 23 °C and at 50 °C and at PARA and PERP
orientations, respectively. It is clearly observable that scarce difference were appreciated between the fracture surfaces obtained at
−50 °C and 23 °C at both orientations. This is consistent with similar JIC values at both temperatures. However, at 50 °C it is evident
high degree of plastic deformation and subsequent tearing along the crack propagation direction. Obviously, this mechanism of
failure requires more energy leading to higher energies at crack growth initiation. Unfortunately, for the very same temperature, no
differences could be detected between the fracture surfaces obtained from specimens tested at different orientations which could
substantiate the differences in the stable crack growth behavior quantified by the exponent N of the J-R curves power laws (Table 2
and Fig. 5).
Regarding the identification of the mechanism of failure of the neat PA12, even the images at low magnification indicate the
presence of crazes (Figs. 7 and 8). The incipient patchwork pattern normally accompanied by micro-ductile tearing is detectable at
−50 °C (Figures at −50 °C and Fig. 9a). As the temperature increases, the dimples associated with craze formation are hindered by
the high elongation of the surrounding filaments and subsequent tearing following the crack propagation direction occurs (Figs. 7 and
8 and at 23 °C and at 50 °C and Fig. 9b). This mechanism of failure has also been reported for injection moulded polyamide 6.6 [32].
The fractographic analysis performed on the fracture surfaces of the composite PA12-R tested at −50 °C, at 23 °C and at 50 °C and
at PARA and PERP orientations is displayed in Figs. 10 and 11, respectively. No difference is discernible when evaluating either the
testing temperature or the testing orientation. Indeed, the fracture surfaces are generally quite plain (much more than those of the

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-50 °C PARA

100 μm

23 °C PARA

100 μm

50 °C PARA

100 μm

Fig. 10. Fracture surfaces of the composite PA12-R tested at PARA orientation at −50 °C, 23 °C and 50 °C. The arrow shows the crack growth
direction.

neat PA12) with lack of plastic deformation, and it is easy to find clusters of glass beads quite frequently (Fig. 11 at 23 °C). A high
magnification study reveals that the surface of the beads is very clean with no trace of any coating suggesting very poor particle-
matrix adhesion (Fig. 12). This could be the reason for the inferior mechanical and fracture properties of the composite in comparison
with the neat PA12. This observation was independent of the testing temperature and the testing orientation (i.e. whether parallel or
perpendicular). Due to the very poor particle-matrix adhesion, load is not transferred to the particles so they do not contribute to
Young’s modulus in the expected way. Further, plastic hole growth, from the debonded cavity walls, does not occur which would
prevent the toughness from increasing due to that mechanism not being operative. Clusters of glass beads with poor (or no) adhesion
between them may act as defects, suppressing toughness.

4. Conclusions

This work has investigated the effects of the temperature and the orientation of the applied load with respect to the layered
structure on the tensile and fracture properties of Selective Laser Sintering polyamide 12 and polyamide 12 reinforced with glass
beads. The tested temperatures were −50 °C, 23 °C and 50 °C as the in-service range of these materials used in aeronautical appli-
cations.
Tensile properties followed the expected trend with temperature in all cases, that is, an increase in the Young’s modulus and the

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A.J. Cano et al. Engineering Fracture Mechanics 203 (2018) 66–80

-50 °C PERP

100 μm

23 °C PERP

100 μm

50 °C PERP

100 μm

Fig. 11. Fracture surfaces of the composite PA12-R tested at PERP orientation at −50 °C, 23 °C and 50 °C. The arrow shows the crack growth
direction.

tensile strength with decreasing temperature and the opposite tendency in the Poisson’s ratio and the elongation at break. On the
other hand, the different tensile properties seemed to be unaffected by orientation, except for the elongation at break. In this case, the
elongation at break at the parallel orientation was higher than at the perpendicular orientation and this difference was more ac-
centuated at high temperature and in the unreinforced material.
Regarding the fracture behavior, a non-linear response was obtained, more accentuated at high temperatures. Some differences in
the value of initiation, JIC, have been observed in the neat polyamide, particularly at 50 °C, where the material is close to its Tg. These
differences are scarce in the case of the composite. In terms of the complete J-R curve, those corresponding to the neat PA12 were
always above those of the composite PA12-R, independently of the orientation and the temperature. The J-R curves of PA12 in the
parallel orientation are undoubtedly steeper than the rest. No significant reinforcement toughening effect has been detected, being
the fracture behavior controlled by microstructural defects such as adhesion faults between layers and a poor adhesion between the
glass beads and the matrix.
These results are supported by the fractographic analysis. The fracture surfaces of the composite were similar independently of the
orientation and the testing temperature, and the glass beads seemed to be badly adhered to the matrix. For the neat PA12, the fracture
surfaces were analogous at −50 °C and 23 °C with crazing being the main micromechanism of failure, while at 50 °C craze formation
followed by macro ductile tearing of the supporting filaments along the crack direction was dominant.

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(a)

50 μm

(b)

20 μm

Fig. 12. (a) Micrograph showing the uncoated glass beads, (b) detail of glass beads.

Acknowledgements

Authors are indebted to Ministerio de Economía y Competitividad of Spain for their financial support through project DPI2016-
80389-C2-1-R.

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