Materials Science and Engineering A 487 (2008) 251257

Functionally graded Nylon-11/silica nanocomposites

produced by selective laser sintering
Haseung Chung a , Suman Das b,
a

Department of Mechanical and System Design Engineering, Hongik University, Seoul, Republic of Korea
Woodruff School of Mechanical Engineering, Georgia Institute of Technology, Atlanta, GA 30332-0405, United States
Received 4 September 2007; received in revised form 4 October 2007; accepted 5 October 2007

Abstract
Selective laser sintering (SLS), a layered manufacturing-based freeform fabrication approach was explored for constructing three-dimensional
structures in functionally graded polymer nanocomposites. Here, we report on the processing and properties of functionally graded polymer
nanocomposites of Nylon-11 filled with 010% by volume of 15 nm fumed silica nanoparticles. SLS processing parameters for the different
compositions were developed by design of experiments (DOE). The densities and micro/nanostructures of the nanocomposites were examined by
optical microscopy and transmission electron microscopy (TEM). The tensile and compressive properties for each composition were then tested.
These properties exhibit a nonlinear variation as a function of filler volume fraction. Finally, two component designs exhibiting a one-dimensional
polymer nanocomposite material gradient were fabricated. The results indicate that particulate-filled functionally graded polymer nanocomposites
exhibiting a one-dimensional composition gradient can be successfully processed by SLS to produce three-dimensional components with spatially
varying mechanical properties.
2007 Elsevier B.V. All rights reserved.
Keywords: Selective laser sintering; Polymer nanocomposites; Functionally graded materials

1. Introduction
Polymer systems are widely used due to their unique
attributes including ease of production, light weight, and often
ductile nature. However, polymers have lower modulus and
strength as compared to metals and ceramics [1]. Fillers including fibers, whiskers, platelets, or particles are important additives
for altering and enhancing the properties of polymers. Using
this approach, polymer properties have been improved while
maintaining their light weight and ductile nature [211]. Particle fillers are frequently employed to improve the mechanical
performance of polymers for engineering applications in which
stiffness and toughness are the most important parameters to
be taken into account. Both stiffness and toughness can be
improved by the addition of inorganic particles, with the particle ranging in size from the micro- to nanoscale. Nanoparticles
have some unique features compared to microparticles. The
higher surface area can promote stress transfer from the matrix

Corresponding author. Tel.: +1 404 385 6027; fax: +1 404 894 9342.
E-mail address: sumandas@gatech.edu (S. Das).

0921-5093/$ see front matter 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.msea.2007.10.082

to the nanoparticles, improving the Youngs modulus of polymers more dramatically than with microscale filler particles. The
required loadings of nanoparticles in polymer matrices are usually much lower than those of microscale filler particles which
are typically in the 1040 vol.% range [12].
Functionally graded materials (FGMs) are materials that
incorporate deliberately designed transitions in materials composition and properties within a component in preferred
directions to optimize the functional value of that component
[13,14]. The FGM concept is applicable to many fields of engineering, for example, aerospace, nuclear energy, chemical plant,
energy conversion, electronics, optics, bio-systems, and commodities [15]. Various processing methods for FGMs have been
discussed elsewhere [1520] but most of these efforts are limited to creating one-dimensional FGMs in simple shapes. While
the ability to manufacture complex components using FGMs
is highly desirable, at present, efficient automated techniques
to build such components with material gradations realized
as per design are limited. In this respect, layered manufacturing techniques such as selective laser sintering (SLS) [21],
have the potential to be ideal techniques to automatically build
such components [1]. SLS creates objects directly from CAD

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models using a layer-by-layer material deposition and consolidation approach. Thin layers of powders are successively
deposited and selectively fused using a computer-controlled
scanning laser beam that scans patterns corresponding to slices
of the CAD model. At present, fabrication of components with
true three-dimensional compositional heterogeneity via SLS
requires significant modification or redesign of powder delivery
mechanisms. Chung and Das [1] successfully demonstrated the
fabrication of one-dimensional microcomposite FGMs by SLS
in a glass-bead particulate-filled polymer. In this paper, the fabrication of one-dimensional nanocomposite FGMs by SLS of a
nanoparticle-filled polymer is demonstrated in the same manner,
showing improved properties over the microcomposite FGM.
Numerous works on nanocomposites including nanoparticleloaded composites exist in the literature. Brechet et al. [23]
proposed a model of interactions between the surface of the
dispersed nanoparticles and their interfacial surface with polymer chains in order to analyze and predict the behavior of
nanocomposite materials, and to better understand the origin of
the high reinforcing effect generally observed. The influence of
filler size on elastic properties of nanoparticle-reinforced polymer composites was investigated by Adnan et al. [24] using
molecular dynamics (MD) simulations. The mechanical properties for neat polymer and nanocomposites were evaluated by
simulating a series of unidirectional and hydrostatic tests, both
in tension and compression. MD simulations by Smith et al. [25]
showed that the properties of polymer-nanoparticle composites
(PNPCs) were strongly influenced by nanoparticle size and filler
fraction, nanoparticle shape, nanoparticle distribution, polymer
molecular weight and the nature of the interactions between
the nanoparticle and polymer matrix. Zhang et al. [12] showed
that smaller particles, especially nanoparticles, may be more
effective for polymer toughening. Recent work by Shah et al.
[26] has led to the development of nanohybrid materials, more
specifically poly-vinylidene fluoride (PVDF) nanocomposites,
which exhibit a simultaneous increase in stiffness and toughness. Beyond these, researches on the mechanical properties of
nanocomposites have been reported elsewhere [2729]. Kim and
Creasy [30] investigated selective laser sintering (SLS) characteristics of clay nanoparticle/Nylon 6 composite for applications
in rapid prototyping and manufacturing (RP&M). Differences
in sintering behaviors between the nanocomposites and neat
polymers were investigated in this work.
2. Experimental
A commercially available SLS machine (SinterstationTM
2000, 3D Systems, Valencia, CA) was used in our experiments.
The selection of materials suitable for the fabrication of FGM by
SLS was based on the following criteria. First, materials must be
available in powder form. For good spreading on the powder bed,
there are limitations on the powder particle size. Powders should
flow freely, even at elevated temperatures, since good powder
flow and spreading are required to form each new layer in SLS
processing. Materials made with diameters less than 10 m were
found to exhibit poor bulk flow at high temperatures, presumably
due to the higher interparticle friction found in extremely fine

Fig. 1. Particle size distribution of Nylon-11 (RilsanD80) by sieve analysis.

powders [31]. On the other hand, a typical build layer thickness

in the SinterstationTM 2000 machine is 100200 m. Therefore,
materials with particle sizes in the 10150 m range are preferred. Semi-crystalline polymers with relatively low melting
point and low melting viscosity are also preferred [32].
For our experiments Nylon-11 (Rilsan D80, Arkema Inc.)
and fumed silica nanoparticles (SigmaAldrich Co.) were chosen. Fig. 1 shows the particle size distribution of Nylon-11 by
sieve analysis. As shown, the majority of particles are in the
106150 m range, desirable for SLS processing. On the other
hand, the fumed silica nanoparticles have 15 nm particle size as
reported by the vendor.
To produce one-dimensional FGMs, particulate loaded
Nylon-11 composites with different loadings of silica nanoparticles were first generated and their tensile and compressive
mechanical properties were tested. The goal was to examine
the effects of different processing parameters on the quality of
the resulting product and to find optimized processing parameters for each mixture composition. Pure Nylon-11 was blended
with different volume fractions of silica nanoparticles over the
26% range in 2% increments, as well as 10% using a rotary
tumbler (784 AVM, U.S. Stoneware, OH) for 24 h.
Two-level factorial design of experiments (DOE) methods
[33] were then used to determine the optimized SLS processing
parameters for achieving high quality parts. DOE is a systematic
method to determine the influence of a set of processing parameters on overall part quality. Here, the optimized SLS processing
parameters are defined as those that result in parts which are fully
dense or near-fully dense in regions where material is present
in the parts design, dimensionally accurate, and easily removed
from its support powder. Procedures previously developed by
Partee et al. [34] for determining the optimized SLS processing parameters for CAPA 6501 polycaprolactone powder were
adopted for the present study. In the context of this study involving polymer nanocomposites, additional criteria were applied

H. Chung, S. Das / Materials Science and Engineering A 487 (2008) 251257

so that the optimized SLS processing parameters resulted in

smoothly deposited powder layers in the shortest possible time,
and yielded SLS processed specimens exhibiting good bonding of the polymer matrix to the silica nanoparticles with no
inter-layer delamination.
Once optimized processing parameters for each material
composition were achieved by DOE, the tensile and compressive mechanical specimens based on these parameters were
produced and mechanical property tests with these specimens were conducted. The microstructure and nanostructure of
these samples was examined through optical microscopy (Leica
DMLM Microscope) and transmission electron microscopy
(JEOL 2010F Transmission Electron Microscope), respectively.
An Instron machine (4502) and a MTS machine (Alliance
RT/30) were used for tensile tests and compression tests (ASTM
standard D-695), respectively.
FGM composites with these material compositions were fabricated based on the optimized processing parameters. Due to the
nature of the powder delivery subsystem in the SinterstationTM
2000 machine, laser sintering of 3D functionally graded multiple
materials is not possible. Therefore, a vertical FGM in discrete
layers in the powder supply cylinders was created manually. As
the SLS process proceeded, the roller deposited material of a
gradually changing composition on the part side piston as the
stacked powders of different compositions were incrementally
consumed. The processing parameters for each composition
were changed synchronously. This technique created multilayer
FGM samples in which the material gradient was oriented along
the build direction [1,22]. Using these techniques, two different components were also fabricated to demonstrate the FGM
approach for complex three-dimensional shapes.

3. Results and discussion

Optimal processing parameters for each composition were
determined by fabricating 10 mm test cubes using different combinations of laser power, scan speed, substrate temperature,
and roller speed by DOE. The fabricated parts were sectioned
and examined by optical microscopy and image-J software
(http://rsb.info.nih.gov/ij/). Similar procedures were previously
developed for glass beads filled composites elsewhere [1,22].
Initially, the same processing parameters for 30% volume fraction of glass beads loaded Nylon-11 composite were
attempted for 2% volume fraction of silica nanoparticles loaded
Nylon-11 composite and the resulting parts had 99.8% density

253

Fig. 2. Cross-sectional optical micrographs of Nylon-11 + 2% silica nanoparticles.

[2,10]. This meant that the same processing parameters could

be used to optimize 2% volume fraction of silica nanoparticles
loaded Nylon-11 composite. Fig. 2 shows the cross-sectional
optical micrograph of the fabricated part for Nylon-11 filled with
2% volume fraction of silica nanoparticles. The fabricated part
was sectioned, dyed using a black marker pen and then wiped
using a smooth cloth. Areas of porosity were indicated by those
regions that remain black when black ink was wiped from the
section face because pores retain some ink while the fully dense
regions do not. Thus, the black regions shown in Fig. 2 indicate
porosity.
However, as the volume fraction of silica nanoparticles was
increased by 2% from 2% to 4%, the process could not be
continued with these parameters. Therefore, DOE was applied
here as well to determine the optimized processing parameters.
Although DOE with large range of each processing parameter
was executed, none of the processing parameters were successful. Therefore, an alternate approach was attempted. Once
pure Nylon-11 bases were generated using the optimized processing parameters developed previously [1,22], 46% silica
nanoparticle-filled composites were fabricated on top of the
bases. DOE was applied to these silica nanoparticle-filled composites. This approach was successful and led to fabrication of
several parts. Table 1 shows the optimized processing parameters
and densities attained by this approach for silica nanoparticles
loaded Nylon-11 composites.

Table 1
Optimized processing parameters and densities for silica nanoparticle-loaded nanocomposites
Processing parameter

Nylon-11 base

Nylon-11 + 2% silica
nanoparticles

Nylon-11 + 4% silica
nanoparticles

Nylon-11 + 6% silica
nanoparticles

Nylon-11 + 10% silica

nanoparticles

Part substrate temperature

set point ( C)
Roller speed (m/s)
Laser power (W)
Scan speed (m/s)
Resulting density (%)

184

184

184

184

184

0.076 (3 in./s)
4.5
1.257 (49.5 in./s)
99.8 0.1

0.076 (3 in./s)
4.5
1.257 (49.5 in./s)
99.8 0.1

0.076 (3 in./s)
4.5
0.889 (35.0 in./s)
99.7 0.1

0.076 (3 in./s)
4.5
0.889 (35.0 in./s)
99.8 0.1

0.076 (3 in./s)
4.5
0.635 (25.0 in./s)
99.0 0.1

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H. Chung, S. Das / Materials Science and Engineering A 487 (2008) 251257

However, the disadvantage of this approach is that postprocessing steps such as turning and milling are necessary to
eliminate the pure Nylon-11 base. To eliminate this procedure,
a second alternate approach was experimented. Ten additional
unsintered layers were added between pure Nylon-11 base and
silica nanoparticle composite so that two parts were separated
without any post-processing. This approach was also successful
up to 6% volume fraction of silica nanoparticles.
Fabrication of the Nylon-11 composite with 10% volume
fraction of silica nanoparticles was also attempted using the
same technique as 46% silica nanoparticles loaded Nylon-11
composites. However, this approach was not successful for the
10% silica nanoparticles loaded Nylon-11 composites. Therefore, the unsintered additional layers were eliminated so that
silica nanoparticle composite was attached directly to pure
Nylon-11 base and DOE was applied to this process. When the
scan speed was decreased from 35 to 25 in./s, while keeping
the other parameters the same, the fabricated part had 99.0%
density.
Cross-sectional optical micrographs can provide the macroscopic density but do not reveal any information of the dispersion
of silica nanoparticles in Nylon-11 matrix. The nanostructure
of the Nylon-11 nanocomposite with 10% volume fraction
of silica nanoparticles was examined by transmission electron
microscopy. Samples were prepared for TEM by using microtome (ULTRACUT E, Reichert-Jung) resulting in samples that
had 100 nm thickness.
Fig. 3 shows the cross-sectional high-angle-annular darkfield (HAADF) micrographs from two different regions of the
fabricated part, acquired in STEM mode with two different magnifications. Silica nanoparticles are distributed homogeneously
as shown in both micrographs. Fig. 3 confirmed that silica
nanoparticles had particle size of about 15 nm as given by vendor.
Tensile and compression specimens were generated using
these optimized processing parameters and mechanical tests
were conducted. Five specimens were generated for each
mechanical test for each composition. While no post-processing
procedure was necessary for 26% silica nanoparticles loaded
Nylon-11, the parts could not be fabricated without postprocessing procedures for 10% silica nanoparticles loaded
Nylon-11. Therefore, pure Nylon-11 bases for specimens with
10% volume fraction of silica nanoparticles were removed by
turning for compression specimens and milling for tensile specimens, respectively.
Fig. 4 shows the mean tensile modulus and the mean strain
at break as a function of the silica nanoparticle volume fraction.
The tensile modulus is a decreasing function of silica nanoparticle composition up to 4% volume fraction of silica nanoparticles
but an increasing function of silica nanoparticle composition
from 4% volume fraction upwards. On the other hand, as the volume fraction of silica nanoparticles increases, the tensile strain
at break increases up to 2% volume fraction but decreases from
2% to 10% volume fraction of silica nanoparticles. We can conclude that as volume fraction of silica nanoparticles increases,
the modulus increases and strain at break decreases meaning that
the parts become stiffer but more brittle. However, there exists

Fig. 3. Cross-sectional HAADF micrographs of Nylon-11 + 10% silica nanoparticles.

a critical composition at which these characteristics undergo an

inversion in their trends.
Fig. 5 shows the mean compressive modulus and the mean
strain at yield as a function of silica nanoparticle volume fraction. The compressive modulus is a decreasing function of silica
nanoparticle volume fraction up to 2% volume fraction but is
an increasing function from 2% to 10% volume fraction. On the
other hand, as volume fraction of silica nanoparticles increases,
the compressive strain at yield decreases up to 4% volume frac-

H. Chung, S. Das / Materials Science and Engineering A 487 (2008) 251257

255

Fig. 5. (a) Compressive modulus and (b) strain at yield as a function of silica
nanoparticle composition.
Fig. 4. (a) Tensile modulus and (b) strain at break due to different silica nanoparticle composition.

tion but increases from 4% to 10% volume fraction. As the

volume fraction of silica nanoparticles increases, the compressive modulus increases and strain at yield also increases. Similar
to the tensile modulus, there exists a critical volume fraction of
silica nanoparticles at which these characteristics undergo an
inversion in their trends.
Finally, the fabrication of two different components was
attempted to demonstrate the FGM approach in this paper.
As mentioned earlier, the roller deposited material of a gradually changing composition on the part build platform as the
stacked powders of different compositions were incrementally
consumed. The processing parameters for each composition
were changed synchronously with transitions in supply powder
composition. This technique created multilayer FGM demonstration component in which the material composition gradient
was oriented along the build direction.

The first component selected for FGM demonstration is a

compliant gripper shown in Fig. 6. The upper part of this compliant gripper has to be hard and stiff to grasp the object properly
while the lower part has to be flexible to efficiently generate the
motions under the action of applied forces. Therefore, this component represents the characteristics of a compliant FGM very
well. A 38.10 mm long component with Nylon-11 filled with
five different volume fractions of silica nanoparticles, each of
7.62 mm length was fabricated.
The second component selected to demonstrate the FGM concept is a rotator cuff scaffold. The rotator cuff is composed of
four muscles and their tendons, and helps to lift and rotate the
arm and to stabilize the ball of the shoulder within the joint. The
goal of rotator cuff repair is to reattach good quality tendon to the
location on the arm bone from which it was torn. The design of
this scaffold and the corresponding fabricated part are shown in
Fig. 7 along with material composition and corresponding property gradations in the investigated material systems. An actual,

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H. Chung, S. Das / Materials Science and Engineering A 487 (2008) 251257

Fig. 6. Schematic description, and fabricated part of compliant gripper.

Fig. 7. Schematic description (courtesy Eiji Saito), and fabricated part of rotator cuff scaffold.

implantable scaffold will likely involve a FGM incorporating

different composition blends of a bioresorbable polymer (e.g.
polycaprolactone) and a biocompatible ceramic (e.g. calcium
phosphate) [1].
4. Conclusions
Selective laser sintering technique was investigated on blends
of Nylon-11 with different volume fractions of silica nanoparticles (210%). Optimized processing parameters for selective
laser sintering of the above compositions were developed by systematic design of experiments (DOE). Optical microscopy and
transmission electron microscopy were used for characterizing
the micro/nanostructures of the resulting parts.
In order to design and fabricate 1D functionally graded
material components, knowledge of mechanical properties as
a function of material composition is necessary. To address this
need, the tensile and compressive mechanical properties for
each composition processed to near full density by SLS were
evaluated.

Finally, the fabrication of 1D functionally graded polymer composite components based on the optimized processing
parameters determined by DOE was successfully demonstrated.
For demonstration, two different parts, namely, a compliant gripper and a rotator cuff scaffold designs were fabricated. This work
demonstrates the fabrication of macroscopic three-dimensional
parts with a one-dimensional material gradient by SLS in a
single, uninterrupted process run.
Acknowledgement
This material is based upon work supported by the National
Science Foundation under Grant No. DMI 0115205.
References
[1] H. Chung, S. Das, Mater. Sci. Eng. A 437 (2006) 226234.
[2] S. Bahadur, A. Kapoor, Wear Int. J. Sci. Technol. Friction Lubr. Wear 155
(1992) 4961.
[3] T.H.C. Childs, A.E. Tontowi, J. Eng. Manuf. 215 (2001) 14811495.
[4] J. Lee, A.F. Yee, Polymer 42 (2001) 577588.

H. Chung, S. Das / Materials Science and Engineering A 487 (2008) 251257

[5] R.K.Y. Li, J.Z. Liang, S.C. Tjong, J. Mater. Process. Technol. 79 (1998)
5965.
[6] J.Z. Liang, R.K.Y. Li, S.C. Tjong, Polym. Test. 16 (1997) 529548.
[7] L. Nicolais, G. Guerra, C. Migliaresi, L. Nicodemo, A.T. Di Benedetto,
Composites (1981) 3337.
[8] Y.C. Ou, Z.Z. Yu, Polym. Int. 37 (1995) 113117.
[9] C.Y. Tang, X.L. Xie, X.P. Zhou, X.H. Jia, R.K.Y. Li, J. Mater. Sci. Lett. 21
(2002) 815818.
[10] M. Ulrich, C. Caze, P. Laroche, J. Appl. Polym. Sci. 67 (1998) 201208.
[11] H. Unal, F. Findik, A. Mimaroglu, J. Appl. Polym. Sci. 88 (2003)
16941697.
[12] H. Zhang, Z. Zhang, K. Freidrich, C. Eger, Acta Mater. 54 (2006)
18331842.
[13] B. Ilschner, J. Mech. Phys. Solids 44 (1996) 647656.
[14] S. Suresh, A. Mortensen, Fundamentals of Functional Graded Materials,
IOM Communications Ltd., 1998.
[15] Y. Miyamoto, Mater. Sci. Res. Int. 6 (2000) 38.
[16] R.J. Butcher, C.E. Rousseau, H.V. Tippur, Acta Mater. 47 (1999) 259
268.
[17] B. Kieback, A. Neubrand, H. Riedel, Mater. Sci. Eng. A 362 (2003) 81105.
[18] M. Krumova, C. Klingshirn, F. Haupert, K. Friedrich, Compos. Sci. Technol. 61 (2001) 557563.
[19] W. Pompe, S. Lampenscherf, S. Rosler, D. Scharnweber, K. Weis, H.
Worch, J. Hofinger, Mater. Sci. Forum 308/311 (1999) 325330.
[20] M. Wang, D. Porter, W. Bonfield, Br. Ceram. Trans. 93 (1994) 9195.

257

[21] C.R. Deckard, Ph.D. dissertation, University of Texas, Austin (1988).

[22] H. Chung, Processing and Properties of Functionally Graded Polymer
Composites Produced by Selective Laser Sintering, Ph.D. dissertation,
University of Michigan, Ann Arbor (2005).
[23] Y. Brechet, J.Y. Cavaille, E. Chabert, L. Chazeau, R. Dendievel, L. Flandin,
C. Gauthier, Adv. Eng. Mater. 3 (2001) 571577.
[24] A. Adnan, C.T. Sun, H. Mahfuz, Compos. Sci. Technol. 67 (2007) 348356.
[25] J.S. Smith, D. Bedrov, G.D. Smith, Compos. Sci. Technol. 63 (2003)
15991605.
[26] D. Shah, P. Maiti, D.D. Jiang, C.A. Batt, E.P. Giannelis, Adv. Mater. 17
(2005) 525528.
[27] M.D. Frogley, D. Ravich, H.D. Wagner, Compos. Sci. Technol. 63 (2003)
16471654.
[28] E.P. Giannelis, Adv. Mater. 8 (1996) 2935.
[29] B. Wetzel, F. Haupert, M.Q. Zhang, Compos. Sci. Technol. 63 (2003)
20552067.
[30] J. Kim, T.S. Creasy, Polym. Test. 23 (2004) 629636.
[31] P. Forderhase, K. McAlea, R. Booth, Solid Freeform Fabrication Symposium, The University of Texas at Austin, 1995, pp. 287297.
[32] J.J. Beaman, J.W. Barlow, D.L. Bourell, R.H. Crawford, H.L. Marcus, K.P.
McAlea, Solid Freeform Fabrication: A New Direction in Manufacturing,
Kluwer Academic Publishers, 1997.
[33] R.E. DeVor, T.H. Chang, J.W. Sutherland, Statistical Quality Design and
Control, Macmillan Publishing Company, 1992.
[34] B. Partee, S.J. Hollister, S. Das, J. Manuf. Sci. Eng. 128 (2006) 531540.