Methods For Quantifying The Stable Sintering Region in Laser Sintered Polyamide-12
Methods For Quantifying The Stable Sintering Region in Laser Sintered Polyamide-12
Methods For Quantifying The Stable Sintering Region in Laser Sintered Polyamide-12
2
Department of Materials, Loughborough University, Loughborough, Leicestershire LE11 3TU, UK
3
Department of Mechanical Engineering, The University of Sheffield, S10 2TN UK
Manufacturing complex parts by the laser sintering amide)-12. Polyamide-12 is the most commonly used
process requires a minimum amount of energy input laser sintering polymer (currently around 95% of the total
for consolidation of polymer particles to occur; how- laser sintering polymer market), however, the range of
ever too much energy can result in a decline in
mechanical properties. This decrease is thought to be available polymer materials is fairly limited in compari-
the result of polymer chain degradation. A stable sin- son to competitive processes such as injection molding
tering region (SSR) has been proposed to describe the [2]. One of the main advantages of laser sintering over
optimum temperature range for successful laser sinter- traditional molding techniques is geometric freedom in
ing. This article will aim to quantify the SSR for poly- part design, which has allowed successful utilization of
amide-12 by using thermogravimetric analysis (TGA) to
provide a framework for identifying key laser sintering the process in diverse applications including ducting for
processing parameters. Weight loss with respect to fighter aircraft, i-Phone cases, and even rideable snow-
temperature is the main measurement output of the board binding prototypes.
TGA procedure. However, the precise temperature and During laser sintering, the build process takes place in
thermal history of a material is difficult to quantify
a nitrogen controlled chamber. The polymer is heated to
during the laser sintering process; instead an energy
input approach has been developed. A degradation an elevated temperature prior to the commencement of
energy was calculated from the TGA data and was the build. The actual sintering takes place on a bed of
used in conjunction with a laser sintering formula powder which in the case of polyamide-12 is heated to a
called energy melt ratio to prescribe build parameters temperature about 128C below the crystalline ‘‘peak’’ melt
for laser sintered parts. The mechanical properties of
these parts illustrated the effect of degradation at temperature. Polyamide-12 is a semi-crystalline polymer
various levels of energy input. Implications for this that has a wide super-cooling region; this has been shown
work include optimizing the material selection process to be a key factor for laser sintering processing [3]. A
for polymer laser sintering materials beyond polyam- direct beam CO2 laser applies energy to the material to
ide-12. POLYM. ENG. SCI., 53:1230–1240, 2013. ª 2012 Soci-
take it above the melting point and to consolidate the
ety of Plastics Engineers
specified area. After a layer of powder is sintered another
layer of material is deposited onto the build using a coun-
ter-rotating roller or a blade. Typically, the laser absorb-
INTRODUCTION ance for laser sintering processes exceeds 90% [4–6]. The
Laser sintering is an additive manufacturing technology unsintered powder surrounding the consolidated cross-sec-
that uses a laser to consolidate prototype and end-use tion serves as a part-support structure. This allows com-
3-dimensional computer aided design objects from pow- plex shapes to be constructed without the need for molds
dered material [1]. Although metal and ceramic powders and tooling [7]. When the build is complete the part is
are frequently processed using laser sintering, the focus of cleaned by removing this loose powder.
this work will be on polymers, specifically nylon (poly- Control of the thermal conditions inside the laser sin-
tering machine is one of the fundamental requirements for
creating parts with good mechanical properties, since this
Correspondence to: Mike Vasquez; e-mail: mvasquez@alum.mit.edu
DOI 10.1002/pen.23386
is controlled by the rheological properties of the polymers
Published online in Wiley Online Library (wileyonlinelibrary.com). at low deformation rates, specifically the temperature
C 2012 Society of Plastics Engineers
V dependence of viscosity [8, 9]. The factors that the
using TA Universal Analysis software at heating rates of properties [27]. Figure 1 shows the build setup and the
58C min21, 108C min21, and 208C min21. dimensions of the test pieces. There was a 6 mm layer
before the first sintered layer and 3 mm after the final
sintered layer. The tensile bars were built in the
Hot Stage Microscopy so-called YX direction on the build area, i.e. on the hori-
Hot stage microscopy was used as a practical measure- zontal plane of the bed, with the long dimension of the
ment of the coalescence of PA-12 powder particles to test piece in the Y-direction.
complement the predicted sintering onset position. A Laser power (between 6 and 25 W) was chosen to be the
Leica light microscope with a dynamic heating rate primary variable between the test specimens. Sets of seven
program between 408C and 2208C at 10 8C min21 was tensile bars were built at each power setting, five of which
used to observe the behavior of a thin layer of polymer were used for testing. Table 1 shows the machine parameters
particles on a glass slide. used during the build. The power parameters were random-
ized throughout the individual layers of the build.
region resulting from the two analytical techniques (DSC, Procedure to Determine Laser Sintering Parameters
TGA) is shown in Fig. 6. Using EMR
The EMR [10] was used as a conduit between the Kis-
TGA Kissinger Method Calculation singer TGA data and the physical settings for the laser
Thermal analysis data from TGA were analyzed using sintering machine. The following steps outline the proce-
the Kissinger method, applied to PA12 at various heating dure developed to predict machine settings that would
rates. The key data points that were necessary to perform induce degradation and quantify the upper limit of the sta-
the calculation are highlighted in Fig. 7. The temperature ble sintering region.
at which the maximum degradation occurred, identified EMR is obtained from practical energy density data,
by the derivative mass loss data, was identified for each relative to the theoretical amount of thermal energy
of the heating rates. The Tmax values for the three heat- required to melt a given layer of polymer within the sin-
ing rates are shown in Table 2. Figure 10 shows the re- tering process. The first step is to determine the energy
sultant Kissinger plot for PA-12. The gel permeation density corresponding to degradation onset as determined
chromatography (GPC) molecular weight data are shown by TGA (Eq. 12). Table 3 shows the values needed for
in Fig. 9 and were used to convert the Kissinger result the calculations where TDegOnset, EA, Mw are the
of 279.5 kJ mol21 to a value of 0.014 kJ g21. temperature for degradation onset, activation energy, and
molecular weight, respectively. The EMR corresponding to degradation was 6.2. This
predicted EMR was then used to determine the machine
EA parameters (laser power, scan spacing, layer thickness,
EDeg ¼ TDegOneset Tm Cp þ Q (12)
Mw and beam speed) that would induce degradation in the
material. The only variable that was changed for the laser
Therefore: sintering builds was laser power. The scan spacing, beam
speed, layer thickness, and scan count were all kept con-
j stant and their values are shown in Table 5. Scan count is
EDeg ¼ 0:43 defined as the number of times the laser scans a given
mm3
section. This was held to one pass.
Next, the energy required to melt a single layer of PA-
12 powder was calculated according to the denominator
of the EMR equation. Table 4 includes the relevant varia- Calculating Machine Parameters at Degradation EMR
bles that are necessary for Eq. 13 where Em is the energy
required to melt a layer of material and F is the packing
density. PS
ðEMRD ÞðEm Þ ¼ (15)
y VB z
Em ¼ Cp ðTm Tb Þ þ hf ðQÞðUÞ
(13)
Em ¼ 0:069
P31
ð6:2Þð0:069Þ ¼
An EMR required for degradation is obtained by divid- ð2500Þ3ð0:1Þ30:20
ing Eq. 12 by Eq. 13.
TABLE 3. Physical parameters for determination of degradation
ED 0:43 energy.
EMRD ¼ ¼ ¼ 6:2 (14)
Em 0:069
EDeg J mm23
TABLE 2. Kissinger data points for PA-12 TGA.
Em J mm23
Tb 172 8C
Tm 185 8C
Cp 3250 J kg21 K21
hf 97.2 J g21
F 0.5 Dimensionless
q 0.97 g cm23
DISCUSSION
The tensile data have shown that there are plateaus and
declines in the mechanical properties that are consistent
P W
S 1 Dimensionless
Y 0.20 mm
Vb 2500 mm s21
Z 0.1 mm
FIG. 9. Molecular weight distribution for PA-12 using GPC.
to affect properties. However, based on the tensile data the reported approach is that through a set of analytical
above, the critical EMR might be close to, but slightly tests on competitive materials (DSC, TGA, and GPC), it is
higher: around 6.38 EMR (or 22 W power). Utilizing the possible to specify a set of parameters that are close to the
method outlined in the previous sections, an EMR value values of property maxima. This could be beneficial not
of 6.38 at these specific laser sintering parameters would only for future development of materials, but also to allow
suggest a measurable TGA weight loss between 1 and optimum process parameters to be specified more exactly
1.25%. In commercial practice, it would be best most use- based upon measured physio-chemical properties of the
ful for users to maintain energy input values just below polymers. Laser sintering can be quite time consuming due
the critical point of degradation from input of the laser. to long warm up and cool down times and this can limit
The small discrepancy in degradation point could be due the amount of materials development that is possible on a
to several reasons including thermal inefficiency, such single machine, thus restricting the commercial potential of
that the total amount of energy imparted by the laser is the process to some extent. In the current study, it is also
only partially absorbed by the polymer. noted that PA-12’s large super cooling window enables a
Laser sintering is a difficult process on which to predict significant range of energy inputs to be tested, which might
exact outcomes, based on a complex set of independent but be difficult to recreate with materials that have a small
interactive variables and some inherent differences from super-cooling process windows that tend to curl or crash
machine to machine. However, one of the main benefits of builds when large temperature differences are introduced
FIG. 11. PA-12 tensile properties data: tensile strength. FIG. 12. PA-12 tensile properties data: elongation at break.