Analyzing the Microstructure and Mechanical Properties of Different Types of PLA By Using

3D Printing Design with Annealing Method.

Hatra Wimana Mulyono
School of Materials Science and Engineering
Washington State University
Pullman, Washington, 99163, USA
Abstract:
This experiment is studying about the mechanical properties of polymers and the
crystallization of the polymer especially in poly (lactic acid) or polylactide (PLA) by
using of 3D printing design. Then annealing is a method which changes the
properties and microstructure of the polymer sample becoming stronger polymer.
Introduction:
Poly (lactic acid) or polylactide (PLA) is a polymer material that extensively
researched and utilized biodegradable and renewable aliphatic polyester where
proven to replace the conventional petrochemical based polymer for industrial as a
biomaterial in medicine [1]. Therefore, it also an aliphatic polyester, moreover, PLA
[ ( C3 H 4 O2 ) ¿ ¿ n]¿ is the first melt-processable natural-based fiber [2]. In addition, it
has helical structure, and it is a synthetic polymer based on lactic acid (C 3 H 6 O3 ).
Therefore, PLA is one of the most promising bio-polymers since the fact that the
monomers maybe produced from non-toxic renewable feedstock as well as to be a
naturally being an organic acid (Anderson, 2016).
In addition, PLA was synthesized in 1932 by Carothers where he is the only one to
be able produce a low molecular weight PLA by heating lactic acid by under the
vacuum while removing the condensed of water (H 2 O) [3]. However, PLA can be
arranged by using different polymerization processes from lactic acid such as
polycondensation, ring opening polymerization, direct methods such as azeotopic
dehydration and enzymatic polymerization [4]. Nevertheless, the method that
currently used are direct polymerization and ring opening polymerization techniques.
Other than process and methods how PLA made, there are some advantages why
PLA better while compare with other biopolymers. First, PLA is Eco-friendly since
the materials made from renewable source such as corn, wheat, or rice. Second, PLA
is biodegradable materials which recyclable and compostable. Then the production
sums carbon dioxide. Third, this material is biocompatibility which is the most
attractive aspect of PLA, especially with respect to biomedical application. In
addition, a biocompatible material will not produce toxic and carcinogenic effects in
local tissues. Then the degradation products will not restrict when the tissue is
healing. Nevertheless, FDA approved PLA for direct contacting with biological
fluids [5]. Fourth, the processability of PLA has better thermal condition when
 compared with other biopolymers such as poly(hydroxyl alkanoate) (PHA),
poly(ethylene glycol) (PEG), and poly(γ-caprolactone) (PCL) [6]. Fifth, PLA
requires 25%-55% less energy to produce petroleum-based polymers, and it
estimates that it can reduces another 10% in future [7]. The lower energy gives some
advantageous such as reduce the cost.
In addition, PLA has poor toughness which it is an exceedingly brittle material with
less than 10% elongation at break. Nevertheless, the tensile stress and elastic
modulus of PLA is lower than poly(ethylene terephthalate), the toughness limit is
used for the application which needed in the plastic deformation at high stress level
[8]. Therefore, PLA is degrading through the hydrolysis of the backbone ester
groups, and it degradations is depending on the crystallinity, Molar weight and its
distribution, morphology, water diffusion rate into polymer, and stereoisomeric
content [9]. The rate of slow degradation rate will bring a long time by in vivo life
time, which will be up to 3 through 5 years. Then PLA relatively hydrophobic
materials with approximately 80 ° C of water contact. As a result, PLA in low cell
affinity and can elicit in some cases such as an inflammatory response from the
living host upon direct contact with biological fluids.
3D printer is a tool to create the PLA polymers, and it was founded in 1986 with
Charles “Chuck” Hull, who has a patent the stereolithography machine which one of
the earliest 3D printers. In few year later in 1988, Scott Crump was invented the
fused deposition modeling (FDM) technology which is another technology in 3D
printing. However, 3D printing is changing in twenty years which evolve extremely
developed and utilized mostly by designers and engineers in business space [10].
In 2005, Dr. Gordon was started the RepRap project which is an open source
community, and his goal is making new 3D printing technologies which able to
access for all materials. In addition, the Bre Pettis, Adam Mayer, and Zach “Hoeken”
Smith was decided to make a market with new technology to the consumers. Then
they found MakerBot in 2009.
There is a term which is additive manufacturing which refers to the process of build a
product by adding many thin layers on it. Then there are three major additive
manufacturing in 3D printing such as Fused Deposition Modeling, Laser Sintering
Platform, and ZPrinter Platform.
In addition, annealing heat treatment is one of the methods to improve the
performance of 3D printing samples. Then it is a process that heating the polymer
samples at a temperature lower than the melting temperature and held at the
temperature for a given time before slowly cooling to room temperature [11].
Materials and Method:
This experiment is aiming the polymers properties and characterization by using
three different poly (lactic acid) or polylactide (PLA) by using tensile test and
 annealing method. Then there are two treated sample with annealing method with
temperatures 100 ° C and 150 ° C for 60 minutes. Therefore, it also determines the
microstructure of the PLA. Furthermore, a PLA was breaking by the tensile test to
get the value of the shear and strain of the materials which will give by the shear-
strain diagram. While the sample tested, the data such as load, deformation,
elongation, and so on was recording in a computer After the tensile test were done,
PLA was slice by using exato-knife with extremely thin layer to analyze. However,
the materials are supposed to be put in the specimen (glass slide) to make an
observation. After the materials were ready and prepared, PLA will analyze by using
the Leica or Zeiss microscope to get a picture of the filament of the material to get a
perfect suggestion of the microstructure. Then the last thing is taking a picture of the
breaking point of PLA to determine how the specimen break. (need to revise)
Results:
All the specimen which PLA are annealed with 100 ° C and 150 ° C will show as a
figure 1 and 2 by using 10x and 20x magnification.

Figure 1: a) PLA 100 ° C sample with 10x magnification. b) PLA 100 ° C sample with 20x magnification.

(a) (b)
(a) (b)
According to the technical error in the Leica microscope, all specimens that annealed
are hard to determine the type of crystallization. However, it still noticeable to
determine, so, the type of crystallization of PLA is amorphous semi-crystallization.
In addition, the properties of the specimen could determine by using tensile stress test
which data can be given in diagram 1, 2, and 3.

Shear-Strain Diagram for PLA Printed

35

30

25

20
Shear (MPa)

15

10

0
-0.01 0 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08
-5
Strain (mm/mm)

Diagram 1: Shear-Strain Diagram for Printed PLA

Shear-Strain Diagram of 150˚C PLA

40
35
30
25
Shear (MPa)

20
15
10
5
0
0 0.005 0.01 0.015 0.02 0.025 0.03
-5
Strain (mm/mm)

Diagram 2: Shear-Strain Diagram for 150 ° C PLA

 Shear-Strain Diagram of 100˚C PLA
40
35
30
25
Shear (MPa)

20
15
10
5
0
-0.01 0 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09
-5
Strain (mm/mm)

Diagram 3: Shear-Strain Diagram of 100 ° C of PLA

Therefore, each of the specimen has different mechanical properties result which will
given in table 1.
Table 1: Mechanical properties of three different PLA samples.

Young Ultimate Tensile Yield Resilienc Toughnes

Modulus Strength Strength e s
GPa MPa MPa
PLA 31.9950672
2.27 32.11617633 0.2107 1.077
Printed 7
33.6722460
150 PLA 2.69 33.83243549 0.2108 0.369341
2
33.6948815
100 PLA 2.11 34.92943791 0.2695 2.01
2

These result is coming from the data that obtianed during the experiment. Then there
are bunch of data that show, but it chosen by three different data such as PLA
printed-1, PLA 150-Hino, and PLA 100-2.
Discussion:
According to figure 1 and figure 2, the crystalline of the specimen are amorphous
semi-crystalline even though it was hard to determine since there is a technical error
with the Leica and Zeiss microscope. Therefore, the annealed samples is more darker
while comparing with the untreated sample (Printed PLA). Nevertheless, by this
samples, it has some collections of crystalline structures, and the cooling processes is
uneven in the surface.
Therefore, the differences of the PLA that annealed with 100 ° C and 150 ° C is the
grain which 150 ° C has more bigger grain rather than the 100 ° C . By that meaning,
since the annealing temperature getting higher, so, the grain and microstructure
getting larger. Nevertheless, annealing process is creating some greater and
undeviating crystal structures in polymer. In addition, figure 3 will explain about the
breaking point of the sample, the grain of the broken sample was streetch which
means the sample was pulled from both of ways which indicating that there is a
tension before it breaks.
Furthermore, diagram 1, 2, and 3 are explaining the different mechanical properties
of each sample, and the result is refer into table 1. Then each data has different shear-
stress diagram which shows that all samples which untreated and treated (annealing)
with different temperatures give a different results.
There are some various properties which have to calculate such as Young modulus,
ultimate stregnth, yield strength, resilince, and toughness. To calculate Young
modulus, the elastic region must be determine with the linear trendline, and the line
is will have a slope which is y=mx+b, where m is the slope of the line. Therefore, the
units of the Young modulus is going to be a Giga pascal (GPa). Thus, the result will
make some conversion from Mega pascal (MPa) to GPa since it’s a universal unit. In
addition, the ultimate strength is the maximum stress value in each diagram and the
unit is MPa. Then to find a yield strength by using 0.002 offset which has to a
parallel line with the elastic region range line. Then the unit of yield strength is going
to be MPa. Resilence is when the stress σ reaches the proportional limit since the
strain-energy density [12]. Then the toughness is another properties which represents
the whole area under the curve. Therefore, it designates the strain-energy density of
the material just before the fractures, and it also important when designing a material
which probably accidentally overloaded [12].
According to table 1, the value of the modulus between three samples are different
where untreated specimen has close enough value with 100 ° C annealing PLA which
are 2.27 Gpa for untreated specimen and 2.11 Gpa for 100 ° C annealing PLA.
Moreover, 150 ° C annealing process has the highest value of the young’s modulus.
In addition, the ultimate strength is inreasing for the specimen such as the printed
PLA and 100 ° C annealing PLA such as 32.11 MPa and34.92 MPa, however, when
it reaches 150 ° C annealing process, the ultimate strength is decreasing to be 33.83
MPa which affect the toughness of the specimen. Furthermore, the yield strength
from those material are increasing from the printed PLA into 100 ° C annealing PLA
 which are 31.99 MPa and 33.69 MPa. However, its values is decreasing while it
reach the 150 ° C annealing process, and the value is 33.67 MPa. Nevertheless, the
resilince value of printed PLA is 0.2107 and 100 ° C annealing PLA is 0.2695 where
the value is increasing due to the annealing processes. Therefore, when it reaches
150 ° C annealing process the value was drop again to 0.2108. In addition, the
toughness is increasing for two samples such as the first sample and the third sample
such as from 1.07 for printed PLA and 2.01 for 100 ° C annealing PLA. Other than
that, the specimen two which is 150 ° C annealing PLA has the lowest toughness,
which means this specimen has the most brittle material for PLA even though it has
annealing process. Thus, from all the specimen data, annealing process is a process to
make a material more harder and stronger, meanwhile, when it reaches at 150 ° C , the
specimen is getting much brittle as data explains. In addition, all the PLA types are
brittle materials which does not have yielding before failure.

Conclusion:
To sum up, polymers materials are a brittle material such as poly (lactic acid)
polylactide (PLA). Therefore, one of the most important thing is annealing process
which makes the materials stronger and changes the microstructures, however, it will
make a specimen more brittle at some point. Furthermore, this process also make a
specimen to be better quality than before since polymer materials has extremely low
toughness, and it’s not strong enough to handle a huge load. In addition, 3D printing
has many benefits for polymers such as creating and designing the specimen every
each filament. Then by using annealing process, the polymers makes the specimen or
sample much more stronger.
Refrence:
1. S. Farah, et al., Physical and mechanical properties of PLA, and their functions in
widespread applications — A comprehensive review, Adv. Drug Deliv. Rev.
(2016), http://dx.doi.org/10.1016/j.addr.2016.06.012
2. J. S. Dugan, Novel Properties of PLA fi bers, Research Fiber Innovation technology,
Inc, INTC 2000, Texas, USA, http://www.fi tfi bers.com/publications.htm, 2000.
3. Avinc, Ozan, and Akbar Khoddami. “Overview of Poly(Lactic Acid) (PLA)
Fibre.” Fibre Chemistry, vol. 41, no. 6, 2009, pp. 391–401., doi:10.1007/s10692-
010-9213-z.
4. Handbook of Polymer Applications in Medicine and Medical DevicesPublished by
Elsevier Inc.©, 2014, http://dx.doi.org/10.1016/B978-0-323-22805-3.00003-7.
5. B. Gupta, N. Revagade, J. Hilborn, Prog. Polym. Sci. 32 (2007) 455–482.
6. R. Auras, B. Harte, S. Selke, Macromol. Biosci. 4 (2004) 835–864.
7. R.M. Rasal, A.V. Janorkar, D.E. Hirta, Prog. Polym. Sci. 35 (2010) 338–356.
8. S. Farah, K.R. Kunduru, A. Basu, A.J. Domb. Edition: 1st edition, Chapter: 8,
Publisher: Elsevier, Editors: P. M. Visakh, M. Liang, 2015, pp. 143–165.
9. A.V. Janorkar, A.T. Metters, D.E. Hirt, Macromolecules 37 (2004) 9151–9159.
10. Matias, Elizabeth, and Bharat Rao. “3D Printing: On Its Historical Evolution and the
Implications for Business.” 2015 Portland International Conference on Management
of Engineering and Technology (PICMET), 2015, pp. 551–558.,
doi:10.1109/picmet.2015.7273052.
11. Kamran, Medhavi, and Abhishek Saxena. “A Comprehensive Study on 3D Printing
Technology.” MIT International Journal of Mechanical Engineering, vol. 6, ser. 2,
Aug. 2016, pp. 63–69. 2.

12. Hibbeler, R C. Mechanics of Materials. Upper Saddle River, N.J: Pearson Education,
2003. Print.