ISSN 1063-7710, Acoustical Physics, 2023, Vol. 69, No. 4, pp. 442–447. © Pleiades Publishing, Ltd., 2023.

Russian Text © The Author(s), 2023, published in Akusticheskii Zhurnal, 2023, Vol. 69, No. 4, pp. 410–416.

NONLINEAR ACOUSTICS

Experimental Investigations of the Influence of 3D Printing at 100%

Filling on the Elastic Properties of PLA Polymer Filament Samples
A. B. Volodarskiia, A. I. Kokshaiskya, N. I. Odinaa, A. I. Korobova, *,
E. S. Mikhaleva, and N. V. Shirginaa
a Faculty of Physics, Moscow State University, Moscow, 119991 Russia
*e-mail: [email protected]
Received December 14, 2022; revised March 10, 2023; accepted March 16, 2023

Abstract—The article presents the results of experimental studies of how 3D printing with 100% filling influ-
ences the elastic properties of PLA filament polymer samples. The static and Thurston–Brugger methods
simultaneously measure the dependence of strain and the relative change in the velocity of elastic waves on
the applied mechanical stress (up to failure) for the initial and 3D-printed samples of the PLA polymer. Based
on the measurement results, the linear and nonlinear Young’s moduli and second-order acoustic nonlinear
parameter are calculated. It has been established that 3D printing leads to a deterioration in the strength and
plastic characteristics of PLA. A different behavior of the nonlinear parameters of the initial and 3D-printed
PLA samples in the loading and unloading region was revealed, associated with a change in the internal struc-
ture of the sample caused by 3D printing.

Keywords: PLA polymer, 3D printing, third-order elasticity coefficient, nonlinear elastic parameter
DOI: 10.1134/S1063771022600693

INTRODUCTION which allows printing 3D models from polymers using

layer-by-layer fusing [13, 14]. A wide selection of
In the last decade, the 3D printing of various mate- printable resins span a vast range of applications: they
rials has become increasingly popular; the technology are used to make flexible or rigid, UV- or acetone-
is actively used not only in laboratories and factories resistant products with an elevated softening point.
with high-precision and mass production, but also at Affordable printers and supplies are responsible for
the household level. 3D printing makes it possible to their widespread use in all applications not requiring
create novel composite samples, including metamate- increased precision or strength comparable to metals.
rials, from various materials, both polymers [1–5] and
metal alloys [6–8]. In the general sense, a 3D printer One of the thermoplastic polymers widely used in
is a computer-controlled machine that uses various 3D printing is PLA (polylactic acid, polylactide).
physical principles to manufacture a part [9]. We list Being nontoxic and having good mechanical proper-
the main types of 3D printing: SLA (stereolithogra- ties, PLA is used for the production of various compo-
phy, laser stereolithography) allows printing samples nents and objects in the food and medical industries,
from photopolymers with very high precision [10]. including biomedical devices [15–19].
SLA printers and supplies are affordable, which con- One important advantage of PLA is that it can be
tributes to their widespread use. A number of 3D- easily produced by FDM- using simple, low-cost
printing technologies, such as DMLS (direct metal commercial 3D printers. The mechanical properties of
laser sintering), SLS (selective laser sintering), and additively fabricated PLA are significantly affected by
SLM (selective laser melting) use alloying or sintering both 3D-printing parameters—such as nozzle size,
of metals with high-power lasers [11]. Supplies and filling percentage and pattern, temperature and print-
printers for these types of printing are the cost-inten- ing speed [20, 21]—and chemical composition (e.g.,
sive on the market, so they are used mainly in labora- pigments introduced to manipulate color also affect
tories and for limited production of complex parts. the mechanical properties and crystallinity level of
These types of printing include EBM (electron beam PLA) [22].
melting), where a cathode-ray tube is used instead of a Numerous studies show that 3D printing signifi-
laser [12]. The scope of this type of printing is limited cantly alter the mechanical characteristics of PLA
to medical applications, aerospace fields, and small- [23–26]. Thus, if the yield strength of the initial cast
scale production of complex parts. The most common PLA can reach 60 MPa [23], then for 3D-printed
technology is FDM (fused deposition modeling), materials, the ultimate strength can significantly

442
 EXPERIMENTAL INVESTIGATIONS OF THE INFLUENCE OF 3D PRINTING 443

decrease (up to 50%) depending on the orientation of included mechanical (for generating mechanical ten-
the filling filaments [24–26]. sile stress) and ultrasonic parts. To measure the rela-
A comparison of the mechanical characteristics of tive change in velocity of elastic waves, an automated
3D-printed and cast PLA, measured by a static pulsed ultrasonic unit was used, developed on the
method, was made in [27]. It was found that for the basis of the Ritec RAM-5000 automated ultrasonic
investigated PLA samples, 3D printing leads to a sig- system. Piezoelectric transducers with a resonance
nificant decrease in tensile strength (from about 52 to frequency of 300 kHz were used to generate and
44 MPa), a decrease in the Young’s modulus (from receive longitudinal acoustic waves. The transducers
about 3.2 to 3 GPa), and yield strength (from about were attached with spring clamps to the ends of trun-
12.7 to 10.5 MPa); at the same time, the ultimate cated cones, in which the ends of the samples were
strain at failure, conversely, was slightly increased for fixed. To eliminate high-frequency components, the
printed samples (from 1.65 to 1.74%). probing signal was passed through a low-pass filter. A
specially developed software package with a graphics
Such a change in the mechanical properties results interface was used to control the course of the experi-
from the change in the microstructure of polymers ment and process the data obtained. It was installed on
caused by thermomechanical effects that occur during a personal computer, allowing simultaneous static and
3D printing: a texture appears, caused by the way the ultrasonic measurements with subsequent archiving
filament is laid; defects appear due to the filament and processing.
characteristics and imperfect adhesion and porosity in
the absence of degassing [27]; and the ratio of crystal- For research, two PLA samples were made. The
line and amorphous phases may change or ordered first (hereinafter referred to as the initial sample) was
substructures may appear [23]. cut from a filament of eSun commercial PLA without
further heat or other treatment. It had the shape of a
Earlier, linear acoustic methods were used to study thin cylinder with length L = 121.7 mm and diameter
the glass transition [28] and degradation [29] of PLA- D = 1.7 mm.
based polymers. In [30], the linear acoustic properties
of 3D-printed samples of eight commercially available The second (hereinafter referred to as the printed
thermoplastic polymers were studied, including PLA. sample) was 3D-printed from the same filament. It
The damping coefficient and sound speed were mea- had the shape of a thin rectangular prism with a length
sured by standard echo-pulse methods for reflection of 118 mm and a base in the shape of a regular hexagon
and transmittance, and the acoustic impedance was with side lengths of 1.05 mm. Printing was done by
calculated. layer-by-layer fusing on a customized 3D printer, with
parameters similar to the 3DQ Mini model, at a tem-
Nonlinear acoustic methods for studying PLA- perature of 160°C, 100% filling, and a nozzle diameter
based polymers were used in [23]. The harmonic gen- of 0.05 mm; the filament was oriented along the long
eration method was used to measure the third-order axis of the prism.
nonlinear acoustic parameter during flexural strain of From the measurement results, both the linear
PLA samples subjected to chemical and physical (linear Young’s modulus E) and nonlinear (nonlinear
impacts. It has been established that the change in the Young’s modulus EN and second-order nonlinear
nonlinear acoustic parameter is most greatly influ-
enced by introduction of an impurity, as well as all the parameter N) elastic parameters for filament samples
combined processing methods used. of both the initial eSun PLA sample and 3D-printed
PLA sample from the initial material were calculated
This article presents the results of experimental by the method described in [31].
studies, using ultrasonic and static methods, of how The linear Young’s modulus (second-order elastic-
3D printing affects the linear and nonlinear elastic ity coefficient) E was determined from the mechanical
properties of filament samples of eSun brand PLA. We stress–strain loading curve by the formula
studied both the linear (using the static method, i.e.,
from the loading curve “mechanical stress/σ-strain ε E = Δσ . (1)
up to failure”) and nonlinear (using the modified Δε
Thurston–Brugger method, which measures the The nonlinear Young’s modulus (third-order elas-
dependence of the relative change in velocity of elastic ticity coefficient) EN was determined from the depen-
waves in a sample on the mechanical tensile stress dence of the relative change in velocity on the applied
applied to it) elastic properties of PLA samples. mechanical stress by the formula

EXPERIMENTAL ( )
E N = 2E ΔV .
Δεst V
(2)
The authors of [31] describe in detail the auto- The acoustic second-order nonlinear parameter N
mated setup used to simultaneously measure, using is calculated by the formula
the static and Thurston–Brugger methods, the depen-
dence of the strain and relative change in velocity of EN
N = . (3)
elastic waves on the applied mechanical stress. It E
ACOUSTICAL PHYSICS Vol. 69 No. 4 2023
444 VOLODARSKII et al.

45 (а) (b)
45
40 40
35 35
30 30
V, МPа

V, МPа
25 25
20 20
15 15
10 10
5 5

0 0.005 0.010 0.015 0.020 0.025 0.030 0 0.005 0.010 0.015 0.020 0.025 0.030
H H

Fig. 1. Experimentally measured loading curve σ(ε) for (a) initial and (b) 3D-printed PLA samples.

RESULTS AND DISCUSSION cycles are given in Table. 2; clearly, the Young’s mod-
As a result of the series of experiments, information uli of both the initial and printed samples slightly
was obtained on the linear and nonlinear elastic prop- increase when the samples are loaded, which can be
erties of the studied samples of the initial and 3D- explained by their hardening. In the first loading–
printed PLA samples and how they were impacted by unloading cycle, in the linear region of the loading
the periodic processes of mechanical loading– curve, the difference between the Young’s modulus of
unloading cycles. Each experiment lasted 4.5 h in the initial and printed samples is on the order of the
total, so the loading process can be considered close to measurement error. In the second loading–unloading
quasi-static. cycle, which already went beyond the linear region,
the initial and printed sample behave differently: the
The results of measuring the stress–strain σ = σ(ε) Young’s modulus of the initial sample remains almost
dependence in the studied samples for 2.5 cycles of unchanged, while the printed one decreases slightly
periodic change in the applied mechanical stress are
after loading.
shown in Fig. 1 for the (a) initial and (b) 3D-printed
samples. For every loading–unloading cycle, an insig- During the experiment, simultaneously with mea-
nificant hysteresis dependence σ = σ(ε) was observed. surement of the loading curve σ(ε), we measured the
After the first cycle, the residual strains were ε ∼ dependences of the relative change in velocity of the
0.0010 ± 0.0003 for the initial and ε ∼ 0.0003 ± 0.0003 longitudinal elastic wave (ΔV/V) in the sample on its
for the printed sample; after the second, ε ∼ 0.0019 ± static deformation εst during loading–unloading,
0.0003 for the initial and ε ∼ 0.0014 ± 0.0003 for the which are plotted in Fig. 3.
printed sample.
The experimental measurements of the stress– It can be seen that for small strains (up to 0.01), the
strain dependence made it possible to determine the dependence of the relative change in velocity of elastic
mechanical characteristics of the studied samples waves on strain under loading–unloading of samples
(yield strength, residual strain at failure, and the is close to linear. This made it possible to calculate the
Young’s modulus). The Young’s modulus was deter- third-order Young’s moduli using formula (2) by the
mined on the linear segments of the loading curves LSM. Figure 4 shows an example of approximation of
according to the method described in [31]. Table 1 the linear part of the dependence of the relative change
presents the mechanical parameter values for the ini- in velocity on strain for the first loading–unloading
tial and 3D-printed PLA samples calculated from the cycle for the initial and printed samples. Note that the
experimental data; clearly, the mechanical properties different behavior of the relative change in sound
of the printed PLA sample deteriorated somewhat: it speed during loading and unloading can already be
has a slightly lower tensile strength and lower residual seen after the first loading cycle.
strain at failure.
According to formula (1), the linear Young’s mod-
uli were calculated in both studied samples during Table 1. Strength and plasticity characteristics of initial and
3D-printed PLA samples
loading and unloading. The linear part of the second
load–unload cycle, which was used to calculate the Initial 3D-printed
Young’s modulus by the least squares method, is
shown in Fig. 2. Young’s modulus, GPa 2.6 ± 0.1 2.7 ± 0.1
Table 2 presents the linear Young’s moduli in the Tensile strength, MPa 44 ± 1 40 ± 1
studied PLA samples for all loading and unloading Strain at failure, % 2.9 ± 0.1 2.3 ± 0.1

ACOUSTICAL PHYSICS Vol. 69 No. 4 2023

 EXPERIMENTAL INVESTIGATIONS OF THE INFLUENCE OF 3D PRINTING 445

10 (а) (b)
12
9 Initial
10 Initial
8 Printed
Printed
7
8
V, МPа

V, МPа
6
5 6
4
3 4
2 2
1
0
0 0.0005 0.0015 0.0025 0.0035 0.0045 0 0.001 0.002 0.003 0.004 0.005 0.006
H H

Fig. 2. Experimentally measured loading curves σ(ε) for second cycle under (a) loading and (b) unloading of initial and 3D-
printed PLA samples.

(а) (b)
0.035 0.035
0.030 0.030
0.025 0.025
0.020 0.020
'V/V

'V/V

0.015 0.015
0.010 0.010
0.005 0.005

0 0.002 0.004 0.006 0.008 0.010 0 0.002 0.004 0.006 0.008 0.010
H H

Fig. 3. Experimentally measured dependences of relative change in longitudinal wave velocity on static strain for (a) initial and
(b) 3D-printed PLA samples.

The third-order elasticity coefficients for all load- parameter N using formula (3); the values are pre-
ing–unloading cycles are presented in Table 3; clearly, sented in Table 4; the nonlinear parameter for both the
loading of both the initial and printed samples initial and printed samples behaves nonmonotonically
increases the nonlinear Young’s modulus, and this under loading. However, the nonlinear parameter of
growth is approximately the same for the initial and the initial sample increases strongly after the first
printed samples. However, whereas the nonlinear loading, then changes weakly. The nonlinear parame-
Young’s modulus of the initial sample increases ter of the printed sample increases both during the first
almost monotonically, its behavior for the 3D-printed and second loading and decreases during the second
sample is nonmonotonic: it increases somewhat in the unloading, which can be attributed to the difference in
loading region and decreases in the unloading region. the internal structure of the initial and 3D-printed
Using the obtained second- and third-order elas- samples.
ticity coefficients, we calculated acoustic nonlinear
In the literature, we have found no data on the
absolute value of the nonlinear parameter PLA. In the
Table 2. Linear Young’s modulus of initial and 3D-printed authors' previous article on determining the elastic
PLA samples during loading and unloading moduli and nonlinear parameter of PLA samples [31],
Young’s modulus, GPa Initial 3D-printed an error was made when calculating the relative
change in the sound speed, which led to a significant
First cycle, loading 2.6 ± 0.1 2.7 ± 0.1 underestimation of the absolute values of the nonlin-
First cycle, unloading 2.7 ± 0.1 2.8 ± 0.1 ear elastic modulus and nonlinear parameter. The cor-
Second cycle, loading 3.0 ± 0.1 2.9 ± 0.1 rected values of the nonlinear parameter are given in
[32] and range from 5.0 ± 0.4 to 5.9 ± 0.5 in a compa-
Second cycle, unloading 3.0 ± 0.1 2.7 ± 0.1
rable strain range, which is close to the values obtained
Third cycle, loading 3.1 ± 0.1 3.2 ± 0.1 in this study within the error limit. The slight differ-

ACOUSTICAL PHYSICS Vol. 69 No. 4 2023

446 VOLODARSKII et al.

(а) (b)
0.012 0.012
Initial
0.010 Initial 0.010 Printed
Printed
0.008 0.008
'V/V

'V/V
0.006 0.006
0.004 0.004
0.002 0.002
0
0 0.001 0.002 0.003 0.004 0.005 0 0.0005 0.0015 0.0025 0.0035 0.0045
H H

Fig. 4. Experimentally measured dependences of relative change in longitudinal wave velocity on static strain for first cycle under
(a) loading and (b) unloading of initial and 3D-printed PLA samples.

ence may be due to aging of the second sample, which Thus, we can conclude that the value of the nonlinear
was examined 2 years later. parameter of the polymer varies depending on which part
The mean values of the nonlinear parameter B/A of the loading curve it is measured. This can be applied to
for a number of polymers (polystyrene, acrylic, poly- nonlinear acoustic testing of loaded polymers.
ethylene terephthalate, polyvinyl chloride, and poly-
carbonate), measured by focused ultrasound, reach
9–11 [33]. The behavior of the nonlinear parameter CONCLUSIONS
under mechanical loading of polypropylene was stud-
ied in [34]. In the initial area of stretching of pure We have experimentally studied how 3D printing
polypropylene, its nonlinear second-order parameter with 100% filling influences the mechanical, linear,
∂V ( ε ) and nonlinear elastic parameters of a sample of eSun
− V behaved nonmonotonically: in the linear industrial PLA.
∂ε
part, it dropped from 7.5 to 5; when it reached the ini- For the 3D-printed PLA sample, a decrease in ten-
tial stage of the plastic region, it again increased to 7.5, sile strength of about 10% and a decrease in residual
and with further stretching, it again began to decrease. strain at failure of ~20% were revealed.
It has been established that periodic loading–
Table 3. Third-order elasticity coefficients of initial and unloading of a sample insignificantly increases the
3D-printed PLA samples under loading–unloading
Young’s modulus E for both the initial and printed
Third-order elasticity samples.
Initial 3D-printed
coefficients, GPa
A nonmonotonic behavior of the nonlinear elastic
First cycle, loading 14.4 ± 0.7 14.6 ± 0.7 modulus and nonlinear parameter under loading was
First cycle, unloading 19.0 ± 0.9 16.9 ± 0.8 revealed, the nature of which differs for the initial and
Second cycle, loading 18.8 ± 0.9 19.7 ± 0.9 printed samples. This difference is associated with the
Second cycle, unloading 20 ± 1 16.2 ± 0.8 difference in the internal structure of the initial and
3D-printed samples.
Third cycle, loading 21 ± 1 22 ± 1
The results provide information on how 3D print-
ing with 100% filling impacts the mechanical, linear,
Table 4. Nonlinear acoustic parameter of initial and 3D- and nonlinear elastic properties of PLA and can be
printed PLA samples under loading–unloading used to create samples of composites and metamateri-
Nonlinear acoustic als in 3D printing; they can also serve as a basis for
Initial 3D-printed developing for nonlinear acoustic control methods for
parameter
loaded polymers.
First cycle, loading 5.5 ± 0.4 5.4 ± 0.4
First cycle, unloading 7.0 ± 0.6 6.0 ± 0.5
Second cycle, loading 6.3 ± 0.5 6.8 ± 0.5 FUNDING
Second cycle, unloading 6.7 ± 0.5 6.1 ± 0.5 The study was supported by a grant from the Russian
Third cycle, loading 6.8 ± 0.5 6.9 ± 0.5 Science Foundation (project no. 19-12-00098).

ACOUSTICAL PHYSICS Vol. 69 No. 4 2023

 EXPERIMENTAL INVESTIGATIONS OF THE INFLUENCE OF 3D PRINTING 447

REFERENCES 16. T. Nakatsuka, Fujikura Tech. Rev., p. 39 (2011).

1. C. Schumacher, B. Bickel, J. Rys, S. Marschner, 17. S. Farah, D. G. Anderson, and R. Langer, Adv. Drug
C. Daraio, and M. Gross, ACM Trans. Graph. 34, Delivery 107, 367 (2016).
136:1 (2015). 18. F. L. La Mantia and M. Morreale, Appl. Sci. Manuf.
2. J. Cantrell, S. Rohde, D. Damiani, R. Gurnani, 42, 579 (2011).
L. DiSandro, J. Anton, A. Young, A. Jerez, D. Stein- 19. K. Hamad, M. Kaseem, M. Ayyoob, J. Joo, and
bach, C. Kroese, and P. Ifju, Adv. Opt. Methods Exp. F. Deri, Progr. Polym. Sci. 85, 83 (2018).
Mech. 3, 89 (2017). 20. J. de Ciurana, L. Serenó, and E. Vallès, Procedia CIRP
3. Y. Kao, Y. Zhang, J. Wang, and B. L. Tai, J. Manuf. Sci. 5, 152 (2013).
Eng. 139, 041006 (2016). 21. M. Fernandez-Vicente, W. Calle, S. Ferrandiz, and
4. R. Zou, Y. Xia, S. Liu, P. Hu, W. Hou, Q. Hu, and A. Conejero, 3D Print. Addit. Manuf. 3, 183 (2016).
C. Shan, Compos. Eng. B 99, 506 (2016). 22. B. Wittbrodt and J. M. Pearce, Addit. Manuf. 8, 110
5. V. A. Boshnyak and A. V. Yazykov, Nauka Obraz. (2015).
MGTU im. N. E. Baumana, No. 12, 311 (2016). 23. G. Zhao, F. P. C. Gomes, H. Marway, M. R. Thomp-
6. J. H. Martin, B. D. Yahata, J. M. Hundley, J. A. Mayer, son, and Zh. Zhu, Macromol. Chem. Phys. 221,
T. A. Schaedler, and T. M. Pollock, Nature 549, 365 1900475 (2020).
(2017). 24. A. Lanzotti, M. Grasso, G. Staiano, and M. Martorelli,
7. C. Ma, Y. Dong, and C. Ye, Procedia CIRP 45, 319 Rapid Prototyping J. 21, 604 (2015).
(2016). 25. M. F. Afrose, S. H. Masood, P. Iovenitti, M. Nikzad,
8. C. Schulze, M. Weinmann, C. Schweigel, O. Keßler, and I. Sbarski, Progr. Addit. Manuf. 1, 21 (2016).
and R. Bader, Materials (Basel) 11, 13 (2018). 26. A. A. Ahmed and L. Susmel, Procedia Struct. Integr. 3,
9. Yu. A. Lantsova and T. G. Pavlenko, in Proc. 11th All- 407 (2017).
Russian Youth Conf. for Young Scientists, Students and 27. C. Oztan, R. Karkkainen, M. Fittipaldi, G. Nygren,
Scholars with International Participation Physics and L. Roberson, M. Lane, and E. Celik, J. Compos. Ma-
Modern Technologies in Agroindustrial Complex, Orel, ter. 53, 271 (2019).
Feb. 19, 2020 (Kartush, Orel, 2020), p. 45 [in Russian]. 28. N. Parker, M. L. Mather, S. P. Morgan, and M. J. Pov-
10. J. Wang, A. Goyanes, S. Gaisford, and A. W. Basit, Int. ey, Biomed. Mater. 5, 055004 (2010).
J. Pharm. 503, 207 (2016). 29. H.-C. Wua, F.-W. Shenb, X. Honga, W. V. Changa, and
11. B. Msallem, N. Sharma, S. Cao, F. S. Halbeisen, H. Winet, Biomaterials 24, 3871 (2003).
H. F. Zeilhofer, and F. M. Thieringer, J. Clin. Med. 9, 30. A. Antoniou, N. Evripidou, M. Giannakou, G. Con-
817 (2020). stantinides, and C. Damianou, J. Acoust. Soc. Am.
12. L. E. Murr, E. Martinez, K. N. Amato, S. M. Gaytan, 149, 2854 (2021).
J. Hernandez, D. A. Ramirez, P. W. Shindo, F. M. Ry- 31. A. I. Korobov, A. I. Kokshaiskii, E. S. Mikhalev,
an, and R. B. Wicker, J. Mater. Res. Technol. 1, 42 N. I. Odina, and N. V. Shirgina, Acoust. Phys. 67 (4),
(2012). 375 (2021).
13. M. Doshi, A. Mahale, S. K. Singh, and S. Deshmukh, 32. A. I. Korobov, A. I. Kokshaiskii, E. S. Mikhalev,
Mater. Today: Proc. 50, 2269 (2021). N. I. Odina, and N. V. Shirgina, Akust. Zh. 69 (2023)
14. S. Wickramasinghe, T. Do, and P. Tran, Polymers 12, (in press).
1529 (2020). 33. S. Saito, AIP Conf. Proc. 1022, 561 (2008).
15. L. T. Lim, R. Auras, and M. Rubino, Prog. Polym. Sci. 34. I. Solodov, K. Pfleiderer, H. Gerhard, and G. Busse,
33, 820 (2008). Ultrasonics 42, 1011 (2004).

ACOUSTICAL PHYSICS Vol. 69 No. 4 2023