inventions
Article
Deterioration of the Mechanical Properties of FFF 3D-Printed
PLA Structures
Asahi Yonezawa 1 and Akira Yamada 1,2, *






Citation: Yonezawa, A.; Yamada, A.
Deterioration of the Mechanical
Properties of FFF 3D-Printed PLA
Structures. Inventions 2021, 6, 1. https://
dx.doi.org/10.3390/inventions6010001
Received: 9 November 2020
Accepted: 19 December 2020
Published: 22 December 2020
Publisher’s Note: MDPI stays neu-
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Inventions 2021, 6, 1. https://dx.doi.org/10.3390/inventions6010001
1 Department of Mechanical Engineering, Graduate School of Engineering, Aichi Institute of Technology,
1247 Yachigusa, Yakusa-cho, Toyota-city, Aichi 470-0392, Japan; p19718pp@aitech.ac.jp
2 Department of Mechanical Engineering, Faculty of Engineering, Aichi Institute of Technology,
1247 Yachigusa, Yakusa-cho, Toyota-city, Aichi 470-0392, Japan
* Correspondence: a-yamada@aitech.ac.jp; Tel.: +81-565-48-8121 (ext. 2326)
Abstract: Poly(lactic acid) (PLA) is a biodegradable polymer material used for the fabrication of
objects by fused filament fabrication (FFF) 3D printing. FFF 3D printing technology has been quickly
spreading over the past few years. An FFF-3D-printed object is formed from melted polymer
extruded from a nozzle layer-by-layer. The mechanical properties of the object, and the changes in
those properties as the object degrades, differ from the properties and changes observed in bulk
objects. In this study we evaluated FFF-3D-printed objects by uniaxial tensile tests and four-point
flexural tests to characterize the changes of three mechanical properties, namely, the maximum stress,
elastic modulus, and breaking energy. Eight types of test pieces printed directly by an FFF 3D printer
using two scan patterns and two interior fill percentages (IFPs) were tested by the aforesaid methods.
The test pieces were immersed in saline and kept in an incubator at 37 ◦ C for 30, 60, or 90 days
before the mechanical testing. The changes in the mechanical properties differed largely between
the test piece types. In some of the test pieces, transient increases in strength were observed before
the immersion degraded the strength. Several of the test piece types were found to have superior
specific strength in the tests. The results obtained in this research will be helpful for the design of
PLA structures fabricated by FFF 3D printing.
Keywords: poly(lactic acid) (PLA); fused filament fabrication (FFF); 3D printer; mechanical property;
strength; tensile test; flexural test; deterioration
1. Introduction
Poly(lactic acid) (PLA), a biodegradable polymer derived from plants such as corn and
cassava, is one of the most widely applied materials in its class [1–6]. PLA can be formed
into decomposable products such as packaging materials or medical devices [2,3,7–15].
The mechanical properties of PLA structures processed by injection molding (IM) deteri-
orate by hydrolysis when exposed to moisture [5,7,16–18]. Though PLA is now widely
adopted as a filamentary material for fused filament fabrication (FFF) 3D printers [19–27],
few studies have examined how the mechanical properties of FFF-3D-printed PLA struc-
tures deteriorate [28,29].
An FFF 3D printer builds up objects by depositing melted polymer extruded from
a fine nozzle. The 3D objects printed by this method are designed using computer-aided
design (CAD) systems [30,31]. The nozzle of the 3D printer traces an XY plane based on
slice data, and repeats layer-by-layer. The structure is built up by a filament of a uniform
diameter, with some clearance left between neighboring filaments. The mechanical proper-
ties of the structure are therefore partly determined by an internal structure that can vary
according to the nozzle scan pattern used for the fabrication [31–37].
Understanding the mechanical properties of a material is important for the design
of objects. Tensile tests, flexural tests, and compression tests have been used to evaluate
the strengths of PLA structures fabricated both by IM [16] and by 3D-printing [32–37].
https://www.mdpi.com/journal/inventions
Inventions 2021, 6, 1 2 of 17

The deterioration of the mechanical properties is an essential factor to consider in the

design of a structure, if the strength is to be adequately maintained or controlled during the
structure’s lifetime. The strength deterioration of PLA formed by IM has been evaluated
by tensile tests [10,12,18,38] and flexural tests [10,39] for medical applications. While FFF-
3D-printed PLA structures are becoming essential components of medical devices and
environment-friendly products, the mechanical properties of 3D-printed structures so far
reported have yet to form a sufficient basis for design guidelines [28,29].
The deterioration rate of PLA depends on several immersion conditions, such as
the buffer used, the pH of the buffer solution, and the immersion temperature [29,40–42].
These conditions are difficult to compare in published studies, as they have varied among
test pieces and have only been partially described [40]. As a consequence, scanty data
have been obtained from tensile and flexural testing of test pieces prepared under uniform
fabrication and immersion conditions.
Our group previously performed uniaxial tensile tests on FFF-3D-printed PLA test
pieces to evaluate how the mechanical properties deteriorated after the test pieces were im-
mersed in saline for certain periods [28]. The tests evaluated test pieces printed using four
nozzle scan patterns with interior fill percentages (IFPs) set at 100%, for comparison with
data obtained on control test pieces produced by IM. The deterioration observed in the tests
varied according to the nozzle scan pattern used to print the test pieces. Flexural testing is
another important method for the mechanical testing of materials, along with assessments
of test piece failure. Yet few data have been reported on flexural tests to evaluate the
deterioration of FFF-3D-printed PLA structures. The IFP is a major fabrication parame-
ter, alongside the nozzle scan pattern, in FFF 3D printing. Experiments to compare the
mechanical properties of test pieces produced by different IFPs and nozzle scan patterns
are also furnishing useful data on how the responses of structures differ according to the
load direction.
In this study we used uniaxial tensile tests and four-point flexural tests to evaluate the
mechanical properties of a series of FFF-3D-printed test pieces formed from PLA. Most of
the conditions used to prepare the test pieces were the same, the exceptions being the
shapes, nozzle scan patterns, and IFPs. The structures were printed out using two different
scan patterns, namely, in parallel with the longitudinal direction (P.) and cross-hatched
at opposing diagonal angles to the longitudinal direction (C.) The IFPs were set at 100%
and 80% for the test pieces printed by each scan pattern. The test pieces were immersed
in saline for 30, 60, or 90 days. The following mechanical properties were examined: the
maximum tensile or flexural stress, the tensile or flexural modulus, and the tensile or
flexural breaking energy.

2. Materials and Methods

2.1. Test Piece Preparation
Two kinds of test pieces were prepared, one for tensile testing and the other for
flexural testing. Figure 1a,b shows the shapes and dimensions of the test pieces. The tensile
test piece (a) was formed in a flat-dumbbell shape and the flexural test piece (b) was
rectangular. Both were designed with a square section (3 × 3 mm) around the breakage
section. The dimensions of the tensile test piece were based on the ASTM D638 Type V
standard, with two modifications: reduction of the width from 3.18 to 3.0 mm to unify
the cross section with the flexural test piece, and reduction of the overall length from
63.5 mm to 30.0 mm to reduce the volume of the immersion solution. The model test
pieces were designed on a three-dimensional computer-aided design (3D-CAD) system
(AutoCAD, Autodesk Inc., Mill Valley, CA, USA) and the model data were output in
a standard triangulated language (STL) format. All of the test pieces were composed of
white, translucent, commercially available PLA (Waves, Osaka, Japan) with a filament
diameter of 1.75 mm, and printed with an FFF 3D printer (Lepton2, MagnaRecta Inc., Tokyo,
Japan) using slicing and controlling software (Simplify3D, Simplify3D LLC, Cincinnati,
OH, USA). The nozzle diameter, nozzle scan speed, nozzle temperature, modeling stage
onsInventions
2021, 6, x2021,
FOR 6, x FOR
PEER PEER REVIEW
REVIEW 3 of 17 3 of 17

Inventions 2021, 6, 1 and and printed

printed with anwith
FFF an
3DFFF 3D printer
printer (Lepton2,(Lepton2, MagnaRecta
MagnaRecta Inc., Tokyo,
Inc., Tokyo, Japan)slic-
Japan) using using slic- 3 of 17
ing and controlling software (Simplify3D, Simplify3D LLC, Cincinnati, OH, USA). The The
ing and controlling software (Simplify3D, Simplify3D LLC, Cincinnati, OH, USA).
nozzle diameter,
nozzle diameter, nozzle
nozzle scan scan nozzle
speed, speed, temperature,
nozzle temperature, modeling
modeling stage temperature,
stage temperature, test test
piece
piece IFP, andIFP, andthickness
layer layer thickness
were set were set at
at φ0.4 mm,φ0.4 mm,
480 480 mm/min,
mm/min, 200 °C,200 °C, 100%
70 °C, 70 °C,or100% or
80%, temperature, test piece IFP, and layer thickness were set at ϕ0.4 mm, 480 mm/min, 200 ◦ C,
80%, and 0.2and
mm,◦0.2 mm, respectively.
respectively.
70 C, 100% or 80%, and 0.2 mm, respectively.

(a) (a) (b) (b)

Figure 1.Figure
Shapes1. Shapes
and
Figure and dimensions
dimensions
1. Shapes of (a)
and theoftensile
(a) the
dimensions tensile
oftest the test
(a) piece piece
[28]
tensile test[28]
and (b) and[28]
the
piece (b)and
the flexural
flexural testthe
(b) test piece.
piece.
flexural test piece.

Figure 2Figure
shows Figure
2 the
shows 2 shows
two the twothe
nozzle two
nozzle
scan nozzle scan for
scan patterns
patterns used patterns
used
the 3D forused
the 3Dfor printing.
printing. the 3Dfirst
The printing.
Thewas a The
first wasfirst
a was
apattern
unidirectional
unidirectional
unidirectional pattern pattern
runningrunning running
withinthe
in parallel
in parallel parallel
with thewith thedirection,
longitudinal
longitudinal longitudinaland direction,
direction,theand theand
second the second
second
was a pattern
was a bidirectional bidirectional
was a bidirectional pattern pattern
cross-hatched cross-hatched
cross-hatched
at opposing at opposing
at opposing
diagonal diagonal
anglesdiagonal
angles
to angles to the longitudinal
to the longitudinal
the longitudinal
direction direction
direction
[28]. In [28]. [28].
In thiswe
this paper In
paperthis paper
weP.
define define we
100% asP. define
the P.
astest
100%P. the100% as the
P. testprinted
piece P. test
piece printed piece
with anwith printed
IFP of IFP with
an100%, an IFP of
of 100%,
and apply 100%, and
andcorresponding apply
apply corresponding corresponding
definitions
definitions definitions
to P.80%,toC.P. 80%,,and
100% to
C.100% P.
C., 80%
and ,
. The
80% C.
C.80% ,
. The
test
100% and C.
test were
pieces .
pieces The
80% fabri-were fabri- were
test pieces
fabricated in aat
room maintained at room ◦
cated incated in
a room amaintained
room maintained room attemperature
room temperature (R.T.) temperature
(R.T.) °C)
(22–25 (22–25
and(R.T.)
°C)
then (22–25
and thenC)
weighed and then
weighed
with weighed
with
with anbalance.
an electronic
an electronic balance. electronic balance.

(a) (a) (b) (b)

Figure 2.Figure
Nozzle2. Nozzle
scan
Figure scan patterns
patterns
2. Nozzlefor for pieces
the test
thepatterns
scan test pieces
testfabricated
forfabricated
the thewith
FFF the
with fabricated
pieces FFF the
3Dwith 3D FFF
printer. printer. (a) Parallel,
(a) Parallel, P.;
P.; (a) Parallel,
3D printer. P.;
(b) Cross-hatched
(b) Cross-hatched
(b) at at opposing
opposing
Cross-hatcheddiagonal diagonal
angles,
at opposing angles,angles,
C.
diagonal C. C.

2.2. Test2.2. 2.2.

Test
Piece TestImmersion
Piece
Immersion Piece Immersion
in Saline in Solution
inSolution
Saline Saline Solution
All of the of All
All test the of
testthe
pieces test
pieces
but pieces
butused
those butfor
those those
used
the forusedthefor the non-immersed
non-immersed
non-immersed test immersed
testimmersed
test were were were
in immersed
in in
solutionsolution solution
before
before the before the
the strength
strength strength tests.
tests.test
tests. Each Each Each
testwas
piece test
piece piece was
was immersed
immersed immersed in
in astyrene
in a small a small
small styrene styrene
case case case
containing
containing
containing 8 mL of8 saline
mL of 8 (0.9%
mL of NaCl)
saline saline (0.9%
(0.9% set
NaCl) NaCl) anset
set within
within within anatincubator
an incubator
incubator attemperature
a constant
at a constant
a constant temperature of
temperature
◦ for 30, 60, or 90 days. After incubation, the test piece was wiped free of moisture and
3760,
of 37 °Coffor
3730,
°C forCor30,90
60,days.
or 90After
days.incubation,
After incubation,
the testthe testwas
piece piece was free
wiped wiped free of moisture
of moisture
and dried adried
andindried in in
vacuum apump
vacuum
a vacuum pump
pump
for forfor
5 min. 5obtain
min.
5 min.
to to to obtain
aobtain
stable a stable
adry
stable dry
dry condition
condition
condition [28]. [28].[28].

2.3. Strength Test

2.3. Strength
2.3. Strength Test Test
The mechanical properties of interest were examined by two test methods, a uniaxial
The mechanical
The mechanical properties
properties of interest
of interest were examined
were examined by two by
testtwo test methods,
methods, a uniaxial
a uniaxial
tensile test and a four-point flexural test, using a universal testing machine (EZ-Graph,
tensile tensile
test andtest and a four-point
a four-point flexuralflexural test,ausing
test, using a universal
universal testing testing
machinemachine (EZ-Graph,
(EZ-Graph,
Shimadzu Corp., Kyoto, Japan) (Appendix A). The loads were measured with a 5 kN load
ShimadzuShimadzu Corp., Kyoto,
Corp., Kyoto, Japan) (Appendix
Japan) (Appendix A). TheA). Thewere
loads loads were measured
measured with a 5with a 5 kN load
kN load
cell (Teada-Huntleigh, Model 615, VPG Transducers, Hampshire, UK). Figure 3 shows the
cell (Teada-Huntleigh,
cell (Teada-Huntleigh, Model
Model 615, VPG615, VPG Transducers,
Transducers, Hampshire,
Hampshire, UK). 3Figure
UK). Figure shows3 the
shows the
shapes of the testing jigs, both of which were specially manufactured by our group. L and
shapes shapes of the testing
of the testing jigs,
jigs, both of both
whichof were
whichspecially
were specially manufactured
manufactured by our group.
by our group. L and L and
L0 in Figure 3b represent the fulcrum distance (28 mm) and indenter distance (8 mm) of
the flexural test jig, respectively, and R is the radius of curvature (2 mm). The crosshead
moving speed in the tensile test and flexural test was set at 1.2 mm/min. for each load
direction. A moving limit of 7 mm was set for the head of the 3 mm thick test piece in the
2021, 6, x FOR PEER REVIEW 4 of 17

L' in Figure 3b represent the fulcrum distance (28 mm) and indenter distance (8 mm) of
Inventions 2021, 6, 1 4 of 17
the flexural test jig, respectively, and R is the radius of curvature (2 mm). The crosshead
moving speed in the tensile test and flexural test was set at 1.2 mm/min. for each load
direction. A moving limit of 7 mm was set for the head of the 3 mm thick test piece in the
flexural
flexural test jig. The testtest
tensile jig.and
Theflexural
tensile test and
wereflexural test were at
both performed both performed
R.T. at R.T. The strength
The strength
of the non-immersedof thetest
non-immersed test piecewithin
piece was measured was measured within
12 h of the 12 h of
test piece the test piece printing.
printing.

(a) (b)
Figure 3. Schematics of the jigs for the (a) uniaxial tensile test and (b) four-point flexural test.
Figure 3. Schematics of the jigs for the (a) uniaxial tensile test and (b) four-point flexural test.
The mechanical properties of each test piece were calculated by the following formu-
The mechanical properties of each test piece were calculated by the following formu-
las [43–45].
las [43–45]. P
σT = , (1)
𝜎 , A (1)
A = b × h, (2)
𝐴 𝑏 ℎ,
σ (2)
ET = T , (3)
εT
𝐸 ,
δ (3)
εT = , (4)
𝜀 , l0
(4)
3P( L − L0 )
σF = , (5)
𝜎 , 2b0 h0 2 (5)
/ P/δ 0

 2 0 02

𝐸 𝐿 𝐿′ EF2𝐿= 2𝐿𝐿 L 𝐿′
− L , 2L + 2LL − L , (6) (6)
8b0 h0 3
𝜀 , εF =
δ
, (7) (7)
/
L/2
𝑈 𝜎 𝜀 𝑑𝜀 , Z ε
Tb
UT = σ(ε T ) dε T , (8) (8)
0
𝑈 𝜎 𝜀 𝑑𝜀 . Z ε Tσmax
(9)
UF = σ (ε F ) dε F . (9)
0
where σT is the tensile stress (MPa), P is the test load (N), A is the outer cross-sectional
where
area of the test piece (mm is bthe
σT2), andtensile stress
h are the width(MPa),
(mm) P is
andthethickness
test load(mm)(N), A ofisthe
the outer cross-sectional
tensile
area of the test piece (mm 2 ), b and h are the width (mm) and thickness (mm) of the tensile
test piece measured before the strength test, ET is the tensile elastic modulus (GPa), εT is
test piece
the strain in the tensile testmeasured
(-), δ is thebefore the strength
displacement of the test, ET is the(mm),
crosshead tensile elastic
l0 is modulus (GPa), εT is
the gauge
the strain in the tensile test ( − ), δ is the displacement
length (10 mm), UT is the tensile breaking energy (MJ/m ), εTb is the breaking strain
3 of the in the (mm), l0 is the
crosshead
gauge length (10 mm), UT is the tensile breaking energy (MJ/m3 ), εTb is the breaking strain
tensile test (-), σF is the flexural stress (MPa), b’ and h’ are the width (mm) and thickness
in the tensile test (−), σ is the flexural stress (MPa), b’ and h’ are the width (mm) and
(mm) of the flexural test piece measuredFbefore the strength test, EF is the flexural elastic
thickness (mm) of the flexural test piece measured before the strength test, E is the flexural
modulus (GPa), εF is the deflection rate in the flexural test (-), UF is the flexural breaking F
elastic modulus (GPa), εF is the deflection rate in the flexural test (−), UF is the flexural
energy (MJ/m3), and εTσmax is the deflection rate at maximum flexural stress. For the flex-
breaking energy (MJ/m3 ), and εTσmax is the deflection rate at maximum flexural stress.
ural tests, we defined a deflection rate, εF, as Equation (7). The breaking energy of the
For the flexural tests, we defined a deflection rate, εF , as Equation (7). The breaking energy
flexural test was calculated by integrating the flexural stress with respect to the deflection
of the flexural test was calculated by integrating the flexural stress with respect to the
rate from zero to the maximum stress at which structurally stable deformation is main-
deflection rate from zero to the maximum stress at which structurally stable deformation
tained in the region [44,45]. The deflection rate expresses a slope of the test piece deflec-
is maintained in the region [44,45]. The deflection rate expresses a slope of the test piece
tion, or the steepness of the deflection, in response to loading.
deflection, or the steepness of the deflection, in response to loading.
The dimensions of the test piece were measured immediately before the strength
test to derive accurate values of the mechanical properties. The b and h were measured
at three points within the gauge length, and the cross-sectional area of the outer shape
Inventions 2021, 6, x FOR PEER REVIEW 5 of 17

The dimensions of the test piece were measured immediately before the strength test
Inventions 2021, 6, 1 to derive accurate values of the mechanical properties. The b and h were measured at three 5 of 17
points within the gauge length, and the cross-sectional area of the outer shape was calcu-
lated from the width and thickness closest to the fractured part. The b’ and h’ were meas-
ured at the central portion, and the cross-sectional area of the outer shape was calculated
was calculated from the width and thickness closest to the fractured part. The b’ and h’
from the measured values. The maximum tensile and flexural stresses were the highest
were measured at the central portion, and the cross-sectional area of the outer shape was
points on the stress–strain curve and stress–deflection rate curve, respectively. The maxi-
calculated from the measured values. The maximum tensile and flexural stresses were
mum stress was considered to be the strength determined by the test method. ET was cal-
the highest points on the stress–strain curve and stress–deflection rate curve, respectively.
culated from the slope by the least-squares approximation in the strain range of 2.2–2.5%
The maximum stress was considered to be the strength determined by the test method.
of E
thewas
stress–strain
calculatedcurve.
from For
the the testing
slope ofleast-squares
by the the immersedapproximation
test piece, the maximum stresses
in the strain range of
T
in 2.2–2.5%
the tensile andstress–strain
of the flexural tests wereFor
curve. compared byofthe
the testing thevalues divided
immersed by the
test piece, theaveraged
maximum
maximum tensile
stresses in and flexural
the tensile stresses
and flexural ofwere
tests the non-immersed
compared by the testvalues
pieces, respectively.
divided ET
by the aver-
and E F were compared by the values divided by the ET and EF of the non-immersed test
aged maximum tensile and flexural stresses of the non-immersed test pieces, respectively.
pieces
E andof the
E same
were test piece type,
compared respectively.
by the values divided by the E and E of the non-immersed
T F T F
test pieces of the same test piece type, respectively.
3. Results
3.1.3.Test
Results
Pieces
3.1.Figure
Test Pieces
4 shows photographs of the tensile test pieces (upper row (a)) and flexural test
Figure row
pieces (lower 4 shows
(b)).photographs
The convex of the tensile
patterns testtest
on the pieces
piece(upper row vary
surfaces (a)) and flexuralto
according test
the nozzle scanning direction and IFP. Figure 5 compares the average masses of non-im-the
pieces (lower row (b)). The convex patterns on the test piece surfaces vary according to
nozzletest
mersed scanning
pieces.direction and IFP.
The average Figure
masses of 5the
compares
tensile the
testaverage
pieces weremasses of non-immersed
P.100% , 0.748 [28];
test
P.80% pieces.
, 0.653; C.The
100%, average masses
0.750 [28]; and C. of80%
the tensile
, 0.644 test pieces
g. When were
the IFP P.100%
was , 0.748 [28];
decreased fromP.100%
80% , 0.653;
to
C.100%
80%, the ,masses
0.750 [28];
of theand C.80%
tensile , 0.644
test pieces g. P.When
and C. the IFP was by
decreased decreased
21.8% and from 100%
13.0%, to 80%,
respec-
the masses
tively. of the masses
The average tensile test
of thepieces P. and
flexural testC.pieces
decreased
were by 21.8%
P.100% andP.13.0%,
, 0.410; respectively.
80%, 0.321; C.100%,
The average masses of the flexural test pieces were P. , 0.410;
0.445; and C.80%, 0.388 g. With same reduction in the IFP, from 100% to 80%, the masses
100% P.80% , 0.321; C. 100% , 0.445;
of
and C.
the flexural , 0.388 g. With same reduction in the IFP, from
80%test pieces P. and C. decreased by 12.7% and 14.1%, respectively. 100% to 80%, the masses of the
flexural test pieces P. and C. decreased by 12.7% and 14.1%, respectively.

Inventions 2021, 6, x FOR PEER REVIEW 6 of 17

Figure 4. Photographs of the exteriors of the test pieces fabricated with the 3D printer. (a) Tensile test
Figure 4. Photographs of the exteriors of the test pieces fabricated with the 3D printer. (a) Tensile
piece and (b) Flexural test piece. (i) P.100% , (ii) P.80% , (iii) C.100% , and (iv) C.80% . Bar: 5 mm.
test piece and (b) Flexural test piece. (i) P.100%, (ii) P.80%, (iii) C.100%, and (iv) C.80%. Bar: 5 mm.

Figure 5. Comparison
Figure 5. Comparison of
of the
the masses
masses of
of the
the non-immersed
non-immersed test
test pieces. Average±
pieces. Average S.D., N
± S.D., N == 5.
5.

3.2. Stress–Strain Curves and Stress–Deflection Rate Curves

Figure 6 shows representative changes in the stress–strain curves obtained from the
tensile tests in saline. The curves of the non-immersed (0 days) test pieces reached the
 Figure 5. Comparison of the masses of the non-immersed test pieces. Average ± S.D., N = 5
Inventions 2021, 6, 1 6 of 17
3.2. Stress–Strain Curves and Stress–Deflection Rate Curves
Figure 6 shows representative changes in the stress–strain curves obtained fr
tensile tests inCurves
3.2. Stress-Strain saline.
andThe curves of Rate
Stress-Deflection the Curves
non-immersed (0 days) test pieces reach
maximumFigure 6stress with increased
shows representative changesstrain,
in thethen decreased
stress–strain curvesgradually
obtained from(a–d).
the The n
tensile tests in saline. The curves of the non-immersed (0 days) test pieces
mersed P. test pieces broke at large strain (P.100%; 236% and P.80%; 45.8%) (e). In th reached the
maximum stress with increased strain, then decreased gradually (a–d). The non-immersed
immersed tests, the breaking energies of the P. test pieces were larger than those o
P. test pieces broke at large strain (P.100% ; 236% and P.80% ; 45.8%) (e). In the non-immersed
test
tests,pieces (ab–cd).
the breaking Theofbreaking
energies the P. test energies
pieces wereoflarger
test than
pieces P.ofand
those the C. changed
C. test pieces differe
response
(ab–cd). The to breaking
the immersion,
energies ofwith that of
test pieces P. decreasing
P. and sharply as
C. changed differently in the immersion
response
to the immersion,
increased, and thatwithof
that
C.ofhardly
P. decreasing sharply
changing as the immersion period increased,
(a–d).
and that of C. hardly changing (a–d).

Figure 6. Representative changes of the stress–strain curves of the tensile test pieces after immersion
Figure 6. Representative
for certain periods. (a) P.100% , changes of C.
(b) P.80% , (c) the stress–strain curves of the tensile test pieces after im
100% , and (d) C.80% . (e) Full curves of P.100% and P.80% .
sion for certain periods. (a) P.100%, (b) P.80%, (c) C.100%, and (d) C.80%. (e) Full curves of P.100% a
Figure 7 shows representative changes of the stress–deflection rate curves obtained
in the flexural tests in response to immersion. The curves of the non-immersed test piece
Figure 7 shows representative changes of the stress–deflection rate curves o
increased to the maximum stress with increased deflection, then slowly decreased (a–d).
in
Thethe flexural tests
non-immersed testinpieces
response toreach
did not immersion.
breaking The
pointcurves of the non-immersed
at a deflection rate of 50%, te
a level of deflection corresponding to a moving range of 7 mm (a–d). The maximum
flexural stress of the P. test pieces decreased sharply as the immersion period increased
(a,b). The non-immersed C.80% test piece showed the smallest maximum flexural stress
among the four non-immersed test pieces examined (a–d). The C. test pieces showed
greater declines in both maximum flexural stress and breaking energy than the P. test
pieces (a–d).
 The non-immersed
stress test pieces
of the P. test pieces did not
decreased reach as
sharply breaking point atperiod
the immersion a deflection rate (a,b).
increased of 50%,Thea
level of deflection
non-immersed corresponding
C.80% to a moving
test piece showed range of
the smallest 7 mm (a–d).
maximum The maximum
flexural stress among flexura
the
stress of the P. test pieces decreased sharply as the immersion period increased
four non-immersed test pieces examined (a–d). The C. test pieces showed greater decline (a,b). Th
non-immersed
in both maximum C.80% test piece
flexural showed
stress the smallest
and breaking maximum
energy flexural
than the P. stress
test pieces among th
(a–d).
Inventions 2021, 6, 1 four non-immersed test pieces examined (a–d). The C. test pieces showed greater 7 of 17 decline
in both maximum flexural stress and breaking energy than the P. test pieces (a–d).

Figure 7. Representative changes of the stress–deflection rate curves of the flexural test pieces afte
immersion for certain periods. (a) P.100%, (b) P.80%, (c) C.100%, and (d) C.80%. The arrow indicates that
Figure 7. Representative changes of the stress–deflection rate curves of the flexural test pieces after
the test 7.
Figure piece has not reached
Representative breakage.
changes of the stress–deflection rate curves of the flexural test pieces afte
immersion for certain periods. (a) P.100% , (b) P.80% , (c) C.100% , and (d) C.80% . The arrow indicates that
immersion for certain periods. (a) P.100%, (b) P.80%, (c) C.100%, and (d) C.80%. The arrow indicates that
the test piece has not reached breakage.
3.3. Non-Immersion
the test piece has not Test
reached breakage.
3.3. Non-Immersion
Figure 8 shows Test the maximum tensile stresses and tensile elastic moduli of the fou
3.3. Non-Immersion
types Figure 8 shows the
of non-immersed Testmaximum
test pieces tensile stressesThe
examined. andaverage
tensile elastic
maximummoduli of thestresses
tensile four were
types of non-immersed
Figure 8 shows test
the pieces
maximum examined.
tensileThe average
stresses andmaximum
tensiletensile
P.100%, 56.1 [28]; P.80%, 56.4; C.100%, 51.3 [28]; and C.80%, 34.5 MPa. The maximum stresselasticstresses
moduli wereof the fou
o
P.100% , 56.1 [28]; P.80% , 56.4; C.100% , 51.3 [28]; and C.80% , 34.5 MPa. The maximum stress
types
P. of non-immersed
80% was almost equal test pieces
to that examined.
P.100% . C.80% hadThe theaverage
smallest maximum
maximum tensile
stressstresses
amongwer the
of P.80% was almost equal to that P.100% . C.80% had the smallest maximum stress among
P.100%, 56.1 [28];test
non-immersed P.80%pieces.
, 56.4; C.
The , 51.3 [28]; stress
100%maximum and C.of 80%C., 34.5 MPa.32.7%
80% was The maximum
lower thanstress that o
the non-immersed test pieces. The maximum stress of C.80% was 32.7% lower than that
P.80%
C.
of 100%was
. The
C.100% almost
average
. The equal
average to elastic
tensile that
tensile P.100%
elastic . C.80%were
moduli
moduli hadP.the
were P.100% smallest
, 1.22 [28]; maximum
P.80%, 1.24;stress
C.100%among th
, 1.22 [28]
100% , 1.22 [28]; P.80% , 1.24; C.100% ,
non-immersed
and[28];
1.22 C.80%and
, 0.97 test
GPa.
C.80% pieces.
The
, 0.97 The
elastic
GPa. maximum
The modulus stress
of P.80%
elastic modulus of was of C.
P.80%almost 80% was
was almost 32.7%
equal lower
to that
equal P.100%
to that than
. The
P.100% . elastio
that
C.100%
modulus
The . Theof
elastic average
modulus oftensile
C.80% was C.20.5% elastic
80% waslower
20.5%moduli
than were
that
lower P.100%
of that
than C. of., C.
1.22
100%[28];
. P.80%, 1.24; C.100%, 1.22 [28]
and C.80%, 0.97 GPa. The elastic modulus of P.80% was almost equal to that P.100%. The elasti
modulus of C.80% was 20.5% lower than that of C.100%.

Figure 8. Maximum tensile stresses and tensile elastic moduli of the non-immersed test pieces.
Figure 8.
Average ± Maximum
S.D., N = 5. tensile stresses and tensile elastic moduli of the non-immersed test pieces.
Average ± S.D., N = 5.
FigureFigure 9 shows the
8. Maximum maximum
tensile stressesflexural stresses
and tensile and
elastic flexural
moduli of elastic moduli of thetest
the non-immersed four
pieces.
types of non-immersed test pieces examined. The average maximum stresses were P.100% ,
Average ± S.D., N = 5.
81.2; P.80% , 78.1; C.100% , 80.7; and C.80% , 69.9 MPa. The maximum stress of P.80% was almost
equal to that of P.100% . The maximum stress of C.80% was 13.4% lower than that C.100% .
The average flexural elastic moduli were P.100% , 2.87; P.80% , 2.77; C.100% , 2.48; and C.80% ,
2.28 GPa. The elastic modulus of P.80% was nearly equal to that of P.100% . The elastic
modulus of C.80% was 7.85% lower than that of C.100% .
 equal
typestoofthat of P.100%. Thetest
non-immersed maximum stress of C.
pieces examined. 80% was 13.4% lower than that C.100%. The
The average maximum stresses were P.100%
average flexural elastic moduli were P.100%, 2.87; P.80%, 2.77; C.100%, 2.48; and C.80%, 2.28 GPa.
81.2; P.80%, 78.1; C.100%, 80.7; and C.80%, 69.9 MPa. The maximum stress of P.80% was almo
The elastic
equal modulus
to that of. P.
of P.100% 80% was nearly equal to that of P.100%. The elastic modulus of C.80%
The maximum stress of C.80% was 13.4% lower than that C.100%. Th
was 7.85% lower than that
average flexural elastic moduliof C.100%. P.100%, 2.87; P.80%, 2.77; C.100%, 2.48; and C.80%, 2.28 GPa
were
Inventions 2021, 6, 1 8 of 17
The elastic modulus of P.80% was nearly equal to that of P.100%. The elastic modulus of C.80
was 7.85% lower than that of C.100%.

Figure 9. Maximum flexural stresses and flexural elastic moduli of the non-immersed test pieces.
Average ± S.D., N = 5.
Figure 9. Maximum flexural stresses and flexural elastic moduli of the non-immersed test pieces.
Figure ±
Average 9. S.D., N = 5. flexural stresses and flexural elastic moduli of the non-immersed test pieces.
Maximum
3.4. Immersion Test
Average ± S.D., N = 5.
3.4. Immersion Test
Figure 10 compares the changes of the average maximum tensile stresses of the four
test Figuretypes10 compares the changesfor of sequentially
the average maximum tensile stresses of the
30 four
3.4.piece
Immersion Test after immersion increased periods. After days of im-
test piece types after immersion for sequentially increased periods. After 30 days of im-
mersion, Figurethe changes
10 compares of the maximum
the changes tensile
of the stresses
average were P. 100%, −17.6%; P.80%, −21.7%;
mersion, the changes of the maximum tensile stresses weremaximum tensile
P.100% , −17.6%; stresses
P.80% , −21.7%;of the fou
C. 100%, −3.47%; and C.80% +11.5%. After 60 days, the changes of the maximum stresses were
test
C. 100%piece
, −3.47%; typesandafter
C.80%immersion
+11.5%. After for sequentially increased
60 days, the changes periods.
of the maximum Afterstresses
30 days of im
P. 100%,P.
were −20.6%;
mersion, 100% the
, − P. 80%, −37.8%;
changes
20.6%; P.80%of , −
the C. 100%, C.
maximum
37.8%; −9.67%;
100% , − and
tensile C.
9.67%; 80%, +5.82%.
stresses
and C. were
80% , After
P.
+5.82%.
100% , 90 days,
−17.6%;
After 90 the
P. changes
80%, −21.7%
days,
were
the
C.100%P., 100%
changes , −44.8%;
−3.47%; wereand P.
P.100%
C.80%, ,−−58.5%;
80% 44.8%; P.
+11.5%. C. , ,−
100%
After
80% −5.07%;
6058.5%; and
days, C.
the C.
, 80%
changes
100% , −1.28%.
−5.07%; andThe
of the C.80%
maximummaximum
, −1.28%. stresses
stresses wer
of
The the P.
maximum test pieces
stresses gradually
of the P. decreased
test pieces over
gradually the 90 days
decreased of
over
P.100%, −20.6%; P.80%, −37.8%; C.100%, −9.67%; and C.80%, +5.82%. After 90 days, the change immersion,
the 90 days ofwhile
immer-the maxi-
sion, while
mum stressthe ofmaximum
the C. teststress piecesof the C. test
hardly pieces hardly changed.
changed.
were P.100%, −44.8%; P.80%, −58.5%; C.100%, −5.07%; and C.80%, −1.28%. The maximum stresse
of the P. test pieces gradually decreased over the 90 days of immersion, while the max
mum stress of the C. test pieces hardly changed.

Figure 10.
Figure 10. Comparison
Comparisonofofthe the changes
changesin the maximum
in the maximum tensile stresses
tensile of theof
stresses four
thetest
fourpiece
testtypes
piece types
brought about by the immersion. Each value was divided by the average
brought about by the immersion. Each value was divided by the average value of the non-im- value of the non-immersed
test pieces
mersed (0 pieces
test days). The plot points
(0 days). werepoints
The plot straggled
were to avoid overlapping.
straggled to avoidAverage ± S.D.,Average
overlapping. N = 5. ± S.D.,
Figure 10. Comparison of the changes in the maximum tensile stresses of the four test piece types
N = 5.
Figure
brought about11 compares the changes
by the immersion. Eachof the average
value was divided maximum flexuralvalue
by the average stresses of the
of the non-im-
four
mersedtest test
piece types
pieces (0 after
days).immersion for sequentially
The plot points were straggled increased
to avoidperiods. After 30
overlapping. days ± S.D.,
Average
Figure 11the compares
changesthe changes of the average maximum were P.flexural stresses of the four
ofNimmersion,
= 5. of the maximum flexural stresses 100% , −1.50%; P.80% ,
test
−10.9%; C.100% , −0.18%; and C.80% , +14.7%. After 60 days, the changes were30
piece types after immersion for sequentially increased periods. After days
P.100% , of im-
mersion,
−18.5%; P.the
Figure 80%11changes
22.1%;of
, −compares C.the themaximum
100% ,− 8.68%; and
changes offlexural
C.80%
the , stresses
−9.04%.
average were
AfterP.
maximum 90100% , −1.50%;
days,
flexural the P.80%of
changes
stresses , −10.9%;
the fou
C.
were100%,P.−0.18%;
test piece , − and
39.7%;
100% types after80% C.
P. 80% ,
, −+14.7%.
60.8%;
immersion for After
C. , 60
− days,
19.2%; the
and
sequentially increased
100% changes
C. 80% , − periods. After 30 days P.
were
16.6%. P.
The , −18.5%;
maximum
100%
im,
of80%
flexural
−22.1%; stresses
C.100% of all of the test piece types declined after 90 days of immersion, with those
mersion, the, changes
−8.68%; of and theC.maximum
80%, −9.04%. After 90 days, the changes were P.100%, −39.7%;
flexural stresses were P.100%, −1.50%; P.80%, −10.9%
of the P. test pieces dropping steeply.
C.100%, −0.18%; and C.80%, +14.7%. After 60 days, the changes were P.100%, −18.5%; P.80%
−22.1%; C.100%, −8.68%; and C.80%, −9.04%. After 90 days, the changes were P.100%, −39.7%
Inventions 2021, 6, x FOR PEER REVIEW 9

P.80%, −60.8%; C.100%, −19.2%; and C.80%, −16.6%. The maximum flexural stresses of all o
test piece types declined after 90 days of immersion, with those of the P. test pieces d
P. 80%, −60.8%; C.100%, −19.2%; and C.80%, −16.6%. The maximum flexural stresses of all o
ping steeply.
Inventions 2021, 6, 1 9 of 17
test piece types declined after 90 days of immersion, with those of the P. test pieces d
ping steeply.

Figure 11. Comparison of the changes of the maximum flexural stresses of the four test piece t
brought about by the immersion. Average ± S.D., N = 5.
Figure 11. Comparison of the changes of the maximum flexural stresses of the four test piece types
Figure 11. Comparison of the changes of the maximum flexural stresses of the four test piece t
brought about by the immersion. Average ± S.D., N = 5.
brought about12
Figure bycompares
the immersion. Averageof
the changes ± S.D., N = 5. tensile elastic moduli of the fou
the average
piece types
Figure 12 after
comparesimmersion
the changes for of
sequentially increased
the average tensile elasticperiods.
moduli of After 30 days
the four test of im
sion, the changes of the elastic moduli were P.100%, +3.77%; P.80%, −4.27%;of
piece Figure
types 12
after compares
immersion the
for changes
sequentially of the
increasedaverage
periods. tensile
After elastic
30 days ofmoduli
immersion,C.the four
100%, −3.
piece types
the changes after
of immersion
the elastic moduli for sequentially
were P.100% , +3.77%; P.80% , −
increased periods.
4.27%; C.After , −
30 days
3.77%;
100% P.80%, +33.6%; of imm
and C.80%, +20.2%. After 60 days, the changes were P.100%, +1.64%; C
and
sion, C. the , +20.2%. After 60 days, the
80% changes of the elastic moduli were P.changes were P. , +1.64%;
100%, +3.77%; 80%
100% P. P. , +33.6%; C.
80%, −4.27%;100% C. ,
100%, −3.7
+0.41%;and
+0.41%; and C.80%
C.80% +12.2%.
+12.2%. AfterAfter
90 days,90 the
days, the changes
changes were P.100%were P.100%
, −35.8%; P.,80%
−35.8%;
, −17.8%;P.80%, −17
and
C.100%C. 80%, +20.2%.
100%,, +5.58%;
+5.58%;and and After
C.80% 60 days,
, +0.13%. the changes were P. 100%, +1.64%; P. 80%, +33.6%; C
C. C.80% , +0.13%. The The elastic
elastic moduli moduli
of the P.oftest
the P. test
pieces piecesover
decreased decreased
+0.41%;
the9090days
the
and
days C. 80% +12.2%. After 90 days, the changes were P.100%, −35.8%; P.80%, −17
of immersion,
of immersion, whilewhile the moduli
the moduli of the C. of
testthe C. test
pieces hardly pieces hardly
changed. The changed.
tensile The
C. 100%,modulus
elastic
sile +5.58%;
elastic ofand
modulus the C. 80%, test
C.of
80%the+0.13%.
C.piece The elastic
temporally
80% test piece moduli
rose after 30of
temporally theafter
days
rose ofP.immersion.
test pieces
30 days of decreased
immersion
the 90 days of immersion, while the moduli of the C. test pieces hardly changed. The
sile elastic modulus of the C.80% test piece temporally rose after 30 days of immersion

Figure Comparison
Figure12.12. of the
Comparison ofchanges of the tensile
the changes of theelastic moduli
tensile of the
elastic four test
moduli of piece typestest
the four brought
piece types
about by the immersion. Average ± S.D., N = 5.
brought about by the immersion. Average ± S.D., N = 5.
Figure 12. Comparison of the changes of the tensile elastic moduli of the four test piece types
Figure 13 compares the changes of the average flexural elastic moduli of the four
brought about13
Figure bycompares
the immersion. Averageof
the changes ± S.D., N = 5. flexural elastic moduli of the fou
the average
test piece types after immersion for sequentially increased periods. After 30 days of
piece typestheafter
immersion, immersion
changes for sequentially
of the elastic moduli were P.increased
100% , +26.6%; periods. After 30
P.80% , +5.67%; days
C.100% , of im
+15.8%;Figure
sion, the 13
andchanges compares
C.80% +1.40%. the
of theAfter changes
60 days,
elastic of the average
the changes
moduli were P.were flexural
100%, P.
elastic
100% , +14.9%;
+26.6%; P.80%P. moduli of
C.the
80% , +7.71%;
, +5.67%; four
100%, +15
piece
C.
and ,types
100%C. −80% after
0.62%; andimmersion
+1.40%. C.After forAfter
80% , −0.85%.
60 days, sequentially
90 days,
the changes increased
the changes
were P.were periods.
P.100% ,After
100%, +14.9%; P.30
+10.1%; P.days
80%, 80%
, of imm
+7.71%; C
−5.48%;
sion, the C.changes
100% , +8.93%;
of and elastic
the C.80% , +3.43%.
moduli The flexural
were P. elastic
100% , moduli
+26.6%; P.fluctuated
80%, +5.67%; within
C. 100%, +15
−0.62%; and C.80%, −0.85%. After 90 days, the changes were P.100%, +10.1%; P.80%, −5.
a range
and C.of about 27%.
80% +1.40%. After 60 days, the changes were P.100%, +14.9%; P.80%, +7.71%; C
C.100%, +8.93%; and C.80%, +3.43%. The flexural elastic moduli fluctuated within a ran
−0.62%;
about 27%.and C.80%, −0.85%. After 90 days, the changes were P.100%, +10.1%; P.80%, −5.4
C.100%, +8.93%; and C.80%, +3.43%. The flexural elastic moduli fluctuated within a rang
about 27%.
Inventions 2021, 6, x FOR PEER REVIEW 10

Inventions 2021,
Inventions 6, x6, FOR
2021, 1 PEER REVIEW 10 of 17 10

Figure 13. Comparison of the changes of the flexural elastic moduli of the four test piece types
brought about by the immersion. Average ± S.D., N = 5.
Figure 13. Comparison of the changes of the flexural elastic moduli of the four test piece types
Figure 13. Comparison of the changes of the flexural elastic moduli of the four test piece types
brought about by the immersion. Average ± S.D., N = 5.
brought about
Figure 14by the immersion.
shows Average
the average tensile± S.D., N = 5.energies and flexural breaking ener
breaking
of the non-immersed
Figure test pieces.
14 shows the average tensileThe tensile
breaking breaking
energies energies
and flexural breaking P.100%, 70.90; P
were energies
of the Figure 14
non-immersed shows the
test average
pieces. The tensile
tensile breaking
breaking energies
energies
10.84; C.100%, 2.72; and C.80%, 1.87 MJ/m . The flexural breaking energies
3 and
were P. flexural
100% , breaking
70.90; P.80%P.
were ener
, 100% , 10
10.84; C. , 2.72; and C. , 1.87 MJ/m 3 . The flexural breaking energies were P. , 10.99,
of80%
P. the non-immersed
, 8.53;
100%C.100%, 16.10; test
80%andpieces. The tensile
C.80%, 18.37 MJ/m 3. breaking energies were 100%P.100%, 70.90; P
P. 3.
80% , 8.53;
10.84; C.100%
C.100% , 16.10;
, 2.72; andand C.,80%
C.80% , 18.37
1.87 MJ/m MJ/m
3. The flexural breaking energies were P.100%, 1
P.80%, 8.53; C.100%, 16.10; and C.80%, 18.37 MJ/m3.

Figure 14. Tensile and flexural breaking energies of the non-immersed test pieces. Average ± S.D.,
Figure
N = 5. 14. Tensile and flexural breaking energies of the non-immersed test pieces. Average ± S
N = 5.
Figure 15 compares the changes of the tensile breaking energies of the four test piece
Figure 14. Tensile and flexural breaking energies of the non-immersed test pieces. Average ± S
types after immersion for sequentially increased periods. After 30 days of immersion,
N = 5.Figure 15 compares the changes of the tensile breaking energies of the four test p
the changes of the breaking energies were P.100% , −96.3%; P.80% , −76.5%; C.100% , −45.6%;
types
and C.80%after
, −immersion
45.8%. After 60fordays,
sequentially
the changes increased
were P.100%periods.
, −94.5%;After P.80% ,30 days of
−82.5%; immersion
C.100% ,
changesFigure
−45.5%; and 15
of C.
the compares
80%breaking
the changes
energies
, −49.1%. After were
90 days, of the tensile
P.100%, −96.3%;
the changes breaking
were P.100% P., 80% energies
, −76.5%;
−99.3%; of the
P.80% ,C.
−100% four test p
, −45.6%;
94.8%;
types
C.100% after immersion
−65.6%;
80%, ,−45.8%. and C.80%
After for
60 days, sequentially
−53.1%. The
the increased
breaking
changes energies
were periods.
of ,the
P.100% After
P. test
−94.5%; pieces30,showed
P.80% days ofmore
−82.5%; immersion
C.100%, −45
changes
pronounced of the
changesbreaking
than the energies
breaking were
energies P.
of ,
the
100% −96.3%;
C. test P.
pieces.
and C.80%, −49.1%. After 90 days, the changes were P.100%, −99.3%; P.80%, −94.8%; 80% , −76.5%; C. 100% , −45.6%; C
C. Figure
, 16
−45.8%. compares
After the
60 changes
days, the of the
changesflexural
werebreaking
P. ,energies
−94.5%; of the
P. four
, test
−82.5%; piece
C. , −45
−65.6%; and C.80% −53.1%. The breaking energies of the P. test pieces showed more
80% 100% 80% 100%
types after immersion for sequentially increased periods. After 30 days of immersion,
and C.80%changes
nounced , −49.1%.thanAfterthe 90 days, the
breaking changes were C. P. , −99.3%; P.80%, −94.8%; C
wereenergies of the test pieces.
100%
the changes of the breaking energies P.100% , −35.5%; P. 80% , −46.1%; C.100% , −57.5%;
−65.6%; and C. 80% −53.1%. The breaking energies of the P. test pieces showed more
and C.80% , −32.4%. After 60 days, the changes were P.100% , −56.2%; P.80% , −50.9%; C.100%
nounced
− 52.1%; and changes
C.80% , −than
66.7%.the breaking
After 90 days,energies
the changes ofwere
the C. test, −pieces.
P.100% 75.5%; P.80% , −82.8%;
C.100% , −77.9%; and C.80% , −74.2%. The immersion reduced the breaking energies of all of
the test piece types in the flexural stress test.
 types after immersion for sequentially increased periods. After 30 days of immersion
changes of the breaking energies were P.100%, −96.3%; P.80%, −76.5%; C.100%, −45.6%
C.80%, −45.8%. After 60 days, the changes were P.100%, −94.5%; P.80%, −82.5%; C.100%, −4
and C.80%, −49.1%. After 90 days, the changes were P.100%, −99.3%; P.80%, −94.8%; C
Inventions 2021, 6, 1 11 of 17
−65.6%; and C.80% −53.1%. The breaking energies of the P. test pieces showed more
nounced changes than the breaking energies of the C. test pieces.

Inventions 2021, 6, x FOR PEER REVIEW 1

Figure 15. Comparison of the changes of the tensile breaking energies of the four test piece ty
brought about by the immersion. Average ± S.D., N = 5.

Figure 16 compares the changes of the flexural breaking energies of the four test
types after immersion for sequentially increased periods. After 30 days of immersion
changes of the breaking energies were P.100%, −35.5%; P.80%, −46.1%; C.100%, −57.5%;
C.80%, −32.4%. After 60 days, the changes were P.100%, −56.2%; P.80%, −50.9%; C.100% −52
and C.80%, −66.7%. After 90 days, the changes were P.100%, −75.5%; P.80%, −82.8%; C
Figure 15. Comparison
−77.9%; and C.80%, of the changes
−74.2%. Theofimmersion
the tensile breaking
reducedenergies of the four test
the breaking piece types
energies of all of th
brought about by the immersion. Average ± S.D., N = 5.
piece types in the flexural stress test.

Figure Comparison
Figure16.16. Comparisonof the
ofchanges of the of
the changes flexural breakingbreaking
the flexural energies of the four of
energies testthe
piece types
four test piece t
brought about by the immersion. Average ± S.D., N =
brought about by the immersion. Average ± S.D., N = 5. 5.

4. Discussion
4. Discussion
In this research we analyzed how the mechanical properties of FFF-3D-printed PLA
structures deteriorated
In this research by weimmersion
analyzedinhowsolution, and how theproperties
the mechanical deterioration
of evaluated
FFF-3D-printed
by tensile testing differed from that evaluated by flexural testing.
structures deteriorated by immersion in solution, and how the deterioration We did so by print-evaluate
ing comparable test pieces for evaluation by the two testing tests and treated them by
tensile testing differed from that evaluated by flexural testing. We did so by printing
identical methods. We then investigated how major fabrication parameters such as the
parable
nozzle scantest pieces
pattern andfor evaluation
IFP affected theby the two found
differences testingin tests and treated
the mechanical them by iden
properties.
methods.
To We then
our knowledge, investigated
no earlier how major
reports comparing thefabrication
abovementioned parameters such
conditions haveasbeen
the nozzle
pattern and IFP affected the differences found in the mechanical properties. To
published. In this discussion we focus on the details of the data obtained from the two
mechanical
knowledge, tests.
no earlier reports comparing the abovementioned conditions have been
lished.
4.1. In this
Analysis discussion
of Mechanical we focus
Properties on the
by Tensile details
Testing of theTesting
and Flexural data obtained from the two
chanical tests.
Tensile and flexural testing are basic test methods to assess mechanical properties such
as maximum stress, elastic modulus, yield stress, breaking strain, and breaking energy.
4.1.know
We Analysis of Mechanical
that flexural testing Properties
data form anby unreliable
Tensile Testing anddecisions
basis for Flexuralon Testing
design pa-
rameters with polymeric materials, as the mechanical equations require distinct
Tensile and flexural testing are basic test methods to assess mechanical geometric prope
assumptions that easily compromise accuracy. The flexural test, however, is an important
such as maximum stress, elastic modulus, yield stress, breaking strain, and breakin
step to determine the relative relation of the flexural parameter itself and the relation be-
ergy.the
tween Weflexural
knowparameter
that flexural testing data
and parameter formbyan
obtained theunreliable
tensile test.basis
In thisfor decisions
research we on de
printed two types of test pieces with cross sections of the same size (3 × 3 mm), one for thedistinct
parameters with polymeric materials, as the mechanical equations require
metric assumptions that easily compromise accuracy. The flexural test, however, is a
portant step to determine the relative relation of the flexural parameter itself and th
lation between the flexural parameter and parameter obtained by the tensile test. In
research we printed two types of test pieces with cross sections of the same size (
mm), one for the tensile testing (Figure 1a; Figure 4, row(a)) and the other for the fle
Inventions 2021, 6, 1 12 of 17

tensile testing (Figure 1a; Figure 4, row(a)) and the other for the flexural testing (Figure 1b;
Figure 4, row(b)), to keep the test conditions as similar as possible for better comparability.

4.2. Mechanical Properties of the Non-Immersed Test Pieces

The maximum tensile stress of the P.100% test piece shown in Figure 8 (56 MPa) agreed
well with the maximum tensile stresses of the FFF-3D-printed test pieces [28,33] and IM test
pieces [7,16,17]. The maximum flexural stress of the P.100% test pieces shown in Figure 9
(81 MPa) was within a proper range compared with the maximum flexural stresses of
previously reported test pieces formed by IM [16].
The average maximum stress of the P.80% test piece was almost equal to that of P.100%
in both tensile and flexural testing (Figures 8 and 9). In contrast, the maximum stress of
C.80% was clearly lower than that of C.100% in tensile testing and slightly lower than that of
C.100% in flexural testing. On the other hand, the masses of the both the scan pattern P. and
C. test pieces shown in Figure 5 decreased by at least 12.7%. From the masses of the test
pieces shown in Figure 5, we can surmise that the actual IFPs almost matched the values
set in the software, 100% and 80%. These findings indicate, for reasons that have yet to be
explained, that we can obtain equal strength with 20% less material in structures printed
by scan pattern P.
The average maximum tensile stress of C.80% was 32.7% lower than that of C.100%
(Figure 8), while the average flexural strength of C.80% was 13.4% lower than that of C.100%
(Figure 9). We can infer that the decreased IFP reduced the tensile strength more than it
reduced the flexural strength in the C. test pieces.
From the stress–strain curves shown in Figure 6a–e, we see that the tensile breaking
strain of P.100% (>200%) far exceeded the tensile breaking strains of the other test piece types.
The large deformation was caused by the tensile force acting in parallel to the longitudinal
direction of the filament constructed. No test piece breakage occurred when the styluses
were displaced by 7 mm, a distance equivalent to a 50% deflection rate, in our four-point
flexural test. This finding was explained by a movement limitation in the structure of the
jigs (Section 2.3 and Figure 7).
The tensile elastic modulus obtained in this work (P.100% and P.80% ) was considerably
lower (1.2 GPa) than that reported in a previous paper (3.4 GPa) [33]. The flexural elastic
modulus of P.100% almost agreed with a previously reported value (2.4 GPa) using IM test
pieces [14], though we can only surmise that the value was obtained from a four-point
flexural test (no description of the flexural test was offered). On the contrary, our scores
were considerably lower than those reported in previous studies [16] using three-point
flexural tests using IM test pieces.

4.3. Mechanical Properties after Immersion in Saline

The maximum stresses of the P. test pieces dropped remarkably over 90 days of
immersion in saline (Figures 10 and 11). The strength reduction rates of the P.80% test
piece were the largest, reaching 58.5% in the tensile test and 60.8% in the flexural test.
The deterioration rates were larger in the P. test pieces than in the C. test pieces in both
types of testing. From these results, we can infer that the differences in the deterioration
rates stemmed from the internal structures fabricated by the nozzle scan patterns. The chief
difference between the two internal structures was the shape of the gaps between the
filaments. While the P. structure was formed with straight gaps between the extruded
lines of the material, resulting in a capillary-like structure, the C. structure was formed
with zigzag-shaped gaps. In comparing the 100% and 80% IFPs in this research, we found
that the structure formed by the IFP of 80% had larger gaps between the extruded lines.
These larger gaps may have accelerated the water uptake into the structure. We can surmise
from the different deterioration rates observed that water was more readily taken up by
the P. test pieces than by the C. test pieces at both the 100% and 80% IFPs.
We can also find distinctive changes. The tensile stress and flexural stress of C.80%
increased temporarily after 30 days of immersion, as can be seen in Figures 10 and
Inventions 2021, 6, 1 13 of 17

11 (described in 4.4). The tensile elastic modulus ratio ranged between −35.8% and
+20.2% (Figure 12). The flexural elastic modulus ratio ranged between −5.48% and +26.6%
(Figure 13). The 90 days of immersion decreased the tensile elastic modulus of the P. test
pieces (Figure 12). The tensile elastic modulus of P.80% , however, rose from 60 days to
90 days, for reasons that remain unclear.
The tensile breaking energies of the non-immersed test pieces varied largely between
the test pieces types, and the breaking energies of the P. test pieces were remarkably larger
than those of the C. test pieces (Figure 14). On the contrary, the flexural breaking energies of
the non-immersed C. test pieces were larger than those of the non-immersed P. test pieces.
The first 30 days of immersion greatly reduced the breaking energies of both test
piece types (Figures 15 and 16). In particular, the tensile breaking energies of the P.100%
test pieces declined by more than 90% versus the extremely large breaking energies of the
non-immersed test pieces. From the comparisons of the changes observed between the
tensile tests and flexural tests (see Figures 10–13), we can report that the breaking energies
of the test pieces declined in the first 30 days of immersion, while the maximum tensile
and flexural stresses showed no notable changes in the same period.
We evaluated the deformation in the flexural tests by calculating the steepness of the
deflection induced by loading and defining it as a deflection rate (Equation (7)). We esti-
mated a flexural breaking energy from the range of structurally stable deformation based
on the Drucker stability postulates [44,45]. This range corresponded to the area below the
stress-deformation rate curve between zero to the deformation rate at the maximum stress.

4.4. Temporary Strength Increase Brought about by Immersion

The maximum strengths of the C.80% test pieces were temporarily increased by 30- and
60-day immersion in the tensile tests (Figure 10) and by 30 days of immersion in the flexural
tests (Figure 11). These temporary increases were observed only in the C.80% structures.
Meanwhile, the tensile elastic moduli of the C.80% structures were temporarily increased by
30 days of immersion, and gradually decreased thereafter (Figure 12). The flexural elastic
moduli of all the test piece types increased over the first 30 days of immersion. We can
infer that the permeation of water into the material induced a transient hardening, as PLA
has a slow degradation rate [9,12,13,15,46]. We can also report that the permeation rate
was larger than the deterioration rate of the material. The deterioration may have reached
a notable level after 30 days of immersion, resulting in the subsequent strength decline.
We have not seen many reports on the transient hardening of PLA. PLA and PLA/wood
composites prepared by injection molding and 3D printing have been evaluated for their
mechanical properties [47]. Studies have also been done to determine how the water
absorption characteristics of polymer materials affect the base resins of dentures [48,49].
In flexural testing, six months of water immersion significantly increased the elastic moduli
of resins treated by various methods [48].

4.5. Test Methods

Our test pieces (Figures 1 and 4) were smaller than those usually applied for evalu-
ations of the tensile [28] and flexural properties of polymer materials. The smaller size
allowed us to immerse each test piece in the solution separately from the other test pieces,
and thus to maintain the same immersion condition for all of the pieces immersed. A uni-
form immersion is preferable, considering the self-catalysis effect of the water-soluble
oligomers [42]. We would have had difficulty collecting data from a large number of test
pieces if the test pieces had been larger in size, as fewer of them would have fit inside
the incubator used for the immersion. Square sections of the same size (3 × 3 mm) were
designed for both test piece types to ensure that the immersion solution permeated into
and diffused within the material and structures under similar conditions. For the purposes
above mentioned, we chose to adopt an ASTM standard, with some modifications.
We adopted a four-point flexural test instead of a three-point flexural test in this
research. While the four-point flexural test can give uniform bending moment to the test
Inventions 2021, 6, 1 14 of 17

piece between the inner loading styluses, the structure reaches the point of breakage under
conditions similar to those in practical use.
As mentioned earlier, the tensile elastic modulus taken from this work was consid-
erably lower than that reported in a previous paper. This difference may have stemmed
from the difference in the method used to deliver the strain. We derived the strain in our
tensile tests from the moving distance of the test piece head, as the test piece was too small
to accept the insertion of a strain gauge with high precision [28].
We decided to select saline as the immersion solution for this work instead of phos-
phate buffer saline (PBS) or distilled water (DW), two other solutions that might have
served the same purpose [28,40,41]. PBS would have more reliably maintained the pH
value of the solution, a factor that influences the deterioration rate of PLA. According to
another group, sodium chloride buffer proved to be the optimal degradation medium in
an investigation of the influence of the degradation medium on the changes of mechanical
behavior [29].
We continued the immersion test for up to 90 days in this work, and the maximum
stress dropped by approximately 60% (Figures 10 and 11). Our 90-day test period brought
about the degree of deterioration we were seeking to use for the design data.
The test pieces were printed using a white translucent PLA filament containing no
dye, as dye is reported to decrease the maximum tensile strength of PLA by accelerating
the crystallinity [50].

4.6. Future Prospects

We found a peculiarity in the deterioration of the PLA structures fabricated by the FFF
3D printer. The structures had inner gaps between neighboring lines that varied according
to the scan pattern and IFP settings in the control software. The true surface area of an
FFF-3D-printed structure is generally larger than that of an IM structure with the same
outer volume, as the curved surfaces of the filament composing the former have a larger
surface area than the plane surface of the latter. The different interaction between the inner
surface of the gap and solution can be expected to result in different deterioration profiles
of the structure. Structures printed with other scan patterns in combination with different
IFPs should be evaluated in the future.

5. Conclusions
PLA test pieces prepared with an FFF 3D printer were immersed in saline and eval-
uated by tensile and flexural tests to characterize the deterioration of their mechanical
properties. The maximum strengths, elastic moduli, and breaking energies of four test
piece types printed using different nozzle scan patterns and IFPs were examined by two
test methods and compared. The immersion in saline substantially changed the mechanical
properties of the FFF-3D-printed structures. The patterns and degrees of change were influ-
enced by the fabrication parameters used to print the structures. In comparing between
the tensile and flexural tests, the immersion was found to bring about different effects
on the mechanical properties of the structure. The strengths of the test pieces tended to
decrease over the 90 days of immersion, though some of the test pieces fabricated under
specific conditions exhibited temporary increases in strength after 30 days of immersion.
Some of the test piece types exhibited comparable levels of strength with smaller quantities
of material. We expect the knowledge obtained in this research to be applied to the design
of FFF-3D-printed structures.

Author Contributions: A.Y. (Akira Yamada) conceived and designed the experiments; A.Y. (Asahi
Yonezawa) performed the experiments and curated the data; A.Y. (Asahi Yonezawa) wrote the draft;
A.Y. (Akira Yamada) wrote and finished the paper. All authors have read and agreed to the published
version of the manuscript.
 Inventions 2021, 6, 1 15 of 17

ventions 2021, 6, x FOR PEER REVIEW 15 of 17

Funding: Part of this work was supported by JSPS KAKENHI (JP18K04183). This study was also
partly supported by an AIT (Aichi Institute of Technology) Special Grant for Education and Research
Data Availability Statement: Please refer to suggested Data Availability Statements in section
(Research B).
“MDPI Research Data Policies” at https://www.mdpi.com/ethics.
Acknowledgments: The authors would like to thank Hisaaki Tobushi and Kohei Takeda for their
Acknowledgments: The authors would like to thank Hisaaki Tobushi and Kohei Takeda for their
available suggestions on this paper. The authors are grateful to Miho Suzuki, Yuki Yoshimi, and Keiya
available suggestions on this paper. The authors are grateful to Miho Suzuki, Yuki Yoshimi, and
Tsukahara for their kind technical support. We are also grateful for the technical support we received
Keiya Tsukahara for their kind technical support. We are also grateful for the technical support we
in preparing the test apparatus for the experiments and for the practical training performed by our
received in preparing the test apparatus for the experiments and for the practical training performed
Department of Mechanical Engineering.
by our Department of Mechanical Engineering.
Conflicts of Interest: The authors declare no conflict of interest.
Conflicts of Interest: The authors declare no conflict of interest.

AppendixAppendix
A A
The photographs in Figure A1 show the test pieces in their jigs (partially shown) while
The photographs in Figure A1 show the test pieces in their jigs (partially shown)
being tested.
while being tested.

(a) (b)
Figure A1. Photographs of the P.100% test pieces in their jigs during loading for the (a) uniaxial tensile
Figure A1. Photographs of the P.100% test pieces in their jigs during loading for the (a) uniaxial ten-
sile test (εT =test (εTand
0.05) = 0.05)
(b) and (b) four-point
four-point flexuralflexural
test (εF =test (εFBar:
0.2). = 0.2). Bar: 10 mm.
10 mm.

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