In Situ Polymerization as an Effective Method, Compared to Melt Mixing, for Synthesis of Flexible Poly(lactic acid) Nanocomposites Based on Metal Nanoparticles

Academic Edi o : F ancesco
To nabene
Recei ed: 19 Sep embe 2025
Re ised: 30 Oc obe 2025
Accep ed: 2 No embe 2025
Published: 5 No embe 2025
Ci a ion: Laza idou, K.; Ioannidis,
R.O.; Bikia is, D.N. In Si u
Polyme iza ion as an E ec i e
Me hod, Compa ed o Mel Mixing,
o Syn hesis o Flexible Poly(lac ic
acid) Nanocomposi es Based on Me al
Nanopa icles. J. Compos. Sci. 2025,9,
610. h ps://doi.o g/10.3390/
jcs9110610
Copy igh : © 2025 by he au ho s.
Licensee MDPI, Basel, Swi ze land.
This a icle is an open access a icle
dis ibu ed unde he e ms and
condi ions o he C ea i e Commons
A ibu ion (CC BY) license
(h ps://c ea i ecommons.o g/
licenses/by/4.0/).
A icle
In Si u Polyme iza ion as an E ec i e Me hod, Compa ed
o Mel Mixing, o Syn hesis o Flexible Poly(lac ic acid)
Nanocomposi es Based on Me al Nanopa icles
Ky iaki Laza idou, Ra ail O. Ioannidis and Dimi ios N. Bikia is *
Labo a o y o Polyme Chemis y and Technology, Depa men o Chemis y, A is o le Uni e si y o Thessaloniki,
GR-541 24 Thessaloniki, G eece; [email p o ec ed] (K.L.); [email p o ec ed] (R.O.I.)
*Co espondence: [email p o ec ed]
Abs ac
A comp ehensi e in es iga ion was conduc ed ocusing on wo se ies o poly(lac ic acid)
(PLA)-based nanocomposi es illed wi h small amoun s (0.5 and 1.0%) o me al (Ag/Cu)
nanopa icles (NPs). Ou wo k aimed o syn hesize PLA/Ag nanocomposi es ia in si u
ing-opening polyme iza ion (ROP), and o compa ison pu poses, he same ma e ials we e
also p epa ed ia solu ion cas ing ollowed by mel mixing. PLA/Cu nanocomposi es we e
also p epa ed ia mel ex usion. Gel pe mea ion ch oma og aphy (GPC) and in insic
iscosi y measu emen s [
η
] showed ha he inco po a ion o Ag nanopa icles (AgNPs)
esul ed in a dec ease in he molecula weigh o he PLA ma ix, indica ing a di ec e ec
o he AgNPs on i s mac omolecula s uc u e. Fou ie - ans o m in a ed spec oscopy
(FTIR) e ealed no signi ican changes in he cha ac e is ic peaks o he nanocomposi es,
excep o an in si u sample con aining 1.0 w % o AgNPs, whe e sligh in e ac ions in he
C=O egion we e de ec ed. Di e en ial scanning calo ime y (DSC) analysis con i med
he semi-c ys alline na u e o he ma e ials. Glass ansi ion empe a u e was s ongly
a ec ed by he p esence o NPs in he case o he in si u-based samples. Mel c ys al-
lized s udies sugges ed po en ial indi ec polyme –NP in e ac ions, while iso he mal mel
c ys alliza ion expe imen s con i med he nuclea ion abili y o he NPs. The mechanical
pe o mance was assessed ia ensile and lexu al measu emen s, e ealing ha he in si u-
based samples exhibi ed ema kable lexibili y. Mo eo e , du ing he h ee-poin bending
es s, none o he in si u nanocomposi e samples b oke. In his con ex , nex -gene a ion
PLA-based nanocomposi es ha e been p oposed o ad anced applica ions, including
lexible p in ed elec onics.
Keywo ds: poly(lac ic acid) (PLA); sil e and coppe nanopa icles; ing-opening polyme iza ion
(ROP); mel mixing; PLA lexible nanocomposi es
1. In oduc ion
The apid inc ease in global plas ic p oduc ion, es ima ed a 150 million ons in 2023
and expec ed o exceed 590 million by 2050, has highligh ed mo e han e e he u gen need
o al e na i e, sus ainable ma e ials [
1
–
3
]. Since indus ial-scale p oduc ion began in he
1950s, app oxima ely 9 billion ons ha e been p oduced, mainly om pe ochemical ma e-
ials, whose pe sis ence poses long- e m sus ainabili y issues [
4
]. Despi e hese conce ns,
con en ional plas ics con inue o domina e in he global ma ke owing o hei a o able
unc ional ad an ages and p ope ies. In esponse o hese challenges, polyme scien is s
J. Compos. Sci. 2025,9, 610 h ps://doi.o g/10.3390/jcs9110610
J. Compos. Sci. 2025,9, 610 2 o 25
and go e nmen s a e inc easingly p omo ing biobased and biodeg adable al e na i es,
suppo ing he ansi ion owa d a ci cula and sus ainable bioeconomy [5–9].
Poly(lac ic acid) (PLA), o en desc ibed as he “polyme o he 21s cen u y”, ep e-
sen s one o he mos p omising candida es in he sea ch o sus ainable ma e ials [
10
,
11
].
PLA is a linea alipha ic he moplas ic polyes e ha can be de i ed om lac ic acid
(2-hyd oxyp opionic acid). This acid is p ima ily ob ained om enewable plan -based
sou ces, such as cellulose, s a ch, co n, and ag icul u al was es. Lac ic acid can be con e ed
in o l- o d-lac ide, ollowing a polyme iza ion s ep o he syn hesis o PLA, ia ROP [
12
].
Owing o i s biocompa ibili y, mel p ocessabili y, and e sa ile pe o mance, PLA
has been widely adop ed in ields such as medical de ices, packaging ma e ials, ilms,
ibe s, he au omo i e indus y, and ag icul u e [
13
–
15
]. Depending on i s molecula weigh
and s e eochemical composi ion, PLA may exhibi ei he semic ys alline o amo phous
beha io , achie ing a balance be ween mechanical obus ness and duc ili y [
16
,
17
]. Despi e
i s ad an ages, PLA p esen s se e al d awbacks, including low mel s eng h, agili y, and
sensi i i y o mois u e and gases. I also has modes an ioxidan capaci y, low he mal
esis ance, and a slow c ys alliza ion and deg ada ion a e [18–20].
To add ess some o hese inhe en limi a ions, ecen esea ch has ocused on he inco -
po a ion o o ganic/ino ganic ille s and nanoaddi i es o op imize i s unc ional p ope ies.
Such de elopmen s ha e inspi ed inno a i e app oaches o imp o e he mechanical, he -
mal, and o he physical cha ac e is ics o PLA, o en a low addi i e concen a ions [
21
–
24
].
Hyb id nano echnology, in pa icula , has c ea ed a new e olu ion in he a ea o ma e-
ial science, de eloping he mos ad anced high- ech composi es o applica ions such
as elec onics [25–28].
Sil e is a so , noble me al wi h well-known conduc i e and an imic obial p ope ies.
In i s nanoscale o m, AgNPs a e classi ied as me al-based nanoma e ials and exhibi
enhanced unc ionali y compa ed o bulk sil e . Me al nanopa icles (MNPs), especially
AgNPs, exhibi excep ional physicochemical p ope ies ha ha e made hem he ocus
o sus ained scien i ic in e es . Owing o hese ea u es, hey a e ex ensi ely s udied o
applica ions ac oss di e se ields such as elec onics, ex iles, senso s, and nanomedicine.
AgNPs s and ou among nanoma e ials due o hei ema kable an imic obial, elec ical,
op ical, he mal, and ca aly ic p ope ies [29–36].
Simila ly, coppe (Cu), a 3d ansi ion me al, exhibi s ema kable op ical, he mal, and
elec ical p ope ies, making i ano he p omising candida e o inco po a ion in o PLA-
based nanocomposi es. Coppe nanopa icles (CuNPs) ha e been syn hesized using a ious
me hods, including chemical educ ion, he mal educ ion, and mic oemulsion echniques.
Thei ea h-abundance and low cos ha e made hem pa icula ly a ac i e o la ge-scale
applica ions. Cu en ly, CuNPs a e widely used in ag icul u al, indus ial, and echnologi-
cal ields, and ha e demons a ed aluable p ope ies such as an imic obial, bac e icidal,
and ca aly ic ac i i y. These p ope ies ha e led o hei use in an ibac e ial pha maceu icals,
ex iles, pho oca alysis, elec ical conduc o s, biochemical senso s, and coa ings o medical
equipmen . Howe e , a signi ican d awback o CuNPs is hei suscep ibili y o oxida ion
du ing syn hesis, which can limi hei s abili y and o e all unc ionali y [37–39].
Se e al s udies ha e in es iga ed he inco po a ion o Ag and Cu NPs in o PLA ma i-
ces, wi h se e al li e a u e documen s indica ing mainly imp o emen s in an imic obial
pe o mance. Speci ically, PLA/Ag sys ems ha e been widely epo ed o hei enhanced
s abili y in biomedical and packaging applica ions. Simila ly, CuNP/PLA nanocomposi es
exhibi ca aly ic ac i i y (based on he li e a u e), wi h po en ial in he mal and elec ical
applica ions. Typical p epa a ion ou es include mel mixing and solu ion cas ing, com-
bined wi h s abilize s o g een syn hesis app oaches o a oid oxida ion and agglome a ion.
Howe e , despi e hese p omising ad ances, he p epa a ion o PLA-based nanocompos-
J. Compos. Sci. 2025,9, 610 3 o 25
i es ia in si u polyme iza ion, a s a egy ha can di ec ly in luence he esul ing ma e ial
p ope ies, has no ye been explo ed [40–44].
In si u ROP [
12
,
45
] enables he de elopmen o s ong in e acial in e ac ions be ween
polyme chains and nano ille s, esul ing in homogeneous ille dispe sion and enhanced
ma e ial pe o mance. G aphene- and biocha - illed nanocomposi es p epa ed ia in si u
ROP ha e demons a ed inc eased elec ical conduc i i y and he mal s abili y, while lignin-
based PLA composi es exhibi ed imp o ed mechanical s eng h, an ioxidan ac i i y, and
UV-shielding p ope ies. Likewise, PLA/sepioli e nanocomposi es syn hesized h ough in
si u ROP e ealed s onge hyd ogen-bonding in e ac ions and enhanced c ys allini y and
mel ing beha io . Fu he mo e, he inco po a ion o o ganically modi ied mon mo illoni e
was shown o p omo e he PLA c ys alliza ion p ocess, whe eas silane-modi ied nanosilica
led o a signi ican enhancemen in c ys allini y accompanied by a ma ked educ ion
in O
2
and CO
2
pe meabili y [
46
–
50
]. To he bes o ou knowledge, he in si u-based
syn hesis o PLA nanocomposi es including Ag NPs was epo ed ecen ly by ou g oup
o he i s ime, whe e he in si u samples exhibi ed imp o ed conduc i e p ope ies [
51
].
Thus, he p esen wo k ocused on he di e en op ical and mechanical p ope ies ha he
ma e ials may exhibi compa ed o hose p epa ed by mel mixing. Mo eo e , p elimina y
expe imen s o iso he mal c ys alliza ion kine ics om he mel we e conduc ed in o de o
in es iga e he c ys alliza ion a es o he ma e ials.
In summa y, his wo k ho oughly in es iga ed he p epa a ion o poly(lac ic acid)
(PLA)-based nanocomposi es inco po a ing coppe and sil e NPs a wo di e en weigh
a ios (0.5 w % and 1.0 w %). The syn hesis o he nanocomposi e ma e ials based on
Ag was ca ied ou using wo dis inc me hods: ROP and mel mixing. The p epa ed
nanocomposi es we e comp ehensi ely cha ac e ized using a wide ange o echniques
and me hods (op ical, in a ed spec oscopy, he mal analysis, mechanical es ing, e c.),
p o iding aluable insigh s in o hei mo phology, s uc u e, he mal beha io , mechanical
pe o mance, and o e all ma e ial p ope ies. The objec i e o his s udy was o assess
he impac o MNP ype and concen a ion on he mul i unc ional pe o mance o PLA-
based nanocomposi es, aiming o unde s and he s uc u e–p ope y ela ionships o hese
ma e ials, o ad anced applica ions such as p in ed elec onics [
52
–
55
]. Las bu no
leas , i is impo an o no e ha he in si u me hod o inco po a ion o AgNPs ha was
sugges ed in he p esen wo k led o lexible PLA nanocomposi e subs a es, indica ing
s ong polyme –NP in e ac ions.
2. Ma e ials and Me hods
2.1. Ma e ials
1-dodecanol, in(II) 2-e hylhexanoa e (Sn(Oc )
2
was supplied om Ald ich Co. (Lon-
don, UK). L-lac ide (LA) (99.9%) was pu chased om PURAC Biochem BV (Go inchem,
The Ne he lands) unde he b and name PURASORB
®
L, and Luminy
®
PLA L175, o
mel low index (MFI) a 8 g/10 min (Flow, 210
◦
C/2.16 kg) and 3 g/10 min (Flow,
190
◦
C/2.16 kg), was pu chased om Co bion N.V. (Go inchem, The Ne he lands). Ag
nanopowde , APS 20–40 nm (99.9%), and Cu nanopowde , APS 20–50 nm (99.9%) nanopa -
icles we e supplied by The moFishe Scien i ic (E lenbachweg 2, 76870 Kandel, Ge many).
All o he ma e ials and sol en s used we e o analy ical g ade.
2.2. Syn hesis o PLA and PLA Nanocomposi es Based on Ag ia Ring-Opening Polyme iza ion
PLA and PLA/Ag nanocomposi es we e syn hesized h ough ROP o L-lac ide
(
Figu e 1
). The polyme iza ion was ca ied ou in a ound-bo omed lask in he p es-
ence o L-lac ide and AgNPs ( o 0.5 and 1.0 w %) (Table 1), and 400 ppm (o 0.1 mmol) o
s annous oc oa e [Sn(Oc )
2
] (as solu ion in oluene). As an ini ia o , 1-dodecanol (0.05 g/mL
J. Compos. Sci. 2025,9, 610 4 o 25
ace one) was dissol ed in ace one and in oduced in o he eac ion mix u e. To elimina e
he p esence o oxygen, he mix u e was degassed by e acua ion/ e illing cycles using
ni ogen. The eac ion was hen conduc ed unde a ni ogen a mosphe e a 160 ◦C o 2 h.
A e polyme iza ion, a high acuum (~5.0 Pa) was g adually applied o e 15 min while
main aining he empe a u e a 180
◦
C o enhance he molecula weigh o he PLA ma ix
and emo e any esidual monome . The eac ion was e mina ed by apidly cooling he
lask o oom empe a u e.
Figu e 1. Rep esen a i e scheme o he p epa a ion me hods.
Table 1. Sample abb e ia ions and composi ions.
Abb e ia ion Con en w %
PLA_in si u 100 -
PLA_mel mixing 100 -
PLA/0.5%Cu_mel mixing 99.5 0.5
PLA/1.0%Cu_mel mixing 99.0 1.0
PLA/0.5%Ag_mel mixing 99.5 0.5
PLA/1.0%Ag_mel mixing 99.0 1.0
PLA/0.5%Ag_in si u 99.5 0.5
PLA/1.0%Ag_in si u 99.0 1.0
2.3. Mas e ba ch P epa a ion ia Sol en Cas ing
P io o mel mixing, PLA-based mas e ba ches con aining ei he sil e o coppe NPs
(Table 1) we e p epa ed using he sol en cas ing me hod (Figu e 1). Comme cial PLA
was dissol ed in chlo o o m a a concen a ion o 40 mg/mL, while sil e and coppe NPs
we e sepa a ely dispe sed in chlo o o m a a concen a ion o 1 mg/mL. Bo h dispe sions
unde wen ul asonica ion o 1 h. A e wa d, he wo solu ions we e mixed and u he
sonica ed o 1 h o ensu e homogenei y. The esul ing solu ion was placed unde acuum
o sol en e apo a ion, o ming hin nanocomposi e ilms. These ilms we e cu in o small
pieces and subsequen ly used as mas e ba ches in he mel mixing p ocess.
2.4. P epa a ion o PLA-Based Nanocomposi es ia Mel Mixing
The mas e ba ch samples oge he wi h comme cial PLA we e in oduced in o a Haake–
Buchle win-sc ew co- o a ing ex ude mel mixe equipped wi h olle blades (Figu e 1).
This me hod was used o p oduce addi ional PLA-based nanocomposi es con aining ei he
J. Compos. Sci. 2025,9, 610 5 o 25
sil e (PLA/Ag) o coppe (PLA/Cu) NPs. P io o p ocessing, bo h polyme ma ices we e
d ied a 80
◦
C unde acuum o 24 h o elimina e mois u e. Mel mixing was conduc ed a
190 ◦C o 5 min a a o o speed o 30 pm.
Film P epa a ion
Comp ession molding samples we e p epa ed using an O o Webe Type PW 30 hy-
d aulic p ess (S u ga , Ge many) equipped wi h an Om on E5AX empe a u e con olle
(Kyo o, Japan). The comp ession molding condi ions di e ed depending on he o igin o
he ma e ial. Fo he ma e ials syn hesized ia ROP (PLA and PLA/Ag samples), molding
was pe o med a 162.5–165
◦
C and 100 mba . In con as , o he nanocomposi es p e-
pa ed ia mel mixing (PLA, PLA/Ag and PLA/Cu samples), he molding empe a u e
was highe , anging om 172.5 o 175
◦
C and 100 mba . The ilms we e hen cooled o
oom empe a u e (Figu e 2). All samples exhibi ed a uni o m hickness o app oxima ely
0.40 ±0.03 mm.
Figu e 2. Comp ession-molded samples o PLA, and PLA nanocomposi es.
2.5. Cha ac e iza ion Techniques
2.5.1. In insic Viscosi y
In insic iscosi y [
η
] measu emen s we e conduc ed using an Ubbelohde iscome e
(capilla y 0c) a 25
◦
C, wi h chlo o o m as he sol en . The solu ions we e il e ed h ough a
disposable Te lon memb ane o emo e any solid esidues. In insic iscosi y was calcula ed
by applying he Solomon–Cui a equa ion:
[η]=2n
o
−ln
o−1o1/2
c(1)
whe e c is he solu ion concen a ion, is he low ime o he solu ion, and
0
is he low
ime o pu e sol en . Each measu emen was pe o med wice.
2.5.2. Gel Pe mea ion Ch oma og aphy (GPC)
The molecula weigh o he ma e ials was de e mined using GPC/SEC analysis. The
analysis was conduc ed on an Agilen 1260 In ini y II LC sys em (Agilen Technologies,
San a Cla a, CA, USA), which included an isoc a ic G7110B pump, an au oma ic ial
sample G7129A, a e ac i e index de ec o (RID) G7162A, a PLgel 5
µ
M (50
×
7.5 mm)
gua d column, and wo PLgel 5
µ
M (300
×
7.5 mm) MIXED-C columns. Calib a ion was
pe o med using poly(me hyl me hac yla e) (PMMA) s anda ds wi h molecula weigh s
anging om 0.535 o 1.591 kg/mol. Samples we e p epa ed by dissol ing hem in CHCl
3

J. Compos. Sci. 2025,9, 610 6 o 25
a a concen a ion o 3 mg/mL and il e ing he solu ion h ough a 0.45
µ
m PTFE mic o il e
o elimina e any solid esidues. Each sample was injec ed in a 20
µ
L olume, wi h a o al
elu ion ime o 30 min. Bo h he column and RID empe a u es we e main ained a 40
◦
C
h oughou he analysis. Each measu emen was pe o med wice.
2.5.3. A enua ed To al Re lec ance Fou ie -T ans o m In a ed Spec oscopy (ATR-FTIR)
FTIR spec a we e eco ded using an IRT ace -100 spec opho ome e (Shimadzu,
Kyo o, Japan) equipped wi h a QATR™ 10 single- e lec ion ATR accesso y. Each spec um
was collec ed in he wa enumbe ange o 4000–500 cm
−1
, wi h a esolu ion o 2 cm
−1
, and
a o al o 32 co-added scans. The ob ained spec a we e no malized p io o analysis.
2.5.4. Colo Measu emen s
Colo measu emen s we e pe o med using a Da acolo Spec a lash SF600 plus CT UV
e lec ance colo ime e (Da acolo , Ma l, Ge many) using he D65 illuminan , 101 s anda d
obse e wi h UV componen excluded and specula componen included. In each case,
i e old measu emen s we e pe o med using a special holde (Da acolo ) and he mean
alues we e calcula ed. The colo alues we e calcula ed using he CIE L*a*b* colo space
sys em. In his sys em, L* ep esen s he ligh ness (L* = 0: black, L* = 100: whi e). The
a* alue co esponds o he g een– ed axis, whe e nega i e a* alues indica e g een and
posi i e a* alues indica e ed hues. The b* alue ep esen s he blue–yellow axis, whe e
nega i e b* alues indica e blue and posi i e b* alues indica e yellow hues.
2.5.5. Di e en ial Scanning Calo ime y (DSC)
Di e en ial scanning calo ime y (DSC) analysis was pe o med using a Pe kinElme
Py is Diamond DSC (Solingen, Ge many) calib a ed wi h pu e indium, in, and zinc s an-
da ds. The ins umen was equipped wi h a Pe kinElme In acoole 2 cooling accesso y
and ope a ed unde a ni ogen a mosphe e. Samples o 5.0
±
0.1 mg we e sealed in alu-
minum pans p io o es ing o e alua e he he mal beha io o he polyme s. In o de o
e ase he he mal his o y o he sample, an ini ial hea ing scan was pe o med (T
m
+ 30
◦
C).
A e he i s hea ing scan, he samples we e quenched a 150
◦
C/min, and hen ehea ed
a 20
◦
C/min o de e mine he glass ansi ion empe a u e (T
g
), cold c ys alliza ion em-
pe a u e (T
cc
), and mel ing empe a u e (T
m
). Finally, he samples we e cooled again om
200 ◦C o Tg−40 ◦C a 10 ◦C/min o de e mine hei c ys alliza ion empe a u e (Tc).
Iso he mal mel c ys alliza ion expe imen s we e pe o med o e alua e he c ys al-
liza ion a es o he ma e ials. The samples we e hea ed a 40
◦
C abo e hei T
m
and held
he e o 3 min o e ase any he mal his o y, and hen a cooling s ep in he DSC a he
highes a e possible was pe o med a speci ic c ys alliza ion empe a u es. The inal s ep
was a subsequen hea ing a 40
◦
C abo e hei T
m
, wi h a hea ing s ep a 20
◦
C/min. All
measu emen s we e pe o med wice.
2.5.6. X-Ray Di ac ion (XRD)
Samples we e subjec ed o X- ay di ac ion measu emen s wi h he MiniFlex II XRD
sys em om Rigaku Co. (Tokyo, Japan) wi h CuKa adia ion (
λ
= 0.154 nm) in he angle 2
θ
ange om 5 o 45
◦
a a scanning a e o 1
◦
C/min. The sample holde o he measu emen s
was app oxima ely 32 mm in diame e . Fo each case, la comp ession-molded samples
we e used.
2.5.7. Tensile P ope ies
The ensile p ope ies o he samples we e measu ed using a Shimadzu EZ Tes Tensile
Tes e (Model EZ-LX) (1, Nishinokyo Kuwaba a-cho, Nakagyo-ku, Kyo o 604-8511, Japan)
equipped wi h a 2 kN load cell, in acco dance wi h ASTM D882, a a c osshead speed o
J. Compos. Sci. 2025,9, 610 7 o 25
5 mm/min. Dumbbell-shaped ensile specimens (cen al po ion: 5 mm wide
×
0.5 mm
hick, 22 mm gauge leng h) we e p epa ed by cu ing he comp ession-molded samples
using a Wallace cu ing p ess. A leas i e measu emen s we e pe o med o each sample,
and mean alues we e calcula ed o he ensile pa ame e s.
2.5.8. Flexu al P ope ies
Th ee-poin bending es s we e conduc ed using a Shimadzu EZ Flexu al Tes e (Model
EZ-LX) equipped wi h a 2 kN load cell, in acco dance wi h ASTM D790-17. Comp ession-
molded samples we e p epa ed using a he mop ess, wi h dimensions o 12.7 mm in wid h
and 1.6 mm in hickness. The samples we e es ed la wise on he suppo span, wi h
a suppo span- o-dep h a io o 16:1 (
±
1 ole ance). Fo each sample ype, a leas i e
measu emen s we e pe o med, and mean alues we e calcula ed o he lexu al modulus
and lexu al s eng h.
2.5.9. Wa e Con ac Angle
Wa e con ac angles we e measu ed using he sessile d op me hod wi h an Ossila Con-
ac Angle Goniome e (model L2004A1; Ossila L d., She ield, UK). All measu emen s we e
pe o med in iplica e, and he esul s a e epo ed as mean and s anda d de ia ion (SD).
3. Resul s and Discussion
3.1. Syn hesis and S uc u al In es iga ion o PLA and PLA/Ag-Cu Nanocomposi es
Gel pe mea ion ch oma og aphy (GPC) (Figu e 3) analysis was pe o med o de e -
mine he numbe -a e age molecula weigh (
Mn
) o he syn hesized in si u nanocomposi e
ma e ials and PLA comme cial samples, along wi h in insic iscosi y [
η
] measu emen s
(Figu e 4). F om he GPC analysis, i was obse ed ha he inco po a ion o AgNPs in o
he PLA ma ix a bo h 0.5 w % and 1.0 w % led o a dec ease in bo h molecula weigh
and in insic iscosi y alues [
46
]. These indings sugges ed ha he p esence o AgNPs
di ec ly a ec ed he mac omolecula s uc u e o PLA. The Ag NPs p obably p o ided
addi ional ac i e si es o he ROP o L-lac ide, acili a ing PLA chain g ow h while main-
aining a nea ly unchanged polydispe si y index [
51
]. This beha io co ela ed wi h he
educed glass ansi ion empe a u e and c ys alline ac ion o he PLA in si u-based
nanocomposi es compa ed o he nea in si u PLA sample.
Figu e 5a shows he ATR-FTIR spec a o he PLA nea and PLA-based nanocomposi es.
The main cha ac e is ic peaks o PLA a e obse ed a 3000–2850 cm
−1
, co esponding
o symme ic and asymme ic C–H s e ching ib a ions; a 1750 cm
−1
, a ibu ed o
ca bonyl (C=O) s e ching; and a 1500–1400 cm
−1
and 1100–1000 cm
−1
, associa ed wi h
C–H bending and C–O s e ching ib a ions, espec i ely. The spec a o he syn hesized
PLA ia in si u ROP con i med he success ul polyme iza ion [
12
,
46
,
51
]. Fo he case
o nanocomposi es, no addi ional peaks ela ed o me allic coppe and sil e NPs we e
de ec ed, indica ing no chemical in e ac ions be ween PLA and he NPs. Pu e me als do
no exhibi cha ac e is ic IR peaks, as me allic bonds do no p esen any speci ic ib a ional
modes as co alen bonds do [56,57].
Focusing on he ca bonyl egion a ound 1750 cm−1(Figu e 5b), he peak’s cu e and
in ensi y emained consis en , which means ha he C=O bond’s elec onic en i onmen
was no a ec ed by he p esence o he me als. Howe e , only in he case o he sample
PLA_1.0%Ag_in si u do we obse e some in e ac ions in he C=O a ea. This suppo s he
p esence o in e acial in e ac ions be ween he Ag NPs and he PLA ma ix, meaning ha
possible polyme –NP bonds could o m du ing ROP.
J. Compos. Sci. 2025,9, 610 8 o 25
51015
PLA_mel mixing
PLA_in si u
PLA/0.5%Ag_in si u
PLA/1.0%Ag_in si u
De ec o esponse (nRID)
Time (min)
Figu e 3. GPC cu es o PLA samples, and PLA/Ag nanocomposi es p epa ed by ROP o he
L-lac ide.
0
20
40
60
80
100
120
140
160
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
Polydispe si y index, D
PLA
in si u
PLA
1.0%Ag
in si u
PLA
0.5%Ag
in si u
PLA
mel
mixing
Molecula weigh (kg/mol)
PLA
1.0%Ag
in si u
PLA
0.5%Ag
in si u
PLA
mel
mixing
PLA
in si u
Samples
(a) (b)
Figu e 4. (a) Numbe -a e age molecula weigh (
Mn
) (GPC) and (b) in insic iscosi y [
η
] o PLA
samples and PLA_Ag/Cu nanocomposi es.
J. Compos. Sci. 2025,9, 610 9 o 25
4000 3500 3000 2500 2000 1500 1000 500
Abso bance (a.u.)
Wa enumbe (cm-1)
PLA/mel -mixing
PLA/in si u
PLA/0.5%Cu_mel -mixing
PLA/1.0%Cu_mel -mixing
PLA/0.5%Ag_mel -mixing
PLA/1.0%Ag_mel -mixing
PLA/0.5%Ag_in si u
PLA/1.0%Ag_in si u
1800 1780 1760 1740 1720 1700
No malized Abso bance (a.u.)
Wa enumbe (cm-1)
PLA_in si u
PLA_mel mixing
PLA/0.5%Ag_in si u
PLA/0.5%Ag_mel mixing
PLA/1.0%Ag_in si u
PLA/1.0%Ag_mel mixing
PLA/0.5%Cu_mel mixing
PLA/1.0%Cu_mel mixing
PLA/Ag in si u
1.0 w %
(a)
(b)
Figu e 5. (a) ATR-FTIR spec a o PLA and PLA nanocomposi es and (b) zoom a ea a he ca -
bonylic egion.
3.2. Op ical P ope ies
The op ical p ope ies o he samples we e assessed and he colo di e ences be-
ween he ma e ials we e exp essed by L*a*b* pa ame e s. The indings a e p esen ed
in Figu e 6, while Figu es 7and 8show he ansmi ance and colo as eco ded by he
spec opho ome e .
−10
0
10
20
30
40
50
60
70
80
90
100
L*
a*
b*
A.U.
PLA
in si u
PLA
1.0%Ag
in si u
PLA
0.5%Ag
in si u
PLA
1.0%Ag
mel
mixing
PLA
0.5%Ag
mel
mixing
PLA
mel
mixing
Sample
PLA
0.5%Cu
mel
mixing
PLA
1.0%Cu
mel
mixing
Figu e 6. CIE L*a*b* coo dina es o PLA samples and PLA nanocomposi es. L*: pe cep ual ligh ness,
a* and b*: ed–g een and blue–yellow.
J. Compos. Sci. 2025,9, 610 16 o 25
samples exhibi ed imp o ed c ys alliza ion a es. Fu he mo e, he addi ion o AgNPs ia
he in si u syn hesis signi ican ly a ec ed he kine ic beha io o he samples, e ealing
hei nuclea ion abili y and also he ac ha he in si u polyme iza ion me hod used in he
p esen wo k di ec ly a ec ed he c ys alliza ion kine ics o he ma e ials [
68
,
69
]. Due o
he high sensi i i y o he iso he mal c ys alliza ion expe imen s and he nume ous ac o s
ha may di ec ly a ec he esul s, compa ison wi h p e ious s udies is a he di icul . Fo
ins ance, amo phous ma e ials end o ha e signi ican ly high c ys alliza ion hal - imes
(i.e., low c ys alliza ion a es) [
61
]. Mo eo e , depending on he c ys alliza ion empe a u e
a which he expe imen s occu ed, he end o he c ys alliza ion a es ollowed he op-
posi e end (i.e., high c ys alliza ion a es) [
70
]. Mo eo e , he subsequen hea ing aces
(Figu e 13d) showed ha all samples exhibi ed mul iple Tm[71].
(a) (b)
(c) (d)
03691215
in si u
samples
No malized Hea Flow (W/g) - Endo up
Time (min)
0.05 W/g
PLA_in si u
PLA_mel mixing
PLA/0.5%Cu_mel mixing
PLA/1.0%Cu_mel mixing
PLA/0.5%Ag_mel mixing
PLA/1.0%Ag_mel mixing
PLA/0.5%Ag_in si u
PLA/1.0%Ag_in si u
in si u
samples
024681012
0
20
40
60
80
100
Rela i e Deg ee o C ys allini y (%)
Time (min)
PLA_in si u
PLA_mel mixing
PLA/0.5%Cu_mel mixing
PLA/1.0%Cu_mel mixing
PLA/0.5%Ag_mel mixing
PLA/1.0%Ag_mel mixing
PLA/0.5%Ag_in si u
PLA/1.0%Ag_in si u
PLA_in si u
PLA/0.5%Ag_in si u
PLA/1.0%Ag_in si u
PLA_mel mixing
PLA/0.5%Ag_mx
PLA/1.0%Ag_mx
PLA/0.5%Cu_mx
PLA/1.0%Cu_mx
1.0
1.5
2.0
2.5
3.0
3.5
4.0
C ys alliza ion hal - ime (min)
Samples
in si u samples
mel mixed samples
120 130 140 150 160 170 180
III
II
I
PLA/1.0%Ag_in si u
PLA/0.5%Ag_in si u
PLA_in si u
PLA/1.0%Cu_mel mixing
PLA/0.5%Cu_mel mixing
PLA/1.0%Ag_mel mixing
PLA/0.5%Ag_mel mixing
subsequen hea ing 0.2 W/g
No malized Hea Flow (W/g) - Endo up
Tempe a u e (oC)
PLA_mel mixing
I
II
III
Figu e 13. Iso he mal c ys alliza ion o he samples o
∆
T = 55. (a) Exo he mic c ys alliza ion
cu es, (b) ela i e deg ee o c ys allini y as a unc ion o ime, (c) c ys alliza ion hal - ime, and
(d) subsequen hea ing aces o he ma e ials.

J. Compos. Sci. 2025,9, 610 17 o 25
3.4. Mechanical E alua ion ia Tensile and Th ee-Poin Bending Tes s
The mechanical pe o mance o he PLA-based nanocomposi es was ho oughly in es-
iga ed h ough s ess–s ain and h ee-poin bending measu emen s (Figu e 14, Table 3).
(a) (b)
0123456
0
10
20
30
40
50
60
PLA/in si u
PLA/0.5%Ag_in si u
PLA/1.0%Ag_in si u
PLA/mel mixing
PLA/0.5%Ag_mel mixing
PLA/1.0%Ag_mel mixing
PLA/0.5%Cu_mel mixing
PLA/1.0%Cu_mel mixing
Tensile S ess (MPa)
Tensile s ain (%)
in si u
samples
0 20406080100120140
0
5
10
15
20
25
30
PLA/0.5%Ag_in si u
PLA/1.0%Ag_in si u
Tensile s ess (MPa)
Tensile s ain
(
%
)
PLA/Ag_in si u samples
Figu e 14. (a) Rep esen a i e ensile s ess–s ain cu es o PLA samples and PLA nanocomposi es,
and (b) he case o PLA/Ag in si u-based samples.
Table 3. Tensile da a o PLA samples and PLA nanocomposi es.
Sample
Tensile S ess a B eak
(MPa)
Tensile S ess a Yield
(MPa)
Elonga ion
(%)
Young’s Modulus
(MPa)
PLA_in si u 35.5 ±4.9 30.7 ±2.2 1.3 ±0.1 3660.7 ±78.9
PLA_mel mixing 53.7 ±2.1 52.1 ±3.7 2.2 ±0.3 3788.1 ±94.7
PLA/0.5%Cu_mel mixing 29.0 ±5.0 30.2 ±4.7 1.8 ±0.5 3149.9 ±680.8
PLA/1.0%Cu_mel mixing 42.5 ±4.7 43.7 ±4.8 1.9 ±0.6 4003.7 ±523.7
PLA/0.5%Ag_mel mixing 47.9 ±3.4 50.4 ±1.7 2.4 ±0.9 3727.9 ±172.7
PLA/1.0%Ag_mel mixing 45.1 ±2.1 48.0 ±2.6 2.3 ±0.4 3687.7 ±87.1
PLA/0.5%Ag_in si u 15.5 ±1.5 17.7 ±6.9 22.2 ±0.5 1772.3 ±378.6
PLA/1.0%Ag_in si u 7.1 ±1.4 10.9 ±5.0 136.9 ±17.2 1484.7 ±360.8
The PLA mel -mixed sample exhibi ed be e mechanical pe o mance compa ed o
he sample syn hesized ia he in si u me hod. Speci ically, he PLA_mel mixing sample
demons a ed a yield s ess o 52 MPa (Figu e 15a), a b eak s ess o 54 MPa, and a Young’s
modulus o ~3790 MPa. In con as , he in si u PLA-based ma e ial showed sligh ly lowe
alues, wi h a yield s ess o 30 MPa, b eak s ess o 35 MPa, and a Young’s modulus o
~3660 MPa. Rega ding he PLA/Ag nanocomposi es, he addi ion o AgNPs a 0.5 w %
and 1.0 w % ia mel mixing did no al e he mechanical esponse o he PLA ma ix. Bo h
yield and b eak s esses emained a high alues (e.g., yield s ess: ~50 MPa and ~48 MPa;
b eak s ess: ~48 MPa and ~45 MPa, espec i ely), and he Young’s modulus (Figu e 15c)
was wi hin he same ange (~3720 MPa and ~3690 MPa) as ha o nea PLA. This can be
explained by he ac ha he addi ion o sil e and coppe NPs ia mel mixing did no
signi ican ly change he c ys allini y o he samples, which di ec ly a ec s he mechanical
pe o mance o he ma e ials (Figu e 10b) [
72
–
75
]. Simila beha io was also epo ed by
J. Compos. Sci. 2025,9, 610 18 o 25
Bau is a and Nabgui e al., whe e he inco po a ion o AgNPs h ough mel mixing did no
signi ican ly a ec he Young’s modulus o PLA-based composi es [
43
,
76
]. A simila end
was obse ed in PLA/Cu nanocomposi es, whe e only he 0.5 w % Cu samples exhibi ed
signi ican ly lowe mechanical pe o mance compa ed o he 1.0 w % Cu sample. These
esul s we e in ag eemen wi h he indings o B una e al., who epo ed ha mel -mixed
PLA/Cu nanocomposi es main ained simila s i ness o nea PLA [38].
0
10
20
30
40
50
60
S ess a Yield (MPa)
Sample
PLA
in si u
PLA
mel
mixing
PLA
0.5%Cu
mel
mixing
PLA
1.0%Cu
mel
mixing
PLA
0.5%Ag
mel
mixing
PLA
1.0%Ag
mel
mi xin g
PLA
0.5%Ag
in si u
PLA
1.0%Ag
in si u
0
10
20
30
40
50
60
S ess a b eak (MPa)
PLA
1.0%Ag
in si u
PLA
0.5%Ag
in si u
PLA
1.0%Ag
mel
mixing
PLA
0.5%Ag
mel
mixing
PLA
1.0%Cu
mel
mixing
PLA
0.5%Cu
mel
mixing
PLA
mel
mixing
PLA
in si u
Sample
(a) (b)
0
500
1000
1500
2000
2500
3000
3500
4000
4500
5000
Young's Modulus (MPa)
PLA
in si u
PLA
1.0%Ag
in si u
PLA
0.5%Ag
in si u
PLA
1.0%Ag
mel
mixing
PLA
0.5%Ag
mel
mixing
PLA
1.0%Cu
mel
mixing
PLA
0.5%Cu
mel
mixing
PLA
mel
mixing
Sample
0
15
20
25
130
135
140
145
150
155
Elonga ion (%)
PLA
0.5%Ag
mel
mixing
PLA
1.0%Cu
mel
mixing
PLA
0.5%Cu
mel
mixing
PLA
mel
mixing
PLA
in si u
Sample
PLA
1.0%Ag
mel
mixing
PLA
0.5%Ag
in si u
PLA
1.0%Ag
in si u
(c) (d)
Figu e 15. Tensile p ope ies o PLA samples and PLA nanocomposi es. (a) S ess a Yield, (b) S ess
a b eak, (c) Young’s Modulus, and (d) Elonga ion as a unc ion o he samples.
In con as , he in si u samples o PLA/Ag nanocomposi es esul ed in ema k-
able di e ences in he mechanical p ope ies among he samples p epa ed by mel mix-
ing. Tensile s eng h (Figu e 15b) educed wi h inc easing sil e con en . Fo ins ance,
J. Compos. Sci. 2025,9, 610 19 o 25
PLA/0.5%Ag_in si u showed a yield s ess o 17 MPa and a b eak s ess o 15 MPa, while
o he PLA/1.0%Ag_in si u sample, hese alues d opped e en u he o 10 MPa and
7 MPa, espec i ely. Co espondingly, he Young’s modulus dec eased o ~1770 MPa and
~1480 MPa. The d as ic change in he mechanical pe o mance o he ma e ials occu ed
due o he educ ion in T
g
compa ed o he nea PLA in si u-based sample. This indi-
ca ed inc eased molecula mobili y in he amo phous egions, leading o a so e and less
igid ma e ial.
Howe e , in he case o elonga ion a b eak o he in si u samples (Figu e 14b), a su -
p ising and no ewo hy end was obse ed. While bo h nea PLA and mel -mixed PLA/Ag
nanocomposi es exhibi ed ex emely low elonga ion alues, he in si u-p epa ed PLA/Ag
samples demons a ed a ema kable inc ease in duc ili y. Speci ically, PLA/0.5%Ag_in si u
exhibi ed ~22% elonga ion a b eak, and PLA/1.0%Ag_in si u eached an imp essi e 137%
(Figu e 15d). This highe duc ili y occu ed because o he inc eased chain mobili y and
lexibili y (lowe T
g
), which allowed he ma e ial o unde go signi ican plas ic de o ma ion
be o e ailu e. Despi e hei low s eng h and s i ness, hese in si u ma e ials exhibi ed
excep ional mechanical pe o mance compa ed o he inhe en b i leness o PLA. These
indings sugges ha PLA/Ag nanocomposi e samples syn hesized ia in si u ROP could
be p omising subs a es o lexible p in ed elec onic applica ions [77–79].
Flexu al es ing is a c ucial echnique in p in ed elec onic applica ions as i e alua es
de ice pe o mance unde bending and de o ma ion. These expe imen s p o ide essen ial
mechanical da a o he design o mo e eliable p in ed de ices and assis in iden i ying he
de o ma ion limi s be o e unc ional ailu e occu s [80].
Mo ing on o he lexu al p ope ies, he esul s (Figu e 16, Table 4) ollowed a simila
end o he ensile es s. Nea PLA p epa ed by mel mixing showed highe s eng h
(Figu e 17a) compa ed o in si u-syn hesized PLA, while he inco po a ion o Ag and Cu
NPs h ough mel mixing did no signi ican ly a ec he o e all mechanical pe o mance o
PLA. In con as , he in si u- ab ica ed PLA/Ag nanocomposi es displayed lowe lexu al
s eng h consis en wi h he end obse ed in he ensile da a. I is impo an o no e ha ,
du ing he h ee-poin bending es s, none o he in si u nanocomposi e samples ac u ed
(Figu e 16), which highligh s hei sui abili y as subs a es o lexible p in ed elec onic
applica ions [
80
]. The lexu al modulus (Figu e 17b) ollowed he same o e all endency,
whe e mel -mixed PLA nanocomposi es showed highe s i ness compa ed o nea PLA,
while he in si u-p epa ed PLA/Ag sys ems exhibi ed a dec eased modulus.
Table 4. Flexu al da a o PLA samples and PLA nanocomposi es.
Samples Flexu al S eng h
(MPa) Flexu al Modulus (MPa)
PLA_in si u 18.8 ±4.6 1126.9 ±230.2
PLA_mel mixing 40.1 ±9.6 1658.3 ±162.9
PLA/0.5%Cu_mel mixing 35.1 ±7.9 1223.3 ±213.4
PLA/1.0%Cu_mel mixing 49.2 ±12.1 1726.0 ±198.7
PLA/0.5%Ag_mel mixing 41.1 ±2.4 1817.1 ±285.3
PLA/1.0%Ag_mel mixing 43.0 ±11.5 1986.5 ±325.6
PLA/0.5%Ag_in si u 0.9 ±0.4 856.9 ±180.6
PLA/1.0%Ag_in si u 20.2 ±2.9 268.6 ±153.7
J. Compos. Sci. 2025,9, 610 20 o 25
01234567
0
10
20
30
40
50
60 PLA/in si u
PLA/0.5%Ag_in si u
PLA/1.0%Ag_in si u
PLA/mel mixing
PLA/0.5%Ag_mel mixing
PLA/1.0%Ag_mel mixing
PLA/0.5%Cu_mel mixing
PLA/1.0%Cu_mel mixing
Flexu al S ess (MPa)
Flexu al s ain (%)
Figu e 16. Rep esen a i e lexu al s ess–s ain cu es o PLA samples and PLA nanocomposi es.
0
10
20
30
40
50
60
Flexu al S eng h (MPa)
Sample
PLA
1.0%Ag
in si u
PLA
0.5%Ag
in si u
PLA
1.0%Ag
mel
mi xing
PLA
0.5%Ag
mel
mixing
PLA
1.0%Cu
mel
mixing
PLA
0.5%Cu
mel
mixing
PLA
mel
mixing
PLA
in si u
0
500
1000
1500
2000
Flexu al Modulus (MPa)
PLA
1.0%Ag
in si u
PLA
in si u
PLA
mel
mixing
PLA
0.5%Cu
mel
mixing
PLA
1.0%Cu
mel
mixing
Sample
PLA
0.5%Ag
mel
mixing
PLA
1.0%Ag
mel
mixing
PLA
0.5%Ag
in si u
(a) (b)
Figu e 17. Flexu al p ope ies o he PLA nanocomposi es ma e ials. (a) Flexu al s eng h, and
(b) Flexu al Modulus o he samples. The Flexu al S eng h indica es he maximum lexu al s ess he
ma e ial can wi hs and du ing he expe imen s.
3.5. Su ace P ope ies
The e ec o he hyd ophilici y o hyd ophobici y o he composi es was explo ed
by measu ing he wa e con ac angle (Figu e 18). The wa e con ac angle o polyme s
depends on a ious ac o s, including su ace p ope ies, p epa a ion me hod, su ace
oughness, chemical composi ion, and empe a u e. The PLA samples (PLA_in si u and
PLA_mel mixing) exhibi ed ela i ely high con ac angles o app oxima ely 85
◦
and 83
◦
,
espec i ely. These alues we e consis en wi h he li e a u e [
81
], indica ing ha nea
PLA has a ela i ely hyd ophobic su ace. The small di e ence be ween he wo samples
J. Compos. Sci. 2025,9, 610 21 o 25
sugges ed ha he ab ica ion me hod (in si u polyme iza ion s. mel mixing) did no
signi ican ly in luence he hyd ophilici y o he PLA ma ix. Wi h he addi ion o coppe
and sil e NPs ia mel mixing, he con ac angle dec eased, indica ing inc eased su -
ace hyd ophilici y. PLA/0.5%Ag_mel mixing shows a con ac angle o ~79
◦
, while o
he sample o PLA/1%Ag_mel mixing, he angle dec eased o ~76
◦
. Simila ly, he Cu-
nanocomposi es exhibi ed con ac angles o ~76
◦
o PLA/0.5%Cu_mel mixing and ~77
◦
o PLA/1%Cu_mel mixing, indica ing a sligh inc ease in hyd ophilici y compa ed o nea
PLA. A simila end was obse ed o he in si u-based samples, whe e PLA/0.5%Ag_in
si u exhibi ed he lowes con ac angle ~72
◦
, whe eas inc easing he Ag con en o 1%_in
si u inc eased he wa e con ac angle.
0
20
40
60
80
100
Con ac angle (o)
PLA
in si u
PLA
1.0%Ag
in si u
PLA
0.5%Ag
in si u
PLA
1.0%Ag
mel
mixing
PLA
0.5%Ag
mel
mixing
PLA
1.0%Cu
mel
mixing
PLA
0.5%Cu
mel
mixing
PLA
mel
mixing
Sample
Figu e 18. Wa e con ac angle o PLA samples and PLA nanocomposi es.
4. Conclusions
Ag nanocomposi e ma e ials based on PLA we e success ully syn hesized ia in
si u ing-opening polyme iza ion (ROP), and addi ional ma e ials we e p epa ed by mel
mixing p io o sol en cas ing based on Ag and Cu NPs. GPC measu emen s con i med
ha he p esence o sil e nanopa icles a ec ed he mac omolecula s uc u e o he PLA,
leading o a educ ion in molecula weigh . Mo eo e , he op ical p ope ies e ealed clea
di e ences be ween he wo p epa ed me hods. The chemical s uc u e was in es iga ed
by FTIR. The al e a ion in he es e g oup ib a ions obse ed in he FTIR spec a o he
PLA_1.0%Ag_in si u sample indica ed polyme –NP in e ac ions. Acco ding o he DSC,
he ma e ials exhibi ed semi-c ys alline cha ac e is ics, as e idenced by XRD analysis.
Mo eo e , T
g
was signi ican ly a ec ed by he p esence o NPs du ing he ROP o L-lac ide,
leading o so e ma e ials wi h inc eased molecula mobili y. Fu he mo e, du ing mel
c ys alliza ion, signi ican di e ences in c ys allini y be ween he wo di e en syn hesized
me hods we e obse ed, indi ec ly indica ing ha s ong polyme –NP in e ac ions can
occu h ough in si u polyme iza ion. Iso he mal mel c ys alliza ion s udies con i med
he nuclea ion abili y o he NPs, especially in he case o he in si u-based me hod o
p epa a ion. The mechanical e alua ion indica ed ha while he mel -mixed samples
main ained high s eng h and s i ness, he in si u nanocomposi es showed ema kable
lexibili y, wi h PLA/1.0%Ag_in si u eaching an imp essi e elonga ion o 137%. Despi e
hei lowe s eng h and s i ness, he in si u-based ma e ials did no b eak du ing he

J. Compos. Sci. 2025,9, 610 22 o 25
h ee-poin bending es s. The su ace p ope ies o PLA did no signi ican ly change wi h
he addi ion o Ag and Cu nanopa icles. This wo k demons a es he ad an ages o in si u
ROP o e con en ional me hods in achie ing supe io unc ional subs a es o ad anced
enginee ing applica ions such as biosenso s and wea able and lexible p in ed elec onics.
Fu u e wo k should ocus on he upscaled p oduc ion o PLA nanocomposi es based on
a ious NPs, such as me al nanopa icles, ia cas ilm ex usion in o de o ob ain cas ilm
shee s, which can be used as subs a es o enginee ing applica ions.
Au ho Con ibu ions: In es iga ion, w i ing—o iginal d a , w i ing— e iew and edi ing, isual-
iza ion: K.L. and R.O.I.; concep ualiza ion, w i ing— e iew and edi ing, supe ision: D.N.B. All
au ho s ha e ead and ag eed o he published e sion o he manusc ip .
Funding: This esea ch was unded by he Eu opean Union unde he GA no 101070556 (Sus ain-
a-P in , h ps://www.sus ainap in .eu/). Views and opinions exp essed a e howe e hose o he
au ho (s) only and do no necessa ily e lec hose o he Eu opean Union o RIA. Nei he he
Eu opean Union no he g an ing au ho i y can be held esponsible o hem.
Da a A ailabili y S a emen : The GPC, FTIR, CIE, DSC, XRD, ensile and lexu al aw da a a e
a ailable on Zenodo (h ps://zenodo.o g/ eco ds/17520935, accessed on 1 No embe 2025). The
es o he da a suppo ing his a icle will be a ailable upon eques o he co esponding au ho s,
uniquely in he ame o p i a e communica ion.
Con lic s o In e es : All au ho s decla e ha he esea ch was conduc ed in he absence o any
comme cial o inancial ela ionships ha could be cons ued as a po en ial con lic o in e es .
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