Compu a ional ools o biodeg adable polyme s and
sus ainable p ac ices
Pe a Baˇ
co á, Ele he ios Ch is o i, Vagelis Ha manda is,
Se gio I. Molina
Depa amen o de Ciencia de los Ma e iales e Ingenie ía Me alú gica y Química
Ino gánica, Facul ad de Ciencias, IMEYMAT, Campus Uni e si a io Río San Ped o
s/n., Pue o Real, Cádiz 11510, Spain
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Role o compu a ional me hods in ma e ial design
D. J. Audus and J. J. de Pablo, ACS Mac o Le e s 2017 6 (10), 1078-1082
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Ma e ial design a Uni e si y o Cádiz
De elopmen o sus ainable polyme -based ma e ials o ien ed
owa ds he design o p oduc s in la ge o ma addi i e
manu ac u ing, PhD hesis, Ped o Bu gos Pin os
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[1,2]
*
[1] h ps://adico k.es/index.php/sec o es/; [2] C ea ed wi h BioRende .com
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Poly(lac ic acid) in addi i e manu ac u ing
3widely popula , easy o p in
3low mel ing poin , no hea ed ay
8sensi i e o sunligh and high
empe a u es
8comme cial samples o unknown
composi ion
úL- s. D- s e eoisome
úaddi i es, polydispe se samples
úempi ical app oach o
nanocomposi e design: basal
ibe s inc ease Tgand CTE [1]
[1] P. Bu gos Pin os, Mas e hesis
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(2) Recocido en el ango de 80-130ºC se puede u iliza pa a p omo e la c is alización y mejo a la empe a u a de de lexión é mica de la
pa e imp esa en 3D.
Pos -annealing in he ange o 80-130ºC can be used o p omo e c ys alliza ion and imp o e he hea de lec ion empe a u e o he 3D
p in ed pa .
0-60 ºC
SMARTFIL PLA 3D850
Physical P ope ies Typical Value Tes Me hod
Ma e ial Densi y 1,24 g/cm3ISO 1183
Chemical Name Polylac ic Acid
Mechanical P ope ies Typical Value Tes Me hod
Flexu al S engh 126 MPa ASTM D790
Flexu al Modulus 4357 MPa ASTM D790
Tensile Yield S engh 65.5 MPa ASTM D882
No ched Izod Impac 40 J/m ASTM D256
The mal P ope ies Typical Value Tes Me hod
Hea De lec ion Tempe a u e 144 ºC 2ISO 75
P in ing P ope ies Typical Value
P in Tempe a u e 210 10 ºC
Ho Pad
Fan Laye On (100%)
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Rheology o poly(lac ic acid)
Ïe ec o he inc easing D-con en
Ï100k, 423K, 10%, 25%, 50%, 100%
101
102
103
104
105
106
107
108
100101102103104105106107
%D
dynamic moduli (G’,G’’)bT (Pa)
angula equency ωαΤ ( ad/s)
G’, D100
G’’, D100
G’, L50D50
G’’, L50D50
G’, L75D25
G’’, L75D25
G’, L90D10
G’’, L90D10
O hman, No hayani, PhD hesis, 2012
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Rheology o poly(lac ic acid)
Ïe ec o ac ici y
Ï≈150k, 50% D, syndio ac ic s. a ac ic
O hman, No hayani, PhD hesis, 2012
L.-E. Chile, P. Meh khoda andi, S. G. Ha ziki iakos, Mac omolecules (2016) 49 (3), 909-919
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Sys ema ic bo om-up simula ion app oach
Compu a ional me hods:
(A) quan um: o ce ield
(B) a omis ic:
chemis y-speci ic
in e ac ions
(C) coa se-g ained: ends a
mesoscale
(D) con inuum
(A)
(B)
(C)
(D)
ime
leng h
Mul iscale:
3quan i a i e p edic ions o mac oscopic p ope ies
8 ime and esou se in ensi e
[1] Guse a, D. V.; Glagole , M. K.; Lazu in, A. A.; Vasile skaya, V. V.; Polym. Re . 2023, 0, 1–39
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Coa se-g aining p ocedu e
Ïmonome -like coa se-g aining,
i e a i e Bol zmann in e sion
0
0.2
0.4
0.6
0.8
1
100101102103104105106107
C( )
[ps]
PLLA, 30me
a omis ic
CG, CG=75 A
0
0.2
0.4
0.6
0.8
1
100101102103104105106107108109
C( )
[ps]
PLLA, 100me
a omis ic
CG, CG=140 A
Ali eza F. Behbahani e al., Mac omolecules (2021) 54 (6), 2740-2762
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S ess elaxa ion modulus G( ): PDLA
Ïequilib ium simula ions:
G( )=V
kBT〈σαβ( )σαβ(0)〉
Ïconnec ing a omis ic and mesoscale models o achie e he
ull elaxa ion spec um
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S ess elaxa ion modulus G( ): PLLA
Ïconnec ing a omis ic and mesoscale models o achie e he
ull elaxa ion spec um: speed up 100x
101
102
103
104
105
10-2 10-1 100101102103104105106107
G( ) [ba ]
[ps]
-0.5
a omis ic, 30me
CG, 30me
a omis ic, 100me
CG, 100me
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Backmapping p ocedu e
(A) a omis ic da ase , 5000 ames pe
sys em, aining se : PLLA100,
PDLA100 and Copo100
(B) encoding and lea ning
úcon olu ional neu al ne wo k
ú e sa ile: bond ec o s and leng hs
úlocal: no in e monome ic and
in e molecula in o ma ion
(C) coa se-g aining, monome -like
ep esen a ion
(D) backmapping
ú e i y he model
ú es ing he ans e abili y
(A)
(B)
(C)
(D)
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Neu al Ne wo ks
ÏT aining s. alida ing se , loss unc ion
ÏWeigh s: impo ance o he co esponding ea u e
ÏO e i ing: pe ec i o aining da a, bad pe o mance
agains unseen da a
ÏUnde i ing: ele an ela ions be ween ea u es and a ge
ou pu s missing
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Backmapping p ocedu e: ans e abili y ac oss Mw
Ï aining se : PLLA100, PDLA100
and Copo100
Ï ans e abili y ac oss Mw:
PLLA30, PDLA30, Copo30
3possible ex ension o any
molecula weigh : indus ially
ele an Mw, polydispe se
samples
PLLA30 PDLA30 Copo30
PLLA100 PDLA100 Copo100
55%D
16%D
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Backmapping p ocedu e: chemical ans e abili y
Ï aining se : PLLA100, PDLA100
and Copo100
Ïchemical ans e abili y
úcopolyme wi h a di e en
copolyme sequence
úcopolyme ained solely on
homopolyme s
3capabili y o c ea ing any
composi ion: mimicking
condi ions du ing syn hesis
PLLA100 PDLA100 Copo100
CopoHOMO CopoRAND
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Mas e plan
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Mas e Plan: Da a se
Model sys ems
4monodispe se
4con ol o e composi ion:
D and copo
8slow equilib a ion
8low Mw
Expe imen al sys ems
8unknown composi ion
8wide ange o Mw
4 eady o be measu ed (i
he me hod a ailable)
4bo h used o ain machine lea ning algo i hms
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Mas e Plan: Cha ac e iza ion
Model sys ems
4Tgas a unc ion o
composi ion
4G( ) as a unc ion o
composi ion o low Mw
8es ima ed G( ) as a
unc ion o composi ion o
low Mw
8Mw om G( )
Expe imen al sys ems
4Tgo comme cial samples
and sus ainable
nanocomposi es
4G( ) as a unc ion o
composi ion o high Mw
8p in abili y condi ions
