Ci a ion: Hejna, A.; Ba czewski, M.;
Kosmela, P.; Mysiukiewicz, O.;
Piasecki, A.; Te cjak, A. Compa ibili y
o Sus ainable Ma e -Bi/poly(ε-
cap olac one)/cellulose
Biocomposi es as a Func ion o Fille
Modi ica ion. Ma e ials 2023,16, 6814.
h ps://doi.o g/10.3390/ma16206814
Academic Edi o s: Ugo D’Amo a,
I an Chodák and Hamed Peidayesh
Recei ed: 17 Sep embe 2023
Re ised: 4 Oc obe 2023
Accep ed: 20 Oc obe 2023
Published: 23 Oc obe 2023
Copy igh : © 2023 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/).
ma e ials
A icle
Compa ibili y o Sus ainable
Ma e -Bi/poly(ε-cap olac one)/cellulose Biocomposi es as a
Func ion o Fille Modi ica ion
Aleksande Hejna 1,2,* , Ma eusz Ba czewski 1, Paulina Kosmela 2, Olga Mysiukiewicz 1, Adam Piasecki 3
and Agnieszka Te cjak 4
1Ins i u e o Ma e ials Technology, Poznan Uni e si y o Technology, Pio owo 3, 61-138 Pozna´n, Poland;
[email p o ec ed] (M.B.); [email p o ec ed] (O.M.)
2Depa men o Polyme Technology, Gda´nsk Uni e si y o Technology, Na u owicza 11/12,
80-233 Gda´nsk, Poland; [email p o ec ed]
3Ins i u e o Ma e ials Enginee ing, Poznan Uni e si y o Technology, Pio owo 3, 61-138 Pozna´n, Poland;
[email p o ec ed]
4G oup ‘Ma e ials + Technologies’ (GMT), Depa men o Chemical and En i onmen al Enginee ing,
Facul y o Enginee ing Gipuzkoa, Uni e si y o he Basque Coun y (UPV/EHU), Plaza Eu opa 1,
20018 Donos ia-San Sebas ian, Spain; [email p o ec ed]
*Co espondence: aleksande [email p o ec ed]
Abs ac :
Despi e hei popula i y and mul iplici y o applica ions, wood–polyme composi es
(WPCs) s ill ha e o o e come pa icula issues ela ed o hei p ocessing and p ope ies. The main
aspec is he compa ibili y wi h plan -based ma e ials which a ec s he o e all pe o mance o he
ma e ial. I can be enhanced by s eng hening he in e acial adhesion esul ing om physical and/o
chemical in e ac ions be ween he ma ix and ille , which equi es in oducing a compa ibilize o a
p ope modi ica ion o one o bo h phases. He ein, he impac o cellulose ille modi ica ions wi h
a ying con en s (1–10 w %) o hexame hylene diisocyana e (HDI) on he compa ibili y o Ma e -
Bi/poly(
ε
-cap olac one) (PCL)-based biocomposi es was e alua ed. An analysis o su ace we abili y
e ealed ha he ille modi ica ion educed he hyd ophilici y gap be ween phases, sugges ing
compa ibili y enhancemen . I was la e con i med ia mic oscopic obse a ion (scanning elec on
mic oscopy (SEM) and a omic o ce mic oscopy (AFM)), which poin ed o he ine dispe sion o
modi ied pa icles and enhanced quali y o he in e ace. The heological analysis con i med inc eased
sys em homogenei y by he educ ion in complex iscosi y. In con as , he mog a ime ic analysis
(TGA) indica ed he e icien modi ica ion o ille and he p esence o he chemical in e ac ions a he
in e ace by he shi o he mal decomposi ion onse and he changes in he deg ada ion cou se.
Keywo ds:
Ma e -Bi; poly(
ε
-cap olac one); cellulose ille ; biocomposi es; ille modi ica ion; in e a-
cial adhesion
1. In oduc ion
Wood–polyme composi es (WPCs) a e a g oup o composi e ma e ials consis ing
o one o mo e plan -based ille s and a mix u e o polyme s. O e he las decades,
he esea ch wo ks on hei de elopmen aim o add ess he main p oblems ela ed o
hei p ocessing: (i) he a ia ions in he quali y o plan -based ma e ials; (ii) he limi ed
he mal s abili y o plan -based ma e ials na owing he p ocessing window o WPCs; and
mos ly, (iii) he limi ed compa ibili y o en be ween he hyd ophobic polyme ma ix and
hyd ophilic ille s [1–5].
Insu icien compa ibili y is a c i ical issue as s ong in e acial in e ac ions a e c ucial
o achie ing he good mechanical p ope ies o composi es [
6
]. Enhancing he compa ibili y
may be ealized by p o iding possibili ies o he chemical bonding o modi ied ille wi h
he unc ional g oups p esen in he polyme backbone o by changing he cha ac e
Ma e ials 2023,16, 6814. h ps://doi.o g/10.3390/ma16206814 h ps://www.mdpi.com/jou nal/ma e ials
Ma e ials 2023,16, 6814 2 o 21
o he ille s’ su ace om hyd ophilic o hyd ophobic, simul aneously enhancing he
ille and ma ix mu ual a ini y. I o en equi es p ope modi ica ions o in oduced
ille s. O e he las decades, mul iple e iew wo ks ela ed o hei chemical modi ica ion,
mainly aimed a enhancing he pe o mance o WPCs, ha e been published by di e en
esea ch g oups [
7
–
12
]. The au ho s men ioned nume ous ille modi ica ions, o which
he mos popula and widely desc ibed a e alkali ea men , silaniza ion, ace yla ion,
malea ion, ac yla ion, o pe mangana e ea men . Less common modi ica ion me hods
include a y acid modi ica ion, sodium chlo ide ea men , benzoyla ion, iazine, o
isocyana e ea men . Collec i ely, hei goal was o p o ide he possibili y o co alen
bonding wi h a polyme ma ix o o educe he hyd ophilici y gap be ween phases.
Gene ally, he mos popula modi ie s o lignocellulosic ille s a e anhyd ides such
as maleic anhyd ide, succinic anhyd ide, dodecenyl succinic anhyd ide, o ph alic anhy-
d ide [
13
,
14
]. These compounds a e o en p esen in biocomposi e manu ac u ing because
hey can be g a ed on o polyme chains, c ea ing s ong co alen bonds wi h hyd oxyl
g oups on he lignocellulosic ille s’ su ace. By de e mining he p ope choice o anhy-
d ide (molecula weigh , po en ial s e ic hind ance), he p ope ies o modi ied ille , e.g.,
c ys allini y o he mal s abili y, can be adjus ed [15].
F om he echnological poin o iew, isocyana es o e simila possibili ies o he
adjus men o modi ie s’ s uc u e and a e commonly used in he plas ics indus y. Hence,
hey a e well known and analyzed. They can c ea e u e hane bonds wi h hyd oxyls on
he su ace o lignocellulosic ille s yielding s ong co alen bonding a he in e ace. The
b oad isocyana e ma ke o e ing mul iple g ades wi h a ious s uc u es and p ope ies
enables many po en ial modi ica ions o lignocellulosic ille s. I has been p o en, e.g., by
Zhang e al. [
15
], ha he modi ie ’s s uc u e signi ican ly in luences he p ope ies o
modi ied ille . The mos c ucial p ope ies a e he molecula weigh , unc ionali y, and
spa ial s uc u e. These modi ie p ope ies a ec he s uc u e o modi ied lignocellulosic
ille s, e.g., i s c ys allini y, which has an essen ial impac on he mechanism and a e o
lignocellulosic ille s’ and composi es’ biodeg ada ion. The e o e, isocyana es seem an
auspicious solu ion o he enhancemen o in e acial in e ac ions.
A con en ious issue always aised in he case o isocyana es’ applica ion is hei oxici y.
They a e conside ed oxic due o highly eac i e isocyana e g oups in hei s uc u e [
16
].
Ne e heless, isocyana e is bonded and eac ed wi h o he unc ional g oups, e.g., hy-
d oxyl o amine g oups, and no oxic e ec s a e obse ed. The e o e, i is possible o
use polyu e hane ma e ials o manu ac u e biomedical-g ade a icles, such as ascula
ca he e s, blood bags, o implan s [
17
]. As men ioned be o e, du ing modi ica ion o ligno-
cellulosic ille s, isocyana e g oups can c ea e u e hane bonds wi h he hyd oxyls p esen
on he su ace o ille s, so he oxic e ec should be signi ican ly educed due o he excess
o hyd oxyl g oups o ille s.
As a g oup, isocyana es ha e been epea edly p o en as excellen coupling agen s o
polyole in-based biocomposi es, e ealing p ope ies supe io o hose compa ibilized wi h
anhyd ides [
18
,
19
]. Va ious esea ch g oups analyzed lignocellulosic ille s’ modi ica ion
wi h isocyana es and u he p ocessing o biocomposi es a empe a u es om 150 o 175
◦
C, which enhanced composi es’ mechanical pe o mance. I is also impo an o men ion
ha he au ho s o hese wo ks used pe iodic me hods. The e o e, he ime o modi ica ion
and he in luence o empe a u e on lignocellulosic ille s was longe han con inuous
me hods. Despi e ha , no ma e ial deg ada ion was obse ed [20,21].
Liew e al. [
22
] analyzed he hexame hylene diisocyana e (HDI) in compa ibiliza ion
o low-densi y polye hylene composi es illed wi h ju e and bamboo ibe s. The au ho s
applied a pe iodic me hod o ille s’ modi ica ion, which included he inco po a ion o
sol en s and an addi ional 24 h p ocess o d ying, which nega i ely impac ed he ille ’s
modi ica ion cos . Ne e heless, modi ica ion o lignocellulosic ibe s wi h HDI no iceably
enhanced he he mal s abili y o he composi e con aining 10 w % o ille s, shi ing he on-
se o he mal decomposi ion by mo e han 100
◦
C, which could be a g ea ad an age om
he echnological poin o iew. I would allow using such modi ied ille s o manu ac u e
Ma e ials 2023,16, 6814 3 o 21
composi es based on polyme s wi h highe p ocessing empe a u es. Mo eo e , isocyana e
ea men o ille s signi ican ly enhanced in e acial adhesion be ween he ma ix and
ille , which was p o en ia SEM analysis, and inc eased he ensile s eng h and Young’s
modulus by 295 and 296%, espec i ely.
Gómez-Fe nández e al. [
16
] in es iga ed lignin modi ica ion wi h isopho one diiso-
cyana e (IPDI). The au ho s p esen ed he unc ionaliza ion o k a lignin in a pe iodic
me hod, using dibu yl in dilau a e as a ca alys o he eac ions be ween he isocyana e
g oups o IPDI and he hyd oxyl g oups p esen on he su ace o lignin. The me hod
in ol ed conduc ing a chemical eac ion a 60
◦
C o 24 h, u he cen i uga ion, washing
in oluene, d ying o ano he 24 h, and g inding he ob ained pa icles. Func ionaliza ion
o lignin was con i med ia a de ailed analysis o he s uc u e and composi ion o he
ille wi h FTIR, liquid, solid-s a e NMR spec oscopy, and elemen al analysis. Mo eo e ,
modi ica ion dec eased he a e age pa icle size, which can be conside ed e y bene icial
om he applica ion poin o iew. Ne e heless, despi e he success ul modi ica ion,
he p esen ed p ocedu e has no iceable disad an ages: ex ended ime, complex cha ac e
(mul iple p ocesses in ol ed), and he use o o ganic sol en s.
A less popula di ec ion is he applica ion o isocyana es o he compa ibiliza ion
o biocomposi es based on sus ainable polyme ma ices. The applica ion o isocyana es
has been analyzed a he in e ms o he compa ibiliza ion o blends, modi ied pea s a ch
and dex in [
23
], poly(
ε
-cap olac one) (PCL) and s a ch [
24
,
25
], o poly(lac ic acid) wi h
poly(bu ylene succina e) [
26
]. Fille modi ica ion wi h isocyana es aimed o enhance
polyole in-based composi es [
22
,
27
,
28
]. Ou p e ious wo k [
29
] showed ha he PCL-based
biocomposi es’ s a ic and dynamic mechanical pe o mance could be signi ican ly boos ed
by app op ia ely modi ying cellulose ille wi h diisocyana es by enhancing in e acial
adhesion. In e es ingly, diisocyana e modi ica ions o cellulose ille also a ec ed he
biodeg ada ion a e o he p epa ed composi es [
30
]. A simila phenomenon has been
no ed o Ma e -Bi/b ewe s’ spen g ain composi es con aining IPDI-modi ied ille [
31
,
32
].
Ha ing in mind he esul s o he abo emen ioned wo ks poin ing o he bene icial
impac o diisocyana es on he compa ibili y o PCL/ he moplas ic s a ch (TPS) blends
as well as he PCL- and Ma e -Bi-based biocomposi es, he p esen ed wo k aimed o
in es iga e he e ec o he modi ica ion o cellulose ille wi h HDI on he s uc u e
and pe o mance o composi es based on he Ma e -Bi/PCL ma ix. The applica ion o
such blends as he ma ix and inco po a ion o PCL was ela ed o he ela i ely poo
pe o mance o Ma e -Bi, which limi s i s applica ion ange [33–37].
2. Ma e ials and Me hods
2.1. Ma e ials
Two polyme ma e ials in he p esen ed s udy ha e been applied as ma ices o he
composi es as ollows: poly(
ε
-cap olac one) (PCL) and Ma e -Bi ype NF803 composed
o poly(bu ylene adipa e-co- e eph hala e) (PBAT), TPS, and PCL. De ails ega ding hei
cha ac e is ics a e summa ized in Table 1.
Table 1. Cha ac e is ics o applied polyme ma e ials.
Ma e ial Poly(ε-cap olac one) Ma e -Bi
T adename Capa 6500 NF803
P oduce Pe s o p (Malmö, Sweden) No amon SPA (No a a, I aly)
Mel low index, g/10 min 3.5 (150 ◦C/5 kg) 7.0 (170 ◦C/2.16 kg)
Mel ing empe a u e, ◦C 110 58–60
P epa ed composi es we e illed wi h cellulose mic ome ic pa icles—A bocel
®
UFC100
om JRS J. Re enmaie & Söhne GmbH (Rosenbe g, Ge many). The applied ille had
an a e age pa icle leng h o 8
µ
m, an aspec a io o 4, a bulk densi y o 160 g/L, and
a mois u e con en o 4.84 w %. I s mo phology is p esen ed in Figu e 1, ob ained wi h
Ma e ials 2023,16, 6814 4 o 21
scanning elec on mic oscopy (SEM). I can be seen ha he applied ille ’s pa icles show a
ela i ely ough su ace, which should ansla e in o he ex ended speci ic su ace a ea.
Ma e ials 2023, 16, x FOR PEER REVIEW 4 o 21
had an a e age pa icle leng h o 8 µm, an aspec a io o 4, a bulk densi y o 160 g/L, and
a mois u e con en o 4.84 w %. I s mo phology is p esen ed in Figu e 1, ob ained wi h
scanning elec on mic oscopy (SEM). I can be seen ha he applied ille ’s pa icles show
a ela i ely ough su ace, which should ansla e in o he ex ended speci ic su ace a ea.
The 98% hexame hylene diisocyana e (HDI) acqui ed om Sigma Ald ich (Poznan,
Poland) was applied as a modi ie o cellulose ille .
Figu e 1. SEM image o as- ecei ed UFC100 cellulose ille .
2.2. Sample P epa a ion
P epa a ion o Ma e -Bi/PCL/cellulose biocomposi es included he modi ica ion o
he as- ecei ed ille wi h 1.0, 2.5, o 10.0 w % o HDI, mel blending wi h he polyme
ma ix, and comp ession molding, as schema ically p esen ed in Figu e 2. The i s p o-
cess was desc ibed in de ail in ou p e ious wo ks [29,38,39]. B ie ly, i was conduc ed in
a ba ch mixe a oom empe a u e o 5 min using a o o speed o 100 pm. Fu he ,
modi ied ille s (30 w %) we e mel -blended wi h a polyme ma ix comp ised o Ma e -
Bi and PCL in a 70:30 a io in he ba ch mixe . The p ocess conduc ed a 140 °C and a a
o o speed o 100 pm las ed 6 min (including he 1 min plas iciza ion phase). Then, he
ma e ials we e comp ession molded a 150 °C and 4.9 MPa o 1 min and kep unde p es-
su e a oom empe a u e o 5 min o enable solidi ica ion. The un illed Ma e -Bi/PCL
ma ix and composi e illed wi h he as- ecei ed ille we e p ocessed as e e ence sam-
ples. Figu e 2 also p o ides he de ails on he po en ial chemical in e ac ions be ween he
ma ix and ille du ing pa icula p ocessing s eps.
Figu e 1. SEM image o as- ecei ed UFC100 cellulose ille .
The 98% hexame hylene diisocyana e (HDI) acqui ed om Sigma Ald ich (Poznan,
Poland) was applied as a modi ie o cellulose ille .
2.2. Sample P epa a ion
P epa a ion o Ma e -Bi/PCL/cellulose biocomposi es included he modi ica ion o
he as- ecei ed ille wi h 1.0, 2.5, o 10.0 w % o HDI, mel blending wi h he polyme
ma ix, and comp ession molding, as schema ically p esen ed in Figu e 2. The i s p ocess
was desc ibed in de ail in ou p e ious wo ks [
29
,
38
,
39
]. B ie ly, i was conduc ed in a ba ch
mixe a oom empe a u e o 5 min using a o o speed o 100 pm. Fu he , modi ied
ille s (30 w %) we e mel -blended wi h a polyme ma ix comp ised o Ma e -Bi and PCL
in a 70:30 a io in he ba ch mixe . The p ocess conduc ed a 140
◦
C and a a o o speed
o 100 pm las ed 6 min (including he 1 min plas iciza ion phase). Then, he ma e ials
we e comp ession molded a 150
◦
C and 4.9 MPa o 1 min and kep unde p essu e a
oom empe a u e o 5 min o enable solidi ica ion. The un illed Ma e -Bi/PCL ma ix and
composi e illed wi h he as- ecei ed ille we e p ocessed as e e ence samples. Figu e 2
also p o ides he de ails on he po en ial chemical in e ac ions be ween he ma ix and
ille du ing pa icula p ocessing s eps.
Ma e ials 2023,16, 6814 5 o 21
Ma e ials 2023, 16, x FOR PEER REVIEW 5 o 21
Figu e 2. Scheme o Ma e -Bi/PCL/cellulose composi es p epa a ion and po en ial in e acial in e -
ac ions du ing pa icula p ocessing s eps.
2.3. Cha ac e iza ion
Fou ie ans o m in a ed spec oscopy (FTIR) was applied o in es iga e he
changes in he chemical s uc u e o p epa ed Ma e -Bi/PCL/cellulose composi es caused
by applying he HDI modi ie . Jasco FT/IR-4600 (Tokyo, Japan) spec ome e was applied.
Measu emen s we e pe o med in a enua ed o al e lec ion (ATR) mode wi h a 4 cm−1
esolu ion om 4000 o 400 cm−1.
Su ace we abili y was s udied ia s a ic wa e con ac angle measu emen s using an
Ossila L2004 con ac angle goniome e (Ossila L d., Sheffield, UK) equipped wi h a came a
and Ossila Con ac Angle so wa e 3.1.2.2. Ten wa e con ac angle (WCA) measu emen s
we e aken in andom posi ions, pu ing d ops o ~1 µL dis illed wa e on o he su ace o
he samples wi h he aid o a sy inge. The a e age alues o a leas se en measu emen s
we e calcula ed and epo ed.
Figu e 2. Scheme o Ma e -Bi/PCL/cellulose composi es p epa a ion and po en ial in e acial in e -
ac ions du ing pa icula p ocessing s eps.
2.3. Cha ac e iza ion
Fou ie ans o m in a ed spec oscopy (FTIR) was applied o in es iga e he changes
in he chemical s uc u e o p epa ed Ma e -Bi/PCL/cellulose composi es caused by ap-
plying he HDI modi ie . Jasco FT/IR-4600 (Tokyo, Japan) spec ome e was applied.
Measu emen s we e pe o med in a enua ed o al e lec ion (ATR) mode wi h a 4 cm
−1
esolu ion om 4000 o 400 cm−1.
Su ace we abili y was s udied ia s a ic wa e con ac angle measu emen s using an
Ossila L2004 con ac angle goniome e (Ossila L d., She ield, UK) equipped wi h a came a
and Ossila Con ac Angle so wa e 3.1.2.2. Ten wa e con ac angle (WCA) measu emen s
we e aken in andom posi ions, pu ing d ops o ~1
µ
L dis illed wa e on o he su ace o
Ma e ials 2023,16, 6814 6 o 21
he samples wi h he aid o a sy inge. The a e age alues o a leas se en measu emen s
we e calcula ed and epo ed.
The su ace oughness o he analyzed samples was e alua ed using an ART300
su ace oughness es e om Sunpoc Co., L d. (Guiyang, China). The sampling leng h
was 0.8 mm. The a e age R
a
alue was calcula ed om i e measu emen s on i e di e en
spo s on he sample’s su ace (25 measu emen s in o al).
The scanning elec on mic oscope (SEM) Tescan MIRA3 (B no, Czech Republic) was
used o analyze he b i le ac u e su aces o he p epa ed samples. The accele a ing
ol age o 12 kV was applied wi h a wo king dis ance o 19 mm. A hin ca bon coa ing o
app oxima ely 20 nm hickness was deposi ed on he samples using he Jeol (Tokyo, Japan)
JEE 4B acuum e apo a o .
A omic o ce mic oscopy (AFM) was used o s udy he mo phology o he p epa ed
ma e ials. The equipmen used was a scanning p obe mic oscope (SPM) (NanoScope IIIa
Mul imode om Digi al Ins umen s, Veeco Ins umen s Inc., San a Ba ba a, CA, USA) in
apping mode (TM-AFM). A one beam can ile e (125 mm) wi h a silicon p obe (cu a u e
nominal adius o 5–10 nm) was used. Samples we e cu using an ul amic o ome Leica
Ul acu R (Wel za , Ge many) wi h a diamond blade and he c oss-sec ion o each p epa ed
ma e ial was analyzed.
Rheological in es iga ions we e ca ied ou using an An on Paa (G az, Aus ia) MCR
301 o a ional heome e , wi h 25 mm diame e pa allel pla es and a 0.5 mm gap unde he
oscilla o y mode. The expe imen s we e conduc ed a 170
◦
C. The s ain sweep expe imen s
we e conduc ed be o e pe o ming he dynamic oscilla o y measu emen s in he equency
sweep mode. The s ain sweep expe imen s o all he samples we e pe o med a 170
◦
C
wi h a cons an angula equency o 10 ad/s in he a ying s ain window 0.001–100%.
The p elimina y in es iga ions allow us o de e mine he alue o he 0.05% s ain as
applicable o he equency sweep expe imen s and loca e all he samples in he linea
iscoelas ic egion (LVE). The angula equency used du ing he s udies was in he ange
o 0.05–500 ad/s.
The he mal p ope ies o he samples we e measu ed ia di e en ial scanning calo ime-
y (DSC) ca ied ou on a DSC 214 appa a us om Ne zsch (Selb, Ge many). Measu emen s
we e pe o med in he empe a u e ange o
−
80 o 170
◦
C unde a ni ogen a mosphe e
(30 mL/min gas low) a a hea ing/cooling a e o 15
◦
C/min. The hea ing was pe -
o med wice o e ase he he mal his o y o he samples. The c ys allini y deg ee X
c
and
supe cooling pa ame e (∆T) we e calcula ed using he ollowing Equa ions (1) and (2):
Xc=∆Hm/((1 −ξ)×∆Hm100%)×100% (1)
∆T=Tm−Tc(2)
whe e
∆
H
m
—sample’s mel ing en halpy, J/g;
ξ
—weigh ac ion o ille ;
∆Hm100%—mel ing
en halpy o 100% c ys alline polyme , o PCL equal o 139.5 J/g [
40
]; T
m
—mel ing
empe a u e, ◦C; and Tc—c ys alliza ion empe a u e, ◦C.
The he mal s abili y o ma e ials was de e mined ia he mog a ime ic analysis
(TGA) wi h he empe a u e se be ween 35
◦
C and 800
◦
C a a hea ing a e o 15
◦
C/min
unde a ni ogen low using a TG 209 F1 Ne zsch (Selb, Ge many) appa a us. Samples o
10.0 ±0.1 mg and ce amic pans we e applied.
3. Resul s and Discussion
3.1. FTIR
Figu e 3p esen s he FTIR spec a o he un illed Ma e -Bi/PCL blend and composi es
made he eo con aining as- ecei ed and HDI-modi ied cellulose ille . Ou p e ious
wo ks dealing wi h he diisocyana e modi ica ions o UFC100 cellulose ille s e ealed
signi ican changes in hei chemical s uc u e [
38
,
39
]. The mos no iceable a ia ions in
he FTIR spec a ha e been no ed o he wa enumbe anges ma ked in Figu e 3wi h
g ey ec angles, which we e associa ed wi h he abo emen ioned chemical in e ac ions
Ma e ials 2023,16, 6814 7 o 21
be ween he highly eac i e ee isocyana e g oups o applied modi ie s and he unc ional
g oups p esen on he su ace o cellulose pa icles (Figu e 2). These changes also a ec ed
he chemical s uc u e o p epa ed biocomposi es. The egion mos a ec ed was om 3100
o 3500 cm
−1
, whe e changes in he in ensi y o b oad O-H s e ching signal we e no ed
along wi h he appea ance o new abso p ion bands a ound 3190 and 3400 cm
−1
. These
changes in he ypically b oad signal can be a ibu ed o he in e ac ions be ween he
HDI isocyana e g oups and he hyd oxyl and ca boxyl g oups p esen in he s uc u e o
polyme ma e ials applied as a ma ix, which may yield no el co alen o hyd ogen bonds.
Ma e ials 2023, 16, x FOR PEER REVIEW 7 o 21
be ween he highly eac i e ee isocyana e g oups o applied modi ie s and he unc ional
g oups p esen on he su ace o cellulose pa icles (Figu e 2). These changes also affec ed
he chemical s uc u e o p epa ed biocomposi es. The egion mos affec ed was om 3100
o 3500 cm−1, whe e changes in he in ensi y o b oad O-H s e ching signal we e no ed
along wi h he appea ance o new abso p ion bands a ound 3190 and 3400 cm−1. These
changes in he ypically b oad signal can be a ibu ed o he in e ac ions be ween he HDI
isocyana e g oups and he hyd oxyl and ca boxyl g oups p esen in he s uc u e o poly-
me ma e ials applied as a ma ix, which may yield no el co alen o hyd ogen bonds.
Be ween he wa eleng h ange o 1610 and 1775 cm−1, he abso p ion band a ibu ed
o he s e ching ib a ions o ca bonyl g oups in he polyme s uc u e is obse ed, as
has been desc ibed in a ious wo ks [41,42]. The in oduc ion o cellulose ille caused a
sligh educ ion in he signal’s in ensi y, which could be associa ed wi h a educed sha e
o he polyme ma ix in he composi e. Howe e , he educ ion deepened a e HDI mod-
i ica ion, which was mainly p onounced o he 10HDI sample. Such a phenomenon may
poin o he pa ial a ac ion o oxygen included in he ca bonyl g oup by he NCO o
NH2 g oups o modi ied ille pa icles and i s in ol emen in hyd ogen bonding. I was
also sugges ed by he sligh peak shi owa d lowe wa enumbe s, which is ypically
no ed o hyd ogen bonding [43]. The in oduc ion o modi ied ille also caused ano he
change in he abo emen ioned ange— he appea ance o a peak a ound 1644 cm−1, which
can be a ibu ed o he conjuga ion be ween he C-N and C=O bonds p esen in he u e-
hane g oups [44]. I has been p e iously no ed in wo ks dealing wi h isocyana e modi i-
ca ion no only o cellulose [45,46], bu also s a ch and dex in [23] as well as cas o oil
[47], so i is a ypical effec o chemical in e ac ions be ween hyd oxyl and isocyana e
g oups.
The abo emen ioned changes we e also mi o ed in he sligh a ia ions in he in en-
si y o mul iple weake signals ela ed o he ib a ions o C-C, C-O, C-H, C-N, and N-H
bonds ypically obse ed in he 950–1310 cm−1 ange.
Figu e 3. The FTIR spec a o un illed Ma e -Bi/PCL blend and p epa ed composi es.
3.2. Su ace We abili y
As men ioned abo e, one o he main aspec s limi ing he pe o mance o polyme
composi es illed wi h plan -based ma e ials is a ibu ed o he hyd ophilici y diffe ence
be ween phases. The e o e, o e coming his issue is among he goals behind modi ying
Figu e 3. The FTIR spec a o un illed Ma e -Bi/PCL blend and p epa ed composi es.
Be ween he wa eleng h ange o 1610 and 1775 cm
−1
, he abso p ion band a ibu ed
o he s e ching ib a ions o ca bonyl g oups in he polyme s uc u e is obse ed, as has
been desc ibed in a ious wo ks [
41
,
42
]. The in oduc ion o cellulose ille caused a sligh
educ ion in he signal’s in ensi y, which could be associa ed wi h a educed sha e o he
polyme ma ix in he composi e. Howe e , he educ ion deepened a e HDI modi ica ion,
which was mainly p onounced o he 10HDI sample. Such a phenomenon may poin
o he pa ial a ac ion o oxygen included in he ca bonyl g oup by he NCO o NH
2
g oups o modi ied ille pa icles and i s in ol emen in hyd ogen bonding. I was also
sugges ed by he sligh peak shi owa d lowe wa enumbe s, which is ypically no ed
o hyd ogen bonding [
43
]. The in oduc ion o modi ied ille also caused ano he change
in he abo emen ioned ange— he appea ance o a peak a ound 1644 cm
−1
, which can
be a ibu ed o he conjuga ion be ween he C-N and C=O bonds p esen in he u e hane
g oups [
44
]. I has been p e iously no ed in wo ks dealing wi h isocyana e modi ica ion
no only o cellulose [
45
,
46
], bu also s a ch and dex in [
23
] as well as cas o oil [
47
], so i is
a ypical e ec o chemical in e ac ions be ween hyd oxyl and isocyana e g oups.
The abo emen ioned changes we e also mi o ed in he sligh a ia ions in he in en-
si y o mul iple weake signals ela ed o he ib a ions o C-C, C-O, C-H, C-N, and N-H
bonds ypically obse ed in he 950–1310 cm−1 ange.
3.2. Su ace We abili y
As men ioned abo e, one o he main aspec s limi ing he pe o mance o polyme
composi es illed wi h plan -based ma e ials is a ibu ed o he hyd ophilici y di e ence
be ween phases. The e o e, o e coming his issue is among he goals behind modi ying
Ma e ials 2023,16, 6814 8 o 21
cellulose ille s in he p esen ed s udy. Acco ding o Ly e al. [
48
], he WCA o cellulose is
a ound 47
◦
, which is a less han ~100
◦
epo ed o PCL [
49
], ~86
◦
o PBAT [
50
], and ~95
◦
o Ma e -Bi [
51
,
52
]. As p esen ed in Figu e 4, he inco po a ion o unmodi ied cellulose
ille esul ed in a sligh d op in he composi e’s WCA om 88.5
◦
o 86.8
◦
, indica ing a shi
owa ds he mo e hyd ophilic cha ac e . Simila e ec s ha e been no ed by Laaziz e al. [
53
]
a e he in oduc ion o 15 w % a gan nu shell pa icles in o poly(lac ic acid) (d op
om 79.4
◦
o un illed PLA o 73.0
◦
) by Tsou e al. [
54
], who inco po a ed 25 w % o
dis ille ’s g ains in o a poly(e hylene e eph hala e) (d op om 91.3
◦
o 87.0
◦
). Such an
e ec can be limi ed by app op ia ely modi ying he applied ille s aimed a masking
hei hyd ophilici y. As epo ed in ou p e ious wo k [
38
], modi ica ion o cellulose
pa icles wi h diisocyana es leads o he changes in su ace pola i y exp essed by he highe
s abili y o hei suspensions in less pola sol en s, which enhances hei compa ibili y
wi h less hyd ophilic o hyd ophobic polyme ma ices. Ca alho e al. [
55
] modi ied
he moplas ic s a ch ilms wi h a 40% phenyl isocyana e me hylene chlo ide solu ion,
shi ing WCA om 63
◦
o 98
◦
, which shows he po en ial o isocyana es in compa ibiliza ion
wi h polyme composi es con aining plan -based ille s. In he p esen ed case, applying
1–10 w % o HDI led o a no iceable inc ease in composi es’ WCA om 86.8
◦
o 89.6–93.5
◦
.
The e iciency o isocyana es in educing he hyd ophilici y o polyme composi es has also
been con i med by he esul s epo ed by Geng e al. [
18
], Zhang e al. [
56
], Liew e al. [
22
],
and A jmand e al. [
28
]. All o hese wo ks poin ed o he signi ican educ ion in he wa e
abso p ion capaci y o composi es a e he applica ion o isocyana es as ille modi ie s.
Concluding, he in oduc ion o isocyana es in o polyme composi es pu s hem on he edge
o hyd ophilici y and hyd ophobici y, making hem auspicious modi ie s conside ing he
po en ial biodeg ada ion, which is s ongly a ec ed by he wa e abso p ion capaci y [
57
,
58
].
No ably, all o he analyzed composi es we e cha ac e ized by a simila le el o su ace
oughness, ypically a ec ing he WCA alues, poin ing o he leading ole o pe o med
HDI modi ica ion in we abili y changes [59,60].
Ma e ials 2023, 16, x FOR PEER REVIEW 8 o 21
cellulose ille s in he p esen ed s udy. Acco ding o Ly e al. [48], he WCA o cellulose is
a ound 47°, which is a less han ~100° epo ed o PCL [49], ~86° o PBAT [50], and ~95°
o Ma e -Bi [51,52]. As p esen ed in Figu e 4, he inco po a ion o unmodi ied cellulose
ille esul ed in a sligh d op in he composi e’s WCA om 88.5° o 86.8°, indica ing a
shi owa ds he mo e hyd ophilic cha ac e . Simila effec s ha e been no ed by Laaziz e
al. [53] a e he in oduc ion o 15 w % a gan nu shell pa icles in o poly(lac ic acid) (d op
om 79.4° o un illed PLA o 73.0°) by Tsou e al. [54], who inco po a ed 25 w % o dis-
ille ’s g ains in o a poly(e hylene e eph hala e) (d op om 91.3° o 87.0°). Such an effec
can be limi ed by app op ia ely modi ying he applied ille s aimed a masking hei hy-
d ophilici y. As epo ed in ou p e ious wo k [38], modi ica ion o cellulose pa icles
wi h diisocyana es leads o he changes in su ace pola i y exp essed by he highe s abil-
i y o hei suspensions in less pola sol en s, which enhances hei compa ibili y wi h less
hyd ophilic o hyd ophobic polyme ma ices. Ca alho e al. [55] modi ied he moplas ic
s a ch ilms wi h a 40% phenyl isocyana e me hylene chlo ide solu ion, shi ing WCA
om 63° o 98°, which shows he po en ial o isocyana es in compa ibiliza ion wi h poly-
me composi es con aining plan -based ille s. In he p esen ed case, applying 1–10 w %
o HDI led o a no iceable inc ease in composi es’ WCA om 86.8° o 89.6–93.5°. The effi-
ciency o isocyana es in educing he hyd ophilici y o polyme composi es has also been
con i med by he esul s epo ed by Geng e al. [18], Zhang e al. [56], Liew e al. [22], and
A jmand e al. [28]. All o hese wo ks poin ed o he signi ican educ ion in he wa e
abso p ion capaci y o composi es a e he applica ion o isocyana es as ille modi ie s.
Concluding, he in oduc ion o isocyana es in o polyme composi es pu s hem on he
edge o hyd ophilici y and hyd ophobici y, making hem auspicious modi ie s conside -
ing he po en ial biodeg ada ion, which is s ongly affec ed by he wa e abso p ion ca-
paci y [57,58]. No ably, all o he analyzed composi es we e cha ac e ized by a simila
le el o su ace oughness, ypically affec ing he WCA alues, poin ing o he leading ole
o pe o med HDI modi ica ion in we abili y changes [59,60].
Figu e 4. The impac o inco po a ing as- ecei ed and HDI-modi ied cellulose ille on he ( ed)
WCA and (blue) su ace oughness o composi es.
Figu e 4.
The impac o inco po a ing as- ecei ed and HDI-modi ied cellulose ille on he ( ed) WCA
and (blue) su ace oughness o composi es.
Ma e ials 2023,16, 6814 9 o 21
3.3. Mic os uc u e
Figu e 5p esen s he images o he p epa ed samples’ mic os uc u e ob ained wi h
scanning elec on mic oscopy. Mo eo e , o a deepe and mo e comp ehensi e unde -
s anding o he changes occu ing a he in e ace a e he modi ica ion o cellulose ille
wi h HDI, AFM analysis was conduc ed. Figu e 6, along wi h Table 2, p o ides he esul s
o he pe o med analysis in quali a i e and quan i a i e e ms.
Table 2.
The pa ame e s desc ibing he oughness o c oss-sec ional a eas o s udied samples de e -
mined ia AFM analysis.
Sample Whole Image 1 mm2Squa e Co e ing he In e ace
Image Size, µm2Su ace A ea, 103µm2Rq,◦Ra,◦Su ace A ea, µm2Rq,◦Ra,◦Rsk Rku
Blend
25
10.1 5.2 3.5 - - - - -
UFC100 17.3 10.9 8.0 501 9.7 6.9 0.356 5.55
1HDI 21.1 15.7 11.9 732 14.4 10.8 −0.895 4.45
2.5HDI 15.8 11.3 8.6 721 12.5 9.5 −0.765 3.86
10HDI 16.9 12.9 9.6 779 14.0 11.2 −0.714 3.50
Ma e ials 2023, 16, x FOR PEER REVIEW 9 o 21
3.3. Mic os uc u e
Figu e 5 p esen s he images o he p epa ed samples’ mic os uc u e ob ained wi h
scanning elec on mic oscopy. Mo eo e , o a deepe and mo e comp ehensi e unde -
s anding o he changes occu ing a he in e ace a e he modi ica ion o cellulose ille
wi h HDI, AFM analysis was conduc ed. Figu e 6, along wi h Table 2, p o ides he esul s
o he pe o med analysis in quali a i e and quan i a i e e ms.
The s uc u e o he un illed Ma e -Bi/PCL blend shows a high le el o he e ogenei y,
poin ing o he limi ed compa ibili y be ween pa icula componen s, PBAT, TPS, and
PCL, which may be a ibu ed o he abo emen ioned diffe ences in hei we abili y ex-
p essed by WCA. Mo eo e , he e a e isible g ain-like pa icles which may be a ibu ed
o he incomple e plas iciza ion o s a ch and i s p esence in semic ys alline o m, which
is epea edly no ed by o he esea che s [51,61,62]. These pa icles a e su ounded by he
ough egions co esponding o he amo phous TPS phase. Smoo h pla e-shaped gaps in-
dica e he PBAT phase, con aining small PCL pa icles wi h signi ican ly smoo he su -
aces han he non-plas icized s a ch phase [35]. AFM analysis o un illed Ma e -Bi/PCL
con i med he p esence o unplas icized s a ch pa icles. Excep o hem, he su ace o
he blend was ela i ely smoo h, especially compa ed o he p epa ed composi es, which
can be exp essed by he lowes R
q
and R
a
alues among all o he analyzed samples.
Figu e 5. Con .
Ma e ials 2023,16, 6814 16 o 21
in e io dispe sion o pa icles esul ing om hei agglome a ion and limi ed es ic ions
in he sphe uli es’ g ow h [
72
]. In he case o HDI modi ica ions, pa icles we e inely
dispe sed, as indica ed by he mic os uc u e analysis, which limi ed he c ys alli e size and
yielded a ine c ys alline s uc u e [
73
]. Mel ing beha io , pa icula ly he mel ing en halpy,
p o ides in o ma ion ega ding he ma e ial’s c ys allini y. As p esen ed in Table 3, he
∆
H
m
a ibu ed o PCL ansi ion dec eased a e ille inco po a ion, which can be mainly
a ibu ed o he educed con en o he polyme phase in a composi e. Howe e , calcula ed
X
c
alues indica e he dec ease in PCL phase c ys allini y a e he HDI modi ica ion o
ille pa icles, which con i ms ou p e ious epo s [
29
]. Such an e ec could be associa ed
wi h he in e ac ions be ween he unc ional g oups o modi ied ille s and PCL, which
limi ed he mobili y o he mac omolecules a he in e ace. Mo eo e , a educ ion in X
c
was no ed despi e he inc ease in c ys alliza ion empe a u e (T
c
), which along wi h he
educed supe cooling pa ame e (
∆
T), poin s o he nuclea ing ac i i y o ille pa icles
and enhanced g ow h a e o he c ys alline s uc u e [74].
The highe - empe a u e egion o he mog ams is less p onounced and he magni ude
o pa icula peaks is no iceably lowe . Conside ing he mel ing beha io o he PBAT
and TPS phases, simila beha io was no ed o PCL. The in oduc ion o as- ecei ed
cellulose ille no iceably inc eased T
m
, while ille modi ica ion caused i s lowe ing o
e en disappea ance o he signal in he case o he 1HDI and 2.5HDI samples. The highes T
c
alues o PBAT we e no ed in he samples con aining a modi ied ille , which poin ed o he
limi ed mo emen o mac omolecules and acili a ed he o ma ion o he c ys alline phase.
3.6. The mal S abili y
The mal s abili y, along wi h he abo emen ioned p ope ies, is also a ec ed by he in-
e acial compa ibili y o polyme composi es [
75
,
76
]. The e o e, i is essen ial o assess he
changes esul ing om he ille s’ modi ica ions aimed a in e acial adhesion enhancemen .
Figu e 10 shows ha he highes he mal decomposi ion onse , de e mined as empe a u e
co esponding o he 2 w % mass loss, was no ed o he un illed Ma e -Bi/PCL blend
(210.6
◦
C), which can be a ibu ed o he excep ional s abili y o PCL, whose sha e was
educed a e he ille in oduc ion [
77
]. Simila alues o he mal s abili y ha e been
epo ed by o he esea che s o di e en Ma e -Bi g ades [
35
,
78
]. Conside ing he cou se
o he mal decomposi ion, he un illed blend showed wo main s eps a ibu ed o he
deg ada ion o s a ch and o he polyme componen s, espec i ely. The i s s ep can be
ela ed o he deg ada ion o s a ch included in he Ma e -Bi ma e ial [
79
]. Acco ding o
Romagnolli e al. [
80
], his decomposi ion s ep is associa ed wi h he b eaking o s a ch
chains and he o ma ion o
β
-(1.6) anhyd ous D-glucopy anose and 2- u aldehyde, which
a e subsequen ly decomposed a highe empe a u es. I can be seen ha o he un illed
Ma e -Bi/PCL blend, he mass loss du ing he i s deg ada ion s ep was ~16 w %, co -
esponding o he TPS con en in he p epa ed ma e ial (20 w % in Ma e -Bi) [
35
]. The
second s ep was associa ed wi h he decomposi ion o PBAT and PCL, accoun ing o he
emainde o he blend [81,82].
Fo composi es con aining as- ecei ed and HDI-modi ied cellulose ille s, a d op in he
he mal decomposi ion onse was no ed, which may be associa ed wi h he deg ada ion o
cellulose s a ing a ound 260
◦
C [
83
]. The mos subs an ial dec ease was no ed o samples
UFC100 and 1HDI, o which decomposi ion s a ed in he 190–195
◦
C ange. Howe e ,
modi ica ion o ille s wi h 2.5 and 10 w % o HDI shi ed he onse o he 202–204
◦
C ange,
indica ing he e icien enhancemen o composi es’ compa ibili y. Simila o he un illed
blend, composi es also showed wo-s ep deg ada ion. Howe e , he magni ude o he
s eps was signi ican ly di e en . The mass loss no ed du ing he i s s ep was be ween
38 and 44 w % and inc eased wi h HDI modi ica ion. Di e ences be ween he composi es
and un illed blend we e ela ed o he abo emen ioned decomposi ion o cellulose ille ,
which o e lapped wi h he s a ch decomposi ion. Mo eo e , as p esen ed in Figu e 2, he
in oduc ion o HDI-modi ied cellulose ille s yielded a gene a ion o co alen bonds a he
in e ace, including u e hane linkages, which depending on he s uc u e o isocyana e and
Ma e ials 2023,16, 6814 17 o 21
alcohol, decompose in he ange o 180–300
◦
C [
84
]. The e o e, he inc easing mass loss
du ing he i s decomposi ion s ep also con i ms he e icien enhancemen o in e acial
in e ac ions esul ing om HDI modi ica ion o he applied ille .
Ma e ials 2023, 16, x FOR PEER REVIEW 17 o 21
Figu e 10. Plo s o (a) mass loss cu es and (b) diffe en ial he mog a ime ic cu es isualizing he
cou se o p epa ed samples’ he mal decomposi ion.
4. Conclusions
The chemical modi ica ion o cellulose ille wi h HDI no iceably enhanced he com-
pa ibili y o sus ainable composi es based on he Ma e -Bi/PCL ma ix. The analysis o
composi es’ chemical s uc u e wi h FTIR spec oscopy poin ed o he gene a ion o u e-
hane bonds a he ma ix/ ille in e ace, enhancing i s quali y and educing ille pull-
ou s, as indica ed by he mic oscopic obse a ions. The gene a ion o u e hane moie ies
was con i med by he changes in he he mal decomposi ion cou se obse ed ia TGA.
Mo eo e , SEM, along wi h he esul s o he heological analysis, poin ed o he limi ed
agg ega ion o ille pa icles obse ed o he UFC100 sample con aining as- ecei ed cel-
lulose ille . Such beha io was induced by he signi ican hyd ophilici y diffe ence be-
ween he applied polyme ma ix and he unmodi ied cellulose pa icles. Modi ica ion
wi h HDI educed his gap, shi ing he su ace cha ac e owa ds hyd ophobici y, which
was exp essed by he WCA inc ease o e 90°, pu ing composi es on he edge o hyd o-
philici y and hyd ophobici y. Concluding, HDI modi ica ion o cellulose pa icles should
be conside ed an auspicious di ec ion in he compa ibiliza ion o composi es based on
sus ainable polyme ma ices as i caused no iceable imp o emen in he in e acial adhe-
sion.
Au ho Con ibu ions: Concep ualiza ion, A.H.; me hodology, A.H., M.B., P.K., O.M., A.P. and A.T.;
so wa e, M.B., P.K., O.M., A.P. and A.T.; alida ion, A.H., M.B. and A.T.; o mal analysis, A.H. and
M.B.; in es iga ion, A.H., M.B., P.K., O.M., A.P. and A.T.; esou ces, A.H. and M.B.; da a cu a ion,
A.H., M.B., P.K., O.M. and A.T.; w i ing—o iginal d a p epa a ion, A.H. and M.B.; w i ing— e-
iew and edi ing, A.H., M.B., O.M. and A.T.; isualiza ion, A.H., M.B. and A.P.; supe ision, A.H.;
p ojec adminis a ion, A.H. and M.B.; unding acquisi ion, A.H. and M.B. All au ho s ha e ead
and ag eed o he published e sion o he manusc ip .
Funding: This wo k was suppo ed by he Na ional Science Cen e (NCN, Poland) in he ame o
SONATINA 2 p ojec 2018/28/C/ST8/00187—S uc u e and p ope ies o lignocellulosic ille s mod-
i ied in si u du ing eac i e ex usion. The s udy was pa ially co- unded unde p ojec wi h g an s
o educa ion alloca ed by he Minis y o Science and Highe Educa ion in Poland execu ed unde
he subjec o No 0613/SBAD/4820.
Ins i u ional Re iew Boa d S a emen : No applicable.
In o med Consen S a emen : No applicable.
Da a A ailabili y S a emen : Da a a ailable on eques .
Con lic s o In e es : The au ho s decla e no con lic o in e es .
Figu e 10.
Plo s o (
a
) mass loss cu es and (
b
) di e en ial he mog a ime ic cu es isualizing he
cou se o p epa ed samples’ he mal decomposi ion.
4. Conclusions
The chemical modi ica ion o cellulose ille wi h HDI no iceably enhanced he com-
pa ibili y o sus ainable composi es based on he Ma e -Bi/PCL ma ix. The analysis o
composi es’ chemical s uc u e wi h FTIR spec oscopy poin ed o he gene a ion o u e-
hane bonds a he ma ix/ ille in e ace, enhancing i s quali y and educing ille pull-ou s,
as indica ed by he mic oscopic obse a ions. The gene a ion o u e hane moie ies was con-
i med by he changes in he he mal decomposi ion cou se obse ed ia TGA. Mo eo e ,
SEM, along wi h he esul s o he heological analysis, poin ed o he limi ed agg ega ion
o ille pa icles obse ed o he UFC100 sample con aining as- ecei ed cellulose ille .
Such beha io was induced by he signi ican hyd ophilici y di e ence be ween he applied
polyme ma ix and he unmodi ied cellulose pa icles. Modi ica ion wi h HDI educed his
gap, shi ing he su ace cha ac e owa ds hyd ophobici y, which was exp essed by he
WCA inc ease o e 90
◦
, pu ing composi es on he edge o hyd ophilici y and hyd ophobic-
i y. Concluding, HDI modi ica ion o cellulose pa icles should be conside ed an auspicious
di ec ion in he compa ibiliza ion o composi es based on sus ainable polyme ma ices as
i caused no iceable imp o emen in he in e acial adhesion.
Au ho Con ibu ions:
Concep ualiza ion, A.H.; me hodology, A.H., M.B., P.K., O.M., A.P. and A.T.;
so wa e, M.B., P.K., O.M., A.P. and A.T.; alida ion, A.H., M.B. and A.T.; o mal analysis, A.H. and
M.B.; in es iga ion, A.H., M.B., P.K., O.M., A.P. and A.T.; esou ces, A.H. and M.B.; da a cu a ion,
A.H., M.B., P.K., O.M. and A.T.; w i ing—o iginal d a p epa a ion, A.H. and M.B.; w i ing— e iew
and edi ing, A.H., M.B., O.M. and A.T.; isualiza ion, A.H., M.B. and A.P.; supe ision, A.H.; p ojec
adminis a ion, A.H. and M.B.; unding acquisi ion, A.H. and M.B. All au ho s ha e ead and ag eed
o he published e sion o he manusc ip .
Funding:
This wo k was suppo ed by he Na ional Science Cen e (NCN, Poland) in he ame
o SONATINA 2 p ojec 2018/28/C/ST8/00187—S uc u e and p ope ies o lignocellulosic ille s
modi ied in si u du ing eac i e ex usion. The s udy was pa ially co- unded unde p ojec wi h
g an s o educa ion alloca ed by he Minis y o Science and Highe Educa ion in Poland execu ed
unde he subjec o No 0613/SBAD/4820.
Ins i u ional Re iew Boa d S a emen : No applicable.
In o med Consen S a emen : No applicable.
Ma e ials 2023,16, 6814 18 o 21
Da a A ailabili y S a emen : Da a a ailable on eques .
Con lic s o In e es : The au ho s decla e no con lic o in e es .
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