Ma

cromo
lecu
larRes
earch
,Vol
.22,N
o.4
,pp4
24-
430(
201
4) www
.sp
rin
ger
.com/1
3233
DOI10
.100
7/s13
233-0
14-20
64-3 p
ISSN1
598
-50
32eISSN2 0
92-76
73

Su
rfa
ce Mod
if
ica
tiono
fCe
llu
loseNanowh
isker
sandTh
eirR
ein
for
cing
E
ffe
ctinPoly
lac
tid
e

J
ooH
yun
gLe
e,S
angH
oPa
rk,andS
eon
g Hun K
im*
D
epa
rtm
ento
fOr
gan
ica
ndNa
noEng
ine
ering
,Han
yangUn
ive
rsi
ty
,Seou
l133
-791
,Ko
rea

R
ece
ive
dOc
tob
er1
2,2
013
;Re
vis
edJanua
ry8
,2014
;Ac
cep
tedJanua
ry8
,2014

Abstrac
t:T heaimo f
t h
iss
tudyw astoimproveth
edispers
abi
lityofthece
llulo
sen anow h
isker
s(CNW )inthen on
-
pol
arenvironm e
nt,andtofab
ric
atei
tsbiocomposi
tes
.T heace
tylat
edc e
llu
losenanow hi
skers(ACN s)wer
eprepared
byint
rodu c
ingthea c
etylgro
upso n
tothecel
lulos
es u
rface
s.T hebiocomposi
tesw e
r eprepar
edb yinc
orpora
ting1
,
2and3w t%o ftheACNi n
tothepoly
lact
ide(PLA)m atr
ixb yusingasolut
ionc a
st
i ngm e
thod.Fromthem orpho
-
log
icalan a
lys
is,i
tw asfoundtha
ttheACNw asdisp
ersedwel
l inPLAm a
trixbecauseofthesur
f a
ceblock
ingeffe
ct
byacety
lg roupso nthecel
lulo
sesurfa
ce,w h
ichledtod ecr
e a
seo fsur
facep o
lar
ity.M oreove
r,theACNs howed
enhanc
inge f
fectsonthetens
il
ep r
oper
ties
,therma
lstab
ility
,dim en
siona
lstabi
li
tya ndd ynamicm e
chani
calprope
r-
t
iesofthePLAc ompos
ite
s.TheACNp rom o
tedcry
sta
lli
zat
ionbehavior
,resu
lt
in ginanincrea
seincrys
tal
lin
ityfo
r
thePLA /CNWc om pos
ite
s.Fromtheresu
ltsofth
isw o
r k
,thed
ispersa
bil
ityofthecel
l u
losecanbeim p
rovedsign
if
-
ican
tlyb ysur
facem odi
fica
tion
,anditcanm aximi
zethere
inforc
ingp o
tent
ialofcellulo
sef o
rthebiopo
lym e
rs.
K
eyw
ord
s:p
oly
lac
ti
de,p
olym
ern
ano
com
pos
it
e,c
el
lu
los
ena
now
his
ker
,su
rfa
cem
odi
fi
cat
ion
.

In
trodu
cti
on h
asabunda nth ydroxy
lg r oupso nitssurface
,anditcanb eeas-
i
lyappl
i edf orc hemi ca
lm odif
ications uchase s
ter
ifi
cation,
1
3-15
Polylac
tide(PLA )isab iodegr adabletherm opl
a s
ti
cp olye
ster e
the
rf
ication,silyla
tion. Moreov e
r,vario
usp o
lym er
sh ave
1 16
tha
tc anb ederivedfromr enew a
bleres ou
r c
ess ucha ssta
rch. b
eengraf
te do ntothec el
l u
lo ses uchasp o
l y
(L-la
ctid
e), poly-
17 18
PLAh asag re atpotent
ialtob ea ppl
iedi nv ar
io u
si ndus
tria
l s
tyr
ene,a ndp o
l y
uretha ne
. H owe ve
r,duetoit
sh ydrophi
lic-
f
ieldsi nc
ludin gbiom ed
icalp r oducts
,f o o
dp ackaging
,a nd i
tyonthes ur
faceareaa n dstro ngh ydrogenbonding
sb etween
au
tom ot
i v
em a
t e
ria
lsd uetoitse xcel
lentstif
fn e
ssa ndstr
ength
. i
nte
ra ndintram ol
ecul a
rm ak ethec e
llulos
efloccu
late
,res u
lt
-
Ina dd
ition,PLAi sc onside
r edag o odalterna
tivet op e
tro- i
nginin e
ffi c
ie n
tc om poun din gwitht hem os
tn onpo
larp oly
-
leum-base dp olym er
s,b ecaus eitc anb ep rocessede a
sily m
erm at
rix.J o noob
ie ta l.r eport
e dt h
atthem echanical
s
im i
lart op o
l yole
fins.H ow ever,t hePLAh ass om edraw- p
rope
rt
ieso fc e
llul
osen anofib e
r(CNF )reinf
orcedPLAp re-
backssucha sb ri
tt
le n
ess
,r e
lati velyp oo
rt herm a
lr esi
stance
, p
aredbym el
tc om pou ndingw ereim proved.H owever
,t hey
2
,3
ands lowc rystal
lizat
ionb eha v
i or
. Tom akeu pf o
rt he f
oundt ha
tt he CNFt en d
st oa ggregatew henloadingl eve
l
1
9
shor
tcom ings
,c ons
i d
erableres earchh asb eenc onductedon i
ncrea
sed. Toe xpan dtheu seo fc e
llulos
en anowhiskersas
impr o
v eme n
to ft hermo-m ec hanicalpr opert
ieso fPLAb y r
ein
forcem e n
t,its houldb ed i spe
rsedh om ogeneou
slyi nthe
us
ingreinforc
em en
t,especi
allyn atura
lreinforcem en
ts.Am ong n
on-po
lare nv
ir onments uc ha sp o
l ymerm atr
ixa n
ds olvent
s.
then a
tura
lr e
i nfor
c ements
,c el
l ulosefiberh asatt
ractedgreat O
nea p
proa chi saredu ct
io no fh ydrophi
lic
ityofthec e
llu
l o
se
4-
6
a
tten
tionasfil
lerforthePLAc om posi
tes
. Cel
luloseisrenew- b
yu s
ings urfacem odif
icatio nw ithv ar
i o
usc hemica
lr eac-
ab
le,biodegrad ab
lea ndo neo ft hem os
ta b undantm ate
rial
s t
ions
.T hea cety
lat
i onr eactioni so neo fthecerta
ins urfa
ce
one a
rth.R ecently
,i so
lat
io no fn anocel
l u
lo s
ef romv arious m
odi
fica
tionm ethodto im pr ovedisp e
rsab
ili
tyofc e
ll
ulose.20
sou
r ce
sf o
ra pplica
tionasr e
inf orcem en
ti nb iocomp os
ite
sh as Inthi
ss tu dy
,c e
llulosen an ow h
isk e
rs(CNW )w e
reprepared
7-
9
beenstudi
e d
. Nanoce
llulosefi bero b
tainedfromr enewabl
e f
romm icroc r
y s
tal
linec e
llul o
s ebya ci
dh ydro
lysi
su s
ings u
lfu-
b
iom assw asw i d
elyu sedasr e inforcem en
t sforthePLA ,i n r
icaci
d,a n dino rde
rt oim pro v
ead i
s pe
rsab
il
ityoftheCNW
or
der t
oo vercom eitsdraw bac ks,b e
c au
s ei
th asa ne xce
ll
e n
t i
nn onpo
lare n vi
ronm e n
ts uch aschlorofo
rm ,th
es u
rfacem od-
mechan
i ca
lp rop e
rt
ies,lowd ensitya ndl owt hermale xpan- i
fi
cat
ionw asc a
rrie
do u
tb ya c e
ty
lat
i onreact
ion
.T heacety
lated
s
ion.T hee nha nc
in gef
fe c
to fn an o
cellu
l oseforthep o
lym e
r c
el
lulos
en anow hi
s ker(ACN )w asp repa
reds uccess
fully
,
1
0-12
com pos
iteshasb eenr e
ported
. Ina ddi
tion toth
is,c e
llu
lose w
hichw asc onfirmedb yt h
er esu
ltso fF our
iertrans
f orm
i
nfra
reds pe c
tr o
sco pybya tten ua
te dtota
lrefle
ctance(FT IR-
*C
orr
espond
ingAu
tho
r.E
-ma
i:k
l im
sh@
han
yan
g.a
c.k
r A
TR)a n ds o
lids t
ate 13Cc r ossp olar
izat
ionm ag
i ca ngl
e

ThePo
lyme
rSoc
ietyo
fKo
rea 4
24
 S
urf
aceM
odi
fic
at
iono
fCe
llu
los
eNa
now
his
ker
san
dTh
eirR
ein
for
cin
gEf
fec
tinP
oly
lac
tid
e

sp
inningnucle
arm agne
ticreson an
cespe c
troscopy(1
3
CCP - co n
tinu ous
l yu n
tilcom ple
telyd isso
l v
e d
.T hes u
s p
e n
sio nw a
s
MASNMR )
.M aintenanc
eo ftheircry
sta
ll
inestruc
tureo fthe co ndi
tio nedtod egas i
ta ndw ast h
e ncasti n
t oaT ef
lo nm old
.
ACNw asevaluat
e dbyw idea ng
l eX-r
ayd i
ffrac
tion(XRD )
. Thec h
l oro
f orm w asa l
low edt oe vapora
t ea tam bienttem -
Th
em orpho
logyo ftheACNw aso b
serv
e dbym eansoft r
ans- peraturea n dp ressuref o
r2 4h .T hes ol
i di
fiedPLA /ACN
m
iss
ionelec
tronm icroscopy(TEM )
.T heresu
ltantm ater
ial
s com posi
tefilm sw erev acuumd r
ie dfor7 2h .N anoc om pos
-
we
reeva
luatedasreinf
orcementforaPLAm atr
ix.Tofabrica
te i
t efilm sco n
taining0 ,1,2,a n d3w t%o fc el
l u
losen anow h
is-
h
igh-pe
rformancen anocel
lulose-re
info
r cedPLAc om pos
ite kersw erepr epared,a ndw er ec ode dasPLA ,PLA /ACN 1
,
f
ilms,
thes u
rfacem od
if
iedcellulose
-loadedPLAc om posi
te PLA /ACN 2a ndPLA /ACN 3,r espect
ively.
f
ilmsw er
ep reparedandc ha
r acte
rize
di ntermsoft hec r
ys- Ch aracterization.F ouriert ransformi nfrareds pectros
-
ta
ll
in
ity
,visi
blecom p
ar
isonof thetr
ansparen
cy,tr
ansm it
tance
, cop y(FT IR,N ic o
let7 60 MAGN a-IRs pectrom e
ter)an dsol
id
mo
rphology
,therm alprope
rti
e sandm echanica
lpro pert
ies
. s
t a
t e13CCP -MAS( crossp olarizat
ion-m agica ngles p
in n
ing)
NMR(AVANCE4 00WB ,B r u ker
)w er
eu sedt od e
term ine
E
xpe
rim
ent
al thes tructureo ftheCNWa ndACN .W id e-angleX -raydif-
fractionp at
t e
r nsw erec o
llect edu singX -ra ydiff
r ac
tom etry
M aterial
s. P ol y
(lact
id e
)(PLA )bi opolym e
r(N a
tureW orks (Ri gak uD en k
i,J apan)at4 0kVa nd6 0mAa ndd if
fracto-
PLA ,4 032Dg ra de
)w i
thad ens
ityo f1. 2
5g /cm3 a ndam o
lar gram sw eres cannedi na2 θr angeo f5 o
- 45o
.T r
a nsmission
masso f5 2,000g /m o
lw asa pp
liedasm atr
ix.M ic
r oc
r y
stal
line e
l ectronm icroscop y(TEM )o bservationsw erep erformed
cellulo se(MCC )w i
t ha m eanp a
rticles izeof2 0μm w as us
i ngaJEM2 100Fe lec
tr onm icroscopea t1 00kV .F ie
ld
useda sr e
infor
c em en
t(S igm a
-AldrichC o.
,)
.S ul
furicacid(98%) em iss
io nscan n
i ngelect
ronm i croscopy(FESEM ,JEOLJSM -
(Si gm a-Aldri
c h)w asu se dforacidh ydrolys
iso fm icroc
rys- 633 0F)w asu sed toident
ifyth em o
r phologyo fthePLA /ACN
tal
li nec e
llu
lose.C hlorofo
rmw asuse dass olven
tf o
rPLA .Ace- com posi
tefilm s.UV - v
isib
l ea bsorptions pectraoft hePLA /
t
i ca nh ydr
ide(AA ),p yr
i d
i n
ea nddim e
t hy
lform amide(DMF ) ACNc om pos
itefilmsw e
rem ea su
re dw ithaUV -v
isib
les pec
-
werep urchasedfromS igm a-Aldr
ichC o.
. trom eter(S-4 100,Scinco,K or ea)betw een1 ,000a nd2 00nm .
Pr ep arat
iono fC el
lul oseN anowh isk er
. MCCw asm od- Theu n
treatedPLAf ilmw ass etasas tandar da ndtherela
tive
if
i edb ysul
f u
rica c
i dh ydrolys
isan dultrasoni
cation
.A pprox
i- transparenc yof thePLA /ACNc omp o
sitefilm sw a
se s
tim a
ted.
mately1 0go f MCC w asd ispe
rse di n1 00mLd eionized Therm o grav
im etrica na
lysis(TGA )o ft h
ePLA /ACNc om-
water.T h
e MCC /w a
ters uspensionw asp lacedo nani cebath positew asp er
f orme dundern itrogenp urgef rom3 0 to6 00oC
andm echan
ic a
llys tir
reda t0oC .T h ens ul
furica c
i dw as a
t2 0Co
/m in
.D im ensiona
lc h ang e
sf ort h
ePLA /ACNc om -
ad dedd ropb yd ropu n
tilthed es
ire dc oncent
r a
tiono f4 4% positefilmsw eree va
l ua
tedb yu singTAI nstrum en
tT hem o
-
wasr ea ched
.T hes olut
i onw asincubatedf or120m ina t45oC mec hanica
la naly z
er(TMAQ 400)atah eat
i ngrateof1 0oC/
w
it hc o n
tinuousstir
ringa ndc oo
ledb ya dding50 0mLo fw a
ter
. m
i n.A ni ni
tialf or
ceo f0.0 5Nw a
sa p p
liedt othes pecim en
Theo b
t a
ineds us p
e ns
ionw a
sc en
trifugeda t3 ,000rpmf o
r w
it ha no r
i g
i na
ll engtho f1 6mm .T herm alb ehav
i o
ro ft he
15m ina ndw ashed repea
t edl
yw i
t hd e
i onizedw a
ter
.F inal
ly
,the PLA /ACNc om pos
itew asi n vest
igatedb yd ifferen
tialscan-
resultings amplesw ereo ven-d
riedinv acuoat6 0oCf o
r2 4h, n
i ngc a
l o
rim et
r y(P erk
inElm er DSC - 7
).A l
ls am plesw e
re
and the nthe“cellulo
s ena now h
isker”p ow derwasc o
llected
. heatedf rom3 0t o2 00oCat2 0oC /minu n dernitrogen
.S am -
Su rf aceM odificationo fCNW .A cetyla
tionrea c
tionw as p
l esw ereh e
lda t2 0 0oCfor5 m ina ndq ue nchedt o3 0oC,
o
perf o
rm edu ndern i
tr ogenatm osph e
r einat hree-nec kfla
sk an dthe nh eateda gainto2 0 0Ca tt hes am er a
te.Fr omt he
eq uipp edw i
thac o ndens e
r.As uspensi onof3 .0gCNWi n obtaine d DSCc urve,therm alp ropert
i e
ss ucha scrystal
liza
-
DMF w asp la
c edi ni ceb athandd isp er
s edbyu lt
r a
s on
ica- t
i ont em perature(Tc)
,m e
ltin gtem p e
rature( Tm)
,e nthalpyo f
tio nf or1h .T he n4. 5go fp yr
idinew asa ddedt oth efla
sk, crystal
lizat
io n( ΔHc),a nde nt ha
l pyofm elting(ΔHm)o ft he
an dt hens ur
fa cem o di
ficationreactio nw asstar
tedb ydrop- PLA /ACNc om p o
sitesw e
rec al cu
lated.T he tens
ilepr ope
rtie
s
wisea ddit
iono f1 14go fa ce
tica nh ydr
i detot her esu
lted oft hePLA /ACNc om po
sitef ilmsw erem easureda tr oom
sus pen s
i o
n.T herea c
tionw asperform edf or1 5ha t1 05oC tem peratur
eu singa nINSTRON4 46 5universalte
st
in gm ach
i n
e.
wi
t hac on
tinuou sst
irring.A fte
rr eaction,theo bta
i nedsus- Sam plesoft hePLA /CNWc om posi
tefilmsw erepreparedw i
th
3
pen sionw asprecipi
t a
te da ndw ashedr epeated
lyw ithd eion
- d
im ens
i on
so f1 00×15×0.1mm .T hegaug elengthandt hecros
s-
ize dw ate
r/meth anol
/ ac
eto nemi x
ture( 1/1/1b yv o
l.fract
ion) heads peedw eresetto5 0mma nd1mm /m i n
,r e
s p
e c
tively
.
toe lim inatealln on-reactedc he
micals
.F inally
,ther esul
ting
sam plesw ereo ven-driedi nv acuoa t6 0oCf o
r2 4h,a nd R
esu
ltandD
iscu
ssi
on
the nt heACNp ow derw asc o
llected.
Pr ep arat
iono fPLA /ACNC omp osites
.B eforepr epa
ra- Ace
tyla
tionoftheCNW .
t
i o no fthePLA /ACNc om p o
si
tes,t hePLAp e
lletw asdried Chemica
lM od
if
ica
tionoftheCNW :Thesu
rfa
cem odi
-
at8 0oCf o
r1 0hi nv acuo.T hedesire dam ountofACNs us- f
ica
tio
no fthe CNW w asperf
ormedbythees
ter
if
ica
tion
pen sionsi nchlor o
f o
rmw aspre pa
re du s
i ngultrason
i ca
tion
. b
etweenhydroxy
lgroupsandalar
geex
ces
soface
ticanhy
-
The nPLAw asa dde dtot heresulte ds u
s pens
io na ndsti
rred d
rid
e.Theb a
siccha
rac
teri
st
icsofchem
ica
lm o
dif
ica
tio
no f

M
acr
omo
l.R
es.
,Vo
l.2
2,N
o.4
,20
14 4
25
 J
.H.L
eee
tal
.

T
abl
eI.Th
eBa
sicCh
ara
cte
ris
tic
sofA
cet
yla
tedC
el
lul
oseN
anowh
isk
er
V
alu
e C
har
act
eri
zat
ion

1
740cm -
1
p
e aks how
sthecarb o
nylst
retching
FT
IRA
nal
ysi
s v
ibr
at
i on( νC=O).1370cm-
1
peakshow sthe
me
thylin-plan ebend
ing(δ -H)
C .1240cm -1

p
ea ks how stheC-Ost
retching(νC-O)

So
lidS
ta
te
1
3
CNMRA na
lys
is

F
igu
re1
.(a
)TEMim
ageo
fth
eACN
,hi
sto
gram
sof(
b)l
eng
tha
nd(
c)d
iam
ete
rfo
rth
eACN
.

ce
llulo
sew e
resumm ar
izedinT ableI .B yu s
in gFT IRs pec- Fromt heFT IRa ndsol
idstateNMRd ata
,itw a
sc onf
irmed
tr
oscop y
,thec h
aract e
ris
ticvibra
tio no fthes u
rfac em o d
ified tha
tt heac e
tyla
tionofCNWw a scarri
edo u
ts u
ccessf
ully
.
ace
tylg roupsw asc on
fi
rm ed,r esp on d
st ot h ec arb on y
l M orph o
l o
g yand C rysta
ll
in eS tructureofth e ACN :
s
tre
t ch
ingv ib
rat
i ona t1740cm -1
(νC=O) ,them e
thyli n
- plane TEMa nalys
isw asp e
rformedt oinv e
st
i g
atem o
r ph
ologyof
bend
ing1 37 -1
0cm ( δC-O)
,12 3
1cm -1
(νC-O),and3 342cm -1
(νO-H)
. theACN .T heACNh adaro d
-likem orpho
logyanddispe
rsed
Thein
tensi
tyofh ydrox y
lgroupstretchi ngpeakw asd ecreas ed
, we
ll,ass how ninF igu
re1 (a
).T helengt
ha nddiam e
terof
i
tm eansthatthe−OHg roups ubstitutedt oa cety
lg r ou p
. theACNw eremeasure
db ydig
italimageanaly
si
sm ethodus
ing
Thea c
etyla
tiono ft he CNWw asa ls oi nd
icatedw i
t h 13C Ima geproplus(M edi
aC yb
erne
tics,USA ).Theobta
inedhis
to-
CP-MASNMRs pectr o
scopy.T heCNWh ass hownt y p
i cal g
ram sa ndc umula
tivecurvesfo rthelengthanddiam e
terof
NMRp eaksass
ig neda sfol
low s:C1( 1 0
5p pm ),C 4cr ystal
- theCNW w eresh owninF igure1 (b
)a nd(c)
,r e
spect
ively
.
l
ine( 89ppm )
,C 4 am orphous(84p pm )
,C 2/C/C
3 5(7 2a nd7 5 Ana verageleng
tha nddiam e
tero ftheCNWw erefoundto
ppm),C 6cryst
all
i ne( 65ppm )
,a ndC 6 am orph ous(63p pm )
. be3 94
. 7nma n
d2 8.1nm,resp ect
ively
.
Af
tersur
f a
cem od
ification
,thec har acteri
st
i c
ss igna
lsf or the PLA /ACNC omp o
si
teF i
lm s.
ace
tylgroupcarbonsi nc
lud
i ngcarbon yla n
dm e
thylgro upc ar- WideAn gleX-Ra yDiffr
actionAn a
lysi
s:T hew ideangl
e
bon
sem ergedat172a nd21ppm( αa n dβc arbon)
,r e
spectiv e
ly
. X-
rayd iff
r a
ctio
np att
ernsfort hep urePLAa ndthePLA /

4
26 M
acr
omo
l.R
es.
,Vo
l.2
2,N
o.4
,20
14
 S
urf
aceM
odi
fic
at
iono
fCe
llu
los
eNa
now
his
ker
san
dTh
eirR
ein
for
cin
gEf
fec
tinP
oly
lac
tid
e

ACNc om positefi
lm saresh ow ni nF igure2.T hep urePLA respect
ively
,c om paredrela
tiv e
lyw i
t ht hetransparenc yo f
f
ilms how st heam orpho u
sp olym e
rp a
tte
r n
s.H owever
,a s purePLAf ilm.A sthew a ve
len g
tho ft helightincrea
se d
,t he
theACNl oa d
i ngl evelincreased,th etw odistin
ctdiffe
r e
nt reduct
ionofr e
lativetranspar
en cyoft hePLA /ACNc om p o
site
peaksw eresh ow nata bout2 θ=16.4o and1 8
.9o
whichass
igned f
ilm sw asde c
rea sed
.B e
c au
seo fal a
r gev olum efrac
tio no f
tothet yp
icalreflect
io nplan
e soft hePLA( 110
/ 200
)a nd(203)
, nano-sc
aledreinforcem en
t,a nda ni ncrem ento fcrys
tall
i ni
ty
respec
ti v
ely.T hism eansthatthec rysta
llin
estr uc
turesofthe forthePLA /ACNc om posi
tefilmd iscusse dab ove
,theo pac-
PLA /ACNc om po s
itef i
lm sw e
r ed eveloped.T hisfeature i
tyo fthePLAc om pos
itew a
si nc
r ea
s ed
.H ow ever
,therelative
su g
geststhatt heACNa ct
sa sn uc
leatinga gentinthePLA t
ra n
sm i
ttancefort hePLA /ACNc om posi
tef i
lm sdecreas edat
matr
ix.T het ypicalp eaksofc elluloseId idn otappear
,d ue ac ons
tantrate
,a st he ACNc ontentin c
r ea
s ed
.Itm eanst ha
t
toasm al
lam o un
to ft heACNl oaded. theACNw hichc anp reven
tt helighttransm i
ttancew erew e
ll
Fi
lmT ran sp a
r enc y
:T het ransparenc yoft hePLA /ACN d
is p
ersedinthePLAm a
tr
i x
.
com posi
tef ilm sc o n
tain
i ng ACNi sd ecreasedd ra
stica
lly MorphologicalP rope r
ties
: T hem orp hologyoffract ured
com paredw ithp ur ePLAf ilm .T h
isr esul
tw asm or
ee valu
- surf
a c
eso ft h
ePLA /ACNc om posi
tef ilm sw asc haracter
-
a
t edb ytheUV - v
isibles pec
t rom e
try
,a ndther e
lat
ivetrans- izedb ySEM ,a n dtheim agesa res how ni nF igure4.T he
m
ittanc
ec urveso ft hePLAc om posi
tesa reshow ninF i
g u
re3. purePLAf ilms h owssm oo
thf ractureds ur
f ace(Figu
re4 (a)
).
Thep urePLAf ilm w a
ss e
ta sas tan d
ard,an dther e
lat
i v
e Ass how ninF ig u
r e4(b),(c)
,a nd( d),f orth ePLA /ACN
reduct
i onoft r
a nsm i
ttanceoft hePLA /ACNc om posi
tefilms com pos
itefi
lm sw i
thfill
erloa dinglev e
li ncreased
,itc a nbe
wasest
im ated.T herew asad ras
ticre duct
ioni ntheam o
u n
t seenthattheACNw asse p
aratedf rome acho theran dd is
-
ofligh
tt ransm it
te dt h
rou ght hePLAc om posi
tefilmsw ith pe
r s
e dh omo g
e neo u
slyi nthePLA m a
trix.T h
isresultc an
ACNf i
llerloadingc om paredt o
t hepurePLAf i
lm .At40 0nm, bee xp
lainedb yt heim provedd i
s pers
ibili
tyo fs u
rfacem o d
-
w
it h
t h
eACNf ill
er loadingle v
elincreased,thePLAc om pos
- i
fiedn a no
cellulosei nth en onpolare n v
iro nm en
t.Ino ther
i
t efi
lm sal
l owt hrou gh60.1% ,3 8
.9%,a nd1 9
.9%o ftheligh
t, respec
t,itc anb ee xp
lainedb yg o odi nterac
tionsb etw een
theACNa ndth ePLAm atr
ixm aket hed ispers
ionstates ta-
b
ilized
.M or
e over,av oidw asn o
tf oun din thefrac
t u
re ds ur
-
face
,a ndt h
eACNw asc ove
r edw itht hePLA m atr
i x
.T hi
s
featur
es uggestst hatstrongi nteract
io nse x
istb e
tw ee nt he
ACNf il
lersa n
dt hePLA m a
tri x.T h
er ichh y d
rox y
lg r oups
onthec e
llulos
es ur
faceres u
ltedi nthei n
terfacialin
teraction
be
tw eent he ACNa ndt hePLA m a
trixi nt hePLA /ACN
com pos
ite.T hesem orphologica
lo bservationsc anb ec o n
-
s
id e
r e
da sthee viden c
e,w hichle ad
i ngt ob e
tterm echa nica
l
p
r oper
ties
,fore ffic
ientstres
st ra n
sf e
rb etw eenthec el
l ulose
andt h
ep olymerm atr
ix.
Mechanica
lP r operti
es: T oe st
im a
tet hereinfor
cinge ffect
o
ft he ACNo nt hePLA m at
ri x,th em echanica
lp rope r
ties
o
ft hec omposi
t efilm sw e
rest ud
i ed
.T hed epe ndenceo fthe
tens
ilestrengtha ndt ens
ilem o dulusoft hePLA /ACNc om -

F
igu
re2
.X-Ra
ydif
fra
ct
ionpa
tt
ern
soft
hePLA
/ACNcomp
osi
te F
igure3.R
ela
tiv
etr
ansm
it
tan
cec
urve
soft
hePLA
/ACNc
om-
f
i
lmswi
thv
ar
iousACNcon
ten
twit
h2dXRDim
age
ssh
ownbe
low. p
osi
tefi
lms
.

M
acr
omo
l.R
es.
,Vo
l.2
2,N
o.4
,20
14 4
27
 J
.H.L
eee
tal
.

F
igu
re4.SEMimage
soft
hefra
ctu
res
urf
aceso
fthe(
a)pu
re
PLA
,(b
)PLA/ACN
1,(c
)PLA/ACN2
,and(d
)PLA/ACN3
.

F
igu
re6.TGAth
ermo
gramso
f(a)t
heCNWa
ndt
heACNa
nd
(
b)th
ePLA/ACNcompo
si
tef
ilm
s.

F
igu
re5
.Ch
ang
esint
hete
nsi
les
tre
ngthandt
ens
il
em od
ulu
sof
the me
tricanal
y si
sw asco nduc
ted.Th eresul
tsoft heTGAt her
-
PLA
/ACNc
ompos
it
efilm
sinre
lat
iontot
heACNc o
nte
nt
. mogramsares how ninF igur
e6 .T heinit
ialan dm axim um
deg
ra d
at
iont empera
turesfortheACNw e
reshiftedt ohigher
posi
tefi
lm sinrela
tiontotheACNc o n
tentissh owninFig- tempera
ture
sb ysurface
sm od
if
ica
tion,asshow ninF igure6(a)
.
ure5.T hetensi
les t
rengtho fthec om p os
it
ef i
lm sw as Thet h
ermals tab
il
ityo f ACN w asim p
roveds ignificant
ly
incre
asedf rom5 2.7 MPaf o
rt hep ur
ePLAf ilmt o5 7
.9
, com pa
redt otheCNW .T h
isresulth a
se f
fecto nth etherm a
l
60.1and6 6
.2 MP aw i
ththea ddi
tiono f1 ,2,a nd3w t% s
tabil
ityfort h
ePLA /ACNc omp os
itesfi
lm sc ontainingthe
ACN,w hichcorr
espondtoa9 .9%,1 4%,an d2 5
.6%i ncr
ease
, ACNf il
ler
s.A ss how ninF igu
re6 (b)
,t heTGAr es u
ltsof
respec
tive
l y
.T h
isr esu
ltsuggest
st h
atthe ACNa pp
liedin thep ur
ePLAa ndt hePLA /ACNc om posi
tefilm sd on o
t
PLA m a
trixh a
sg oodm e
chanica
lp roper
tiesa ndthatthe
re show m uchdiffe
rence,asthec u
r ve
sa reclosetoe achother
isastronginte
rfac
ialadhesionbetweenth ePLAm at
rixand a
tah ighw eightreductio
nt emperatur
e s
.H ow ever,thed eg-
the ACN .T hetens
ilem odulusoft hepu rePLAf ilm w a
s rada
tiontem pera
turesataw eightreductionof1 0w t%w e
re
o
measu
reda s2.7GP a
,a ndinthecaseofthePLA /ACNc om- incr
e a
seds ystemica
llyfrom3 30 Cf orpurePLAf ilmt o
posi
tefi
lm sc on
tain
i ng1,2,a nd3w t% ACN ,thetensi
le 338oCf o
rt hePLA /ACN 1
,3 41oCf orthePLA /ACN 2and
o
modulu
sw asm easuredas2 .8
,2 .9
,a nd3 .2GP a,respec
- 345 Cforth ePLA/ACN 1,respec
tively
.As im i
lart endency
t
i ve
ly
.T het ens
il
em odulu
so fthePLAw asincrea
sedc on
- waso b
servedataw e
i gh
tr educt
i onof8 0%.T hei ncrement
s
ta n
tlyb ya ddingthe ACN w hichh asah ighstif
fness
. ofthermals tab
il
ityi nt he PLA /ACNc om positec a nb e
Moreove
r,o n
lysm al
lstandardd ev
ia
tionsw ereo bse
rvedin a
ttr
ib u
tedt oa nintroduct
iono fr e
i n
f o
rcem entw hichh as
tens
ilem odulus
,w hichindicat
esthatthe ACN w a
sh om o
- goodthermalstabi
lit
ya ndag oodc om pat
ibi
li
t yb e
tw ee nthe
geneous
lyd i
str
ibutedinan on-po
larPLAm at
rix
. PLAm a
trixa ndACN .
Thermo grav
im et
ric Analysi
s:T oe s
tim a
tet hethermal TheTGAk ine
tica na
lysisw a
sp er
form edf o
rt hePLA /
s
ta b
il
ityoft hePLA /ACNc om po
si
tefilm s
,at hermo g
ravi
- ACNc omp os
itefi
lm si no rde
rt oc lar
ifyth er e
i nforc
ing

4
28 M
acr
omo
l.R
es.
,Vo
l.2
2,N
o.4
,20
14
 S
urf
aceM
odi
fic
at
iono
fCe
llu
los
eNa
now
his
ker
san
dTh
eirR
ein
for
cin
gEf
fec
tinP
oly
lac
tid
e

po
tent
ialoftheACNo nthe
rma
lstabi
li
tyofthec omp
o s
it
e
f
ilms.Theact
i v
at
ionfort
hethe
rm a
ld e
grada
tio
n(Eα)ofthe
PLA/ACNc om po
si
tef
ilmscanbedet
ermin
edfromtheTGA
th
erm o
gramsb y
theHorowi
tz-M
etz
gerin
teg
ralk
inet
icme
t hod
g
ivenbelow:2
1

–1 Eaθ
ln
[ln
(1–α)]=-
--
-
--
-
-
2
-
-
-
RTdm
where αi st hew eig h
tl oss
;Eai st hea cti
v a
tione nerg yf o
r
thet herm ald egrad a
tio n;Tdmi st hetem per
at u
rea tt hem axi
-
mumr ateo fw e
i ghtlo s; θi
s sd e
fin eda sθ=T -Tdm a ndRi s
theu niv ersa
lg asc onstatnt.T h ea ct
i va
tione nergyc anb e
calcul
ate db yu sin gt hes lopeo ft hep lotofl n[
l n(1-α) -1
]v s
.
θ.Th eEa v aluesw erei n crea
s edfr om2 20.9k J
/m olf orthe
PLAf ilmt o2 29.8,2 5 8.8,a nd2 75.4k J/molf ort hePLA / F
igu
re7
.Chan
gesint
hecoe
ff
ic
iento
fthe
rma
lexp
ans
ionoft
he
ACNc om pos
itefilm sc ontain
in gthe1% ,2% ,a n d3%o ft he PLA
/ACNc
om po
si
tefi
lmsi
nrel
at
iontot
heACNcon
ten
t.
ACN ,res pect
i ve
l y
.T h
i sr esul
tc anb ee xp
lainedb yt h einter-
act
io n
sb etw ee ntheACNa ndt hePLAm a
trix
.
T
ableII
.Therm
alD
ataf
orthePLA
/ACN C
omp
osi
teF
ilm
s
D
im en s
i onalS tabil
ity:D ime ns
ion a
ls tab
il
ityisa nim portan
t
C
alcu
lat
edf
romDSC2ndHea
tin
gSc
an
propertyfo rcompo s
it e
sinv ariousapp l
ications.B ecause
thePLAh asap oord im ensionalstabi
lity,i
ts houldb eim pr oved T Tm ΔHc ΔHm
S
amp
le c

forPLAa ppliedt ow i def i

led.3
Toi n ves
tigated im e ns
i ona
l (
o
C) (
o
C) (
J/g
) (J
/g)
s
t ab
ili
tyo ft hePLA /ACNc om po s
itefilms,theTMAa nalysi
s PLA 1
31.
9 1
64.
2 4
.5 3
.4
wasc arr
i edo u
ta n dt hec oef
fic iento ft herm a
le x pansion PLA
/ACN
1 1
31.
9 1
65 3
.7 3
.4
(CTE )w a sc a
l culated.F i gur
e7s how st hec han gesi nt he
PLA
/ACN
2 1
29.
3 1
65.
3 4
.2 4
.5
CTEo ft hec om positea saf unct
i ono ft h
eACNc o n
t ent
.A s
theACNc ontenti ncrease d
,CTEv alu esw e
red ecre a
s ed.T hi
s PLA
/ACN
3 1
28.
2 1
64.
7 4
.8 5
.0
resul
ta ttr
i butedt ot heim p
r ovedt herm alstabi
lityo f ACN ,
orstrongi nte
rf ac
iala d hesionb etwe ent heACNa n dt hePLA ure8.Int heglassyregio
n,w h
ichc orrespondstob elow4 5oC,
mat
rix. thestora gem o du
lusfort hePLAc om pos
itefilm sincreased
Therm alP rope r
ties:T oinvestigatet heeffec
to ft h eACN w
itht heg raduala ddi
tiono ft he ACNu nti
l2w t%o ft he
contento nth et herm alb e havior
,a DSCa nalysisw asp e
r- ACN lo aded,ass howninF ig u
re8 ( a
).Itm eansthatt hes
tif
f-
form edo nt hep ur ePLAa ndPLA /ACNc om p osi
t efilm s
. nessofth ePLAc om pos
itesw asim p
ro v
edb yadditi
o nofthe
Thet herm alp roperties,s ucha sc oldc ryst
alliza
tio nt em per
- ACN .T hisr e
inforcingeffecto fth e ACNo nPLA m a
trix
ature( T)a
c ndm eltingt em perature( Tm)o ft hePLA /CNW m
i ghtb ee xplainedb yt hef o
rm ationo fs t
r ongh y d
r o
g e
n
com posi
t ef i
lm sw erec alc ula
tedf roms eco nd DSCh eating bonde dc e
llulosen e
tw o
r ksa ndt hestres
st ransfe
rf romt he
scansa n da res umm arizedi nT ableI I
.H ow ever
,t hec o
ld PLAm atrixtot heACN .H ow ever,thein c
rem ento fsto
r a
ge
crys
tal
liz a
ti ontem peraturew asd ecreasedfr om1 31.9oCf or modulusr eache dat hre
s ho
l dat3w t%o f ACNl oadedto
thep urePLAt o1 2 8
. 2oCf orPLA /ACN 3
.T hepr ese nceo f PLAm at
rix,an dnosigni
ficantdifferenceofd ynami cm echan
-
ACNc anp rom o
tet hec ol dcryst allizat
ionb ehavio ro ft h
e icalb eha v
iori nw ho
let em pera
tu resca nn
i ngr egionw as
PLA m atr
i x.T hem e
ltin gt em pera
t urew a
si ncrea sedf rom foun dbetw eent hePLA /ACN 2a n dthePLA /ACN 3.Inthe
164.2oCf orth epu rePLAf ilmto165 ,165.3,and1 6 4
. 7oC g
l as
stran s
itionregion,w hichc o
rre spondstob etw een45oC
forPLA /ACNc om positef i
lmc ontaining1w t% ,2w t%a nd to8 0oC,d ras
ticdr op
si nthes tora gem od u
l u
so ft hePLA /
3w t% ACN ,r esp ect
i vely
.A st he ACNc onten
ti ncreas e
d, ACNc om pos
itefilmsw eref ound.T h
isa ttr
ibutedt ot he
theh e a
to ff usiono ft hePLAc om p o
sit
ef ilm si ncre as
ed g
l as
st ransi
tione f
fectoft hePLA m atr
ix.T h
eg lasstrans
i-
com paredt ot hep urePLAf i
lm .T hisi nd
icatedt ha
tt h eACN t
i ontem p e
rature(Tg)
,w h
ichc orrespo nd
st othep eakoftan
hada ne ffe c
to nt hec rystall
inityo fPLAc om positef ilm s
. del
tac urves,w ere6 2
.4oCf orthep urePLA ,63.4,6 3.8
,a nd
Ane xplan at
io nf ort h
isi st hatt hes urfaceo fthe ACNc an 63.1oCf orthePLAc om pos
itesc ontain
in g1,2,a nd3w t%
actasan u c
leatings itef orcr y
stall
iz a
ti onoft hePLAm atrix
. ofthe ACN ,r espec
tive
l y
.M oreov er
,d am pingi nt
e ns
ityin
Dynam i cM ech an ical An alysis:T oinvestigateh owt he theg la
sst rans
itionregiono fthePLA /ACNc om posi
tesw a
s
st
iffnesso ft hePLAc om p o
sitesi sa ffec
te db yt h e ACN decrea
sedw ithg radua
lad d
it
io nofth eACN ,a ssh ow ninFig-
contents
,d ynam icm ec hanicala nalysisw asc arr
ie do u
t.T he ure8(b).B yg radualaddit
iono ft heACN ,t heTgo ft hePLA
storagem odulusa ndt and e
ltac urv esoft h
e PLA /ACN com posi
t esw asincrea
se dbe causet hepresenceo ftheACN
com positesa saf unct
i ono ft em peraturew eres how ni nF i
g- rest
rictedthem obi
lit
yo fPLAc ha
i ns
.

M
acr
omo
l.R
es.
,Vo
l.2
2,N
o.4
,20
14 4
29
 J
.H.L
eee
tal
.

enh
ancemen
to fth
etherma
lst
abi
li
tyanddim e
nsionalst
abi
li
ty
o
ft hePLA /ACNc ompos
it
es.The ACNh ada ne f
fec
to n
the
rm a
lpro p
ert
iesofPLAt ha
tthecry
st
al
liza
t
i ont
em pe
ra
tur
e
o
fthePLA /ACNc om po
si
te
sw asdecr
easedan dthem e
lt
ing
temper
atureofthePLA /ACNc ompos
it
esw asinc
rea
sedwit
h
inc
rea
sin
gACNc on
ten
ts
.T h
estorag
em odulusf o
rthePLA
compos
itefilmsw asincre
asedb yaddi
tiono fthe ACN,
imply
ingtha
tthes
tif
fnes
softh
ePLAc omposi
tesw a
sim p
rov
ed
byaddi
tio
no ftheACN .

Ackn
owledgmen
ts
.T hi
sres
ear
chw a
ssuppor
tedbyt
he
N
at
iona
lR e
sea
rchFoun
dat
ionofKor
ea(Pr
oje
ctN o
.201
2-
0
47656
).

R
efe
ren
ces
(1
)D .G arlo
tta
,J.P o
lym .E n
rir on
.,9,6 3( 2001)
.
(2
)L .S uryaneg
ara,A.N .N a kagai
to,an dH.Y a no
,Cel
lulose,17,
7
7 1(2 010
).
(3
)S.H .P ark,S.G.L e
e,an dS .H.K im ,Com pos
.P artA :A p
pl
.
S
ci.M a
n u
f.,46,1 1(2013).
(4)S.H .L ee
,S.W an g
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t o
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l.P ol
ym .Sci
.,
1
0 8,8 70(2008)
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(5
)A .P.M a
thew,K .O ksm an,a ndM .S ain
,J.A ppl
.P olym.Sci
.,
9
7 ,2 014(2005)
.
(6
)R .Z uluaga
,J.L.P u
taux,J.C ruz
,J.V e
lez,I.M on d
rago n
,and
P
.G anan,C a
rb o
h ydr
.P o
l ym., 73,5 1(200 9
).
(7
)B .M .C her
ian,A.L .L eao
,S .F.S ouz a
,S.T hom as
,L .P o
than
,
a
n dM .K ot
ta
isam y
,C arboh ydr
.P o
lym .,81,7 20(2 01
0).
F
igu
re8.Thes
tor
agemodu
lus(
a)a
ndtan
gentdel
ta(
b)cu
rveso
f (8)E.A braham,B .D eepa,L.A .P o
than,M .J aco b
,S.T h omas
,
t
hepurePLAandthePLA/ACNcom
pos
itefi
lmsinre
la
tio
nto U
.C velba
r,a ndR .A nan dj
iwala,C arb
o hydr
.P o
lym.,8 6,
t
emper
atu
re
. 1
4 68( 201
1).
(9
)A .St ur
cova,G.R .D avi
es,a ndS.J.E ichhom ,B
iom acrom o
le-
c
ules, 6
,1 055(2 005)
.
C
onc
lus
ion
s
(
10)K .O ksm an
,A .P.M at
hew ,D.B ondes o
n,a ndI.K vie
n,C om-
p
os.S ci
.Techn o
l.,66,2 77 6(2006)
.
Ce
llulo
sen anowh
isker
sw ereisola
tedfromm icrocr
ysta
ll
ine (
11)M .K owalcz
yk,E .Piorkow ska,P
.K ulp
ins k
i,andM .P race
lla
,
ce
llulosepow derbysulfu
ricacidtreatme n
ta ndu l
trason
ica- C
om p os
.P ar
tA :A ppl
.S c
i.M anuf
., 42,1 509( 2011)
.
t
io n
.A cety
lat
e dce
llu
losenanowhiskerw aspreparedfromcel- (
12)S.H .P ark
,K .W .O h
,a ndS .H.K im ,Com pos.Sci
.T echnol
.,
lu
l o
sen anow h
iske
rp owderbys ur
facem od
if
ic a
tionreact
ion. 8
6 ,8 2(2013)
.
ByFT IR-ATRa ndsol
idsta
teNMRa nalys
is,i
tw a
sc onf
irmed (
13)S.I fuku,M .N ogi
,K .A be,K .H anda,F.N aka
tsubo,a ndH.
tha
tt hereac
tionw a
sc a
rri
edo uts uc
cessful
ly
.T hePLA /ACN Y
an o
,B iom a
crom olecu
les, 8,1 973( 2007).
com pos
itef
ilmsc o
nta
i n
ing1,2,a nd3w t%o ft heACNr e
in- (
14)H .Y uan,Y.N ishiyam a
,M .W ada
,a ndS.K uga
,B iomacro-
forcem en
tw ereprep
aredb yas o
l u
tionc as
tingm e
thod.D ue m
olec u
les,7,6 96( 2006)
.
tothen uc
leat
ioneff
ectofloadedACN ,thecrystal
lin
ityofthe (
15)C .C o u
sse
,H .C hanzy
,G .E xco
ffie
r,L .S oub e
yrand,a ndE.
PLA/ACNc om pos
i
tefilmsw ase levat
ed.T helighttransmi
t- F
leury,P o
lymer, 43,2 645( 2002)
.
tanceofthePLA /ACNc omp o
sitefi
lm sw asd ec
r ea
sedc om- (
16)C .Y an,J.Z hang,Y.L v,J .Y u
,J .W u
,J.Z hang
,a ndJ .H e
,
pa
redw ithpurePLAf i
lm.T hem echan
icalproper
tiesofPLA / B
iom acrom o
lecules,10,2 0 13(2009).
(
17)G.M orand
i,L .H eath
,a ndW .T h
i el
em ans,L angmuir,25,
ACNc om pos
it
esw e
reincre
asedb ye n
hancem en
to fdispe
rs
ibi
l-
8
2 80( 2009
).
i
t yoft he ACNi nno n
-polarenvironm ent
ss ucha sc h
loro-
(
18)A .P e
i,J.M alho,J.R uokolainen
,Q .Z hou
,a ndA .B ergl
und,
formb ecauseofthesurf
aceb l
o ckingeffec
to fac e
tylgroups M
ac romolecu
les, 4 4,4422( 2011
).
onthec e
llu
losesur
faceandd ec
rem entofsurfa
c ep o
lar
ity
.T he (
19)M .J onoobi
,J.H arun,A.P .M a
thew,a ndK .O ksman,Com-
tens
ilestreng
tha ndm odu
lusw eree nhancedb y2 5%a nd p
os.S ci
.Techn o
l.,70,1 74 2(2010)
.
18.5%f orPLAc om pos
itefilm sc on
taining3w t% ACN , (
20)N .S.C e
tin
,P.T in g
a u
t,N .O zm en
,N .H enry
,D .H arper
,M .
com pa
redtot hepur
ePLAf i
lm.A saresultofTGAa na
lysi
s, D
adm um,andG .S ebe
,M a crom o
l.Bio s
ci
., 9 ,997( 2009)
.
thet he
rm a
ls tab
il
ityoft he ACN w a
sim p
roved,resu
lt
ingin (
21)B .G uo,D.Jia,andC .C ai
,E ur
.P olym.J., 40,1 743(20 0
4).

4
30 M
acr
omo
l.R
es.
,Vo
l.2
2,N
o.4
,20
14