Microelectronic Engineering 110 (2013) 329334

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Microelectronic Engineering
j o u r n a l o ! e " a g e # $ $ $ % e l s ev i e r % c o ! & l o c a t e & ! e e
E''ect o' s(ntesis con)itions on te "ro"erties o' citric*aci) coate) iron
o+i)e nano"articles
,% ,i
a
- .%/% Ma0
a
- C%1% ,eung
b
- .%/% Can
c
- 1%.% Can
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- 1% 2ong
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- 3%1%4% 3ong
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a
De"art!ent o' Electrical an) Electronic Engineering- 4e 5niversit( o' 6ong .ong- 6ong .ong
b
De"art!ent o' 7""lie) 3(sics- 6ong .ong 3ol(tecnic 5niversit(- 6ong .ong
c
De"art!ent o' Ce!istr(- 4e 5niversit( o' 6ong .ong- 6ong .ong
)
De"art!ent o' 3(sics- 8anjing 5niversit(- Cina
a r t i c l e i n ' o
7rticle istor(#
7vailable online 29 :ebruar(
2013
.e($or)s#
Magnetic nano"article
Citric aci)
Si;e
4e!"erature
a b s t r a c t
Citric aci) is a $i)el( acce"te) coating !aterial in nano"article 'abrication 'or bio!e)ical
a""lications $ile iron o+i)e is one "o"ular !agnetic !aterial $it e+cellent "ro"erties 'or use in
nano"article 'or!% 6o$ever- te e''ect o' s(ntesis con)itions on te "ro"erties o' iron o+i)e
nano"articles is not su''i*cientl( un)erstoo)% 6ere- citric*aci) coate) iron o+i)e nano"articles $ere
s(ntesi;e) base) on te co*"reci"itation !eto) troug bot one*ste" an) t$o*ste" "rocess-
res"ectivel(% 4e citric aci) $as a))e) at )i''erent stages- an) various coating te!"eratures $ere
use) in te t$o*ste" "rocess% 4e nano*"articles $ere caracteri;e) b( !ulti"le tecni<ues
inclu)ing :ourier trans'or! in'rare) s"ectrosco"(- trans!ission electron !icrosco"(- )(na!ic ligt
scattering- ter!ogravi!etric anal(sis- an) vibrating sa!"le !agneto!etr(% =t $as 'oun) tat te
a))ition o' citric aci) at )i''erent stages can alter te nano*"article core si;e- $ile te coating
te!"erature a''ects citric aci) a)sor"tion aroun) nano"articles sur*'ace an) alters te nano"article
()ro)(na!ic si;e% 4e e''ect o' citric*aci) coating on te !agnetic beavior $as also investigate)
on 9 n! an) 2> n! iron o+i)e nano"articles%
2013 Elsevier ?%V% 7ll rigts
reserve)%
1% =ntro)uction
Magnetic nano"articles ave attracte) broa) attention )ue
to teir "otential bio!e)ical a""lications- suc as contrast
agents 'or !agnetic resonance i!aging (M@=)- A1B eating
!e)iators 'or cancer tera"( (("erter!ia)- A2B an)
!agnetic labels 'or bio*sensing A3 B% 4e s"eci'ic nano"article
"ro"erties !ust be tailore) to eac a""lication to obtain te
)esire) results% Magnetic nano*"articles are generall(
re<uire) to be su"er"ara!agnetic- $it su'*'icient !agnetic
saturation- an) a s!all si;e co!"arable to te anal(tes o'
interest A4 B%
=ron o+i)e is one "o"ular !agnetic !aterial $it e+cellent
"ro"erties 'or use in nano"article 'or! A>-9 B% =n recent
)eca)es- !ulti"le iron o+i)e nano"article s(ntesis !eto)s
ave been re*"orte) in literature inclu)ing co*"reci"itation-
ter!al )eco!"osi*tion- !icro*e!ulsion- ()roter!al
s(ntesis- sono*ce!ical s(ntesis- an) so on AC9 B% D'
tese tecni<ues- co*"reci"itation is a 'acile an) convenient
$a( to 'abricate iron o+i)e nano"articles $it si;e less tan
20 n!% 4o ensure bioco!"atibilit( an) "revent
agglo!eration- iron o+i)e nano"articles are usuall( coate)
$it bioco!"atible organic or inorganic !aterials% 6o$ever-
one o' te !ain callenges 'or te use o' te !agnetic
nano"articles is
; Corres"on)ing autor% 4el%# EF>2 2F>C F491(0)G 'a+# EF>2
2>>9 FC3F% E*!ail a))ress# ""ongHeee%0u%0 (3%1%4%
3ong)%
019C*931C&I * see 'ront !atter 2013 Elsevier ?%V% 7ll rigts
reserve)% tt"#&&)+%)oi%org&10%1019&j%!ee%2013%02%04>
to 'in) a goo) !eto) to 'unctionali;e te sur'ace o'
nano"articles $it te a""ro"riate ce!icals A10 B% 4o i!"art
a))itional 'unc*tionalit( an)&or conjugate $it biologicall(
active agents- iron o+i)e nano"articles usuall( bear 'unctional
grou"s on teir sur*'aces- suc as "os"ates- sul"ates-
an) carbo+(lates% D' tese 'unctional grou"s- carbo+(late is
te strongest bin)er A11 B% Dn te oter an)- so!e bin)ing
a''init( !a( be lost troug steric in)rances b( large
sur'actant !olecules or long "ol(!er cains- $ic coul) be
easil( overco!e $it te use o' s!all !olecules A12B%
7!ong various s!all !olecules- citric aci) (C96FDC)- a bio*
co!"atible sort*caine) tri*carbo+(lic aci)- as been
e+tensivel( use) 'or te "re"aration o' a<ueous stable iron
o+i)e nano"articles 'or bio!e)ical a""lications A1219 B%
7ccor)ingl(- citric aci) can be a)sorbe) onto te sur'ace o'
te iron o+i)e nano"articles b( coor*)inating via one or t$o o'
te carbo+(late 'unctionalities- leaving at least one carbo+(lic
aci) grou" e+"ose)- !a0ing te nano"arti*cle sur'ace
()ro"ilic- "reventing "article agglo!eration- an) "rovi)ing
'unctional grou"s to be use) 'or 'urter sur'ace )eriva*tion
A20B% Citric aci) as been e!"lo(e) co!!erciall( as te coat*
ing sur'actant o' iron o+i)e nano"articles- suc as in te M@=
contrast agent VSD3 C1F4 A13 B% Citric*aci) coate) iron o+i)e
nano*"articles ave also been $i)el( stu)ie) 'or teir
a""lications in )rug )eliver(- targete) cellular i!aging-
("erter!ia- an) bio*)etection A12-1419 B% During
s(ntesis- nano"article coating can be a""lie) troug eiter
a one*ste" "rocess- $ere te sur'actant
330 ,% ,i et al% & Microelectronic Engineering 110 (2013) 329334
is a))e) )uring te "article nucleation an)
gro$t A21-22 B- or via a t$o*ste" "rocess
$ere te sur'actant coating is a""lie)
in)e"en*)entl( a'ter nano"article s(ntesis
A23B% Since te citrate ions are 0no$n to
inter'ere $it te 'or!ation an) gro$t o' iron
o+i)e nano"articles- A21B an) "rocess
te!"erature as been 'oun) to i!*"act te
nanocr(stal sur'ace ligan) )(na!ics- A24B it is
$ort$ile to investigate te in'luences o' te
s(ntesis con)itions on te nano"articles%
4is is a critical an) 'un)a!ental $or0 to
caracter*i;e te s(ntesis o' !agnetic
nano"articles in or)er to o"ti!i;e teir
resulting "ro"erties%
6ere- $e ave s(ntesi;e) citric*aci)
coate) iron o+i)e nano*"articles using te co*
"reci"itation !eto) troug bot a one*ste"
an) t$o*ste" coating "rocess% 4e e''ects
intro)uce) b( )i''er*ent s(ntesis con)itions-
a))ing te citric aci) at )i''erent stages an)
using various coating te!"eratures in t$o*
ste" "rocess- are ten co!"are)% 4e i!"act
o' te citric*aci) coating on te !ag*netic
beavior is also investigate) on uncoate) iron
o+i)e cores $it )i''erent si;es%
2% E+"eri!ents
2%1% Materials
:erric clori)e e+a()rate (:eCl3 962D-
P99J)- 'errous sul*'ate e"ta()rate (:eSD4
C62D- P99%0J)- so)iu! ()ro+i)e (P9FJ)-
an) citric aci) (P9FJ) $ere "urcase) 'ro!
Sig!a7l*)ric (5S7)% 7ll ce!icals $ere
use) as receive)% 4e uncoate) iron o+i)e
nano"articles $it si;e close to 9 n! (59)
$ere su"*"lie) b( ,i<ui)s @esearc- ,t) (5.)%
4e uncoate) iron o+i)e nano*"articles $it
si;e close to 2> n! (52>) $ere "urcase)
'ro! 8anostructure) an) 7!or"ous
Materials- =nc% (5S7)%
2%2% 8ano"article s(ntesis
Dur s(nteses $ere base) on te co*
"reci"itation !eto)% :i't( !illiliter eac o'
:eSD4 C62D an) :eCl3 962D $ere !i+e) to*
geter in a !olar ratio o' 1#2- $ic $as
a))e) )ro"*$ise into 200 !l so)iu!
()ro+i)e (1%F M) a<ueous solution at F0 ,C
$it vigorous !ecanical stirring% 4e reaction
continue) 'or 1> !in- an) ten te blac0
"reci"itates $ere obtaine) as uncoate) iron
o+i)e nano"articles (50)% 4e coating o' citric
aci) $as ten con*)ucte) troug tree
)i''erent $a(s o' a))ing citric aci)% 1st !et*
o) ("re*a))ition !eto))# te citric aci) $as
"re*a))e) into te 'errous an) 'erric solution-
an) ten te !i+ture $as a))e) )ro"*$ise
into te a<ueous solution o' so)iu!
()ro+i)e% 4e reaction "rocee)e) at F0 ,C
'or 1> !in- ten at 90 ,C 'or 1 un)er
vigorous stirring% 4e 'inal "ro)ucts $ere
retrieve) b( !agnetic )ecantation- an) ten
$ase) $it D= $ater% 2n) !eto) ("ost*
a))ition !eto))# te citric aci) $as a))e)
$en te "reci"itation o' uncoate) iron o+i)e
nano"articles occurre)% 4e reaction ten
"rocee)e) at 90 ,C 'or 1 un)er rigorous
stirring% 4e 'inal "ro)*ucts $ere retrieve) b(
!agnetic )ecantation- an) $ase) $it D=
$ater% 3r) !eto) (t$o*ste" !eto))# a t$o*
ste" "rocess- ini*tial s(ntesis o' uncoate)
nano"articles an) a "ost*s(ntesis coat*ing o'
citric aci)% :irst- te uncoate) iron o+i)e
nano"articles s(ntesi;e) as "reviousl(
)escribe) $ere collecte) b( !agnetic
)ecantation- $ase) $it D= $ater- an)
l(o"ili;e)% Secon)- tese uncoate)
nano"articles "o$)ers $ere re*)is"erse) in
200 !l D= $ater un)er sonication- an) ten
te slurr( $as eate) to a set te!"erature
'ollo$e) b( te a))ition o' citric aci)% 4e
coating reaction "rocee)e) 'or 1 at te set
te!"erature un)er vigorous stirring% 4e 'inal
"ro)ucts $ere retrieve) b( !agnetic
)ecantation an) $ase) $it D= $ater% 4e
citric aci) coating concentration (0%> g&!l) $as
el) constant 'or eac !eto)% 4e sa!"les
are )es*ignate) b( teir 'abrication !eto)-
coating te!"erature- an) core
si;e- as su!!ari;e) in 4able 1% Sa!"les C1
an) C2 $ere obtaine) b( using te 1st
!eto) an) 2n) !eto)- res"ectivel(%
Sa!"les C3*50*90- C3*50*C0- C3*50*>0- an)
C3*50*30 $ere obtaine) b( using te 3r)
!eto) un)er )i''erent coating te!"eratures%
Sa!*"les C3*59*90 an) C3*52>*90 $ere
obtaine) b( coating te co!*!erciall(
"urcase) uncoate) nano"articles $it citric
aci) using te "ost*s(ntesis coating "rocess
(3r) !eto)) at 90 ,C $it si;es o' 9 n! (59)
an) 2> n! (52>)- res"ectivel(%
2%3% 8ano"article caracteri;ation
4e "resence o' caracteristic 'unctional
grou"s coate) on te nano"article sur'aces
$as )eter!ine) using :ourier trans'or!
in'rare) s"ectrosco"( (:4*=@)% 4e :4*=@
s"ectra o' te sa!"les $ere obtaine) $it a
Si!a);u :4=@*F300 s"ectro!eter using .?r
"ellets% 4e si;e an) !or"olog( o' te
sa!"les $ere observe) b( trans!ission
electron !icrosco"( (4EM- 3ili"s CM100)%
4e ()ro)(na!ic si;e o' te nano"articles in
$ater $ere !easure) b( )(na!ic ligt
scattering (D,S) using a Malvern 2etasi;er
3000 (Malvern- 5.)% 4e !agnetic "ro"ert( o'
te l(o"ili;e) sa!"le "o$)ers $as
!easure) at roo! te!"erature b( using a
vibrating sa!"le !agneto!eter (VSM-
,a0esore VSM C400)% 4e !agneti*;ation
$as !easure) over a range o' a""lie) 'iel)
'ro! 10-000 De to 10-000 De% 4e iron o+i)e
co!"osition $as )eter*!ine) b( using
ter!al gravi!etric anal(sis (4K7- 3er0in*
El!er 4K7*C)% 4e !ass loss o' >10 !g o'
l(o"ili;e) sa!"le $as !on*itore) un)er 82
at te!"eratures 'ro! >0 ,C to 900 ,C at a
rate o' >0 ,C&!in%
3% @esults an) )iscussion
Success'ul citric*aci) enca"sulation o' te
iron o+i)e nano"arti*cles- s(ntesi;e) using
te !eto)s as )escribe) in te e+"eri!en*tal
section- $as con'ir!e) b( te :4*=@ results%
:ig 1 so$s te re"resentative :4*=@
s"ectru!s o' te citric aci) coate) "articles
(C1- C2- C3*50*90- C3*59*90- an) C3*52>*
90)% 4e "ea0s at aroun) >C0 c!
1
in)icate
te "resence o' an iron o+i)e s0eleton in all
te sa!"les% 4e "ea0s near 1930 c!
1
an)
141> c!
1
- re"resenting carbo+(late (CDD )
stretcing- $ere 'oun) in all te citric aci)
coate) sa!"les in our e+"eri!ents% 4e
"resence o' tese "ea0s is evi)ence o' te
'or!ation o' te citric aci) coating aroun) te
iron o+i)e cores A12-2>-29 B%
3%1% =n'luence o' a))ing citric aci) at )i''erent
stages
@e"resentative 4EM i!ages o' te citric*
aci) coate) iron o+i)e nano"articles
s(ntesi;e) un)er si!ilar te!"eratures using
eac o' tree enca"sulation tecni<ues (C1-
C2- an) C3*50*90)- as $ell as te uncoate)
nano"articles (50)- are so$n in :ig% 2%
4roug one*ste" 'abrication tecni<ues (1st
!eto) an) 2n) !eto))- sa!"le C1 ( :ig%
2a) an) C2 ( :ig% 2b) so$ an average si;e o'
9 n! an) 11 n!- res"ectivel(% 4e t$o*ste"
s(ntesi;e) (3r) !eto)) sa!"le C3*50*90 (
:ig% 2c)- an) te uncoate) sa!"le 50 ( :ig%
2)) )is"la(e) si!ilar s"erical !or"olog(
$it a si;e aroun) 13 n!- in)icating tat te
"ost*s(ntesis coating o' citric aci) as te
sur'actant a'ter te s(ntesis o' iron o+i)e
nano"articles as no signi'icant e''ect on te
"article si;e% 4is observation is consis*tent
$it te e+"eri!ental results re"orte)
"reviousl( A2> B% :or te iron o+i)e
nano"articles s(ntesi;e) using te co*
"reci"itation !eto)- it is 0no$n tat tere are
t$o stages inclu)e) in tis "ro*cess-
nucleation an) gro$t A2C B% Co!"are) to te
t$o*ste" sa!*"le C3*50*90- te s!aller
"article si;e o' C2 soul) be attribute) to te
i!!e)iate "resence o' citric aci) a'ter te
"reci"itation o' nano"articles- since te
a)sor"tion o' citrate ions on te nano"ar*ticle
sur'aces in)ers "article gro$t a'ter
nucleation A2> B% 4e
,% ,i et al% & Microelectronic Engineering 110 (2013) 329334 331
4able 1
:abrication con)itions o' citric coate) an) uncoate) iron o+i)e nano"articles%
a
8o!enclature @eaction t("e
S(ntesis
te!" Coating te!"
50 5ncoate) F0 8&7
C1 1st !eto) ("re*a))ition !eto))
F0-
90
C2 2n) !eto) ("ost*a))ition !eto)) F0 90
C3*50*90 3r) !eto) (2*ste" !eto)) F0 90
C3*50*C0 3r) !eto) (2*ste" !eto)) F0 C0
C3*50*>0 3r) !eto) (2*ste" !eto)) F0 >0
C3*50*30 3r) !eto) (2*ste" !eto)) F0 30
C3*52>*90 3r) !eto) ("ost coating) 8&7 90
C3*59*90 3r) !eto) ("ost coating) 8&7 90
a
Sa!"les C1 an) C2 $ere obtaine) b( using te 1st !eto) an) 2n) !eto)- res"ectivel(%
Sa!"les C3*50*90- C3*50*C0- C3*50*>0- an) C3*50*30 $ere obtaine) b( using te 3r)
!eto) un)er )i''erent coating te!"eratures (90 ,C- C0 ,C- >0 ,C- an) 30 ,C)% Sa!"les C3*
59*90 an) C3*52>*90 $ere obtaine) b( coating te uncoate) nano"articles o' )i''erent si;es
(average )ia!eters o' 9 n! an) 2> n!) $it citric aci) using te "ost coating "rocess o' 3r)
!eto) un)er te coating te!"erature o' 90 ,C%
:ig% 1% :4*=@ s"ectra o' citric aci) coate) (C1- C2- C3*
50*90- C3*59*90- an) C3*52>*90) an) uncoate) (50)
iron o+i)e nano"articles%
ultra*s!all si;e o'
C1 soul) be
)ue to te
"resence o' citric
aci) )uring te
nucleation ste"-
since te citric
aci) $as "re*a))e) into te 'errous an) 'erric
solutions be'ore te co*"reci"itation reaction
starte)% 4e a)sor"tion o' citrate ions on te
nuclei sur'aces can e''ectivel( inibit te
gro$t o' te nuclei- A21B $ic causes te
'inal "ro)uct C1 $it !uc s!aller si;es (9
n!) tan sa!"les C2 an) C3*50*90%
7))itionall(- te iron o+i)e nano"articles in
sa!"le C2 )is"la(e) a less s"erical
!or"olog( tan te oter tree sa!*"les%
Since te sa"e o' te iron o+i)e
nano"articles can be a''ecte) b( te "6 value
)uring sa!"le "re"aration- A19B te less
s"erical !or"olog( o' sa!"le C2 !igt be
)ue to te "6 cange cause) b( te a))ition
o' citric aci) )uring "article gro$t% 4e
!ecanis! o' tis "eno!enon nee)s 'urter
stu)(%
3%2% =n'luence o' coating te!"erature in t$o*
ste" "rocess
4e e''ect o' )i''erent coating te!"erature
in te t$o*ste" "ro*cess (3r) !eto)) on te
a)sor"tion o' citric aci) aroun) "article
sur'ace an) te "article ()ro)(na!ic si;e
$ere stu)ie) using 4K7 an) D,S-
res"ectivel(% 4e citric*aci) coate) sa!"les
C3*50*90- C3*50*C0- C3*50*>0- an) C3*50*
30 $ere s(ntesi;e) using te 3r) !eto)
using )i''erent "ost*s(ntesis coating
te!"era*tures o' 90 ,C- C0 ,C- >0 ,C an) 30
,C- res"ectivel(% 4e $eigt "er*centage o'
te iron o+i)e cores in te sa!"les C3*50*90-
C3*50*C0- C3*50*>0- an) C3*50*30 $ere
a""ro+i!atel( 94%FJ- 9>%3J- 99%2J an)
99%>J- res"ectivel( ( :ig% 3)% 4e )ecrease o'
te citric aci) coat*
ing content coul) be observe) 'ro! >%2J to
3%>J as te "ost*s(n*tesis coating
te!"erature )ecrease) 'ro! 90 ,C to 30 ,C%
4e 'or!ation o' a citric aci) coating la(er on
te "article sur'ace is 0no$n to be te
ce!ical bon) 'or!ation bet$een te
carbo+(l grou"s o' citric aci) on te :e*D6
sites o' te iron o+i)e nano"ar*ticles A2F B%
Since te ce!ical reaction rate increases
$it te!"er*ature- te a)sor"tion o' citric aci)
onto te "article sur'ace coul) be enance)
b( te increase) coating te!"erature% 4us-
te in*crease) coating te!"erature coul)
enance te citric*aci) coating rate- an) ere
it $as 'oun) tat te sa!"le C3*50*90 $it
coating te!"erature o' 90 ,C containe) te
igest sur'ace coverage o' cit*ric aci) on te
nano"articles%
4e average ()ro)(na!ic si;es $eigte)
b( intensit( an) "ol()is"ersit( values o' tese
sa!"les are re"orte) in 4able 2%
4e ()ro)(na!ic si;e o' C3*50*90 (>2%9 n!)-
(99%1
n!)-
C3*50*
>0
(91%1 n!)-
an)
C3*50*
30
crease)
as te coating te!"erature
)ecrea
se)
30 ,C% Since te iron o+i)e core si;es in tese
sa!"les $ere te sa!e as te uncoate)
nano"articles 50 (13 n!- :ig% 2))- teir in*
crease) ()ro)(na!ic si;e $it )ecrease)
"ost*s(ntesis coating te!"erature coul) be
e+"laine) b( a re)uction in te citric aci)
coating on te iron o+i)e cores as te
te!"erature )ecrease)- $ic $as con'ir!e)
b( te 4K7 results ( :ig% 3)% 4e nano"article
clusters coul) be 'or!e) $en tere $ere not
enoug sur'actants to 0ee" te! se"arate)-
an) te clustering coul) increase te
()ro)(na!ic si;e o' nano"articles A29 B% 4e
nano"articles (50) $it no coating aggregate)
into large clusters in D= $ater $it
()ro)(na!ic si;es o' tens o' !icro*!eters%
4e si;e )istribution o' te sa!"les is
e+"resse) in te "ol()is"ersit( in)e+ (3%=%)-
$ic corres"on)s to te variance o' te si;e
)istribution o' te nano"ar*ticles% 4e 3%=%
value o' te sa!"les $it citric aci) coating at
)i''er*ent te!"erature- C3*50*90- C3*50*C0-
C3*50*>0- an) C3*50*30- $ere 0%22- 0%19-
0%2>- an) 0%29- res"ectivel(% 6o$ever- it
soul) be note) tat te si;e )istribution o'
tese sa!"les )oes not ave a si!"le
correlation $it te citric aci) sur'actant
coverage aroun) nano"articles alone% 4e
C3*50*90 containe) te igest content o'
citric aci) sur'actant coating in tese 'our
sa!"les as in)icate) b( 4K7 result ( :ig% 3)
but so$e) less o!ogeneous nano"article
si;e )istribution (0%22) tan te one o' C3*50*
C0 (0%19) $ile te C3*50*C0 )is"la(e) te
s!allest 3%=% value a!ong tese 'our sa!*"les
in our stu)(% :or te sa!"le ()ro)(na!ic
si;e )istributions- "art o' te )is"ersit( $as
resulte) 'ro! "ol()is"ersit( in te single citric*
aci) coate) iron o+i)e nano"articles $ile
so!e )is"ersit( !a( be cause) b( variations
in te nanocluster si;es% Dn one an)- te
si;e )istribution o' te in)ivi)ual nano"articles
beca!e nar*ro$er as te sur'actant*to*$ater
ratio )ecrease) A24 B% 4us as te content o'
citric aci) )ecrease) in te 'inal "ro)ucts- te
si;e )istribution o' te single citric aci)*coate)
iron o+i)e $oul) be
332 ,% ,i et al% & Microelectronic Engineering 110 (2013) 329334
:ig% 2% 4EM i!ages o' s(ntesi;e) citric aci) coate) iron o+i)e nano"articles troug tree !eto)s an) uncoate) iron o+i)e nano"articles (a) C1- (b) C2- (c) C3*50*90- an)
()) 50%
4able 2
6()ro)(na!ic si;e o' iron o+i)e nano"articles coate) $it citric aci) at )i''erent
te!"eratures- in D= $ater%
Sa!"les
Mean )ia!eter
a
(n!) an) "ol()is"ersit( in)e+
b
C3*50*90
>2%9
A0%2
2B
C3*50*C0
99%1
A0%1
9B
C3*50*>0
91%1
A0%2
>B
C3*50*30
132%9
A0%2
9B
a
Mean "article si;e result 'ro! tree !easure!ents- $eigte) b( intensit(%
b
3ol()is"ersit( in)e+ values (3%=%)- given in brac0ets- range 'ro! 0 to 1G a iger
value in)icates a less o!ogeneous nano"article si;e )istribution%
:ig% 3% 4K7 results o' iron o+i)e nano"articles coate) $it citric aci) at )i''erent
te!"erature in te 3r) !eto) (C3*50*90- C3*50*C0- C3*50*>0- an) C3*50*30)%ASee
te electronic version o' te Lournal 'or a color version o' tis 'igure%B%
narro$er% Dn te oter an)- $en tere $ere not enoug sur'ac*tants
to 0ee" te nano"articles se"arate)- 'ractal aggregates coul) be
'or!e) $it a $i)e si;e )istribution A2> B% 7s suc- as te con*tent o'
citric aci) )ecrease) in te 'inal "ro)ucts- te si;e )istribu*tion o' te
nanoclusters $oul) beco!e broa)er% Due to tese t$o e''ects- te si;e
)istribution o' te 'inal sa!"les )oes not ave a si!"le correlation $it
te content o' citric aci) sur'actant coating%
3%3% =n'luence o' "ost*s(ntesis coating $it citric aci) on !agnetic
beavior
4e in'luence o' "ost*s(ntesis coating $it citric aci) at 90 ,C in
te 3r) !eto) (t$o*ste" "rocess) on te !agnetic beavior o' te
nano"articles $as investigate) on t$o 0in)s o' uncoate) iron o+i)e
nano"articles $it )i''erent si;es o' 9 n! (59) an) 2> n! (52>)% 7s
)eter!ine) 'ro! 4EM i!ages ( :ig% 4a an) b)- te iron o+i)e core
si;es o' te citric*aci) coate) sa!"les C3*59*90 an) C3*52>*90 $ere
still aroun) 9 n! (!ean si;e o' sa!"le 59) an) 2> n! (!ean si;e o'
sa!"le 52>)- res"ectivel(% =t in)icates tat te sur'actant coating )i)
not in)uce signi'icant cange o' te nano"article core si;es% 4e
!agnetic beaviors o' te sa!"les $ere !easure) using te VSM at
roo! te!"erature- as so$n in :ig% 4c an) )% 4e saturation
!agneti;ation (Ms) 'or te iron o+i)e cores o' te citric aci) coate)
sa!"les C3*59*90 an) C3*52>*90 $as )eter!ine) to be >0 e!u&g
an) 49 e!u&g- al!ost te sa!e as te Ms o' te corres"on)ing
uncoate) iron o+i)e nano"articles 59 (>1 e!u&g) an) 52> (49 e!u&g)-
res"ectivel(% 4e( are less tan
,% ,i et al% & Microelectronic Engineering 110 (2013) 329334 333
:ig% 4% 4EM i!ages an) VSM results o' citric aci) coate) iron o+i)e nano"articles $it core si;es o' 9 n! an) 2> n! in 3r) !eto)% (a an) b) 4EM i!ages o' (a) C3*59*90 an)
(b) C3*52>*90% (c an) )) VSM results o' (c) C3*59*90 an) ()) C3*52>*90% 4e insets in (c) an) ()) are te corres"on)ing !agni'ie) vie$s o' te M6 loo"s in te lo$ !agnetic 'iel)%
te Ms 'or bul0 :e3D4 (92 e!u&g) an) te Ms 'or bul0 c*:e2D3 (C4
e!u&g) A30 B- but are co!"arable to te e+"eri!ental values 'or Ms o'
!agnetite nano"articles s"anne) te 30>0 e!u&g range A31B% 4e
insets in :ig% 4c an) ) $ere te corres"on)ing !agni'ie) vie$s o' te
M6 loo"s in te lo$ !agnetic 'iel)% ?ot o' te un*coate) sa!"le 59
an) te citric*aci) coate) sa!"le C3*59*90 )is*"la(e) a
su"er"ara!agnetic beavior $it negligible coercivit(% 4e coercivit(
o' uncoate) sa!"le 52> an) citric*aci) coate) sa!*"le C3*52>*90
$as 49 De an) 3F De- res"ectivel(% 4e coercivit( )ecrease o' 52>
a'ter coate) $it citric aci) coul) be attribute) to te increase)
)istance bet$een te nano"articles cause) b( cit*ric*aci) coating-
$ic le) to te re)uction o' te inter*"article )i*"ole)i"ole interaction
an) tus s!aller coercivit( A23 B% :or iron o+i)e nano"articles $it si;e
s!aller tan 20 n!- te ter!al en*erg( overco!es te )i"ole)i"ole
interaction- an) te ter!al 'luctuations can cange te )irection o'
!agneti;ation o' te entire cr(stal% A32B 4us- te uncoate) 9*n!
nano"articles in sa!"le 59 e+ibit a su"er"ara!agnetic beavior $it
no coercivit( at roo! te!"erature% Even toug te citric*aci) coating
can increase te )istance bet$een te nano"articles an) re)uce te
inter*"article )i"ole)i"ole interaction- te su"er"ara!agnetic nature
o' te 9 n! nano"articles )oes not cange an) tus te coercivit( o'
te citric aci) coate) sa!"le C3*59*90 sta(s to be ;ero% 4ere'ore-
te citric*aci) coating )i) not alter te su"er"ara!agnetic beav*ior o'
te iron o+i)e nano"article $it si;e close to 9 n!- an) coul) re)uce
te coercivit( o' iron o+i)e nano"articles $it si;e close to 2> n!%
4% Conclusion
4is stu)( )e!onstrates te e''ect o' te s(ntesis con)itions
inclu)ing te a))ition o' citric aci) an) te coating te!"erature on te
"ro"erties o' citric*aci) coate) iron o+i)e nano"articles%
4e core si;es o' te citric*aci) coate) nano"articles coul) be a)*
juste) 'ro! aroun) 9 n! to 13 n! b( a))ing te citric aci) at )i'*'erent
stage in te s(ntesis "rocess# "re*a))ition into 'errous an) 'erric
solution (1st !eto))- "ost*a))ition $en nano"articles "reci"itate)
(2n) !eto))- an) "ost*s(ntesis coating a'ter un*coate) nano"article
s(ntesi;e) in a t$o*ste" "rocess (3r) !et*o))% =n te t$o*ste"
"rocess 'or s(ntesis- te )ecrease) coating te!"erature resulte) in
increase) ()ro)(na!ic si;es o' te s(n*tesi;e) citric*aci) coate)
nano"articles% 4us- te in'luences o' te a))ition o' citric aci) an) te
coating te!"erature on te si;e o' te 'inal "ro)ucts $ere reveale)%
:or te s!all si;e) ( 9 n!) uncoate) iron o+i)e nano"articles $it a
su"er"ara!agnetic beavior- te citric*aci) coating $oul) not a''ect its
su"er"ara*!agnetic 'eature% :or te larger si;e) ( 2> n!) iron o+i)e
nano*"articles $it coercivit(- te citric*aci) coating $oul) )ecrease
teir coercivit(% 4is $or0 in)icates te s(ntesis con)itions coul) be
a""ro"riatel( controlle) to 'abricate te citric*aci) coate) nano"articles
'or a s"eci'ic "ur"ose%
7c0no$le)g!ents
4is $or0 $as su""orte) b( te See) 'un)ing 3rogra! 'or ?asic
@esearc 'ro! te 5niversit( o' 6ong .ong- te @KC*K@: Krant
(6.5 C049&113)- an) 5niversit( Krants Council o' 6ong .ong (con*
tract no% 7oE&3*04&0F)% 1e are tan0'ul 'or te "roo'rea)ing o' our
!anuscri"t b( Cris @oberts%
@e'erences
[1 S% 1agner- =nvestigative @a)iolog( 3C (2002) 19C%
[2 =% 6ilger- .% :rMau'- 1% 7n)rN- @% 6iergeist- @% 6ergt- 1%7% .aiser-
7ca)e!ic @a)iolog( 9 (2002) 19F202%
[3 K% ,i- S% Sun- @%L% 1ilson- @%,% 1ite- 8% 3our!an)- S%O% 1ang- Sensors
an) 7ctuators 7# 3(sical 129 (2009) 9F109%
[4 V%.% Vara)an- D%,%:% Cen- L% Oie- 1ile(- 200F%
334 ,% ,i et al% & Microelectronic Engineering 110 (2013) 329334
[5 7%.% Ku"ta- M% Ku"ta- ?io!aterials 29 (200>) 399>4021%
[6 L% Oie- L% 6uang- O% ,i- S% Sun- O% Cen- Current Me)icinal Ce!istr( 19
(2009) 12CF1294%
[7 .% 1oo- L% 6ong- S% Coi- 6%1% ,ee- L%3% 7n- C%S% .i!- S%1% ,ee-
Ce!istr( o' Materials 19 (2004) 2F142F1F%
[8 /% ,u- /% /in- ?%4% Ma(ers- /% Oia- 8ano ,etters 2 (2002) 1F31F9%
[9 1% 1u- P% 6e- C% Liang- 8anoscale @esearc ,etters 3 (200F) 39C41>%
[10 E% 3arton- @% De 3al!a- K% ?orgs- Soli) State 4ecnolog( >0 (200C) 4C%
[11 @% 1eissle)er- ?%D% @oss- 7% @ee!tulla- S%S% Ka!bir- Molecular
=!aging# 3rinci"les an) 3ractice- 3eo"leQs Me)ical 3ublising 6ouse- 2010%
[12 S% 8iga!- .% ?aric0- D% ?aa)ur- Lournal o' Magnetis! an) Magnetic
Materials 323 (2011) 23C243%
[13 C% ?o(er- M%@% 1itta0er- V% ?ul!us- L% ,iu- 4%3% Davis- 83K 7sia Materials
2 (2010) 2330%
[14 E% Munnier- S% Coen*Lonatan- C% ,inassier- ,% Dou;iec*E(rolles- 6%
Marcais- M% SoucR- .% 6ervR- 3% Dubois- =% Cour"a- =nternational Lournal o'
3ar!aceutics 393 (200F) 1C01C9%
[15 .%D% 1ani- @% .itture- 7% 7!e)- 7%S% Cou)ari- S%L% .o""i0ar- S%8% .ale-
@% .aul*Kane0ar- Lournal o' ?ionanoscience > (2011) >99>%
[16 M%7% Daniele- M%,% Saugness(- @% @oe)er- 7% Cil)ress- /%3% ?an)era-
S% :oulger- 7CS 8ano C (2012) 203213%
[17 L%3% :ortin- :% Ka;eau- C% 1ilel!- Euro"ean ?io"(sics Lournal 3C (200F)
223 22F%
[18 ,% ,i- .% Ma0- C% ,eung- .% Can- 1% Can- 1% 2ong- 3% 3ong- =EEE
4ransactions on Magnetics 4F (2012) 32993302%
[19 7% ,a"resta*:ernSn)e;- 4% Doussineau- S% Dut;- :% Steiniger- 7%L% Moro-
K%L% Mor- 8anotecnolog( 22 (2011) 41>>01%
[20 C% ,iu- 3% 6uang- Soil Science Societ( o' 7!erica Lournal 93 (1999) 9>
C2%
[21 7% ?ee- @% Massart- S% 8eveu- Lournal o' Magnetis! an) Magnetic
Materials 149 (199>) 99%
[22 C% 6ui- C% Sen- 4% /ang- ,% ?ao- L% 4ian- 6% Ding- C% ,i- 6%L% Kao- 4e
Lournal o' 3(sical Ce!istr( C 112 (200F) 1133911339%
[23 7% 4o!ita0a- 4% .osi- S% 6atsugai- 4% /a!a)a- /% 4a0e!ura- Lournal o'
Magnetis! an) Magnetic Materials 323 (2011) 139F1403%
[24 S% 1an- L% 6uang- M% Kuo- 6% 2ang- /% Cao- 6% /an- .% ,iu- Lournal o'
?io!e)ical Materials @esearc 3art 7 F07 (200C) 9499>4%
[25 @%7% :ri!"ong- L% Dou- M% 3ecan- L%2% 6ilt- Lournal o' Magnetis! an)
Magnetic Materials 322 (2010) 329331%
[26 E% Ceragi"our- S% Lava)"our- 7%@% Me)i;a)e- Lournal o' ?io!e)ical
Science an) Engineering > (2012) >%
[27 C%S%S%@% .u!ar- Micro'lui)ic Devices in 8anotecnolog(# 7""lications-
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@esearc 1> (2000) 21142120%
[31 ,%7% 6arris- L%D% Ko''- 7%/% Car!icael- L%S% @i''le- L%L% 6arburn- 4%K% St%
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[32 C%S%S%@% .u!ar- Magnetic 8ano!aterials- 1ile(- 2009%