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Acicular iron nanoparticles protected against sintering with aluminium oxide

Abstract

Acicular iron nanoparticles have been obtained by thermal reduction with hydrogen of a goethite precursor protected against sintering with Al cations, either by doping during the synthesis or by a further coating and the relation between microstructure and magnetic properties of the final Fe particles has been studied in order to evaluate the efficiency of both protecting methods. Uniform goethite and Al-doped goethite precursors were prepared by oxidation with air of FeSO4 solutions, containing Al(NO3)3 when required, previously precipitated with Na2CO3, while the Al oxide coating on the undoped goethite precursor was carried out by heterocoagulation. In both protecting methods, Al cations were mainly concentrated in the particle outer layers of the goethite precursors and the final iron. Due to this Al enrichment, the growth of iron crystals during the reduction process is minimised resulting Fe particles with improved coercivity and squareness. Nevertheless, the coating procedure seems to be more effective giving rise to the iron particles with the largest coercivity, probably due to a better preservation of the acicular morphology in this case.

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Acicular iron nanoparticles protected against sintering with aluminium oxide

Author: Pozas, R.; Morales, M. P.; Serna Pereda, Carlos J.; Ocaña Jurado, Manuel
Publisher: Sociedad Española de Cerámica y Vidrio
Year: 2004
Source: https://idus.us.es/bitstreams/9bcf927f-fd1c-41b0-96df-7be4fd6cd54b/download
796
BOLETIN DE LA SOCIEDAD ESPAÑOLA DE
ARTICULO
Ce ámica y Vid io
Acicula i on nanopa icles p o ec ed
agains sin e ing wi h aluminium oxide
R. PozAs1, M. P. MoRAles2, C. J. seRnA2, M. oCAñA1
1
Ins i u o de Ciencia de Ma e iales de Se illa (CSIC-UNSE), Amé ico Vespucio s/n, Isla de la Ca uja, 41092 Se illa, Spain.
2
Ins i u o de Ciencia de Ma e iales de Mad id (CSIC), Can oblanco, 28049 Mad id, Spain.
Acicula i on nanopa icles ha e been ob ained by he mal educ ion wi h hyd ogen o a goe hi e p ecu so p o ec ed agains sin e ing wi h
Al ca ions, ei he by doping du ing he syn hesis o by a u he coa ing and he ela ion be ween mic os uc u e and magne ic p ope ies o
he inal Fe pa icles has been s udied in o de o e alua e he e iciency o bo h p o ec ing me hods. Uni o m goe hi e and Al-doped goe hi e
p ecu so s we e p epa ed by oxida ion wi h ai o FeSO
4
solu ions, con aining Al(NO
3
)
3
when equi ed, p e iously p ecipi a ed wi h Na
2
CO
3
,
while he Al oxide coa ing on he undoped goe hi e p ecu so was ca ied ou by he e ocoagula ion. In bo h p o ec ing me hods, Al ca ions
we e mainly concen a ed in he pa icle ou e laye s o he goe hi e p ecu so s and he inal i on. Due o his Al en ichmen , he g ow h o
i on c ys als du ing he educ ion p ocess is minimised esul ing Fe pa icles wi h imp o ed coe ci i y and squa eness. Ne e heless, he
coa ing p ocedu e seems o be mo e e ec i e gi ing ise o he i on pa icles wi h he la ges coe ci i y, p obably due o a be e p ese a ion
o he acicula mo phology in his case.
Keywo ds: Aluminium, Goe hi e, I on nanopa icles, Magne ic p ope ies
Nanopa ículas acicula es de hie o p o egidas en e a la sin e ización con óxido de aluminio
Se han ob enido nanopa ículas acicula es de hie o po educción é mica con hid ógeno de un p ecu so acicula de goe i a que ue p o egido
en e a la sin e ización po la adición de ca iones Al median e dopado du an e su sín esis o po ecub imien o pos e io , es udiándose la
elación en e la mic oes uc u a y las p opiedades magné icas de las pa ículas inales de α-Fe con obje o de e alua la e icacia de ambos
mé odos de p o ección. Los p ecu so es uni o mes de goe i a y de goe i a dopada con Al se p epa a on po oxidación con ai e de disoluciones
de FeSO
4
o de FeSO
4
y Al(NO
3
)
3
, p e iamen e p ecipi adas po la adición de Na
2
CO
3
, mien as que el ecub imien o con óxido de aluminio
sob e las pa ículas de goe i a ue lle ado a cabo po un p ocedimien o de he e ocoagulación. En ambos mé odos de p o ección, los ca iones
aluminio es aban p incipalmen e concen ados en las capas más ex e nas de las pa ículas, an o de los p ecu so es de goe i a como del
hie o. Debido a es e en iquecimien o en Al, se minimiza el c ecimien o de los c is ales de hie o du an e el p oceso de educción esul ando
pa ículas de Fe con mayo es alo es de coe ci i idad y de cuad a u a de la cu a de his é esis. No obs an e, las pa ículas de hie o p o egidas
median e ecub imien o p esen aban alo es de coe ci i idad lige amen e mayo es, p obablemen e debido a la mejo conse ación de la
mo ología acicula en es e caso.
Palab as cla e: Aluminio, Goe i a, Nanopa ículas de hie o, P opiedades magné icas
1. INTRODUCTION
Comme cial me al pa icles o eco ding media a e usually
p oduced s a ing om di e en i on hyd oxide o oxide p ecu so s
which, h ough dehyd oxyla ion o hema i e (α-Fe2O3) when equi ed,
a e con e ed o α-Fe me al pa icles a e he mal educ ion. The
p oduc s a e subjec ed also o a passi a ion ea men o ming a
su ace laye o i on oxide a ound he pa icle in o de o p e en
u he oxida ion o he me al co e (1,2). Fo his applica ion acicula
nanopa icles o α-Fe a e equi ed due o he low alue o he
demagne iza ion ield along he majo axis, which d i es o highe
coe ci i y alues (3). Fo he p epa a ion o hese i on pa icles, goe hi e
ha g ow hs as elonga ed pa icles ollowing i s c ys allog aphic
habi , is usually used as p ecu so , which mus be ans o med o i on
p ese ing he acicula mo phology. In gene al, educ ion o hese
p ecu so s des oys he acicula mo phology, which has undesi able
e ec on he magne ic p ope ies o he inal e omagne ic me al co es.
Fo his eason, he addi ion o p e en ing sin e ing agen s, such as Al,
B, Si, P and Sn, o he s a ing goe hi e pa icles has been sugges ed o
p ese e hei acicula mo phology du ing he o ma ion o he me al
pa icles (4).
Recen ly, we ha e p epa ed acicula i on nanopa icles by
educ ion o uni o m goe hi e pa icles ob ained in he p esence o
ca bona e ions (5). Mo eo e , i was also shown ha he use o an
Al-doped p ecu so esul ed in an impo an imp o emen o he
magne ic p ope ies o he inal me al pa icles (6). In his wo k, Al
ca ions ha e been inco po a ed o he undoped p ecu so pa icles by
coa ing a e hei syn hesis h ough a he e ocoagula ion p ocess, and
he ela ionship be ween he mic os uc u al ea u es and he magne ic
p ope ies o he inal α-Fe pa icles was s udied and compa ed o
hose o he Al-doped sys em, in o de o e alua e he e iciency o
bo h p o ec ing me hods o p e en sin e ing.
2. EXPERIMENTAL PROCEDURE
2.1. P ecu so p epa a ion
Fo he p epa a ion o he acicula goe hi e, a 0.15 mol dm-3 Fe(II)
sulpha e (FeSO4·7H2O, Ald ich, 99%) aqueous solu ion was p ecipi a ed
by he addi ion o 0.225 mol dm-3 sodium ca bona e (Na2CO3, Ald ich,
Bol. soc. esp. Ce am. V., 43 [4] 796-800 (2004)
797
99.5%) and he esul ing dispe sion was hen oxidized a cons an
empe a u e (40ºC) by bubbling ai a cons an low a e (2 dm3min-1)
o 6 hou s, ollowing he me hod desc ibed ea lie (5). The p ecu so
syn hesized by his me hod is named as G.
Al(III)-doped goe hi e pa icles we e ob ained by adding he desi ed
amoun o Al(III) ni a e (Al(NO3)3·9H2O, Fluka, 99%) o he Fe(III)
sulpha e aqueous solu ion be o e he addi ion o sodium ca bona e (6).
The sample syn hesized by his me hod is named as GAl.
Undoped goe hi e pa icles (sample G), we e coa ed wi h aluminium
hyd ous oxide laye s. The coa ing p ocess in ol ed i s he dissolu ion
o he desi ed amoun o Al(NO3)3 in 150 ml o double dis illed wa e
and he addi ion o a 10% NaOH aqueous solu ion o each a pH o 12.5.
The goe hi e pa icles (150 mg) we e homogeneously suspended in his
solu ion using an ul asonic ba h and, inally, he pH was lowe ed o
8.5 by he slow addi ion o HNO3 (0.5 mol dm-3) in o he slu y (7). The
sample syn hesized by his me hod is named as G(Al).
All p ecipi a es we e cen i uged and washed se e al imes wi h
deionised wa e o pu i ica ion. Finally, he powde ed solids we e
collec ed by il a ion and d ied a 50ºC be o e analyses.
2.2. The mal Reduc ion
To ob ain he inal me al pa icles, he goe hi e samples (~60
mg) we e dehyd a ed by hea ing in ai o 4 h yielding hema i e
which was hen educed, a cons an empe a u e in a hyd ogen
(99.9999%) s eam ( low a e = 20 l h-1) o 4 h. Dehyd oxyla ion and
educ ion empe a u es we e op imised in each case o ge comple e
educ ion, as well as o minimise pa icle sin e ing. A e educ ion,
he samples we e cooled down o oom empe a u e, unde he
hyd ogen a mosphe e, and, inally, passi a ed by exposing hem o
alcohol apou s o 1 hou , which we e gene a ed by bubbling N2 gas
(99.999%) a cons an low a e (40 dm3h-1) in o a lask con aining pu e
e hanol (99.8%). Me al samples p epa ed a e educ ion o G, GAl and
G(Al) powde s a e named as Fe, FeAl and Fe(Al) espec i ely.
2.3. Cha ac e isa ion Techniques
T ansmission Elec on Mic oscopy (TEM, Philips 200 CM)
was used o examine he mo phology o he pa icles. The pa icle
size dis ibu ion o he powde s was e alua ed om he elec on
mic og aphs by coun ing a ound one hund ed pa icles. F om hese
da a, he deg ee o polydispe si y, de ined as he s anda d de ia ion
(SD)/mean size (8), was e alua ed. The mean and he SD alues
associa ed wi h he axial a io (L/W) we e e alua ed om he L/W
a ios ob ained o each pa icle.
Phase iden i ica ion was ca ied ou by X- ay di ac ion (XRD) in a
Siemens D501 appa a us using CuKα adia ion and a di ac ed beam
g aphi e monoch oma o . An es ima ion o he c ys alli e size was
de e mined om he ull wid h a hal maximum o he XRD selec ed
e lec ion by using he Sche e equa ion (9). Di e en ial he mal
(DTA) and he mog a ime ic analyses (TGA) (Seiko, EXSTAR 6000)
we e ca ied ou in ai a a hea ing a e o 10ºC min-1.
The quan i a i e composi ion o he samples in e ms o he Al
and Fe con en s was de e mined by X- ay luo escence (XRF, Siemens
SRS 3000). Ene gy dispe si e X- ay analysis (EDX, Philips DX4),
ins alled in he TEM mic oscope, was also used o gain in o ma ion
on he homogenei y o he pa icles composi ion. The a ia ion o he
aluminium and i on concen a ions in he pa icle ou e laye s du ing
he ans o ma ion om goe hi e o hema i e, and inally o i on was
ob ained om he X-Ray Pho oelec on spec a (XPS), eco ded in a
VG Escalab 220 using he MgKα exci a ion sou ce. Calib a ion o he
binding ene gy scale o he spec a was done a he C1s peak o he
su ace ca bon con amina ion aken a 284.6 eV. A omic pe cen ages
o he elemen s we e calcula ed om he peaks a eas a e backg ound
sub ac ion (Shi ley backg ound). The a eas we e e e ed o he
sensi i i y ac o s o he elemen s as supplied by he ins umen
manu ac u es.
Tempe a u e p og ammed educ ion (TPR) expe imen s we e
pe o med in a con en ional appa a us connec ed o a compu e o
da a s o ing and p ocessing, using a he mal conduc i i y de ec o ,
(TCD) calib a ed using di e en amoun s o CuO, as p e iously
desc ibed (10). The eac i e gas (5% H2 in A , low a e = 50 cm3 min-1)
was passed h ough 5 mg o sample, which was hea ed up o 600ºC a
a cons an hea ing a e o 5ºC min-1.
Magne ic cha ac e iza ion o he samples was ca ied ou in
a ib a ing sample magne ome e (MLVSM9 MagLab 9 T, Ox o d
Ins umen ). Magne iza ion cu es we e eco ded a oom empe a u e
by i s sa u a ing he sample in a ield o 3 T; hen, he sa u a ion
magne iza ion (Ms), he squa eness (M /Ms, whe e M is he emanen
magne iza ion) and he coe ci i y (Hc) we e de e mined o each
sample. The Ms alues we e e alua ed by ex apola ing o in ini e ield
he expe imen al esul s ob ained in he high ield ange whe e he
magne iza ion linea ly inc eases wi h 1/H.
3. RESULTS AND DISCUSSION
3.1. P ecu so s P epa a ion
Uni o m goe hi e pa icles (Fig. 1) o 118 nm in leng h wi h axial
a io o 5 (Table I) we e ob ained ollowing he me hod desc ibed
in expe imen al sec ion (Sample G). Unde he same condi ions,
he addi ion o Al ca ions up o a Al/Fe+Al mole a io = 5%
(Sample GAl) yielded single phase goe hi e pa icles (Fig. 1) wi h
an aluminium con en simila o ha ini ially added (Table I). The
p esence o aluminium yielded sho e pa icles (62 nm in leng h)
ha he undoped ones, keeping simila pa icle wid h, and b oade
size dis ibu ion (Table I). These mo phological changes ha e been
a ibu ed o isomo phous subs i u ion o Al3+ o Fe3+ in he goe hi e
s uc u e (11). I has been al eady epo ed ha he Al ca ions we e
mainly concen a ed in he pa icle ou e laye s in spi e o being in he
eac ion medium om he beginning o he goe hi e p epa a ion (6).
Table I.- ComposITIon and mo phologICal Cha aCTe IsTICs (lengTh,
wIdTh and axIal aTIo) obse ed o goeThITe p eCu so s (The ela-
TI e sTanda d de IaTIons a e InCluded In pa enThesIs).
Mo phological Cha ac e is ics Al/Fe+Al mole a io
Sample Leng h
(nm)
Wid h
(nm)
Axial
Ra io
Nominal
(%)
XRF
(%)
XPS
(%)
G118 (20) 24 (29) 5 (30) - - -
GAl 62 (28) 23 (33) 3 (33) 5 5 17
G(Al) 118 (20) 24 (29) 5 (30) 5 5 80
Goe hi e pa icles we e also coa ed wi h uni o m laye s o an
aluminium hyd ous oxide using an Al/Al+Fe a io simila o ha o
he doped sample (Al/Fe+Al mole a io = 5%). As i can be seen in
he TEM images (Fig. 1), only acicula pa icles we e p esen in he
coa ed sample, sugges ing ha all p ecipi a ed aluminium hyd ous
oxide was deposi ed on he su ace o goe hi e pa icles. The amoun
o aluminium inco po a ed on he goe hi e su ace was con i med o
be simila o ha ini ially added (Table I) and EDX analyses con i med
he p esence o Al in all analysed pa icles. Finally, XPS spec oscopy
ACICULAR IRON NANOPARTICLES PROTECTED AgAINST SINTERINg wITh ALUMINIUM OxIDE
Bol. soc. esp. Ce am. V., 43 [4] 796-800 (2004)
798
showed a mo e impo an en ichmen o Al (Al/Fe+Al mole a io =
80%) in he pa icle ou e laye s in compa ison wi h he Al(III)-doped
goe hi e sample (17% mole), which is as i should be expec ed om he
coa ing p ocedu e (Table I).
A sligh inc ease in he he mal s abili y o he goe hi es p epa ed
in he p esence o aluminium wi h espec o he Al- ee goe hi es
was de ec ed by TG and DTA analyses as illus a ed o he coa ed
sample (Fig. 2). As obse ed, he s ong endo he mic peak, which is
due o he con e sion o goe hi e o hema i e, was displaced om
250ºC o sample G o 257ºC o sample G(Al). This highe empe a u e
o dehyd oxyla ion can be a ibu ed o he en ichmen o aluminium
in he pa icle ou e laye s since i could hampe he anspo o he
eleased wa e (12).
3.2. I on Me allic Pa icles
3.2.1. THERMAL REDUCTION OF SAMPLES
The goe hi e pa icles we e ans o med o me allic i on in wo
s eps, aiming o educe in e nal po osi y and a oid u he al e a ions
o he pa icle mo phology (1). Fi s , he goe hi e pa icles we e
ans o med o hema i e by hea ing up o maximum empe a u e so
ha he pa icle mo phology emained una ec ed in he unp o ec ed
sample (300ºC). The so-ob ained hema i e samples we e hen educed
o me al i on, o which he educ ion empe a u e was also op imized
in o de o minimize he possible pa icle mo phology al e a ion du ing
his ea men . Fo his pu pose, empe a u e p og ammed educ ion
(TPR) expe imen s we e ca ied ou . The TPR p o iles o he undoped
goe hi e samples (Fig. 3) clea ly showed ha he educ ion p ocess
ook place unde he non-iso he mal condi ions, om 250ºC o 550ºC
in wo well- esol ed educ ion s eps. The hyd ogen up akes ob ained
Figu e 1.- TEM images o goe hi e (G), Al(III)-doped goe hi e (GAl)
and Al(III)-coa ed goe hi e (G(Al)) samples and he co esponding i on
pa icles ob ained a e educ ion (Fe, FeAl and Fe(Al) samples).
Figu e 2.-TG and DTA analyses o goe hi e (G) and Al-coa ed goe hi-
e (G(Al)) samples.
Figu e 3.- TPR p o iles o he hema i e samples ob ained by hea ing
a 300ºC he undoped (G), Al(III)-doped (GAl) and Al(III)-coa ed (G(Al))
goe hi e p ecu so s.
R. POzAS, M. P. MORAALES, C.J. SERNA, M. OCAÑA
Bol. soc. esp. Ce am. V., 43 [4] 796-800 (2004)
799
by nume ical in eg a ion o he peaks a eas indica ed ha he i s
s ep (~340 ºC) was due o he ans o ma ion o hema i e o magne i e
(Fe3O4), whe eas he second one (~470 ºC), was due o he magne i e-
me al i on educ ion. Finally, he TPR p o iles also sugges ed ha he
p esence o aluminium ca ions in he hema i e p ecu so s (ei he in he
doped o coa ed samples) e a ds he educ ion p ocess (Fig. 3). In ac ,
an iso he mal ea men a 600 ºC was u he equi ed in bo h cases o
comple e he educ ion eac ion (Fig. 3). I has been epo ed ha he
educ ion a e o i on is mos ly con olled by he emo al o wa e (13).
The e o e, i seems ha he p esence o Al ions a he pa icle su ace
hampe he anspo o wa e , needing highe educ ion empe a u es
o i s o al elease. Fig. 3 also shows ha he only app eciable di e ence
in he educ ion beha iou be ween he doped (GAl) and coa ed (G(Al))
samples is ha he i s educ ion s ep (Fe3O4 o ma ion) akes place a
lowe empe a u e o he o me .
In iew o hese esul s, he hema i e samples we e educed unde
he iso he mal condi ions desc ibed in he expe imen al sec ion, a
inc easing empe a u es s a ing om 250ºC o ind he minimum
empe a u e equi ed o comple e educ ion which, as expec ed, was
highe o bo h Al-doped and Al-coa ed samples (400ºC) han ha o
he unp o ec ed one (325ºC).
X- ay di ac ion pa e ns o all he samples educed a he abo e
empe a u es a e shown in Fig. 4. Samples Fe and Fe(Al) display a
simila pa e n wi h di ac ion peaks only due o α-Fe. Howe e , in
addi ion o he main di ac ion peaks due o α-Fe, sample FeAl shows
a b oad and e y weak peak a ound 35º (2θ), which could be due o he
p esence o small c ys alli es o an i on oxide wi h a spinel s uc u e
(14). This oxide could be o med du ing he passi a ion p ocess ca ied
ou o s abilize he pa icles. The highe amoun o oxide in his sample
could be due o i s smalle pa icle size (Fig. 1), and he e o e highe
su ace a ea. The c ys al size measu ed om he (100) e lec ion o i on
was obse ed o dec ease o he Al(III)-p o ec ed me al samples (Table
II). These da a sugges ha he p esence o aluminium minimises he
g ow h o i on c ys als du ing he he mal educ ion p ocess, and
clea ly e idence i s ole in p e en ing sin e ing.
Table II.- magneTIC p ope TIes (Ms = saTu aTIon magneTIzaTIon, Hc =
Coe CI ITy, M = emanenT magneTIzaTIon and M /Ms = squa eness)
and C ysTal sIze obTaIned o I on (Fe), al-doped I on (FeAl) and Al-
CoaTed I on (Fe(Al)) samples.
Sample Reduc ion
Tempe a u e (ºC)
C ys al Size
(nm)
Hc
(Oe)
Ms
(emu/g) M /Ms
Fe 325 200 110 205 0.05
FeAl 400 30 920 125 0.5
Fe(Al) 400 35 1050 120 0.4
Me al pa icles ob ained om he goe hi e samples show di e en
mo phological cha ac e is ics. Thus, in he absence o aluminium
(sample Fe), he pa icles sin e ed du ing he educ ion p ocess
losing he elonga ed shape (Fig. 1), which is in acco dance wi h he
highe c ys al size measu ed o his sample (Table II). Howe e , his
p ocess ook place in a lesse ex ension o he FeAl and Fe(Al) samples,
in which mo e elonga ed pa icles emained, especially in he case
o sample Fe(Al) (Fig. 1). I is clea ha in his sample, he aluminium
oxide coa ing is he esponsible o p e en ing sin e ing. Fo a
be e unde s anding o he beha iou obse ed o sample FeAl, he
a ia ion o he Al(Fe+Al) a io a he pa icle ou e laye s du ing he
ans o ma ion om goe hi e o hema i e and hen, o me al i on, was
ollowed by XPS inding ha he mola pe cen age o Al(III) inc eases
om 18% (goe hi e) o 36 % (i on) (Fig. 5). Thus, he e is a u he
clea Al en ichmen in he pa icle ou e laye s du ing educ ion,
which explains he absence o a signi ican sin e ing obse ed o
his sample, in which hese ca ions we e in oduced in o he goe hi e
p ecu so du ing i s syn hesis (6). This en ichmen was highe o he
Al(III)-coa ed pa icles ( om 80% o goe hi e, o 95% o i on) (Fig. 5),
which would explain he be e acicula mo phology obse ed o his
sample (Fig. 1). I should be no ed ha he posi ion o he Fe2p3/2 peak
obse ed in he XPS spec a (710.1 eV) (da a no shown) was consis en
wi h he p esence o he abo e men ioned oxidized i on in he pa icle
ou e laye s, which seems o be consis o a e imagne ic oxide simila
o Al(III)-doped maghemi e, as i has been sugges ed om Mössbaue
s udies ca ied ou on he FeAl sample (6).
Figu e 4.- X-Ray di ac ion pa e ns o samples Fe, FeAl and Fe(Al)
me al samples.
Figu e 5.- Va ia ion o he aluminium concen a ion in he pa icle
ou e laye s ob ained om XPS spec a du ing he ans o ma ion
om goe hi e o hema i e and inally o me al i on o Al-doped
goe hi e (GAl) and Al-coa ed goe hi e (G(Al)) samples.
ACICULAR IRON NANOPARTICLES PROTECTED AgAINST SINTERINg wITh ALUMINIUM OxIDE
Bol. soc. esp. Ce am. V., 43 [4] 796-800 (2004)
800
3.2.2.
MAGNETIC PROPERTIES OF IRON NANOPARTICLES
The magne ic pa ame e s ob ained om he magne iza ion cu es
ep esen ed in Fig. 6 a e summa ized in Table II. All alues ob ained
o sa u a ion magne iza ion (Ms) a e lowe han i is expec ed o bulk
Fe (~220 emu/g) (15), due o he p esence o i on oxide on he pa icle
su ace esul ing om passi a ion (6). The la ges Ms alues ob ained
o he Fe sample when compa ed wi h he Al(III)-p o ec ed samples,
can be explained by he highe c ys al size o he o me , which
he e o e in ol ed a lowe ela i e oxide amoun in he passi a ion
laye , and ob iously by he p esence o non-magne ic aluminium
oxide on he pa icle su ace in he p o ec ed samples (16).
I should be no ed ha he inc ease in he M /Ms (Squa eness)
alues obse ed o he Al(III)-p o ec ed pa icles ( om 0.05 o sample
Fe o 0.4 and 0.5 o samples Fe(Al) and FeAl, espec i ely) sugges s a
change om a mul idomain beha iou o he Al(III)- ee samples o
a monodomain beha iou o Al(III)-p o ec ed samples, acco ding o
he dec ease in he Fe c ys al size obse ed by X- ay di ac ion om
200 o 30-35 nm (Table II) (17).
The inco po a ion o aluminium ca ions o he p ecu so pa icles
ei he by doping o coa ing, also had posi i e e ec s on he coe ci i y
(Hc) o he inal me al samples (Table II). Thus, he coe ci i y inc eases
om 110 Oe o he unp o ec ed sample (Fe) o 920 and 1050 o
samples FeAl and Fe(Al), espec i ely. This inc ease seems o be due o
he minimisa ion o sin e ing, p ese ing he acicula mo phology o
he pa icles, since i is well known he main ac o ha con ibu es
o he inc ease o coe ci i y in hese ma e ials is shape aniso opy.
Sligh ly highe Hc alue (1050 Oe), was ound o he sample p o ec ed
by coa ing (Fe(Al) sample), indica ing ha his p o ec ing p ocedu e
is sligh ly mo e e ec i e o p oduce i on me al pa icles wi h be e
magne ic p ope ies.
4. CONCLUSIONS
Bo h p o ec ing me hods o goe hi e pa icles, Al(III)-doping and
Al(III)-coa ing, d i e o an Al-en ichmen on he goe hi e pa icles
su ace, which is inc eased du ing he ans o ma ion o i on. This
en ichmen minimises he g ow h o i on c ys als and be e p ese es
he acicula shape in he inal i on pa icles, which has a a ou able
e ec on he squa eness and coe ci i y o bo h me al samples. This
beha iou indica es he e ec i eness o bo h me hod o p o ec he
acicula i on nanopa icles agains sin e ing and he e o e o ob ain
ma e ials wi h imp o ed magne ic p ope ies. Ne e heless, he
coa ing p ocedu e seems o be sligh ly mo e e ec i e gi ing ise o he
i on pa icles wi h he la ges coe ci i y.
ACkNOWLEDGMENTS
This wo k was suppo ed by he Spanish CICYT unde p ojec s
MAT2002-04001-C02 and MAT2003-01479. The ellowship o R. Pozas
om he Spanish Minis e io de Ciencia y Tecnología is g a e ully
acknowledged.
Figu e 6.- Magne iza ion cu es a oom empe a u e o samples Fe,
FeAl and Fe(Al) me al pa icles ob ained by he mal educ ion o he
goe hi e p ecu so s.
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