Beruflich Dokumente
Kultur Dokumente
Journal of
Nanoscience and Nanotechnology
Vol. 13, 77177722, 2013
RESEARCH ARTICLE
In this work, a combination of nanoparticles of Nd2 Fe14 B hard magnetic phase and -Fe soft magnetic phase were synthesized by one pot chemical synthesis technique using solgel method. A gel
of NdFeB was prepared using NdCl3 6H2 O, FeCl3 6H2 O, H3 BO3 , citric acid, and ethylene glycol
by pechini type solgel method. The gel was subsequently calcined and annealed to obtain the
mixed oxide powders. The produced metal oxide particles were identied with XRD, SEM, TEM to
obtain the crystal structure, shape and domain structure of them. The nanoparticles of mixed phase
of Nd2 Fe14 B/-Fe were obtained from these oxides by a process of reduction-diffusion in vacuum by
employing CaH2 as reducing agent. During this process it was optimized by controlling temperature,
reaction time and concentration of the reducing agent (CaH2 . The phase formation of Nd2 Fe14 B
was resulted by the direct diffusion of NdH2 , Fe and B. The magnetic property of produced hard
Delivered by Publishing Technology to: Korea Institute of Science & Technology (KIST)
and soft phases was successfully identied with vibrating sample magnetometer (VSM). The mixed
IP: 161.122.106.136 On: Fri, 03 Jan 2014 08:54:14
domains of the hard and soft
phases were
identied
with selected
area electron diffraction method
Copyright:
American
Scientific
Publishers
(SAED) patterns.
Keywords: Hard Magnet, Soft Magnet, Exchange Spring Magnet, Ferromagnetic Exchange
Coupling, Pechini Type SolGel, Reduction-Diffusion.
1. INTRODUCTION
Research in the area of magnetism and magnetic materials is solely a combination of fabrication, characterization, theoretical concepts and engineering applications.1
Since the discovery of the excellent magnetic properties of Nd2 Fe14 B, intense research has been focused
on magnetic properties of nanostructured Fe-rich rareearth magnetic alloy, its novel synthesis techniques and
optimum micro structural development.2 Powder metallurgy and rapid quenching are the most commonly
used techniques to synthesize Nd2 Fe14 B which require
high purity starting materials and intensive energy.3
Magnetic particles of Nd2 Fe14 B with desired shape
and size distribution are used to explore anisotropy,
magnetism of single domain particles and exchange
coupling.4 5 A great interest for researchers lies in magnetic nanoparticles because of their wide range of disciplines like magnetic uids, energy conversions, magnetic
1533-4880/2013/13/7717/006
doi:10.1166/jnn.2013.7833
7717
RESEARCH ARTICLE
One Pot Synthesis of Exchange Coupled Nd2 Fe14 B/-Fe by Pechini Type SolGel Method
Hussain et al.
This coupling effect between the hard and the soft magethylene glycol (C2 H6 O2 , 99.8%, Sigma Aldrich) were
used to synthesize NdFeB gel without further puricanetic materials makes it possible to create materials with
tion. Pechini-type solgel method was adopted in preparaimproved energy product (BH)max not achievable in single
tion of the metal (Nd, Fe, and B) oxides. In this process,
phase materials.11 Exchange coupling supplies the extra
the common metal salts are used as precursors and citric
anisotropy which is needed for magnetization stabilizaacid is used as chelating ligands of metal ions. Polyhytion and thus generates magnetically stable nanoparticles.5
droxy alcohol is used as a cross-linking agent to form a
Exchange biased magnets have been used in the applicapolymeric resin on molecular level. This reduces the segtions such as spintronics and recording media.5
regation of particular metal ions and ensures the compoNd2 Fe14 B alloy is reactive and prone to oxidation hence
sitional homogeneity. This process overcomes most of the
its synthesis with controlled size and magnetic moment is
difculties and disadvantages that frequently occur in the
quietly challenging.1214 The oxidation problem in metalalkoxides based solgel process. In this experiment, stoilic particles in nano regime is due to their intrinsic instachiometric amounts of neodymium chloride hexahydrate,
bility over longer periods of time.15 These nanoparticles
iron chloride hexahydrate and boric acid for the nomialso tend to form agglomerates reducing the energy asso16
nal composition of Nd2 Fe14 B were dissolved in deionized
ciated with their high surface area to volume ratio. The
water
to form an aqueous solution. Another aqueous soluoxidation of naked metallic nanoparticles in air causes
16
tion
of
citric acid and ethylene glycol in a 2:1 molar ratio
the loss of magnetism and dispersibility. It is much
to
metal
salts was prepared separately and added to the
important to develop the protection strategies for chemsolution
of
metal salts to form a thermally stable sol. The
ical stability of magnetic nanoparticles against magnetic
17
pH
value
of
the solution remained in the range of 1.92.
degradation during and after the synthesis. The chemical
The
mixed
solution
was heated at 90 C for evaporation
synthesis routes have recently been employed to synthesize
purposes which resulted in a viscous gel. The gel was
nanostructured permanent magnetic materials.8 1823 The
dehydrated at 200 C for 2 hrs. This dried gel was ground
chemical synthesis of Nd2 Fe14 B has also been attempted
in an agate mortar for 20 min and then heated at 400 C
by the reduction of suitable salts of iron and neodymium
for 2 hrs for calcination followed by annealing at 800 C
with sodium borohydride.18 19 Another chemical way is the
for 2 hrs to prepare NdFeB oxide powder. The oxide
polyol reduction in which a polyalcohol serves as a reducpowder was then characterized by X-ray diffraction. This
ing agent to reduce the organometallic complex of iron and
Delivered by Publishing Technology to: Korea powder
Institutewas
of Science
& Technology
(KIST)
further subjected
to reduction-diffusion
proneodymium.20 24 In chemical synthesis
the
nanoparticle
IP: 161.122.106.136 On: Fri, 03 Jan 2014 08:54:14
cess
to
obtain
the
desired
Nd
Fe
B
phase.
2
14
size can be controlled by adjusting theCopyright:
reaction parameters
American Scientific Publishers
such as time, concentration of reagents and temperature.25
2.2. Nd2 Fe14 B Synthesis
The chemical synthesis of Nd2 Fe14 B by a solution phase
method followed by high temperature reduction-diffusion
Nd2 Fe14 B powder was synthesized by mixing NdFeB
method has been reported previously.1822 In this work
oxide powder with 1:1 wt% of reducing agent CaH2 (95%,
we used the metal precursors for Nd:Fe:B in stoichiometSigma Aldrich) and annealing at 800 C for 2 hrs in vacric composition 2:14:1 and used the solgel method to
uum at increasing rate of 6 C/min. During the process of
synthesize the chemically homogeneous oxides of metals
reduction the chemical reactions took place as;21
(Nd, Fe and B). The reduction-diffusion of these oxides
CaH2 Ca + 2H
at elevated temperatures resulted in Nd2 Fe14 B and -Fe
powders. Here the preparation of Nd2 Fe14 B was done by
MO3 + 3Ca M + 3CaO
the modied process reported by Deheri et al.21 The ratio
M + nH MHn M metal
of metal precursors was modied to get the appropriate
amount of -Fe soft phase necessarily needed for the pur2H H2
pose of exchange coupling. The reaction conditions such
The pulverization caused by the release of hydrogen
as temperature and pH were modied to obtain the ne
gas during heating, resulted in the higher surface area
and non agglomerated nanoparticles. The ratio of CaH4 to
of oxide particles in contact with the reducing particles,
metal ions was modied during reduction to increase their
which accelerated the process of reduction. The calcium
surface area in contact.
oxide with residual calcium metal was a major by-product
in the reaction. For the removal of CaO, the reaction mix2. EXPERIMENTAL PROCEDURES
ture was washed with dilute acetic acid and deionized
water. Chemical leaching out of CaO may be shown as;21
2.1. Synthesis of NdFeB Oxides by SolGel Method
Neodymium chloride hexahydrate (NdCl3 6H2 O, 99.9%,
Sigma Aldrich), iron chloride hexahydrate (FeCl3 6H2 O,
Acros), boric acid (H3 BO3 , 99.5%, Duksan), citric
acid monohydrate (C6 H8 O7 , 99.5%, Sigma Aldrich) and
7718
CaO + H2 O CaOH2
Finally, the powder was washed with acetone and stored
in n-hexane. A schematic diagram of the synthesis process
is shown in Figure 1.
J. Nanosci. Nanotechnol. 13, 77177722, 2013
Hussain et al.
One Pot Synthesis of Exchange Coupled Nd2 Fe14 B/-Fe by Pechini Type SolGel Method
Fe2O3
FeBO3
NdBO3
500
400
Citric Acid +
Ethylene Glycol
Intensity/a.u
De-Ionized Water
300
200
100
30
40
50
60
70
80
2/deg
Fig. 2. The XRD pattern of NdFeB gel calcined at 400 C for 2 hrs. In
the pattern the three phases of Fe2 O3 , FeBO3 and NdBO3 were identied.
2.3. Characterizations
Fe2O3
500
400
300
200
B2O3
Nd2O3
100
FeNdO3
600
Intensity/a.u
700
0
100
20
30
40
50
60
70
80
2/deg
Fig. 3. The XRD pattern of NdFeB oxide powder annealed at 800 C
for 2 hrs. In the pattern the four phases of metal oxides Nd2 O3 , B2 O3 ,
Fe2 O3 and NdFeO3 were identied.
7719
RESEARCH ARTICLE
HeatTreatment at 400 C
and 800 C, each for 2 hrs
One Pot Synthesis of Exchange Coupled Nd2 Fe14 B/-Fe by Pechini Type SolGel Method
800
400
300
200
Nd2Fe14B
-Fe
250
400
100
300
Intensity/a.u
Intensity/a.u
-Fe
350
Nd2Fe14B
600
CaO
700
500
Hussain et al.
200
150
100
50
0
0
100
30
40
50
60
70
80
2/deg
20
30
40
50
60
70
80
2/deg
800
Intensity/a.u
RESEARCH ARTICLE
20
Nd2Fe14B
-Fe
600
400
200
20
30
40
50
60
70
80
2/deg
Fig. 5. The XRD pattern of washed product after reduction of metal
oxides in vacuum at 800 C for 2 hrs. Two magnetic phases were identied, a hard phase Nd2 Fe14 B and a soft phase -Fe in the pattern.
7720
Hussain et al.
One Pot Synthesis of Exchange Coupled Nd2 Fe14 B/-Fe by Pechini Type SolGel Method
Weight%
Atomic%
Fe K
88.11
95.03
Nd L
11.89
4.97
Totals
100.00
Fig. 10. EDS of the sample annealed at 920 C for 2 hrs. This conrms
50
25
0
Magnetization (emu/g)
Magnetization (emu/g)
75
25
50
75
10
5
0
5
400 200
Fig. 9. SAED pattern of the sample annealed at 920 C for 2 hrs. This
shows the polycrystalline nature of the sample and gives the diffracting
planes, all included in the standard diffraction pattern of Nd2 Fe14 B.
200 400
100
9000
6000
3000
3000
6000
9000
7721
RESEARCH ARTICLE
Fig. 8. HRTEM of the sample annealed at 920 C for 2 hrs. This shows
the polycrystalline nature of the sample and conrms the presence of
Nd2 Fe14 B phase.
Element
RESEARCH ARTICLE
One Pot Synthesis of Exchange Coupled Nd2 Fe14 B/-Fe by Pechini Type SolGel Method
Hussain et al.
7722