Hard Magnetic Nanoparticles

C.B. Rong
Department of Physics
University of Texas – Arlington

Department of Physics
Magnetic Conference,
 Outline

• Why hard magnetic nanoparticles?

• Preparation and characterization
of ferromagnetic nanoparticles.
• Building up new magnets with the
nanoparticles.
Why ferromagnetic nanoparticles?

d D=
W 12-15 nm

δ N SS NN SS NN SS NN S
B Recording Medium
Superparamagnetic Challenge!

Unstable Stable

K U V < KB T KUV ≫ K BT
 Size dependent magnetism

Fe2O3
Ni
Fe3O4
FeCo Dsp
Co Dsd

CoFe2O4 100 nm

CoPt 610 nm

FePt 340 nm
SmCo5 850 nm

Nd2Fe14B 230 nm
0 20 40 60 80 100
D (nm)
 Outline

• Why hard magnetic nanoparticles?

• Preparation and characterization
of ferromagnetic nanoparticles.
• Building up new magnets with the
nanoparticles.
A breakthrough:
4 nm monodisperse FePt particles
Sun et al, Science 2000, 287, 1889.

If one particle is one bit

and the gap is also 4 nm,
number of bits per square
inch will be

(2.54X107)2/82 = 1.0X1013 =
10 Tbit

If 8 nm particles are
chosen, the density will be
2.5 Tbit
 How to prepare
ferromagnetic nanoparticles?

Co2(CO)8 Co

Fe(acac)3 Fe3O4

Fe(CO)5 + Pt(acac)2 FePt

200 - 300°C

Chemical solution methods

 (a) (e)

FePt size control

h

g
(b) (f)
f
Intensity(a.u.)

b (c) (g)
a

30 40 50 60 70 80 90

2 theta(degree)

(a) 2 nm; (b) 3 nm; (c) 4 nm; (d) 5 nm (d) (h)

(e) 6 nm; (f) 7 nm; (g) 8 nm; (h) 9 nm
Nandwana, et al, J. Phys. Chem. C,
111(2007), 4185.
FePt nanorods and nanowires

15 nm 50 nm

D)

D)

(001)

150 nm HRTEM
 Life is never simple and easy….
Transition of isordered fcc to Ordered L10
As-synthesized FePt nanoparticles Annealed FePt nanoparticles
Fe
Pt

Heat treatment

20 nm
 Current Approaches
for Preventing Sintering
¾ Non-magnetic shell coating such as SiO2, MnO2,
TiO2…
¾ Reducing fcc-fct transition temperature by
doping Ag, Au and Cu,…
¾ Increasing synthesis temperature…
¾ Annealing with high melting-point powder like
Cu…
Æ It is still a challenge to produce monodisperse fct FePt
nanoparticles with high coercivity and free of non-
magnetic impurities
 Salt-Matrix Annealing Technique
Solution

Salt

FePt particles

Elkins et al., J. Phys. D: Appl. Phys., 38, 2306 (2005).

 TEM Morphology
As-synthesized
2 nm 4 nm 6 nm 8 nm 15 nm

2 nm 4 nm 6 nm 8 nm 15 nm
Annealed at 700 oC for 4 hours in salt-matrix

Rong et al., Advanced Materials,18 (2006), 2984.

 The Smallest Permanent Magnets

1000

800
15 nm
8 nm
600
6 nm
4 nm
400
M (emu/cm )
3

200

0
1000

-200 900
Ms (emu/cm )
3

800
-400 700
600
-600 500
400
-800 0.05 0.10 0.15 0.20 0.25
-1 -1
d (nm )
-1000
-60 -40 -20 0 20 40 60
H (kOe)

Ferromagnetic nanoparticles
(single domain and single
crystal) have coercivity up to
3 tesla!
 High Resolution-TEM
of polycrystalline L10 nanoparticles

4 nm

15 nm

8 nm
Size-dependent long-range ordering
1
Fe
⎛ I 001 ⎞ 2
S ≅ 0.85 ⋅ ⎜ ⎟
Pt

⎝ 002 ⎠
I
o (1 1 1 )
700 C 4 hours
o
700 C 2 hours
o
600 C 2 hours
A s-synthesized
Normalized Intensity (A.U.)

(2 0 0 )
(0 0 1 ) (1 1 0 ) (0 0 2 )

1.0

0.9

20 25 30 35 40 45 50 55 0.8

S
2 T h e ta (d e g re e )

0.7
The structural
ordering is size 0.6

dependent! 0.5
2 4 6 8 10 12 14 16
Particle Size (nm)
 2 nm FePt Nanoparticles
¾ XRD peaks could not be located due to the huge background
signal caused by the small grain size 1.0
o
700 C 8 hours

¾ Electron diffraction was used for phase characterization

0.5

M/Ms (A.U.)
0.0

Ordering (L10 transition) does not occur

-0.5

Î -1.0

-15 -10 -5 0 5 10 15
Applied field (kOe)

111

200

As-synthesized 700 oC 8 h
 Finite size effect for “zero”
dimensional ferromagnets
−1 / v
Tc (∞) − Tc (d ) ⎛ d ⎞
= ⎜⎜ ⎟⎟
780
Direct experiment
Tc (∞) ⎝ d0 ⎠
760

740

K. Binder, Physica 62, 508 (1972). 720

700

Tc (K)
680
Fitting: 660
Tc(∞) = 795±10 K,
640
d0 = 0.84±0.05
620
nm, and v 4 6 8 10 12 14 16
d (nm)
=0.91±0.10
Size-dependent Curie temperature

780
Direct experiment
760 After correction

740 Fitting:
720 Tc (∞)
800
=775±20K, v
700
Tc (K)

750
=0.67±0.11 and
Tc (K)
680 700
d0=0.90±0.10nm.
660 650 Experiments
Fitting line
600
640 0.6 0.7 0.8 0.9 1.0
S
620
4 6 8 10 12 14 16
d (nm)

Rong et al., Advanced Materials,18 (2006), 2984.

An Easy approach to hard nanoparticles
— SmCo nanoparticles by ball milling

SmCo SmCo SmCo

SmCo
Nanoparticles
SmCo SmCo

SmCo SmCo SmCo

Slurry

Chakka et al.,J. Applied Physics, 99 (2006), 08E912.

 SmCo nanoparticles by ball milling
with size selection 1.0

Normalized Moment
0.5 6nm

13nm
0.0
23nm
-0.5

-1.0

-15000 -10000 -5000 0 5000 10000 15000

Applied Field (Oe)

6nm

Intensity (a.u.)
13nm

23nm
(111)
starting pow der
(101) (110) (002) (202)

20 40 60 80
2 θ (degrees)
60

Number of particles
40 3
20
0
60
40 2
20
0
200
Y. Wang et al., Nanotechnology, 18 (2007) 465701. 100
1

0
5 10 15 20 25 30 35
S iz e o f p a r tic le s (n m )
 NdFeB nanoparticles
--- Size-dependent spin-reorientation

Permanent floating

3h settle-down
Intensity (a.u.)

Unpublished, presented in 2010

Slurry MMM conference
Raw materials

25 30 35 40 45 50 55 60 65
2θ (deg.)
 10 Hz
100 Hz
1 kHz
10 kHz
χ'

Particles Tsr (AC)

Materials
(K)

10 Hz Raw (micro) 120±2

100 Hz Slurry (300 nm) 117±4
1 kHz MQC
10 kHz 3h settle (20 nm) 85±5
χ"

Top (6 nm) 47±2

raw(micro) 135±3
slurry(300 nm) 122±5
0 50 100 150 200 250 300
EEC
3h settle(20 nm) 103±5
Temperature (K)
top(6 nm) 87±3
AC susceptibility
 Outline

• Why hard magnetic nanoparticles?

• Preparation and characterization
of ferromagnetic nanoparticles.
• Building up new magnets with the
nanoparticles.
 Super stable L10 nanoparticles!

40

35

30
Grain Size (nm)

25
L10 3 nm
20 L10 8 nm
fc c 8 n m
15

10

0
0 200 400 600 800 1000 1200
o
A n n e a lin g te m p e r a tu r e ( C )

Dependence of grain (particle) size of on the annealing temperature

 Carbon coated FePt L10 nanoparticles
4nm L10 particles
8nm L10 particles

Intensity (a.u.)
Graphite
disordered

0 500 1000 1500 2000 2500 3000

-1
Wavenumber (cm )

High resolution TEM image of the 8 nm L10 particles

Raman spectra of the salt-matrix annealed 4 nm and 8 nm FePt nanoparticles;

EDS give an rough carbon content around 15-25%
 Au coated FePt nanoparticles

FePt FePt/Au

20 nm

50 50

40 40
ƒ Particles size increased

Percentage (%)
Percentage (%)

30 (8 nm → 10 nm) 30
ƒ Morphology changed 20
20
ƒ Au shell thickness :1 nm
10 10

0 0
6 7 8 9 10 8 9 10 11 12 13
Particle size (nm) Particle size (nm)
 FePt/Au nanoparticles

Au (111)
420
nmnm 0.232 nm

0.6
(single FePt/Au
0.5 Au nanoparticle)
0.4 Selected Area Electron
Absorbance

FePt/Au Pt
0.3
Diffraction, Nano-Beam
Au
Pt Diffraction, UV-Vis absorption
0.2 Fe Au spectra and Nano-EDS
FePt
0.1 analysis
0.0
400 500 600 700
Wavelength (nm)
Why coated ferromagnetic nanoparticles?
Drug Targeting and Hyperthermia

⎛1 ⎞
Fm = V m Δ χ ∇ ⎜ B • H ⎟
⎝2 ⎠
• When external magnetic field is
applied, the force exerted on
superparamagnetic
nanoparticles:

• When the drug/carrier is

concentrated at the target the
drug can be released via
enzymatic activity, pH change or
temperature.
 Permanent Magnets
— Old materials with increasing new applications

Compass in ancient China

Exchange-coupled nanocomposites
4 nm:4 nm 0.4
0.2

m (arb. unit)
0.0
-0.2
-0.4 A
-60 -40 -20 0 20 40 60
H (kOe)
0.2
4 nm:8 nm
0.1

m (arb.unit)
0.0

-0.1

-0.2 B
-60 -40 -20 0 20 40 60
H (kOe)
0.3
4 nm:12 nm 0.2
Self-assembled

m (arb.unit)
0.1

FePt – Fe3O4 0.0

-0.1
nanocomposite -0.2
C
magnets -0.3
-60 -40 -20 0 20 40 60
H (kOe)
50% enhanced energy product
in isotropic nanocomposite magnet

10
(A) Fe 58 Pt42
8 (B) FePt:Fe 3 Pt
6
(BH)max ~
B (kG)

20.1 MGOe
4
(BH)max~
2 14.7 MGOe

-2
-8 -6 -4 -2 0
H (kOe)
Zeng et al.
Nature,
420, 395 (2002).
Core-shell structure: FePt@Fe3O4

4nm@1nm

4nm@0.5nm

4nm@3nm
FePt/CoFe2O4 brick-like nanoparticles

Fe(acac)3 + HDD + Co(acac)2

Phenyl ether Oleic acid/Oleylamine

FePt seeds Ar

1000
20 mins 100°C deg 800
A
B

600
400

M(emu/cc)
60 mins 200°C deg 200
0
-200
-400
-600
30 mins 265°C deg -800
-1000
-30 -20 -10 0 10 20 30 40 50

H(kOe)
FePt CoFe2O4
Synthesis of FePt@FeCo nanoparticles

Fe(acac)3 + HDD + Co(acac)2

FePt
FePt
FePt
FePt
Oleic acid/Oleylamine
FePt
FePt
FePt
FePt FG

100°C deg

120
90 mins 300°C deg FePt
FePt@FeCo
80
40

M (emu/g)
FePt
FePt 0
FePt
FeCo FePt -40
FePt
FePt -80
FePt
FePt -120

-20 0 20 40
H (kOe)
 Warm compaction
of nanoparticles and
nanocomposite particles
10 tons
Traditional compaction and consolidation press Hydraulic
techniques do not work for nanostructured pump
bulk material fabrication because of Temperature 150 tons Main
excessive grain growth and lack of controller press
dislocations in nanoparticles
Warm compaction of FePt and FePt/Fe nanoparticles
25
14 97
As-compacted
Annealed under FG at 500C
20 Annealed under FG at 600C 13 90

Density percent (%)

12 83

Density (g/cm )
15

Grain size (nm)

3
11 76

10

10 69

20 nm 5
9 62

TEM of the compacted bulk sample 0

RT 200 300 400 500 600
8
20 200 300 400 500 600 700
55

Compaction Temperature (C) Compacted temperature (C)

Cross-section SEM images of the FePt bulk samples compacted at different temperatures.
 The soft-phased distribution

EFTEM of the
SmCo5/Fe bulk
magnets by warm
compaction

41
 Exchange-coupled nanocomposite
isotropic SmCo/Fe magnets in bulk

Left: The dependence of (BH)max on Tcp of the bulk samples compacted

from amorphous and crystallized powders.
Right: Second-quadrant B–H curves of the bulk nanocomposite and
single-phase magnets with maximum energy products.

42
NonotechWeb News
 Summary
• Ferromagnetic FePt, SmCo and NdFeB
nanoparticles have been successfully
synthesized by salt-matrix annealing,
surfactant-assisted ball milling and
innovated chemical synthesis methods;
• Size dependent ferromagnetism is
observed;
• Novel applications of the ferromagnetic
nanoparticles are on the way.
 Thank you!
MURI

Nanostructured magnetic materials group led by Prof. J.P. Liu