magnetic nanomaterials. some biomedical applications ...ebm/ix/arquivos/mc4-1.pdf · magnetic...
TRANSCRIPT
Francisco H. Sánchez
G3M, Physics Department and La Plata Institute of Physics, FCE,UNLP,
CONICET, Argentina
Physics Building, 1905
Magnetic Nanomaterials.
Some Biomedical Applications: Magnetofection, Magnetic
Hyperthermia, and Ferrogels for Drug Delivery
http://www.fisica.unlp.edu.ar/Members/sanchez/escola-de-magnetismo-vitoria-es-
brasil-03-11-13-al-08-11-13
Introduction to Magnetic Materials B.D. Cullity,
(Massachusetts, Addison-Wesley, 1972).
Introduction to the Theory of Ferromagnetism, Amikam
Aharoni, Oxford Science Publications, 1998.
Modern Magnetic Materials, Robert C. O’Handley, John
Wiley & Sons, 1999
Introduction to Magnetism and Magnetic Materials,
David Jiles, Chapman & Hall 1996.
Nanomedicine: design and applications of magnetic
nanomaterials, nanosensors and nanosystems
Vijay K. Varadan, Linfeng Chen, Jining Xie, 2008
John Wiley & Sons, Ltd
Selected articles
Bibliography
http://www.fisica.unlp.edu.ar/Members/sanchez/curso-de-posgrado-
nanomateriales-magneticos-intema/bibliografia
http://www.fisica.unlp.edu.ar/
Actividad Académica
Docentes
Profesores
Sánchez, Francisco Homero
Two links:
Escola de Magnetismo - Vitoria, ES,
Brasil
Curso de Posgrado "Nanomateriales
Magnéticos"
Index
Class 1
Brief revision: contributions to energy in magnetic nanoparticles
Stoner – Wohlfarth model
Two levels model
Paramagnetism
Superparamagnetism
Interacting superparamagnets
Demagnetizing factor NDef in samples with disperse magnetic NPs
Class 2a
Understanding SAR and searching for high performance nanomaterials
zinc-doped magnetite nanoparticles and ferrofluids for hyperthermia
applications
Citric Acid Coated Magnetite Nanoparticles for Magnetic Hyperthermia
In vitro experiments
Class 2b
In Vitro Magnetofection: Magnetic Force Influence
Ferrogels PVA/Fe oxide
magnetite
magnetsmall domainsingle
Magnetic Nanocomposites. Examples:•Ferrofluids•Virus/NPs complexes•Ferrogels: magnetic hydrogels
8
A brief introduction to nanomaterials magnetic state:
Exchange interactionMagnetic anisotropyMagnetostatic energy: dipolar interactionZeeman interaction: response to an applied field
Magnetic Anisotropy – phenomenological description
eK : anisotropy energyper volume unity
42
3
2
2
2
1123
222
i
i
iji
ij
iji
i
iK mKmmmKmmKmKe
EK : anisotropy energy dVeE KK
mi : magnetizationdirector cosines
...,,
3,2,1M
Mm
zyx
2m
3m
1m
x
y
z
Material K1
(105 J/m3)K1
(105 J/m3)Easy axis
Co 4.1 1.0 hexagonal
SmCo5 1100 - hexagonal
4
2
2
1 sinsin KKeK
Magnetocrystalline Anisotropy in Hexagonal Crystals
Magnetocrystalline Anisotropy in Cubic Crystals
2
3
2
2
2
12
22
1 mmmKmmKe ji
ij
K
Material K1
(105 J/m3)K2
(105 J/m3)Eje fácil
Ni -0.045 -0.023 (111)
Fe 0.480 0.05 (100)
2m
3m
1m
x
y
z
21 nmKe SK
interface
Surface Anisotropy
sup//0 mKS
sup0 mKS
Interface anisotropy
Exchange anisotropy*
Sx
SSK umH
umKe
2
anti
ferr
o
Exchange bias field
n
Su
ferr
o
*called also unidirectional
cos2
mH
e xK
H
M
xH
ef
VBef SKKK
d
KKK s
Bef
d
KKK s
Bef
6
SSSSef
V Kd
Kr
K
r
r
V
SKK
S
63
3
4
4
3
2
sphericalNP
Bødker et. Al (1994)
surfaces/interfaces:
-Compositional and configurational discontinuity
- Large anisotropic effect
KS = 10-5-10-4 J/m2, anisotropy energyper surface area
unit
surface
bulk
Surface anisotropy in nanoparticles
F. Luis, J.M. Torres, L.M. Gracía, J. Bartolomé, J. Stankiewicz, F. Petroff, F. Fettar, J. L.
Maurice and A. Vaurés. Phys. Rev B, 65 (2002) 094409
Co/Al2O3
Bulk
Surface anisotropy in nanoparticles
Single domain NPs
Uniaxial anisotropy
Stoner – Wohlfarth Model
K
no interactions among NPsIdentical NPs
H
H
K
K
H
K
cossin 0
2 HMsVKVEEE HK
Easy
axis
-
H
z =MV
anisotropy Zeeman
-1 0 1 2 3 4-3
-2
-1
0
1
2
3
h = 0.25
h = 0.00
h = 1.00
h = 0
h = 1.25
E
cos2sin2 hKVE
KH
Hh
H
S
KM
KH
0
2
hcos
hKV2
0
hKV2
Field in the easy direction
E.C. Stoner y E.P. Wohlfarth, IEEE Transactions on Magnetics 27, 3475-3518 (1991)
MK
HK
-HK HK
-HK
H
HH
H
S
KM
KH
0
2
KT 0
Stoner – Wohlfarth Model
kT
E
ij
ij
ec
00
0
ijT
0cijT
Atempt Frequency
kT
E
ij
ij
ec
1
0
Jump Frequency
Relaxation Time-1 0 1 2 3 4-1
0
1 12
21
1
2
H = 0.25 HK
E
2)1( hKV
2)1( hKV
2)1( hKVEij
KT 0
Extending the Stoner – Wohlfarth Model
SKC
M
KHH
0
2
M
HHK
HC
T=0
T0
Coercive Field Temperature Dependence
-2 -1 0 1 2 3 4 5
-1
0
1
h = 0,75
E
K
HMHHh S
K2
/ 0
hKV2
hKV2)1( 2hKV
21 hKVE
kT
hKV
e
21
021
moment inversion occurs when21 exp
Extending the Stoner – Wohlfarth Model
0exp
2/ln1 kThKV
0exp /ln1
KV
kTh
0exp /ln1
KV
kTHTH KC
KC HH 479.00
0exp /ln148.0
KV
kTHTH KC
KH
//
HK
H
NPs Random Orientation
Coercive Field Temperature Dependence
Extending the Stoner – Wohlfarth Model
2/1
12
BS
CT
T
M
KH
Magnetic Interactions in ferromagneticnanotubes of LaCaMnO and LaSrMnO,
J.Curiale et al., AFA 2006
Uso extendido de la expresión
Marina Tortarola, Thesis, IB, 2008
M
HHK
HC
T=0
T0
Ferrogel of maghemite NP (8 nm) in PVA hydrogel, Mendoza Zélis et al.
Extending the Stoner – Wohlfarth Model
Coercive Field Temperature Dependence
KVE1E2
kTEe
/
011
kTE
e/
022
1
11211 1 ppt
p
tfHt
H
pMM
H
S
0
1 12
dHtfM
M
H
MdM
HS
S 12
0
1
Two levels model
Magnetostatic Energy (dipolar interactions)
M uniformGeneral Case
Hint NO uniform
2nd degree surface
(conics)
Hint uniform
M uniform
1
222
c
z
b
y
a
x
ellipsoid
MNHD
ˆ
Demagnetizing
fieldDemagnetizing
Tensor
Diagonal if
coordinate axis
coincide with
ellipsoid ones
Number if M
iM S
jM S
kM S
Unit Trace
1 zyx NNN
2220
2zzyyxxM MNMNMN
VE
Non quadratic surfaces
Valid also for bodies with non
quadratic surfaces: cubes, prisms,
cilinders, octahedra, etc.
( Brown-Morrish theorem)
Cube,
octahedra,
tetrahedra
3/1 zyx NNN
Regular
prism,
cilinder
zyx NNN
Limit case, z
0;2
1 zyx NNN
zyx NNNcba
22202220
22zzyxxNNzzyyxxM MNMMN
VMNMNMN
VE
xy
constMNNV
constMNNV
E SxzzxzM 22020 cos
22
constVKconstMNNV
E MESxzM 2220 sinsin
2
2222
zyxS MMMM
2sinVKE MEM 20
2SzxME MNNK
Shape anisotropy: ellipsoidal NPs
Demagnetizing Factors– references
Formulae, tables y graphs for demagnetizing factors, Chen et al. IEEE Trans. Magnetics
27, 3601-19 (1991)
Demagnetizing Field y Magnetic Measurements, J.A. Brug y W.P. Wolf, J.Appl.Phys. 57,
4685-701 (1985)
Demagnetizing factors calculations,
http://magnet.atp.tuwien.ac.at/dittrich/?http://magnet.atp.tuwien.ac.at/dittrich/content/tool
s/magnetostatics/streufeld.htm
35
Paramagnetism
J
kTHx /0
Ion angular moment
Cr3+ (J=3/2)
Fe3+
(J=5/2)
Gd3+
(J=7/2)
A/mK/T
Agreement withexperimental
results
BgJ
J
x
Jx
J
J
J
JTMxBTMTHM SJS
2coth
2
1
2
12coth
2
12)(,
36
0xT
C
kT
N
H
M
3
2
0
-1
-0.4 -0.2 0.0 0.2 0.4
-0.4
-0.2
0.0
0.2
0.4
J=>inf
J=3/2
J=1/2
M/MS
x=g
BJH/kT
Paramagnetism
37
Superparamagnetism
exp
B NP
xxTMxLTMTHM SS
1coth)(,
For a NP moment distribution
dkT
HLfNTHM
0
0,
dedf2
02
2
/ln
2
1
TNdfNTM S
0
38
-2000 -1000 0 1000 2000
-60
-40
-20
0
20
40
60
10 20 30 4061
62
63
64
65 Ms(T)=Ms(0) (1-T)
M(A
m2/k
g)
T (K)
M (
Am
2/k
g)
H (kA/m)
10K
40K
90K
140K
190K
240K
290K
Superparamagnetism
et al.
2181055.1 Am
Tesla0
Tesla2.0
9/2/ 32
0max kTdV 380/0 kTH
18104.18 HCennmd magnetita
F.H. Sánchez
-2 -1 0 1 2 3 4 5
0.0
0.5
1.0
KV+Eint
H = 0
E
kTEBe/
0
DFB proposition
2sinBK EE
BtotB EE intfor
F.H. Sánchez
-2000 -1000 0 1000 2000
-60
-40
-20
0
20
40
60
10 20 30 4061
62
63
64
65 Ms(T)=Ms(0) (1-T)
M(A
m2/k
g)
T (K)
M (
Am
2/k
g)
H (kA/m)
10K
40K
90K
140K
190K
240K
290K
KTforHC 400
TMTM SS 10
F.H. Sánchez
0 200 400 600 800 1000 1200 1400 1600
0
50
100
150
200Ferrogel
Water
Ferrogel
Hydrogel
M
Time (min)
Alcohol+Ibuprofen
F.H. Sánchez
Ferrogel swelling
0 100 200 3000
10
20
Dry
Hydrated
M (
Am
2/k
g)
T (K)
Tb
d=25K
Tb
h=17K
ZFC-FC, H=8kA/m
kTEKV
hyd
hyd
e/
0int
kTEKV
dry
dry
e/
0int
hyd
B
dry
B
hyddryTTEE
intint
F.H. Sánchez
0 5000 10000 150000.0
0.5
1.0
1.5
parallel
M(A
m2/k
g)
H(A/m)
perpendicular
H
H
parallel perpendicular
Shape effects
F.H. Sánchez
ginteractinnon
B 41058.1
ginteractin
B 41058.1
ginteractinnon
B 3104
Analysis of an interacting superparamagnet with theoretical expressions valid for non interacting systems (Langevin)
F.H. Sánchez
aparent
true
F.H. Sánchez
Analysis of an interacting superparamagnet with theoretical expressions valid for non interacting systems (Langevin)
Dipolar interactions
Hypothesis: dipolar interactions give rise to an aparent higher temperature
3
2
0d
D
d
*TTTa
con *kTD
1
kT
HL
M
THM
S
0),(
*
),( 0
TTk
HL
M
THM
S
N
M
kT S
2
0*
F.H. Sánchez
Dipolar interactions
*),( 00
TTk
HLN
kT
HLNTHM a
aa
TT
a/*1
1
NTTNNTT
NN aaaa /*1/*1
1
when
0* 0
0
3
0
3
0
3
T
SSD
aM
kT
dM
kTdkTdkT
T
T
*TT
*kTD 3
2
0d
D
F.H. Sánchez
Low field susceptibility
*3
2
0
TTk
N
N
M
kT S
2
0*
3
333*3312
0
2
0
2
0
2
2
0
2
2
0
2
0
S
S
SS M
TkN
N
M
kMN
kN
MN
TkN
N
kT
N
kT
331
2
0
SM
TkN
F.H. Sánchez
Allia et al. show that when a NP moments distribution exists former expression becomes:
3
32
0
SM
TkN
where
2
2
2
2
a
a
F.H. Sánchez
N
M SN
M
kT S
2
0*
*kTD
2
SM
T3
0/3 kN
slope
measurements
At different temperatures
HvsM
0 50 100 150 200 250 3000
2000
4000
6000
8000
10000
FT
GA
a
p(A
m2/k
g)
T (K)
Aparent moment variation with temperature
F.H. Sánchez
3
32
0
SM
TkN
FG
NPs
mass
mass
3/ mkg
2
2
nmd
nmD
J
FT
p
D
B
26
1.8
1037.1
9500
21
nmd
nmD
J
GA
p
D
B
32
1.9
1038.2
12600
21
F.H. Sánchez
ii
i
ii
i
ii
i
iM VHMHBE
222
1 00
Case 1: continuous material
Interacción among materials dipoles
mi
Hi iij
dip
ji rHH
i
dVHM
2
0
MNH D
Magnetostatic energy or magnetic self energy
66F.H. Sánchez
Demagnetizing factor NDef in samples with disperse magnetic NPs
D
i
j
ijd
D
ijij Ded
If NPs are in contact: 1(case of a continuos magnetic material)
Case 2: magnetic NPs disperse in non magnetic media
67
...2,3/22,3/2,1..
...5,2,2,1..
ij
ij
ebccei
esquareei
Is a normalized array describing the geometry of NPs arrangementije
F.H. Sánchez
d
d: distance between neighbors
“dilution “ factor
iii
i
ii
i
iM HHE
00
2
1
2
68
Identical NPs: .,6/,1;3 etcDV
F.H. Sánchez
4/13
1333333
j ij
ij
j
jijijj
ij
ie
s
Dvuuv
eDH
ii v
jijijjij vuuvs
3
Dipolar field on NP i:
33DH i
i
j ij
ij
ie
s3
defining
Just depends on the geometry of the NPs array, on the relative orientations between moments and relative orientations between them and the segment joining them. may take different orientations.
i
ijs
Sii MH adimensional
,,,, i
69F.H. Sánchez
.,6/,1;3 etcDV using
SSpp VMMV 3 “global” sample magnetization
Volume per particle
MH S
ii
Assumption for non saturated sample: same proportionality constant between H and M holds.
SDN MNMH DSD
Averaging i on sample
S
S
i
S
i MH
Saturated sample, i corresponds to the saturation (sij) configuraciónS
i
70
Aproximation done: MM S
iSi
F.H. Sánchez
Using magnetization of magnetic phase (NPs)pM
MM p
3
pDefp
S
ii MNMH
3
hence
3D
Def
NN
71F.H. Sánchez
Determined by shapeDetermined by shape and NP dilution
DDef NNif 1.016.3 D
Dd
DDef Nd
DN
3
or
1. NPs homogeneously distributed. ND is the demagnetizing factor which corresponde to sample shape.
2. NPs are aggregated in clusters, and clusters do not interact among them. ND is the demagnetizing factor which corresponds to cluster average shape.
3. NPs are aggregated in clusters, and clusters interact among them. ND is the demagnetizing factor which corresponds both to sample shape and to cluster average shape.
72F.H. Sánchez
Cases of interest
Case of interest 3
pccp nnn NP nuber
73F.H. Sánchez
3. NPs are aggregated in clusters, and clusters interact among them. ND is the demagnetizing factor which corresponds both to sample shape and to cluster average shape.
CECC Dd
CDCD
Dd IC
D
6cn
7pcn
DIC
CD
D
333 DnD ICpcC
s
D
pc
S
ECS
IC
sample
D Nn
N
c
D
S
IC
cluster
D NN
Leads to
333
ECIC
cluster
D
sample
D
IC
cluster
DDef
NNNN
74
This is the sought result, it gives the dependency of the effective demagnetizing factor in terms of cluster and sample ones, and the characteristic distances (dilution factors) of the problem.
F.H. Sánchez
Continuous NPs distribution
1;1 ECIC Continuous Material
muestra
75F.H. Sánchez
Particular cases
s
D
ECIC
c
D
s
D
IC
c
DDef N
NNNN
333
Cluster with almost no interior demagnetizing field
76F.H. Sánchez
H
33333
ECIC
s
D
ECIC
c
D
s
D
IC
c
DDef
NNNNN
Clusters of random shape with orientations randomly distributed.
3/1c
DN
If clusters are far away from each other
33
1
IC
DefN
If clusters are in contact
3
IC
s
DDef
NN
77F.H. Sánchez
If sample does not present demagnetizing effect
H
33333
131
3
1
EC
s
D
ICECIC
c
D
s
D
IC
c
DDef
NNNNN
33
11
3
1
ECIC
DefN
79
Other considerations
pccp nnn
NPs Magnetization3D
Mp
p
cluster Magnetization3
IC
p
C
MM
333
ECIC
p
EC
CMM
M
CD
D
F.H. Sánchez
Sample Magnetization
c
D
s
D
EC
c
DD NNNN 3
1
c
D
s
D
c
DD
S
pS
IC
c
DD
c
D
s
D
EC
NN
NN
M
M
NN
NN
3
3
Lead to
33
1
ECICppS
S
M
M
M
M
80F.H. Sánchez
SMpSMy are measured. The dilution factors product can be estimated:
81
For an isotropic clusters orientation distribution
3
11
3
13
s
D
EC
D NN
3/1
3/1
3/1
3/1
3
3
s
D
D
S
pS
IC
D
s
DEC
N
N
M
M
N
N
Leads to
F.H. Sánchez
3/1c
DN
Analysis with Langevin model. Comparison with Allia’s proposition
dipap HHH
kT
HHLM
kT
HLMM
dipap
pSpSp
00
pDef
dip MNH
82
Assumptions dip
p HHM
kT
MNHL
VkT
MNHLMTHM
pDef
ap
p
pDef
ap
pSp
00,
F.H. Sánchez
83
p
pDef
ap
pkTV
MNHM
3
2
0
When Langevin function argument is << 1
Def
p
ap
p
NkTV
HM
2
0
3
F.H. Sánchez
Measured susceptibility of magnetic phase.
Def
ppSp
NVM
kT
2
0
31
Def
pS
p
p
NM
kTN
2
0
31
pp VN /1
84
Def
pS
p
p
NM
TkN
2
0
31
p
pS
p
p M
TkN
3
312
0
According to Allia
It’s concluded that pDefN 3
F.H. Sánchez
85
For a sample with a distribution of NP moment sizes, Allia shows
p
pS
p
p M
TkN
3
32
0
2
2
2
2
a
a
and are NP moments. The former are “aparent” values which are obteined when analizing without considering dipolar interactions. The latter are values “corrected” from
a THM ,
ppDef
pS
p
p
VNNM
TkN/1,
32
0
F.H. Sánchez
In the present case
p
pS
N
M
86
D
pS
D
pS
NVM
kTN
VM
kT32
0
3326
0
3
33
As a function of sample “global” magnetization for a homogeneous sample, SM
ppppp VVN 3/1/1 D
S
ppN
M
TkN
2
0
3
F.H. Sánchez
Measured sample susceptibility
3/1)3 AlliaND
87
Measuring M vs. H at several temperatures, and plotting / vs. T/MS2 ND and Npp can
be retrieved
2/ pSMT
ppN
DN
From straight line slope
Data from M vs H
pp
S
N
M
pp
D
N
MN
2
2
0
Max dipolar energy per NPpp
SD
N
MN
2
2
0
88
If there are clusters, SM
F.H. Sánchez
3266
0
33
3
IC
D
SpECICECIC
N
M
T
V
k
Def
pSp
NM
T
V
k
2
0
3
pp
ppm
p
m
pcc
pICEC
pICpcECcm NVV
n
V
nn
VVnnV
1133
33
using
3233
0
33
3
IC
D
SECIC
pp
ECIC
N
M
TkN
DEC
S
ppN
M
TkN3
2
0
3
H
H
parallel perpendicular
Shape effects
F.H. Sánchez
0 5000 10000 150000.0
0.5
1.0
1.5
parallel
M(A
m2/k
g)
H(A/m)
perpendicular
//
Ferrogel PVA/maghemite 15.7% mass concentration
91
Assuming a uniform distribution of NPs
//
//3
DefDef
DD
NN
NN
1.2
kgm /1013.1 33
//
kgm /1008.1 33
//
3
//
11
4
10
DefDef NN
0.80 =
0.06 = //
N
N
De la forma de la muestra
F.H. Sánchez
D
Dd
Estimation of from FG density and mass concentration of Fe oxide x, assuming a uniform
distribution of NPs
FG
oFe
m
mx
FG
FGFG
V
m
3
33
666
xxd
DD
xV
N
xV
mN
xV
m
FG
NP
FG
NPNP
FG
oFeFG
3/1
6
FGx
F.H. Sánchez