1st Nanoforum Workshop, Sinaia,

Romania, 5-7 October, 2003

1
MAGNETIC NANOFLUIDS
Preparation, properties and some
applications
L.VKS and Doina BICA
Laboratory of Magnetic Fluids Centre of Fundamental and
Advanced Technical Research, Romanian Academy,
Timisoara Division, Timisoara, Romania
1st Nanoforum Workshop, Sinaia,
Romania, 5-7 October, 2003
2
Magnetic nanofluids
Magnetic nanofluids (magnetic fluids, ferrofluids):
ultrastable colloidal suspensions of magnetic
nanoparticles (3-15 nm) in non-polar and polar carrier
liquids; S. Pappel, NASA (1965), Rosensweig, Nestor,
Timmins (1965)
Nanofluids- novel enhanced heat transfer fluids;
S.U.S. Choi, Argonne National Lab.(1995)
Magnetizable complex fluids: magnetic fluids,
emulsions, magnetofluidic composites, magneto-
rheological nano/micro fluids
Magnetic soft matter a special category of soft
matter composites: magnetic
nanofluidsmagnetorheological fluidsmagnetic
nanocompositesmagnetic gels
1st Nanoforum Workshop, Sinaia,
Romania, 5-7 October, 2003
3
Magnetic nanofluids
New MHD: ferrohydrodynamics,
Neuringer and Rosensweig (1964)
=0
0
an extension of classical MHD:
0 =
0
Magnetic fluids as magnetizable complex
fluids with internal angular momentum
non-symmetrical stress tensor
1st Nanoforum Workshop, Sinaia,
Romania, 5-7 October, 2003
4
Magnetic nanofluids
Ferrohydrodynamics-specific phenomena
1st Nanoforum Workshop, Sinaia,
Romania, 5-7 October, 2003
5
Magnetic nanofluids
1st Nanoforum Workshop, Sinaia,
Romania, 5-7 October, 2003
6
Magnetic nanofluids
Preparation of magnetic nanofluids
Synthesis of magnetic nanoparticles by
chemical condensation
Stabilization/dispersion of magnetic
nanoparticles in various carrier liquids
1st Nanoforum Workshop, Sinaia,
Romania, 5-7 October, 2003
7
Magnetic nanofluids
Aqueous solutions
Fe
3+
, Fe
2+
Coprecipitation
NH
4
OH
(solution 25%)
Subdomain Fe
3
O
4
nanoparticles
Surfactant
(pure oleic acid 96%)
353 K
Sterical stabilisation
(chemisorption)
Phase separation
Magnetic
decantation
Aqueous solution of
residual salts
Monolayer covered
magnetic particles
Distilled water
t = 70 - 80
o
C
Repeated washing
Magnetic decantation
Aqueous solution
residual salts
Monolayer covered
magnetic nanoparticles +
free oleic acid
Acetone Extraction
Magnetic decantation
Acetone, water,
free oleic acid
Stabilised magnetic
nanoparticles
Hydrocarbon Dispersion
t=120-130
o
C
Primary monolayer
stabilised magnetic fluid
on light hydrocarbon
carrier
Magnetic decantation /
filtration
Repeated flocculation /
redispersion of surfacted
nanoparticles
Free oleic acid
NONPOLAR PURIFIED MAGNETIC FLUID
Preparation procedure of nonpolar magnetic fluids
1st Nanoforum Workshop, Sinaia,
Romania, 5-7 October, 2003
8
Magnetic nanofluids
- Coprecipitation Fe
2+
, Fe
3+
, NH
4
OH sol. 25%
- Sterical stabilisation, (chemisorbtion, oleic
acid 96%)
- Phase separation
- Repeated washing
- Dispersion
Primary magnetic fluid on
light hydrocarbon carrier
- Magnetic decantation
- Filtration
- Repeated flocculation /
redispersion of surfacted
nanoparticles
Free oleic acid
Nonpolar purified
magnetic fluid
Acetone Flocculation
Magnetic decantation Acetone + hydrocarbon
Monolayer stabilised
magnetic nanoparticles
DBS or PIBSA (C8) - Secondary stabilisation
(physical adsorbtion)
- Dispersion
Alcohols C
3
-C
10
/HVO/
Diesters(DOA/DOS)
MF/HIGH
VACUUM OIL
MF/ALCOHOLS
(Polialcohols)
MF/DIESTERS
(DOA, DOS)
VEGETAL
OILS
Fe
3+
, Fe
2+
solutions
=75-80
o
C
Nanoparticle synthesis
Fe
3
O
4
, - Fe
2
O
3
NH
4
OH 25 %
Magnetic
decantation
Aqueous solution of
residual salts
Distilled water
t = 70 - 80
o
C
Magnetic nanoparticles
Repeated washing
up to pH=8.5
Magnetic decantation
Aqueous solution
residual salts
DBS and/or lauric
acid (LA) =75
o
C
Double layer stabilization
and dispersion
Ultrasonation (2)
MF/Water (primary)
Magnetic decantation/
filtration
MAGNETIC FLUID/Water
Preparation procedure of polar magnetic fluids Preparation procedure of water based magnetic fluids
1st Nanoforum Workshop, Sinaia,
Romania, 5-7 October, 2003
9
Magnetic nanofluids
MAGNETIC FLUIDS
for fundamental and applied researches
Medium and high concentration magnetic fluids (selection)
Nr. Indicative Carrier liquid Nominal
magnetization (G)
* 1. TM P petroleum/nonpolar 200-400-800
* 2. TM K kerosen/nonpolar 200-400-800
* 3. TM T toluen/nonpolar 200-400-800
4. TM Izo izooctan/nonpolar 200-400-800
5. TM H heptan/nonpolar 200-400-800
6. TM Cyc cyclohexan/nonpolar 200-400-800
7. TM - TR 30 transformer
oil/nonpolar
200-400-800
8. TM DHN decahydronaphtalene/
nonpolar
200-400-800
9. TM HVO high vacuum oil/polar 200-400-800
10. TM DOA dioctyladipate/polar
(synthetic oil)
100-300-700
11. TM DOS dioctylsebacate/polar
(synthetic oil)
100-300-700
12. TM Prop propanol/polar 100-300-600
13. TM But butanol/polar 100-300-600
14. TM Pent pentanol/polar 100-300-600
** 15. TM Hexa hexanol/polar 100-300-600
16. TM Hept heptanol/polar 100-300-600
** 17. TM Octa octanol/polar 100-300-600
18. TM Nona nonanol/polar 100-300-600
19. TM Deca decanol/polar 100-300-600
20. TM H
2
O water/polar 50-300-600
* Specially developed for inductive sensors (AEM Co, Timioara).
** Specially developed for capacitive sensors (Inst. for Space Sciences, Bucharest).
1st Nanoforum Workshop, Sinaia,
Romania, 5-7 October, 2003
10
Magnetic nanofluids
Structural investigations
Transmission electron microscopy (TEM):
size distribution of magnetic nanoparticles
Small angle neutron scattering (SANS) and
small angle X-ray scattering (SAXS):
structure of surfactant covered nanoparticles,
ordering processes, particle interactions and
pre-existing or field induced agglomerates,
interface structures
1st Nanoforum Workshop, Sinaia,
Romania, 5-7 October, 2003
11
Magnetic nanofluids
The Guinier plots of ln(I
n
(Q,x)) versus
Q
2
for several values of D-benzene
volume fraction (0, 0.2, 0.5, 0.8 and 1.0).
Good straight lines are evident.
JINR Dubna
Guinier plot of SAXS measurement
of cyclohexane based magnetic
fluid. The linearity up to small q
indicates that clusters are absent.
Debye Inst. Utrecht
1st Nanoforum Workshop, Sinaia,
Romania, 5-7 October, 2003
12
Magnetic nanofluids
Mean intensity <I> as a function of time after demagnetization for water based
magnetic fluid sample (a) and pentanol based magnetic fluid sample (b).
Horizontal lines in the graphs correspond to the mean intensity value of the
initial ferrofluids before they are set in the magnetic field:
, - applied field (B=1.2 T); , - zero field (B=0 T).
Budapest Neutron Center
(a) Water based magnetic fluid (b) Pentanol based magnetic fluid
1st Nanoforum Workshop, Sinaia,
Romania, 5-7 October, 2003
13
Magnetic nanofluids
-0,02 0,00 0,02 0,04 0,06 0,08 0,10 0,12 0,14 0,16 0,18
1E-8
1E-7
1E-6
1E-5
1E-4
1E-3
0,01
0,1
1
10
R
e
f
l
e
c
t
i
v
i
t
y
q
z
, A
-1

Structure of magnetite/oleic acid/benzene magnetic
nanofluid at the interface with silicon (1)
Typical scattering pattern (Sample 1)
from the interface of silicon and
ferrofluids under study.
Example of the experimental reflectivity curve
(Sample 1) and model calculations. Solid line
corresponds to the best fit of the two-layer model;
dashed line corresponds to the model with
additional surfactant layer.
ILL - Grenoble
1st Nanoforum Workshop, Sinaia,
Romania, 5-7 October, 2003
14
Magnetic nanofluids
-40 -20 0 20 40 60 80 100 120 140
-1
0
1
2
3
4
5
6
7

1
0

6
A
-
2


h,A
OA
C
6
D
6
Fe
3
O
4
<>
-40 -20 0 20 40 60 80 100 120 140
-1
0
1
2
3
4
5
6
7

1
0

6
A
-
2


h,A
OA
C
6
D
6
Fe
3
O
4
<>
Structure of magnetite/oleic acid/benzene magnetic
nanofluid at the interface with silicon (2)
Scattering density profiles for Samples 1 3 (a) and 4, 5 (b). Color solid
lines show values of the bulk scattering length density of the fluids and its
components.
ILL - Grenoble
1st Nanoforum Workshop, Sinaia,
Romania, 5-7 October, 2003
15
Magnetic nanofluids
The normalized sedimentation velocity U/U
o
as a function of the volume fraction of the
aqueous magnetic dispersions FF7-H
2
O,
FF7-TMA and FFWA. The solid line is the
result of a linear fit
The normalized sedimentation velocity
U/U
o
against the volume fraction of the
ferrofluid MaS in 1-pentanol. The solid
line is the result of a linear fit
Debye Inst. Utrecht
1st Nanoforum Workshop, Sinaia,
Romania, 5-7 October, 2003
16
Magnetic nanoparticles
Flow properties
Dynamic viscosity vs. particle volume fraction
Dynamic viscosity vs. temperature
Effective viscosity vs. applied magnetic field
induction, magnetoviscous effect
Field induced structure formation, non-Newtonian
behaviour, degree of colloidal stability
Fits to various semi-empirical and theoretical
formulas
1st Nanoforum Workshop, Sinaia,
Romania, 5-7 October, 2003
17
Magnetic nanoparticles
VAND
( )
|
|
|
.
|

\
|

+
=
h
2
h
1 2 2 h 1
o
Q 1
k k r k
exp

- the viscosity of the magnetic fluid

0
- the viscosity of the carrier liquid

h
=p

- the hydrodynamic volume fraction

- the volume fraction of the dispersed solid particles

p - a proportionality factor
Q=0.609 - a constant that characterizes the hydrodynamical interactions
k
1
=2.5 - the shape factor for isolate spherical particles
r
2
=4 - a time constant for binary collisions
k
2
=3.175 - the factor for the ensemble of two colliding particles
3
h
d
2
1 p
|
.
|

\
|
+ = =

CL S
CL MF

=
- surfactant layer thickness
d - mean physical diameter of magnetic nanoparticles

MF
- magnetic fluid density

CL
- carrier liquid density

S
- solid particles density
1st Nanoforum Workshop, Sinaia,
Romania, 5-7 October, 2003
18
Magnetic nanoparticles
KRIEGER-DOUGHERTY
[ ]
x
x
h
o
1 exp

|
|
.
|

\
|
=

x
- the maximum packing fraction (the fraction at which )
[] - intrinsic viscosity
QUEMADA

2
x
h
o
1 exp

|
|
.
|

\
|
=

CHOW
(
(

+
|
|
.
|

\
|

=
x
2
h
2
h
h
h
o
A 1
A
1
5 . 2
exp

- A - the coupling coefficient between particles
1st Nanoforum Workshop, Sinaia,
Romania, 5-7 October, 2003
19
Magnetic nanoparticles
1st Nanoforum Workshop, Sinaia,
Romania, 5-7 October, 2003
20
Magnetic nanoparticles
VAND QUEMADA KRIEGER-DOUGHERTY CHOW
t
(
o
C)
p=
h
/


(fit
parameter)
=(p
1/3
-1)d/2
(effective stabilizant
layer thickness) (nm)

m
Q
(max. hydrodyn. vol.
fraction)

m
K
(max. hydrodyn.
vol. fraction)
[ ]
(intrinsic
viscosity)
A
(fit with
m
Q
)
A
(fit with
m
K
)
-10 3.897 2.466 0.703 0.670 2.858 3.186 3.317
0 3.763 2.389 0.693 0.654 2.886 3.491 3.663
10 3.620 2.305 0.685 0.637 2.925 3.747 3.975
20 3.541 2.255 0.678 0.625 2.953 3.910 4.170
30 3.425 2.182 0.675 0.614 2.971 4.051 4.356
40 3.366 2.146 0.672 0.607 2.980 4.135 4.460
50 3.308 2.108 0.669 0.600 2.988 4.208 4.552
60 3.272 2.083 0.668 0.596 2.997 4.241 4.599
70 3.251 2.067 0.667 0.593 3.000 4.261 4.627
A
theor
(Chow)=4.67
Volumic concentration dependence of dynamic
viscosity for pentanol magnetic fluids
1st Nanoforum Workshop, Sinaia,
Romania, 5-7 October, 2003
21
Magnetic nanoparticles
1st Nanoforum Workshop, Sinaia,
Romania, 5-7 October, 2003
22
Magnetic nanoparticles
1st Nanoforum Workshop, Sinaia,
Romania, 5-7 October, 2003
23
Magnetic nanofluids
Magnetic properties
Full magnetization curves
Low field reduced magnetization
curves, particle agglomerates
Fits to theoretical models
1st Nanoforum Workshop, Sinaia,
Romania, 5-7 October, 2003
24
Magnetic nanofluids
Reduced magnetization curves of high concentration C
3
- C
10
alcohol based magnetic fluids
1st Nanoforum Workshop, Sinaia,
Romania, 5-7 October, 2003
25
Magnetic nanofluids
1st Nanoforum Workshop, Sinaia,
Romania, 5-7 October, 2003
26
Magnetic nanofluids
MF water (1985): 50.38 kA/m (630 G)
MF pentanol (2000): 56.92 kA/m (715 G)
MF warter (1999): 14.95 kA/m (190 G)
Full magnetization curves
of strongly polar magnetic fluids
1st Nanoforum Workshop, Sinaia,
Romania, 5-7 October, 2003
27
Magnetic nanofluids
Initial susceptivity vs. physical volume fraction. Comparison
between polar (Pent) and nonpolar MFs (TR30)
The non-linear behaviour can be a result f both particle
interaction and aggregate formation in the samples. A
preliminary fit with Ivanovs model (Col. J., 2001)
shows that the interactions might play the main role.
1st Nanoforum Workshop, Sinaia,
Romania, 5-7 October, 2003
28
Initial susceptibility vs. magnetic volume
fraction for Pentanol MF sample
Magnetic nanofluids
Measured initial susceptibility for Pent samples, and calculated initial
susceptibilities with various models vs. magnetic volume fraction. For
Pent based samples the deviation from ideal behaviour is mainly due to
particle interactions; Thermodynamic Perturbation Theory and Mean
Spherical Model almost fit the data.
1st Nanoforum Workshop, Sinaia,
Romania, 5-7 October, 2003
29
Magnetic nanofluids
Non-magnetic fluid/magnetic nanofluid
interfaces in magnetic field
Bubbles and drops in magnetic field
Nucleate boiling of magnetic nanofluids in applied
magnetic field
Magnetically controlled boiling in reduced gravity
conditions
Magnetically controlled heat transfer processes
1st Nanoforum Workshop, Sinaia,
Romania, 5-7 October, 2003
30
Magnetic nanofluids
Above: Without buoyancy or convection, boiling fluids behave quite
differently in space. Image courtesy NASA Glenn Research Center .
1st Nanoforum Workshop, Sinaia,
Romania, 5-7 October, 2003
31
Magnetic nanofluids
Heat transfer in the presence of an electric field Heat transfer in the presence of a magnetic field
( )
E
f u g T p u u
t
u
r
r r r r
r
+ + =
|
.
|

\
|
+

2
,
0 = u
r
p
e
c
E
T a T u
t
T

2
2
+ = +

r
0 E =
r
0 E =
r
0
v
J
t

+ =
r
( ) T p p , =
( )
M
f u g T p
Dt
u D
r
r r
r
+ + =
2
, (1)
0 = u
r
(2)
( ) + =
|
.
|

\
|

+ T
Dt
DH
T
M
Dt
DT
c
H
p

0
(3)
0 = B
r
(4)
0 = H
r
(5)
( ) H T M M , = (6)
( ) T p p , = (7)
Governing Equations of Heat Transfer in the Presence of an
External Field (Electric or Magnetic)
1st Nanoforum Workshop, Sinaia,
Romania, 5-7 October, 2003
32
Magnetic nanofluids
Experimental bench :
1 compressor, 2 reservoir, 3 pressure
gauge,
4 electromagnet power supply,
5 gaussmeter; 6 Hall probe,
7 electromagnetic poles, 8 precision valve,
9 experimental cell,
10 flow regulating valve,
11 PC with NIST DAQ system,
12 flow transducer,
13 pressure transducer
N S
1 2 3 4 5 6
7
8
9
10 11 12 13
Experimental researches regarding the effects of a magnetic field on
the dynamics of gas bubbles injected in a complex magnetizable fluid
1st Nanoforum Workshop, Sinaia,
Romania, 5-7 October, 2003
33
Magnetic nanofluids
The influence of magnetic induction
and of its gradient on the relative
bubble emission frequency
Variation of the relative volumic gas
flow rate through a submerged needle
in magnetic fluid in nonuniform
magnetic field
Behaviour of complex magnetizable nanofluids
in microgravity conditions
1st Nanoforum Workshop, Sinaia,
Romania, 5-7 October, 2003
34
Magnetic nanofluids
Lattice Boltzmann model for the simulation of interfacial
phenomena in magnetic fluids
Deformation of a magnetic fluid
drop in magnetic field
Magnetic field induced deformation
of gas bubbles in magnetic fluid
Development of normal field instability
1st Nanoforum Workshop, Sinaia,
Romania, 5-7 October, 2003
35
Magnetic nanofluids
Applications
Magnetofluidic leakage-free rotating seals
Magnetogravimetric separations, low noise MF bearings
Acceleration/inclinations sensors
Aerodynamic sensors: differential pressure, volumic flow
Magnetic nanofluids for polymeric nanocomposites
Nano/micro-structured magnetorheological fluids for semi-
active vibration dampers
Biomedical applications in plant genetics (e.g.
biostimulators) and veterinary medicine(e.g. radioprotecting
and antiinflammatory composites, magnetically driven
drugs(citostatics))
1st Nanoforum Workshop, Sinaia,
Romania, 5-7 October, 2003
36
|H|10
9
A/m
2
Magnetic nanofluids
Principle of magnetic fluid rotating seals
High vacuum magnetic fluid
feedthrough - ROSEAL Co.
1st Nanoforum Workshop, Sinaia,
Romania, 5-7 October, 2003
37
Magnetic nanofluids
Magnetorheological suspensions
damping mechanisms
1st Nanoforum Workshop, Sinaia,
Romania, 5-7 October, 2003
38
Magnetic nanofluids
Flow behaviour of nano/micro-structured
magnetorheological fluids for semi-active vibration dampers
1st Nanoforum Workshop, Sinaia,
Romania, 5-7 October, 2003
39
Magnetic nanofluids
X 5
X 20 X 50
Optic microscopy of nanomagnetic composite
Optic microscopy of reinforced nanomagnetic composite
X 5 X 20
1st Nanoforum Workshop, Sinaia,
Romania, 5-7 October, 2003
40
Magnetic nanofluids
Conclusions
Magnetic nanofluids and composites
are magnetic soft matter materials with
magnetically controllable fluid properties
wide range of technological and biomedical
applications
1st Nanoforum Workshop, Sinaia,
Romania, 5-7 October, 2003
41
Magnetic nanofluids
Lab. of Magnetic Fluids - Romanian Academy, Timisoara
Division;
National Center for Engineering of Systems with Complex
Fluids Univ. Politehnica Timioara;
Univ. of Agricultural Sciences and Veterinary Medicine,
Timisoara;
Romanian Space Agency; Institute of Space Sciences
Bucharest;
ZARM Univ. Bremen; Vant Hoff Lab. Univ. Utrecht;
Frank Lab. JINR, Dubna; Budapest Neutron Center
(Hungarian Academy of Sciences); ILL Grenoble; Inst. of
Experimental Physics (Slovak Academy of Sciences)
Kosice; Univ. Pisa Dept. of Energetics;
Industrial partner: ROSEAL Co. Odorheiu Secuiesc,
Romania (manufacturer of rotating seals with nanomagnetic
fluids).
Research partners
1st Nanoforum Workshop, Sinaia,
Romania, 5-7 October, 2003
42
Magnetic nanofluids
Prof.Dr.Eng. Ioan ANTON,
member of the Romanian Academy, Director of
CFATR Timisoara
Prof.Dr.Eng. Ioan DE SABATA
Acknowledgements
1st Nanoforum Workshop, Sinaia,
Romania, 5-7 October, 2003
43
Magnetic nanofluids
LMF - CFATR Timisoara:
Dr. Doina BICA, Senior scientist; Dr. Victor SOFONEA, Senior scientist;
Dipl.-Eng. Iosif POTENCZ, Senior scientist;Dr.-Eng. Calin POPA,
Senior scientist; Dipl.-Phys. Artur CRISTEA, Researcher, PhD student
NCESCF - Univ. Politehnica Timisoara:
Dr.-Eng. Floriana STOIAN, Assoc. Prof.;Dr.-Eng. Gheorghe POP,
Assoc. Prof.; Dr. Daniela S.-RESIGA, Assoc. Prof.; Dr.-Eng. Nicolae
CRAINIC, Assoc. Prof.; Dipl.-Phys. Oana MARINICA, Researcher, PhD
student; Dr. Marin LITA, Assoc. Prof.; Dipl.-Eng. Virgil STOICA, PhD
student
Univ. of Agricultural Sciences and Veterinary Medicine Timisoara:
Dr. Gallia BUTNARU, Prof. and Dr. Mariana SINCAI, Prof.
Industrial partner ROSEAL Co., Odorhei: Dipl.Eng. Istvan
BORBATH, director and group leader
Timisoara MF research team: