FULLTEXT01

Synthesis, Characterisation and Applications of
Iron Oxide Nanoparticles
GERMAN SALAZAR-ALVAREZ
Doctoral Thesis
Stockholm, Sweden 2004
KTH Materialvetenskap
ISRN KTH/MSE--04/59--SE+CHEM/AVH SE-100 44 Stockholm
ISBN 91-7283-884-1 SWEDEN
Akademisk avhandling som med tillstånd av Kungl Tekniska högskolan framlägges

till offentlig granskning för avläggande av filosofie doktorsexamen fredagen den
17 december 2004 kl 10.00 i D3, Huvudbyggnaden, Kungliga Tekniska högskolan,
Lindstedtsvägen 5, Stockholm.
c German Salazar-Alvarez, december 2004
Tryck: Universitetsservice US AB
iii
Abstract
This thesis deals with the synthesis, characterisation, and some applications
of ferrimagnetic iron oxide nanoparticles. The iron oxide systems presented in
this work are Fe3 O4 , γ-Fe2 O3 , Nix Fe3−x O4 , Cox Fe3−x O4 .
Iron oxide nanoparticles were prepared using chemical synthesis methods.
Nanoparticles with a narrow size distribution were synthesised using zone confi-
nement methods such as nanoemulsions and the novel flow injection synthesis.
The flow injection method consisted of the precipitation of iron oxide nanopar-
ticles in a continuous or segmented flow in a capillary reactor under laminar
flow. Also, the preparation of particles in a ∼ 40 g/batch scale was carried out
in a computer controlled stirred reactor which allowed reproducible synthesis
conditions such a ∆pH ∼ 0.1 and ∆T ∼ 1 ◦ C. Several chemical and hydrodyna-
mic parameters were optimised to achieve high phase purity and magnetisation.
These methods allowed the preparation of particles with tailored mean particle
size from 3 up to 12 nm.
Spinel iron oxide nanoparticles were also doped with Ni and Co. The
influence of the synthesis parameters on the morphological and magnetic pro-
perties of nickel- and cobalt-doped magnetite (Nix Fe3−x O4 and Cox Fe3−x O4 )
was studied. Particle size, morphology, and composition of the materials are
strongly dependent on reaction conditions, e.g., metal to hydroxide ratio and
temperature. Cubic, spherical, and particles of Cox Fe3−x O4 with varying mor-
phology could be obtained by varying the metal to hydroxide ratio. Mössbauer
studies indicated a disordered structure with a relatively low degree of inver-
sion in the spinel structure. The coercivity of the particles increased with the
cobalt content. High resolution microscopy and electron diffraction studies
showed that cubic particles are monocrystalline.
Iron oxide nanoparticles (Fe3 O4 and γ-Fe2 O3 ) with a particle size of about
10 nm were coated with layers of inorganic materials such as silica and gold to
render the particles higher functionality and vary the surface properties. Iron
oxide nanoparticles were coated with silica in a controlled manner producing
either single coated particles, with a mean particle size varying from 12 to 60
nm, or multiparticle-beads with mean particle size in the range of 50-250 nm.
The use of iron oxide nanoparticles in two applications was studied, i.e.,
for DNA purification and as optical power limiting agents. Silica-coated iron
oxide particles were investigated for use in magnetic purification of plasmid
DNA of the size range 0.1–1.7 kbp. The prepared nanoparticles have shown
higher DNA recovery yields when compared to commercial particles. Single
silica-coated nanoparticles have DNA recovery yield of about 70%, while the
beads of multiple particles showed a recovery of approximately 50%.
The optical power limiting application of coated and non-coated iron oxide
nanoparticles was investigated. Both aqueous suspensions of pristine iron oxide
nanoparticles consisting mainly of γ-Fe2 O3 and silica-coated iron oxide nano-
particles had a clamping level of about 3 µJ. The photoinduced nonlinear light
scattering is the dominating nonlinear mechanism. Silica-coated nanoparticles
have shown a better performance as a result of their higher colloidal stability.
iv
Sammanfattning
I denna avhandlingen diskuteras syntes, karakterisering och tillämpningar

för nanopartiklar av järnoxid. De olika järnoxidsystem som presenteras i arbetet
består av Fe3 O4 , γ-Fe2 O3 , Nix Fe3−x O4 , Cox Fe3−x O4 .
Nanopartiklarna av järnoxid har framställts via kemiska syntesmetoder.
Nanopartiklar med liten varians i storleken (σ < 20%) och en storleksdistri-
bution 3-8 mm framställdes i den zon isolering från inverterade miceller och i
ett nyutvecklat metod som bygger på flödesinjektion (flow injection synthesis).
Å andra sida, för att få reproducerbar betingelser vid syntes av nanopartik-
lar i 40 grams skala har en automatiserad reaktor använts (∆pH ∼ 0.1 och
∆T ∼ 1 ◦ C). Flera kemiska och hydrodynamiska parametrar optimiserades
för att högre fasrenhet och bättre magnetiska egenskaper skulle erhållas. Des-
sa reaktionsbetingelser tillåter framställning av nanopartikar i relativt stora
mängder i storleksområdet 3-12 nm.
Järnoxid nanopartiklar med spinell struktur framställdes via doping med
nickel och kobolt. Effekterna från syntesbetingelserna på morfologin och magne-
tiska egenskaper hos partiklarna har studerats hos nickel och koboltdopad mag-
netit (Nix Fe3−x O4 respektive Cox Fe3−x O4 ) . Partiklarnas storlek, morfologi
och kemiska sammansättning var beroende av koncentrationsförhållandet mel-
lan metall-/ hydroxidjon. Via ändringar i detta förhållande kunde Cox Fe3−x O4
partiklarnas utseende styras så att kubiska, sfäriska eller till och med odefinie-
rade partiklar bildades. Mössbauersspektroskopi har pekat på en oregelbunden
katjondistribution i strukturen. Partiklarnas koercivitet ökade med kobolthal-
ten. Högupplösande transmissionselektronmikroskopi och elektrondiffraktion
visade att de kubiska partiklarna var monokristaller.
För att kunna påverka partiklarnas funktionalitet och ytkemiska egenska-
per har nanopartiklar av järnoxid med en partikelstorlek på 10 nm framställts
med ett ytskikt av oorganiskt material, såsom kiseloxid och guld. Kiseloxid och
guld användes för att de har välkända kemiska egenskaper och har använts un-
der en längre tid inom biologiska applikationer och i supraledareindustrin. Ett
ytlager av kiseloxid har belagts både på ytan av enskilda nanopartiklarna i stor-
leksordningen 12-60 nm och på partikelaggregat, s k beads i storleksordningen
50-250 nm.
Kiselbelagda nanopartiklar av järnoxid har studerats för användning inom
tillämpningar för rengörning av plasmid DNA i storleksspannet 0,1-1,7 kbp,
och som optiska limiter. Återvinning av DNA med enskilda partiklar är upp
till 70%, medan beads visat återvinning av ca 50%.
Optiska begränsning studerades med suspensioner av coatade och uncoa-
tade järnoxid nanopartiklar. Båda suspensionerna har en klämnivå av ca 3 µJ.
Ickelinjära spridning av laserljuset är den dominerande mekanism.
v
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ñîñòàâëÿåò ëèøü ñòî øàãîâ.
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Preface
My graduate studies were originally related to studies on the recovery of heavy

metals from aqueous media by polymeric membranes. This was an extension of the
studies I carried out in Mexico and for which I received my Bachelor in Science in
1999. The work was completed by presenting the Licentiate in Engineering in 2001.
During the period 1999-2001, most of my colleagues were working with the
synthesis of nanoparticles for various applications ranging from electronic to bio-
medical. It was this interdisciplinary environment what caught my interest. After
a discussion with my supervisor I started to perform some experiments and read
more about the nanoworld immediately after presenting my Licentiate. Within half
a year I joined the European project magnanomed, which was oriented towards
some biomedical applications of iron oxide-based nanoparticles. During the time of
the project we produced nanomaterials to be used for DNA separation and purifi-
cation, work which we carried out in collaboration with the Max Planck Institute
for Molecular Genetics in Berlin-Dahlem. The initial magnetic characterisation of
the materials was undertaken by Liquids Research Ltd. at Bangor, Wales. Shortly
after the end of the magnanomed project, in 2003, discussion were held with
people from the Department of Polymer Technology at KTH to produce nanopar-
ticles of substituted ferrites to be incorporated into polymeric composite structures.
The discussions were extended a bit and they turned into two manuscripts -so far.
Concomitantly with the main research efforts, during the period 2001-2004 small
projects were carried out in collaboration with FOI to investigate the applicability
of nanomaterials as optical limiting agents against laser radiation. During this last
stage, collaborations were also established with the Department of Physics at Uni-
versitat Autònoma de Barcelona and the Department of Physicochemical, Inorganic
and Structural Chemistry at Stockholm University.
Regarding the present work, I would like to point out certain things. As far as
it was possible, SI units and terminology∗ were used throughout the thesis and the
manuscripts. The values for various physical and chemical constants were obtai-
ned from the Compendium of Chemical Terminology edited by the IUPAC.† Also,
∗
The definition of several terms can be found in http://wikipedia.org/
†
For more information about the chemical symbols, values of universal constants, etc., please
refer to http://www.iupac.org/
vii
viii PREFACE
in addition to the regular bibliographic information provided by the references to

scientific articles, the document object identifier, DOI, was added whenever it was
available.∗
G.S.A.
∗
For more information about the DOI please refer to http://www.doi.org/.
LIST OF PUBLICATIONS ix
List of publications
I G. Salazar-Alvarez, A.A. Zagorodni and M. Muhammed, Magnetite core-inorganic
shell nanoparticles for biomedical applications by novel confined-zone synthe-
sis, Proceedings of the 2nd IEEE Conference on Nanotechnology 2002, 75-78.
II G. Salazar-Alvarez, M. Muhammed and A.A. Zagorodni, Novel flow injection

synthesis of iron oxide nanoparticles with narrow size distribution,
Submitted to Chemistry of Materials.
III R.T. Olsson, G. Salazar-Alvarez, M.S. Hedenqvist, U.W. Gedde, F. Lindberg

and S.J. Savage, Controlled synthesis of near-stoichiometric cobalt ferrite na-
noparticles,
To be submitted to Chemistry of Materials.
IV R.T. Olsson, M.S. Hedenqvist, U.W. Gedde, G. Salazar-Alvarez, M. Muham-

med, and S.J. Savage, Synthesis and characterisation of cubic cobalt ferrite
nanoparticles,
J. Am. Ceram. Soc., in press.
V G. Salazar-Alvarez, R. Reinhardt, and M. Muhammed, Silica-coated superpa-

ramagnetic iron oxide nanoparticles for the purification of plasmid DNA,
Submitted to Chemistry of Materials.
VI G. Salazar-Alvarez, E. Björkman, C. Lopes, A. Eriksson, S. Svensson and M.

Muhammed, Synthesis and nonlinear light scattering of nanoemulsions and na-
noparticle suspensions,
Submitted to Journal of Materials Chemistry.
x PREFACE
Contributions of the author

I Performing experiments, characterisation of the samples, evaluation of the re-
sults, and writing.
II Planning of experiments, performing experiments, characterisation of the samples,

evaluation of the results, and writing.
III Planning of experiments, characterisation of the samples, evaluation of results,

and writing. HRTEM analysis done by Stockholms University.
IV Design of experiments, characterisation of the samples, evaluation of results,

and writing.
V Planning of experiments, characterisation of the samples, analysis of results,

and writing. DNA purification carried out by Max Planck Institute for Mole-
cular Genetics.
VI Planning of experiments, characterisation of the samples, analysis of results,

and writing of the manuscript. Optical measurements by the Swedish Defence
Research Agency.
Other work not included

1 G. Salazar-Alvarez, A.N. Bautista-Flores, E. Rodrı́guez de San Miguel, M. Mu-
hammed and J. de Gyves, Transport characterisation of a PIM system used for
the extraction of Pb(II) using D2EHPA as carrier.
Journal of Membrane Science, in press.
2 A. Uheida, G. Salazar-Alvarez, E. Björkman and M. Muhammed, The removal

of Co2+ from aqueous solution by γ-Fe2 O3 and Fe3 O4 nanoparticles.
To be submitted to Separation Science and Technology.
3 G. Salazar-Alvarez, J. Nogués, F. Lindberg, R.T. Olsson, U.W. Gedde, M. Mu-

hammed, On the structure and magnetic properties of disordered Cox Fe3−x O4−δ
nanoparticles.
In preparation
4 E. Björkman, G. Salazar-Alvarez and Mamoun Muhammed, Measurement of the

H2 sorption properties of UO2(s) and fuel alloy particles
Project report to Swedish Nuclear Fuel and Waste Management, SKB
Symbols and acronyms
Latin
A Hamaker constant (N·m)
B magnetic flux density (A/m, T, or Oe)
Bhkl full width at half maximum (rad)
C Curie’s constant
CZ molar concentration of species Z(m=mol/dm3 )
D particle size (nm)
E energy (J)
E electrode potential (V)
g gravitational acceleration constant (9.81 m/s2 )
H magnetic field strength (A/m, T or Oe)
HC coercive field strength (A/m, T or Oe)
J exchange energy (J)
k Boltzmann’s constant (1.38 × 10−23 J/K)
k kinetic formation constant
K anisotropy constant (J · m−3 )
m magnetic moment (J/T)
M magnetisation (A · m−1 · kg−1 or emu·cm−3 )
n a number (dimensionless)
R ratio of occupied octahedral and tetrahedral sites
R1 spin-lattice relaxation rate (s−1 )
R2 spin-spin relaxation rate (s−1 )
Re Reynold’s number (dimensionless)
S surface area (m2 )
T1 spin-lattice relaxation time (s)
T2 spin-spin relaxation time (s)
T temperature (K)
V particle volume (m3 )
w size polydispersity (dimensionless)
Z formula units per cell
xi
xii SYMBOLS AND ACRONYMS
Greeks
ζ electrokinetic surface potential or zeta-potential(mV)
θ crystallographic measuring angle (deg or ◦ )
λ wavelength (nm)
µB Bohr magneton (9.274015 × 10−24 J/T)
ρ density (g/cm3 )
σ standard deviation
τ relaxation time (s)
φ phase
χ magnetic susceptibility (dimensionless or emu/Oe·g)
Subscripts
av average
b bulk
bk backward reaction
B Brown
B blocking
C coercive
C Curie
fw forward reaction
H hydrodynamic
i initial
in input
out output
M magnetic
N Néel
P physical
R remanence
s sample
S saturation
SA surface area
T thermal
v volume
X crystallite
Superscripts
◦ measured at standard room temperature and pressure
xiii
Acronyms
AFF anionic ferrofluid
CFF cationic ferrofluid
DSC differential scanning calorimetry
ED electron diffraction
fcc face-centred cubic
fis flow-injection synthesis
HRTEM high resolution transmission electron microscopy or micrograph
IMS immumomagnetic separation
IUPAC International Union of Pure and Applied Chemistry
JCPDS Joint Committee on Powder Diffraction Standards
MRI magnetic resonance imaging
OPL optical power limiting
SAED selected area electron diffraction
SI Système International d’Unités
SPIO small particles of iron oxides
SQUID superconductive quantum interference device magnetometry
SFTR segmented flow tubular reactor
STP standard temperature and pressure (298 K and 0.101 325 MPa)
TEM transmission electron microscopy or micrograph
TEOS tetraethyl orthosilicate
THPC tetrakis(hydroxymethyl)phosphonium chloride
TMAOH tetramethylammonium hydroxide
USPIO ultra-small particles of iron oxides
XRD X-ray diffraction or diffractogram
xiv SYMBOLS AND ACRONYMS
Contents
Preface vii
List of publications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ix
Symbols and acronyms xi
Contents xv
1 Background 1
1.1 Crystal structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.2 Magnetic properties . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.3 Applications of iron oxides . . . . . . . . . . . . . . . . . . . . . . . . 8
1.4 Scope of this work . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
2 Fabrication of iron oxide nanoparticles 15

2.1 Chemical methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
3 Materials and methods 21

3.1 Synthesis of nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . 21
3.2 Characterisation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
3.3 DNA assays . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
4 Results and discussion 31

4.1 Synthesis of various iron oxides . . . . . . . . . . . . . . . . . . . . . 31
4.2 Magnetic characterisation . . . . . . . . . . . . . . . . . . . . . . . . 43
4.3 Applications of magnetic nanoparticles . . . . . . . . . . . . . . . . . 45
5 Conclusions 51
Bibliography 57
xv
One
Background
The iron oxides (generic name for iron oxides, hydroxides, oxyhydroxides, and other
related compounds) have been known for millennia. Such minerals were used origi-
nally as pigments for paints during the Palaeolithic. Much later, they were used in
the magnetic compass when it was invented in China. This was the first application
of magnetic iron oxides, also known as lodestones, used by early navigators to locate
the magnetic ’north’. The most plentiful deposits of these stones were found in the
district of Magnesia in Asia Minor, hence the mineral’s name became magnetite.
Magnetite can be found naturally occurring in molluscs, bees, pigeons, magneto-
tactic bacteria, and algae. The biogenic formation of magnetite crystals in Magne-
tobactericum sp. has received a great deal of attention[Sch99] due the narrow-size
distribution of the crystals (magnetosomes) and their magnetic properties.[PM02]
Synthetically, magnetite can be formed by precipitation in alkaline aqueous me-
dia of a mixture of Fe3+ and Fe2+ , by oxidation of Fe(II) solutions or Fe(OH)2 ,
by interaction of Fe2+ with ferrihydrite, or decomposition of organic precursors,
etc.[CS03, WKC+ 04]
1.1 Crystal structure

Several iron oxides share crystal structure with other minerals. For instance, goe-
thite is isostructural with diaspore (α-AlOOH), haematite with corundum (Al2 O3 ),
and magnetite with spinel (Mg Al2 O4 ). Thus, the denomination spinel ferrites∗ for
the latter case.
The structure of iron oxides is dominated by the arrangement of the oxygen or
hydroxide anions. The cations occupy different positions relative to these layers
of anions. Table 1.1 lists crystallographic information regarding some of the iron
oxides. In the case of spinel ferrites, the oxygens form a fcc sublattice with the
∗
Ferrites are defined as a material composed of Fe3+ ions as the main cationic component. There
are three main families of ferrites: spinel ferrites, garnet ferrites, and hexaferrites. In metallurgy,
the term ferrite has a different meaning.
1
2 CHAPTER 1. BACKGROUND
c
a
c a
Fe+3 Fe
Fe+2.5 O
O-2
(a) (b)
Figure 1.1: Representation of the inverse spinel structure of (a) magnetite and
(b) maghemite.
cations occupying 16 octahedral (B-sites) and 8 tetrahedral positions (A-sites).

Figure 1.1 shows the unit cell corresponding to magnetite and maghemite, typical
inverse spinel ferrites.
Maghemite has basically the same crystal as magnetite. However maghemite can
be considered as an Fe(II)-deficient magnetite with formula (FeIII III
8 )A [Fe40/3 8/3 ]B O32 ,
where represents a vacancy, A indicates tetrahedral positioning and B octahedral.
Table 1.1: Crystallographic information for various iron oxides, from [CS03]. A = Cl− ; 1/2 SO2−
4 , Z is the number of
formula units in the unit cell.
Mineral Chemical Crystallographic Space Unit cell dimensions (nm) Z
Composition system group a b c β◦
Goethite α-Fe O OH Orthorhombic Pnma 0.9956 0.30215 0.4608 4
1.1. CRYSTAL STRUCTURE
Lepidocrocite γ-Fe O OH Orthorhombic Bbmm 0.3071 1.2520 0.3873 4

Akaganéite β-Fe O OH Monoclinic I2/m 1.0560 0.3031 1.0483 90.63 8
Schwertmannite Fe16 O16 (OH)y (SO4 )z · nH2 O Tetragonal P4/m 1.066 0.604
δ-Fe O OH Hexagonal P3ml 0.293 0.449 1
Feroxyhyte δ 0 -Fe O OH Hexagonal P3ml 0.293 0.456 2
High pressure Fe OOH Orthorhombic Pn21 m 0.4932 0.4432 0.2994 2
Ferrihydrite Fe5 O8 · 4H2 O Hexagonal P31c; P3 0.2955 0.937 4
Bernalite Fe OH3 Orthorhombic Immm 0.7544 0.7560 0.7558 8
Fe OH2 Hexagonal P3ml 0.3262 0.4596 1
Haematite α-Fe2 O3 Hexagonal R3̄c 0.5034 1.3752 6
Magnetite Fe3 O4 Cubic Fd3m 0.8396 8
Maghemite γ-Fe2 O3 Cubic P43 32 0.83474 8
-Fe2 O3 Orthorhombic Pna21 0.5095 0.879 0.9437 8
β-Fe2 O3
Wüstite Fe O Cubic Fm3m 0.4302
3
(a) (b) (c) (d)
Figure 1.2: Different orientations of magnetic dipoles: (a) paramagnetic, (b) fer-
romagnetic, (c) antiferromagnetic, and (d) ferrimagnetic.
1.2 Magnetic properties
There are various forms of magnetism that arise depending on how the dipoles
interact with each other. Figure 1.2 shows a schematic representation of the different
types of arrangements of magnetic dipoles.
1.2.1 Paramagnetism
Due to the magnetic field generated by unpaired electrons, atoms may behave as
small magnets under the influence of an external magnetic field. However, when
the applied magnetic field is removed the thermal fluctuations would make the
magnetic moment of the paramagnetic material to move randomly. Under relatively
low magnetic field saturation this effect can be described by Curie’s law:
B
M =C (1.1)
T
where M is the resulting magnetisation, B is the magnetic flux density of the applied
field, T is the absolute temperature, and C is a material-specific Curie constant.
The expected behaviour is that paramagnetic materials would increase their ma-
gnetisation with the applied magnetic field but decrease with the temperature. In
general paramagnetic effects are small and the response of the material to the ma-
gnetic field, i.e., the magnetic susceptibility, χ, is in the order of 10−3 to 10−5 , which
is several orders of magnitude smaller than that of ferromagnetic materials.
Saturation magnetisation,MS , is the point at which all the spins are aligned
with the magnetic field; the coercive field, HC , is the internal magnetic field of
the material; and the remanent magnetisation, MR , is the magnetisation retained
by the material. Figure 1.3 depicts the position of the aforementioned points in a
diagram so-called ’hysteresis loop’.
1.2. MAGNETIC PROPERTIES 5
MS
Mr
χi
HC H
Figure 1.3: Magnetisation (M ) vs. applied field (H) for ferromagnetic (solid line),
paramagnetic (broken line), and diamagnetic materials (dotted line).
HC represents the coercive field of the material, MS the saturation
magnetisation, Mr the remanent magnetisation, and χi the initial
susceptibility.
1.2.2 Ferrimagnetism
In many ionic crystals the exchange energy,∗ J, between the spins of two neigh-
bouring atoms is negative. This occurs due to the fact that the spin of the shared
electron from the metal ions with the oxygen follows Hund’s rule and Pauli’s prin-
ciple. Thus, if the metal ion have an outer shell less than half-occupied all the spins
will be aligned parallel inside the shell and antiparallel with respect to the other
metal ion. This means that antiparallel arrangement is the one that provides with
the lowest energy.
As mentioned earlier, in the case of spinel ferrites, the metal ions in the unit
cell exist in 8 tetrahedral and 16 octahedral positions, where the metal ions are
arranged into two sublattices A and B corresponding to tetrahedral and octahedral
places. Neutron diffraction studies showed that there are two types of spinel fer-
∗
The difference in energy of two electrons in a system with antiparallel and parallel spins is
called the exchange energy.
E1
E0 Jeff
M1 O M2
Figure 1.4: Ground state and excited state of two metal ions, M1 and M2 . The
spin configurations as drawn become intermingled, causing an extra
reduction of ground state energy; this does not occur if M1 and M2
have parallel spins. Adapted from [SW59].
rites: normal and inverse. Studies demonstrated that the normal spinel ferrites are
paramagnetic whereas the inverse spinel ferrites behaved as ferromagnetic. In the
case of normal spinel ferrites, the divalent metal ions are located in the sublattice
A and the iron(III) ions are located in the sublattice B; whereas in the case of in-
verse spinel ferrites one half of the iron(III) ions occupy the sublattice A with the
sublattice B occupied by the other half of iron(III) ions and the divalent metal ions.
In spinel iron oxides, the metallic ions are separated by an oxygen(II) ion and
since the distance between the metallic ions is too large, it was proposed that there
is a superexchange between the metallic ions through the oxygen ion.[Née48, Née52]
Figure 1.4 shows a schematic representation of the superexchange interactions bet-
ween two metal ions through an oxygen.
Half-century ago Louis Néel explained why in the case of inverse spinel ferrites
the metal ions in the sublattice A are antiparallel with respect to the metal ions in
the sublattice B.[Née49] The net magnetic moment of the material is the difference
in magnetic moments of sublattices A and B, which explained why the magnetic
moment per formula unit was lower than the otherwise expected value. Thus, the
higher the magnetic moment of the divalent cation, the higher the magnetisation.∗
For instance, manganese ferrite having Mn(II) with 5 unpaired electrons, i.e., 5 µB
has a larger saturation magnetisation than that of nickel ferrite which is 2 µB .
∗
This rule does not apply for compositions containing both paramagnetic ions and diamagnetic
ions.
1.2. MAGNETIC PROPERTIES 7
1.2.3 Superparamagnetism
Superparamagnetic relaxation[BL59] can be explained using spherical particles –
with uniaxial anisotropy– as a model system. If we consider spherical particles, the
magnetic anisotropy can be approximated to be proportional to the particle volume,
V . The energy barrier that separates easy magnetisation axes is the magnetic
anisotropy energy, Kv V , with Kv as the volume anisotropy constant. For a small
particle, the particle volume (size) is small and the magnetic energy Kv V may
become comparable to (or lower than) the thermal energy (see Eq. (1.2)). Thus,
the magnetic moment of the particle may fluctuate behaving as a paramagnetic
atom but with a total magnetic moment that can be up to 1000 times larger than
that of a single atom. Hence the term superparamagnetism.
Kv V ≤ 25kT (1.2)
Nevertheless, the moments of the particles follow a Boltzmann distribution when
subjected to external applied magnetic field and thermal equilibrium. The orien-
tation of the magnetic moment of the (non-interacting) paramagnetic particles can
then be described by the Langevin function given by Eq. (1.3).[AK22]

1 mH
mav = m coth α − ; α= (1.3)
α kT
where H is the applied magnetic field, k is Boltzmann constant, T is the absolute
temperature, and m is the magnetic moment.
Beside the dependence of the magnetisation on the particle size and composition,
the magnetic properties depend greatly on the temperature. From Eq. (1.2) it is
possible to obtain a critical temperature defined as the blocking temperature, TB ,
above which ferro- or ferrimagnetic particle will behave as superparamagnetic (Eq.
(1.4)).
Kv V
TB = (1.4)
25k
1.2.3.1 Magnetic relaxation
Considering particles under the influence of an external magnetic field, it can be

shown that when the applied magnetic field is removed the magnetisation of the
particles is reversed. There are two main mechanisms for the magnetisation reversal:
spin rotation or particle rotation, which describe whether the change in direction of
the magnetic moment of the particle is due to the reversal of the magnetic spin of
the particle or the actual physical rotation of the particle.
The time required for the reversal of the magnetic moment of the particle (spin
rotation) is related to the magnetic anisotropy of the material, Néel relaxation time,
τN . The mathematical expression of Néel relaxation time is shown by Eq. (1.5).

Kv VM
τN = τ0 exp ; τ0 ∼ 10−9 s (1.5)
kT
The characteristic time for the randomisation of the magnetisation due mainly to
the thermal motion of the particle is known as Brown relaxation time, τB , expressed
by Eq. (1.6).
3VH η
τB = (1.6)
kT
For a superparamagnetic material τN τB , which means that the magnetisation
reversal occurs by rotation of the magnetic axis. Alternatively, when the magnetic
moment of the particle is locked to a given crystallographic direction (easy axis),
the particle is thermally blocked and τB τN .
Previously it was mentioned that, under certain circumstances of particle size
and temperature, ferro- or ferrimagnetic particles may be considered superparama-
gnetic (see Eq. (1.2) and (1.4)). The criterion of superparamagetism is regularly
assumed considering particles with a relaxation time lower than 100 s.
The experimental techniques used for the measurement of magnetic properties
have different measuring times and thus a particle may appear as superparamagne-
tic using a slow technique such as SQUID or VSM (characteristic measuring time
tens of seconds) whereas when measured with a fast technique such as Mössbauer
spectroscopy (characteristic measuring time 10−7 s), it may appear as ferri- or ferro-
magnetic. In the case of Fe3 O4 with an anisotropy constant, Kv = 4.4 · 104 J · m−3 ,
the critical superparamagnetic particle size at room temperature, T = 290 K, is
between 9 and 17 nm.
1.3 Applications of iron oxides

In the recent years there has been an increased interest in the application of nano-
technology to biotechnology.[WH00] Thus, a number of different uses of nanoobjects
has been investigated. In the case of iron oxide-based materials, the focus has been
on separations and diagnostics,[WKJ83, Shi02] DNA analysis,[Uhl89] and recently,
on the use of iron oxides as contrast enhancers for magnetic resonance imaging
(MRI)[JLJ+ 88, SWE+ 88], among others.
1.3.1 Biomedical applications

1.3.1.1 Cell separations
Micrometre-sized magnetic particles have been used as commercial applications in

biology, biomedicine and biotechnology for the separation of cells. The separation
of cells, or immumomagnetic separation (IMS), is achieved by covalently binding
1.3. APPLICATIONS OF IRON OXIDES 9
magnetic nanoparticles –or magnetised beads∗ – to the cells. The bead carrying a
specific antibody -usually monoclonal antibodies- on the surface binds selectively
the target cell which can then be removed from the suspension with the help of a
magnet.
The IMS has been used for the purging and isolation of cancer cells, studies
of HIV and AIDS, isolation of granulocytes, isolation of cells from various tissues,
stem cells, etc.[PBMPS97]
1.3.1.2 DNA analysis

The separation and purification of nucleic acids has become more and more impor-
tant for the accurate mapping of the genome. Nucleic acids are usually extracted
from other cell components after cytolysis and repetitive washing procedures. The
use of superparamagnetic particles for the analysis of plasmids and nucleic acids
was introduced nearly 20 years ago by Uhlén et al.[SHO+ 88]
Separation and purification of DNA with magnetisable microspheres (with a ty-
pical size range of 200–2000 nm) has been reported by numerous groups.[SHO+ 88,
Uhl89, HOMRS94, DTSB98] The DNA molecule is able to wrap around nanoob-
jects in a similar way it does around the histone core in the nucleosomes.[LMR+ 97]
This finding indicates that DNA purification can be achieved even with simple non-
functionalised nanoparticles such as silica nanoparticles. However, to improve the
efficiency and selectivity of the process the surface of the particles is functiona-
lised with specific molecules, e.g. streptavidin, which can bind non-covalently to
biotinylated-DNA.[SHO+ 88]
1.3.1.3 MRI contrast agents

Magnetic resonance imaging (MRI) is based on the nuclear magnetic resonance of
protons in the molecules, mainly water, that exist in a given tissue. Since the local
environment of a given tissue varies depends on its position in the body it is possible
to use MRI to identify various types of tissues. The characteristic measure in MRI
is the proton relaxation rate or its inverse, the proton relaxation time, R1 ≡ 1/T1
and R2 ≡ 1/T2 .
In this technique there are two different types of proton relaxation times: the
longitudinal relaxation time, T1 , (spin-lattice relaxation) and the transverse relaxa-
tion time, T2 (spin-spin relaxation). Hence, there are two types of contrast agents:
positive agents, which act on T1 providing a positive enhancement of the signal,
appearing bright on the MRI scan; and the negative agents, which reduce the signal
and give a negative enhancement, appearing as dark spots in the scan.[Pro22]
Typical positive contrast agents are paramagnetic compounds based on rare
earth ions, typically gadolinium-containing chelates. Nevertheless, other alterna-
∗
Beads is the term hereby used for particles or group of particles dispersed in an inorganic or
organic matrix in a second step after the synthesis of the particle. The beads usually have a size
from 100 nm to several micrometres and spheroidal shape.
tives are sought after due to the high toxicity of the heavy metals and the low
contrast enhancement. However, negative contrast enhancers (T2 agents) as iron
oxide nanoparticles have been used due to a much higher magnetisation per concen-
tration unit,[JLJ+ 88, SWE+ 88] reported to be at least one order of magnitude
higher than gadolinium-containing molecules.[Bjø02] For a more complete survey
of the relaxation effects induced by superparamagnetic particles refer to Roch et
al.[RMG99]
Passive targeting Insofar there have been two different types of superparama-
gnetic contrast agents based on iron oxides that are clinically approved: the small
particles of iron oxides (SPIO, 40 < DH < 200 nm) and the ultra-small particles
or iron oxide (USPIO, DH < 40 nm). Due to their large size, the SPIO agents
are rapidly cleared (several minutes) from blood by the reticuloendothelial system
organs such as liver and spleen, thus enabling the imaging of lesions in such organs.
On the other hand, the smaller USPIO agents have longer residence times (hours),
allowing for imaging of the lymphatic system.[MVGD04] Furthermore, it has been
reported that the use of USPIO permits imaging for more than 24 h, and sometimes
as long as five days.[NVB+ 04] USPIO have lower T1 /T2 ratio than SPIO, which leads
to a higher contrast on T2 -weighted images and enables the use of relatively weak
magnetic fields (< 0.5 T).[KFG+ 99]
Active targeting The surface of USPIO and SPIO agents is functionalised with
specific biomolecules to actively target certain tissues to be visualised by MRI tech-
nique. Several attempts have been performed to improve their surface properties,
e.g. coating with different types of biocompatible materials, such as protein, po-
lysaccharide, DNA fragments, etc.[MKCB+ 04, PST+ 04, ICB+ 01] A schematic re-
presentation of the degree of functionalisation required for such particles is given
by Fig. 1.5. The visualisation of certain organs needs special functional proper-
ties of coating layer.[AMOB03] Thus, for instance, Kim et al. reported the use of
polysaccharide-coated superparamagnetic iron oxide nanoparticles (SPION) for the
MR imaging of brain tissue.[KZK+ 01, Kim02]. Also, in case of lesions detection in
the brain, e.g., multiple sclerosis, Alzheimer’s disease, etc.; The MRI contrast agent
has to pass across the blood brain barrier (BBB).[RPB+ 03, PWC+ 02] However,
there are limited reports on the penetration of the BBB by nanoparticles.[NH02]
Moreover, after passing the BBB those agents have to be recognised and up-taken
by cells. Receptor mediated endocytosis has been proposed as possible way to intro-
duce contrast agent in vivo and several studies have been performed where various
types of cells were labelled by SPIO and further visualised by MRI.[AFHH+ 03]
1.3. APPLICATIONS OF IRON OXIDES 11
Figure 1.5: Representation of functional nanoparticles with a protective coating

layer enhanced with specific ligands.
1.3.2 Other technological applications

1.3.2.1 Optical power limiting agents
Advances in the development new communication methods and new sources of ra-
diation, particularly optical power sources such as lasers, had resulted in research
oriented towards the protection from exposure to such sources. In this context,
the development of optical power limiting (OPL) has been focused on the design
of novel materials having nonlinear optical phenomena upon irradiation with high
energy sources.[Hol99] Figure 1.6 shows linear and nonlinear optical phenomena as
well as the clamping level that can be achieved with a nonlinear mechanism. The
clamping level demonstrates that a very pronounced optical limiting can be achieved
even at high energy fluences. Among the processes that produce optical limiting are
two-photon absorption, reverse saturable absorption, nonlinear scattering, nonlinear
beam fanning, beam steering, photochroism, etc.[PHJ+ 99]
Several types of laser blocking compounds and being extensively studied for pro-
tection from laser radiation, including liquid crystals,[UCS86, THD+ 97, KWG+ 98]
dyes,[WHS+ 92, MRL98] and suspensions of carbon nanotubes,[VAR+ 99, LZQ+ 03]
fullerenes[NW95, BS02] and different nanoparticles.[MSS92, JBHF98]
1.3.2.2 Ferrofluids
Ferrofluids are made of ferro- or ferrimagnetic single-domain particles suspended in

a continuous medium with no long-range order between the particles. Some appli-
cation areas of ferrofluids are: sealing, vibration damping, heat transfer, bearing,
sensing/detection, etc.[RM90]
E out
linear absorption
clamping level
nonlinear absorption
E in
Figure 1.6: OPL curves: the solid line represents the linear limiting mechanism
whereas the broken line shows the nonlinear mechanism. The dotted
line shows the possible clamping level that can be achieved.
There are certain stability requirements for the preparation of ferrofluids.[Ros85]

These are influence by the thermal energy ET = kT , the magnetic energy EM =
µ0 M HV , and the gravitational energy EG = δρV gDP . It is then possible to es-
tablish dimensionless relationships that provide information on the stability of a
ferrofluid under the influence of a particular field. The maximum particle size that
would be stable against settling under the influence of a small hand-held magnet
can be determined by Eq. (1.7)
ET kT
= ≥1 (1.7)
EM µ0 M HV
Rearrangin Eq. (1.7) for the particle diameter DP = (6V /π)1/3 and assuming that
H = 8 × 10−4 A/m, M = 4.46 × 105 A/m, and T = 298 K, gives a DP ∼ 8
nm. At room temperature the normal gravitational field have little influence on the
stability of a ferrofluid. Also, the attractive van der Waals forces must be taken
into consideration. These fluctuating dipole-dipole interactions are always present
and are of great importance in neutral particles.
1.4 Scope of this work

This work is concerned with the synthesis of iron oxide nanoparticles with inverse
spinel structure using different chemical methods with controlled particle size, par-
ticle size distribution, composition, and morphology. The surface modification of
the particles was undertaken with different inorganic materials, namely silica and
gold. Also, the particles were investigated to evaluate their application for the pu-
rification of DNA, as a contrast agent for magnetic resonance imaging, and as novel
optical power limiting agents.
1.4. SCOPE OF THIS WORK 13
Papers I and II deal with the use of a novel method for the synthesis of these
particles by flow-injection technique for the manufacturing of iron oxide nanopar-
ticles in the size range of 1-10 nm with a narrow size distribution. In this study we
investigate the hydrodynamic effects of different mixing schemes on the preparation
of magnetite nanoparticles, as well as the factors influencing the size distribution of
the synthesised particles.
Papers III and IV are related to studies on the synthesis of cobalt ferrite par-
ticles. These papers present a detailed study of the effect of the chemical synthesis
parameters (concentration and concentration ratios, temperature, digestion time
and addition rate) on the particle characteristics: composition, particle sizes, par-
ticle size distribution, crystal structure, degree of crystallinity and morphology.
The studies on the application of iron oxide nanoparticles are presented in pa-
pers V and VI. In paper V, the work is focused on the preparation of magnetic
nanoparticles of magnetite (Fe3 O4 ) and maghemite (γ-Fe2 O3 ) with high saturation
magnetisation, their coating with silica and their application in the magnetic pu-
rification of DNA. The suspensions of particles were characterised with traditional
vibrating sample magnetometry and the novel nuclear magnetic relaxation. Finally,
paper VI is concerned with studies on the effectiveness of nanoemulsions and sus-
pensions of pristine and silica-coated iron oxide nanoparticles as novel optical power
limiting agents against laser radiation.
Two
Fabrication of iron oxide nanoparticles
2.1 Chemical methods

In the last decade, the chemical methods of preparation of nanoparticles have
been used for the fabrication of several types of nanoparticles where a greater
control on the size, composition, etc., could be achieved. Iron oxide nanopar-
ticles have been prepared by a variety of methods[WKC+ 04] including sonoche-
mical reactions,[SKG+ 97] mechanochemical synthesis,[JZRM95] hydrolysis[KKA96,
SSI98] and thermolysis[HCP+ 02] of precursors, polymeric matrices,[CGLQRR97,
HY02] and co-precipitation in bulk,[TM82, PK89] flow injection synthesis,[SAMZ04]
and in the confined zones of microemulsions.[MP96]
The previous methods were used to prepare particles with homogeneous com-
position and narrow size distribution. However, the co-precipitation method in
bulk has shown to be an economic and versatile technique used to synthesise large
amounts of materials with different compositions and particle sizes.[Mat98] It has
been found that the particles obtained in batch operation of the co-precipitation
method have a broad size distribution and therefore a higher control of the synthesis
conditions are required.
2.1.1 Synthesis of magnetite and maghemite

Magnetite can be formed by the addition of alkali solution to an aqueous so-
lution containing Fe3+ and Fe2+ in a molar ratio of 2, which leads to the for-
mation of green rust complexes and thence to a dark red complex with formula
2+
FeII FeIII
2 Ox (OH)2(3−x) · xH2 O from which magnetite particles precipitates.[CS03]
Also, it has been suggested that the formation of magnetite involves the interac-
tion of Fe2+ with precipitated ferrihydrite. In all cases the solubility product of
magnetite has to be exceeded to be able to precipitate.
The hydrolysis of iron(III) species proceeds through the formation of low mole-
cular weight species (Eq. (2.1)) and that above OH/Fe ∼ 1 these species interact
to produce polynuclear species (Eq. (2.2)).
15
16 CHAPTER 2. FABRICATION OF IRON OXIDE NANOPARTICLES
Fe3+ + H2 O Fe OH2+ + H+ (2.1a)

Fe OH 2+
+ H2 O Fe(OH)+
2 +H +
(2.1b)
kf w
2Fe OH2+ )
−−
−− Fe2 (OH)4+
* 2 (2.2)
kbk
The formation of the dimer is a fast reaction with a kf w = 630 m/s whereas
the dissolution is very slow in the absence of protons, which suggest that further
polymerisation may be very fast.[CS03]
In the particular case of the spinel ferrites, the formation of magnetite, for
instance, can be considered to proceed according to the overall reaction expressed
by Eq. (2.3).
Fe2+ + 2Fe3+ + 8OH− → Fe3 O4 + 4H2 O (2.3)

whereas maghemite is formed primarily by the topotactic∗ oxidation of magnetite
(Eq. (2.4)). The oxidation of synthetic magnetite to maghemite occurs via the
formation of a solid solution of γ-Fe2 O3 in Fe3 O4 [CGLS65, GFM68] with the ca-
tions migrating to the surface and layers of oxygen being added to the structure to
preserve the crystal structure.[GFM68]
   
 2H2 O2   2H2 O 
4Fe3 O4 + 2H2 S O4 → 6γ − Fe2 O3 + 2H2 SO3 (2.4)
O2 −
   
From Eq. (2.3) it is clearly seen that in order to obtain Fe3 O4 the spontaneous
oxidation of Fe2+ (E◦Fe3+ /Fe2+ = 0.77 V) by O2 (E◦O2 /H2 O = 1.23 V) has to be
prevented. Otherwise, the most common by-products of the hydrolysis of Fe3+ , i.e.,
goethite and haematite, are formed.
Fe3+ + 3OH− → α − Fe OOH + H2 O(at around 25 ◦ C) (2.5a)

3+ − ◦ C)
2Fe + 6OH → α − Fe2 O3 + 3H2 O(at around 100 (2.5b)
It has been reported that the end product of the oxidation (STP and below 600
◦ C) of small crystals (< 3000 Å) of pure magnetite is γ-Fe2 O3 , whereas the end
product of the oxidation of large crystals (> 3000 Å) is α-Fe2 O3 .[FG70] Neverthe-
less, it has been also reported that samples of magnetite containing impurities of
α-Fe2 O3 transforms completely into haematite via epitaxial growth† on the [111]
∗
A topotactic transformation is characterised by internal atomic displacements, which may
include either loss or gain of material, so that the initial and final lattices are in coherence.
†
Epitaxial growth is the growth of crystals of one mineral on the crystal face of another mineral,
such that the crystalline substrates of both minerals have the same structural orientation.
2.1. CHEMICAL METHODS 17
Figure 2.1: Schematic representations of reverse micelles and nanoemulsions (a)

o/w nanoemulsion, (b) w/o nanoemulsion, (c) bi-continuous disper-
sion, (d) isolated and aggregated o/w dispersion, and (e) isolated and
aggregated w/o dispersion.
faces of the spinel crystal whereas large crystals form nuclei of α-Fe2 O3 , and that
it is the formation of nuclei what determines the behaviour of the particles when
exposed to oxygen.[CFG+ 68]
2.1.2 Confined-zone processing

The fabrication of nanoparticles with a given composition and structure requires a
high degree of control on the reproducibility of the synthetic procedures. Some of
the known problems are an uncontrolled mixing, low production (small units), lack
of control of the residence time, etc.
Zone confinement has been used to produce monodispersed particles, i.e., par-
ticles with very narrow size distributions, and to tailor the particle’s morphology.
One of the techniques applied recently, is the confinement of the reaction to ca-
vities with pre-defined size and shape, so-called templating, e.g., synthesis of par-
ticles in micro-emulsions,[OKC+ 01, MP96, PP97] sol-gel porous matrices,[MZM+ 02]
aerogels,[CRM+ 02] ion exchange resins,[SFIB01, ZGW+ 92] and in cellulose.[SFIB01]
2.1.2.1 Synthesis in nanoemulsions
Emulsions consist of two (or more) immiscible liquids, such as oil (organic solvent)
and water (aqueous solution), in which a discontinuous phase is formed as fine
droplets dispersed in a continuous phase. The dispersion is achieved by mechanical
mixing to produce turbid, thermodynamically unstable solution, where the droplet
size of the dispersed phase is in the order of 1 – 50 µm.
18 CHAPTER 2. FABRICATION OF IRON OXIDE NANOPARTICLES
The addition of a surfactant with a suitable concentration stabilises the emulsion

as it reduces the interfacial tension thus producing thermodynamically stable and
transparent solutions, known as microemulsions. The droplet size in microemulsion
systems is generally below 150 nm and therefore transparent to visible light. Na-
noemulsion is actually an updated term of microemulsion as its dimension of the
droplets is limited to the nanometre scale.
The formation of the dispersed phase in an oil-surfactant-water (o/s/w) na-
noemulsion system can be controlled at will; i.e. to form oil-in-water (o/w) or
water-in-oil (w/o) nanoemulsions (see Figure 2.1). The oil and water phases often
contain several dissolved components and therefore the selection of the surfactant
(and co-surfactant) employed depends on the physicochemical characteristics of the
system. Thus, a nanoemulsion requires to be designed for specific solutes in either
the organic or aqueous phases by selecting an appropriate polar head (hydrophilic-
lipophilic balance). Several types of surfactants as cationic, anionic, or non-ionic
can be used.
The specific composition of a nanoemulsion can be determined according to a
ternary phase diagram of the o/s/w system. Therefore, it is essential to determine
such phase diagrams for different organic solvents (oils) and surfactants, which
determine the structures and properties of a nanoemulsion to be concerned.
2.1.2.2 Concept of flowing confined-zone synthesis
The flow-injection synthesis (fis) technique consists of continuous or periodic mi-

croinjection of reactants into a carrier solution. The fis technique takes advantage
of the flow-injection systems introduced by Růžička and Hansen[RH82, RH00] and
have such characteristics[VdC84]:
– Injection of reactant directly into the carrier stream, achieving always condi-
tions of laminar flow (Reynolds number, Re 2000) which provides with
high mixing homogeneity.
– Possibility of segmenting the flow with inert fluids, thus providing the system
with pool zones confined to volumes of few microlitres.
– Control over the dispersion of the injected reactants by manipulation over the
geometric and hydrodynamic conditions of the system.
– High degree of automation by including a computerised detector in the mani-
fold array.
– High reproducibility in injection volumes and residence times.
The fis integrates several components, such as the injection system, the propul-
sion unit, the capillary reactor, and the detector or container. The injection system
consists, generally, of a T-shaped injector where the reactants mix head-on with
high precision in time and volume. The injector can be replaced by a computer-
controlled manifold that enables the system with segmentation capabilities. The
injection system can be tailored so as to provide the chemical reaction with the
2.1. CHEMICAL METHODS 19
required limitations such as inert atmosphere, temperature control, etc. The pro-
pulsion unit comprehends the reactant, carrier, inert media solutions, and a mean
for the transportation of sample such as a peristaltic pump. The capillary reactor
consists of a capillary system where the solutions are injected and where the reac-
tion takes place. The residence time of the reactants and products in the reactor
which is the extent of the reaction, is controlled by the length of the capillary and
the pumping rate of the solutions. The fis capillary reactor is constructed of Teflon
tubing and has an internal diameter of 0.1 to 1 mm and a varied length so as to
provide reaction pools of few microlitres without the need of using microsystems
technology.
One of the main characteristics of the system, along with the reduced volumes
is that the reaction point can be adjusted. For a continuous injection where the
carrier participates as reactant, the reaction takes place at the point of mixing, i.e,
the injection point, which as opposite to the earlier reported[JDB+ 03] segmented-
flow tubular reactor (SFTR) where the reaction takes place in a micromixer outside
of the capillary system. In both cases the reaction evolves under laminar flow
conditions, whose advantages in mixing have been recently reported.[HBBR03] The
fis methodology can be used for the production of nanosized materials, whereas
the SFTR has been applied to the synthesis of micron-sized ceramic powders.
Three
Materials and methods
3.1 Synthesis of nanoparticles

Two different approaches were used for the synthesis of the magnetic nanoparticles:
bulk solution and confined-zone processing. The bulk solution processing was car-
ried out in a stirred batch reactor with volumes of 100 to 1000 cm3 . The pH,
temperature and stirring sped were carefully adjusted to minimise variations throu-
ghout the reaction time. In the second method, the reaction was carried out in
confined zones provided by nanoemulsions and our earlier developed method of flow
injection synthesis with constant hydrodynamic conditions.[WM99]
3.1.1 Batch synthesis in stirred reactor

3.1.1.1 Synthesis of Fe3 O4 and γ − Fe2 O3
Iron(II) and iron(III) chlorides (CFe(III) /CFe(II) = 2) were dissolved under argon at-
mosphere in a deoxygenated aqueous solution of HCl 0.2 m to a total iron concen-
tration of 1.5 m(iron source solution).
The iron source solution was added to a deoxygenated aqueous solution of
N H4 OH at 70 ◦ C under mechanical stirring. The reaction was allowed to pro-
ceed for 45 min under an atmosphere of argon followed by decantation using a
magnet to retain the black gel containing the magnetite nanoparticles.
Magnetite particles were obtained by washing the gel several times with deoxyge-
nated water, adjusting the pH to neutral, and drying it under vacuum. Maghemite
particles were obtained by washing the gel several times with an aqueous solution
of H N O3 0.2 m and finally drying the particles in air.
3.1.1.2 Synthesis of Nix Fe3−x O4

An aqueous solution of nickel(II) chloride was mixed with a freshly prepared aqueous
solution of iron(II) chloride. The metal solution was then added to an ammonium
hydroxide solution under vigorous mechanical stirring. The pH of the reaction was
21
22 CHAPTER 3. MATERIALS AND METHODS
kept at 11.5-12.5 with additions of ammonium hydroxide solution and the reaction
was allowed to proceed 20 min after a dark colouration appeared. The gel was then
washed several times with water and dried.
3.1.1.3 Synthesis of Cox Fe3−x O4

An aqueous solution containing iron(II) sulfate and cobalt(II) chloride (CFe2+ /CCo2+ =
2) was heated up to 90 ◦ C and added to an aqueous solution of sodium hydroxide and
potassium nitrate under mechanical stirring. The total mass balance in the finally
mixed system was constant. The potassium nitrate was used as a mild oxidation
agent in order to oxidise ferrous ions to ferric ions.[TM82] During all experiments
the concentration ratio of nitrates to iron(II) was kept constant and equal to 0,66.
A black precipitate was formed after mixing of the two solutions. The reaction
mixture was allowed to proceed for a given period of time, after which the superna-
tant was decanted by sedimenting the particles using a magnet. The particles were
washed with water, dried, and milled manually.
3.1.1.4 Controlled stirred batch reactor

In order to exert higher degree of control over the synthesis conditions, a fully-
automated computer-controlled batch reactor was constructed. The reactor has a
production capacity of ca. 40 g per batch of iron oxide. Among the controllable
conditions are pH, temperature, stirring speed, and rate of addition of reactants.
As schematically depicted in Figure 3.1, the reactor consists of iron source solu-
tions that are pumped to the reaction vessel by peristaltic pumps, whose speed is
controlled by the main computer. With a computerised pH meter in the reaction
vessel the addition of acidic or basic solutions are regulated as to keep a constant pH
throughout the synthesis with a σ = 0.1 pH units. The feedback obtained from the
temperature probe provides information used to regulate the synthesis temperature
within 1 ◦ C variation.
3.1.2 Synthesis in confined zones

3.1.2.1 Synthesis of iron oxides by Flow Injection
The design of the flow injection system is described elsewhere.[WM99] The home-
built system included a multi-channel peristaltic pump (Gilson Minipuls 2, France),
0.5 mm Teflon tubing lines, and a T-shaped connector or a manifold injector. The
valve of a Flow Injection Analysis apparatus Fia05 (Biofak, Sweden) was used as the
manifold valve gave periodic and reproducible microinjections when controlled by a
computer system. The Reynolds number was calculated for the different manifold
configurations and flow rates and it was always below 200, indicating that conditions
of laminar flow were always attained.
Typically, an acidic solution of iron with an Fe3+ : Fe2+ ratio of 2 was mixed with
a stream of Na OH . The synthesis temperature was controlled with a thermostat
3.1. SYNTHESIS OF NANOPARTICLES 23
Figure 3.1: Schematic representation of the automated batch reactor and its per-
ipheral components.
and set to 80 ◦ C. The particles were then collected into a separation vessel where an
external magnet was used to collect the product that was later washed thoroughly.
Samples were dried in air and under vacuum.
3.1.2.2 Synthesis of iron oxides in nanoemulsions
Nanoemulsions composed of reverse micelles were used for the synthesis of iron oxide
nanoparticles. The nanoemulsion system consisted of AOT-BuOH/cHex/H2 O with
a molar ratio of surfactant to water of 2,85 and a surfactant to co-surfactant molar
ratio of 1. A sequential synthetic procedure was used in order to prepare the nano-
particles. One nanoemulsion containing the iron source and another containing a
solution of sodium hydroxide, were mixed to form the magnetite nanoparticles. The
nanoemulsion was lysed with acetone to remove the particles from the surfactant
and washed several times with ethanol.
3.1.3 Surface modification of nanoparticles

3.1.3.1 Preparation of ferrofluids
Cationic and anionic ferrofluids were prepared modifying the procedures described
by Massart.[Mas81] Briefly, the black gel obtained from the synthesis of the particles
was peptised with nitric acid solution at pH=2, followed by rinsing with degassed
water, the last step was repeated four times. A cationic ferrofluid (CFF), consisting
mainly of maghemite, was obtained by rinsing one more time the gel with HNO3
solution, whereas an anionic ferrofluid (AFF) consisting mainly of magnetite was
prepared by rinsing the gel with a TMAOH solution. Finally, the ferrofluids were
dialysed against the respective acidic or alkaline solution for 24 h refreshing the
solutions every 8 h. This procedure would yield stable ferrofluids with a wide
concentration range, from 1 mg/cm3 to 40 mg/cm3 .
3.1.3.2 Silica coating of particles

Materials Besides the reagents already reported for the preparation of iron oxide,
other chemicals used are tetraethyl orthosilicate (TEOS, 99%, Aldrich) and sodium
trisilicate (27% Si O2 in 14% Na OH, Aldrich).
Procedure Iron oxide particles from solutions AFF and CFF were coated∗ with
a dense silica layer. A solution of sodium trisilicate was passed through an cationic
exchange and the pH of the eluate was kept at 9. The thickness of the silica shell
was varied by mixing the acidified silicate solution with the AFF or CFF at different
silica/iron oxide ratios ranging from 0.05 to 5.4.
To further increase the thickness of the coating shell, the silica layer on the par-
ticles was grown using the Stöber method. [SFB68] Ammonia and various amounts
of TEOS were dissolved in pure ethanol, to which a suspension of particles was
added, the vessel was capped and shaken for 24 h. The suspension was neutrali-
sed with a H Cl solution, dialysed against water and concentrated by evaporation.
Multi-particle beads were prepared by varying the initial mass ratio of iron oxide
to sodium trisilicate and growing the shell with the Stöber method. To check the
quality of the silica coating, the coated particles were added to a 0.1 m HCl solution
and the iron concentration which could eventually be leached was measured after
one day.
3.1.3.3 Gold coating of particles

Materials Besides the reagents already reported for the preparation of iron oxide,
other chemicals used are hydroxylamine (NH2 OH, 98%, Aldrich), tetrakis(hydr-
oxymethyl)phosphonium chloride (THPC, 80% in water, Aldrich) and gold pellets
(99.9999%).
∗
A coated nanoparticle is defined as a fully surrounded particle by a well defined close layer of
another material.
3.2. CHARACTERISATION 25
Procedure Iron oxide nanoparticles were prepared by dissolving iron(III) chloride

and iron(II) sulfate with a molar ratio of CFe3+ /CFe2+ = 2 in a deoxygenated aqueous
solution containing 0.1 m H Cl . The iron source solution was added to an aqueous
solution of Na OH . The reaction was allowed to proceed for 1.5 h at 80 ◦ C under
mechanical stirring. The gel containing the particles was rinsed with deoxygenated
water several times and collected with a magnet.
2.5 cm3 of a suspension of the iron oxide nanoparticles with a concentration
of about 20 mg/cm3 were diluted to 100 cm3 with water. To this, 50 cm3 of 1.87
mm N H2 OH ·H Cl were added under mechanical stirring. The pH after the addition
of hydroxylamine was around 11. After 10 min 100 cm3 of a solution containing
0.44 µm Au(OH)3 was added.∗ The colour of the solution turned from dark brown
to dark purple after 10-20 min and the reaction was allowed to proceed for 40 more
min. After the last step the particles were rinsed with water several times.
3.2 Characterisation
3.2.1 Crystal structure
Phase identification of the precipitated powders was performed by comparing X-ray
powder diffraction (XRD) data obtained with a PW 1830 diffractometer (Philips,
λ = 0.154021 nm) against the JCPDS standards database. The obtained spec-
tra were corrected for instrumental line broadening and refined with the program
celref.[LB22]
3.2.2 Electron microscopy

Particle imaging was undertaken with a JEM-2000EX (JEOL) transmission electron
microscope operating at an accelerating voltage of 200 kV. Specimens were dispersed
in ethanol under sonication and deposited onto 200 mesh carbon-coated copper grids
(Agar Scientific). The excess of solvent was blown-dried with a gentle stream of N2 .
High resolution images and single-particle electron diffraction patterns were ac-
quired with a JEM-3010 (JEOL) high resolution transmission electron microscope
operating at an accelerating voltage of 400 kV using a camera distance of 1 m. Speci-
mens were dispersed in butanol under sonication and deposited onto carbon-coated
grids. The excess of solvent was evaporated with light irradiation.
3.2.3 Surface characterisation

3.2.3.1 ζ-potential
The electrokinetic surface potential of the particles was determined by measuring
the electrokinetic sonic amplitude (ESA) with a ESA-9800 (Matec Sciences).
∗
The Au(OH)3 solution was prepared by adding 2.49 g of K2 C O3 to 1 dm3 of an aqueous
solution containing 0.44 µm Au3+
3.2.3.2 Surface area
Specific surface area (SSA ) of the powders was determined by measuring the nitrogen
desorption using the BET method in a Flowsorb II 2300 (Micromeritics).
3.2.4 Magnetic characterisation
3.2.4.1 Vibrating Sample Magnetometry
The principle of VSM is the measurement of the electromotive force induced by

a ferromagnetic sample when it is vibrating at a constant frequency, under the
presence of a static and uniform magnetic field. Magnetic characterisation of the
materials was undertaken by analysing approximately 40 mg of powder in fields up
to 11 kOe at a vibration frequency of 67 Hz. The magnetic field error was estimated
to be 2 Oe.
The measurements were carried out at room temperature in an Oxford Instru-
ments 1.2 VSM, at the Laboratori de Propietats Magnètiques i tèrmiques of the
Universitat Autònoma de Barcelona.
The powders were weighted, pressed into a small quartz container and finally
mounted at the end of a rigid ceramic rod. To avoid the movement of the powders
inside the tube they were compacted using quartz wool. To get optimum signal the
samples are previously centred in angle and height, applying a field of 2 kOe. Sub-
sequently they are demagnetised using a sequence of alternating decreasing fields.
The VSM was calibrated in magnetic moment and sample temperature. The
magnetic moment calibration was carried out using a Ni standard (sphere) with
known saturation magnetization (MS = 54.4 emu/g). The temperature calibration
was performed using ferromagnetic alumel and Ni standards, with Curie tempera-
tures of 438 and 627 K, respectively.
3.2.4.2 Mössbauer spectroscopy
The Mössbauer effect is based on the absorption of γ-radiation by 57 Fe . The source

are 57 Co atoms in a matrix of Rh. The 57 Co nuclei decay to 57 Fe in the excited state
with spin 5/2 (half-life time approx 10−9 s) and these transform fast to the state
3/2 (half-life time approx 10−7 s) and then to the state 1/2. The radiation emitted
during this last step is the one that allows for the excitation of the 57 Fe atoms
present in the sample. The abundance of 57 Fe is 2.2 %, which permits an efficient
and statistically large enough population of atoms for a quantitative measurement.
Mössbauer spectra for different samples were recorded at room temperature
using a source of 57 Co atoms in a matrix of Rh. The working speed range was from
-8 mm/s to 8 mm/s. A thin foil of α − Fe was used as standard to determine the
baseline of the speed.
3.2. CHARACTERISATION 27
a b
DP
DH
c d
DM DX
Figure 3.2: Schematic representation of particle sizes as determined with various

techniques.
3.2.5 Thermal analysis

Thermochemical analysis of the produced particles was performed with a differential
scanning calorimeter DSC 2920 (TA Instruments). Measurements of the heat flow
in the temperature range of 25-600 ◦ C were recorded for few milligrams of sample
placed in aluminium pans and heated at a rate of 10 ◦ C/min.
3.2.6 Particle size measurements

The developments in the preparation of particles have led to a wide number of
particulate materials with different characterisation techniques providing different
information on the materials. Thus, there are a number of ’particle sizes’ that arise
depending on the measuring technique, as shown schematically in Figure 3.2.
a) Physical size, DP : This refers to the “true” size of the particle and is usually
obtained with electron microscopy.
b) Hydrodynamic size, DH : The hydrodynamic size or diameter of a particle is
usually determined using photon correlation spectroscopy (PCS). This length indi-
cates the diameter of a particle including the fluid molecules around the electrostatic
double layer.
c) Magnetic size, DM : Means the size of the magnetic core of a particle. The
size is usually determined from magnetic hysteresis loops. The magnetic size is
the crystalline core and it does not include the non-stoichiometric surface layer.
Therefore this is generally smaller than the physical size.
d) Crystallite size, DX : The size corresponds to the mean value of the crystalline
domain size of the particles, calculated from Scherrer’s equation which uses the line
broadening of X-ray diffraction measurements.
e) Surface areal size, DS : Calculated from the gas adsorption isotherms assuming
a specific shape of the particles.
3.2.6.1 Physical size measurements
The diameters of >500 particles were measured on digitised TEM micrographs with
the image analysis program ImageJ.[Ras01] Mean diameters were thus obtained by
fitting the experimental data with a lognormal distribution function, as suggested
by O’Grady and Bradbury,[OB83] i.e.,
0 )2
((ln DP ) − ln DP
1
f (DP ) = √ exp − 2 (3.1)
2πwP DP 2wP
with mean diameter < DP >= DP 0 exp(w 2 /2) and w as the standard deviation
P P
0 . The standard deviation of the mean diameter σ is
around ln DP P
0 2 2 1/2
σP = DP [exp (2wP ) − exp (wP )] (3.2)
3.2.6.2 Hydrodynamic size measurements
All samples were measured by dynamic light scattering (DLS) to quantify the degree
of agglomeration. DLS measurements were carried out with a BI-90 particle sizer
(Brookhaven Instruments Corp.).
3.2.6.3 Magnetic size measurements
Measurements were carried out at room temperature in particle suspensions. The

size of the magnetic cores DM were determined by assuming a lognormal distribution
of particle volumes for the Langevin function, i.e.,
r 1/3
18kT χi
DM = (3.3)
πMsb 3Ms · H0
which has a standard deviation wVSM around the magnetic core of
1/2
1 3χi
σM = ln (3.4)
3 Ms · 1/H0
k represents Boltzmann’s constant, T is the temperature, Msb is the saturation
magnetisation of the bulk material and Ms is that of the sample; χi is the initial
susceptibility (χi = dM/dHH→0 ), and 1/H0 is the intercept on the 1/H for the
high field extrapolation of the magnetisation versus 1/H.
3.3. DNA ASSAYS 29
3.2.6.4 Crystallite size measurements

The crystallite size DX was determined from XRD measurements using the Scher-
rer’s equation
0.9λ
DX = (3.5)
Bhkl · cos θ
where Bhkl represents the full width at half maximum of the main peak expressed
in radians and θ is the position of the peak.
3.2.6.5 Surface area measurements

Particle sizes (DSA ) were calculated from the SSA and the specific density of the
particles measured assuming spherically shaped particles according to:
6000
DSA = (3.6)
ρ · SSA
3.3 DNA assays

Pristine (uncoated) iron oxide nanoparticles and silica-coated particles were used to
purify plasmid DNA fragments of various sizes in the range 0,1–4 kbp (1 kb=1000
base pairs). Purifications were carried out both manually and using 96- and 384-
well experimental set-ups. Initial manual DNA purification with the magnetic beads
was carried out by binding the DNA to the beads, removing excess of materials by
washing the beads, and eluting the DNA from the particles.
Four
Results and discussion
In this chapter are presented the results of the investigation of the different factors
that influence the synthesis of superparamagnetic and ferrimagnetic iron oxide na-
noparticles , i.e., iron, cobalt and nickel spinel ferrites with narrow size distribution
and different morphologies. The incorporation of the materials into stable ferro-
fluids and the coating with inorganic compounds, such as silica and gold, as well as
organic surfactants is also reported. In the last section of the chapter some of the
investigated applications of iron spinel ferrites are presented.
4.1 Synthesis of various iron oxides

4.1.1 Preparation of magnetite and maghemite
4.1.1.1 Control of crystallographic phase
The synthesis of particles was accomplished using the information provided by che-
mical equilibrium diagrams. Several experiments were performed in order to inves-
tigate the effect of the synthesis temperature on the final crystallographic phase of
the particles. Figure 4.1 shows the DSC analysis of the prepared particles, where it
is possible to observe two transitions, one endothermic at ∼100 ◦ C, associated to the
desorption of surface water; and an exothermic at ∼450 ◦ C, related to the oxidation
of magnetite to maghemite, Fe3 O4 → γ-Fe2 O3 . Particles were then synthesised at
temperatures higher than 60 ◦ C to minimise the presence of adsorbed water.
Experiments were also performed using different iron(III) to iron (II) ratios to
determine the boundaries at which spinel iron oxides are formed (Figure 4.2(a)).
According to the results, it is possible to see that goethite is formed when there
is no Fe(II) present and that even a small amount of iron(II), i.e., a high Fe(III)
to Fe(II) ratio, is enough to induce the formation of the inverse spinel structure.
However, due to the peak broadening associated with the small size of the particles,
it is not possible to make a differentiation between magnetite and maghemite based
solely on the XRD results. The particles were characterised by differential scanning
31
32 CHAPTER 4. RESULTS AND DISCUSSION
o
80 C
o
70 o C
60 oC
50 C
Exo
o
40 C
0 100 200 300 400 500 600

Temperature (oC)
Figure 4.1: Calorimetric analysis of the particles synthesised at different tempe-

ratures.
calorimetry (Figure 4.2(b)) showing an endothermic peak centred at ∼ 270 ◦ C,

which was associated to the dehydroxylation of hydroxide species present in goethite,
2α-FeO OH → α-Fe2 O3 +H2 O . It is therefore important to avoid the excess of Fe2+
during the wet preparation of Fe3 O4 .
Magnetite particles were synthesised and the digestion time was investigated.
The size of the particles, as determined by XRD, did not change significantly. On
the other hand, the most drastic change was found in the density of the materials. In
order to eliminate the possibility of interference by water or incomplete dehydration,
the as-synthesised powders were dried for 6 h at 120 ◦ C.
Figure 4.3 shows the density variations with the digestion time, which is a result
of the variation in the formation of different phases. In section 2.1.1 it was indicated
that the formation of magnetite (or maghemite) proceeds through the formation
of polynuclear hydroxide complexes. Hence, the gradual dehydroxylation of these
complexes yields Fe3 O4 (or γ-Fe2 O3 ). The formation of different (hydr)oxide with
the time result in large variations in the macroscopic density of the materials. Table
4.1 shows the density of different iron(II) and iron(III) (hydr)oxide compounds.
However, the XRD diffractograms did not indicate the presence of such secondary
phases, although their absence of such secondary phases may be due to the high
noise-to-signal ratio arising from the low crystallinity of the samples.
4.1. SYNTHESIS OF VARIOUS IRON OXIDES 33
Ratio = 2
Ratio = 1
* *
Ratio = oo
*
**
* ** * *
* * * * *
20 30 40 50 60 70
o
Diffraction angle ( 2θ)
(a)
Exo
0 100 200 300 400 500 600

o
Temperature ( C)
(b)
Figure 4.2: (a) XRD (b) and DSC analysis of particles synthesised with
Fe(III):Fe(II) ratios of 1, 2, ∞ in a batch reactor. The symbols indi-
cate peaks corresponding to (∗) α-FeOOH, to () inverse spinel, and
to () α-Fe2 O3 .
5,0
4,8
Density (g·cm3)
4,6
4,4
4,2
10 100 1000
time (min)
Figure 4.3: Variation in the density of iron oxide nanoparticles as a function of

reaction time.
Table 4.1: List of properties of some iron (hydr)oxide compounds. Values obtai-
ned from [Lid04].
Compound Density (kg/m3 )
Fe(OH)2 3200
Fe(OH)3 3120
Fe O OH 4260
α-Fe2 O3 5250
Fe3 O4 5170
Co Fe2 O4 5240a
a Theoretical value.
(a) Flow-injection synthesis (b) Batch synthesis
Figure 4.4: TEM micrograph and respective particle size distribution analysis for
iron oxide nanoparticles prepared by fis (a) and batch methods (b).
4.1.1.2 Control of particle size and size distribution

Particle analysis by TEM revealed spheroidal particles with sizes in the nanometre
scale. Figure 4.4 shows the TEM for particles obtained with the continuous injection
scheme (Scheme A) under standard conditions and those obtained in a small batch
reactor (∼ 50 cm3 ) in identical chemical conditions. From the respective particle size
distribution analysis it can be seen that the particles synthesised using a fis-based
method have a lower particle size and lower polydispersity than those obtained in a
batch reactor. The values determined for particles prepared in a fis reactor were
3,3 nm with a polydispersity of 0,23 compared to 4,3 nm with polydispersity of 0,33
determined for particles prepared in a batch reactor.
The differences in size and distribution width (polydispersity), provides indi-
cation that the mixing in the capillaries is much faster and homogeneous than in
batch reactor. The Reynolds number was calculated for the fis conditions hereby
studied and it was always close to zero, indicating that conditions of laminar flow
were always attained.
4.1.2 Synthesis of nickel and cobalt-doped magnetite

4.1.2.1 Synthesis of Nix Fe3−x O4
Spinel ferrite nanoparticles were initially prepared using only iron salts as starting
material. However, the properties of the ferrites vary dramatically as their compo-
sition changes. The synthesis of nanoparticles with more complex composition was
then studied. The synthesis of ferrite nanoparticles based on nickel with a chemical
composition Nix Fe3−x O4 was carried out. The as-precipitated particles were cha-
racterised for the composition with XRD. The obtained diffractograms are shown
in Figure 4.5.
*
(d) *
* * *
* *
20 30 40 50 60 70
(c)
o o o
o
20 30 40 50 60 70
(b)
20 30 40 50 60 70
(a)
20 30 40 50 60 70
o
Scattering angle ( 2θ)
Figure 4.5: XRD diffractograms of Nix Fe3−x O4 particles prepared with an ini-
tial nickel content of (a) 0, (b) 5, (c) 10, and(d) 30 at%. The sym-
bols represent the identified peaks for spinel ferrite (∗) and haematite
phases(◦ ).
The results shown in Figure 4.5 indicate the formation of the spinel ferrite phase
in all samples. The presence of haematite was detected only in the samples prepa-
red with low amount of nickel (5 and 10 at%). Chemical analysis of the powders
revealed that the nickel content in the samples that developed haematite is nearly
negligible, whereas the sample prepared with a nickel content (30 at%) close to the
stoichiometric one had an actual nickel content of about 20 at%. The crystallite
size, as determined with Scherrer’s equation, was about 25 nm for all samples. The
latter suggests that the nickel has practically no influence on the particle formation
and that it might incorporate into the spinel lattice at an intermediate stage.
The development of haematite in Nix Fe3−x O4 and Fe3−x O4 nanoparticles has
been observed whenever there was an excess of Fe2+ in solution. As discussed
earlier, haematite can grow epitaxially on magnetite or maghemite and therefore
the surface area influences the kinetics of transformation.
4.1.2.2 Synthesis of Cox Fe3−x O4
Figure 4.6 shows that the cobalt content in the analysed solids can be adjusted in
a controlled manner by varying the metal ion to hydroxide ion concentration ratio
5,2
5,1
5,0
Density (g·cm-3 )
4,9
4,8
4,7
4,6
4,5
0,80 0,85 0,90 0,95 1,00 1,05 1,10 1,15 1,20
x (Cox Fe3-x O4 )
Figure 4.6: Iron/cobalt molar ratio of nanoparticles as a function of the metal ion-
hydroxide ion molar ratio of the mixed suspension, [Me2+ ]M /[OH− ]M .
The digestion time was 3 h.
in the mixed solution, [Me2+ ]M /[OH − ]M .

The control of the particle composition can also be achieved by varying the initial
iron to cobalt ratio.[TFM90, LK03] In the present study, particles with a cobalt
composition corresponding to x values in the range 0,86 to 1,14 were synthesized.
Although the initial iron to cobalt ratio prior to mixing was constant (stoichiometric
ratio) the resulting phase has varying composition.
Figure 4.7 shows the variation of density as a result of varying the metal to
hydroxide ratio [Me2+ ]M /[OH− ]M . The pronounced decrease in density can be
attributed to the gradual increase of secondary phases. Table 4.1 shows the density
of various metal (hydro)oxides that may form during the precipitation of cobalt
ferrite. The density values for magnetite, cobalt ferrite, and haematite are quite
similar. However, the density of the hydroxide species is much lower. The redox
potential in the system imposed by nitrate and iron(II) ions discard the existence of
Fe(OH)2 . Hence, the secondary phases that may lower the density are Fe(OH)3 and
Fe O OH . The presence of these phases was detected by XRD measurements carried
out on particles withdrawn from the reaction liquors at regular time intervals and
at high [Me2+ ]M /[OH− ]M .
4.1.2.3 Variation of particle morphology

Variation of the metal to hydroxide ratio [Me2+ ]/[OH− ] resulted in particles with
different morphology. The particles were mainly cubic and spherical, although
irregularly shaped particles were also observed. Fig. 4.8 shows electron micro-
5200
5100
5000
Density (kg·m-3 )
4900
4800
4700
4600
4500
0,30 0,35 0,40 0,45 0,50 0,55 0,60
-
[Me2+]M /[OH ]M
Figure 4.7: Variation of the density of the particles with the metal to hydroxide
ratio. The amount of metal ions was varied while keeping a constant
amount of sodium hydroxide, nOH− = 0, 528 mol. The volume of the
suspension was 1,6 dm3 and all the samples were digested for 3 h.
graphs of particles observed under different conditions. Spherical and cubic par-
ticles were equal in amounts when the precipitation conditions were adjusted to
generate the compositions close to the empirical stoichiometric value for cobalt fer-
rite, Cox Fe3−x O4 , x = 1.
Several physical properties of particles are dependent on the surface composition.
In this work we also studied the crystallinity and the presence of amorphous phases
in the particles with HRTEM. Figure 4.9 shows the ED pattern and HRTEM of a
cubic particle taken from a [111] zone axis. The measured lattice fringes correspond
to the unit cell of inverse spinel ferrite. Also, the high crystallinity of the particles
can be observed, for which we can assume that each cubic particle is a single crystal
with no noticeable amorphous surface layers.
4.1.3 Surface modification

According to the double layer theory, most of the transition metal oxides have
a point of zero charge (PZC) when suspended in aqueous media. At the PZC
there is a minimum in the surface charge density and due to the positive Hamaker
constant that exist between two surfaces of the same composition, there would be a
strong attraction between the particles. Therefore, at neutral pH values iron oxide
nanoparticles (PZC∼7) tend to aggregate into large clusters, causing the loss of
properties related to superparamagnetic relaxation. The surface properties can be
varied by coating the particles with a layer of organic surfactant.
Figure 4.8: TEM of particles prepared with a [M2+ ]/[OH− ] ratio of (top) 0,2,
(middle) 0,3, and (bottom) 0,5. Note the different scale bars used in
the figures.
Figure 4.9: ED pattern and HRTEM of a cubic particle of cobalt ferrite taken
from the zone axis [111]. The lattice fringes correspond to the unit
cell of inverse spinel ferrite.
4.1.3.1 Coating of iron oxide nanoparticles by silica

In this work we studied the coating of iron oxide nanoparticles with a shell of
silica since it has been previously reported that silica does not affect the magnetic
properties of the coated magnetic particles.[dGBMP99]
The thickness of the coating layer was further increased by growing the silica
shell via slow hydrolysis of tetraethoxy silane. It was observed that the thickness of
the shell could be controlled by adjusting the total amount of added silane. From the
graph, it can be seen that the thickness of the shell increases with the TEOS added
and has a maximum at 0.15 cm3 of TEOS, then it decreases abruptly and increases
at a slow rate. From the electron micrographs (4.10) it was observed that at this
concentration of TEOS there is a homogeneous nucleation of silica which increases
steadily with the TEOS added to the suspension.The reason why the nuclei do not
increase in size is due to the fact that the number of nuclei increases instead.
4.1.3.2 Coating of iron oxide nanoparticles with gold

Experiments were carried out in order to coat iron oxide nanoparticles with a layer
of gold. The first test were oriented towards the preparation and characterisation
of gold nanoparticles. The citrate reduction method following the protocol repor-
ted by Kooij et al.[KBWP02] which yields gold particles with an average size of
about 20 nm. However, the gold particles prepared by this route are too large and
other systems were investigated. The method developed by Duff et al. was used to
have a better size control.[DB93] Gold seeds with a particle size below 1 nm (below
detection limit of JEOL-2000FX) were grown with the seed-mediation method. Fi-
gure 4.11 shows the TEM of gold nanoparticles grown with a single iteration of the
growth process. The size of the particles could be tailored up to 20-30 nm adjusting
the number of iteration steps in the growth process.
Figure 4.10: Electron micrographs showing the coating of iron oxide nanoparticles
with silica layers of different thickness. The cores consisted of iron
oxide nanoparticles with a size of about 10 nm.
Figure 4.11: TEM of gold particles grown by the seed-mediation method.
Following this, several alternatives were tested in order to obtain iron oxide nano-
particles with a gold shell. Among the investigated alternatives were the sequential
synthesis in batch, sequential synthesis in nanoemulsions, surface reduction, etc.
The only method that proved to be effective is the adsorption of hydroxylamine
on the surface of the nanoparticles with the further reduction of gold(III) ions on
such surfaces. The size of the gold clusters that form on the surface of the na-
noparticles was increased by a seed-growth method. Figure 4.12 shows iron oxide
nanoparticles with small gold clusters of about 1 nm on their surface. The gold
coverage of the particles was measured to be about 40 %. The reduction of gold
by hydroxylamine is a heterogenous nucleation process that required an existing
surface to nucleate upon. Experiments performed without iron oxide nanoparticles,
this is, in the absence of seeds, did not show the formation of gold crystals.
Lyon et al.[LFS+ 04] have recently shown that the coating of iron oxide nano-
particles with a particle size of about 9 nm with a shell of gold with a thickness of
about 50 nm using a similar methodology. The findings in this work and in that
of Lyon et al. demonstrate that it is possible to attach gold particles to the sur-
face of iron oxide nanoparticles. The full covering of the iron oxide nanoparticles
can be then achieved with the seed-mediated growth of the gold clusters, as earlier
reported.[Hay89]
4.2. MAGNETIC CHARACTERISATION 43
Figure 4.12: TEM of iron oxide nanoparticles coated by smaller gold nanoparticles
grown by the seed-mediation method. The image was focused on
the small gold particles. The arrow indicates an isolated iron oxide
nanoparticle for clarity.
4.2 Magnetic characterisation

4.2.1 Silica-coated iron oxide nanoparticles
Measurements of the magnetisation versus applied magnetic field undertaken on
the starting ferrofluids as well as on suspensions of the silica-coated materials are
displayed in Figure 4.13. Bulk saturation magnetisation values were calculated from
the saturation magnetisation values of the ferrofluids and the total iron concentra-
tion of each sample assuming that all iron was in the form of maghemite. None of
the samples exhibited magnetic hysteresis at room temperature and the saturation
magnetisation value for particles with silica monolayer was found to be 74 emu/g,
whereas the value found for pristine particles was 79 emu/g. It is important to
highlight that the saturation magnetisation value for the pristine particles is about
90% of the theoretical value for maghemite.[PS95]
From a plot of the reduced saturation magnetisation (M/MS ) it was seen that all
the curves converge into a master curve. Therefore, it is possible to assume that at
this level of magnetic volume fraction ( 7-10 mg/cm3 ) there are no particle-particle
interactions and thus, the magnetisation of the suspension is proportional to the
volume fraction of the magnetic content, i.e., M (H, φ) = M (H)(φmag ).
1.2
1.0
0.8
Reduced magnetisation
0.6
0.4
0.2
0.0
-0.2
0 2000 4000 6000 8000 10000
Applied field (Oe)
Figure 4.13: Magnetisation curves for pristine iron oxide nanoparticles (open
squares) and particles with a silica monolayer (open circles).
Table 4.2: List of samples analysed with Mössbauer spectroscopy.

Sample ID Density (g/cm3 ) DS (nm)
Co19 4,44 91
Co21 4,56 95
Co22 5,01 80
Co23 5,02 90
Co25 4,84 92
4.2.2 Cobalt ferrite nanoparticles

Analysis of the particles carried out below the blocking temperature of cobalt ferrites
showed almost identical Mössbauer spectra. Figure 4.14 presents the results of the
measurements carried out at 90 K. It can be seen that the peaks of the samples are
superimposed, which does not allow for an unambiguous determination of the the
degree of inversion of the sample, i.e., [B]/(A) ratio.
The spectra taken at room temperature were fitted with four sub-spectra (1
for A sites, 3 for B site). The fits of the spectra taken at room temperature for
samples Co19, Co21, Co22, Co23, and Co25 shown in Figure 4.15 result in a ratio
R = [B]/(A) between 1.66 and 2.0. The numbers for the distribution of the iron
ions in the different sites depend on the precise information about the total Fe/Co
ratio as determined from chemical analysis.
For instance, for sample Co25 with a [B]/(A) = 1, 68, (Co0,25 Fe0,75 )[F e1,25 Co0,75 ]O4
for a Fe/Co = 2,0. On the other hand, we obtain (Co0,30 Fe0,70 )[F e1,28 Co0,72 ]O4 for
4.3. APPLICATIONS OF MAGNETIC NANOPARTICLES 45
Figure 4.14: Mössbauer spectra taken at 90 K for samples Co19, Co21, Co22,
Co23, and Co25. Note that only sample Co19 shows a minor com-
ponent in the central part of the spectrum.
Co21 with a [B]/(A) = 1,77 if Fe /Co = 2, 0. However from chemical analysis, we

have that Fe /Co = 2, 42, thus the composition of the material can be written as
(Co0,24 Fe0,76 )[F e1,35 Co0,65 ]O4 .
From the measurements at 90 K and room temperature it can be observed that
all samples have similar pattterns except Co19 which showed a small fraction of
superparamagnetic components. Analysis of the results showed a disordered inverse
spinel structure, which normally has the cobalt ions occupying only [B]-sites. The
fits shown here are approximate since for an unambiguous determination of the
distribution of the iron and cobalt ions in the (A) and [B] sites, it is required to
obtain Mössbauer spectra under an external magnetic field.
4.3 Applications of magnetic nanoparticles

4.3.1 DNA separation
Different types of iron oxide nanoparticles were used for the purification of DNA:
pristine nanoparticles , single-core iron oxide nanoparticles coated with a silica
monolayer and with a layer of 1-2 nm, and also silica beads containing several iron
oxide cores with a bead size of 100-250 nm .
The results presented in Table 4.3.1 show that the recovery capacity of the silica-
coated particles with a thin layer (b) is the highest among the different particles
tested. To evaluate the origin of such a difference the hydrodynamic radius was
Figure 4.15: Mössbauer spectra taken at room temperature for samples (a) Co19,
(b) Co21, (c) Co22, (d) Co23, and (e) Co25. The dots represent the
measured points and the continuous lines correspond to the fitting.
Table 4.3: Recovery of DNA using iron oxide nanoparticles with and without si-
lica coating using a 384-well plate. (a) corresponds to pristine nano-
particles, (b) to single-core iron oxide nanoparticles coated with a very
thin layer of silica, a layer of 1-2 nm (c), (d) to silica beads containing
several iron oxide nanoparticles, and (e) Nanomag-D beads (Micromod
GmbH, Germany) with particle size of 130 nm.
Sample DNA Plasmid Recovery yields for different concentrations (%)
size (kbp) 15 µg/rxa 7,5 µg/rx 3,75 µg/rx 1,875 µg/rx
(a) 1,7 26 45 37 6
(b) 1,7 67 63 55 51
1 57 61 – –
0,5 44 55 – – a
0,256 57 53 – –
0.1 8 22 – –
(c) 1,7 25 20 18 19
(d) 1,7 29 47 55 –
(e) 1,7 44 – – –
15 µg of total iron per reaction correspond approximately to 100 µg of particles per reaction.
measured. It was found that the particles in (a) had a hydrodynamic particle size
of about 30 nm, considerably smaller than that of the other samples. The values
obtained with the beads (d) are higher than those obtained with the aggregates par-
ticles (b). This may be explained by the fact that the recovery yields are measured
per concentration unit of iron. Hence, the beads have a larger amount of silica per
particle which results in a higher surface area per iron oxide particle. Nevertheless,
the recovery of the beads is significantly lower than that obtained with the particles
in (a). Mornet et al.[MVB+ 00] suggested that there are two possible places in the
DNA double strand that may accommodate the nanoparticles in a manner that
resembles the wrapping of the DNA around the histone core in the cellular nucleus.
However, the suggested sites have a size of few nanometres, hence the beads may be
too large (with a particle size larger than 150 nm) to be accommodated in the same
position as the smaller particles. This also explains why increasing the concentra-
tion of beads does not increase the recovery rates whereas in the case of (b) an
increase of the concentration of the particles increases the recovery to nearly 70%.
The recovery of DNA with the studied particles is comparable to that reported
by Yoza et al.[YMM02] who used amine-functionalised particles in the size range
50–5000 nm. The positively charged amino group (around neutral pH) binds elec-
trostatically to the negatively charged DNA. Although the particles used in this
work are non-functionalised, the recoveries are in the same order of magnitude and
in some cases higher that those reported for amine-functionalised materials. A great
advantage of using silica-coated particles resides in the fact that these particles can
be readily regenerated by ’salting out’ the DNA form their surface and re-use them
several times.[HOMRS94]
100
10
Eout (µJ)
0,1
0,1 1 10 100 1000
Ein (µJ)
Figure 4.16: Optical power limiting of iron oxide nanoparticles coated with a silica
monolayer.
4.3.2 Optical limiting

Suspensions of pristine iron oxide nanoparticles were used to study their optical
limiting properties. The particles studied had a spheroidal morphology with a
diameter of about 10 nm and a standard deviation of 25%. The secondary particle
size, as determined by DLS (DH ), was about 60 nm, which implies that agglomerates
consisting of tens of nanoparticles were formed. Also, iron oxide nanoparticles with
a silica monolayer were studied. The silica layer modifies the surface properties
of the particles by lowering the point of zero charge from about 7 to around 3
(results not shown). At pH values close to the point of zero charge the surface
charge density is very low and the electrostatic repulsion can no longer prevent the
particle aggregation. The secondary particle size of iron oxide nanoparticles with a
silica coating was 25 nm, i.e., the agglomerates consisted only of few particles, which
increased the concentration range that can be used and improves the hydrodynamic
stability of the suspension. Furthermore, the silica coating on the particles improves
not only the colloidal stability of the suspension but also serves as a protective layer
to avoid leaching of Fe3+ ions from the surface.
The transmission spectra of pristine iron oxide nanoparticles and silica-coated
iron oxide nanoparticles was measured at 532 nm. The transmittances were quite
similar and in excess of 60%. The transmittance of both iron oxide suspensions
was dependent of the wavelength and a maximum of about 84% transmittance
was measured for both samples at around 750 nm. Figure 4.16 shows the results
of the optical power limiting measurements for silica-coated iron oxide nanopar-
ticles. The clamping level was determined to be around 3 µJ for both suspensions
of pristine and silica-coated iron oxide nanoparticles. It has been suggested that
carbon nanoparticles present a strong nonlinear scattering associated to a laser-
induced plasma formation and generation of bubbles.[MSS92] Considering that the
iron oxide nanoparticles are also inorganic materials it could be assumed that a si-
milar mechanism is responsible for the non-linear behaviour. Yu et al. reported that
colloidal suspensions of Fe2 O3 nanoparticles show a very large nonlinear refractive
index.[YZG+ 97, YZG00] However, it is not clear in the report which crystallogra-
phic phase with the composition Fe2 O3 was studied. In addition, it has been repor-
ted that the nonlinear mechanism might be associated with the excitation of the
magnetically-coupled Fe3+ ions as well other electronic resonances.[HYY96] Hence,
there are clear differences in the electronic properties of the materials associated
with the crystallographic structures.
Five
Conclusions
In the present study the synthesis of iron oxides nanoparticles and their use in
two different applications is reported. Several types of iron oxide nanoparticles
with various composition, i.e., Fe3 O4 , γ-Fe2 O3 , Cox Fe3−x O4 , and Nix Fe3−x O4 ; all
with the inverse spinel structure were prepared. Iron oxide nanoparticles consisting
mainly of γ-Fe2 O3 with an average particle size of about 10 nm have have shown
higher saturation magnetisation and proton relaxivity rates than most of the reports
in the literature. The increase in magnetisation of the particles was attributed to a
higher crystallinity.
Also, a new method for the synthesis of iron oxide nanoparticles with a narrow
size distribution by the flow-injection technique was developed. The particles thus
synthesised have smaller size and narrower particles size distribution than those
obtained with a stirred batch reactor. It was found that segmentation of the flow is
not required for the synthesis of iron oxides and that continuous flow can be used
without altering the particles’ morphology or quality. The flow-injection synthesis
of particles can be performed in aqueous or bi-phasic media reducing considerably
the volumes of organic phase needed in microemulsion-based synthesis.
Particles with a composition of Cox Fe3−x O4 and Nix Fe3−x O4 have been prepared
and showed the spinel structure and the metal doping, x was was varied in the
range 0, 8 ≤ x ≤ 1, 2. The composition of the iron oxide particles was tailored by
co-precipitating a mixed metal solution with hydroxide ions. The degree of doping
was found to be dependent on the molar ratio of the metal solution to hydroxide
solution, this is, on the presence of excess of metal ions or hydroxide ions. The
purity of the samples was initially characterised by large changes in the density of
the material and confirmed by X-ray diffraction measurements.
Stable aqueous ferrofluids were prepared by oxidising the surface of magnetite
nanoparticles, which were later used to coat the particles with a silica layer. The
silica shell thickness was adjusted by varying the mass ratio of silica to iron oxide,
whereas sonication was used to decrease the number of particles with multiple core
without requiring the centrifugation of the material.
In the present study, iron oxide nanoparticles have been evaluated for their use
51
52 CHAPTER 5. CONCLUSIONS
in biomedical applications and for the magnetic separation of DNA. The particles
present a very large contrast which is related to the relatively large magnetic moment
of the nanoparticles. The particles presented a large R2 /R1 ratio, which indicates
that they can be used for in-vitro diagnostic applications.
The magnetic separation of DNA by silica-coated magnetic nanoparticles was
readily achieved. The recovery rates of the particles were similar to commercial
materials and particles containing surface functional groups with the advantage of
having non-specific interactions between the particles and the nucleic acids. The
recovery rates were greatly affected by the hydrodynamic particle size. The presence
of two different mechanisms for the binding of DNA depending on the particle size is
suggested by the differences in recovery rates for small particles (below 50 nm) and
large particles (above 150 nm). The high magnetisation of the particles combined
with a large surface area allows a faster and more efficient purification methods to
be achieved.
The optical power limiting application of coated and non-coated iron oxide na-
noparticles was investigated. Both aqueous suspensions of pristine iron oxide na-
noparticles consisting mainly of γ-Fe2 O3 and silica-coated iron oxide nanoparticles
were yellowish and had a clamping level of about 3 µJ. The photoinduced nonlinear
light scattering proved to be the dominating nonlinear mechanism. The slight bet-
ter performance of the silica-coated particles was attributed to their higher colloidal
stability.
Suggested future work

The synthesis of iron oxide nanoparticles with few different compositions was stu-
died. Nevertheless, there are a number of applications that require materials with
more complex stoichiometry and metal ions with different aqueous behaviour. Hence,
the investigation of parameters found to have a large impact on the composition of
the nanoparticles, such as the metal to hydroxide ratio, is required.
Once the chemical parameters are fixed, the flow-injection synthesis method
can be used to prepare materials with a smaller particle size and narrower particle
size distribution than those obtained with stirred reactors. However, the yield is
still very low and it requires further studies to scale it up. Also, materials with
compositions that need careful mixing conditions could be investigated.
Regarding the surface modification of iron oxide nanoparticles, the silica-coating
proved to be advantageous for the preparation of dispersed suspensions. Nonethe-
less, the surface properties can be greatly modified to enhance their functionality.
For instance, it has been shown that folate-functionalised particles can be used for
the labelling of certain types of cancerous cell. Tissues with a high concentration
of these particles can later be imaged with magnetic resonance imaging.
The magnetic and structural properties of the prepared materials were studied
by different techniques. Nevertheless, it is not clear the role of the secondary phases
in the case of doped-magnetite. Furthermore, magnetometry and XRD investiga-
53
tions carried out in the present studies are insufficient for the detailed characteri-
sation of the particles. The magnetic properties of the particles are dependent on
their structure, composition, and morphology. Hence, a more detailed study on the
structure-properties relationship may be needed. A clear understanding of this re-
lationship is required to understand magnetic phenomena related to, e.g., exchange
bias mechanisms, microwave absorption, magnetic relaxation, etc.
Acknowledgements
First of all I am indebted to my supervisor, Prof. Mamoun Muhammed, for the

efforts put during the course of the work, his confidence in me and all the support
through the years.
I also appreciate the efforts from Eva Björkman, Maria Mikhaylova, and Mu-
hammet Toprak for their help, valuable scientific and non-scientific advices, proof-
reading this thesis and standing by me in tough times.
I would like to acknowledge the fruitful collaboration and discussions with Ri-
chard T. Olsson, Ulf W. Gedde, and Mikael S. Hedenqvist at the Department of
Polymer Technology; Cesar Lopes, Sören Svensson, and Steven J. Savage at the
Departmenf of Functional Materials of FOI; Fredrik Lindberg at the Department of
Structural, Physical and Inorganic Chemistry of the Stockholm University; Josep
Nogués, at the Department of Physics of the Universitat Autònoma de Barcelona;
Sophie Laurent and Robert Muller at the Department of Organic Chemistry of the
University of Mons-Hainaut in Belgium.
I thank the local collaborators for without their discussions/chat/àíåêäîòû this
work would have been much harder: Andrei Z, Erik L, Uheida, Othonas, Zongyin,
Pascale, Andy, Michel, Y Zhang, Kim, Shanghua, Jian, Jackie call-me-Bill, Raph,
Tibå. Also, I thank the people at the innebandy club: Hasse, Wolfgang, Dilip,
David, Johan Ö, Johan E, Sylwester; and people from other divisions in MSE:
Lyuba, Amita, Fred, Nabil, Ulf, K2 , Athula, Bengt, Martin Schwind, Patrik F,
Anders T, Thobias S, Tosse, Rosa, Ricardo, Era, and Tripathi.
Parts of this work have been supported through grant from the EU-Fifth Frame-
work programme Contract GRD5-CT2000-00375; Swedish Defence Research Agency,
FOI; Swedish Nuclear Fuel and Waste Management, SKB; and KTH Rektors gåvo-
medel.
55
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“It goes like this. Let’s see now: ’Protect me from knowing
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that I decided not to know about. Amen’ . . .
Oh yes, add ’Lord lord lord’, it makes it
more profound: ’Lord lord lord. Protect me
from the consequences of the above . . . ’
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Synthesis, Characterisation and Applications of

Iron Oxide Nanoparticles

Akademisk avhandling som med tillstånd av Kungl Tekniska högskolan framlägges

c German Salazar-Alvarez, december 2004

I denna avhandlingen diskuteras syntes, karakterisering och tillämpningar

Ïðîãóëêà â ìèëþ ñ ëþáèìîé æåíùèíîé

ñîñòàâëÿåò ëèøü ñòî øàãîâ.

My graduate studies were originally related to studies on the recovery of heavy

in addition to the regular bibliographic information provided by the references to

II G. Salazar-Alvarez, M. Muhammed and A.A. Zagorodni, Novel flow injection

III R.T. Olsson, G. Salazar-Alvarez, M.S. Hedenqvist, U.W. Gedde, F. Lindberg

IV R.T. Olsson, M.S. Hedenqvist, U.W. Gedde, G. Salazar-Alvarez, M. Muham-

V G. Salazar-Alvarez, R. Reinhardt, and M. Muhammed, Silica-coated superpa-

VI G. Salazar-Alvarez, E. Björkman, C. Lopes, A. Eriksson, S. Svensson and M.

Contributions of the author

II Planning of experiments, performing experiments, characterisation of the samples,

III Planning of experiments, characterisation of the samples, evaluation of results,

IV Design of experiments, characterisation of the samples, evaluation of results,

V Planning of experiments, characterisation of the samples, analysis of results,

VI Planning of experiments, characterisation of the samples, analysis of results,

Other work not included

2 A. Uheida, G. Salazar-Alvarez, E. Björkman and M. Muhammed, The removal

3 G. Salazar-Alvarez, J. Nogués, F. Lindberg, R.T. Olsson, U.W. Gedde, M. Mu-

4 E. Björkman, G. Salazar-Alvarez and Mamoun Muhammed, Measurement of the

Symbols and acronyms xi

2 Fabrication of iron oxide nanoparticles 15

3 Materials and methods 21

4 Results and discussion 31

1.1 Crystal structure

cations occupying 16 octahedral (B-sites) and 8 tetrahedral positions (A-sites).

Lepidocrocite γ-Fe O OH Orthorhombic Bbmm 0.3071 1.2520 0.3873 4

(a) (b) (c) (d)

1.2 Magnetic properties

1.2.3.1 Magnetic relaxation

Considering particles under the influence of an external magnetic field, it can be

1.3 Applications of iron oxides

1.3.1 Biomedical applications

Micrometre-sized magnetic particles have been used as commercial applications in

1.3.1.2 DNA analysis

1.3.1.3 MRI contrast agents

Figure 1.5: Representation of functional nanoparticles with a protective coating

1.3.2 Other technological applications

Ferrofluids are made of ferro- or ferrimagnetic single-domain particles suspended in

There are certain stability requirements for the preparation of ferrofluids.[Ros85]

1.4 Scope of this work

Fabrication of iron oxide nanoparticles

2.1 Chemical methods

2.1.1 Synthesis of magnetite and maghemite

Fe3+ + H2 O Fe OH2+ + H+ (2.1a)

Fe2+ + 2Fe3+ + 8OH− → Fe3 O4 + 4H2 O (2.3)

Fe3+ + 3OH− → α − Fe OOH + H2 O(at around 25 ◦ C) (2.5a)

Figure 2.1: Schematic representations of reverse micelles and nanoemulsions (a)

2.1.2 Confined-zone processing

2.1.2.1 Synthesis in nanoemulsions

The addition of a surfactant with a suitable concentration stabilises the emulsion

2.1.2.2 Concept of flowing confined-zone synthesis

The flow-injection synthesis (fis) technique consists of continuous or periodic mi-

Materials and methods

3.1 Synthesis of nanoparticles

3.1.1 Batch synthesis in stirred reactor

3.1.1.2 Synthesis of Nix Fe3−x O4

3.1.1.3 Synthesis of Cox Fe3−x O4

3.1.1.4 Controlled stirred batch reactor

3.1.2 Synthesis in confined zones