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ferrogels
Abstract: Ferrogels (FG) based on poly(acrylamide) (PAAm) with embedded multidomain iron magnetic
nanoparticles (MNPs) were synthesized by radical polymerization in water. Iron MNPs prepared by the electrical
explosion of wire were spherical in shape and have an average diameter around 100 nm. MNPs were modified by a
surfactant oleic acid to improve their dispersion in water. DLVO theoretical consideration was done to understand
the stability of dispersions. By microcalorimetry it was shown that the oleic layer on the surface of MNPs prevents
their interaction with PAAm network of FG. Mechanical testing of the compression modulus and the deformation of
FGs in magnetic field show up their prospectiveness as a material for magnetically sensitive MEMS and actuators.
Keywords: Iron nanoparticles, extended DLVO theory, poly(acrylamide), ferrogels, magnetodeformation, interfacial
interaction.
*
Corresponding author: ashankar@urfu.ru
Corresponding address: Chair of macromolecular compounds, Institute of natural sciences, Ural federal university,
Yekaterinburg, Russia.
Contact no.: +7 343 261 6046
1. Introduction. Ferrogels (FGs) are a soft type of of gels with varying MNPs content. Then, 20 L of
highly elastic polymer composites which have catalyst - N,N,N,N-Tetramethylethane-1,2-diamine
magnetic particles as a constituent. The particles can (Merck) was added to the reaction mixture with
be multidomain, single domain or superparamagnetic vigorous stirring for few seconds. Polymerization took
in nature. Their significant response through place in poly(ethylene) cylindrical tubes for 4 hours
controllable deformation in magnetic field has [5]. The gels were taken out of mold and washed for
attracted considerable interest for their application as two weeks with distilled water renewal at a two-day
smart materials[1]. Their biological applications, interval. The equilibrium swelling degree () of gels
namely, viz. targeted delivery, labelling, radio was calculated by = (ms - md)/ md, where ms is mass
frequency methods and contrast enhancements in of swollen gel and md is mass of dried gel. This value
imaging are few examples where size of filler particles was further used in calculation of volume fraction of
are needed to be ~ 1 m or less [2]. This dimension oleate coated MNPs () in swollen FGs.
usually corresponds to multidomain regime of
applicable materials like Fe, Ni, Fe3O4 etc. To use Methods. XRD diffractorgrams were obtained using a
them in preparation of FGs, a stable concentrated diffractometer Bruker D8 Discover in copper radiation
dispersion is required. Making stable aqueous (Cu K1,2 = 1,542) with a graphite monochromator
dispersion of multidomain iron magnetic nanoparticles in the diffracted beam. The Rietveld refinement of
(MNPs) is a challenging task [3]. Moreover, XRD pattern was performed using Topas-3 software.
functionalization procedure for these MNPs, post Transmission electron microscopy (TEM) was
synthesis, further complicates this problem due to high performed were performed using a JEOL JEM2100
particle aggregation. In present study a room microscope operating at 200 kV. Dynamic light
temperature grinding method was employed to modify scattering (DLS) and zeta-potential measurements
the surface of Fe MNPs to achieve their stable were performed using Brookhaven instruments BI-90
dispersion. The dispersion was later used in Plus Particle Size Analyzer. Bright field optical
preparation of FGs with poly(acrylamide) (PAAm) microscopy was done using BX51 Olympus
network microscope. Specific surface area of MNPs was
measured using Micromeritics TriStar3000 sorption
2. Experimental section. analyzer. Microcalorimetry studies of the enthalpy of
Materials The iron MNPs were synthesized by the interfacial adhesion between PAAm and MNPs were
electric explosion of wire technique [4]. Surface performed using Calvet micro calorimeter of a
functionalization of MNPs was carried out under laboratory construction [6]. Youngs modulus was
ambient conditions by grinding air-dry MNPs with measured using a laboratory setup provided
surfactant, oleic acid. In a typical procedure, 0.5 g of compressive loading of gel samples and optical
MNPs and 1.5 g of KOH were ground by mixing in registration of their deformation. Deformation of
agate mortar for 5 min. After homogenization, 4.5 g of ferrogels in magnetic field was monitored by an
surfactant was added followed by grinding for ~80 min optical system in a laboratory setup. A magnetic
till highly viscous films are formed. The mixture was system of NdFeB permanent magnets provided a
washed till neutral pH and then dispersed in distilled uniform field 420 mT in the central zone 10 X 10 X 10
water for desired concentration of MNPs. The visual mm3[7].
assessment of sedimentation stability of dispersion
3. Results and discussion.
was ~15-20 min.
FGs were synthesized at room temperature by free
radical polymerization of acrylamide (AAm,
AppliChem, Darmstadt, Germany). Aqueous solutions
of a cross-linker N,N methylene diacrylamide
(MDAA, Merck, Schtuchardt, Germany) (48 mM),
initiator ammonium persulphate (APS) (50 mM) and
aqueous dispersion of MNPs (6.3% w/w) were
prepared prior to the reaction. Reactants were used as
received. In a typical synthesis procedure, 1 mL of
MDAA solution was added to the 0.341 g of AAm and
homogenized. 0.3 mL APS solution was added
followed by addition of 3 mL of water or dispersion of
MNPs or both in specified amount for the preparation
Fig. 1. M-H loop of bare MNPs at 298 K. Inset 1a shows = 282.46 g mol-1, vaccum permeability, o= 1.25 X 10-6 H m-1 and
magnified view of magnetization curve. Inset 1b shows the remanent magnetization, Mr= 157.7 kAm-1 (from fig. 1). Arrows
TEM micrograph of bare FNPs. Inset 1c shows size indicate respective ordinates of curves.
distribution of MNPs from several TEM images. The red
curve is lognormal fit on distribution. Inset 1d shows the The van der Waals interactions were calculated in a
rietveld refinement of XRD pattern of oleate coated MNPs. classical manner excluding retardation effects. This
attractive interaction energy term (VvdW) can be
The structural and magnetic characterization of bare expressed as
and oleate modified MNPs is shown in fig.1.
The colloidal stability of MNPs dispersion employed The short range steric interactions among MNPs.
in preparation of FGs was qualitatively modeled by imparted by surfactants including osmotic effect and
extended DLVO approach [3]. Interaction energy elastic repulsions were taken as [13]
curves simulated for current aqueous dispersion are 4 ak B T 2 1 s 1 s
p 2 ln
shown in fig. 2. v 2 2 4
2 ak B T s ln s 3 ( s / ) 6 ln 3 ( s / ) 3 1 s
2 2
for s <
p
Vstr Mw 2 2
4 ak B T 2 1
2
s
v p for < s < 2
2 2
0 for s > 2
(3)
Although no magnetic field was applied to a
suspension the multidomain Fe MNPs could still get
magnetized due to their numerous collisions in the
preparation. The maximum magnetic attraction energy
(VM) among multidomain MNPs in the absence of
field was estimated as
Fig. 2. Normalized interaction energy curves for two identical
8o M r2 a3
(4)
MNPs as a function of surface-to-surface separation (s). The VM 3
parameters used for the calculation of energy curves are: the radius s
9 2
of particles, a = 54.5 nm, Hamaker constant, A = 2.94 X 10-19 J a
[3,8,9], relative permittivity of carrier liquid, r = 80.4, vaccum
permittivity, o = 8.85 X 10-12 Fm-1, o is the surface potential which The overall particle-particle interaction energy (VT)
is approximated here with measured zeta potential, = -35 mV, T = can be written as VT = VvdW + Ves + Vst + VM. An small
298 K, kB = 1.38 X 10-23 JK-1, elementary charge, q = 1, NA = 6.023 energy barrier of ~ 7 kBT imparted by non-magnetic
X 1023 mol-1, valency of ions (approximated here with ionized forces can be seen. In addition, an order of magnitude
constituents of free surfactants i.e. K+ and oleate), zi= 1, ionic
difference between magnetic and non-magnetic forces
concentration, ci = 0.001 M, volume of a water molecule, = 0.03
can be noticed (fig. 2). The magnetic forces are greater
nm3, volume fraction of coated surfactant, p= 0.05, Flory-Huggins than the sum of van der Waals, electrostatic and steric
parameter, = 0.42, adsorbed layer thickness, = 3.0 nm [10],
forces. Thus, the aggregation of MNPs and subsequent
density of surfactant, = 0.895 g cm-3, molar mass of surfactant, Mw
sedimentation process cannot be avoided completely mean size of aggregates with = 0.71 X 10-4 and 1.56
in such dispersions X 10-4 were found to be 2.6 m and 3.1 m
respectively. These dimensions are larger than
Stability of dispersion was monitored using DLS
hydrodynamic size of aggregates as observed from
measurements. Figure 3 shows multimodal
DLS. Larger aggregates can be related to reaction
distribution of hydrodynamic sizes of MNPs in a
conditions as it might have also perturbed the stability
freshly prepared dispersion. Here, bimodal
of MNPs by unravelling of outer surfactant layer.
distribution indicates the presence of two types of
species in dispersion. The first mode at 200 nm may The interaction between MNPs and polymer network
correspond to surfacted MNPs while the second mode in FGs can be understood on the basis of the enthalpy
at 800 nm obviously represent aggregates. The relative of mixing of PAAm-MNP composites. As the
volume fractions of individual MNPs and their enthalpy of mixing of a polymer with MNPs cannot be
aggregates show that the sufficient stability of the measured directly, an indirect route was followed. [6]
dispersion for the preparation of ferrogels can be To make a comparison, separate composites of both
maintained at least at short time scale. bare and oleate modified MNPs were prepared with
linear PAAm (MW. = 56.9 kDal; determined by
viscometry). The filler compositions were varied in
the entire range. The enthalpy of mixing of polymer
composites (Hm) can be written as Hmix= fill
Hwet+ pol Hdis pol - Hdis comp, where fill and pol are
weight fractions of filler (i.e., bare or coated MNPs)
and linear PAAm respectively. Hwet, Hdis pol and
Hdis comp are heat of dissolution of filler, linear PAAm
and composites in solvent, respectively. They were
measured directly and used for the calculation of the
enthalpy of mixing. The concentration dependence of
Hmix for the composites is shown in fig. 5.
Fig.3 Volume weighted distribution of hydrodynamic
diameters of aqueous dispersion. Stock dispersion was
diluted to 4.2 mg/L for DLS measurements.