FERROFLUIDS: PREPARATION AND PROPERTIES

I) INTRODUCTION
Among the physical properties of nanomaterials, the magnetic properties of ultrafine
particles are very attractive. Ferrofluids are colloidal suspensions of magnetic nanoparticles
that remain separated from one another in the liquid medium. Surfactants are used to
prevent the nanoparticles from approaching one another too closely. The response of
ferrofluids to an external magnetic field makes feasible to exert a real control on the
location of the solution. As a result, ferrofluids have the captivating property of exhibiting
“spikes” when placed in the proximity of a strong magnet (Fig. 1).

Although the array of spikes on the surface of the ferrofluid is spectacular, this property is
not particularly useful. However, ferrofluids have found a wide variety of applications,
including ferrofluidic seals used in rotating equipment. In these seals the ferrofluid is
suspended in place by use of a permanent magnet and forms a physical barrier to contain a
fluid. The ferrofluid behaves as a liquid O-ring, eliminating most of the friction produced in
a traditional mechanical seal. These rotating shaft seals are used in vacuum chambers found
in the semiconductor industry, in rotating anode X-ray generators, and in high-speed
computer disk drives. In hard disks, a small amount of ferrofluid is held within the gap
between the magnet and the shaft by its attraction to the magnet. The ferrofluidic dispersion
forms a barrier which prevents from harmful dust particles or other impurities, which could
cause the reading heads to crash, entering the interior of the hard drive. Another application
of ferrofluids is in improving the performance of loudspeakers. In a loudspeaker, the
magnetic field induced by electric currents causes a coil to vibrate and thus produces sound.
In many high-frequency speaker drivers (tweeters), ferrofluids provide heat conduction
from the voice coil to the surrounding assembly dissipating heat from excess energy
supplied to the coil, as well as mechanical damping to reduce undesired resonances. Both of
these factors lead to an overall improved sound quality. The ferrofluid is kept in place in
the magnetic gap due to the strong magnetic field and is in contact with both the magnetic
surfaces.

Finally, there is much hope for future biomedical applications of ferrofluids. For example,
researchers are attempting to design ferrofluids that can carry medications to specific
locations in the body through the use of applied magnetic fields. Other ongoing work is
investigating the use of ferrofluids as contrast agents for magnetic resonance imaging
(MRI). Magnetite is a natural magnet, hence the name, giving it a clearly distinguishing
characteristic. Magnetite is a member of the spinel (MgAl 2O4) group which has the
standard formula AB2O4 (Fig. 2). The A and B represent usually different metal ions that
occupy specific sites in the crystal structure. In the case of magnetite, Fe 3O4, the A Fe2+
ions are in octahedral sites, while Fe3+; ions occupy the two different metal ions specific
sites. This situation is called an inverse spinel. Fe3O4 magnetite nanoparticles can be
produced by mixing Fe(II) and Fe(III) salts together in a basic solution. The global reaction
can be expressed as:

2 FeCl3 + FeCl2 + 8 NH3 + 4H2O → Fe3O4 + 8 NH4Cl

Once prepared, ionic surfactants can be used to enhance the electrostatic repulsion between
magnetite nanoparticles in an aqueous medium. Quaternary alkyl ammonium hydroxides
are useful surfactant compounds, in which the hydroxide ions are attracted to the surface of
each magnetite particle, forming a negatively charged layer at the magnetite surface. The
alkyl ammonium cations are attracted to the negatively charged layer, forming a positive
layer. When magnetite particles approach each other the repulsions between their
positively-charged layers keeps them apart.

II. EXPERIMENTAL DETAILS

II.1) Materials

Stock solutions for about 50 preparations:

- 2 M HCl (21 mL conc HCl in 250 mL water) for making iron solutions. The iron solutions
need to be completely dissolved, well sealed and free of any particles.

- 1 M FeCl3 in 2 M HCl. Each student needs 4 mL. Dissolve 54.1 g in 200 mL 2 M HCl.
This solid often dissolves slowly.

- 2 M FeCl2 in 2 M HCl. Each student needs 1 mL. Dissolve 19.9 g in 50 mL 2 M HCl.

(This solid dissolves readily but Fe(II) is air sensitive, and the solution reacts with oxygen
and should be freshly prepared. The color of Fe(II) and Fe(III) solutions are clearly
different.

- 1.0 M NH3 in water. Each student needs 50 mL. Dilute at least 200 mL of concentrated
ammonium hydroxide with water to 3.0 L. Caution: Although 1 M NH 3 is fairly dilute, NH3
is a strong base. Open containers of ammonia will smell bad and their concentration will
decrease leading to poor results.

- 25% tetramethylammonium hydroxide in water (commercially available). A strong, fishy,

amine odor indicates hydrolysis products which may interfere with the synthesis. Plastic
weighing boats. Disposable gloves. Stir bars. Strong craft magnets. Cow magnets.

II.2) Ferrofluid preparation

Add 4.0 mL of 1M FeCl3 and 1.0 mL of 2M FeCl2 solution to a 100 mL beaker. Add a
magnetic stirring bar and begin stirring. Continue stirring throughout the slow addition over
a period of 5 minutes of 50 mL of 1.0 M aqueous NH 3 solution. After an initial brown
precipitate, a black precipitate will form (magnetite). One way to accomplish a slow
addition is to drip the ammonia solution from a buret or separatory funnel or by using a
dropper to transfer the solution.
Turn off the stirrer and immediately use a strong magnet to work the stir bar up the walls of
the beaker (Fig. 3b). Remove the stir bar with tongs or a gloved hand before it touches the
magnet.

Let the magnetite settle, then decant (pour off) and discard the clear liquid without losing a
substantial amount of solid. You can speed the settling process by putting a magnet under
the container. Transfer the solid to a weighing boat with the aid of a few squirts from a
wash bottle.

Use a strong magnet to attract the ferrofluid to the bottom of the weighing boat. Pour off
and discard as much clear liquid as possible (Fig. 3c). Rinse again with water from a wash
bottle and discard the rinse as before. Repeat the rinsing a third time.
Add 1-2 mL of 25% tetramethylammonium hydroxide. Gently stir with a glass rod for at
least a minute to suspend the solid in the liquid. Use a strong magnet to attract the ferrofluid
to the bottom of the weighting boat. Pour off and discard the dark liquid. Move the strong
magnet around and again pour off any liquid. If the ferrofluid does not spike, continue to
move the strong magnet around, pouring off any liquid.

Record all changes that you observe by placing a strong magnet below the weightng boat
with your ferrofluid.

III) FINAL QUESTIONS

1. Describe the structure of magnetite.

2. Calculate the saturation magnetization of magnetite.
3. Use the references to find other procedures of preparation of synthetic magnetite.
4. Describe at least three solids in which the magnetic properties are affected on
decreasing grain size.
5. Draw the molecular structure of the surfactant used in this work. Draw a
schematic plot of the magnetite particle-surfactant complex.
6. Is magnetite an electrical conducting solid? What is the conduction mechanism?
7. Suggest other ferrite compounds and surfactants that could form ferrofluids.
8. Explore different applications of ferrofluids.
9. Were you able to prepare ferrofluid and observe spiking in the presence of a magnet?
Pick one spike in the middle. How many spikes were immediately around that spike and
how were they arranged? (You might draw a picture viewed from above. If you did not
observe spiking with your sample, you will need to inspect a sample that did spike.)
10. Examine the starting FeCl2 and FeCl3 solids used to prepare magnetite (leave the solids
in their sealed containers.) How do they respond to a magnet? Which is magnetic?
11. What is the purpose of the surfactant? Explain chemically how the surfactant works to
keep the nanoparticles suspended.
12. What evidence do you have for the formation of nanoparticles?

Materials

 One buret of 50 mL.

 Two 100 or 150 mL beakers.
  Two glass rods for stirring.
 Two plastic weighing boats.
 One wash bottles.
 Magnetic stirrer.
 Strong craft magnets.
 Two magnets.

Stock solutions

 2 M HCl for making iron solutions.

 2.0 M FeCl2(H2O)4 in 2 M HCl.
 1.0 M FeCl3(H2O)6 in 2 M HCl.
 1.0 M NH3 in water.
 25% tetramethylammonium hydroxide in water.

Equipment

 Magnetic stirrer.

IV) REFERENCES
- P. Berger, N.B. Adelman, K.J. Beckman, D.J. Campbell, A.B. Ellis, G.C. Lisensky, J.
Chem.
Educ., 76 (1999) 943
- B.E. Shriver, W.P. Atkins, C.H. Langford, “Química Inorgánica”. Ed. Reverté (1997).
- B. Bhushan, (Ed.) Springer Handbook of Nanotechnology. Springer 2004.