EXP4 – Synthesis and diffraction properties of PMMA-based colloid crystals

Part A. Synthesis of Monodisperse PMMA submicron Spheres

1. Add a 20x10 mm oval-shaped magnetic stir bar to a 25 mL round bottom flask (2 entrances).
2. Add a teflon sleeve to the end of a condenser.(Not using a teflon sleeve usually results in a
permanently PMMA fused joint at the end of the experiment.)
3. Add 16 mL pure water and stir under a slow flow of nitrogen. The nitrogen enters through a
glass joint and exits through a short needle passing through a septum in the top of a condenser
and then to a bubbler to monitor flow. A Corning stirrer-hotplate spins the stir bar at maximum
speed and keeps the temperature at 70 °C. A crystallizing dish containing water helps minimize
temperature fluctuations.
4. Add 3.0 mL methyl methacrylate. Maintain the 70 °C temperature and rapid stirring. The size of
the spheres produced depend on temperature, stir rate, and concentration. The methyl
methacrylate should form a suspension with uniformly sized spherical particles in the water.
5. When conditions are stable, quickly add 0.015 to 0.020 g 2,2-azobis(2-methylpropionamidine)
dihydrochloride and resume nitrogen flow. This compound decomposes with heat to produce a
free radical initiator for the polymerization reaction.
6. A milky white suspension is observed as the polymerization proceeds. Keep adjusting the
temperature to maintain 70 °C for the next 40 minutes.
7. After 40 minutes of heating, remove the condenser. There should not be a noticeable odor if the
polymerization was successful. Be sure to return the Teflon joint sleeve.
8. Transfer part of the suspension to a 0.5 mL microcentrifuge tube to save for use in optical
diffraction experiment (see Part B).

9. Transfer the half of rest of the suspension to a test tube to measure the sphere size by Stoke's
Law. Monitor the height of the spheres in the solution for at least a week. Plot the height in mm
as a function of the number of settling hours.

10. Spin your sample at 5000 rpm for 15 minutes. Always balance the centrifuge by pairing tubes
such that opposing tubes have the same amount of solution. (Spinning at 10,000 rpm appears to
crush the product.)

11. Remove and discard the water above the polymerized polymethylmethacrylate spheres.
Successful product will change colors with the angle of observation or lighting; the product
should look irridescent.

12. Transfer product to a pre-weighed open container and let the water evaporate overnight to leave
a dry powder. Record the weight of product obtained.

Part B. Diffraction from PMMA Nanospheres

Evaporation of a dilute suspension of polymer nanospheres creates a close packed layer on the
surface of a glass slide suspended in the solution. The particle size can be calculated from the
visible absorption maximum of this colloidal crystal.

1. Dilute 50 microliters of previously prepared PMMA nanospheres in 20 mL distilled water. (try

other two concentrations at your choice in the range 20-200 microliters, label the beckers
A,B,C).
2. Clean a glass cover slip by soaking in isopropanol for 10 minutes followed by soaking in pure
water for 5 minutes.

3. Suspend the glass slide into the diluted PMMA nanosphere suspension you prepared earlier. If
desired, more than one glass slide can be suspended in each solution as long as they do not
touch each other.

4. To promote the growth of high quality close packed layers on the glass slide, evaporate the
solution in a controlled temperature environment such as an oven. At 50 degree C, the solution
will evaporate in about 36 hours.

5. After the solution has evaporated, a dry film of the close-packed nanospheres remains on the
glass slide.

6. Observe the color of the film under reflected light conditions by holding the slide under a bright
light source. Observe the color of light transmitted through the film by holding the glass slide up
and looking at a bright light source through the slide. How are the colors of reflected and
transmitted light related?

7. Obtain the visible absorption spectrum when the glass slide is perpendicular to the beam in the
400-800 nm range.

8. Impregnate the colloid crystal with water (n=1.333). Cover with an glass seal with parafilm and
measure the visible absorption spectrum again.
EXP4 – Synthesis and diffraction properties of PMMA-based colloid crystals

Questions

1. Define Opal.

2. Explain the origin of the color in the case of the spectrum measured in the Lab.

3. Use the Bragg-Snell equation to calculate the size of the nanoparticles as explained in Lesson 6.

4. Use the Stoke equation to extract the PMMA particle dimensions.

5. What is the reason why the visible absorption peak shifts if the air is substitute by water?

6. Estimate the λmax in the case of Ethyl Acetate (nD=1.3724) and Toluene (nD=1.4969). Remember
that in case of air, nD=1.

7. Dry your colloidal crystal and confirm the estimation at least for Toluene. (Be quick because
PMMA is soluble in both solvents).