Advanced Powder Technol., Vol. 18, No. 5, pp.

567– 577 (2007)

© VSP and Society of Powder Technology, Japan 2007.
Also available online - www.brill.nl/apt

Original paper

Growth processes of poly methylmethacrylate particles

investigated by atomic force microscopy

TETSUYA YAMAMOTO 1,∗ and KO HIGASHITANI 2

1 Department of Chemical Engineering, Hiroshima University, 1-4-1, Kagamiyama,
Higashi-Hiroshima 739-8527, Japan
2 Department of Chemical Engineering, Kyoto University, Katsura, Nishikyo-ku, Kyoto-shi,
Kyoto 615-8510, Japan

Received 14 November 2006; accepted 6 February 2007

Abstract—The growth processes of poly methylmethacrylate (PMMA) particles prepared by soap-

free emulsion polymerization at a reaction temperature 70◦ C are observed using scanning electron
microscopy and atomic force microscopy to clarify the growth mechanisms at the molecular scale.
Here, the use of a cationic initiator, V-50, enables us to synthesize positively charged PMMA, which
then adsorbs electrostatically on the negatively charged mica plate with molecular scale smoothness.
As a result, the following results are found. If the monomer concentration is high, PMMA particle
size increases with increasing initiator concentration, otherwise particle size decreases with increasing
initiator concentration. In the former case, the growth mechanism is very similar to that of the
polystyrene particles we proposed; in the latter case, the phenomenon is thought to follow the LaMer
diagram.

Keywords: Growth mechanism; atomic force microscopy; soap-free emulsion polymerization; poly
methylmethacrylate particle.

1. INTRODUCTION

The nucleation and growth mechanisms of polymeric particles prepared by various

polymerizations have been academically interesting, industrially important and
discussed [1 –3]. In our recent research [4 –8], we investigated the nucleation and
growth mechanisms of polystyrene particles prepared by the soap-free emulsion
polymerization with V-50 using atomic force microscopy (AFM). V-50 as a cationic
initiator enabled us to synthesize positively charged polystyrene, which then
adsorbed electrostatically on the negatively charged mica plate with molecular scale

∗ To whom correspondence should be addressed. E-mail: ytetsuya@hiroshima-u.ac.jp

568 T. Yamamoto and K. Higashitani

Table 1.
Experimental conditions of the polymerization of methylmethacrylate

Distilled-deionized water 120 g

Methylmethacrylate monomer mg
V-50 solution w g/10 g water
Reaction temperature 70◦ C

smoothness. AFM allowed us to observe the processes of polymerization in situ and

on a molecular scale.
In the present study, we pay attention to the methylmethacrylate monomer, which
is more water soluble than the styrene monomer, and the growth processes of
poly methylmethacrylate (PMMA) particles prepared by the soap-free emulsion
polymerization with V-50 are investigated by scanning electron microscopy (SEM)
and AFM to discuss the difference between the growth mechanisms of polystyrene
and PMMA particles.

2. EXPERIMENTAL
2.1. Material
Methylmethacrylate (Tokyo Chemical Industry) and 2,2 -azobis(2-methylpropion-
amidine) dihydrochloride (Wako Pure Chemical), which is called V-50, were
used as monomer and radical initiator, respectively, without further purification.
This cationic initiator is employed to make all the synthesized polymers charged
positively, so that they are able to adsorb electrostatically on the negatively charged
mica surface when they are sampled. Pure water used here was purified as
follows. After the water was distilled and deionized by a distillation apparatus
(WGA-28; Yamato Scientific), it was further purified by a Milli-Q purification
system (Millipore). Finally, nitrogen gas was bubbled into the water for at least
2 h to remove the dissolved oxygen.

2.2. Polymerization
The soap-free emulsion polymerization of methylmethacrylate was performed in a
round-bottom reactor of 500 ml with four necks for stirring mechanically with a
Teflon turbine blade, condensing the reflux with cold water, purging with nitrogen
gas and sampling an aliquot of the solution with a pipet. The temperature of the
reactor was controlled by a water bath with a precision of ±0.1◦ C. The experimental
conditions of polymerization employed are shown in Table 1.
Polymerization experiments were carried out as follows. First, a given amount of
pure water was poured into the reactor under nitrogen atmosphere and heated to a
given temperature, agitating with an impeller speed of 185 r.p.m. Methylmethacry-
late monomer was added after the temperature and agitation were settled. Finally,
an aqueous solution of V-50 was added to start the polymerization.
 Growth processes of PMMA by AFM 569

2.3. Determination of particle size

The size of particles was measured mainly by field emission (FE)-SEM (JSM-
6340FS; JEOL). SEM samples were prepared as follows. A small amount of
solution was sampled from the reactor at a given time and then a drop of the solution
was placed on the freshly cleaved mica plate. The excessive reactants and particles
in the drop were removed by rinsing with pure water. Then, the specimen was
freeze-dried following the usual procedure and coated with a thin gold film by the
chemical vapor deposition method. The particle size was determined by averaging
the data of around 200 particles.

2.4. AFM

A Nanoscope III (Digital Instruments) was used to observe the molecular-scale

images of all the material transferred on the mica surface by AFM. Samples were
prepared as follows. A drop of the solution was sampled from the reactor at a
given time and then cast on the mica surface, such that cationic products produced
by polymerization are able to be transferred by adsorbing on the mica surface
electrostatically. After the plate was set to the AFM liquid cell, pure water is injected
into the cell to remove excessive materials and to terminate the polymerization at
the same time.
Height images of PMMA adsorbed on the mica surface were obtained using the
tapping-mode procedure, where the driving frequency of the cantilever was adjusted
around their resonance frequency. The interaction forces between the tip of AFM
probe and the PMMA particles adsorbed on the mica were also measured following
the typical force-mode procedure with cantilevers with a microfabricated Si tip of
spring constant of 0.58 N/m [9]. All the AFM measurements were carried out at the
temperature of 25 ± 2◦ C.

3. RESULTS AND DISCUSSION

3.1. Influence of monomer and initiator concentrations on particle growth

Figure 1 shows the influence of initiator concentration on particle growth at the

various monomer concentrations.
The dependences of the particle size on the initiator concentrations are classified
into two types: one is the increase of the particle size with increasing initiator
concentration as in the conditions of m = 28.3 and 14.2 g, and the other is
the decrease of the particle size with increasing initiator concentration as in the
condition of m = 2.83 g. For each case, we investigate the growth processes in
detail in the next two sections.
570 T. Yamamoto and K. Higashitani

Figure 1. Influence of the monomer and initiator concentrations on particle size.

3.2. Growth processes in the cases of m = 28.3 and 14.2 g

Figure 2 represents SEM images of the final PMMA particles in the case of
m = 28.3 g. It is found that particle size increases with increasing initiator
concentration. In particular, in Fig. 2(a), there exist smaller particles on the mica
plate. To obtain a more clear image of the smaller particles, the image of the
adsorbates at w = 0.034 g is zoomed up to the area surrounded by the dotted lines
in Fig. 2(a), as shown in Figure 2(a ). Our previous research [6] on the growth of the
polystyrene particles clarified that such smaller particles, oligomers and polymers,
which were named polymeric materials, that were generated continuously through
the polymerization process in the bulk in the growth period, could contribute to
making the particles grow. An increase of the initiator concentration led to an
increase in the number of polymeric materials that could make a contribution to
the growth process and, hence, the final particle size became larger. This growth
mechanism can probably be applied to the growth processes of PMMA particles at
m = 28.3 and 14.2 g. To confirm the adequacy, the growth processes at m = 14.2 g
are investigated furthermore.
Figure 3 represents the growth curves by SEM measurements in the case of
m = 14.2 g, and shows that the growth of PMMA particles formed at w = 0.034
and 0.061 g is terminated completely at around tr = 120 min. In particular, the
growth process at w = 0.034 g is picked up and investigated using SEM and AFM
in detail.
 Growth processes of PMMA by AFM 571

Figure 2. SEM images of the PMMA particles at m = 28.3 g and various initiator concentrations:
(a and a ) w = 0.034, (b) 0.186 and (c) 0.305 g.

Figure 3. Growth curves of the particles at m = 14.2 g and various initiator concentrations.
572 T. Yamamoto and K. Higashitani

Figure 4. Changes of SEM images of the PMMA particles at m = 14.2 g and w = 0.034 g with
reaction time: (a) tr = 5, (b) 10, (c) 15, (d) 25, (e) 60 and (f) 120 min. The arrows indicate the
polymeric materials on the mica surface.

SEM images of the PMMA particles at w = 0.034 g and tr  120 min are
shown in Fig. 4. At tr = 5 and 10 min, monodisperse particles are formed, as
shown in Fig. 4(a and b). In Fig. 4(c and d), the color contrasts of the particles
at tr = 15 and 25 min may be classified into two types: most particles with
dark gray color and some particles with bright gray color, which indicates that the
former particles are flattened on the substrate probably because they are swollen
by absorbing monomers and extremely soft [8]. To examine whether the features
estimated above are appropriate or not, the force curves between the cantilever tip
and the particles were measured using the force-mode procedure.
 Growth processes of PMMA by AFM 573

Figure 5. Changes of force curves between a probe tip and a particle top with reaction time: (a) tr = 5,
(b) 10, (c) 15, (d) 25, (e) 60 and (f) 120 min.

Figure 5 shows the approaching and separating force curves for the particles at
tr = 5, 10, 15, 25, 60 and 120 min. The following features are clarified. As for
Fig. 5(a and b), the approaching force curves at tr = 5 and 10 min become repulsive
at a small separation. Also, the approaching force curves at tr = 15 and 25 min
become repulsive at a larger separation, as shown in Fig. 5(c and d). These features
are typically found in force curves between a hard material, such as a cantilever tip,
and a soft domain, such as bubbles and an immiscible liquid drop [10, 11]. On the
574 T. Yamamoto and K. Higashitani

other hand, Fig. 5(e and f) shows that both the approaching and separating force
curves are always repulsive and short-ranged at smaller separations. This indicates
that the particles here are much more solid-like than the particles at tr = 15 and
25 min. It is found that the rigidity of the PMMA particles changes from soft to
hard with the reaction time, which is consistent with the estimation for the SEM
observations.
The growth of particles at tr  25 min is considered to be attributable mainly to
particle swelling by absorbing monomers from the bulk. The growth at tr  25 min
is due to the deposition of the polymeric materials, as the white arrows indicate in
Fig. 4(d), in the bulk on the particle surface and their simultaneous swelling by
monomers in the bulk. Then, the particles are composed of the core solidified by
their polymerization. In the present study, the nucleation process is not discussed
and the details are given elsewhere [4, 8]. Comparing the growth processes of
PMMA particles at m = 28.3 and 14.2 g with those of the polystyrene particles
in our previous research [5, 6], no remarkable difference is found.

3.3. Growth processes in the case of m = 2.83 g

In this section, the growth processes of PMMA particles prepared under the
condition of m = 2.83 g are discussed. Figure 6 shows the changes of SEM images
of the final particles with the initiator concentration. Particle size decreases with

Figure 6. SEM images of the particles at m = 2.83 g and various initiator concentrations:
(a) w = 0.0006, (b) 0.003 and (c) 0.034 g.
 Growth processes of PMMA by AFM 575

increasing initiator concentration, which cannot be explained by the discussion in

the preceding section. Generally speaking, because a large number of nuclei are
formed at the initial stage of increasing initiator concentration, the final particle
size becomes small for a given amount of monomer assuming that the coagulation
process cannot occur in the growth process. This mechanism is often understood
using the LaMer diagram [12].
Figure 7 shows the molecular scale height images of the surrounding area of
the final particles at w = 0.0006, 0.003 and 0.034 g. For the condition of
w = 0.0006 g, it is found that there exist no microscopic adsorbates on the mica
surface. If any, the amount is expected to be very small because of the extremely
small amount of the initiator. On the other hand, Fig. 7(b and c) shows that the
polymeric materials remain in the bulk without contributing to the growth process

Figure 7. AFM height images of the surrounding area of the final particles at m = 2.83 g and various
initiator concentrations: (a) w = 0.0006, (b) 0.003 and (c) 0.034 g. This figure is published in color
on http://www.ingenta.com
576 T. Yamamoto and K. Higashitani

Figure 8. Schematic drawing for the possible processes of the growth of PMMA particles in soap-free
emulsion polymerization. This figure is published in color on http://www.ingenta.com

when the monomer conversion reaches 1.0; in other words, the deposition of the
polymeric materials in the bulk on the particle surface is least likely to occur at
low monomer concentration. Hence, the final particle size becomes smaller as the
initiator concentration increases.
The above discussion is summarized to procedure a schematic representation
about the growth process of PMMA particle, as shown in Fig. 8.

4. CONCLUSIONS

The following conclusions are drawn for the PMMA particles prepared by soap-
free emulsion polymerization according to the experimental conditions as shown in
Table 1 from the molecular-scale observations using SEM and AFM.
(i) At high monomer concentrations, such as the experimental conditions of m =
28.3 and 14.2 g in Table 1, as the initiator concentration increases, the final
particle size increases. The reason is because the polymeric materials are
generated in the bulk continuously and contribute to the growth process. This
growth mechanism is the same as that of the polystyrene particle [6].
(ii) At low monomer concentrations, such as the experimental condition of m =
2.83 g in Table 1, as the initiator concentration increases, the final particle
 Growth processes of PMMA by AFM 577

size decreases. The polymeric materials are not born in the bulk continuously
because of the small amount of monomers. Hence, an increase of the initiator
concentration does not enable the particles to grow. The growth processes are
explained by the LaMer diagram.

REFERENCES
1. W. D. Harkins, A general theory of the mechanism of emulsion polymerization, J. Am. Chem.
Soc. 69, 1428–1444 (1947).
2. W. V. Smith and R. W. Ewart, Kinetics of emulsion polymerization, J. Chem. Phys. 16, 592–599
(1948).
3. M. Arai, K. Arai and S. Saito, Polymer particle formation in soapless emulsion polymerization,
J. Polym. Sci., Polym. Chem. Ed. 17, 3655–3665 (1979).
4. T. Yamamoto, Y. Kanda and K. Higashitani, Molecular-scale observation of formation of nuclei
in soap-free polymerization of styrene, Langmuir 20, 4400–4405 (2004).
5. T. Yamamoto, T. Fukushima, Y. Kanda and K. Higashitani, Molecular-scale observation of the
surface of polystyrene particles by AFM, J. Colloid Interface Sci. 292, 392–396 (2005).
6. T. Yamamoto, M. Nakayama, Y. Kanda and K. Higashitani, Growth mechanism of soap-free
polymerization of styrene investigated by AFM, J. Colloid Interface Sci. 297, 112–121 (2006).
7. T. Yamamoto, Y. Kanda and K. Higashitani, Initial growth process of polystyrene particle
investigated by AFM, J. Colloid Interface Sci. 299, 493–496 (2006).
8. T. Yamamoto, Y. Kanda and K. Higashitani, Nucleation and growth process of polystyrene
particle investigated by AFM, J. Chem. Eng. Jpn. 39, 596–603 (2006).
9. A. L. Weisenhorn, P. K. Hansma, T. R. Albrecht and C. F. Quate, Forces in atomic force
microscopy in air and water, Appl. Phys. Lett. 54, 2651–2653 (1989).
10. M. Preuss and H.-J. Butt, Direct measurement of particle-bubble interactions in aqueous
electrolyte: dependence on surfactant, Langmuir 14, 3164–3174 (1998).
11. M. Sakamoto, Y. Kanda, M. Miyahara and K. Higashitani, Origin of long-range attractive force
between surfaces hydrophobized by surfactant adsorption, Langmuir 18, 5713–5719 (2002).
12. V. K. LaMer and R. H. Dinegar, Theory, production and mechanism of formation of monodis-
persed hydrosols, J. Am. Chem. Soc. 72, 4847–4854 (1950).