ISSN 10637834, Physics of the Solid State, 2011, Vol. 53, No. 11, pp. 23652369.

Pleiades Publishing, Ltd., 2011.

Original Russian Text A.O. Pozdnyakov, A.P. Voznyakovskii, E.O. Popov, O.F. Pozdnyakov, 2011, published in Fizika Tverdogo Tela, 2011, Vol. 53, No. 11, pp. 22462250.

POLYMERS

Fine Structure of the Thermal Decomposition Kinetics

of Polymethylmethacrylate Filled
with Detonation Nanodiamonds
A. O. Pozdnyakov*, A. P. Voznyakovskii, E. O. Popov, and O. F. Pozdnyakov
Ioffe PhysicalTechnical Institute, Russian Academy of Sciences, Politekhnicheskaya ul. 26, St. Petersburg, 194021 Russia
* email: ao.pozd@mail.ioffe.ru
Received April 18, 2011

AbstractA comparison has been made of the specific features of the fine structure of thermodesorption
spectra of polymethylmethacrylate and its composites with nanocarbon fillers: detonation nanodiamonds,
fullerene C60, and multiwalled carbon nanotubes. The influence of the fillers on the shape of the thermodes
orption spectra has been interpreted as a result of the chemical interaction between functional groups of mac
romolecules of the polymer matrix and active centers of filler nanoparticles.
DOI: 10.1134/S1063783411110254

1. INTRODUCTION
One of the problems of modern polymer materials
science is to create polymer materials complying with
strict requirements of ecological safety for environ
ment. At present, the monomer base for largescale
production polymers is exhausted. In these condi
tions, creation of polymer materials with a complex of
improved properties is associated with formation of
polymer nanocomposites [1]. Generally, this term
means a composite material such that the dispersion
state of one or several of its components lies in the
nanodimensional region (particles with a diameter of
100 nm). The effect of strengthening attained upon
introducing a nanodispersed modifier into the poly
mer matrix is often interpreted as a result of formation
of supramolecular structures of a nanocomposite
under the action of force fields of fractal clusters of
nanodispersed particles [25]. It should be noted that,
in many cases of practical application, it is not neces
sary to improve the whole complex of exploitation
parameters. It often suffices to enhance one parame
ter. In the case of polymers, this can be wear resis
tance, tribological parameters, freeze resistance, and
impact resistance.
Since recently, many research groups have worked
on creation of socalled smart polymers, which are
understood as materials capable of responding on
changes in the environment in a prescribed way [6].
From the viewpoint of polymer materials science, the
conception of smart polymers can be very useful for
solving such an ecologically important problem as
reprocessing of secondary polymers.
Let us consider the possibility of solving this prob
lem in the framework of the concept of polymer nano
composites. Intuitively, it is difficult to predict the

influence of a nanodispersed modifier on the proper

ties of the final material. The previously made work
leads to the conclusion that all nanodispersed sub
stances make it possible to attain a significant
strengthening effect [7, 8]. In addition to the size, the
significant (and, possibly, decisive) influence on the
final properties of a nanocomposite is exerted by the
fine internal organization of nanoparticle clusters. As
an illustrious example, Figs. 1a and 1b show the results
of computer simulation of clusters of the same hydro
dynamic radius but with a different internal organiza
tion. Earlier, we assumed that the complex of proper
ties of a nanocomposite are significantly stronger
influenced by clusters with the fractal spatial organiza
tion (Fig. 1b) than by clusters with a predominantly
intracluster interaction (Fig. 1a). This circumstance
results from the fact that fractal structure, being a
dynamic one, possesses the properties of accumula
tion and transmission of information [9, 10]. Thus,
even a minimal modifying doping with nanostructured
particles (less that 1 wt %) introduced into the polymer
matrix can lead to a significant variation in the proper
ties of the material.
Therefore, studying the polymerfractal nanodi
mensional modifier systems is not only of scientific
significance but of practical one as well. From the
practical point of view, it is natural to choose, as the
object of study, nanostructured substances available in
amounts sufficient for real industrial usage. In partic
ular, it is justified to qualify detonation nanodiamonds
(DND) as such substances.
Our systematic massspectrometric (MS) and ther
modesorption (TD) studies of polymers and corre
sponding composites [1114] make it possibleby
the analysis of kinetics of their decompositionto

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with nanoparticle concentration of 5 wt % with respect

to the mass of the polymer. Films were obtained by
drying the polymer solution at the substrate surface.
Samples for TD studies were cast directly on the sur
face of foil of stainless steel (X18H9T, thickness of
200 m and the working area of 1.0 0.5 cm2) with
subsequent drying in forvacuum conditions at a tem
perature of 80C in a vacuum furnace (Kendro Lab.
Products). In this case, the film thicknesses is ~1 m.
The TD spectra obtained for layers prepared from
PMMA solution in toluene enable one to judge on the
thermal stability of the initial polymer (without per
turbing influence of the filler). In fact, these TD spec
tra served as references for comparison with the data
on polymer composite films.

(a)

(b)

2. EXPERIMENTAL SAMPLES

3. EXPERIMENTAL TECHNIQUE
The MS studies were performed in a high vacuum
at a constant pumping rate of the vacuum chamber.
The TD spectra were detected by an MCX6 mass
reflectron modernized by us for conducting experi
ments on thermodecomposition of ultrathin polymer
films on a substrate in the vacuum chamber of a spec
trometer. The substrate with a thermocouple welded to
it was heated by electric current with the rate of 7 K s1
on attainment of a vacuum of ~5 105 Pa. During the
experiment, simultaneous computer recording of the
kinetics of variation in the intensity of chosen mass
spectrum lines of volatile products (VP), the current
temperature of the sample, and the pressure in the vac
uum chamber was performed [14].
The analysis of the VP thermodesorption mass
spectra of studied samples has shown that they consist
mainly of the corresponding monomer, i.e. methyl
methacrylate (MMA) (CH2=CH3COOCH3). This
agrees with the literature data [15]. Thus, registration
of the kinetics of thermodecomposition of PMMA
macromolecules may be performed by the rather
intensive peak in the mass spectrum of MMA. We have
chosen the molecular ion of MMA. Henceforward,
the TD spectrum of PMMA will be understood as the
fine structure of the MMA formation kinetics and its
variation depending on the nature of the filler and
other factors.

As the polymer matrix, we have chosen PMMA of

radical polymerization with the number average
molecular weight Mn ~ 5 105 and, as nanomodifiers,
DND of ZAO Almaznyi Tsentr, MWCNT of
Arkema company, and fullerene C60 (more than 98%
purity) of company Fullerenovye Tekhnologii,
St. Petersburg.
We used as solvents chemically pure toluene and
orthoxylene. For obtaining homogeneous PMMA
MWCNT and PMMADND compositions, we used
preliminary ultrasound treatment of MWCNTs and
DND suspensions in orthoxylene on a Sapfir4
installation. In our work, we used PMMA composites

4. RESULTS AND DISCUSSION

In many areas of practical application of DND,
they are supposed to be used as suspensions in liquid
lowmolecular media. Therefore, the industrial tech
nology presumes obtainment of DND as a final com
mercial product in the form of water suspensions. On
the other hand, for application as polymer materials,
DND suspensions in nonpolar liquid media must be
used. As a rule, such suspensions can be conveniently
obtained from dry powders of DND. In [8], a model
was proposed in which the formation of DND aggre
gates was associated with formation of intercluster

Fig. 1. Computer models of the organization of clusters of

highly dispersed substances: (a) cluster with the predomi
nantly intracluster organization and (b) cluster with the
fractal organization.

reveal the action of the filler on thermostability of a

created composite system. The aim of the present
work is to study polymethylmethacrylate (PMMA)
modified by DND and to compare the results with
those for PMMAfullerene (PMMAC60) and
PMMAmultiwalled carbon nanotubes (PMMA
MWCNT) structures.

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FINE STRUCTURE OF THE THERMAL DECOMPOSITION KINETICS

2367

100
dnMMA/dt, rel, units

(a)
1000

75
W, %

1
50
2

25

b
500
a
0

0
10

100

300

1000

500

600

700

800

T, K

d, nm

100

400

Fig. 3. Temperature dependences of the rate of release of

MMA for (a) the neat PMMA and (b) PMMAC60 com
positions.

(b)
80
1
W, %

60
40
2

20
0
10

100

1000
d, nm

Fig. 2. Polydispersity distribution curves of DNDs in

orthoxylene: (1) number average and (2) mass average after
(a) 1min and (b) 40min ultrasound treatments.

hydrogen bonds. Starting from the proposed model,

for surface hydrophobization, we treated dry DND
powder by dibutyl tin dilaurate. This reagent is noted
for a high activity with respect to functional groups
containing a labile proton.
The powder of modified DNDs was used for pre
paring a suspension in orthoxylene. The dispersiveness
of the suspension was characterized by the method of
dynamic light scattering (see Fig. 2). Figure 2 shows
the polydispersity distribution curves of the number
average and mass average distributions of DND aggre
gates in suspension in orthoxylene. In this work, it was
of interest to study the relationships between the sus
pension structure and the character of thermodecom
position of PMMA nanocomposites.
As follows from the data presented in Fig. 2a (the
ultrasound treatment time of 1 min), our technique
enabled us to obtain DND particles with the number
average diameter of 30 nm from dry powder. An
important characteristic of suspensions is the mass
fraction of particles that can be qualified as highly dis
persed. The number and mass average distributions
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demonstrate the effectiveness of the applied method of

dispergating. As we can judge from the data presented
in Fig. 2, the mass fraction of DND particles that can
be qualified as highly dispersed (300 nm) is 80.0 and
1.2 wt % are found in the form of aggregates with a
diameter >500 nm. Figure 2b presents the curves of
polydispersiveness of DND particles in suspension
after sounding for 40 min. When comparing the data in
Figs. 2a and 2b, it should be noted that the ultrasound
treatment time substantially affected the polydisper
sity curves. On the one hand, the increase in the ultra
sound treatment time has led to transition of DND
particles to less dispersed aggregates. On the other
hand, the fraction of less dispersed aggregates
(>500 nm) has significantly decreased (from 21 to
6 wt %). As a result, a suspension of a significantly
more homogeneous structure has been formed
(72 wt % of the aggregates is found in the interval 200
300 nm). The obtained suspensions were used for for
mation of PMMADND compositions.
It is worth noting the following. As is known, in
addition to normal chemical bonds (the stage of their
thermodecomposition is denoted by the sign in
Fig. 3), PMMA macromolecules synthesized by radi
cal polymerization include a certain number of defect
chemical bonds, interpreted as headtohead bonds or
macromolecules with end double bonds [16]. The cor
responding stages are denoted in Fig. 3 by the signs
and , respectively. The relative intensity of these
stages (, , ) reflects the fraction of normal and
energetically weakened, defect chemical bonds in
PMMA macromolecule chains, respectively. Thus,
the comparison between the structure of TD kinetics
of the initial PMMA with desorption spectra of the
nanocomposite give a qualitative and quantitative
information concerning the influence of the filler on
the thermal stability of macromolecules of the matrix.
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POZDNYAKOV et al.

In addition, the intensity distribution and positions

of the stages of TD kinetics on the temperature axis
proved to be sensitive to details of preparation of the
composite. Let us compare the TD spectra corre
sponding to the PMMADND composition after
short (Fig. 4, curve b, 1 min) and long (Fig. 4, curve c,
40 min) ultrasound treatment of DND suspension.
The short treatment has led to emergence of a distinct
kinetic peak at ~520 K, whereas the long ultrasound
treatment leads to emergence of a wider kinetic peak

5. CONCLUSIONS
In this work, the following results have been
obtained.
(1) By the TD and MS methods, a strong influence
of DND on thermal stability of the PMMA matrix,
depending, in particular, on the method of prelimi
nary preparation of suspension, has been established.
The prospects of development of this approach for

dnMMA/dt, rel, units

Figure 4 shows the kinetics of MMA formation on

heating of two types of the PMMADND composi
tion, formed with different durations of ultrasound
action on the suspension. For convenience of compar
ison, the TD spectrum of the initial PMMA is pre
sented in the same plot (Fig. 4, curve a). The influence
of DND on TD spectra of PMMA is quite obvious. A
significant increase in the intensity of the lowtemper
ature stage of the matrix decomposition is observed.
The position of different stages of the TD spectrum on
the temperature axis reflects the corresponding differ
ence in the thermal stability of the compositions under
study. In other words, introducing the filler has led to
a substantial increase in the fraction of weakened
chemical bonds in PMMA chains.

of thermal decomposition in the temperature range of

450650 K.
As is shown in [11], the method of studying the TD
spectra of thin polymer layers, used in this work,
makes it possible to register the true kinetics of decom
position of a sample, that is not limited by diffusion of
the detected product of decomposition in the bulk of
the polymer. Modeling of TD spectra is a complex
problem [17, 18], which, to a great extent, is deter
mined by the chosen model of decomposition. It
should also be noted that calculating the activation
energy for lowtemperature stages by onestage mod
els of kinetics (i.e., solution of equation dn(t)/dt =
k0 exp(U/RT)n(t), where dn(t)/dt and n(t) are the
rate of monomer desorption and the number of MMA
molecules at the substrate, respectively; k0 is the pref
actor; U is the activation energy; R is the gas constant,
and T is the absolute temperature) gives in our case
reasonable values U ~ 6070 kJ/mol. This indicates
weakening of CC bonds in a macromolecule as com
pared to their initial values of about 300 kJ/mol.
When considering the results presented in Fig. 4, it
is worth noting the difference in the thermal stability
of compositions subjected to different ultrasound
treatment of suspensions. As is evident from Fig. 1, the
role of ultrasound consists in dispersion of initial
DND particles. Probably, this means that ultrasound
treatment of different types leaves after it ensembles of
DND particles with variable sizes and variable chemi
cal activity, manifesting itself in the given case in the
changes in the thermostability of the obtained
PMMADND compositions. This conclusion may be
confirmed, e.g., by the results of [19], where the elec
tron subsystem of the surface of ultradispersed dia
monds and the results of [12, 13], concerning polymer
nanocomposites, were studied.
The analysis of the specific features of TD kinetics
did not give so far a possibility of quantitative interpre
tation of the mechanism of the polymernanoparticle
interaction. Nevertheless, the presence of functional
chemical groups of different nature and origin on the
surface of DND particles [20] offers a possibility of a
wide spectrum of interactions on the interface between
the components of the composite. Such questions are
the subject of current research, especially in connec
tion with the necessity of more precise control of the
ways and methods of creating new polymer nanocom
posite materials.

1000

b
500
a
0
300

400

500

600

700

800

T, K
Fig. 4. Temperature dependence of the rate of release of
MMA for (a) the initial PMMA and PMMADND com
positions after (b) 1min and (c) 40min ultrasound treat
ments of the suspension.

Figure 3 presents the kinetics of MMA formation

on heating of the neat PMMA (curve a) and PMMA
C60 composition (curve b). In the case of PMMAC60,
we observe an increase in the fraction of the sample
decomposed at lowtemperature stage of decomposi
tion, with the maximum temperature of ~540 K.
Practically no influence of MWCNT on the TD
spectrum of the PMMAMWCNT composition has
been detected in the conditions of our experiment.
This result agrees well with our earlier studies of simi
lar compositions [12, 13].

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FINE STRUCTURE OF THE THERMAL DECOMPOSITION KINETICS

solving a wide range of problems concerned with

studying the interactions on the interface and phase
stability of polymernanocarbon composition sys
tems are evident.
(2) Introducing highly dispersed DND particles
into the bulk of polymer helps to obtain a polymer
material whose strength parameters exceed those of
the initial polymer. On the other hand, as shown in this
work, nanodispersed filler reduces the temperature of
the beginning of decomposition. For explaining the
mechanism of the process, it is natural to use the
model of displacement of the electron density from
macrochains of the polymer to the electrondeficit
DND surface, which reduces the strength of inter
atomic bonds in polymer chains.
It should be noted that chemical interaction
between the filler and polymer molecules, which leads
to weakening the bonds inside a macromolecule and
reduction in the thermal stability, is not an undesired
effect from the viewpoint of the technology of produc
tion of any composite material. It is this interaction
that provides the necessary adhesion bonding between
a nanoparticle and polymer, which results in improve
ment of mechanical properties of the polymer nano
composite material as a whole. It should be noted that
the adhesion strength in traditional composite materi
als may include both chemical and mechanical com
ponents (detents and hooks on the interface
between phases [21, 22]). Obviously, the mechanical
component (if it is present) does not play an important
role. Therefore, this fact emphasizes the role of chem
ical interaction and the importance of its detailed
study for polymer nanocomposite materials. As is
known, without optimal adhesion, it is impossible to
create a composite material with improved physico
chemical properties.
ACKNOWLEDGMENTS
This study was supported by the Russian Founda
tion for Basic Research (project nos. 090801076a,
090890410UKR_f_a, and 100890000Bel_a)
and the Branch of Physical Sciences of the Russian
Academy of Sciences within the framework of the pro
gram Physics of New Materials and Structures.

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Translated by E. Chernokozhin

2011