ISSN 1063-7710, Acoustical Physics, 2009, Vol. 55, No. 1, pp. 5560. Pleiades Publishing, Ltd., 2009.

Original Russian Text S.V. Baryshnikov, B.F. Borisov, A.V. Gartvik, A.G. Gorchakov, E.V. Charnaya, W. Bhlmann, D. Michel, 2009, published in Akusticheski Zhurnal, 2009,
Vol. 55, No. 1, pp. 3238.

PHYSICAL ACOUSTICS

Acoustic Studies of Melting and Crystallization of Sodium Nitrite

Nanocrystals in the Pores of Mesoporous Silicate Matrices
S. V. Baryshnikova, B. F. Borisovb, A. V. Gartvikb, A. G. Gorchakovb, E. V. Charnayab,
W. Bhlmannc, and D. Michelc
a

Blagoveshchensk State Pedagogical University, ul. Lenina 104, Blagoveshchensk, 675000 Russia
b Institute of Physics, St. Petersburg State University,
ul. Ulyanovskaya 1, Petrodvorets, St. Petersburg, 198504 Russia
e-mail: gartwik@mail.ru
c Faculty of Physics and Geosciences, University of Leipzig, 5 Linnestrasse, D-04103 Leipzig, Germany
Received October 11, 2007

AbstractA conventional phase-pulse acoustic method was used to study melting and crystallization of
sodium nitrite embedded in the pores of mesoporous silicate matrices. The pore diameter was 20, 37, and 52 .
The measurements were performed at a frequency of 38 MHz in the temperature interval 290560 K. The temperature dependence of ultrasonic velocity was found to exhibit anomalies corresponding to phase transitions
of sodium nitrite. The transitions were smeared in temperature and shifted to lower temperatures from the melting point Tb of bulk sodium nitrite; the shift in crystallization temperature was greater than that of the melting
temperature. The irreversible character of melting was revealed. The size dependence of the melting temperature of sodium nitrite was obtained. Phenomena observed in the experiments were discussed with the use of
different size effect models.
PACS numbers: 62.65.+k, 64.70.Dv, 68.65.-k
DOI: 10.1134/S1063771009010059

INTRODUCTION
Various processes that occur in nanocomposite
materials are of considerable interest to modern condensed-matter physics. One of the methods widely used
for obtaining nanocomposites is their fabrication on the
basis of nanoporous silicate matrices, which are filled
with the necessary substance.
Among the methods used to study materials
embedded in silicate matrices, a special place is occupied by acoustic methods. The latter possess a number
of advantages: the simplicity of the techniques; the
rapidity of information extraction; in the case of a
varying temperature field, the possibility to vary the
temperature and the rate of its variation over wide
intervals and the precise control of these parameters;
and the high precision of experimental results. An
important consequence of these advantages is the possibility of using acoustic methods for studying the
kinetics of processes.
Earlier, acoustic methods were mainly used for
studying melting and crystallization of substances
embedded in the pores of silicate matrices. All the characteristic features of such phase transitions in confined
geometry were observed: their smearing in temperature, the shift of the melting point to lower temperatures
with respect to that of bulk material, and the temperature hysteresis between melting and crystallization. The

temperatures corresponding to the beginning and end of

the acoustic response to a phase transition, as well as
the changes in velocity and attenuation of ultrasonic
waves in the samples, were measured.
Until the mid-1990s, acoustic studies of melting and
crystallization in nanocomposites were performed with
the use of shear ultrasonic waves [1]. This choice was
based on the evident idea that shear waves are much
more sensitive to changes in the aggregate state, as
compared to longitudinal waves.
Our studies of phase transitions in mercury [2] and
decane [3] embedded in nanoporous matrices demonstrated that this idea failed: shear and longitudinal
waves proved to be almost equally sensitive to phase
transitions. In addition, it was shown [25] that the
magnitude of acoustic effects depends on the filling factor Z characterizing the degree to which the pores are
filled with the substance under investigation. The influence of this parameter depends on the character of
interaction between the substance and the matrix. As Z
decreases, a nonwetting substance (e.g., mercury in
glass) equilibrates first in the widest pores [4], whereas
a wetting substance (decane or indium) fills the narrowest pores at small values of Z [3, 5].
The sensitivity of acoustic methods to melting and
crystallization of substances in pores was studied using
matrices with different pore structures: (i) the through
55

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BARYSHNIKOV et al.
v / v0, %
Tb

10

20

30

40

50

60

300

350

400

450

500

550
T, K

Fig. 1. Temperature dependence of the velocity of longitudinal ultrasonic waves in sample 1: crosses, squares, and diamonds refer
to the first, second-to-third, and fourth-to-eleventh heating cycles, respectively.

pores of macroporous [6] and microporous [15]

glasses; (ii) isolated spherical pores [7] in glass; and
(iii) pores of opals [5, 8] between closely packed
spheres of amorphous silica. However, the applicability
of acoustic methods to studying melting and crystallization of substances in the tubelike pores of mesoporous silicate matrices remained open to discussion.
Among the variety of substances that were studied in
porous matrices, ferroelectrics form a separate group.
The number of publications devoted to their properties
in porous matrices is very small.
In [911], NMR studies of ferroelectrics (in particular, sodium nitrite (NaNO2)) in mesoporous silicate
matrices were described. The main was on the parameters of the ferroelectric phase transition and, partially,
on melting and crystallization of NaNO2. An evolution
of some of the properties of NaNO2 (the ferroelectric
transition temperature and the permittivity) toward the
properties of bulk NaNO2 was observed as the heating
cycles were repeated many times [911]. However,
possible specific applications of low-dimensional ferroelectric particles in engineering require much more
information on not only the ferroelectric phase transition, but also the set of all other properties of the given
material.
In this paper, we present the results of acoustic studies of melting for particles of NaNO2 embedded in the
pores of mesoporous lattices with different characteristic pore sizes.

SAMPLES AND EXPERIMENT

Mesoporous silicate matrices of the MCM-41 and
SBA-15 types, which served as the basis of our samples, had the form of tube structures with parallel onedimensional pores. The cross sections of such matrices
were honeycomb-shaped. The effective diameter of a
hexagonal one-dimensional pore was 37, 20, and 52
for sample nos. 1, 2, and 3, respectively. Samples 1 and
2 were fabricated on the basis of the MCM-41 matrices,
and sample 3, on the basis of the SBA-15 matrix.
The powder of mesoporous matrices (each grain
represented a separate matrix) was immersed in a saturated aqueous solution of NaNO2. After the solution
penetrated into the pores, the mixture was dried and
pressed under a pressure of 60007000 kg/cm2 to form
cylindrical samples with a diameter of 810 mm and a
height of about 3 mm.
Temperature variations of velocity and attenuation
of longitudinal ultrasonic waves propagating in the
samples were measured by the conventional phasepulse acoustic method [12] for longitudinal ultrasonic
waves in the frequency range 38 MHz in the temperature interval 290560 K. The acoustic contact was provided by vacuum lubricant. The sensitivity to ultrasonic
velocity variation was on the order of 5 104. Simultaneously, an additional ultrasonic attenuation coefficient was measured with an accuracy of ~5 dB/cm. The
error in temperature measurement was ~0.1 K.
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57

, dB/cm
20

20

40

60

80

100

300

350

400

450

500

550
T, K

Fig. 2. Temperature dependence of the additional attenuation coefficient in sample 1: squares and diamonds correspond to the third
and fourth-to-eleventh heating cycles, respectively.

RESULTS AND INTERPRETATION

Study of Sample 1
Figure 1 shows the temperature dependences of the
relative variation of ultrasonic velocity in sample 1 in
the course of its heating from 290 K (the melting point
of bulk NaNO2 is 544 K).
One can see that, at the initial stage of heating, the
ultrasonic velocity as a function of temperature
decreases approximately linearly; in the high-temperature region up to 543 K, its behavior is of a pronounced
nonlinear character.
Note that, in every subsequent cycle of heating, the
nonlinearity of the dependence v(T)/v0 begins at a
progressively higher temperature. Heating is terminated when the signal level approaches the noise level.
As the temperature decreases, the signal recovers. Figure 2 shows the temperature dependences of the additional attenuation coefficient of ultrasonic waves for the
third and fourth heating cycles. One can see that a
monotonic decrease in the additional attenuation coefficient as a function of temperature terminates with an
abrupt jump of ~ 80 dB/cm. Comparison of Figs. 1 and
2 shows that the beginning of the increase in attenuation corresponds to the beginning of the nonlinear
behavior of the dependence v(T)/v0.
The scatter of experimental points does not allow us
to reveal any considerable temperature hysteresis
between the heating and cooling branches.
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The dependences shown in Fig. 1 have a form typical of melting of almost all the substances studied in the
pores of silicate matrices (water [13], gallium [2, 6, 8,
13, 14], mercury [2, 4], indium [2, 5], hydrogen [15],
argon [16], decane [3], etc.). In all of the listed cases, a
sharp nonlinear decrease in ultrasonic velocity with
increasing temperature corresponded to melting of the
substance embedded in the pores. In most of the experiments, this relation was verified by NMR studies.
Small anomalies observed in ultrasonic velocity within
the temperature interval 320420 K (Fig. 1) can be
attributed to the liquidvapor transition of water occurring in the pores.
Earlier [911], NMR studies of the melting process
were carried out for NaNO2 nanocrystals in various
matrices, including a sample identical to sample 1 used
in the present work [10, 11]. In [911], it was noted that
the samples were studied after their preliminary heating, which could not be avoided.
According to the aforementioned progressive
increase observed by us in the melting temperature for
NaNO2 particles in each subsequent heating cycle, the
preliminary heating in [10, 11] can be interpreted as the
first heating cycle, which shifts the melting interval by
~4050 K toward higher temperatures (Fig. 1). The
melting temperature intervals reported in [10] correspond to the intervals observed in the second and third
heating cycles of the present experiments.

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BARYSHNIKOV et al.
v/v0, %

v/v0, %

2
2

6
1

8
280

3
300

320

340

360

380

400
T, K

300

280

320

340

360

380

400
T, K

Fig. 3. Results of acoustic studies of sample 2. The order of

temperature variation: 293362294 K (empty and full circles, first cycle); 293350293 K (empty and full triangles,
second cycle); 293393 K (crosses, third cycle).

Fig. 4. Variation of the parameters of acoustic response to

melting of NaNO2 in the pores of sample 2: 293393 K
(crosses, third heating cycle); 295427 K (diamonds, fourth
heating cycle).

Thus, comparison of our data with the data reported

in [10] testifies to a good agreement between the results
of acoustic and NMR studies.

decays into N2, NO, NO2, and Na2O [17]. Hence, the
heating of the sample to relatively high temperatures
may lead to a decrease in the filling factor Z characterizing the degree of pore filling with sodium nitrite. One
more mechanism that leads to a decrease in Z may be
evaporation of liquid NaNO2.
According to theoretical models describing the
melting of small isolated spherical particles on the basis
of the GibbsThompson equation or the assumption of
balance between the solid, liquid, and vapor phases
[18], as well as according to the geometric model [16],
the melting temperature TM linearly decreases with an
increase in the inverse diameter of particles d1. In particular, from the GibbsThompson equation, we obtain
the relation

Study of Sample 2
Figure 3 shows the experimental results for sample 2.
We can see that, unlike sample 1, in sample 2 the melting point of NaNO2 does not change from one heating
cycle to another (compare the first and third cycles).
The substance melts within the interval 334360 K
(experimental points deviating from the asymptotes).
The decrease in ultrasonic velocity due to melting is
3.6% (the distance in the vertical between the asymptotes at 347 K, which is the mean temperature of the
melting interval).
The absence of the evolution of the NaNO2 melting
point allowed us to measure the boundaries of the temperature range of crystallization for NaNO2 particles
(the first cycle, solid circles). As seen from Fig. 3, crystallization occurs within the interval 315340 K, which
is 1920 K below the melting interval. Such a noticeable width of the hysteresis loop had not been observed
earlier for meltingcrystallization of NaNO2 in pores.
The increase in the ultrasonic velocity due to crystallization is 4.1 % (at T = 328 K, which corresponds to the
middle of the crystallization interval).
Data of the second cycle (triangles in Fig. 3) testify
to the irreversible character of melting for NaNO2 in the
pores. This was also observed for the first time in the
present experiments.
The melting point of bulk NaNO2 is Tb = 544 K.
When the temperature rises above 590 K, this substance

4
TM TM
------------------- = ---------sl-,
0
Ld
TM

(1)

where T M is the melting temperature in a bulk sample,

sl is the coefficient of surface tension at the boundary
between the solid and liquid phases, L is the specific
heat of melting, and is the density of a particle. If we
take into account the formation of a liquid layer on the
particle surface with the layer thickness increasing with
temperature (the liquid coat model [19, 20]), we
obtain a smearing of the melting process and a nonlinearity in the dependence on d1. This, however, does not
change the general trend: the smaller the particle, the
lower its melting (or crystallization) temperature.
According to experimental data [2, 4, 5], a decrease
in factor Z should be accompanied by narrowing of the
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v/v0, %

59

TM, K
600

10

500

400

20

300
30
0
40
400

420

440

460

480

500

520
T, K

0.02

0.04

0.06
d 1, 1

Fig. 6. Size dependence of the melting temperature of

NaNO2 in pores: the solid square corresponds to a bulk
sample and the open circles represent the data of the present
experiment.

Fig. 5. Temperature dependence of the relative variation of

ultrasonic velocity in sample 3 in the first heating cycle.

temperature intervals of phase transitions, i.e., by

a decrease in their smearing.
Wetting of the matrix material by the filler leads to
narrowing of the meltingcrystallization intervals due
to the decrease in the temperature corresponding to the
upper boundary of the phase transition, because, when
Z decreases, the substance is redistributed into the pores
of minimal size [2, 5]. In the nonwetting case, the substance occupies the largest pores and, therefore, narrowing of the phase transition intervals occurs due to
the increase in the temperature corresponding to the
lower boundary of the phase transition [2, 4]. In both of
these cases, narrowing of the phase transition intervals
is accompanied by weakening of the acoustic response
to the phase transition.
Figure 4 shows the results of the third and fourth
heating cycles for sample 2. In the fourth cycle, we
observe a noticeable narrowing of the melting interval,
as compared to the third cycle, which, in view of the
aforesaid, allows us to characterize NaNO2 as a substance that wets the material of the matrix. Indeed, in
[21] it was found that NaNO2 wets the surface of glass
at an angle of (5 2).
Study of Sample 3
The results obtained for sample 3 are shown in Fig. 5.
As in the case of sample 1, in every subsequent heating
cycle, the temperature interval of melting for NaNO2 in
sample 3 steadily shifts, approaching the melting point
of bulk NaNO2. In the first heating cycle, the boundaries of the melting interval were 429 and 499 K (the
experimental points that deviate from the linear asymptotes). The decrease in the ultrasonic velocity due to
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melting was 12.6 % (the distance between the asymptotes at a temperature of 464 K corresponding to the
midpoint of the melting interval).
Size Dependence of the Melting Point
In Fig. 6, we combined the results for all the three
samples (open circles). The ordinates of the points correspond to the mean temperatures of melting intervals.
The solid square represents the melting point (Tb) of
bulk NaNO2.
Within the experimental error, it turns out that the
experimental results lie on a single straight line with the
point corresponding to Tb. This suggests that melting of
NaNO2 particles in the pores of mesoporous lattices
should preferably be described by the models of geometric thermodynamic size effect, rather than the liquid
coat model. The dependence TM(d1) is numerically
expressed as follows:
T M(d ) = kMd + Tb
1

= (3870 250)d + 544 = (3900 300)d + 544.

1

CONCLUSIONS
(i) Acoustic methods are sufficiently effective for
studying the meltingcrystallization phase transitions
of substances embedded in mesoporous lattices. Melting of NaNO2 in the pores of mesoporous matrices corresponds to a decrease in the velocity of ultrasonic
waves and an increase in their attenuation coefficient.
(ii) Melting of NaNO2 crystals in the pores of mesoporous silicate matrices is smeared in temperature and
shifted toward lower temperatures with respect to the
melting point of bulk NaNO2. As the inverse diameter
of pores increases, the mean melting temperature of

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BARYSHNIKOV et al.

NaNO2 linearly decreases. The study of sample 2

shows that a considerable temperature hysteresis may
exist between melting and crystallization of thermally
untreated samples and that the process of melting of
NaNO2 in the pores is of irreversible character.
(iii) Data obtained by the acoustic method revealed
the evolution of the NaNO2 melting point in the course
of thermal cycling. This effect was observed for the first
time.
ACKNOWLEDGMENTS
This work was supported by the Russian Foundation
for Basic Research, project no. 07-02-00189.
REFERENCES
1. K. Warner and J. R. Beamish, Phys. Rev. B 50, 15896
(1994).
2. A. V. Gartvik, Candidates Dissertation in Physics and
Mathematics (St. Petersburg, 2005).
3. B. F. Borisov, A. V. Gartvik, A. G. Gorchakov, et al., in
Proceedings of XVI Session of the Russian Acoustical
Society (GEOS, Moscow, 2005), Vol. 1, p. 12.
4. B. F. Borisov, A. V. Gartvik, F. V. Nikulin, and E. V. Charnaya, Akust. Zh. 52, 172 (2006) [Acoust. Phys. 52, 138
(2006)].
5. B. F. Borisov, A. V. Gartvik, Yu. A. Kumzerov, et al., in
Proceedings of XV Session of the Russian Acoustical
Society (GEOS, Moscow, 2004), Vol. 1, p. 140.
6. B. F. Borisov, E. V. Charnaya, W. D. Hoffman, et al.,
J. Phys.: Condens. Matter 9, 3377 (1997).
7. A. I. Nedba, I. T. Khodzhakhonov, and E. V. Charnaya,
Akust. Zh. 34, 181 (1988) [Sov. Phys. Acoust. 34, 102
(1988)].

8. J. M. Dereppe, B. F. Borisov, E. V. Charnaya, et al., Fiz.

Tverd. Tela 42, 184 (2000) [Phys. Solid State 42, 193
(2000)].
9. S. Tien, E. V. Charnaya, S. V. Baryshnikov, et al., Fiz.
Tverd. Tela 46, 2224 (2004) [Phys. Solid State 46, 2301
(2004)].
10. C. Tien, E. V. Charnaya, M. K. Lee, et al., Phys. Rev. B
72, 104105 (2005).
11. S. V. Baryshnikov, E. V. Stukova, E. V. Charnaya, et al.,
Fiz. Tverd. Tela 48, 551 (2006) [Phys. Solid State 48,
593 (2006)].
12. M. B. Gitis, I. G. Mikhalov, and V. A. Shutilov, Akust.
Zh. 15, 28 (1969) [Sov. Phys. Acoust. 15, 25 (1969)].
13. B. F. Borisov, M. R. Gruzman, and E. V. Charnaya, in
Acoustics of Inhomogeneous Media (Novosibirsk, 1997)
[in Russian].
14. B. F. Borisov, E. V. Charnaya, A. V. Gartvik, et al., Fiz.
Tverd. Tela 46 (12), (2004) [Phys. Solid State 46 (12),
(2004)].
15. M. Schindler, A. Detringer, Y. Kondo, and F. Robell,
Phys. Rev. B 53, 11451 (1996).
16. E. Molz, A. P. Y. Wong, M. H. W. Chan, and J. R. Beamish,
Phys. Rev. B 48, 5741 (1993).
17. I. L. Knunyants, Chemical Encyclopedia in Five Volumes (Bolshaya Sov. ntsiklopediya, Moscow, 1992),
Vol. 3, p. 183 [in Russian].
18. Yu. I. Petrov, Physics of Small Particles (Nauka, Moscow, 1982) [in Russian].
19. Ph. Buffat and J-P. Borel, Phys. Rev. A 13, 2287 (1976).
20. E. V. Charnaya, Cheng. Tien, M. K. Lee, and Yu. A. Kumzerov, Phys. Rev. B 75, 144101 (2007).
21. V. A. Ivantsov, Candidates Dissertation in Physics and
Mathematics (Leningrad, 1988).

Translated by E. Golyamina

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