ISSN 0965-545X, Polymer Science, Series A, 2016, Vol. 58, No. 6, pp. 10151022. Pleiades Publishing, Ltd., 2016.

Original Russian Text A.N. Ilyasova, G.A. Shandryuk, Ya.V. Kudryavtsev, T.N. Lebedeva, M. Lutovac, K.V. Pochivalov, 2016, published in Vysokomolekulyarnye Soedineniya, Seriya A,
2016, Vol. 58, No. 6, pp. 661670.

INVESTIGATION
METHODS

Phase Equilibria and Transformations

in Low-Density Polyethylenep-Xylene System
A. N. Ilyasovaa, G. A. Shandryukb, Ya. V. Kudryavtsevb, T. N. Lebedevaa,
M. Lutovacc, and K. V. Pochivalov a*
a Institute
b

of Chemistry of Nonaqueous Solutions, Russian Academy of Sciences, Akademicheskaya 1, Ivanovo, 153045 Russia
Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, Leninskii pr. 29, Moscow, 119991 Russia
c
Nikola Tesla UNION University, Cara Duana 6264, Belgrade, 11000 Serbia
*-mail: pkv@isc-ras.ru
Received June 7, 2016; Revised Manuscript Received June 30, 2016

AbstractThe state diagram of the low-density polyethylenep-xylene system that contains the solubility
curve of p-xylene in the polymer is first built using the optical method with the involvement of the DSC data.
It has been shown that, at 72C, in a blend with a polymer mass fraction of 0.28, the full amorphization of the
polymer proceeds simultaneously with the dissolution of p-xylene in it. Blends with a lower polymer content
are also homogenized at the same temperature, although the duration of this process can take several days. In
blends with a high polymer content, homogenization occurs at a higher temperature. This process is preceded
by the formation of microheterogeneous single-phase gel with network junctions as polymer crystallites and
amorphous regions saturated by p-xylene. Cooling of the homogeneous blends to 20 is not accompanied
by the full separation of low- and high-molecular-mass phases; in this case p-xylene not only forms an individual crystalline phase, but also partially crystallizes in amorphous regions of the polymer.
DOI: 10.1134/S0965545X16060092

Introduction
Different points of view about the phase state of
partially crystalline polymers are available in the literature. According to one of them, the aforementioned
polymers are single-phase and form substantially
defective crystals. This conception is widely used in
consideration of the blends of partially crystalline
polymers with liquid and crystalline low-molecularmass compounds [14]. Another point of view
assumes that crystalline and amorphous phases coexist; this idea is convenient for describing mass transfer
in these polymers [510].
The thermodynamic analysis of our results and the
literature experimental data [11] makes it possible to
state that both of these points of view are contradictory. Not adducing all arguments let us note that the
weak point of the first approach is connected with the
unreasonable use of macromolecules as an elementary
object of crystallization, while in the case of the second approach, the weak point is related to the impossibility of separating crystalline and amorphous
regions of polymers without destroying tie chains.
Our investigations of partially crystalline polymers
are based on the idea that, in macroscopic thermodynamics, they should be considered to be single-phase
liquid systems [11] with the following specifics:

(i) at the microlevel, they are substantially heterogeneous, but as macrophases, they are homogeneous
in accordance with Gibbs because the structural
parameters of macrosamples of any size are similar;
(ii) because of the incompleteness of the crystallization of the polymer unit, they are thermodynamically nonequilibrium and because of the physical indivisibility of microvolumes with different levels of order
in the spatial location of the polymer units, they are
internally stressed;
(iii) in terms of structural chemistry, these are
polymer gels with thermotropic junctions as crystallites, in which the volumes of junctions and interjunction spaces are comparable (in contrast to vulcanized
elastomers that consist of three dimensionally structured liquids).
With regard to semicrystalline polymerlowmolecular-mass compound systems, two types of processes are of interest, i.e., mixing two liquids, one of
which is polymeric and can be in the specific state
described above, and dissolution in the polymeric liquid and crystallization of the low-molecular-mass
component from it.
Using the original optical method [12], full state
diagrams of LDPE [1315], HDPE [16], and PP [15,
1719] blends with different low-molecular-mass
compounds were built. They can be qualified as dia-

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ILYASOVA et al.

grams of the polymergood solvent, polymerpoor

solvent, and polymercrystalline compound systems.
All of them contain the boundary curve of full polymer
amorphization that, according to our conception,
describes a change in the polymer physical state without a change in the system phase state. Let us note that
a similar situation is observed for pseudobinary blends
of PS [20], the diagram of which contains the temperature boundary of transformation of a glassy polymer into the rubbery one instead of the above-mentioned curve.
The thermal properties of the semicrystalline polymerlow-molecularmass compound systems are
also studied using the DSC method [21]. In contrast to
the data of the optical method, which can be used to
build the state diagram, the thermograms require a
certain interpretation that cannot always be unambiguous [19]. Moreover, the application of DSC, regardless of the rate of heating or cooling provides no way to
obtain the phase curve of the low-molecular-mass
component solubility in the polymer; as a result, the
state diagram turns out to be incomplete.
In the present work, investigating the LDPEpxylene system, which is methodically convenient (the
melting points of both components are above 0 and
differ by almost 100), we have quantitatively analyzed and compared the data obtained by the optical
method and by using DSC in order to build the full
state diagram and to show how these methods complement each other during the study of thermal properties
of semicrystalline polymerlow-molecular-mass
compound system.
EXPERIMENTAL
Low-density polyethylene of the 15083-020 trademark (OOO Tomskneftekhim) with an MFI of 1.32
0.05 g/10 min measured on an IIRT-5M apparatus at
190 under a load of 2.16 kg (Specifications 2211001-14596232/ DIN EN ISO 1133:2005) and a pycnometric density of 0.915 0.003 g/cm3 determined at
25 was used in this study. The melting point of
LDPE (107.9 0.5C) was found on a Boetius small
heating stage equipped with an RNMK-05 imaging
device (Veb Analytic) at a heating rate of 4 grad/min.
P-Xylene (1,4-dimethylbenzene, Acros Organics,
99%) was used as a low-molecular-mass component
of the blend without additional purification.
DSC thermograms were obtained using a Mettler
Toledo DSC 823e calorimeter at rates of heating and
cooling of 10 grad/min, a sample mass of 713 mg,
and standard calibration. According to the DSC data
(the second heating), the melting points of the components were 105.8 0.3C (melting maximum of
LDPE) and 11.5 0.3C (the onset of p-xylene melting); the specific melting enthalpies were 122 1 J/g
(LDPE) and 155 1 J/g (p-xylene).

The calorimetric studies of LDPEp-xylene systems of various compositions were performed in the
following mode: cooling of the initial blend to 20,
first heating to 150, holding at this temperature for
5 min, cooling to 20, thermostating for 5 min, and
a second heating to 150. After the experiment, a
crucible with the sample was additionally weighed to
control the possible loss of p-xylene.
The state diagrams were built using the optical
method described in detail in [12, 14, 19]. This
method is based on step-by-step heating of the initially
heterogeneous blend and determination of the temperature at which the full amorphization of the polymer and the transformation of the initial two-phase
system into a single phase occurs using a cathetometer.
The accuracy of the method was 0.5.
RESULTS AND DISCUSSION
The state diagram of the LDPEp-xylene system
built based on optical experiments is shown in Fig. 1
(open circles). This includes the ascending ABC curve,
which characterizes the temperature boundary of full
polymer amorphization in the presence of a liquid and
the descending ABD curve, which reflects the complete dissolution of p-xylene in the polymer.
In accordance with the plotting method, these
curves are in the single-phase region over the corresponding coexistance curves on the theoretical phase
diagram; however, the difference between them does
not exceed the optical method accuracy (0.5);
therefore, hereafter we consider ABC and ABD curves
as boundary. These lines divide the diagram into the
following three regions:
region I is a single-phase component blend that
is homogeneous at the molecular level;
region II is a single-phase microheterogeneous
blend that is a solution of a low-molecular-mass component in amorphous regions of the semicrystalline
polymer;
region III is a two-phase blend of liquid p-xylene
(which can contain oligomeric fractions of LDPE that
do not form crystallites) above the melting point of
p-xylene and it solution in amorphous regions of the
polymer and, below this temperature, the two-phase
blend that consists of crystalline p-xylene and its solution in amorphous regions of the polymer.
The meaning of the truly phase line has only the
ABD solubility curve that separates the single-phase
region of the state diagram from the two-phase one.
On the AB segment, this curve coincides with the ABC
boundary curve, as is typical of semicrystalline polymerthermodynamically good solvent systems [22].
The value of TB corresponds to the imaging point B,
which characterizes the minimum temperature of full
LDPE amorphization in the presence of liquid
p-xylene.

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As follows from Fig. 1, during the heating of the

initial blend of solid components, where the polymer
mass fraction 2 exceeds the threshold value 2 =
0.28, the microheterogeneous single-phase system
forms first, after which its homogenization occurs. In
the region of compositions that correspond to conditions 2 < 2, at T = TB = 72, the two-phase liquid
(p-xylene solution in fully amorphized LDPE and
p-xylene excess) optically transparent system forms; it
becomes homogeneous after several days without any
additional heating.
Let us note that, at a temperature below the melting
point of p-xylene (11.5C), its dissolution in the LDPE
amorphous regions must occur via the vapor-phase
mechanism [23]. The possibility of dissolving a lowmolecular-mass component in a polymer without
their immediate contact has been previously demonstrated in [15] on the example of the HDPE1,2,4,5tetrachlorobenzene system by placing the low-molecular-mass component into a small open tube inside of
an ampoule with the polymer.
Curves ABC and ABD in Fig. 1 are plotted from the
data of the optical method. The attempt to use the
DSC thermograms (Fig. 2) for this purpose encounters objective difficulties. In fact, heating the blend
with composition 2 > 2 is accompanied by two processes, i.e., the dissolution of p-xylene in amorphous
regions of the polymer and the thermomechanical
amorphization of the polymer (as a result of the joint
action of temperature and swelling pressure). The circumstance that these processes proceed simultaneously almost excludes possibility to separate their thermal effects. In the region 2 < 2, there are two calorimetrically indistinguishable processes, i.e., the
formation of a homogeneous blend of composition
2 and its mixing with p-xylene excess. Consequently, in an analysis of DSC thermograms, one can
only conventionally speak about polymer melting
bearing in mind the total thermal effect that describes
the formation of the LDPEp-xylene homogeneous
liquid blend.
Figure 1 shows that the ABC curve of LDPE amorphization in the presence of different amounts of
p-xylene can only approximately be plotted from the
DSC data (closed circles). For blends with compositions close to 2, the best agreement with the optical
method data is achieved when the maximum of polymer melting peak (triangles) is taken as the temperature of full amorphization; for the other blends, the
value that corresponds to the end of this peak
(rhombs). At the same time, as for other binary systems investigated before, the BD fragment of the
p-xylene solubility curve cannot be plotted using the
DSC method.
Figure 1 also shows EFG and EFH curves plotted
from the temperature that corresponds to the onset of
the p-xylene melting peak on the DSC thermogram.
On the EF fragment, this temperature is constant and
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1017

T, C
125
C

I
100

75 A

B
II

50
III
25

D
E

0
H
25

0.2

0.4

0.6

0.8

1.0
2

Fig. 1. State diagram of the LDPEp-xylene system in

coordinates Tweight fraction of polymer 2. Curves of
the full amorphization of LDPE (ABC) and p-xylene
forming the individual phase (EFG) and crystallized in
LDPE amorphous regions (FH) are given, as well as the
curve of p-xylene solubility in (ABD). See text for explanations.

corresponds to a melting point of pure p-xylene of

11.5C within the accuracy of the method, regardless
of the presence of oligomeric (noncrystallizable)
LDPE fractions. Note that, in the region of 2 2
0.69 on the thermograms of the blends (Fig. 2), the
melting peak expands and can be divided into two
peaks, one of which corresponds to the same temperature, while the other one corresponds to a lower temperature. With a decrease in the content of p-xylene,
the intensity of both peaks falls so that only the first
peak is observed at 2 = 0.80, while at 2 > 0.80, the
thermal effect of p-xylene melting is not detected
using DSC.
On the basis of classical ideas that the melting point
of crystals for a low-molecular-mass compound
decreases with a reduction in their size, it can be
assumed that the descending branch of the FH liquidus curve corresponds to the melting of p-xylene crystals; the smallest crystals in its own phase melt at
11.5. Such crystals of a limited size can form in
pores of a capillary-porous body that forms during
thermally induced microphase separation of the

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ILYASOVA et al.

exo

1
2
3
4
5
6
7
8
9
10
11
12
13

20

20

40

60

80

100

120

140
T, C

Fig. 2. DSC thermograms obtained during the second heating of LDPE in the presence of 1 = 1 2 = (1) 0, (2) 0.093, (3)
0.201, (4) 0.309, (5) 0.333, (6) 0.397, (7) 0.501, (8) 0.598, (9) 0.699, (10) 0.801, (11) 0.900, (12) 0.973 wt fractions of p-xylene,
and (13) during heating of pure p-xylene.

cooled binary system. The pores of this body are filled

with p-xylene, while its walls represent a single-phase
gel, i.e., the solution of p-xylene in the amorphous
regions of LDPE and polymer crystallites as physical
crosslinks. As is clear from common considerations,
the lower the content of the low-molecular-mass
component in the initial blend, the smaller the size of
the forming pores and, respectively, crystals formed in
them; hence, the lower their melting point. For blends
depleted of low-molecular components (2 0.70),
the size of p-xylene crystals in the polymer becomes so
small that the DSC apparatus does not register the
thermal effect of their melting.
Knowing temperature TmL of crystallite melting, its
thickness L may be estimated through the Thomson
Gibbs ratio

L=

2 s Tm0
.
H (Tm0 TmL )

(1)

Substituting the tabular data for molar mass =

0.106 kg/mol, density = 861 kg/m3, surface tension
coefficient at 5C s = 2.99 102 J/m2, molar
enthalpy H = 17.1 kJ/mol, and equilibrium melting
point Tm0 = 13.2C of p-xylene [24], we find that the
size of these crystals increases from 6 to 17 nm as the
mass fraction 1 of p-xylene in the initial blend with
LDPE is increased from 0.3 to 0.6. After the removal
of the low-molecular-mass component, pores of the
corresponding size should remain in the polymer; in
principle, these pores can be detected by electron
microscopy.

The coincidence of EFD and EFG lines on the EF

fragment that corresponds to approximately the same
region of compositions as the AB fragment (2 2)
implies that in this case crystals of p-xylene that melting at a conventional temperature of 11.5 are formed
both on the surface and in the volume of the semicrystalline polymer (after preliminary homogenization of
system during the first heatingcooling cycle).

Let us now analyze the DSC data in detail using not

only thermograms of the second heating (Fig. 2), but
also the preceding first heating (Fig. 3) and cooling
(Fig. 4) thermograms, which represent the standard
thermal cycle for the p-xyleneLDPE system of cooling heating cooling heating.
In a typical experiment, two endothermal processes are detected in the system during heating. As
was mentioned above, these processes can be only
conventionally identified as the melting of p-xylene
(process 1) and LDPE (process 2). As follows from
Figs. 5 and 6, the absolute magnitude of the specific
enthalpy of these processes H1 and H2, respectively,
depends on content 2 = 1 1 of LDPE in the blend.
It can be seen that differences between the thermal
effects during cooling, first heating, and second heating are more substantial for the low-molecular-mass
component than that for the polymer. This finding
may be explained by the fact that the melting or crystallization of the most part of p-xylene occurs in the
individual phase. In the range of compositions 2 >
2, its formation is significantly affected by the
kinetic effects (diffusion of p-xylene into polymer vol-

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1019

exo

2
3
4
5
6
7
8
9
10
11
12
13

20

20

40

60

80

100

120

140
T, C

Fig. 3. DSC thermograms obtained during the first heating of LDPE, p-xylene, and their blends. Curve description is in Fig. 2.

exo

13
12
11
10
9
8
7
6
5
4
3
2
1
20

20

40

60

80

100

120

140
T, C

Fig. 4. DSC thermograms obtained during cooling of LDPE, p-xylene, and their blends. Curve description is in Fig. 2.

ume or from it), while the LDPE amorphization is not

connected with the macroscopic phase separation.
Using the approximating linear functions determined by the least-squares method H1(2) =
157.42 + 146.5 (J/g) (first heating), H1(2) =
223.92 + 157.2 (J/g) (cooling), and H1(2) =
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184.22 + 151.2 (J/g) (second heating), some characteristics of the blend at 20 may be calculated,
that is, immediately before the first heating, right after
cooling, and immediately before the second heating.
These are fraction of crystallized p-xylene with
respect to the total mass of p-xylene, fraction of liquid p-xylene with respect to the mass of the whole sys-

1020

ILYASOVA et al.

H2, J/g

H1, J/g
160

100
1
120

75

3
80

50

40

25

0.2

0.4

0.6

0.8

1.0
2

Fig. 5. Dependence of the absolute value of melting

enthalpy (crystallization) of p-xylene on the weight fraction 2 = 1 1 of LDPE in the blend for (1) the first
heating, (2) cooling, and (3) the second heating. Approximating linear functions are designated by solid, dashed,
and dotted lines, respectively.

H1
,
(1 2 ) H 10
1' =

= (1 )(1 2 ),

,
+ 2

0.2

0.4

0.6

0.8

1.0
2

Fig. 6. Dependence of the absolute value of melting

enthalpy (crystallization) of LDPE on weight fraction 2
= 1 1 of LDPE in blend for (1) first heating, (2) cooling, and (3) the second heating. Approximating linear
functions are designated shown by solid, dashed, and dotted lines, respectively.

tem, and weight fraction 1' of liquid p-xylene in its

solution in LDPE

(2)

where H 10 = 157.5, 158.9, and 155.0 J/g are the absolute values of the specific enthalpy of melting (crystallization) of pure p-xylene determined by DSC during
the first heating, cooling, and second heating, respectively.
The dependences of , , and 1' values on the
blend composition are built in Fig. 7. It follows from
Fig. 7a that some of the p-xylene does not crystallize
and apparently remains dissolved in the polymer. With
an increase in the content of LDPE, the fraction of
crystallized p-xylene falls. A comparison of curves 1
3 that correspond to different thermograms shows that
the value of is maximum before first heating (curve
1), when the interpenetration of system components
that were brought into contact at room temperature,
then cooled to 20 is the least pronounced. In contrast, right after the system is cooled from the melt, the
degree of mixing of the components, along with the
degree of solvation of p-xylene is maximum (curve 2).
Exposure for 5 min at 20 leads to the additional
crystallization of p-xylene in amorphous regions of the
polymer; as a result, the value of increases (curve 3).
Simultaneously, both the weight fraction of liquid

p-xylene in the system (compare curves 2 and 3 in

Fig. 7b) and its fraction 1' in the blend with LDPE
playing role of a solvent decrease (compare curves 2
and 3 in Fig. 7c).
In the range of compositions 2 > 2, the amount
of solvated p-xylene increases in proportion to the
amount of polymer. In this case, the mass of pxylene that remained liquid at 20 per blend mass
unit must really increase in proportion to the weight
fraction 2 of polymer, whereas the composition 1' of
the blend of liquid p-xylene with LDPE should not
depend on 2. This behavior is characteristic of systems in which both components were preliminarily
homogenized through heating over the melting point
of LDPE (curves 2 and 3 in Figs. 7b, 7c). The violation
of these regularities at a low polymer content (2 <
2) is apparently connected with a change in the spatial structure of the polymer gel that plays the role of
an osmotic cell for a low-molecular-mass compound.
The other behavior (Figs. 7b, 7c, curves 1 in) was also
demonstrated by the blend before the first heating.
This blend was obtained by the cooling of the initial
system from room temperature, when it represented
polymer granules covered by a low-molecular-mass
liquid. In this case, the amount of liquid p-xylene at
20 comprises about 7% of the blend mass independently of its composition. This observation may be
explained by the substantially heterogeneous state of
the system.

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The thermal effect of the second process on the

DSC thermograms is described by ratios H2(2) =
101.22 + 1.8 (J/g) (first heating), H2(2) =
100.82 + 7.1 (J/g) (cooling), and H2(2) =
104.72 + 4.5 (J/g) (second heating). In this case, for
pure LDPE, the specific melting enthalpy during the
first and second heating is H 20 = 108.2 and 122.1 J/g,
respectively. These values correspond to degrees of
crystallinity of the polymer of 37 and 42% because, for
fully crystalline LDPE, H 20 = 293 J/g [25].
The feature of point on the phase diagram
(Fig. 1) is that the spontaneous dissolution of the lowmolecular-mass liquid in the polymer occurs simultaneously with its full amorphization in the blend with
2 = 2. Consequently, in this case, the thermal
effect measured during DSC experiments should be
numerically equal to the polymer melting enthalpy
2H 20 . Setting H2(2B) to be equal to 2BH 20 , we find
that in both cases point B corresponds to the blend
composition 2B = 0.26. This result is close to a value
of 0.28 obtained by the optical method. When 2 <
2, the additional energy required to mix components
of the system under the conditions of DSC experiments; that is, H2(2B) > 2BH 20 and, when 2 > 2,
on the contrary, the melting of LDPE is promoted by
the osmotic pressure of p-xylene penetrated the amorphous regions of the polymer at a lower temperature;
therefore, H2(2B) < 2BH 20 . Note that it is impossible to use the DSC cooling curve to find a position of
point B because meltingcrystallization temperature
hysteresis is characteristic of polymers [2], which is
caused by the formation of crystal nuclei.
Figure 8 shows how the position of the full LDPE
amorphization curve changes (DSC data), if this curve
is plotted using the results of the first heating (open
circles) instead of the second heating (closed circles).
The temperatures of both the maximum and, to a
greater degree, the end of polymer melting peak turn
out to be systematically overestimated. Moreover, this
effect is the most pronounced in blends with compositions 2 < 2, when the content of p-xylene inside
the LDPE granules is substantially lower than the
thermodynamic equilibrium value. As a result, poor
agreement between the DSC data and the results of
optical studies should be expected than that the ABC
curve in Fig. 1.
It may be stated that, during the first heating, a
low-temperature peak of p-xylene melting with an
almost constant temperature of its onset and a hightemperature peak that reflects the amorphization of
LDPE in the presence of p-xylene, which dissolved in
it during the DSC experiment, is observed in the entire
range of the blend composition. Consequently, the
initial structural inhomogeneity of the blend that disappears after melting both components during the first
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1.0

1021

()

0.8

1
3

0.6

0.4
0.2

0.2

0.4

0.6

0.8

1.0
2

(b)

0.3

2
0.2
3
0.1

0.2

0.4

0.6

0.8

1.0
2

1'
(c)
0.6

0.4
2
3

0.2

1
0

0.2

0.4

0.6

0.8

1.0
2

Fig. 7. Dependence of fraction of crystallized p-xylene in

relation to (a) the total mass of p-xylene, fraction of liquid p-xylene in relation to (b) the mass of the whole system, and (c) the weight fraction 1' of liquid p-xylene in its
solution in LDPE on polymer content in blend at (1)
20 before first heating, (2) after cooling, and (3) before
second heating.

1022

ILYASOVA et al.

T, C
C
105

90
1
2
75

60

0.2

0.4

0.6

0.8

1.0
2

Fig. 8. Dependence of temperature of (1, 2) maximum and

(3, 4) end of LDPE melting peak in the blend with pxylene on the weight fraction of polymer 2 by data of DC
during (1, 3) first and (2, 4) second heating.

heating is the main reason why the data of the second

heating should be used in the calorimetric experiments
with the semicrystalline polymerlow-molecularmass compound binary system.
The homogenization of the binary system leads to a
substantial increase in the contact area between its
components. At the same time, after cooling the blend
remains two-phase and contains the microheterogeneous LDPE gel with p-xylene dissolved (solvated) in
its amorphous regions and crystals of p-xylene that
have different melting points depending on their size.
On the whole, although DSC cannot be considered to
be the main method of building the state diagram of
the semicrystalline polymerliquid system, which is a
useful addition to the optical method that makes it
possible to ambiguously register change in the number
of phases in the system and in the physical state of the
polymer component.
ACKNOWLEDGMENTS
This work was supported by the Russian Foundation for Basic Research, project no. 15-33-50598.
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1. B. Wunderlich, Macromolecular Physics (Acad. Press,

New York, 1980), Vol. 3.

POLYMER SCIENCE, SERIES A

SPELL: OK

Translated by K. Aleksanyan

Vol. 58

No. 6

2016