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e-Polymers 2003, no. 035.
ISSN 1618-7229

Kinetics of non-isothermal melting and crystallization of

gamma-irradiated isotactic polypropylene

Emanuel Nedkov *, Tatyana Dobreva

Bulgarian Academy of Sciences, Institute of Polymers, bl. 103-A, akad. G. Bonchev

Blvd., 1113 Sofia, Bulgaria; etnedkov@polymer.bas.bg

(Received: May 28, 2003; published: July 9, 2003)

Abstract: The non-isothermal kinetics of melting and crystallization of gamma-irra-

diated isotactic polypropylene were investigated by differential scanning calori-
metry. At constant temperature the melting rate increased with the dose. During
the melting, the average lamellar thickness, the free surface energy and the
transport energy through the phase boundary reduced with increasing the dose.
The crystallization rate decreased with increasing dose at constant temperature.
Mixed α-γ spherulites were grown during crystallization. The non-isothermal
crystallization rate expressed, in fact, the rate of secondary nucleation of the
lamellae in the spherulites and their growth. Raising the irradiation doses led to a
decrease of the crystallization temperature. A critical dose of irradiation of about
200 kGy was found, where the dependences of the calculated kinetic parameters
underwent an important change. This change could be successfully connected with
the effect of radiation annealing and melting.

Introduction

Theories of non-isothermal crystallization

Jeziorny’s method [1] is based on the assumption that the crystallization rate can be
expressed by a first-order kinetic equation:
dX t
= (1 − X t )kt (1)
dt
Xt is the degree of conversion, t is time, and k a constant.
Jeziorny introduced a correction for the cooling rate: log Zc = log Zt /(dT/dt); where Zt
is a rate constant, and Zc the corrected rate constant. In the same way, the author
corrected the so-called ‘kinetic crystallizability’ G1 and obtains a final form of Gc: Gc =
G1/(dT/dt). Following Jeziorny, both parameters Zc and Gc could be successfully used
for describing the kinetics of non-isothermal crystallization since they do not depend
on the cooling rate. However, Jeziorny’s method is based on the assumption that
crystallization runs isothermally and later the values are corrected to compensate for
the non-isothermal nature of the process.
Ozawa [2] offered an equation for the rate of non-isothermal crystallization, which
describes the degree of conversion x(t) at temperature T:

1
X (t ) = 1 − k exp( −v 0n ) (2)
It is similar to the Avrami equation and after taking the double logarithm, the para-
meters k and n are estimated as the cut and the slope of the plot log[-log(1-x)] vs. v0:
log[-log(1-x(t))] = k - n log v0 (3)
Borohovski et al. [3] achieved an other equation, which has been evolved from
Avrami’s equation. After taking the double logarithm, k and n are calculated as the
cut and the slope of the plot log[-log(1-x)] vs. log(v0t):
x(t) = 1 - exp[-k(v0tn)] (4)
Ziabicki [4] described the non-isothermal crystallization process with the differential
equation:
dx (t )
= (1 − x )G (T ) (5)
dt
G(T) ≈ Gmax exp[-4 ln2(T - Tm0)2/W1/22] (6)
where Gmax is the maximum crystallization rate. W1/2 is the half-width of the non-
isothermal peak. T and Tm0 are the current temperature and the equilibrium melting
point, respectively. Up to now the non-isothermal crystallization rate has been
described only by the variation of the temperature. Here, it is a function of super-
cooling. This difference gives a new, clearer physical meaning of the non-isothermal
kinetics.
Lim and Lloyd [5] applied both Ozawa’s and Ziabicki’s theories on polypropylene
(PP), and the result was identical: instantaneous nucleation and three-dimensional
growth of spherulites. They calculated the overall crystallization rate, taking the
suggestions of Ziabicki:

G(T ) dT = (π / ln 2) Gmax (W1/ 2 / 2)

Tm
∫
1/ 2
G= (7)
Tg

where the integral is from the glass transition temperature Tg until the melting temper-
ature Tm.
Atanasov and Nedkov [6] have proposed another equation (Eq. (8)) for the total rate
of the non-isothermal process. The whole non-isothermal process was defined as a
series of isothermal processes in corresponding infinitesimal temperature intervals.
dH dα
∞

dT
Tn
∫0 dT
dT
G = v0 (8)
∆H F ∞ dα
∫Tn dT dT
where G is the total rate at the temperature Tn; v0 is the heating or the cooling rate;
dH/dT is the enthalpy for the given narrow temperature range at the current temper-
∫ (dH / dT )dT
∞
ature Tn; ∆HF is the enthalpy of melting of an ideal crystal; is the
0
enthalpy of the whole quantity of the substance, molten from beginning to the end of
∫ (dH / dT )dT is the enthalpy of the quantity of the substance
∞
the phase transition;
Tn
which remains to be transformed into the other phase, and is the correction function
[7,8].

2
The process of non-isothermal crystallization as a nucleation-controlled crystal
growth with folded chains is based on the biexponential equation of Turnbull and
Fisher [9] modified according the theory of Hoffman et al. [10]; both equations refer to
isothermal crystallization.
Ed πσ 2a Tm0
log G = log G −
0
− (9)
2.3RT 2.3R∆HF T∆T
where G0 is the number of attempts of passing of the crystal segment through the
phase boundary; Ed is the transport energy through the phase boundary; R is the gas
constant; σ is the folded surface energy of crystallites; Tm/(T∆T) is the temperature
factor.
Monasse and Haudin [12] used only the theory of Ozawa in the temperature range of
non-isothermal crystallization of PP, from 107 to 129°C. The same authors found a
critical temperature of 122°C for PP, at which the homogeneous nucleation trans-
forms into a heterogeneous one.
Mubarak et al. [13] applied the known kinetic models to predict the non-isothermal
crystallization behaviour of PP. The results suggested that the available mathe-
matical models were not successful in describing the non-isothermal crystallization of
isotactic PP (iPP) over a wide range of cooling rates. They modified the Ozawa
model to include an induction time for a better quantitative description of non-iso-
thermal crystallization of PP.
A review of up-to-date non-isothermal crystallization theories was made by Lorenzo
et al. [14] They found that there is no theory, which could be applied for all types of
polymers. A possible explanation can be found in the different crystallization mecha-
nisms that some polymers can undergo. In the case of a low degree of conversion of
the polymer until about 0.5, there is a low overall crystallization rate or diffusion-
controlled crystallization and Ozawa’s method could be successfully applied. How-
ever, it does not give an account of the secondary crystallization [11-14]. At higher
degree of conversion of the polymer until about 0.9, Ziabicki’s theory could be
applied more successfully. The crystallization rate hastens, due to athermal nuclei,
which appear sporadic at lower temperature [14-16].
The non-isothermal kinetics of melting and crystallization according to Eq. (8) was
subject of studies in refs. [17-19] The results of gamma-irradiated PP gel showed that
the melting rate increases with the dose at the same temperature. But the crystalli-
zation rate decreases with the dose at the constant temperature [17]. Foamed, cross-
linked low-density polyethylene was investigated [18], as well as block copolymers
[19], by means of a computer program. The transport energy through the phase
boundary, free surface energy, lamella thickness, and the degree of crystallinity were
estimated [18].
The aim of the present work is to study the kinetics of non-isothermal melting and
crystallization of gamma-irradiated isotactic polypropylene by means of the method of
Atanasov and Nedkov [6,7]. Determining the above parameters we found some
conclusions concerning the behaviour of iPP during gamma-irradiation.

Materials and methods

We studied a series of samples of isotactic polypropylene in blocks ‘PROFAX’ made
by HERCULES-USA with a molecular weight of 5·105 and a degree of isotacticity of

3
94%. The test specimens were massive plates with a thickness of 4 mm, in accor-
dance to Bulgarian standard, produced by injection molding. The samples were
irradiated at room temperature, in air, with a gamma 60Co source. The rate of dose
increase was 10 kGy/h. The doses were: 50, 100, 500, 1000, 1500 and 2000 kGy.
Differential scanning calorimetry (DSC) was conducted with a DSC-7 Perkin-Elmer
thermal analyzer. The rates of heating and cooling were constant: 8°C/min. The
samples were heated to 473 K (200°C) and they have been kept at this temperature
for 5 min. After that, they were cooled with the same rate.

Kinetics of non-isothermal melting

The rate of non-isothermal melting Gm was calculated according to the equation:
dH T2 dH
dTn ∫
T1 dT
dT
Gm = v 0 (10)
∆H F T2 dH
∫Tn dT dT
dT dH
where Gm is proportional to v 0 = , the heating rate of the polymer. is the
dt dTn
T2 dH
quantity of molten substance at the current temperature Tn; ∫ dT is the enthalpy
T1 dT

T2 dH
of melting of the whole process; ∫ dT corresponds to the enthalpy that accounts
Tn dT

for the quantity of substance, which still has not been molten.

Fig. 1. Graphical illustration of Eq. (10)

The non-isothermal melting rate could be represented theoretically [6,17-19] by

means of the following equation:

4
 Ed 3a 2 M v ∆H F ∆T
Gm = Gm0 exp − exp (11)
RT L001M 0Tm0 RA T

where:
Gm0 = 10-13 s-1.
( )
Tm0 = 453 K 180 ° C is the minimal value found in the literature [20].
Tm0 = 476 K (203 C) is the maximal value found in the literature [21].
°

Tm0 = 460 K (187.7 C) is an average value, which was estimated from the literature
°

data by Cheng and Wunderlich [22].

a = 6·10-10 m is an average intermolecular distance in the crystal.
Mv = 5·105 is the viscosity-average molecular weight.
Mo = 42 is the molecular weight of the monomer, forming the polymer chain.
∆HF = 10 860 J/mol [23].
А = 2·10-8 m is the length of a statistical segment.
∆T = Tm0 − Tn is the supercooling, where Tn is the current temperature (T1 < Tn < T2).
L001 is the lamellar thickness, i.e., the average size of the melting crystal.
The logarithmic view of Eq. (11) is:

Edcm 1 3a 2Mv ∆HF ∆T

log Gm = log Gm0 − − (12)
2.3RT 2.3 L001M0Tm0RA T
The dependence of log Gm versus the temperature factor is a straight line:
( )
logGm0 − E dcm / (2.3RT ) is the cut from where Ed was calculated.

1/ 2.3 3a Mv ∆HF
2
is the slope from which the melting lamellae’s thickness
LM0Tm0RA
was calculated. After that, the free surface energy of the melting lamella was
calculated according to the Thomson-Gibbs equation (Eq. (13)).
L∆H F ∆T
σ= (13)
2Tm0

Kinetics of non-isothermal crystallization

The crystallization rate was estimated via formula (14) similar to Eqs. (8,10).
dH T2 dH
dTn ∫T1 dT
dT
Gc = v 0 (14)
∆HF T2 dH
∫Tn dT dT
This formula for an exo-process is identical to Eq. (10) for an endo-process and the
designations have the same meaning, see Fig. 2.
The rate of non-isothermal crystallization could be represented theoretically by the
Lauritzen-Hoffman equation:

5
 Ed πσ 2 Tm0
Gc = Gm0 exp − exp (15)
RT R∆HF T∆T
After taking the logarithm of Eq. (15) we obtain Eq. (16):
Edmc πσ 2a Tm0
log Gc = log G −
0
m − (16)
2.3RT 2.3R∆HF T∆T
The dependence of log Gc versus the temperature factor is a straight line. Its cut is
the first part of Eq. (16) and its slope is the second part of Eq. (16). The activation
energy through the phase boundary melt–crystal was calculated from the cut, and the
free surface energy was calculated from the slope. The lamellar thickness was
calculated according to the Thomson-Gibbs equation (Eq. (17)).
2Tm0σ
L= (17)
∆HF ∆T

Fig. 2. Graphical illustration of Eq. (14)

Results of non-isothermal melting

Fig. 3a gives the endothermal melting curves of PP samples, irradiated with different
doses of gamma rays. The melting kinetics was estimated (Fig. 4). All temperatures
Tstart, Tmax, Tstop decrease exponentially with increasing the irradiation doses. It is
worth to mention that up to 200 kGy the curves are almost constant. The temperature
curves sharply decrease (with about 30°) above this dose. The degree of crystallinity
as a function of the dose is shown in Fig. 5. This crystallinity sharply decreases by
about 25%. Fig. 3b presents the dependence of the melting rate on the temperature.
All curves show exponential behaviour, i.e., they can be described with the theo-
retical Eq. (11). The exponential curves are shifted towards lower temperatures in
raising the irradiation doses. The dependence of log Gm on ∆Τ / Τ is shown in
Fig. 3c. We estimated the following thermodynamic parameters using the cut and the
6
slope of the straight lines fitted to Eq. (12): L, the average size of a melting lamella
(Fig. 6); σ, the free surface energy (Fig. 7); Ed, the energy of activation trough the
phase boundary (Fig. 8).

Fig. 3. (a) Melting endotherms of IPP gamma-irradiated with different doses. (b) The
melting rate Gm vs. the temperature. (c) log Gm vs. the temperature factor, calculated
via Eq. (12)

All of them were calculated at the three equilibrium melting temperatures: 453, 460.7
and 476 K. The values of the three figures, obtained at the above-mentioned temper-
atures, are presented as separate points in Figs. 6 - 8. The values averaged for each
separate dose are shown. The deviations of the single values, relative to the average
values of three different parameters, are in within 10%. This is quite acceptable for a
thermodynamic estimation. These dependencies interrupt at 200 kGy, which is
shown by a vertical line in each of the figures. The lamellar thickness, the free
7
surface energy and the transport energy through the phase boundary melt–crystal
decrease below this critical dose, while all dependencies increase after this dose.

Tstart
445
Tmax
440
Tstop
435
430
425
T (K)

420
415
410
405
400
395
390
385

1 10 100 1000

Dose (kGy)

Fig. 4. Melting temperature vs. dose

65

60
crystallinity (%)

55

50

45

40

35
1 10 100 1000

Dose (kGy)

Fig. 5. Degree of crystallinity vs. dose estimated from the melting enthalpy

8
 L453
L460
18 L476

16
L (nm)

14

12

10

1 10 100 1000

Dose (kGy)

Fig. 6. Lamellar thickness versus dose

S453
S460
S476
9

8
(mJ/m )
2

5
σ

2
1 10 100 1000

Dose (kGy)

Fig. 7. Free surface energy, obtained by the melting kinetics, vs. dose

9
 Ed453
Ed460
Ed476
90

85
Ed (kJ/mol)

80

75

70

65

60

55

50

45
1 10 100 1000

Dose (kGy)

Fig. 8. Activation energy, obtained by melting kinetics, vs. dose

Results of non-isothermal crystallization

The exothermal crystallization curves at different doses are represented in Fig. 9a.
For increasing irradiation doses, the DSC curves are shifted towards lower temper-
ature (Fig. 9a). Their integral intensity decreases with the doses. The curves of the
non-isothermal crystallization rate Gc vs. the temperature decrease exponentially
(Fig. 9b). This means that they could be described with Eq. (15). The exponential
curves are shifted towards lower temperatures in increasing irradiation doses. It can
be clearly seen from Fig. 9c that the dependencies of log Gc on the temperature
factor are well fitted through straight lines. The temperature range in which the
crystallization kinetics was estimated can be seen in Fig. 10. All temperatures Tstart,
Tmax, Tstop exponentially decrease when raising the irradiation doses. It can be noted
that the temperature curves remain almost constant up to 200 kGy. But beyond this
dose they decrease sharply, with about 30°. In Fig. 11, the degree of crystallinity is
shown as a function of the dose. It slightly decreases up to 100 kGy, but after that, it
sharply falls by about 30%.
The following thermodynamic parameters – lamellar thickness (average size of the
crystals) (Fig. 12), free surface energy (Fig. 13), and transport energy through the
phase boundary (Fig. 14) – were determined by means of the cut and the slope of
the fitted lines from Fig. 9c. All of these parameters were calculated at the three
equilibrium temperature points 453, 460.7 and 476 K. The values of the three figures,
obtained at the above-mentioned temperatures, are presented as separate points.
The values averaged for each separate dose are shown in Figs. 12 - 14. The fitted
curves were made over the average values.

10
These dependencies interrupt above 200 kGy, which is shown by a vertical line in
each of the figures. The free surface energy and the lamellar thickness increase
below and above this critical dose, but the transport energy through the phase
boundary melt–crystal only decreases.

Fig. 9. (a) Crystallization exotherms for iPP gamma-irradiated with different doses.
(b) The crystallization rate Gc vs. the temperature. (c) log Gc vs. the temperature
factor, calculated via Eq. (16)

Discussion
The present samples contain mainly monoclinic and triclinic phases. The fraction of
the triclinic phase increased when raising the irradiation doses (Tab. 1) [24]. It is
known that the triclinic phase melts at lower temperature [24]. Thus, the melting
peaks are shifted towards lower temperatures, due to the gamma irradiation.
The γ phase, obtained under pressure [25], transforms into the α phase by means of
a solid-solid transition before melting. We found in a previous paper that the gamma

11
phase, which is obtained as a result of irradiation, transforms directly into a melt [31]
so that the melting temperatures could be observed by WAXS (Tab. 1).

Tstop
Tmax
Tstart
395

390

385

380

375
T (K)

370

365

360

355

350

345

340
1 10 100 1000

Dose (kGy)

Fig. 10. Crystallization temperature vs. dose

80

70
crystallinity (%)

60

50

40

30

20

1 10 100 1000
Dose (kGy)

Fig. 11. Degree of crystallinity vs. dose estimated from the crystallization enthalpy

12
 L453
50 L460
L476
48

46

44
L (nm)

42

40

38

36

34 radiation radiation
annealling melting
32
1 10 100 1000

Dose (kGy)

Fig. 12. Average lamellar thickness L, obtained by crystallization kinetics, vs. dose

2.8 S453
S460
S476
2.6

2.4
σ (mJ/m )
2

2.2

2.0

radiation radiation
1.8
annealing melting
1 10 100 1000

Dose (kGy)

Fig. 13. Free surface energy during the non-isothermal crystallization of iPP gamma-
irradiated with different doses
13
 Ed453
Ed460
60 Ed476

55

50

45
Ed (kJ/mol)

40

35

30

25

20 radiation radiation
annealing melting
15
1 10 100 1000

Dose (kGy)

Fig. 14. Transport energy through the phase boundary, Ed, during the non-isothermal
crystallization of iPP gamma-irradiated with different doses

Tab. 1. Results from WAXS and SAXS. XWAXS and XDSC melting are the degrees of
crystallinity by WAXS and DSC, respectively; D110 is the size of crystallites estimated
by Sherer’s equation; Tstop is the end temperature of the melting by both WAXS and
DSC; L is the lamellar thickness calculated by SAXS; 2Rg is the size of crystallites
according the gyration radius, and Lmelt is the lamellar thickness calculated from DSC

Dose XWAXS XDSC Content D110 Tstop Tstop LSAXS 2Rg Lmelt
in in % in % of γ- in Å WAXS DSC in Å in Å in Å
kGy phase
in K in K
in %
0 63.79 65.2 15.7 222 434 442 110 104 139
50 59.05 55.8 17.3 218 433 439 107 114 111
100 50.34 46.7 21.1 213 427 436 111 121 77
500 44.45 44.7 37.3 200 416 427 111 130 75
1000 48.17 38 63.8 204 415.5 421 214 142 50
1500 49.29 45 76.1 174 413 418.8 207 156 68
2000 52.42 44 78 167 403 401 260 166 137

We assume that only α crystals exist in a non-irradiated sample. We also assume

that in a sample, irradiated with 2000 kGy, the γ phase predominates (Tab. 1). The

14
used method enables us to compare the melting rates Gm of the different samples at
the same temperature and the heating rate (Fig. 15). This rate increases expo-
nentially with the doses. We could confirm that an α-γ phase transition does not exist
in our case because the whole sample is transformed into the melt at 410 K. The
melting crystallinity from DSC sharply reduces at different irradiation doses (Fig. 5).
The WAXS crystallinity is in the same order and diminishes, too [24] (Tab. 1). Via
WAXS and SAXS we determined that the reduction of the degree of crystallinity was
due to an increase of crystal defects with irradiation. This confirmation is proved by
Fig. 4 where a shift towards lower temperatures is clearly observed as a result of irra-
diation. Because of the great number of defects, the crystals melt at lower temper-
atures. The reduction of the calculated lamellar thickness from DSC during melting,
up to the critical dose, is naturally connected to the increase of the defectiveness of
melting crystals during the irradiation (Fig. 6. and Tab. 1). In an estimation of the
lamellar thickness from SAXS no essential changes could be found up to the critical
dose.

0.016

0.014

0.012

0.010
Gm (s )

0.008
-1

0.006

0.004

0.002

0.000

1 10 100 1000

Dose (kGy)

Fig. 15. The melting rate at 410 K vs. the different doses

The increase of the lamellar thickness in both methods is due to the process of
radiation melting, according to Keller and Ungar [24]. Estimating the sizes of Sherer’s
crystallites from the reflex 110 we found a smooth decrease (Tab. 1). We connected
it with the continuous increase of the defectiveness of the crystals with the doses.
The free surface energy of the melting lamellae decreases to the critical dose (Fig.
7). It could be indicated that the lamellar surface becomes better arranged. This
contradicts to the observed phase transitions during irradiation, i.e., that the transition
of α into γ phase leads to an increase of defects. However, we determined by SAXS
that the difference between the crystal and amorphous lamellar densities diminished,
i.e., the mass transport from the crystal part into the amorphous region is realized
because of the process of radiation melting [24]. In this way the phase boundary
between amorphous and crystal parts gradually disappears when raising the

15
irradiation dose. The surface interactions between both phases decrease, too. That is
way the free surface energy reduces.

0.08

0.07

0.06

0.05
Gc (s )
-1

0.04

0.03

0.02

0.01

0.00

1 10 100 1000

Dose (kGy)

Fig. 16. Crystallization rate vs. dose at 372 K

In the same way, it could be explained why the transport energy through the phase
boundary crystal–melt decreases to the critical dose (Fig. 8). It is known that this
energy is connected to the viscosity of the molten crystals. The reduction of inter-
molecular interactions on the boundary between crystal and amorphous parts, during
the melting of the lamella, will decrease the transport energy through the phase
boundary.
Gamma rays commonly cause scission and crosslinking of molecules [6,7,17,24]. At
low irradiation doses, until about 200 kGy, we observed radiation annealing, but at
high irradiation doses up to 2000 kGy radiation melting occurred [24,26-28]. Both
radiation processes are connected to molecular scission and crosslinking. The same
PP samples divided into sol/gel fractions were studied in ref. [17] The sol and micro-
gel fractions were investigated morphologically and showed mixed-type small α-γ
spherulites. Up to now the macrogel was not studied morphologically. In the present
paper both fractions, microgel and macrogel, were investigated by DSC and with the
same method for non-isothermal melting and crystallization. The present samples
consist simultaneously of both fractions and show somewhat higher values for the
transport energy through the phase boundary, Ed, though micro- and macrogels have
recrystallized from solution.
The mixed α-γ spherulites have grown during the crystallization and have been
described morphologically in refs. [29-32] In the present case the spherulites were
formed non-isothermally at lower temperatures in raising the doses. The used
method enables us to compare the crystallization rate of different samples at the
same temperature, 372 K. Raising the dose leads to an almost linear reduction of this
rate (Fig. 16). The non-isothermal crystallization rate shows, in fact, the rate of
16
secondary nucleation of the lamellae in the spherulites and their growth. The rate of
spherulitic growth was determined by the kind and properties of the melts. The melts,
obtained from gamma-irradiated polypropylene, manifest a decreasing viscosity. The
dependence of the transport energy through the phase boundary melt–crystal on the
different doses (Fig. 14) is an evidence for it. All dependences in Figs. 12 - 14
interrupt at a critical dose near about 200 kGy. Over this dose the viscosity sharply
increases and then again decreases. The effect of the interruption could be
connected to the effect of radiation annealing and radiation melting. Below the critical
dose the viscosity reduces because of the molecular scission in the lamellar-
amorphous surfaces due to radiation annealing. Crosslinking prevails above this
dose, and with raising the doses, scission becomes predominating again. The
transport energy through the phase boundary melt–crystal decreases again.
The same critical dose at the interruption of the curves could be seen in the values of
the free surface energy and of the average lamellar thickness. The latter grows up to
200 kGy, probably because more and more perfect α lamellae form. At the same
time they become more defective and this leads to an increase of the free surface
energy. Suddenly above the critical dose of 200 kGy a sharp change in the lamellar
kind, size and perfection is observed. A great number of γ lamellae and α-γ twins are
formed. This leads to an increase of the average lamellar thickness and its imper-
fection, because of the formation of non-fluid, crosslinked melts.

[1] Jeziorny, A.; Polymer 1978, 19, 1142.

[2] Ozawa, T.; Polymer 1971, 12, 150.
[3] Borohovski, A.; Gasparian, K.; Mirozoev, R.; Sevastianov, L.; Baranov, G.;
Vysokomol. Soedin., Ser. B 1975, 1, 35.
[4] Ziabicki, A.; Appl. Polym. Symp. 1967, 6, 1.
[5] Lim, G.; Lloyd, D.; Polym. Eng. Sci. 1993, 33, 529.
[6] Atanasov, A.; Nedkov, E.; IUPAC-Macro 1983, Bucharest, Romania, Abstr. Struct.
Prop. 4, 156 - 159.
[7] Atanasov, A.; Nedkov, E.; Commun. Dep. Chem., Bulg. Acad. Sci. 1984, 17, 143.
[8] Hay, R.; British Polym. J. 1979, 11,137.
[9] Turnbull , P.; Fisher, J. C.; J. Chem. Phys. 1949, 17, 71.
[10] Hoffman, J. D.; Lauritzen, J. I.; Passaglia, E.; Ross, G. S.; Frolen, F. J.; Weeks,
J. J.; Kolloid Z. Z. Polym. 1969, 231, 564.
[11] Lim, G. B. A.; McGuire, K. S.; Lloyd, D. R.; Polym. Eng. Sci. 1993, 33, 537.
[12] Monasse, B.; Haudin, J. M.; Colloid Polym. Sci. 1986, 264, 117.
[13] Mubarak, Y.; Harkin-Jones, E. M. A.; Martin, P. J.; Ahmad, M.; Polymer 2001,
42, 3171.
[14] Di Lorenzo, M. L.; Silvestre, C.; Prog. Polym.Sci. 1999, 24, 917.
[15] Ziabicki, A.; Colloid Polym. Sci. 1996, 274, 705.
[16] Ziabicki, A.; Sajkiewicz, P.; Colloid Polym. Sci. 1998, 276, 680.
[17] Nedkov, E.; Stoyanov, A.; Krestev, V.; Rad. Phys. Chem. 1991, 37, 305.

17
[18] Kotzev, G.; Touleshkov, N.; Christova, D.; Nedkov, E.; J. Cell. Plastics 1999, 35,
1, 1.
[19] Buzarovska, A.; Koseva, S.; Cvetkovska, M.; Nedkov, E.; Eur. Polym. J. 2001,
37, 141.
[20] Wyckoff, H. W.; J. Polym. Sci. 1962, 62, 83.
[21] Fujiwara, Y.; Colloid Polym. Sci. 1987, 265, 1027.
[22] Bu, H. S.; Cheng, S. Z. D.; Wunderlich, B.; Makromol. Chem., Rapid Commun.
1988, 9, 76.
[23] Fatou, V. G.; Eur. Polym. J. 1971, 7, 1057.
[24] Nedkov, E.; Dobreva, T.; Rad. Phys. Chem., in press.
[25] Pae, K. D.; J. Polym. Sci. 1968, A-2, 657.
[26] Mihailova, M.; Kresteva, M.; Aivazova, N.; Krestev, V.; Nedkov, E.; Rad. Phys.
Chem. 1999, 56, 581.
[27] Misheva, M.; Djourelov, N.; Nedkov, E. T.; Rad. Phys. Chem. 2001, 62, 379.
[28] Misheva, M.; Mihailova, M.; Djourelov, N.; Kresteva, M.; Krestev, V.; Nedkov, E.;
Rad. Phys. Chem. 2000, 58, 39.
[29] Nedkov, E.; Krestev, V.; Colloid Polym. Sci. 1990, 268, 1028.
[30] Nedkov, E.; Stoyanov, A.; Krestev, V.; Rad. Phys. Chem. 1991, 37, 299.
[31] Krestev, V.; Dobreva, B.; Kresteva, M.; Minkova, L.; Nedkov, E.; Bulg. J. Phys.
1988, 15, 3, 265.
[32] Nedkov, E.; Dobreva, T.; e-Polymers 2002, no. 042.

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