Structure of the in situ produced

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 Composites Science and Technology 167 (2018) 148–154

Contents lists available at ScienceDirect

Composites Science and Technology

journal homepage: www.elsevier.com/locate/compscitech

Structure of the in situ produced polyethylene based composites modified T

with multi-walled carbon nanotubes: In situ synchrotron X-ray diffraction
and differential scanning calorimetry study
Mariya A. Kazakovaa,b,∗, Alexander G. Selyutina, Nina V. Semikolenovaa, Arcady V. Ishchenkoa,b,
Sergey I. Moseenkova, Mikhail A. Matskoa, Vladimir A. Zakharova, Vladimir L. Kuznetsova,b
a
Boreskov Institute of Catalysis, SB RAS, Lavrentieva 5, Novosibirsk, 630090, Russia
b
Novosibirsk State University, Pirogova 2, Novosibirsk, 630090, Russia

A R T I C LE I N FO A B S T R A C T

Keywords: Polyethylene based composites modified with multi-walled carbon nanotubes (MWCNTs) were produced via in
Multi-walled carbon nanotubes situ polymerization of ethylene with the Ti-Ziegler–Natta catalyst preliminarily immobilized on MWCNTs. The
Polyethylene composites composite structure was characterized with transmission and scanning electron microscopy, differential scan-
In situ polymerization ning calorimetry (DSC) and in situ synchrotron X-ray Diffraction (in situ XRD). For the first time the Ti-containing
Polymer crystallization
catalyst species of the size 2–3 nm were observed on the MWСNTs surface stabilized in the polymer matrix. A
In situ synchrotron X-ray diffraction
comparative study of the melting-crystallization cycles of neat polyethylene (PE) and MWCNT-PE composites
with in situ XRD and DSC provide information on the nucleation of PE crystals. For the first time, the in situ XRD
technique was used for estimation of the coherent scattering region of PE blocks during the melting-crystal-
lization cycles. These experiments and molecular dynamic modeling showed that MWCNTs act as the template
for the PE chain orientation and as the nucleating agent for PE crystallization. However, the nucleation of PE
crystals in composites occurs on the nanotube surface and also within the space between nanotubes. Thus, the
relative volume of PE nucleated on nanotubes depends on their content in the composite and can be significant
only for the composites with high nanotube loading.

1. Introduction properties of polymer-CNT composites. The common methods for the

The outstanding mechanical, electrical and thermal properties of
carbon nanotubes (CNTs) have made them promising materials for a
wide range of applications [1–10]. Generally, most of CNTs are used as
fillers of polymer composites which have the improved mechanical
properties [11–14]. At the same time, CNT incorporation in polymers
provides not only a reinforcement but also an enhancement of other
physical and chemical properties, such as electrical and thermal con-
ductivity, thermal, fire and corrosion resistance [15–23]. The compo-
site properties are determined by the type of CNTs distribution in the
polymer matrix, which in turn is determined by the nature of the na-
notube-polymer interface and the method of CNT incorporation in the
polymer matrix. The interface strength and the wetting ability of na-
notubes with polymer matrices can be varied via functionalization of
the CNT surface [18,24]. The formation of strong interfaces promotes a
better distribution of CNTs in polymer matrices, while the method of
CNT incorporation into polymer is another factor affecting the
preparation of CNT-polymer composites include mechanical mixing
with extrusion, solution mixing, melt blending, coagulation precipita-
tion technique and in situ polymerization [14,25–28].
Previously [25,26], we performed a comparative study of the in-
fluence exerted by the uniformity of the multi-walled carbon nanotubes
(MWCNTs) distribution on the electrophysical properties of MWCNT-PE
composite materials prepared by mechanical mixing in a polymer melt,
coagulation precipitation, and in situ polymerization of ethylene using
Ziegler-Natta catalyst supported on MWCNTs. It was shown that in situ
polymerization yields composite materials with a more uniform dis-
tribution of MWCNTs in the polyethylene (PE) matrix, compared to the
other methods. Investigation of the electrophysical properties of com-
posite materials has shown that uniform distribution of MWCNTs in
polyethylene ensures high values of conductivity, correlating with high
values of the complex dielectric permittivity. At the same time, CNTs
have been reported to act as the nucleating agent for polymer crystal-
lization as well as the template for polymer chain orientation

∗
Corresponding author. Boreskov Institute of Catalysis, SB RAS, Lavrentieva 5, Novosibirsk, 630090, Russia.
E-mail address: mas@catalysis.ru (M.A. Kazakova).

https://doi.org/10.1016/j.compscitech.2018.07.046
Received 13 May 2018; Received in revised form 28 July 2018; Accepted 31 July 2018
Available online 01 August 2018
0266-3538/ © 2018 Elsevier Ltd. All rights reserved.
M.A. Kazakova et al.
[23,29,30].
In the present work, the in situ polymerization technique has been
applied for the preparation of MWCNT/polyethylene composites with
various loadings and morphological structural properties of MWCNTs.
Special attention has been paid to the in situ XRD study on the forma-
tion of structured polyethylene blocks in the melting-crystallization
process. For the first time the in situ synchrotron XRD technique was
used for estimation of the coherent scattering region of PE blocks
during the melting-crystallization cycles. This allowed us to identify the
most important structural features of MWCNT-PE composites that are
related with nucleation and crystallization of PE blocks promoted by
the nanotube surface.
2. Material and methods
Synthesis and post-treatment of MWCNTs. MWCNT samples were
prepared by catalytic gas-phase decomposition of ethylene on the sur-
face of Fe–Co catalyst at 680°С. The MWCNT preparation is described in
more detail in Refs. [31–34]. The characteristics of the prepared
MWCNTs were as follows: the mean diameter 9.4 nm (transmission
electron microscopy data) and the specific surface area 265 m2 g−1
(BET data (SORBI-M instrument, ZAO Meta, Russia). Traces of the
catalyst were removed from the MWCNT samples by boiling in 15%
HCl, followed by washing with distilled water to a neutral pH value.
The MWCNT surfaces were functionalized by boiling for 2 h in con-
centrated nitric acid (ultrapure grade, Reakhim) via grafting of car-
boxyl groups (Fig. 1 A). After the oxidative treatment, the MWCNT
sample was washed with distilled water to a neutral pH value. The
oxidized MWCNT samples are denoted as MWCNT-Ox. Titrimetric
analysis of acidic oxygen-containing groups on the MWCNT surface was
performed using a reverse acid–base titration technique described by
Boehm. Such oxidation conditions provide the formation of 2.4 car-
boxyl groups per 1 nm−2 of the MWCNT surface. According to the TEM
data, the overall morphology of the MWCNT does not practically
change after oxidation treatment. According to the HRTEM, the oxi-
dation of MWCNT leads to a decrease in the amount of amorphous
carbon on the surface of the MWCNT [35]. Moreover, after such oxi-
dative treatment the specific surface area of the MWCNT change within
experimental error ( ± 5%) and was 260 m2/g for MWCNT-Ox.
Deaggregation of MWCNT-Ox, which was aimed to attain more a
uniform distribution in the polyethylene matrix was, performed with an
AGO-2 planetary mill developed at the Institute of Solid State
Chemistry and Mechanochemistry, Siberian Branch of the Russian
Academy of Sciences. The mean length of the milled nanotubes was
about 350 nm (the length varied in the range of 100–3000 nm and was
determined from TEM images of the nanotubes deposited on a Cu grid
from the suspensions in dimethylformamide (Fig. 1B and C) [36]). The
milled MWCNT samples are denoted as MWCNT-M.
Preparation of catalytic systems and synthesis of MWCNT–PE
composite materials by in situ polymerization technique. All ma-
nipulations were carried out under argon atmosphere using standard
Fig. 1. TEM images of oxidized (A) and oxidized-milling (B) MWCNTs. (C) the length distributions of MWCNT-Ox after milling.
149
Composites Science and Technology 167 (2018) 148–154
Schlenk techniques. A MWCNT sample (1–2 g) was placed in a three-
necked glass reactor and dried in a vacuum at 250°С for 4 h. Then, it
was cooled to room temperature and the reactor was filled with argon.
After that, 50–100 mL of heptane was added to the MWCNT samples. A
solution of TIBA in heptane (0.8 mmol/g of MWCNTs) was then added;
the mixture was stirred at room temperature for 1 h and allowed to
settle for 12 h. The liquid phase was decanted and the precipitate was
washed with two portions (50 mL) of pure heptane. The washed sample
of MWCNT/TIBA was supplemented with, 50 mL of heptane, and a
solution of TiCl4 in heptane (0.35 mmol of Ti per gram of MWCNT) was
added under vigorous stirring. The mixture was stirred at room tem-
perature for 30 min, after which the precipitate was allowed to settle
and washed with two portions (50 mL) of pure heptane. Then, 230 mL
of heptane was added, and the catalyst was dispersed by ultrasonic
treatment using an ultrasonic bath Sapfir, 1.3 L. Thus prepared catalyst
suspension was charged into a 1 L steel polymerization reactor pre-
liminarily dried by evacuation at 80 °C and filled with argon. The,
aluminum trialkyl cocatalyst (TIBA or TEA) was added (1.1 mmol), the
mixture was heated to the desired temperature, and ethylene was fed.
During the reaction, the stirring speed, temperature and ethylene
pressure were maintained constant through an automatic computer-
controlled system for the ethylene feed, which recorded the ethylene
consumption. The reaction was performed until the required amount of
the polymer, ensuring the required concentration of MWCNT in the
polymer, was obtained. The samples of MWCNT-PE composite mate-
rials containing 10, 19, 24, 29, and 30 wt% of MWCNTs were prepared.
The polymerization conditions for each experiment are listed in
Table 1. The resulting product was separated, washed with heptane and
ethanol, and dried to the constant weight. Composite films were pre-
pared by pressing of the obtained powder using a hand hot press be-
tween two polished steel plates covered with Teflon® film and copper
frame with a thickness of 0.5 mm as a spacer.
2.1. Characterization of MWCNT–PE composite materials
Transmission electron microscopy (TEM) was carried out using a
JEOL JEM-2010 microscope operating at 200 kV accelerating voltage
and allowing a resolution of 1.4 Å. Energy dispersive X-ray spectro-
scopy (EDS) was undertaken using an EDAX Phoenix system. For TEM
characterization of composite structure, the sample's powder was
placed onto TEM sample support mesh with an amorphous carbon
layer. The size distributions were estimated from a statistical count of
the nanotubes from several frames taken on different parts of the
samples.
Scanning electron microscopy (SEM) was carried out using
JSM6460LV JEOL microscope with acceleration voltage of 25 kV. For
SEM characterization of polymer, composite films were cut into plates
with the size of ca. 8 × 3 × 0.5 mm3, which were glued to the copper
stand with breaks upwards using silver glue. In order to avoid surface
changes during SEM investigations.
Differential scanning calorimetry (DSC) measurements were
M.A. Kazakova et al.
Table 1
The amount of adsorbed TIBA on the surface of different type MWCNTs.
Samples The amount of adsorbed TIBA
MWCNT-ini 0.09 wt % (0.04 mmol Al/g MWCNT)
MWCNT-Ox 0.7 wt % (0.27 mmol Al/g MWCNT)
MWCNT-Ox-M 0.87 wt % (0.34 mmol Al/g MWCNT)
performed using a DSC 204 F1 instrument (Netzsch, Germany) in ac-
cordance with ASTM D3418-82 and ASTM D3417-83 procedures in an
argon atmosphere (flow rate 30 mL min−1) in closed 25-μL aluminum
crucibles. The device was calibrated in accordance with [37,38]. The
calibration was made using indium (99.999%, Aldrich) and zinc (98+
%, Aldrich) as reference samples. The measurement was performed in
the melting–crystallization–melting mode over the temperature range
of 25–180°С at a rate of 10 deg min−1. The melting point Тm and en-
thalpy of melting ΔНm were determined in the second melting run. The
quantity ΔНm was calculated taking into account the MWCNT content
of the sample. The degree of crystallinity Х was calculated using the
equation
X= (ΔHm /290) × 100%,
where ΔНm is the enthalpy of melting of the sample (J g−1), and 290 is
the enthalpy of melting of ideal polyethylene with 100% degree of
crystallinity.
In situ X-ray diffraction (in situ XRD) measurements and de-
termination of the temperature dependence of substructural char-
acteristics of the material's particles after sample annealing were per-
formed on the VEPP 3 Precision Diffractometry station at the Siberian
Center of Synchrotron and Terahertz Radiation. The sample was placed
in an XRK 900 X-ray reactor chamber (Anton Paar, Austria). Heating
was performed in an inert atmosphere from room temperature to 150 °C
at a speed of 10 °C/min, and then the sample was cooled under the same
conditions. Simultaneously, X-ray patterns were recorded on an OD-3M
350 position sensitive detector in the range of 2θ ∼15°–45° with a
discontinuity of ∼0.01° (the operating wavelength 0.1731 nm). Thus,
reflections PE (110) and PE (200) were in the recording range. The
exposure time was 1 min/frame. The X-ray patterns were processed by
measuring the widths of reflections at half-maximum with approxima-
tion of the reflection profile by a pseudo-Voigt function.
2.2. Model and simulation method molecular dynamics simulations of
MWCNT–PE interactions
The molecular modeling software package GROMACS [39–41],
version 4.6.6 was employed to carry out MD simulations using the
OPLS-AA force field [42] in the isothermal–isobaric ensemble (NPT
ensemble). For the NPT ensemble, the number of NPT molecules, the
pressure and temperature of the system are kept constant. The systems
were first stabilized by an energy minimization using 5000 steps of the
steepest descent energy minimization. Further, the MD simulation was
done for 20 ns. All simulations were computed at 300 K and 1 atm, with
a time step of 0.002 ps, and coordinates were stored every 5000 steps,
or 10 ps. Both the temperature and pressure were controlled using the
Berendsen method. For initial equilibration, long-range interactions
were treated with a Coulombic and van der Waals cutoff distance of
1.4 nm to decrease the simulation time. Analyses were performed by
using facilities within the GROMACS package and Visual Molecular
Dynamics (VMD).
3. Results
3.1. Catalyst deposition and polymerization of ethylene
Samples of the initial and oxidized MWCNTs have different
150
Composites Science and Technology 167 (2018) 148–154
Fig. 2. The scheme of immobilization of the catalyst complex on the MWCNT
surface followed by PE polymerization.
functional surface composition. Thus the surface of oxidized MWCNT-
Ox has a large amount of oxygen-containing groups (2.4 carboxyl
groups per 1 nm−2 of the MWCNT surface), and therefore the stability
of their suspensions in heptane differs significantly. Initial MWCNTs
were dispersed carefully in heptane under sonication (the prepared
suspensions with the MWCNT concentration of 20 mg/mL have high
viscosity). Fig. 2 displays the scheme of immobilization of the catalyst
for ethylene polymerization on the surface of MWСNTs.
The amount of the surface centers able to interact with aluminum
trialkyl compound on initial, oxidized and oxidized-milled MWCNTs
was determined by adsorption of the TIBA excess with further careful
washing of the sample. Data on the content of aluminum, determined
by inductively coupled plasma atomic emission spectroscopy, are listed
in Table 1.
We have found that the nature of MWСNTs exerts a pronounced
effect on the amount of adsorbed TIBA used for preparation of the
catalytic system MWСNT-TIBA/TiCl4. The analysis showed that the
oxidation leads to the formation of a large amount of centers that can
react with TIBA on the surface of MWСNTs. Mechanical milling of
oxidized MWCNTs also leads to an additional increase in the adsorption
capacity of TIBA. The amount of adsorbed TIBA correlates with the
surface concentration of carboxylic groups produced via the oxidation
treatment of MWCNTs. The catalytic systems MWCNT-TIBA/TiCl4 were
prepared using different types of MWCNTs and applied for ethylene
polymerization. Table 2 shows the typical conditions for preparing
MWCNT–PE composites by in situ polymerization technique. The sam-
ples of MWCNT-PE composite materials containing 10, 19, 24, 29, and
30 wt% of MWCNTs were produced.
3.2. MWCNT-PE composite characterization
3.2.1. SEM and TEM study of MWCNT-PE composites
Structure and morphology of the prepared MWCNT-PE composites
were studied using TEM and SEM. The SEM analysis of MWCNT-PE
composites was performed to investigate the internal structure of the
materials. The corresponding micrographs of the typical fractures of
MWCNT-PE composites are displayed on Fig. 3.
The distribution of the active catalyst component along the surface
of MWСNTs and uniformity of MWСNTs distribution in the volume of
the polymer matrix were determined by TEM (Fig. 4). The high re-
solution electron micrographs show the 2–3 nm dispersed catalyst
particles (Fig. 4 B) that are distributed quite uniformly along the surface
of the nanotubes. According to EDX analysis data, it was shown that the
polymerization catalyst particles fixed on the MWCNT surface contain
Ti, Cl and Al elements. These data are in a good agreement with our
earlier results obtained by studying the PE morphology that was formed
M.A. Kazakova et al. Composites Science and Technology 167 (2018) 148–154

Table 2
Conditions for preparing MWCNT–PE composites by in situ polymerization technique.
Sample Polymerization conditions Total yield of PE + MWCNTs, g Sample composition, %

MWCNT type and weight, g PC2H4, atm PH2, atm T, °C τ, min PE MWCNTs

1 – 2 – 40 5 8,9 100 –
2 MWCNT initial, 1g 5 – 40 30 3,3 70 30
3 MWCNT-Ox, 2g 3 – 40 21 10.5 81 19
4 MWCNT-Ox, 2g 3 – 40 60 7.0 71 29
5 MWCNT-Ox-M, 1g 4 4 70 33 10.3 90.3 9.7
6 MWCNT-Ox-M, 1g 4 4 70 14 4.4 75.9 24.1
7 MWCNT-Ox-M, 1g 4 4 70 8 4.7 70.3 29.7

at the surfaces of catalyst fillers prepared by TiCl4 anchoring on alu-
minosilicate minerals [43]. As it is evidenced by the formation of
polymer films on the surface of the tubes without a clearly defined
droplet, MWCNTs are uniformly covered by PE molecules (contact
angles cannot be registered, this corresponds to a high work of adhesion
of the polymer to the nanotube surface). The interaction of carbon
nanotubes with polyethylene molecules results in a surface wetting
with polymer, which depends strongly on both the surface composition
of CNTs and the surface properties of the polymer.
3.2.2. In situ XRD and DSC study of MWCNT-PE composites
The structure of all the obtained composites and neat polyethylene
was investigated using in situ XRD on synchrotron radiation. To this
end, the samples were heated in an inert gas to a temperature above the
melting point of PE and then cooled directly in the X-ray reactor
chambers. Fig. 5 shows the typical time resolved XRD patterns of
MWCNT-PE composites during their melting–crystallization cycle.
These data allow getting accurate information on the melting and
crystallization temperatures of PE crystal blocks within the composites
as well as the mean size and defectiveness of PE blocks.
It should be mentioned that the lattice parameter of PE crystals
estimated from the position of the most intensive reflections (110 and
200) did not change after MWCNT incorporation into the composite.
This corresponds to the absence of insertion of nanotube fragments
directly into the polymer crystals. The Scherrer equation was used to
calculate of the size of coherent scattering region (CSR), which corre-
sponds to the mean size of the ordered (crystalline) domains of PE. The
CSR values calculated using the main intensive reflects of PE (110 and
200) were the same for each sample. Fig. 6 summarizes data on the
temperature dependence of CSR of PE crystals during the melting-
crystallization cycles for two sets of composites. The Tcryst values esti-
mated from XRD data are listed in Table 3. Note that Tcryst corresponds
to the temperature of appearance of weak PE reflections (110 and 200),
which were not used for the calculations of CSR due to the low signal-
noise ratio (Fig. 6).
According to the DSC data (Table 3), the introduction of different
type MWCNTs into the polyethylene matrix decreases the melting point
of the polymer by 3–5 °C and the degree of crystallinity by 10–15% in
comparison with neat polyethylene. On the other hand, the melting
point and degree of crystallinity remain high, and the shapes of the
melting and crystallization peaks in the DSC curves are similar to those
of the peaks of neat polyethylene. This fact indicates that the in-
troduction of MWCNTs into polyethylene does not lead to a significant
disordering of its crystal structure. So, we can suppose the existence of
extensive fragments of crystalline polyethylene. This observation cor-
relates with XRD data (the coincidence of the positions of (110) and
(200) reflections with the literature data). DSC data show that Tcryst. for
MWCNT-PE composites is the same or higher than that for neat
polymer. At the same time in situ XRD technique (due its higher sen-
sitivity) registered PE nanocrystals formation at higher temperature.
3.2.3. Molecular dynamics simulations of the formation of MWCNT-PE
composites
To qualitatively assess the formation of MWCNT-PE composites
during the synthesis, the interaction of MWCNTs and PE was simulated
using the molecular dynamics package Gromacs in the OPLS-AA force
field. The first (Fig. 7) image shows the simulated perpendicular ar-
rangement of polyethylene molecules around the tube, which corre-
sponds to the assumed primary direction of growth during the poly-
ethylene synthesis. The initial system consisted of 126 polyethylene
molecules, and each molecule had 180 carbon atoms. The total simu-
lation time was 1500 ps. Eventually, structuring of polyethylene mo-
lecules around the nanotube was observed. Thus, the presence of
MWCNTs provides the appearance of the local preferred direction of
polyethylene growth and the formation of polymer lamellae oriented
along the nanotube axis. From the presented data, it is evident that
MWCNTs contributes to the formation of extended crystal polymer due
to wetting of nanotube by the polymer molecules.
4. Discussion
According to in situ XRD analysis, the CSRs of neat PE (∼150 nm for
110 and 200 reflections), which was produced without nanotube ad-
ditives, were smaller than those of MWCNT-PE composites (∼210 nm,

Fig. 3. Typical SEM images of the MWCNT-PE composite film breaks obtained after cracking at the liquid nitrogen temperature. Bright fragments (dots or villi are
attributed to nanotubes).

151
M.A. Kazakova et al. Composites Science and Technology 167 (2018) 148–154

Fig. 4. TEM images of 30% MWCNT-PE composite. A) MWCNTs homogeneously distributed in the PE matrix; B) PE molecules demonstrate high wetting ability of
nanotube surface; one can see also the 2–3 nm dark spots corresponding to the Ti-containing catalyst particles.

Fig. 5. Typical time resolved in situ XRD patterns of

MWCNT-PE composites during their melting-crystal-
lization cycle. The insert shows variation of the
composite temperature with time. For clarity, only
some of the patterns are presented. It can be seen that
the intensity of PE reflections decreases and dis-
appears near the melting temperature, and then, as
the temperature is lowered, the appearance of PE
reflections is observed again, which corresponds to
crystallization of the polymer. The intensity of the
(002) reflections of MWCNTs was much lower and
much wider than that of PE.

Fig. 6. Temperature dependence of the calculated size of the polyethylene CSR for different composites during the melting-crystallization cycle. A) data for the first
set of the composite produced using MWCNTs without ball milling; B) data for the composite set produced using MWCNTs that were milled and oxidized before
catalyst deposition, and also for neat PE produced without nanotubes. Solid and empty symbols correspond to melting and crystallization, respectively; arrows show
the process direction.

Fig. 6B). A comparison of the CSR changes during PE crystallization in (Fig. 6 A, B). This can be attributed to the fact that the crystallization is
neat polymer and PE-MWCNT composites demonstrates that in the case initiated and initially proceeds on the nanotube surface, and then
of neat PE the size of the polymer crystallites increases during crys- crystallites begin to form in the nanotube free parts of the polymer
tallization, while the PE crystallite size decreases for all the composites volume. Due to the limited volume of the free polymer in the

152
M.A. Kazakova et al.
Table 3
DSC and in situ XRD data of MWCNT-PE composites.
Samples MWCNT-PE composites DSC data Tmelting,°Ca
1 Neat PE 138
2 30% MWCNT-initial/PE 132
3 29% MWCNT-Ox/PE 133
4 19% MWCNT-Ox/PE 135
5 30% MWCNT-Ox-M/PE 136
6 24% MWCNT-Ox-M/PE 138
7 10% MWCNT-Ox-M/PE 139
a
Tmelting corresponds to the maximum of the DSC crystallization curve recorded with a heating rate of 10 °C/min.
b
Tcryst estimated from XRD data corresponds to the temperature of appearance of PE reflections 110 and 200.
Fig. 7. The simulation of the interactions of PE molecules with the surface of MWCNTs.
composites, free polymer crystals of a smaller size are formed. This
leads to a decrease in the relative fraction of the crystallites bound to
the surface of the nanotubes, and, correspondingly, to a decrease in the
observed average size of the polymer crystallites. In the case of neat PE,
the crystallite sizes increase continuously during the crystallization
process. Thus, the relative volume of PE nucleated on nanotubes de-
pends on their content in composite and it can be significant only for
the composites with high nanotube loading.
The oxidation of MWCNTs before the catalyst deposition results in
the formation of smaller PE crystallites (the melting curves in Fig. 6 A)
as compared to the use of initial MWCNTs. The ball milling of the
oxidized MWCNTs before the catalyst deposition results in the forma-
tion of PE crystallites of the same size (the melting curves in Fig. 6 B).
The use of nanotubes not, milled before the catalyst deposition leads to
the formation of PE crystallites of different size because of the diffusion
limitations of ethylene polymerization within the primary aggregates of
nanotubes.
The crystallization of PE after the melting of the composites results
in the formation of PE crystallites which size depends on the MWCNT
content in composites. Thus, the increase in the nanotube content de-
creases the polymer crystallite size (Fig. 6 A, B).
These facts undoubtedly indicate that nanotubes are involved in the
crystallization of PE molecules which are formed directly on the cata-
lyst species generated on the nanotube surface. In other words, CNTs
serve as the nucleating agent for PE crystallization as well as the tem-
plate for the PE chain orientation. This is consistent with the data of
other researchers obtained for different polymers [22] and with the
results of our modeling of the interaction of PE molecules with the
surface of nanotubes.
The comparison of the nucleation of PE initiated by regular nucle-
ating agents (NAs) [44,45] and that initiated by MWCNTs leads to the
conclusion that they should provide a different type of bulk organiza-
tion of the forming polymer crystals during the crystallization following
the nucleation. The nucleation caused by commercial NAs usually
proceeds via the formation of lamellae nucleation centers with their
subsequent transformation into spherulites, which are spherically
153
Composites Science and Technology 167 (2018) 148–154
DSC data Crystallinity, X% DSC data XRD data
Tcryst., °C Tcryst., °Cb
58 113 130
57 115 126
44 113 125
46 114 128
59 114 115
62 112 120
65 113 130
shaped clusters of crystallinity that grow radially from each nucleation
center during crystallization. The spherulites continue to grow until
they reach on the adjacent the spherulites and create a spacefilling
polycrystalline matrix. In the case of PE nucleation on the nanotube
surface lamellae are oriented along the nanotube surface and crystallize
into the PE blocks covering the nanotube.
TEM images of MWCNT-PE composites produced at the early stages
of polymerization do demonstrate the formation of the polymer layers
covering nanotubes. The molecular modeling also supports the or-
ientation of PE lamellae along the nanotube surface. Nevertheless, in
the case of MWCNT-PE composites, the nucleation and crystallization of
PE crystals within the space between nanotubes is also possible during
crystallization stage. The ratio of polymer blocks surrounding a nano-
tube and crystallized in the volume between nanotubes depends on the
concentration of MWCNTs in the composite.
5. Conclusions
The effect of MWCNTs pre-treatment conditions, such as oxidation
and milling, on the formation of MWCNT-PE composites by in situ
polymerization technique has been investigated by in situ XRD, DSC,
SEM and HRTEM. The controlled oxidation and milling treatment of
MWCNTs increases the adsorbing ability of the TIBA-TiCl4 poly-
merization catalyst system with the increased activity. It provides a
homogeneous distribution of the catalyst particles along the nanotubes
and finally a homogeneous coverage of the nanotube surface with PE
molecules. For the first time, we have observed the Ti-containing cat-
alyst species of the size 2–3 nm on the MWСNTs surface stabilized in the
polymer matrix. It was found that CNTs serve as the nucleating agent
for PE crystallization as well as the template for the PE chain orienta-
tion. The crystallization process is initiated and initially proceeds on the
nanotube surface, and then crystallites begin to form in those parts of
the polymer volume that do not contact with nanotubes. Due to the
limited volume of the free polymer in the composites, free polymer
crystals of a smaller size are formed. As revealed by in situ synchrotron
XRD, the oxidation of MWCNTs before the catalyst deposition results in
M.A. Kazakova et al.
the formation of PE crystallites of a smaller size compared with the
initial MWCNTs. The ball milling of the oxidized MWCNTs before the
catalyst deposition results in the formation of PE crystallites of the same
size. The crystallization of PE after the melting of composites results in
the formation of PE crystallites which size depends on the MWCNT
content in the composites. Thus, the increase in the nanotube content
decreases the polymer crystallite size.
In conclusion, we have shown that the use of the in situ poly-
merization technique opens the possibility for the production of
MWCNT-PE composites with a homogeneous distribution of MWCNTs.
MWCNT-PE composites with a high concentration of homogeneously
distributed nanotubes are promising as the polymer carbon nanotubes
conductive masterbatches.
Acknowledgements
This work (study and modeling of composites) was supported by the
Russian Science Foundation (grant 17-73-20293), composites were
produced with support of the Federal Agency of Scientific
Organizations Project.
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 But there were with him the son of the thousand-man and his
equerry, and they pressed him and said: “Go, O Prince, back to
Russia, if the Lord will deliver you!” But the time was not propitious.
As we said before, the Pólovtses returned from Pereyáslavl, and
Ígor’s advisers said to him: “You harbour a proud thought and one
that is not pleasing to God; you do not intend to take the man and
run with him, but why do you not consider that the Pólovtses will
return from the war, and we have heard that they will slay all the
princes and all the Russians, and there will be no glory for you, and
you will lose your life.” Prince Ígor took their advice to heart, being
afraid of the return of the Pólovtses, and bethought himself of flight.
He was not able to run away either in daytime or at night, for the
guards watched him, but he found an opportune time at the setting of
the sun. And Ígor sent his equerry to Lavór, saying: “Cross on the
other side of the Tor with a led horse,” for he intended to fly to Russia
with Lavór. At that time the Pólovtses were drunk with kumys; and it
was towards evening when his equerry came back and told him that
Lavór was waiting for him. Ígor arose frightened and trembling, and
bowed before the image of the Lord and the honourable cross, and
said: “Lord, knower of hearts! If Thou, Master, wilt save me,
unworthy one,”—and he took the cross and the image, lifted the
tent’s side, and crawled out. His guards were gambling and feasting,
for they thought that the Prince was asleep. He arrived at the river,
waded across, and mounted the horse; thus they both rode by the
tents.
This deliverance the Lord granted on a Friday, in the evening. He
then walked eleven days to the town of Donéts, and thence he went
to his Nóvgorod, and they were much rejoiced. From Nóvgorod he
went to his brother Yarosláv in Chernígov, to ask for help in the
Posémie. Yarosláv was glad to see him, and promised him aid. Ígor
travelled thence to Kíev to Grand Prince Svyatosláv, and Svyatosláv
was glad to see him, as was also Rúrik.

FOOTNOTES:
 [19] For notes consult the Word of Ígor’s Armament (p. 80 et
sqq.).
[20] A Finnish tribe.
[21] Town in the country of the Vyátiches.
[22] The country along the river Sem.
 The Word of Ígor’s Armament. (End of XII.
century.)
No other production of Russian antiquity has roused so
much interest in Russia and abroad as this version of Ígor’s
expedition by an unknown poet of the end of the twelfth
century. Thirty-five translations into modern Russian,
numerous translations into Little-Russian, Polish, Bohemian,
Servian, Bulgarian, Hungarian, German, French, witness to
the enormous popularity this production has attained. The
historical background of the poem is found in the recital from
the Kíev Chronicle, which is given on pp. 71-80. The disasters
which befell Ígor and his army are probably told with better
effect in that prosaic version; but the superior value of the
Word lies in its being a precious relic of the popular poetry of
the end of the twelfth century, such as no other nation can
boast of. The Nibelungenlied and the Chanson de Roland are
chiefly productions of a literary character, while the Word
bears every evidence of representing the untutored labour of
a popular bard.
Who the author was, when he lived, for whom he sang, are
all unanswered questions, but from internal evidence we
glean that he sang for his contemporaries while Ígor was still
alive. From his apostrophe to Yarosláv Osmomýsl, who died
in 1187, we may infer that the poem was written before that
year, and it is not unlikely, from his vivid description of the
battle at the Kayála, that he was an eye-witness of the
expedition which took place in 1185. From the absence of
biblical references it is generally assumed that the author was
not a member of the clerical profession. Here, however,
various difficulties arise. It is quite incomprehensible why
there should be so many references to pagan divinities at a
time when Christianity had been deep-rooted in Russia for
fully two centuries; why, except for the evident imitation of
many passages in the Zadónshchina, there should be no
 reference to the poem by any medieval writer, and why only
one copy of so remarkable a work should have been
preserved. If this poem came so very near being lost to
posterity, how many other remarkable productions of that
early period have disappeared? It is not at all impossible that
there existed an extensive popular poetry, of which only the
barest traces have come down to us. This suspicion is
strengthened by the emphatic mention by the author of the
Word of a poet Boyán who had lived before his days.
A copy of the poem was discovered by Count A. I. Músin-
Púshkin, Procurator-General of the Holy Synod, in 1795. He it
was who in rummaging St. Petersburg bookstalls had
discovered the manuscript of Néstor’s Chronicle. From a
monk he procured a collection of eight pieces, the fifth of
which was this poem. He published the Word, as this poem is
called in the manuscript, in 1800, with a modern Russian
translation. The manuscript itself was burnt in the Moscow
conflagration of 1812. The poem has since been edited a
countless number of times, and equally large is the mass of
critical essays to explain the many dark and corrupt places of
what now must pass for the original. When we consider that
there are not less than six versions of the Word in French, it
seems strange that it is now first rendered into English in its
entirety. There is an imperfect translation of a small part of it
in H. H. Munro’s The Rise of the Russian Empire, Boston and
London, 1900.

Were it not well for us, O brothers, to commence in the ancient

strain the sad story of the armament of Ígor,[23] Ígor son of
Svyatosláv? And let the song be told according to the accounts of
the time, and not according to the cunning of Boyán[24] the Wise, for
Boyán the Wise, when he wished to make a song, soared with his
thoughts in the tree, ran as a grey wolf over the earth, flew as a
steel-grey eagle below the clouds. When he recalled the strife of
former time, he let loose ten falcons o’er a flock of swans, and every
swan each touched sang first a song: to old Yarosláv,[25] to brave
Mstisláv[26] who slew Redédya before the Kasóg army, to fair
Román Svyatoslávich.[27] But Boyán, O brothers, did not let loose
ten falcons on a flock of swans, but laid his inspired fingers on the
living strings, and they themselves sounded the glory to the princes.
Let us begin, O brothers, this tale from Vladímir[28] of old to the
late Ígor who strengthened his soul by his valour, and sharpened it
by the courage of his heart, and having filled himself with a manly
spirit, led his valiant army for the land of Russia into the country of
the Pólovtses.[29]

II

Then Ígor looked up to the bright sun, and saw that he had
covered in darkness[30] all his warriors. And Ígor spoke to his
druzhína: “O brothers and druzhína! It is better to be cut to pieces
than to be made a captive! Let us, O brothers, mount our swift
horses that we may behold the beautiful Don!”
A strong desire filled the Prince’s soul to drink from the great Don,
and his eagerness blinded him to the evil omen.
“For I wish,” he said, “to break the spear on the border of the
Pólovts land together with you, sons of Russia! I want to lay down
my head, and drink with my helmet from the Don!”
O Boyán, nightingale of ancient time! It were for you to spell this
army, soaring like a nightingale over the tree of thought, flying like an
eagle below the clouds, stringing together words for the deeds of
that time, racing over Troyán’s[31] footsteps over fields to the
mountains. You ought to have sung a song to Ígor, his grandson:
“Not a storm has driven the falcons over the broad fields: flocks of
crows hasten to the great Don.”... Or you might have sung thus,
inspired Boyán, grandson of Velés[32]:
 “The horses neigh beyond the Sulá[33]; glory resounds in Kíev;
trumpets blare in Nóvgorod[34]; the standards are at Putívl[35]; Ígor
waits for his beloved brother Vsévolod. And Vsévolod, the Grim
Aurochs, spoke to him: “My only brother, my only light, glorious Ígor,
we are both sons of Svyatosláv! Saddle, O brother, your swift steeds,
for mine are ready for you, having been saddled in advance at
Kursk! My Kurians are tried warriors, nurtured by the sound of
trumpets, rocked in helmets, fed at the point of the spear. The roads
are known to them; the ravines are familiar to them; their bows are
drawn; their quivers open, their swords—whetted. They race over
the fields like grey wolves, seeking honour for themselves, and glory
for their Prince.”

III

Then Prince Ígor stepped into the golden stirrup and galloped over
the clear field. The sun barred his way in darkness; night groaning
with the cries of birds awoke him; beasts howled, and Div[36] called
in the top of a tree, sending the news to the unknown land, to the
Vólga, the Sea border,[37] the Sulá country, Surózh[38] and Korsún,
[39] and to you, idol of Tmútorokan![40] But the Pólovtses hastened
by untrodden roads to the great Don; the carts creaked at midnight,
like swans let loose.
Ígor leads his soldiers to the Don: the birds in the thicket forbode
his misfortune; the wolves bristle up and howl a storm in the
mountain clefts; the eagles screech and call the beasts to a feast of
bones; the foxes bark for the crimson shields. O Russian land, you
are already beyond the mound![41] Night is long and murky; the
dawn withholds the light; mist covers the fields; the nightingale’s
song is silent; the cawing of the crows is heard. The Russians bar
the long fields with their crimson shields, seeking honour for
themselves and glory for the Prince.

IV
 Early in the morning, on the Friday, they crushed the pagan
Pólovts host, and, spreading like arrows over the field, seized fair
Pólovts maidens, and with them gold and gold-worked stuffs and
costly velvet; with cloaks and coats and Pólovts lace they bridged
their way over bogs and muddy places. A red flag, white pennon, red
panache, silver cross-beam, for the brave son of Svyatosláv!...[42]
Olég’s valiant brood has flown afar and dreams in the field! They
thought not to offend the falcon, gerfalcon, nor you, black raven,
pagan Pólovts! But Gza ran like a grey wolf, with Konchák[43] in his
track, to the great Don.

Very early the next morning a bloody dawn announces the day.
Black clouds come from the sea and try to veil four suns,[44] while
blue lightnings quiver through them. There is to be a mighty thunder,
and the rain is to go down in arrows by the great Don! There spears
will be broken; there swords will be blunted against Pólovts helmets
on the Kayála,[45] by the great Don. O Russian land, you are already
beyond the mound!
Behold the winds, Stribóg’s[46] grandchildren, blow arrows from
the sea on Ígor’s valiant army. The earth groans, the rivers flow
turbid; dust covers the fields; the banners whisper. The Pólovtses
come from the Don, and from the sea, and from all sides: the
Russian army recedes. The devil’s children fill the field with their
cries, but the brave Russians line it with their crimson bucklers.
Grim Aurochs Vsévolod! You stand in the van; you pour arrows on
the warriors; you thunder with steel swords against their helmets.
Wherever you, Aurochs, lead, gleaming with your golden helmet,
there fall the heads of the pagan Pólovtses, their Avar[47] helmets
cloven by your tempered swords, Grim Aurochs Vsévolod! What
wound does he brook, O brothers, having forgotten his honours and
manner of life, and Chernígov town, his paternal golden throne, and
the caresses of his sweetheart, Glyeb’s fair daughter,[48] and the
habits and customs of his home?
 VI

Troyán’s age is past, gone are the years of Yarosláv; past are the
expeditions of Olég,[49] the son of Svyatosláv. That Olég had
fostered discord with his sword, and had sowed arrows over the
land. In Tmútorokan city he stepped into the golden stirrup. Great
Yarosláv, that was, heard the tocsin,[50] and Vsévolod’s son Vladímir
closed his ears all the days at Chernígov.[51] But Glory brought
Borís,[52] the son of Vyachesláv, before the judgment seat and
bedded him, brave young prince, on the green feather grass of the
steppe, through Olég’s offence....
Then, in the days of Olég Gorislávich,[53] feuds were sown and
grew, and Dazhbóg’s[54] grandchildren perished, and the years of
men were shortened by the discord of the princes. In those days the
warriors rarely walked behind the plough in the Russian land, but the
ravens croaked as they divided the dead bodies, and crows
chattered, flying to the banquet. Such were the wars and expeditions
then, but the like of this war was never known.

VII

From early morning until evening, from evening until daylight fly
tempered arrows, thunder the swords against the helmets, resound
the steel spears in a strange field, within the country of the
Pólovtses. The black earth beneath the hoofs was sown with bones,
and watered with blood, and a harvest of sorrow went up in the
Russian land.
What noise is that, what din, so early in the morning before dawn?
Ígor leads his army; he is sorry for his beloved brother Vsévolod.
They fought a day, they fought another[55]; upon the third at noon fell
the standards of Ígor. The brothers separated on the bank of the
swift Kayála. Here there was not enough of bloody wine; here the
brave Russians ended the feast: they gave their host their fill to
drink, and themselves fell for the Russian land. The grass withered
from sorrow, and the trees in anguish bent down to the earth.[56]

VIII

There befell a hapless hour, O brothers! Already had the

wilderness covered Russia’s hosts, when Mischief arose in the hosts
of Dazhbóg’s grandchildren: she walked as a maiden in Troyán’s
land,[57] splashed her swan pinions in the blue sea,[58] and splashing
them in the Don, recalled heavy times.
Through the feuds of the princes ruin came from the pagans, for
brother spoke to brother: “This is mine and that is mine also,” and
the princes said of trifling matters, “They are important,” and created
discord among themselves; and the pagans came from all sides
victorious into the Russian land.
Oh, far has the falcon[59] flown, driving the birds by the sea, but
Ígor’s brave army will rise no more! Konchák called, and Gza raced
over the Russian land, hurling fire from a flaming horn.[60] Russian
women wept, saying: “No longer will our thoughts reach our dear
ones, nor shall we ever see them with our eyes, nor be adorned with
tinkling gold and silver!”
And Kíev groaned under its sorrow, and Chernígov on account of
its misfortunes. Sadness spread over the Russian land, and a heavy
gloom. The princes fostered discord among themselves, and the
pagans victoriously overran the country, receiving tribute, a
squirrel[61] from each house.
It is Ígor and Vsévolod, Svyatosláv’s brave sons, who through their
discord had wakened dishonour which their father, Svyatosláv[62] of
Kíev, the great, the mighty, had put to sleep: he had invaded the
Pólovts land and had carried terror to them, with his mighty armies
and tempered swords; had levelled their hills and ravines, ruffled
their rivers and lakes, dried up their streams and swamps; and, like a
whirlwind, had snatched pagan Kobyák[63] away from his mighty,
steel-clad Pólovts army by the Ázov Sea, until Kobyák fell in Kíev
city, in the council-room of Svyatosláv. Germans, Venetians, Greeks
and Moravians sing the glory of Svyatosláv, but blame Prince Ígor
who had merged his wealth in the Kayála, the Pólovts river, and had
filled it with Russian gold. Here Ígor was unseated from his golden
saddle and placed upon the saddle of a slave.

IX

The city walls were silent, and merriment was dead. Svyatosláv
saw a troubled dream: “In Kíev on the mount you enveloped me last
night,” he said, “in a black shroud on a bed of yew; they poured out
to me blue wine mixed with bitterness; from empty quivers they
showered large gems upon my lap, and tried to comfort me. Already
are there boards without a cross beam in my hall of gold, and all
night have the devilish crows been cawing.”[64] ...
The boyárs spoke to the Prince: “Prince, sorrow has enthralled
your mind. Two falcons flew from their paternal throne of gold to find
the city of Tmútorokan, and anxious to drink from the Don with their
helmets. The falcons’ wings have been clipped by the pagan swords,
and they have been enmeshed in iron fetters. On the third day it was
dark: two suns were dimmed,[65] two red torches went out, and with
them two young moons, Olég[66] and Svyatosláv, were shrouded in
darkness. On Kayála river darkness veiled the day: the Pólovtses
had invaded the Russian land, like a litter of lynxes.... Fair Gothic[67]
maidens sing upon the shore of the blue sea, tinkling with the
Russian gold: they sing the times of Bus, recall Sharokán’s[68]
revenge. But we, your druzhína, are anxious for the feast.”
Then great Svyatosláv uttered golden words, mingled with tears:
“Oh, my nephews, Ígor and Vsévolod! Too early did you begin to
strike the land of the Pólovtses with your swords, and to seek glory
for yourselves. You were vanquished ingloriously, for ingloriously
have you spilled the blood of the pagans! Your brave hearts are
forged with hard steel and tempered in daring exploits. See what you
have done with my silvery hair! I no longer see with me my mighty,
warlike brother Izyasláv with his Chernígov druzhína.... They
overwhelmed their enemies with dirks, not bearing bucklers, but
raising a warcry and resounding the glory of their forefathers. But
you spoke: ‘We alone will vanquish! Let us ourselves gain the future
glory, and share the glory of our fathers!’ Why should not an old man
feel young again? When the falcon is moulting, he drives the birds
far away, and allows not his nest to be hurt. But alas, the princes will
not aid me! My years have turned to nothing. At Rim[69] they cry
under the swords of the Pólovtses, and Vladímir[70] groans under his
wounds. Bitterness and sorrow has befallen the son of Glyeb!”

Grand Prince Vsévolod![71] Fly from afar not only in thought, but
come to protect your paternal throne: for you could dry up the
Vólga[72] with your oars, and empty the Don with your helmets. If you
were here, a Pólovts slave-girl would be worth a dime, and a man-
slave—half a rouble.[73] And you know, together with the brave sons
of Glyeb, how to hurl the Greek fire on land.
You, Grim Aurochs Rúrik and David![74] Did not your golden
helmets swim in blood? Did not your valiant druzhína bellow like
aurochses, when they were wounded by tempered swords in a
strange field? Put your feet, O lords, into your golden stirrups to
avenge the insult to the Russian land, the wounds of Ígor, the valiant
son of Svyatosláv!
Yarosláv Osmomýsl of Gálich![75] You sit high upon your throne
wrought of gold, propping with your iron-clad army the Carpathian
mountains, barring the king’s path, closing the gates of the Danube,
hurling missiles higher than the clouds, sitting in judgment as far as
the Danube. Your thunders pass over the land, and you hold the key
to the gates of Kíev; sitting on your paternal throne, you slay the
sultans in their lands. Slay, O lord, Konchák, the pagan villain, to
avenge the Russian land, the wounds of Ígor, the valiant son of
Svyatosláv!
 And you, valiant Román[76] and Mstisláv! A brave thought carries
you into action.[77] You fly high in your onslaught, like a falcon
circling in the air, about to swoop down upon the birds. You wear iron
hauberks under Latin helmets, and the earth has trembled from you
in many a pagan land: the Lithuanians, Yatvyágans, Deremélans and
Pólovtses threw down their warclubs and bent their heads under
those tempered swords. But now, O Prince, Ígor’s sun is dimmed,—
the tree, alas, has shed its leaves. Along the Ros[78] and the Sulá
the Pólovtses have sacked the towns, but Ígor’s brave army will rise
no more. The Don calls you, O Prince, and the other princes to
victory!
Olég’s sons have hastened to the war. Íngvar and Vsévolod,[79]
and the three sons of Mstisláv,[80] a mighty winged brood! Not by the
lot of war have you acquired power. Of what good are your golden
helmets, and Polish warclubs and shields? Bar the enemy’s way with
your sharp arrows, to avenge the Russian land, the wounds of Ígor,
the valiant son of Svyatosláv!

XI

The Sulá no longer flows with a silvery stream by Pereyáslavl

town,[81] and the Dviná flows turbid by mighty Pólotsk, agitated by
the pagans. Izyasláv,[82] Vasílko’s son, alone made his sharp swords
ring against the Lithuanian helmets, outstripping the glory of his
grandfather Vsesláv, but himself was worsted by Lithuanian swords,
and fell under crimson shields, upon the bloodstained grass. Lying
on his death-bed, he spoke[83]: “O Prince, the birds have covered
your druzhína with their wings, and the beasts have lapped their
blood.” There was not present the brother Bryachisláv, nor the other,
Vsévolod; alone he lost the pearl soul out of his valiant body through
the golden necklace. The voices were subdued, merriment died
away. The trumpets blare at Goródno.
Yarosláv and all grandchildren of Vsesláv![84] Furl your standards,
sheath your blunted swords, for you have leaped away from your
grandfather’s glory! You have with your discords invited the pagan
hosts against the Russian land, against the life of Vsesláv, for
through your strife has come the enslavement by the Pólovts land.
In the seventh age of Troyán,[85] Vsesláv cast his lot for his
beloved maiden.[86] He bestrode his horse, and galloped to the city
of Kíev, and with the thrust of the spear possessed himself of
golden-throned Kíev. He galloped hence as a grim beast to the south
of Byélgorod,[87] and disappeared in the blue mist; next morning he
clanked with the battering-ram, and opened the gates of Nóvgorod;
he shattered the glory of Yarosláv,[88] and raced as a wolf to the
Nemíga from Dudútki.[89]
On the Nemíga, ricks are stacked with heads, and they flail with
tempered chains; the body is placed on the threshing-floor, and the
soul is winnowed from the body. Not with grain were sown the bloody
banks of the Nemíga, but with the bones of Russian sons.
Prince Vsesláv sat in judgment over his people, apportioned cities
to the princes, but himself raced a wolf[90] in the night, and by
cockcrow reached from Kíev to Tmútorokan, and as a wolf crossed
the path of great Khors.[91] When they rang the bell in the church of
St. Sophia for matins, early in the morning at Pólotsk, he heard the
ringing in Kíev. Though his cunning soul could pass into another
body, yet he often suffered woe. Thus wise Boyán of old has justly
said: “Neither the cunning, nor the agile, nor the swift bird can
escape the judgment of the Lord!”
Oh, the Russian land must groan as it recalls the former days and
the ancient princes! It was not possible to nail Vladímir to the hills of
Kíev[92]: now there are standards of Rúrik, and others of David....[93]

XII

Yaroslávna’s[94] voice is heard; like a cuckoo in a lonely spot she

calls plaintively in the morning: “I will fly,” she says, “like a cuckoo
along the Danube,[95] will wet my beaver sleeve in the river Kayála,
will wipe off the Prince’s bloody wounds on his manly body!”
Yaroslávna weeps in the morning at Putívl town on the wall,
saying: “O wind, mighty wind! Why, master, do you blow so strong?
Why do you on your light wings carry the Khan’s arrows against the
warriors of my beloved one? Is it not enough for you to blow on high
below the clouds, rocking the ships on the blue sea? Why, master,
have you dispersed my happiness over the grass of the steppe?”
Yaroslávna weeps in the morning at Putívl town on the wall,
saying: “O famous Dnieper, you have pierced the rocky mountains
across the country of the Pólovtses! You have rocked on your waves
the boats of Svyatosláv as far as the army of Kobák.[96] Fondly bring
to me, master, my sweetheart, that I may not in the morning send
tears after him out to sea.”
Yaroslávna weeps in the morning at Putívl town on the wall,
saying: “Bright, three times bright sun, you give warmth and joy to
all! Why, master, have you thrust your burning beams on the warriors
of my beloved one? Why have you in the waterless plain dried up
their bows, and sealed their quivers in sorrow?”

XIII

The sea is agitated at midnight: mists are borne in the darkness.

God shows to Ígor a way out of the land of the Pólovtses into the
country of Russia to his father’s golden throne. The evening twilight
has gone out. Ígor sleeps; Ígor is awake: Ígor in his thought
measures the plains from the great Don to the small Donéts. His
steed is ready at midnight. Ovlúr whistles beyond the river, gives a
sign to the Prince,—Prince Ígor will be no more!
The earth resounded, the grass rustled, the Pólovts’ tents
trembled. But Ígor raced like an ermine in the reeds, like a white
duck over the water; he jumped on a swift steed, dismounted as a
light-footed wolf, and hastened to the plain of the Donéts; and as a
falcon flew through the mist, killing geese and swans for his
breakfast and dinner and supper. When Ígor flew as a falcon, Ovlúr
raced as a wolf, shaking off the cold dew, for they had worn out their
swift steeds.
The Donéts spoke: “Prince Ígor, great is your honour, and the grief
to Konchák, and joy to the Russian land!”
Ígor spoke: “O Donéts, great is your honour, having rocked the
Prince on your wave, having spread out for him the green grass on
your silver banks, having cloaked him with warm mists under green
trees. You have guarded him as a duck on the water, as a gull on the
waves, as a mallard in the air. Not thus the river Stúgna[97]: though
having a scanty stream, it has swallowed other brooks, and has
spread the floods over the bushes. To the young Prince Rostisláv the
Dnieper has closed its dark banks. Rostisláv’s mother weeps for the
young Prince. The flowers faded in their sorrow, and the trees bent in
anguish to the ground.”
It is not magpies that are in a flutter: Gza and Konchák ride in
Ígor’s track. Then the raven did not croak, the jackdaws were silent,
the magpies did not chatter, only leaped from branch to branch. The
woodpeckers indicated the road to the river by their pecking; the
nightingales announced the day by their merry song.
Said Gza to Konchák: “Since the falcon is flying to his nest, let us
shoot the fledgling[98] with our golden darts.”
Said Konchák to Gza: “Since the falcon is flying to his nest, let us
enmesh the fledgling with a fair maiden!”
And Gza spoke to Konchák: “If we enmesh him with a fair maiden,
we shall have neither the young falcon, nor the fair maiden, and the
birds will attack us in the Pólovts plain.”

XIV

Boyán has said: “Hard it is for you, O head, to be without your

shoulders; ill it is for you, O body, to be without a head.” Even so is
the Russian land without Ígor.
 The sun shines in the heaven,—Prince Ígor in the land of Russia!
Maidens sing at the Danube: their voices are carried over the sea to
Kíev. Ígor rides over the Boríchev,[99] to the church of the Holy Virgin
of Pirogóshch. The country is happy, the towns rejoice; they sing
songs to the elder princes, and then to the younger. Let us sing the
glory of Ígor Svyatoslávich, of Grim Aurochs Vsévolod, Vladímir
Ígorevich! Hail, princes and druzhína, who battle for the Christians
against the pagan host! Glory to the princes and the druzhína!
Amen!

FOOTNOTES:

[23] Ígor was the son of Svyatosláv Ólgovich of Nóvgorod

Syéverski, and grandson of Olég of Tmútorokan.
[24] From the references to the princes whose praise he sang,
it is evident that he lived at the end of the eleventh and the
beginning of the twelfth centuries. Nothing else is known of this
famous poet.
[25] Yarosláv, the son of Vladímir, lived from 1019-1054: he was
the author of the Russian Code (see p. 45).
[26] Mstisláv, Prince of Tmútorokan, was the brother of
Yarosláv ( † 1036). In 1022 he killed in duel the giant Redédya,
chief of the Kasógs who dwelt between the Black and Caspian
seas, and conquered their country.
[27] Román was a brother of Ígor’s grandfather Olég; he was
killed by the Pólovtses in 1079.
[28] Vladímir the Great, father of Yarosláv.
[29] A Turkish tribe, related to the Pechenyégs, who called
themselves Cumanians. They occupied the south of Russia as far
as Hungary.
[30] See account of the eclipse in the Chronicle (p. 72).
[31] Troyán is counted among the ancient Russian divinities in
The Holy Virgin’s Descent into Hell (p. 97); but evidently he is also
a reminiscence of the Roman Emperor Trajan, whose ramparts
and roads are still to be traced along the Danube.
 [32] The god of the flocks, i. e., of wealth and abundance. It is
not quite clear why the poet is called his grandson.
[33] Tributary of the Dnieper.
[34] Nóvgorod Syéverski, Ígor’s capital, in the Government of
Chernígov.
[35] The appanage of Ígor’s son Vladímir, in the Government of
Kursk.
[36] A bird of ill-omen; according to some, divinity of darkness.
[37] The border of the Black Sea.
[38] The Ázov Sea.
[39] The ancient Tauric Chersonese, near the modern
Sebastopol.
[40] An ancient city of the Khazars, on the eastern shore of the
Ázov Sea, on the peninsula of Tamán. It became a Russian
possession in the tenth century.
[41] A frequently recurring sentence, the meaning of which
seems to be: You are lost beyond redemption!
[42] The trophies won by Ígor.
[43] Gza and Konchák, khans of the Pólovtses, were the
leaders of the expedition. See p. 77.
[44] The four suns are: Ígor, his brother Vsévolod, his son
Vladímir of Putívl, and his nephew Svyatosláv Ólgovich of Rylsk.
[45] Tributary of the Don.
[46] God of the winds.
[47] Descendants of the Avars still live between Georgia and
Circassia.
[48] Her name was Ólga.
[49] Olég is the grandfather of Ígor. The poet here recalls
former encounters with the Pólovtses. Not having been able to
agree with his uncles, Izyasláv who had occupied the throne in
Kíev, and Vsévolod who had his appanage of Chernígov, Olég
escaped to Román the Fair of Tmútorokan, and decided to get his
rights by means of arms. He led three times the Pólovtses into
Russia (in 1078, 1079 and 1094).
[50] That is, in the other world.
 [51] Vladímir Monomákh hastened to his father’s aid. See his
Instruction, p. 55.
[52] Olég and his cousin, Borís, were at that time absent from
Chernígov. When they arrived and opposed themselves to the
superior force of Izyasláv, Olég advised Borís to surrender; but he
would not listen and made an attack upon his uncle’s army and
was killed.
[53] Olég is called the son of “Góre,” i. e., woe.
[54] The Russians are sons of Dazhbóg, the god of the sun,
while the enemy are the “devil’s children.”
[55] The first day the Russians defeated the Pólovtses; the
next, the Pólovtses defeated the Russians; on the third day, which
was a Sunday, the Kovúans ran away, and at noon Ígor was
made prisoner. See the Chronicle, p. 74.
[56] Nature sympathises with the Russians.
[57] That is, far away; see note 5, p. 82.
[58] The Sea of Ázov.
[59] That is, Ígor; the Pólovtses are the birds.
[60] The Chronicle says the Pólovtses hurled the Greek fire.
[61] A silver coin.
[62] This Svyatosláv, the son of Vsévolod Ólgovich, had been
the Prince of Chernígov. He was Grand Prince of Kíev from 1174-
1194. He had to give up his throne twice, but in 1181 ascended it
for the third time. He is called Ígor’s and Vsévolod’s father by
seniority, though he was only their uncle by relationship.
[63] The Russians obtained a famous victory over the
Pólovtses, of whom 7000 were taken prisoners, in 1184.
[64] A series of evil omens.
[65] Ígor and Vsévolod.
[66] Probably the son of Ígor; but he was only eleven years old
during the expedition.
[67] Descendants of the Goths who had settled along the Black
Sea had been found and described as late as the sixteenth and
even seventeenth centuries in the Crimea and in the Tamán
peninsula.
 [68] These Gothic girls evidently sang the exploits of Pólovts
princes. Sharokán had made an incursion into Russia in 1107, but
he was defeated and had to flee. In 1111 Sharokán returned with
an immense army to avenge his defeat.
[69] Now Rómen, in the Government of Poltáva.
[70] Vladímir of Pereyáslavl. See the Chronicle, p. 78.
[71] Vsévolod Yúrevich, Prince of Súzdal, whose father, Yúri
Dolgorúki, had been Grand Prince at Kíev.
[72] In 1183 Vsévolod made an expedition against the
Bulgarians of the Vólga; he went down the Vólga as far as Kazán,
and then proceeded on foot.
[73] That is, if Vsévolod were there, he would be so victorious
against the Pólovtses as to lower the price of Pólovts slaves.
[74] The sons of Rostisláv Mstislávich, and great-grandchildren
of Vladímir Monomákh.
[75] Yarosláv Osmomýsl ( † 1187) was the Prince of Gálich,
which in his days extended as far as the Prut and the Danube and
included part of Moldavia. His daughter was Ígor’s wife.
[76] Román Mstislávich ( † 1205), Prince of Volhynia, twice
occupied the throne in Gálich. He fought successfully against the
Lithuanians and Yatvyágans, and when he was Prince of Gálich
he saved Constantinople from the impending danger of a Pólovts
and Pechenyég invasion. The Chronicle says of him: “He rushed
against the pagans like a lion, raged like a lynx, and destroyed
them like a crocodile, and crossed their lands like an eagle, for he
was as brave as an aurochs,” and “The Pólovtses used to frighten
their children with his name.”
[77] Mstisláv was probably the brother of Íngvar and Vsévolod,
mentioned below.
[78] Tributary of the Dnieper.
[79] The sons of Yarosláv Izyaslávich, Prince of Lutsk, who was
Grand Prince of Kíev in 1173.
[80] Román, Svyatosláv and Vsévolod, sons of Mstisláv, great-
grandchildren of Vladímir Monomákh.
[81] The Pólovtses divided among themselves the towns along
the Sulá. See the Chronicle, p. 77.
 [82] Izyasláv’s appanage was Goródno, in the Government of
Minsk, hence farther down “The trumpets blare at Goródno.”
[83] Izyasláv addresses himself.
[84] These are opposed to the brave Izyasláv, who is also a
descendant of Vsesláv. Vsesláv Bryachislávich, Prince of Pólotsk,
was, in 1064, defeated by Izyasláv and his brothers on the
Nemíga; later he was enticed by Izyasláv to Kíev, where he was
imprisoned. In 1067 Izyasláv was driven out by the Kíevans, and
Vsesláv was made Grand Prince. Izyasláv attacked Vsesláv at
Byélgorod, but the latter fled to Pólotsk.
[85] The exact meaning of the “seventh age of Troyán” is not
known; some distant time is designated.
[86] That is, for Kíev.
[87] Ten versts from Kíev.
[88] Tributary of the Svísloch, in the Government of Minsk.
[89] Near Nóvgorod.
[90] The chronicles and popular tradition make Vsesláv a
werewolf and a sorcerer.
[91] Another name for Dazhbóg, the god of the sun.
[92] That is, for ever to retain Vladímir in Kíev.
[93] Now there is discord.
[94] Evfrosíniya (Euphrosyne), daughter of Yarosláv Osmomýsl
of Gálich, Ígor’s second wife.
[95] A standing formula for rivers in general, here the Kayála.
[96] Expedition of 1184.
[97] A swampy river in the Government of Kíev. Rostisláv
Vsévolodovich, the son of Vsévolod and Anna, the daughter of a
Pólovts Khan, and the brother of Vladímir Monomákh. After an
unsuccessful attack upon the Pólovtses, he escaped from
captivity by jumping into the Stúgna, but being in heavy armour
he was drowned.
[98] Vladímir, the son of Ígor, who was also taken captive. He
really married Konchák’s daughter and returned with her to Kíev
in 1187.