Solid State Phenomena Vol.

188 (2012) pp 102-108

© (2012) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/SSP.188.102

Characterization of Electron Beam Irradiated Polyvinylpyrrolidone-

Dextran (PVP/DEX) Blends
DUMITRAŞCU Maria1,a, ALBU Mădălina Georgiana2,b, VÎRGOLICI Marian3,c,
VANCEA Cătălin1,d MELTZER Viorica4,e
1
National Institute for Lasers Plasma and Radiation Physics, 409 Atomiştilor Street, 077125,
Măgurele, Romania
2
Leather and Footwear Research Institute - INCDTP, Collagen Department, 93 Ion Minulescu
Street, 031215, Bucharest, Romania
3
Horia Hulubei National Institute of Physics and Nuclear Engineering - IFIN-HH, 407 Atomiştilor
Street, 077125, Măgurele, Romania
4
University of Bucharest, Faculty of Chemistry, 4-12 B-dul Regina Elisabeta, 030018, Bucharest,
Romania
a
maria_dumitrascu@yahoo.com, balbu_mada@yahoo.com, cvirgolicimarian@yahoo.com,
d
catalin.vancea@yahoo.com,viomel@gw-chimie.math.unibuc.ro

Keywords: Biomaterials, Dextran, Electron beam Irradiation, Polymeric blends, PVP, PVP/DEX
blends

Abstract. In recent years an increased interest to create new polymeric blends used for biomaterials
with applications in pharmaceutics and in the medical field in general, has appeared. Electron beam
irradiation is a well known method of producing important structure changes in polymers, being an
alternative to chemical synthesis of biomaterials based on polymeric materials. The present study is
aimed at investigating the behaviour of some polyvinylpyrrolidone-dextran (PVP/DEX) blends after
electron beam irradiation. Aqueous solutions of PVP with molecular weights of 360 kDa (PVP
360), 40 kDa (PVP 40), and Dextran with molecular weight of 500 kDa (DEX), were mixed as to
obtain 50:50 blends of PVP360/DEX and PVP40/DEX. The obtained blends were irradiated with an
electron beam at different radiation doses. The PVP/DEX blends were characterized by using
infrared spectroscopy (FT-IR) and thermal analysis. The analyses were conducted in order to
establish the relation between radiation dose and changes of structural and thermal properties.

Introduction
In recent years an increased interest to create new polymeric blends used for new types of
biomaterials with application in the medical field has appeared. Blends of synthetic and natural
polymers represent a new class of materials with better mechanical properties and biocompatibility
than those of the single components [1]. Ionizing radiation has long been recognized as a suitable
tool for the formation of hydrogels. Easy process control, possibility of hydrogel formation and
sterilization in one technological step, no necessity to add any initiators, crosslinkers, etc., having
no waste, and relatively low running costs, are some advantages of ionizing radiation. These
advantages make irradiation a method of choice in the synthesis of hydrogels, especially for
biomedical use [2]. Polyvinylpyrrolidone (PVP) is an interesting water-soluble synthetic polymer
with a broad range of applications. PVP has been used for preparation of synthetic plasmas
(substitute of blood plasma), for hydrogel production by radiation methods and for creations of
hydrophilic gels [3]. Dextran (DEX) is a class of polysaccharides with a linear polymer backbone
with mainly 1,6-α-D-glucopyranosidic linkages. It is obtained from bacterial cultures of
Leuconostoc mesenteroides [4]. DEX is widey used as plasma expanders, blood substitutes, bone
healing promoters, and also for dermal and subcutaneous augumentaion [5]. Polymeric blends from
DEX and PVP [6], have been performed, but the influence of electron beam irradiation has not been
yet investigated regarding this type of polymeric blends. The goal of this study was to determine the
influence of electron beam irradiation on two type of polymeric blends composed of PVP and DEX
with different molecular weights (Mw).

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 Solid State Phenomena Vol. 188 103

Experimental

Materials. Three water-soluble polymers: polyvinylpyrrolidone (PVP360) with average molecular

weight (Mw) of 360 kDa; PVP40 with Mw of 40 kDa and dextran (DEX) with Mw of 500 kDa were
used in this study. All materials were purchased form Sigma-Aldrich.
Polymeric blends were prepared by mixing suitable weights of PVP360, PVP40 and DEX aqueous
solution to obtain the final weight ratio of 50:50 (w/w). We performed two type of blends made
from PVP360 and DEX, denoted as PVP360/DEX; and the second blend was performed from
PVP40 and dextran, denoted as PVP40/DEX.
Electron beam irradiation. The obtained blends were irradiated in Petri dishes with radiation
doses ranging from 0 kGy up to 50 kGy with a dose rate of 2 kGy/min. Irradiation was performed
with a linear electron accelerator (ALIN-10) with the following main technical characteristics: EEB
= 6.23 MeV; IEB = 75 mA; PEB = 164 W (fEB = 100 Hz, τEB = 3.5 µs). The experiments were carried
out at room temperature and atmospheric pressure. The absorbed radiation doses were cheked by
chemical dosimetry using ceric-cerrous dosimeter. The irradiated blends were freeze-dried as to
obtain solid samples.
FTIR analysis. Fourier transform infrared (FTIR) spectra of unirradiated and irradiated blends
were taken with a Vertex 70 class instrument (Bruker Optics, Germany). Spectra were aquired in
ATR mode and each spectrum consisted of 32 scans/sample in the 4000-400 cm-1 wavenumeber
range at a resolution of 4 cm-1.
Thermal analysis. The TG/DSC experiments were performed on a Simultaneous Thermal Analyzer
STA 409 PC Luxx (NETZSCH Geratebau GmbH, Germany) equipped with TG/DSC type S which
was used to study the thermal stability of pure PVP, DEX, PVP360/DEX, PVP40/DEX. All
samples were investigated under a nitrogen atmosphere with a flow rate of 80 mL/min, sample mass
about ~10 mg at the heating rate of 10 K min-1, in the temperature range 25-500°C. The TG/DTG
and DSC curves were obtained using NETZSCH Proteus Thermal Analysis software. The heating
of the sample was performed in an aluminum crucible and an empty crucible was used as reference.

Results and discussions

FTIR analysis. Fourier transform infrared (FTIR) spectroscopy has been widely used to study the
formation of polymeric blends [7]. FTIR spectra provide information regarding intermolecular
interaction which corresponds to stretching or bending vibrations of particular bonds and the
position at which these peaks appear depends directly on the force constant or bond strength.
Hydrogen bonding or other interactions between chemical groups on the dissimilar polymers should
theoretically cause a shift in peak position of the participating groups. This kind of behaviour is
exhibited by miscible blends that show extensive phase mixing. Hydrogen bonding interaction
usually moves the stretching frequencies of the participating groups e.g. O–H, N–H, C=O towards
lower wavenumbers and causes an increase in intensity and peak broadening. The shift in peak
position will depend on the strength of the interaction [3]. The FTIR spectra of pure PVP and DEX
are shown in Fig.1. In the FTIR spectrum of PVP, there is a strong C=O absorption peak from the
amide group of PVP located at 1652 cm-1, the C−N group appeared at 1287 cm-1 and C−H
stretching and bending vibration frequencies can be observed between 2800-3000 cm-1 and 1423-
1493 cm-1, respectively. In the FTIR spectrum of DEX the presence of −OH groups could be
confirmed by the appearance of a band at 3351 cm-1, C−H stretching at 2906 cm-1, C−H bending
and rocking vibrations at 1417 cm-1 and 917 cm-1. The broad band observed at 1200 to 1050 cm-1
with a maximum at 1007 cm-1 characterizes the asymmetrical −C−O−C− stretching of the ring. For
the polymers studied, C=O− bond intensity, C-H stretching, C−N bond, –O−H stretching and
bending vibrations are the peaks of particular interest in FTIR analysis. The increase in intensity of
the 1652 cm-1 band which characterizes the C=O− bonds of amide, may indicates that the PVP
content of the blend has increased [6]. In DEX, there are three different hydroxyl groups, and these
groups take part in inter- and intramolecular interactions by forming hydrogen bonds.
104 Advanced Materials and Structures IV

Fig. 1. FT-IR of spectra of pure PVP and DEX

The FTIR spectra of unirradiated and irradiated PVP360/DEX blend is presented in Fig.2. As can
be seen in Fig.1-a, the unirradiated PVP360/DEX blend exhibited the following absorption
characteristics: a broad band at 3410 cm-1 and 2948 cm-1 bands which can be assigned to the O-H,
C−H and CH2 stretching vibrations; strong C=O absorption peak at 1650 cm-1, C−N bond at 1280
cm-1, C−H bending vibrations at 1429 cm-1 and a low absorption located at 1015 cm-1. According to
Barsbay et al. [8], the shifting towards lower wavenumbers reveals that there is a favorable
interaction between two polymers. In our case, favourable interaction between PVP and DEX can
take place through the carbonyl group of PVP and hydroxyl group of DEX. With increasing of
radiation dose, we observed the shifting of characteristic absorption bands towards lower
wavenumbers. The band from 3410 cm-1 was shifted to 3388 cm-1 and the one from 2948 cm-1 to
2944 cm-1. The highest shifting was observed for the samples irradiated with 50 kGy. For the
characteristic absorption band of amide group of PVP (1652 cm-1) lower shifting was observed with
radiation dose, and their intensity was not affected by radiation dose. Thus, the intensity of specific
bands located between 3000 and 3600 cm-1, and the band between 1100 and 1050 cm-1 had
increased after electron beam irradiation. The highest intensity of band between 3000 and 3600 cm-1
was observed for the sample irradiated at 5 kGy, while for the band located between 1100 and 1050
cm-1 it was at 50 kGy. The Fig.3 shows the FTIR spectra of unirradiated and irradiated PVP40/DEX
blends. The characteristic absorption bands for unirradiated blend are: 3426 cm-1, 2952 cm-1, 1651
cm-1, 1429 cm-1, 1280 cm-1 and 1015 cm-1. The band form 3426 cm-1, after electron beam irradiation
was shifted considerably towards lower wavenumbers up to 3332 cm-1 at the radiation
dose of 50 kGy.
The band from 2949 cm-1 assigned to the C−H stretching vibration was also shifted toward lower
wavenumbers up to 2924 cm-1 for the sample irradiated with 50 kGy. After electron beam
irradiation, the intensities of the 1651 cm-1 bands, which characterize the C=O− bonds of amide
group of PVP and the band from 1015 cm-1, which characterizes the O−H bending vibration of
DEX, varied considerably function of applied radiation dose. The intensity of specific bands located
between 3000 and 3600 cm-1 increased considerably for the samples irradiated with 25 kGy (Fig.2 –
e) and 50 kGy (Fig.2 – f), respectively.
 Solid State Phenomena Vol. 188 105

Fig. 3. FT-IR spectra of unirradiated and

Fig. 2. FT-IR spectra of unirradiated and
irradiated PVP40/DEX blend (B);
irradiated PVP360/DEX (A) blends;
a - 0 kGy; b - 1.25 kGy; c - 2.5 kGy;
a - 0 kGy; b - 1.25 kGy; c - 2.5 kGy;
d - 5 kGy; e – 25 kGy; f - 50 kGy
d - 5 kGy; e – 25 kGy; f - 50 kGy

Thermal analysis. Thermal stability of PVP, DEX and their unirradiated and irradiated blends was
checked by thermogravimetric (TG/DTG) and differential scanning calorimetry (DSC) analyses. In
Fig.4 and Fig.5 the characteristic TG/DTG and DSC curves for PVP and DEX are presented. In a
nitrogen atmosphere, the free PVP decomposes in two distinctive decomposition stages. The first
decomposition step is located between 40°C and 140°C, with a maximum decomposition rate at 92.5
°
C and a mass loss of 1.93% representing the water loss. The second decomposition step between
360°C and 500°C, with a maximum at 439.7°C and a weight loss of 80.77 % represents a
degradation process, which may be related to the breakdown of the organic skeleton [9]. From the
TG/DTG curve recorded for DEX, it can be observed that this polymer also has two different
decomposition stages. The first decomposition process is related to water loss, which starts at 40°C
and ends at 155°C, with a maximum at 97.5°C and a weight loss of 5.04%. The second
decomposition starts at 257°C and ends at 379°C, with a maximum at 301.9°C and a weight loss of
68.37%. The decomposition behaviour of unirradiated and irradiated PVP360/DEX and
PVP40/DEX blends were examined by thermogravimetry analysis as shown in Fig.6 and Fig.7. The
TG curves recorded for PVP360/DEX blends shows one step decompositions for the unirradiated
blend, while for irradiated PVP360/DEX blends, three decompositions steps are present. As can be
seen from Fig.5, the weight loss of unirradiated sample has been observed to amount of 7.80% at
101.7°C in the first step of decomposition whereas, in the second step of decomposition shows a
weight loss of 77.69% at 441.2°C. The unirradiated PVP40/DEX blend exhibited, three
decomposition steps, first one shows a weight loss of 4.31% at 95.7°C, the second one shows a
weight loss of 26.88% at 307.8°C and the third one shows a weight loss of 41.52% at 441.8°C.
Table 1 summarizes the values of weight loss and the maximum of DTG peak function of radiation
dose. The weight loss and DTG peak varied with applied radiation dose, thus an exact relation
cannot be determined between this parameters and the applied radiation dose. In general, DSC is the
most convenient method to determine the miscibility of polymer blends. One of the main indicators
of miscibility behaviour in polymer blends is the glass transition temperature (Tg) [10]. Glass
transition is defined as the difference between onset and end of the glass transition process [3]. Fig.
5 illustrates the glass transition process (Tg) of PVP and DEX. The DSC curves recorded for PVP
(179.8°C) and DEX (224.6°C) shows only one glass transition temperature as can be seen in Fig.5.
In Table 2 are summarized the glass transition temperature determined for the irradiated samples.
106 Advanced Materials and Structures IV

Table. 1. Values of the maximum of DTG peak determined for unirradiated and irradiated blends

DTG peak temperature

Dose,
T1 T2 T3 T1 T2 T3
[kGy]
PVP360/DEX PVP40/DEX
0 101.7 - 441.2 95.7 307.8 441.8
1.25 101.9 307.1 444.1 94.8 304.9 442.2
2.5 92.6 317.2
444.0 101.2 303.1 437.4
5 107.6 306.8 444.9 91.6 302.9 436.3
25 97.6 306.1 440.0 98.5 308.6 442.7
50 95.6 304.3 437.0 97.4 300.1 440.6
Weight loss, %
0 7.80 - 77.69 4.31 26.88 41.52
1.25 7.95 26.87 40.03 5.18 24.14 43.95
2.5 4.67 14.00 59.69 5.89 28.95 36.83
5 4.36 22.05 45.25 6.69 30.23 31.55
25 7.12 55.05 13.44 6.18 22.87 45.10
50 7.27 45.76 17.22 6.44 26.11 39.48

Fig. 4. TG/DTG curves of pure PVP and Fig. 5. Glass transition process of PVP and
DEX DEX

Table 2. Glass transition (Tg) processes of PVP, DEX and their studied blends

Dose, PVP360/DEX PVP40/DEX PVP DEX

[kGy] Tg,1 Tg,2 Tg,1 Tg,2 Tg,1 Tg,1
0 182.0 - 181.4 213.9 179.8 224.6
1.25 182.1 221.4 191.1 228.5 - -
2.5 181.8 212.1 184.8 228.7 - -
5 207.4 - 207.2 - - -
25 216.4 - 219.9 - - -
50 220.9 - 206.1 - - -
 Solid State Phenomena Vol. 188 107

Fig. 7. TG curve of unirradiated and irradiated

Fig. 6. TG curve of unirradiated and irradiated PVP40/DEX blends
PVP360/DEX blend

After irradiation dose of 5 kGy, both blends exhibited only one glass transition temperature, which
can be explained by the fact, that after electron beam irradiation new hydrogen bonds are formed,
resulting in a single homogenous compound. Thus in the case of unirradiated PVP360/DEX blends,
where more than one glass transition appeared, may be an indication that the system had suffered a
process of phase separation.

Conclusions
This study has investigated the influence of electron beam irradiation on two types of polymeric
blends, PVP360/DEX and PVP40/DEX. FT-IR and (TG/DTG/DSC) thermal analysis results clearly
indicated increasing of polymers interaction by increasing of specific bands intensity and their
shifting to lower wavenumbers, as well as only one glass transition was present, a behaviour that
was observed when the blends were irradiated with dose of 5, 25 and 50 kGy.

Acknowledgements
The authors would like to thanks to National Authority of Scientific Research (ANCS) by founding
of Nucleu Program PN 09 39.

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