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Radiation Physics and Chemistry 79 (2010) 335338

Contents lists available at ScienceDirect

Radiation Physics and Chemistry

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

Crosslinking of rigid PVC by ionizing radiation to improve

its thermal properties
eda a, R. Benavides a,,1, M.E. Martnez-Pardo b, R.M. Uribe c,
C. Garca-Castan
b

, G. Martnez a
H. Carrasco-Abrego
a

Centro de Investigaci
on en Qumica Aplicada, Blvd. Enrique Reyna 140, Saltillo Coahuila, Mexico
Instituto Nacional de Investigaciones Nucleares, Apartado postal 18-1027, Col. Escand
on, 11801 Me xico, D.F., Mexico
c
Kent State University, College of Technology and Program on Electron Beam Technology, P.O. Box 5190, Kent, OH 44242-0001, USA
b

a r t i c l e in fo

Keywords:
PVC
Crosslinking
Ionizing radiation

abstract
Rigid PVC formulations containing two different stabilizer systems (tin and Ca/Zn) and TMPTMA as a
crosslinking agent were treated with ionizing radiation (gamma and electron beam) at different doses
and irradiation atmospheres. The objective was to increase thermal and mechanical properties of this
material. Polyene formation was followed through the yellowing index (YI), the extent of crosslinking by
gel percentage, thermal resistance by Vicat temperature and the mechanical properties by DMA. Both
formulations became colored with irradiation, especially with gamma as a result of a longer treatment
time; the gel formation and the Vicat temperature were also higher for gamma treated samples,
suggesting that values were enhanced by oxidation. However, DMA elastic modulus traces were almost
similar for both treatments. The main difference observed for Ca/Zn samples compared with traditional
tin samples was the lower ability of the former system in protecting the material against processing
conditions.
& 2009 Elsevier Ltd. All rights reserved.

1. Introduction
PVC is a thermoplastic polymer of major consumption due to
its low production and processing costs. It is used intensively in
rigid form especially for hydraulic pipes; however, in case of hot
water applications its use is restricted since PVC is highly
susceptible to thermal degradation during which it produces
sequences of double bonds (polyenes) and releases HCl (Endo,
2002).
A possible solution to enhance thermal resistance as well as
other physical properties consists in crosslinking the polymer by
means of physical or chemical methods. Radiation crosslinking of
polymers is a method commonly used in industry because of its
capability to induce reactions in the solid state at low tempera eda Facio et al., 2004,
tures and at high rates of processing (Castan
2007 with references therein).
At present the use of radiation (high energy) in the polymer
area is employed to induce several chemical processes such as
polymerization and graft reactions. Nevertheless, from a practical
point of view the most important reaction that is obtained when

 Corresponding author. Fax: +52 844 438 9839.

E-mail address: robertob@ciqa.mx (R. Benavides).

Sabbatical leave at UNESC, Criciuma (20082009), Brasil.

0969-806X/$ - see front matter & 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.radphyschem.2009.08.004

polymers are irradiated is the crosslinking of the chain molecules

(Bhattacharya, 2000; Singh, 2001).
Considering that PVC has a low yield of chemical crosslinking
during irradiation, one must use polyfunctional monomers
capable of promoting the crosslinking of the polymer chains.
The most effective compounds for such a purpose are the
polyfunctional acrylates and metacrylates, especially trifunctional
monomers such as trimethylolpropane trimetacrylate (TMPTMA),
an usual crosslinking agent, which produces a high concentration
eda Facio et al., 2004;
of radicals during irradiation (Castan
Nethsinghe and Gilbert, 1988).

2. Experimental
2.1. Materials
An industrial PVC resin of K value 6567 was used to prepare
formulations. The polyfunctional monomer used was TMPTMA
obtained from Sartomer. The main stabilizers were butyl tin
mercaptide for formulation 1 and a mixture of Ca/Zn stearates
(2/1%w) for formulation 2, both of industrial grade. Tetrahydrofuran (THF) was used as a solvent in the extraction, to evaluate gel
percentage. Other components as the ller (CaCO3) and pigment
(TiO2) were industrial grade. Description of the components can
be seen in Table 1.

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eda et al. / Radiation Physics and Chemistry 79 (2010) 335338
C. Garca-Castan

336

2.2. Preparation of samples

was set at 5 MeV. The speed of the cart was calculated from the
dosimetry results to obtain 50, 75 and 100 kGy.

Samples were prepared by mixing the ingredients in an

intensive mixer, Henschel model ZS 332-11Y. The resin alone
was placed in the mixer at a speed of 2800 rpm and a temperature
of 40 1C; subsequently, the thermal stabilizer was added and when
the temperature reached 50 1C, the rest of the additives were
added. The mixing continued until the nal temperature of 60 1C
was reached. The TMPTMA was added at that nal temperature,
after which homogenization was allowed to take place for 1 min.
The melting process was carried out in a double screw
extruder, Brabender model CTSE-V, at a speed of screw of
70 rpm and temperatures of 150, 160, 170 and 180 1C (die) for
each heating zone. A molten paste was obtained for each
formulation, then taken to a hot hydraulic press (PHI model
Q230) to make plates
18 in thick. Finally, the plates were cut into
coupons of 12  18  2 18 in.

2.4. Dosimetry
The irradiation facilities (gamma and electron accelerator) had
dosimetry studies to evaluate homogeneity and determine the
time needed for specic doses. For the gamma treatment, red
acrylic dosimeters, type L8-C1, were used; color changes were
then measured with an AECL BC-2 dosimeter reader whose
arbitrary values were converted to kGy based on the reader chart.
For the electron beam treatment, Risf B3 radiochromic dye lms
were used; after irradiation they were kept in an oven at 60 1C for
15 min, after which they were evaluated in a Genesis 20 UV
spectrophotometer. The same conditions for the sample treatments (gamma and electron) were maintained during the
dosimetry studies for both types of irradiation.

2.3. Irradiation

2.5. Characterization of irradiated samples

Gamma. The treatment was carried out in a 60Co research

irradiator Transelektro LGI-01 IZOTOP, which belongs to the
Instituto Nacional de Investigaciones Nucleares (ININ, National
Institute of Nuclear Research). The time required to irradiate the
PVC samples to the doses of 50, 75 and 100 kGy was calculated
from the dosimetry results; the irradiation was carried out in
argon atmosphere in an aluminum chamber.
Electron beam. A Dynamitron accelerator equipped with a cart
conveyor system for irradiating samples, property of Kent State
University, was used for this treatment. The electron beam energy

The yellowness index was measured with a colorimeter, Color

Eye Model XHT, according to ASTM D-1925. The gel content of
samples was obtained by Soxhlet extraction for 24 h, using THF as
the solvent. Vicat temperatures were measured with TINUS
OLSEN equipment, according to the method NMX-E-213-CNCP2004. And nally DMA measurements were carried out in a
Dynamic Mechanical Analyzer, TA Instruments 983, at a ramp
temperature of 5 1C/min from 35 to 130 1C, 0.1 Hz oscillation
frequency, and 0.3 mm amplitude.

Table 1
Composition of the different formulations of PVC.

3. Results and discussion

Components (phr)

Sn

Sn/TMPTMA Ca/Zn Ca/Zn/TMPTMA

PVC
100
100
CaCO3
7
7
1
1
TiO2
External lubricant
1.15
1.15
Internal lubricant
0.6
0.6
Butyl tin mercaptide
0.65
0.65

CaSt2

ZnSt2
Co-stabilizer

Process aid

TMPTMA (crosslinking agent)

10

100
7
1
2
1

2
1
1
1

100
7
1
2
1

2
1
1
1
10

Dosimetry studies for the Transelektro irradiator showed a

dose rate of 3.89 kGy/h. This means that 12, 19 and 25 h of
irradiation were needed to obtain 50, 75 and 100 kGy, respectively.
In the case of the electron accelerator irradiations, dosimetry
measurements showed that a cart speed of 0.16 m/s was enough
to reach a dose of 25 kGy; thus, for doses of 50, 75 and 100 kGy it
was necessary to maintain the speed and pass the sample under
the electron beam 2, 3 and 4 times, respectively.
A simple but valuable technique for color evaluation is the
yellowing index (YI) which provides a specic indication as to the
formation of conjugated double bonds during the treatment.
When such a conjugation increases the yellowness increases as
well, considering that both crosslinking and degradation occur

60

60

50

50
40
YI

YI

40
30

30

20

20

10

10

0
0

20

40
60
Dose (kGy)

80

100

20

40
60
Dose (kGy)

80

100

Fig. 1. Effect of the irradiation dose on the yellowness index for PVC samples irradiated with (a) gamma radiation or (b) electron beam. Sn (), Sn/TMPTMA (K), Ca/Zn (m),
Ca/Zn/TMPTMA (.).

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100

100

80

80

60

60

% Gel

% Gel

eda et al. / Radiation Physics and Chemistry 79 (2010) 335338

C. Garca-Castan

40

40

20

20

0
0

25

50
75
Dose (kGy)

337

100

25

50
75
Dose (kGy)

100

Fig. 2. Effect of the irradiation dose on the gel percentage for PVC samples irradiated with (a) gamma radiation and (b) electron beam. Sn (), Sn/TMPTMA (K), Ca/Zn (m),
Ca/Zn/TMPTMA (.).

90

Temperature (C)

85
80
75
70
65
25

50
Dose (kGy)

75

100

Fig. 3. Effect of the irradiation dose on the Vicat temperature for PVC samples
irradiated with an electron beam. Sn (), Sn/TMPTMA (K), Ca/Zn (m), Ca/Zn/
TMPTMA (.).

3000
2700
2400
2100
E' (MPa)

during irradiation. The latter mechanism can be monitored

through this method. Fig. 1a and b show the YI results of
samples treated with both types of radiation. Treatment with
electron beam does not promote the yellowness in formulations
as seen in the treatment with gamma radiation; such behavior can
be explained considering the total time of treatment to which the
samples were subjected. The treatment time in the electron
accelerator system was considerably shorter than with gamma
radiation; such time does not promote the generation of
chromophoric groups responsible for yellowness.
The graphs clearly reveal that the Sn additive in the formulations induced lower values of yellowness in comparison with the
ones stabilized with Ca/Zn. Moreover, the effect was present even
for the untreated samples (blanks), indicating that due to the high
temperatures applied during the extrusion processing, a certain
level of degradation occurred in the Ca/Zn formulation.
As a consequence of ionization during irradiation, PVC chains
crosslink and form interpenetrated networks or polymeric gels
which are difcult to dissolve. Therefore, an insoluble fraction in
THF is considered as a level of crosslinking, also known as gel
percentage. Fig. 2a and b, shows the level of gels obtained for the
samples following their treatment with gamma and with
electrons, respectively. The formulations containing TMPTMA
exhibited higher levels of gel fractions than those without it
when they were irradiated with both methods. Noticeably, the
formulation stabilized with Ca/Zn always obtained lower gel
levels than the one stabilized with tin probably because of the
greater stability of the latter during processing. The treatment
with gamma radiation was also seen to produce more gels than
the irradiation with electrons; this was due to the longer
irradiation time as well as to the inuence of the inert
atmosphere which enhances possibilities of crosslinking. Vicat
temperature is used in the polymer industry to identify the
thermal resistance property of a material under similar end-use
conditions involving stress and temperature. Fig. 3 presents these
results indicating that the formulations without the TMPTMA
(crosslinking agent) did not exhibit signicant effects at the
irradiation doses included in this study.
However, the formulations containing the TMPTMA did
present interesting features. The untreated samples showed a
lower Vicat temperature which is a consequence of the plasticizing effect given by the polyfunctional monomer; this temperature
was lower for the tin formulation because the Ca/Zn formulation
was partially degraded during processing.
The effect of the added TMPTMA was markedly observed when
the samples were irradiated and the Vicat temperatures reached
up to 86 1C. One sees that mechanically there is not much

1800
1500
1200
900
600
300
0
30

40

50

60
70
80
Temperature (C)

90

100

110

Fig. 4. Effect of the irradiation dose on the elastic modulus (E0 ) for PVC samples
irradiated with an electron beam. Not irradiated (), 50 kGy (- - -), 75 kGy (y),
100 kGy (. - . - .).

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eda et al. / Radiation Physics and Chemistry 79 (2010) 335338

C. Garca-Castan

difference in those values with respect to the applied doses, since

almost the same Vicat temperature was obtained for both
formulations irradiated at 50, 75 or 100 kGy. The traces obtained
for gamma treated samples revealed the same trend but the Vicat
temperature reached up to 90 1C (not shown here).
Dynamic mechanical analyses were carried out so as to
evaluate changes in the viscoelastic properties of formulations
in an interval from ambient temperature up to Tg. Fig. 4 shows the
curves of the formulation that was stabilized with tin containing
TMPTMA and treated with an electron beam at different doses.
Clearly, the loss of elastic modulus (E0 ) happened at a higher
temperature when the samples were irradiated, independently of
the dose used for their treatment. DMA ndings support the
results obtained previously for Vicat temperatures and they
distinctly reect the enhancement of thermal properties after
crosslinking the material. Similar results were observed for Ca/Zn
formulations and for gamma irradiated samples (not shown here).

4. Conclusions
Rigid PVC formulations with an added crosslinking agent as
TMPTMA and thermally stabilized with tin and Ca/Zn additives
improved signicantly in their mechanical properties after
irradiation with gamma radiation or electron beams. The reason
was the formation of interpenetrated networks within the
polymer chains through the crosslinking agent. The difference
found between thermal additives used in the formulations was

basically due to the lower ability of the Ca/Zn system to stabilize

the PVC during the processing step. Besides, the method used for
irradiation, gamma or electrons, produced small differences in the
nal properties due to the intrinsic treatment time required for
applying the needed doses, which in turn changed the equilibrium
crosslinking/degradation process during irradiation.

Acknowledgement
The authors are pleased to acknowledge the Consejo Nacional
de Ciencia y Tecnologa (Me xico) for the grant given to C. Garca eda and to Pla sticos Rex for the materials supplied.
Castan
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