Radiation Physics and Chemistry 63 (2002) 493–496

Radiation crosslinking of polyamide 610

W. Fenga,*, F.M. Hub, L.H. Yuana, Y. Zhoua, Y.Y. Zhoua
a
Faculty of Chemistry, Key Laboratory for Radiation Physics and Technology of Ministry of Education, Institute of Nuclear Science and
Technology, Sichuan University, Chengdu 610064, Sichuan, People’s Republic of China
b
Chenguang Research Institute of Chemical Industry, Chengdu 610041, Sichuan, People’s Republic of China

Abstract

In the present paper the gel formation of polyamide 610 by g-ray irradiation in the presence of polyfunctional
monomer and g-crystal nucleating agent under vacuum or air atmosphere had been studied. It was found that the gel
formation was dependent on the content of polyfunctional monomer and nucleating agent. However, there was very
little difference between gel contents irradiated under vacuum and air atmosphere. The results showed that the
crosslinking by g-irradiation enhanced the mechanical properties of PA610 especially at high temperature in the
presence of polyfunctional monomer and g-crystal nucleating agent. The mechanism of radiation crosslinking and
scission was discussed according to the composition and quantity of gas released from three kinds of PA during
irradiation. r 2002 Published by Elsevier Science Ltd.

Keywords: Polyamide 610; Irradiation; Crosslinking

1. Introduction 2. Experimental

Polyamide resins are in the category of engineering 2.1. Material

plastics since they have excellent physico-mechanical
properties. Further enhancing the physico-mechanical
properties especially the heat-resistance by means of
radiation crosslinking is still interesting to many
radiation chemists (Zhang et al., 1984; Li et al.,
1996a,b; Ueno, 1990). The crosslinking reaction of
polyamide is often simultaneous with the scission
reaction during irradiation. The relationship between
crosslinking and scission for polyamides is dependent
mainly on the length of methylene group chain in the
polyamide macromolecules and the condition of crystal-
linity (Deev et al., 1980). In this paper the radiation
crosslinking of polyamide 610 in the presence of
crosslinker, g-crystal nucleating agent and filler have
been studied. The possible mechanism of crosslinking
and scission was discussed.
*Corresponding author. Tel.: +86-28-541-0252.
E-mail address: wfeng95@163.net (W. Feng).
PA610 was purchased from Helongjiang Institute
of chemical Industry; triallyl isocyanate (TAIC) was
imported from Russia; potassium iodide (KI), iodine (I2 )
and m-cresol were obtained from Shanghai Chemical
Reagent Station. Talcum powder was in commercial
grade. All materials were used without further handling.
2.2. Sample preparation
PA610 samples for radiation were prepared by
blending the different additives in a twin-screw extruder.
The samples for tensile strength test were prepared in the
injection machine (made in Germany ARURG). The
granular of PA were charged into the specially made
ampoules. After being subjected to evacuation of the
ampoules for 24 h, the samples were sealed in ampoules
followed by irradiating with 60Co g-ray at various
irradiation doses.

0969-806X/02/$ - see front matter r 2002 Published by Elsevier Science Ltd.

PII: S 0 9 6 9 - 8 0 6 X ( 0 1 ) 0 0 6 3 5 - 1
494 W. Feng et al. / Radiation Physics and Chemistry 63 (2002) 493–496

2.3. The measurement of gel content

80

0.3 g of irradiated samples of PA610 at various dose

were accurately weighed and put into the Soxhlet 60

Gel Content/%
extractor. After extracting with m-cresol for 48 h and
with methanol for 24 h, the residue was dried in the
40
vacuum oven till the constant weight was obtained,
based on which the gel content was calculated.
20

2.4. The measurement of properties

0

The size of dumbbell sample was 60
10
3
2 mm. 0 75 150 225 300 375 450

The tensile strength and elongation were determined by
using WD-5 Electron Universal Testing Equipment. The
tensile strength at 2201C was measured by the machine
equipped with a heat oven designed by us.
The total quantity and composition of gas released
from the PA samples during irradiation were measured
by gas chromatography (PERKAN-ELMER SIG-
Dose/kGy
Fig. 2. The effect of filler content on gel formation of PA610
during irradiation in vacuum (TAIC: 3 phr) talcum: (’) 25 phr;
() 8 phr; (m) 4 phr (.) 2 phr; (E) 0 phr.
80

MA15).
60

Gel Content/%
3. Results and discussion
40

3.1. The effects of additives and irradiation atmosphere

on PA610 20

The effects of various additives of TAIC, filler of 0

talcum powder and g-crystal nucleating agents of KI and 0 75 150 225 300 375 450

Dose/kGy
I2 (Deev et al., 1980) on the formation of gel of PA610
during irradiation are shown in Figs. 1–4. It can be seen Fig. 3. The effect of filler content on gel formation of PA610
from the Fig. 1 that there was almost no formation of during irradiation in air (TAIC: 3 phr) talcum: (’) 25 phr; ()
gel in the absence of TAIC, indicating that the cross- 8 phr; (m) 4 phr; (.) 2 phr; (E) 0 phr.
linking and scission occurred simultaneously during
irradiation of PA610. While the addition of 5 phr TAIC
80
led to a marked increase of the gel content up to about
75%, which demonstrated that the crosslinking pre-
dominated over the scission reaction. On comparing 60

PA610-TAIC it can be clearly seen that the overall

Gel Content/%

40

80

20
60
Gel Content/%

0
40 0 75 150 225 300 375 450
Dose/kGy

20 Fig. 4. The effect of crystal nucleating agent on gel formation

of PA610 during irradiation in air (TAIC: 3 phr) KI+I2: ()
0.06 wt%+0.06%; (’) 0 wt%.
0
0 75 150 225 300 375 450

Dose/kGy
tendency in density of the network is in the order of
Fig. 1. The effect of polyfunctional monomer on gel formation PA610-5 phrTAIC>PA610–3 phrTAIC>PA610. Thus,
of PA610 during irradiation in air TAIC: (’) 5 phr; () 3 phr; TAIC is very effective here as a crosslinking additive for
(m) 0 phr. PA 610 under irradiation.
 W. Feng et al. / Radiation Physics and Chemistry 63 (2002) 493–496 495

It is noteworthy that in the presence of both talcum 250

and TAIC the gel content rose faster with the increasing
of content of talcum powder than that in the presence of 200

TAIC as shown in Figs. 2 and 3. This implies that the gel

Elongation/%
formation can also be accelerated both in vacuum and 150

air with talcum as an additive. In this case the residual

filler of talcum was not found from the crosslinked 100

PA610 upon extraction. It may suggest that during

irradiation of PA610 the link was formed between 50

talcum and macromolecule of PA610. Besides, there is

very little difference in the formation of gel for PA610 in 0
the atmosphere of air and vacuum. The minor influence 0 75 150 225 300 375 450
Dose/kGy
of air atmosphere on the process of gel formation may
be accounted for by the fact that PA610 was in granular Fig. 6. The effect of filler content on the elongation of PA610
state and the diffusion of oxygen to the inside of during irradiation in air talcum+TAIC: (’) 0 phr X
granular was very difficult. In the meanwhile KI+I2 was talcum+3 phrTAIC: X: (E) 8 phr; (.) 4 phr; (m) 2 phr; ()
0 phr.
found to be of benefit to gel formation during
irradiation of PA610 as shown in Fig. 4.The result is
similar to that reported by Deev (Deev et al., 1980) 10

3.2. The mechanical properties of radiation crosslinked 8

PA610 Tensile Strength/MPa

6

In Figs. 5 and 6 are given the influence of both

polyfunctional monomer and fillers on the mechanical 4

properties of PA610 during irradiation in air. For

PA610 with TAIC and filler the tensile strength grew 2
and the elongation at break decreased with increasing
the irradiation dose. In contrast, the tensile strength and 0
the elongation of PA610 without TAIC and talcum fell, 0 10 20 30 40 50 60
Dose/kGy
reflecting the degradation of PA610 during irradiation.
These results indicated that the presence of talcum Fig. 7. The effect of filler content on tensile strength at 2201C
contributed to the formation of gel and density of of PA610 (3 phr TAIC) at different dose in air X talcum (’)
network of PA610-TAIC. The tensile strength of 8 phr; () 4 phr; (m) 2 phr; (.) 0 phr.
irradiated PA610 at 2201C is shown in Fig. 7. Obviously,
the irradiated PA610 still had certain tensile strength at stationary. The tensile strength for irradiated PA610-
this high temperature. The tensile strength increased 3 phrTAIC-8 phr talcum at 2201C was raised to 8 MPa.
with the increasing of gel content and then tended to be In contrast, the unirradiated PA610 already melted at
this temperature. Thus the PA 610 prepared here under
130
g-irradiation in the presence of TAIC or talcum via
crosslinking possessed the advantage in heat-resistance
120 over the unirradiated one at higher temperature.
Tensile Strength/MPa

110
3.3. Gases released from pure PA610 during irradiation
100
According to the structure of aliphatic polyamide the
macromolecule consisted of different length of methy-
90
lene group incorporated with amide group. However,
the similar backbone as polyethylene did not provide the
0 75 150 225 300 375 450 similar radiation-initiated reaction as observed here in
Dose/kGy the scission reaction due to the weaker cyanic link in the
Fig. 5. The effect of filler content on the tensile strength of amide group. It means that the crosslinking and scission
PA610 during irradiation in air talcum+TAIC: (’) 0 phr X were concomitant during irradiation of PA610. Mean-
talcum+3 phr TAIC: X: (E) 8 phr; (.) 4 phr; (m) 2 phr; () while, gases were released accompanying the process of
0 phr. crosslinking and scission of PA610 (Deev et al., 1980).
496 W. Feng et al. / Radiation Physics and Chemistry 63 (2002) 493–496

Table 1 d d
Released gases from polyamides during irradiation 2CH2 2 C O þ N H2CH2 2CH2 2H2
Gas Radiation chemical yield (molecule/100 eV) -2CH2 2CHO þ NH2 CH2 2CH2 2
PA6 PA610 PA1010
2CH2 2CH2 2CH2 2CHO
H2 0.098 0.115 0.123 d d
r
CO 0.0013 0.035 0.011 2 2CH2 2 C H2 þ C H2 2CHO
CH3CHO Trace Trace Trace
Total 0.0994 0.151 0.134
d
2 C H2 2CHO þ H2 -2CH3 2CHO:

Gas chromatographic analysis demonstrated that the

gases were mainly composed of H2, CO and trace of 4. Conclusion
acetaldehyde. The yield of gases or G value of these
gases was dependent on the polyamide or the length of 1. The crosslinking and scission occurred simulta-
the chain of methylene group in the polyamide macro- neously during irradiation of PA 610. The presence
molecule. The results of analysis are summarized in of TAIC, filler of talcum powder and g-crystal
Table 1. Obviously, hydrogen gas accounted for the nucleating agents of KI and I2 was beneficial to
majority among the three components released and its radiation crosslinking of PA 610
amount increased with increment of length of the chain 2. PA 610 in the presence of TAIC or talcum by g-
of methylene group. irradiation crosslinking possessed the advantage in
Based on the above results, a similar mechanism heat-resistance over the unirradiated one, especially
(Deev et al., 1980) of radiation crosslinking and scission at higher temperature (2201C), the tensile strength
of PA610 during irradiation was proposed as follows: was almost retained for irradiated PA 610.
2CH2 CONH2CH2 CH2 2 3. The mechanism of crosslinking and scission during
d d
irradiation of PA 610 was discussed based on the gas
r
2 2CH2 2CONH2 C H2CH2 2 þ H released.
d
2CH2 CONH2CH2 CH2 2 þ H
d References
-2CH2 2CONH2 C H2CH2 2 þ H2
d Deev, U.S., Subbotin, U.S., Riabov, E.A., 1980. Radiation-
22CH2 CONH2 C H2 CH2 2 chemical modification of polyamide. Plastmasse 4, 52.
Li, B.Z., Zhang, L.H., Yu, J.Y., 19963a. g-radiation damage to
-2CH2 2CONH2CH2CH2 2CH2 crystalline polyamide 1010 containing heterogeneous. J.
2CONH2CH2CH2 2 Radiat. Res. Radiat. Proc. 14, 4.
2CH2 2CONH2CH2 CH2 2 Li, B.Z., Zhang, L.H., Yu, J.Y., 1996b. Post radiation effects on
d d
polyamide 1010. J. Radiat. Res. Radiat. Proc. 14, 153.
r
2 2CH2 2 C O þ N H2CH2 2CH2 2 Ueno, K., 1990. Section 2.3. CrosslinkingFthe radiation
crosslinking process and new products. Radiat. Phys. Chem.
d d
2CH2 2CH2 2 C O-2CH2 2 C H2 þ CO 35, 126.
Zhang, L.H., Li, S.Z., He, Z.D., Su, W., Zhang, Z.C., 1984.
d Radiation-induced crosslinking of polyamide 1010. J.
22CH2 2 C H2 þ H2 -22CH2 2CH3 Radiat. Res. Radiat. Proc. 3, 32.