E. T. Contis et al.

(Editors)
Food Flavors: Formation, Analysis and Packaging Influences
© 1998 Elsevier Science B.V. All rights reserved 767

Effects of ionizing radiation on properties of monolayer and

multilayer flexible food packaging materials

K.A. Riganakos^. W.D. KoUer^, D.A.E. Ehlermann^, B. Bauer^ and M.G.

Kontominas^

^University of loannina, Department of Chemistry, Laboratory of Food

Chemistry and Technology, GR-45110, loannina, Greece.

^Federal Research Centre for Nutrition, Institute of Process Engineering,

Engesserstr. 20, D-76131, Karlsruhe, Germany.

Abstract
Volatile compounds produced in flexible food packaging materials (LDPE,
EVAc, PET/PE/EVOH/PE) during electron beam irradiation were isolated by
purge and t r a p technique and identified by combined gas chromatography-
mass spectrometry (GC/MS), after thermal desorption and concentration. For
comparison purposes non-irradiated films were also studied. Film samples
were i r r a d i a t e d a t low (5 kGy, corresponding to cold pasteurization),
intermediate (20 kGy, corresponding to cold sterilization) and high (100 kGy)
doses. It was observed that a number of volatile compounds are produced after
irradiation in all cases. Furthermore the amounts of all volatile compounds
proportionally increase with increasing irradiation dose. Both primary
(methyl- derivatives etc.) as well as secondary i.e. oxidation products (ketones,
aldehydes, alcohols, carboxylic acids etc.) are produced upon irradiation. These
products may affect organoleptic properties and thus shelf-life of prepackaged
irradiated foods. No significant changes were observed in the structure of
pol5mier matrices as exhibited by IR spectra after irradiation of the materials at
doses tested. Likewise, no significant changes were observed in gas
permeability of plastics packaging materials after irradiation.

1. EVTRODUCTION

Irradiation of prepackaged foodstuffs using gamma and electron beam

radiation is steadily gaining ground as a method of food preservation
worldwide. While many workers have dealt with specific eff*ects of ionizing
radiation on various food constituents, relatively few investigations have dealt
with the effects of ionizing radiation on plastics packaging materials. [1-6].
768

Another use of ionizing radiation is in the improvement of polymer mechanical

properties. [7-8].
Physical and chemical changes resulting in plastics are of prime importance
in applications such as food packaging where such changes may directly affect
the shelf-life of packaged foodstuffs. [9].
Radiation-induced changes in pol5m[iers are shown to depend on: a) chemical
structure of the polymer, b) additives used to compound the plastic, c)
processing history of the plastic, and d) specific irradiation conditions, namely,
the absorbed dose, the irradiation atmosphere and, in certain cases, the dose
rate. [10].
The major chemical changes that are reported to occur in polymers as a result
of ionizing radiation are: a) simultaneous scission and cross-linking of the
polymeric chains, their net effect determining the changes in polymer
properties, b) formation of gases and low molecular weight radiolysis products
and c) formation of unsaturated bonds. [10].
In the presence of oxygen, there is additional oxidative chain scission and
oxidation of the polymer, leading to the formation of peroxide, alcohol and
carbonyl fi:*actions as well as carbon monoxide and carbon dioxide and various
oxygen-containing low molecular weight compounds. Large amounts of
hydrogen, methane and hydrocarbons may also result. As a general rule, the
amounts of gases produced increase with increasing radiation dose. Such
products, upon migration into the packaged foods, may affect the sensory
properties (off-odors and off-flavors) and/or safety of prepackaged foods. [11-12].
Radiolysis compounds produced upon irradiation may also be responsible for
an unpleasant odor of the packaging materials after irradiation. [13-18].
The FDA h a s regulated the use of ionizing radiation in single layer plastic
packaging m a t e r i a l s while today multilayer m a t e r i a l s (laminated or
coextruded) are almost exclusively being used in advanced food packaging
applications. [19].
There is practically no information in the literature on the effect of irradiation
in substrates such as multilayer coextruded plastic packaging materials. [10].
The objective of this work was: i) to identify volatile compounds produced
during electron beam irradiation (in the presence of air) at low, intermediate
and high doses of two monolayer plastic food packaging films (LDPE, EVAc)
and one multilayer film (PET/PE/EVOH/PE), ii) to investigate the possible
structural changes in the above plastic films, as a result of irradiation and iii)
to investigate possible changes in barrier properties of the above materials as a
result of irradiation.
Such composite flexible packaging materials are being experimentally
produced in our laboratory and are being used in specific food packaging
applications, (i.e. the extension of shelf-life of specific foodstuffs such as meat,
sausages, poultry etc.).
 769

2. EXPERIMENTAL

Materials and Methods

1. Materials
Three types of food packaging materials were used:l)LDPE (thickness 30 |im)
typical representative of a homopolymer, 2)EVAc (thickness 20 [im) typical
representative of a copolymer and 3)PET/PE/EV0H/PE (thickness 70 |im) one of
many coextruded multilayer materials, all widely used in food packaging
applications.
[LDPE = low density polyethylene, EVAc = ethylene-vinyl acetate copol3m[ier,
PET = poly(ethylene terephthalate), EVOH = ethylene-vinyl alcohol copolymer].

2. Methods

a) Irradiation
Approximately 1.2-1.6 g of each packaging material were weighed into glass
head space vials 22 mL in capacity. The vials were sealed using an aluminium
covered silicon rubber disc and an aluminum crimp cap. The plastic films
were then irradiated at doses of 5, 20 and 100 kGy in the presence of air.
Irradiation doses were measured using a Far West dosimeter, at an energy of
10 MeV.

b) Isolation of volatiles
Helium gas, at a flow rate of 30 mL/min, was passed for 20 min through the
head space vials which were maintained at SO^C. Volatile compounds were
collected on a Tenax GC plug filled into the glass liner of an Optic PTV-
Injector.

c) Identification of volatile compounds from non-irradiated and irradiated

samples
Volatile compounds were identified using a GC/MS system consisting of an
HP (Hewlett Packard) 5890 II Gas Chromatograph, an HP 5985 B Mass
Spectrometer and a Teknivent Data base System.
Gas Chromatography (GC) conditions were:
Carrier Gas: Helium (at 2 bar column pressure).
PTV-Injector program: 50oC to 220oC, at a rate of le^C/sec, splitless injection
mode, cryofocussing with liquid N2.
Oven temperature program was 40oC/5min then 6^0 to 220^0.
Separation was carried out on a 60 m x 0.25 mm i.d. CW 20m Quadrex fused
silica capillary column.
Mass Spectrometry (MS) conditions were:
70 eV electron energy and 200^0 ion source temperature.
Volatile products were identified by comparing the mass spectra of the relevant
chromatographic peaks with those from the GC/MS system library.

d) IR analysis
IR spectra of irradiated and non-irradiated films fi:-om all the samples were
recorded on a Perkin Elmer 783 IR spectrophotometer. Cleaned plastic films,
770

cut into appropriate pieces, were used for the spectrophotometric

measurements of irradiated and non-irradiated films. IR spectra were
recorded in the wavelength region 4000-200 cm"^
e) Permeability measurements
Permeability coefficients were estimated for oxygen with the Mocon Oxtran
MH 2/20 instrument. All tests were performed at RH=80% and at a
temperature of 20^0.

3. RESULTS AND DISCUSSION

a) Determination of volatile compounds
Gas chromatograms for the three plastic food packaging films non-
irradiated and irradiated at doses 5, 20 and 100 kGy, are given in Figs. 1-3.
Comparison of chromatogram Fig. la to lb, Ic and Id shows that a nimiber of
volatile compounds are formed during irradiation. These compounds are
absent in the chromatograms of the non-irradiated samples. Furthermore, the
amounts of all volatile compounds proportionally increase with increasing
absorbed radiation dose. The same pattern is shown in Figs. 2 and 3.

3.5e+007

3.0e*007

2.5e*007

2.0e^007

1.5e+007
L-Awu JUi(A_*-
(d)

l.Oe+007

5e+006 AJLJU »_JU_^..J1 i JL 1

(b)
12.8

Oe+000-
I . 1 1 16
10 15 20
Time ( m i n u t e s )

Figure 1. Chromatograms for non-irradiated (a) and irradiated samples of

LDPE at 5 kGy (b), 20 kGy (c) and 100 kGy (d).
 771

2.5e+007

2.06+007-^

1.5e+007

l.Oe+007 wyuUduLjiLL^ (d)

•-*AJ>AJUUL_A_A. «._
(c)

5e+006
(b)
25.79
20,18
Oe+000- IMt- ,AA^ i , - (a)
10 15 20 25 30 32
Time (minutes)

Figure 2. Chromatograms for non-irradiated (a) and irradiated samples of

EVAc at 5 kGy (b), 20 kGy (c) and 100 kGy (d).

3.0e+007

2.5e+007

2.0e+007

1.5e+007

Uius .JLLJU^LliJ^ IAA-AJIJ. (d)

l.J3e+007
uyjiUiiLj (c)
^4
5e+006
ii. IJL^^LJUJLOJL (b)

Oe+OOO-l JsLLo^iiiii. 18.9 25^63 (a)

10 15 20 25 30 32
Time (minutes)

Figure 3. Chromatograms for non-irradiated (a) and irradiated samples of

PET/PE/EVOH/PE at 5 kGy (b), 20 kGy (c) and 100 kGy (d).
772

Volatile compounds identified in LDPE, EVAc and PET/PE/EVOH/PE using

GC/MS are given in Tables 1-3. These include several aldehydes, ketones,
alcohols, hydrocarbons, carboxylic acids etc.
Table 1 gives volatile compounds recorded in non-irradiated and irradiated at
100 kGy LDPE. Of 52 volatile compounds recorded in non-irradiated LDPE, 35
were identified by GC/MS. Of 74 volatile compounds recorded in irradiated
LDPE, 49 were identified by GC/MS. Main classes of compounds identified in
non-irradiated LDPE include s a t u r a t e d hydrocarbons (from hexane to
hexadecane), aldehydes (such as hexanal, octanal), carboxylic acids (from
acetic acid to octanoic acid), ketones (such as acetone etc.), phenols (such as
dimethylphenol, BHT), etc. In addition to the above, unsaturated hydrocarbons
(hexene, heptene), other ketones (such as hexanone, heptanone, octanone),
esters (hexyl formate, octyl formate), aromatic compounds (such as benzene,
ethylbenzene), as well as several methyl derivatives were identified in the
irradiated LDPE film samples. It has been reported in the literature t h a t
unsaturated carboxylic acids are produced upon thermal oxidative degradation
of PE [20]. However, no production of u n s a t u r a t e d carboxylic acids was
observed in the irradiated PE film samples.
Table 2 gives volatile compounds found in non-irradiated and irradiated at 100
kGy EVAc. Of 58 volatile compounds recorded in non-irradiated EVAc, 45 were
identified by GC/MS. Of 102 volatile compounds recorded in irradiated EVAc, 63
were identified by GC/MS. Main classes of compounds identified in non-
i r r a d i a t e d EVAc include s a t u r a t e d hydrocarbons (from h e x a n e to
heptadecane), aldehydes (such as hexanal, heptanal, octanal, nonanal),
alcohols (butanol, heptanol), carboxylic acids (from acetic acid to octanoic acid),
several aromatic compounds (such as toluene, ethylbenzene, xylene, limonene,
naphthalene, dimethyl alcohol, BHT), esters (propylene carbonate, dimethyl
phthalate), etc. In addition to the above, unsaturated hydrocarbons (hexene,
heptene), ketones (heptanone, octanone), as well as several methyl derivatives
were identified in the irradiated EVAc film samples.
Table 3 gives volatile compounds identified in non-irradiated and irradiated
PET/PE/EVOH/PE. Of 70 volatile compounds recorded in non-irradiated
PET/PE/EVOH/PE, 54 were identified by GC/MS. Of 102 volatile compounds
recorded in irradiated PET/PE/EVOH/PE, 79 were identified by GC/MS. Main
classes of compounds identified in non-irradiated PET/PE/EVOH/PE include
saturated hydrocarbons (from hexane to hexadecane), carboxylic acids (fi:'om
acetic acid to nonanoic acid), several aromatic compounds (such as derivatives
of benzene, menthol, phenol, naphthalene, BHT), etc. In addition to the above,
u n s a t u r a t e d hydrocarbons (nonene), aldehydes (hexanal, octanal), ketones
(hexanone, h e p t a n o n e ) , alcohols (methyl-butanol, h e p t a n o l ) , methyl
derivatives, other aromatic compounds (toluene), etc were identified in the
irradiated PET/PE/EVOH/PE film samples.
Based on the above information the following observations can be made:
a) All three plastic materials produce similar volatile compounds (such as
s a t u r a t e d hydrocarbons, carboxylic acids, aldehydes, ketones, aromatic
compounds, esters etc.).
b) Irradiation produces methyl-derivatives, unsaturated hydrocarbons, esters,
other aldehydes, ketones, aromatic compounds, etc.
c) EVAc (non-irradiated and irradiated) produces more odor or flavor active
substances t h a n the other two polymer materials, such as limonene, xylene.
 773

naphthalene etc. which may affect the odor/flavor of foodstuffs packaged in this
plastic material.
The results for LDPE are in general agreement with those of Azuma at al.
[14]. These authors irradiated LDPE films in air at a dose of 20 kGy and
recorded more than 100 volatile compounds in the headspace of film samples.
50 of the compounds were identified by GC/MS.
Rojas de Gante and Pascat (6) irradiated LDPE and OPP films in air at doses of
10 and 25 kGy and obtained similar results. Irradiation in air produced 100
volatiles in LDPE and 58 in OPP films.

Table 1
Volatile compounds identified by GC/MS of irradiated (100 kGy) and non-
irradiated LDPE films.

Irradiated at 100 kGy Non-irradiated

No Name Retention Name Retention
time (min ) time (min)
T" Hexane 7.76 Hexane ^778
2 1-hexene 7.81 Heptane 7.96
3 ? 7.87 Octane 8.23
4 3-methyhexane 7.92 Acetone 8.38
5 Heptane 7.96 Trans-l-butyl-2-methyl- 8.46
cyclopropane
6 2-heptene 8.02 Nonane 8.84
7 Octane 8.28 Decane 9.88
8 Acetone 8.40 Hexanal 11.26
9 3-ethyl-4-methyl- 1-pentene 8.49 Undecane 11.35
10 T r a n s - l-butyl-2-methyl- 8.53 1- [ 1-cyclohexen- 1-yl] - 12.01
cyclopropane ethanone
11 3-ethylheptane 8.67 4-hydroxy-4-methyl- 12.26
pentanone
12 Nonane 8.91 ? 12.80
13 Benzol 9.28 ? 13.24
14 ? 9.76 Dodecane 13.42
15 Decane 9.93 2,3-dehydro-4-methyl- 13.73
furan
16 ? 10.26 Dimethyphenol 14.55
17 3-hexanone 10.77 1,3,5,7-cyclooctatetraene 14.83
18 ? 11.08 Octanal 15.51
19 Hexanal 11.26 Tridecane 15.55
20 ? 11.30 9 16.02
21 Undecane 11.50 6-methyl-5-hepten-2-one 16.69
22 Ethylbenzol 12.03 9 17.41
23 1- [ 1-cy clohexen- 1-yl] - 12.05 Tetradecane 17.91
ethanone
2A 4-hydroxy-4-methyl- 12.26 2,3,6-trimethyl-l,5- 18.09
pentanone heptadiene
25 ? 12.45 9 18.81
26 3-heptanone 12.69 Acetic acid 19.43
774

27 ? 12.80 ? 20.00
28 ? 13.26 Pentadecane 20.15
29 Dodecane 13.48 ? 20.78
30 2,3-dehydro-4-methyl- 13.73 Propanoic acid 21.30
furan
31 Dimethylphenol 14.42 9 21.62
32 3-methyl- 1-butanol 14.70 9 21.88
33 5-methyl-3-heptanone 14.77 2,2-dimethylpropanoic acid 22.04
34 1,3,5,7-cyclooctatetraene 14.83 Hexadecane 22.29
35 2-octanone 15.48 3,5,5-trimethyl-2- 22.56
cyclopenten-1-one
36 Octanal 15.51 Butanoic acid 23.19
37 Tridecane 15.64 ? 23.64
38 ? 16.09 Acetophenone 23.84
39 2-methyl-4-octanone 16.34 9 24.04
40 6-methyl-5-hepten-2-one 16.69 9 24.47
41 5-methyl-l-heptene 16.90 9 24.65
42 Hexyl formate 16.99 9 25.43
43 ? 17.37 Pentanoic acid 25.64
44 Tetradecane 17.89 3-methyl-2-butanoic acid 26.67
45 2,3,6-trimethyl-l,5- 18.09 9 27.35
heptadiene
46 9 18.81 Hexanoic acid 27.50
47 Acetic acid 19.43 6,10-dimethyl-5,9- 27.62
undecadien-2-one
^ 9 20.13 Butylated hydroxytoluene 28.65
49 Pentadecane 20.20 9 29.10
50 ? 20.62 9 29.26
51 Propanoic acid 21.30 Heptanoic acid 29.48
52 Octyl formate 21.50 ? 31.05
53 ? 21.83 Octanoic acid 31.35
54 2,2-dimethylpropanoic acid 22.00
55 ? 22.28
56 Hexadecane 22.29
57 3,5,5-trimethyl-2- 22.73
cyclopenten- 1-one
58 ? 23.04
59 Butanoic acid 23.25
eo ? 23.63
61 Acetophenone 23.81
62 ? 24.00
63 ? 24.47
64 9 24.65
65 9 25.36
66 Pentanoic acid 25.76
67 3-methyl-2-butanoic acid 26.63
68 9 27.11
69 ? 27.40
70 Hexanoic acid 27.47
71 ? 29.10
72 Heptanoic acid 29.44
73 9 29.86
74 Octanoic acid 31.33
 775

Table 2
Volatile compounds identified by GC/MS of irradiated (100 kGy) and non-
irradiated EVAc films.

Irradiated at 100 kGy Non-irradiated I

No Name Retention Name Retention
time (mir0 time (min)
i" Hexane 7.84 Hexane 7.77
2 1-hexene 7.89 Heptane 7.92
3 3-methylhexane 7.95 Octane 8.23
4 Heptane 7.99 1-octene 8.44
5 Trans-1,2-dimethyl- 8.11 Nonane 8.84
cyclopentane
6 3-heptene 8.16 3-metliylbutanal 9.08
7 Octane 8.32 Methyl isobutyrate 9.21
8 ? 8.43 7 9.74
9 1-octene 8.48 Decane 9.89
10 3-ethyl-4-methyl- 1-pentene 8.55 7 9.93
11 Nonane 8.98 Toluene 10.57
12 3-methylbutanaI 9.08 7 10.77
13 Methyl isobutyrate 9.21 Hexanal 11.26
14 7 9.33 Undecane 11.36
15 7 9.85 7 11.49
16 Decane 9.97 l-methyl-2-cyclohexene-1- 11.65
ol
17 7 10.23 Ethylbenzene 11.96
18 7 10.33 p-xylene 12.12
19 Toluene 10.60 1,3-dimethylbenzene 12.24
20 7 10.80 1-butanol 12.50
21 7 11.13 heptanal 13.20
22 Hexanal 11.30 d,l-limonene 13.26
23 Undecane 11.35 Trifluoroacetyl-alpha- 13.62
terpineol
24 7 11.52 7 15.13
25 l-methyl-2-cyclohexene 11.68 1,3,5-trimethylbenzene 15.30
26 Ethylbenzene 12.00 Octanal 15.49
27 p-xylene 12.16 Tridecane 15.60
28 1,3-dimethylbenzene 12.28 7 16.22
29 7 12.48 7 16.41
30 7 12.63 6-methyl-5-hepten-2-one 16.63
31 3-heptanone 12.75 Nonanal 17.86
32 7 13.08 Tetradecane 17.91
33 heptanal 13.22 7 18.20
34 d,l-limonene 13.30 l-(l,2-dimethylpropyl)-l- 18.85
methyl-2-nonyl-
cyclopropane
35 7 13.35 9-methylnonadecane 19.20
36 2,3-dimethyl-2-hexanol 13.51 Acetic acid 19.43
37 3-octanol 13.62 Cis-5-methyl-2-(l- 19.55
methylethyl)-
cyclohexanone
776

38 Trifluoroacetyl-alpha- 13.65 2-propyl- 1-pentanol 20.00

terpineol
39 ? 13.86 Pentadecane 20.18
40 ? 14.12 3,7-dimethyl-1,6-octadien- 21.28
3-ol
41 ? 14.30 Propanoic acid 21.34
42 3-methyl- 1-butanol 14.79 Hexadecane 22.31
43 ? 14.85 ? 22.65
44 ? 15.17 5-methyl-2-(l-m- 23.34
ethylethyl)-cyclohexanol
45 ? 15.20 Heptadecane 24.37
46 1,3,5-trimethylbenzene 15.34 Naphthalene 25.65
47 Octanal 15.50 1,3-butanediol 25.74
4S 2-octanone 15.53 ? 27.49
49 Tridecane 15.64 6,10-dimethyl-5,9- 27.56
undecadien-2-one
50 3-heptanol 15.70 Propylene carbonate 28.12
51 ? 15.78 Benzyl alcohol 28.30
52 9 16.18 Butylated hydroxytoluene 28.59
53 ? 16.25 1-phenylethanol 28.99
5t ? 16.46 ? 30.68
55 6-methyl-5-hepten-2-one 16.72 Octanoic acid 31.37
56 ? 16.88 9 32.00
57 Hexyl formate 17.07 ? 33.15
58 4-hydroxy-4-methyl- 17.58 Dimethyl phthalate 35.75
pentanone
59 Nonanal 17.81
eo Tetradecane 17.85
61 ? 18.20
62 l-(l,2-dimethyl)- 18.85
cyclopropane
63 9-methylnonadecane 19.10
64 Acetic acid 19.20
65 9 19.28
66 Cis-5-methyl-2-(l- 19.55
methylethyl)-
cyclohexanone
67 9 19.88
68 2-propyl- 1-pentanol 20.00
69 2-ethyl- 1-hexanol 20.05
70 Pentadecane 20.18
71 ? 20.50
72 Benzaldehyde 21.05
73 3,7-dimethyl- 1,6-octadien- 21.08
3-ol
74 Propanoic acid 21.14
75 ? 21.41
76 Octyl formate 21.50
77 Dimethylpropanedioic acid 21.82
78 Hexadecane 22.28
79 9 22.65
80 Butanoic acid 23.08
81 5-methyl-2-( 1-m- 23.34
ethylethyD-cyclohexanol
 777

82 Nonanol 23.61
83 2-methoxy- 1-phenyl- 23.80
ethanone
84 ? 24.00
85 Heptadecane 24.37
86 9 25.05
87 9 25.14
88 Pentanoic acid 25.37
89 Naphthalene 25.62
90 1,3-butanediol 25.74
91 9 27.10
92 9 27.46
98 6,10-dimethyl-5,9- 27.54
undecadien-2-one
9i Propylene carbonate 28.12
95 Benzyl alcohol 28.30
96 ? 29.05
97 Heptanoic acid 29.43
98 ? 30.68
99 ? 31.02
100 Octanoic acid 31.34
101 9 32.60
102 ? 33.15

Table 3
Volatile compounds identified by GC/MS of irradiated (100 kGy) and non-
irradiated PET/PE/EVOH/PE films.

Irradiated at 100 kGy Non-irradiated

No Name Retention Name Retention
time (min) time (min)
T" HHeptane
2
exane 7.74
7.91
Hexane
Heptane
7.77
7.90
3 3,4,5-trimethylheptane 8.11 Octane 8.30
4 Octane 8.22 Trans-l,2-dimethyl- 8.35
cyclohexane
5 Trans-1,2-dimethyl- 8.35 Cis-l-butyl-2- 8.50
cyclopentane methylcyclopropane
6 Cis-l-butyl-2- 8.43 Trans-l-butyl-2- 8.59
methylcyclopropane methylcyclopropane
7 4-methyloctane 8.56 4-methyl-3-heptene 8.67
8 Trans-l-butyl-2- 8.59 ? 8.83
methylcyclopropane
9 3-ethylheptane 8.62 Nonane 8.92
10 4-methyl-3-heptene 8.67 3,5-dimethyloctane 9.09
11 ? 8.80 9 9.17
12 Nonane 8.83 9 9.40
13 3,5-dimethyloctane 9.06 9 9.55
778

14 ? 9.14 Tetramethyloctane 9.58

15 2-nonene 9.20 Decane 10.05
16 ? 9.36 ? 10.17
17 4-methylnonane 9.40 9 10.58
18 2,6,7-trimethyldecane 9.50 ? 10.80
19 ? 9.55 5-( l-methylpropyl)-nonane 10.97
20 Tetramethyloctane 9.58 7 11.08
21 ? 9.71 Undecane 11.60
22 Pentanal 9.73 Ethylbenzene 12.18
23 Decane 9.89 1,3-dimethylbenzene 12.31
24 ? 10.12 9 12.48
25 ? 10.24 ? 12.83
26 2,6-dimethylundecane 10.47 1-methylethylbenzene 12.94
27 Toluene 10.53 1,3-dimethylbenzene 13.23
28 ? 10.58 9 13.44
29 3-hexanone 10.75 Dodecane 13.50
30 ? 10.80 Propylbenzene 13.70
31 5-( l-methylpropyl)-nonane 10.97 l-ethyl-3-methylbenzene 14.06
32 ? 11.02 Cyclododecane 14.39
33 ? 11.08 1,3,5-trimethylbenzene 14.52
34 Hexanal 11.23 1,3,5,7-cyclooctatetraene 14.83
35 Undecane 11.60 l-ethyl-4-methylbenzene 14.89
36 ? 11.89 l-methyl-2-(l- 14.99
methylethyl)-benzene
37 Ethylbenzene 12.18 1,2,4-trimethylbenzene 15.38
38 1,3-dimethylbenzene 12.31 Tridecane 15.70
39 ? 12.48 l-methyl-3-propylbenzene 15.78
40 3-heptanone 12.60 1,4-diethylbenzene 15.94
41 ? 12.83 l-ethyl-3,5-dimethyl- 16.29
benzene
42 1-methylethylbenzene 12.94 1,2-diethylbenzene 16.43
43 2-heptanone 13.17 a-methylstyrene 16.49
44 ? 13.41 2,5-dimethylbenzaldehyde 16.56
45 Dodecane 13.50 1,3,5-trimethylbenzene 16.63
46 Propylbenzene 13.68 ? 16.95
47 ? 13.94 2-ethyl-l,4-dimethyl- 17.10
benzene
^ l-ethyl-3-methylbenzene 14.06 l-methyl-2-(l- 17.28
methylethyD-benzene
49 Tert-butylbenzene 14.27 Tetradecane 17.95
50 Cyclodecane 14.39 ? 18.85
51 1,3,5-trimethylbenzene 14.52 Cyclotetradecane 18.88
52 3-methyl- 1-butanol 14.64 Acetic acid 19.46
53 1,3,5,7-cyclooctatetraene 14.83 9 20.00
54 l-ethyl-4-methylbenzene 14.89 Pentadecan 20.10
55 l-methyl-2-(l- 15.04 1,7,7-trimethyl- 20.83
methylethyD-benzene bicyclo[2,2,l]heptan-2-one
56 1,2,4-trimethylbenzene 15.38 ? 21.50
57 2-octanone 15.44 Hexadecane 22.28
58 Octanal 15.48 Cyclohexadecane 23.23
59 Tridecane 15.70 Menthol 23.32
60 l-methyl-3-propylbenzene 15.78 2-methoxy- 1-phenyl- 23.86
ethanone
61 1,4-diethylbenzene 15.84 Trichloromethylbenzene 24.69
 779

62 l-ethyl-3,5- 16.24 Naphthalene 25.63

dimethylbenzene
63 1,2-diethylbenzene 16.40 Hexanoic acid 27.51
64 a-methyls t y r e ne 16.44 6,10-dimethyl-5,9- 27.61
undecadien-2-one
65 1,3,5-trimethyl-benzene 16.60 Butylated hydroxytoluene 28.61
66 6-methyl-5-hepten-2-one 16.63 ? 30.28
67 ? 16.87 Phenol 30.68
68 Hexyl formate 16.92 Octanoic acid 31.33
69 2-ethyl-l,4-dimethyl- 17.10 Nonanoic acid 33.15
benzene
70 l-methyl-2-(l- 17.28 Bis-( 1, l-dimethylethyD- 35.42
methylethyl)-benzene phenol
71 Tetradecane 18.20
72 l,3-bis-(l,l-dimethyl)- 18.68
benzene
73 ? 18.85
74 Hexanol 19.24
75 Cyclotetradecane 19.28
76 Acetic acid 19.70
77 ? 19.98
78 Pentadecane 20.12
79 9 20.70
80 1,7,7-trimethyl- 20.83
bicyclo[2,2,l]heptane-2-one
81 Propanoic acid 21.21
82 Octyl formate 21.44
83 3-methyl- Ih-pyrrole 21.57
84 2,2-dimethylpropanoic acid 21.97
85 Hexadecane 22.28
86 Butanoic acid 23.08
87 Cyclohexadecane 23.23
88 Menthol 23.32
89 ? 23.62
90 2-methoxy- 1-phenyl- 23.86
ethanone
91 Trichloromethylbenzene 24.69
92 ? 25.05
98 Pentanoic acid 25.36
94 Naphthalene 25.69
95 Dimethylbenzenemethanol 25.84
96 Hexanoic acid 27.45
97 Heptanoic acid 29.43
98 ? 30.28
99 Phenol 30.68
100 Octanoic acid 31.31
101 Nonanoic acid 33.09
102 Bis-(l,l-dimethylethyl)- 35.36
phenol
780

b) IR analysis
No significant changes were observed in IR spectra of irradiated film
samples at all doses tested, suggesting that irradiation does not affect the
molecular structure of the films under study.
Present results are in agreement with those of Rojas de Gante and Pascat (6)
who have observed no significant changes in the IR spectra of LDPE and OPP
with absorbed doses of 0-50 kGy and Bersch et al. (18) who found no "definite
and assignable changes" with HDPE, LDPE, PET, PS, PVC, PMTE
[poly(monochloro-trifluoro-ethylene)] and r u b b e r hydrochloride films
irradiated with 56 kGy either under vacuum or in air.

c) Gas permeability measurements

Table 4 gives oxygen permeability values of the three polymeric films. As
shown in Table 4 there are no significant changes observed in gas permeability
of irradiated film samples at all doses tested.

Table 4
Oxygen permeability values of non-irradiated and irradiated at 100 kGy
polymeric films.

No Material O2 Permeability (cm^/m^.day)

Non-irradiated Irradiated at 100 kGy

1 LDPE (30 ixm) 6,268 6,520

2 EVAc(20pim) 11,250 11,865

3 PET/PE/EVOH/PE (70 [xm) 0.68 0.70

Present work is being extended to a series of 3-,4- and 5- layer coextruded

flexible food packaging films experimentally produced in our laboratory to be
irradiated u n d e r various atmospheric conditions (modified atmosphere
packaging) in contact with selected food products.

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