Professional Documents
Culture Documents
net/publication/228758071
CITATIONS READS
25 1,774
3 authors, including:
Some of the authors of this publication are also working on these related projects:
The application of innovative methods in monitoring of proteolytic, lipolytic and oxidative changes throughout the dry-
cured ham process View project
Development of Biocompatible Hydroxyapatite Based Materials for Bone Tissue Engineering Applications View project
All content following this page was uploaded by Marica Ivanković or Opalički on 28 May 2014.
3
University of Zagreb, Faculty of Chemical Engineering and Technology
Marulićev trg 19, 10000 Zagreb, Croatia
KEY WORDS: Crease strains, gas permeance, laminates, films, flex tests.
INTRODUCTION
resistant [2] whereas others will fail by pinholing or total fracture after
bending only a few times. Even if failure does not occur, certain properties
of the film may be seriously impaired. For example, permeability to gases
or water vapor, tensile or optical properties may be seriously affected
[3,4]. Additives to a plastic material to modify its properties generally
increase the permeability. This increase is further affected with increased
crease stress on polymers [4,5].
Orientation of polymer materials reduces gas diffusivity. In a study of
permeability of carbon dioxide (CO2) through ultradrawn polystyrene,
Wang and Porter [6] pointed out that the solubility remains nearly
constant while the diffusion coefficient decreases with draw.
Today’s polyolefin packaging can have a range of functional require-
ments, among them high flexibility, optical clarity, low water loss,
sealability, extended shelf life, slow permeability to oxygen (O2) and CO2,
lack of leachables, dimensional stability during sterilization, flex
resistance, biocompatibility and environmental compatibility, and low
cost. PE was the first commodity plastic used for food packaging. PE films
are often laminated with other polymers for applications in which PE is
used for heat sealing and/or as a barrier to water vapor. Biaxially oriented
polypropylene film (BOPP) is also a widely used transparent packaging
material. Its advantageous properties include low density, no toxicity,
good moisture resistance, good mechanical strength, and dimensional
stability and printability. Commercial BOPP films have special inner
structures obtained by the stretching of the thick, extruded sheets at high
temperatures in the machine direction and in the transverse direction [7].
Polyamide has frequent use as a component in these multilayer film
structures [8] due to its unique combination of mechanical strength,
puncture resistance, transparency, thermal stability, O2 and aroma
barrier, and thermoformability. A number of papers report on the effect
of drawing on polymers permeability [6,9–11].
Barrier Properties of Polymeric Films 241
EXPERIMENTAL DETAILS
The investigated test films are listed and specified in Table 1. Films
were obtained, without graphics, directly from the producer,
Aluflexpack d.o.o., Umag, Croatia.
peer-00572074, version 1 - 1 Mar 2011
Permeance Measurement
Thickness
Polymer Abbreviation (mm) Comments
1 Polyethylene PE 75 Polyethylene low
density, PE-LD
2 Polyamide PA 15 Polyamide 6; Density
(23 C) ¼ 1.15 g cm3
3 Bioriented coextruded BOPP coex 20
polypropylene
4 Bioriented coextruded BOPP coex.met 20 Vacuum deposited
metallized polypropylene aluminum
5 Polyamide/Polyethylene PA/PE 15/75 2.2–2.7 g m2
polyurethane solvent
based adhesive
6 Polypropylene bioriented BOPPcoex./PE 20/75 2.5–3.0 g m2
coextruded/Polyethylene polyurethane solvent
based adhesive
7 Polypropylene bioriented BOPPcoex.met./PE 20/75 2.5–3.0 g m2
coextruded metallized/ polyurethane solvent
Polyethylene based adhesive
8 Polypropylene bioriented BOPPcoex./ 20/20 2.0–2.5 g m2
coextruded/Polypropylene BOPPcoex.met solventless adhesive
bioriented coextruded
metallized
9 Polypropylene bioriented BOPPcoex./ 20/20 2.0–2.5 g m2
coextruded/Polypropylene BOPPcoex solventless adhesive
bioriented coextruded
242 S. MRKIĆ ET AL.
Permeability Coefficient
P ¼ k2 ql ð2Þ
where:
k2 ¼ 1.16 109
l ¼ polymer thickness (cm)
Standard Coefficient of
Polymers deviation Average variability (%)
PE 2.2 109 1
2.3 1011
PA 2.8 1010 2
6.1 1012
BOPPcoex 4.83 1012 6.98 1010 1
BOPPcoex.met. 6.14 1012 3.7 1010 2
PA/PE 2.1 109 2
3.4 1011
BOPPcoex/PE 2.8 109 1
2.8 1011
peer-00572074, version 1 - 1 Mar 2011
DSC Experiments
The DSC analysis was carried out on a Netzsch DSC 200 differential
scanning calorimeter operating in the temperature range between 100
and 500 C at a heating rate of 10 C min1 in a nitrogen atmosphere.
Calibrations for both the temperature and the enthalpy were achieved
from measurements of melting temperature and enthalpy of indium.
From DSC thermograms, the heat of fusion Hf and the degree of
crystallinity Xc were determined according to the equation:
Hf
Xc ¼ ; ð4Þ
Hf ,th
Thermal Properties
5
Exo
PA
4 PE
Normalized heat flow (W/g)
3 BOPPcoex.
2 BOPPcoex.met.
PA/PE
1
BOPPcoex./PE
peer-00572074, version 1 - 1 Mar 2011
−1 BOPPcoex.met./PE
2.0
Exo
1.5
Normalized heat flow (W/g)
1.0
0.5
0.0
50 100 150
Temperature (°C)
Figure 2. DSC thermograms of as-received (solid line) and stressed (110 crease stress
cycles, dotted line) PE films obtained at heating rate of 10 C min1.
Permeance Properties
to CO2 is at least 4 times that of O2 [18,19]; however, this was not the
case for the samples in this series as will be discussed later.
PA film showed the highest increase of O2 permeability with increased
stress cycles (Figure 3), while a negligible effect of stress cycles from
30 to 70 was observed in the case of N2 and air permeability.
High permeability changes due to mechanical stress were also observed
for BOPPcoex.met where O2 permeability (Figure 3) increased with
stress cycle increase (50 cycles) in the entire temperature range
investigated. In the case of CO2, significant permeability increase
was obtained (above 40 C) for 110 cycles applied, and for N2 when
70 and 110 cycles were applied, at temperature 420 C.
The results of G’Sell et al. [20] showed that structural damage takes
place as the plastic deformation proceeds in tension, while only little
damage is recorded in shear.
Another important feature, according to the same authors [20], is the
progressive damage suffered by the semicrystalline structure at large
strains. The evidence of this phenomenon, for both PE and PP, is the
decrease of density probably due to progressive fragmentation of
crystallites and micro-cavitations at stress concentrated zones.
The effect of mechanical stress on gas permeance of BOPPcoex/PE
laminate was observed at 50 cycles applied and did not change with
further cycles (Figure 4). For BOPPcoex.met/PE a slight increase in
permeance was observed even at 30 cycles for all gases investigated,
while with further stress cycles a negligible effect on permeance was
observed.
Generally the highest changes in gas permeance with increased stress
cycles were observed with films having a metallized layer in the
structure, namely BOPPcoex/BOPPcoex.met and, to a lesser extent,
BOPPcoex.met/PE laminates. Similar observation was reported by
Oliveira et al. [3]. Although the barrier properties of metallized
peer-00572074, version 1 - 1 Mar 2011
10000
10 20 30 40 50 60
1000
q (cm3m−2d−1bar−1)
100
0 50 110 0 50 110 0 50 110 0 50 110
PE BOPPcoex.met PA BOPPcoexv
Figure 3. Influence of temperature (10–60 C) and crease stress (0, 50, and 110 cycles) on O2 permeability in monofilms.
Barrier Properties of Polymeric Films
247
peer-00572074, version 1 - 1 Mar 2011
248
1000
S. MRKIĆ ET AL.
10 20 30 40 50 60
q (cm3m−2d−1bar−1)
100
0 50 110 0 50 110 0 50 110 0 50 110 0 50 110
PE BOPPcoex.met PA BOPPcoex
Figure 4. Influence of temperature (10–60 C) and crease stress (0, 50, and 110 cycles) on O2 permeability in laminates.
Barrier Properties of Polymeric Films 249
5.7
y (0) = −158.78x + 6.0262 y (30) = −91.228x + 5.8412 y (50) = −69.307x+ 5.7634
R2 = 0.9319 R2 = 0.8599 R2 = 0.8432
5.65
y (70) = −158.25x + 6.0653 y (110) = −288.16x + 6.5092
R2 = 0.6668 R2 = 0.7766
ln q (cm3 m−2 d−1 bar−1)
5.6
5.55
5.5
0 30 50 70 110
5.45
0.0029 0.003 0.0031 0.0032 0.0033 0.0034 0.0035 0.0036
1/T (K−1)
Figure 5. Influence of temperature (1/T ) and crease stress cycles (0–110) on
CO2 transmission rate through PA/PE laminate.
250 S. MRKIĆ ET AL.
1.8
BOPPcoex (0)
BOPPcoex (50)
1.6 BOPPcoex (110)
BOPPcoex/PE (0)
BOPPcoex/PE (50)
1.4
BOPPcoex/PE (110)
O2 /CO2
PE (0)
1.2 PE (50)
PE (110)
0.8
peer-00572074, version 1 - 1 Mar 2011
0.6
0 10 20 30 40 50 60 70
Temperature (°C)
Figure 6. Effect of temperature (10–60 C) and stress cycles (0, 50, 110) on O2/CO2
permselectivity of some polymers.
PA (10–60 C)
BOPPcoex.met (10–40 C);
BOPPcoex/PE (10–50 C);
BOPPcoex.met/PE (10–40 C);
BOPPcoex/BOPPcoex.met (10–40 C)
A decreased O2/CO2 permselectivity is obtained for the following films
exposed to stress cycles:
BOPPcoex (40–60 C);
PA/PE (t430 C);
BOPPcoex/BOPPcoex (t 40 C)
Barrier Properties of Polymeric Films 251
60000
O2 N2 Air CO2 BOPPcoex.met
PA
50000
BOPPcoex
PE
40000 PA/PE
BOPPcoex/PE
Ea (J mol−1)
30000 BOPPcoex.met/PE
BOPPcoex/BOPPcoex.met
20000 BOPPcoex/BOPPcoex
10000
0
peer-00572074, version 1 - 1 Mar 2011
−10000
0 50 110 0 50 110 0 50 110 0 50 110
Stress cycles
Figure 7. The effect of crease stress (0, 50, and 110 cycles) on activation energy for the
gas permeability coefficient through polymers.
CONCLUSIONS
ACKNOWLEDGMENTS
REFERENCES
BIOGRAPHIES
Saša Mrkić
Kata Galić
Marica Ivanković