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Structure and properties of polypropylene cast films: Polymer type and

processing effects

Conference Paper · May 2016

DOI: 10.1063/1.4949644

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 Structure and properties of polypropylene cast films: Polymer type and processing
effects
Daniela Mileva, Markus Gahleitner, and Dietrich Gloger

Citation: AIP Conference Proceedings 1736, 020069 (2016); doi: 10.1063/1.4949644

View online: http://dx.doi.org/10.1063/1.4949644
View Table of Contents: http://scitation.aip.org/content/aip/proceeding/aipcp/1736?ver=pdfcov
Published by the AIP Publishing

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 Structure and Properties of Polypropylene Cast Films:
Polymer Type and Processing Effects
Daniela Milevaa, Markus Gahleitnera, Dietrich Glogera
a
Borealis Polyolefine GmbH, Innovation Headquarters, St. Peterstr. 25, 4021 Linz, Austria

Abstract. The influence of processing parameters in a cast film extrusion process of thin films of isotactic polypropylene
homopolymer and random propylene-ethylene copolymer was analyzed. Variation of the chill roll temperature allowed
changing the supercooling of the melt and thus the generation of different crystal polymorphs of iPP. Additional focus
was placed on the effect of flow induced crystallization via changing the output rate of the line. The crystal structure and
morphology of the materials were evaluated and correlated to selected optical and mechanical properties.
Keywords: Polypropylene, Random Propylene-Ethylene Copolymer, Cast Film, Crystallisation
PACS: 81.05.Lg, 81.10.Fq, 81.30.Fb, 07.79.Lh, 07.85.Jy

INTRODUCTION

Isotactic polypropylene can form different crystal structures, among which the monoclinic D-form and mesophase
structure are of primary interest in the present work. It has been shown that the formation of these polymorphs can
effectively be controlled by the rate of solidification and/or supercooling of the isotropic melt [1]. The cooling
conditions for generation of D-crystals or mesophase were quantified either by analysis of the X-ray structure of
samples cooled at different rate [2,3], or by analysis of the temperature of the phase transformation as a function of
the rate of cooling using a fast scanning chip calorimeter [4,5]. Fully amorphous and glassy iPP was obtained by
cooling the relaxed melt below the glass transition temperature of 260–270 K at rates higher than about 103 K s–1.
Cooling at rates lower than about 102 K s–1 resulted in formation of monoclinic D-crystals of lamellar geometry
organized within a spherulitic superstructure at relatively high temperatures/low supercooling [6,7]. According to the
literature data the mesophase formation of iPP is fastest at 300 K, while crystallization is fastest at around 340–350
K. Random insertion of ethylene or higher 1-alkene co-units slows down the kinetic of structure formation and shifts
to lower temperatures the maximum half-time of structure formation [8,9].
Profound studies have been dedicated to defining correlations between the structure formed at different pathways of
crystallization and properties. Besides the amount of the ordered phase in semicrystalline polymers, it was shown
that crystal geometry is an additional important parameter governing the final mechanical properties. A study on iPP
showed that samples containing monoclinic lamellar crystals have higher stiffness in comparison to samples with
monoclinic nodular domains at identical degree of crystallinity [10]. However, most of the efforts are confined to the
area of solidification from the quiescent melt [10, 11, 12]. There are few studies dedicated to cast film extrusion of
iPP and propylene-ethylene or propylene-1-butene random copolymers [13, 14, 15, 16]. These studies have
confirmed that at high supercooling i.e. 300 K chill roll temperature, mesophase forms in case of the iPP-Eth and
monoclinic crystals develop in iPP, respectively.
The supercooling or the rate of solidification is a crucial technological parameter, but during cast film extrusion the
shear and extension rates in production play an important role, as well [17]. In the present work, an attempt is made
to relate in a systematic approach the structure development of polypropylene via controlling both the supercooling
and the deformation during cast film extrusion. The effect of the macromolecular architecture has been considered
by analyzing iPP homopolymer and random propylene-ethylene copolymer. Cast films of 50 Pm thickness were
produced via variation of the chill roll temperature and the drawing rate.

VIII International Conference on “Times of Polymers and Composites”

AIP Conf. Proc. 1736, 020069-1–020069-4; doi: 10.1063/1.4949644
Published by AIP Publishing. 978-0-7354-1390-0/$30.00

020069-1
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 EXPERIMENTAL

Materials
We used commercial isotactic polypropylene and random propylene-ethylene copolymer (4.9 wt% ethylene) from
Borealis AG. The polymers have a similar mass-average molecular weight (Mw) of 350×103 g/mol, a similar
molecular weight distribution and melt flow rate (MFR) of 8 g/10min, respectively (two polymers from a series
studied before [11,18]).
Film Preparation
Cast films of 50 Pm thickness were produced from both polymers by changing the chill roll temperature and line
speed / output. The polymer was melted in a single-screw extruder to a final temperature of 503 K cast in a
coathanger die of 1 mm width and afterwards solidified at chill roll temperatures as followed: 288, 313, 343 K. The
output rate was varied between 60 and 120 kg/h, keeping the overall deformation from 1000 to 50 μm constant but
varying the deformation rates. The films were produced on a cast film line Battenfeld BA60 using an extruder with 4
heating zones. Subsequently the samples were stored at room temperature and tested after at least 96 h.
Instrumentation
WAXS measurements were performed to gain information about the structure of crystals in the various samples of
different history of crystallization, and chemistry. The diffractograms data were collected in symmetric transmission
mode with Ni-filtered CuKα x-rays on a D8 Discover diffractometer from Bruker. The amorphous halo obtained
from an atactic PP sample was properly scaled and subtracted. AFM investigations were done in AC mode with an
Asylum Research MFP3D.Tensile stress-strain curves for the analyzed materials were recorded on a testing machine
Zwick Z030 according to ISO 527. The experiments were performed at room temperature. The strain rate during the
initial test period of 10 s was 1 mm min-1 for modulus determination. Haze and clarity were determined according to
ASTM D1003.

RESULTS AND DISCUSSION

Considering the rate of melt-crystallization and the shear forces during processing of cast films as crucial
engineering parameters, this study focuses on the effect of variation the chill roll temperature and output rate during
the structure formation in isotactic PP homopolymer (iPP) and random copolymer with ethylene (iPP-Eth).

(a) 120 kg/h (b) 60 kg/h

iPP
Intensity

monoclinic monoclinic
Tchill roll=288 K
meso / mono mesomorphic
Tchill roll=313 K
mesomorphic mesomorphic
Tchill roll=343 K

iPP-Eth
Intensity

monoclinic monoclinic
Tchill roll=288 K
monoclinic meso / mono
Tchill roll=313 K
mesomorphic mesomorphic
Tchill roll=343 K

10 15 20 25 10 15 20 25
Scattering angle 2Q Scattering angle 2Q

FIGURE 1. WAXS data as a function of the scattering angle collected on films of iPP (top) and iPP-Eth (bottom) solidified at
different chill roll temperatures 288 K (blue), 313 K (black) and 343 K (red). The films were produced with (a) 120 kg/h and (b)
60 kg/h.

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 The crystal/mesophase polymorphism, morphology and final properties of the ordered phase were analysed on the
films. Figure 1 shows WAXS data intensity as a function of the scattering angle of samples of iPP (top row) and
iPP-Eth (bottom row) solidified at different chill roll temperatures, as indicated on the right side of the graph i.e.
288, 313 and 348 K. Figure 1a shows X-Ray patterns obtained on films produced with 120 kg/h and Figure 2b with
60 kg/h output rate, respectively. Solidification of the melt at 348 K triggers crystallization of the monoclinic form
in both iPP and iPP-Eth. Decrease of the chill roll temperature to 313 K slightly supresses the formation of the
monoclinic phase and causes development of mesomorphic phase. Due to the higher shear forces, films produced at
120 kg/h output rate show higher content of monoclinic phase in comparison to those produced at 60 kg/h for both
of the polymers. Quenching the films at 288 K triggers exclusively mesophase formation due to the high
supercooling from the melt.

(a) iPP (b) iPP-Eth 288 K, chill roll

313 K, chill roll
348 K°C, chill roll
1200
Tensile modulus (MPa)

1000

800

600

400

200

0
throughput: 120 kg/h 60 kg/h 120 kg/h 60 kg/h

FIGURE 2. Tensile modulus measured in machine direction as a function of the throughput rate of films quenched at different
chill roll temperatures. 2a data collected on films of iPP homopolymer, 2b data collected on films of iPP-Eth.

The amount of crystal fraction is an important parameter affecting the mechanical properties in semicrystalline
polymers. The effect of the degree of crystallinity and crystal habit on the modulus of elasticity and yield strength of
iPP homopolymer has already been shown [18]. In the present work, a relation between structure and properties as a
function of the processing parameters is analysed. The tensile behavior of the films was checked, Figure 2 showing
the tensile modulus as a function of output rate and chill roll temperature for iPP (a) and iPP-Eth (b). Even at
comparable crystallinity, films of iPP homopolymer are stiffer than from iPP-Eth. The tensile modulus of films
solidified at different temperatures decreases proportionally with decrease of the chill roll temperature. At 348 K the
stabile monoclinic phase of iPP forms which is characterized with high degree of order, lamellar crystals and high
stiffness. With lowering the chill roll temperature the percentage of monoclinic phase in the polymers decreases
which leads to lower tensile modulus. Beside the chill roll temperature which determines the final supercooling, the
crystal structure and properties can be controlled by the output rate which is responsible for the flow induced
crystallization [17,19]. High output rate results in increased shear forces, accelerated crystallization, higher degree of
ordered phase and thus increased stiffness. Similar effects were also observed for the optical performance (haze &
clarity).

SUMMARY
The present work focuses on the analysis of the crystal structure and related properties in polypropylene films. In
particular, a variation of the conditions for structure formation of iPP and iPP-Eth in a realistic processing setup for
cast film extrusion was studied. The crystal structure and properties were greatly influenced by the final temperature
of solidification / supercooling and the output rate. Variation of the chill roll temperature and the induced
deformation rate could be used as a successful approach for design of materials with different structure and
properties. In general, inclusion of ethylene co-units in the iPP decreased the Young’s modulus, but not only due to
the reduced degree of crystallinity, and flow-induced crystallisation played an important role for optics and
mechanics on top of supercooling.

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 ACKNOWLEDGMENTS
The authors would like to acknowledge Davide Tranchida for the excellent WAXS analyses and Walter Schaffer for
the AFM work (both are colleagues at Borealis).

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