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Polymer 49 (2008) 2578–2586

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Polymer
journal homepage: www.elsevier.com/locate/polymer

Relationship between biaxial orientation and oxygen permeability of polypropylene film
Y.J. Lin a, P. Dias a, H.Y. Chen b, A. Hiltner a, *, E. Baer a
a

Department of Macromolecular Science and Engineering and Center for Applied Polymer Research, Case Western Reserve University, Cleveland, OH 44106-7202, United States b New Products – Materials Science, Core R&D, The Dow Chemical Company, Freeport, TX 77541, United States

a r t i c l e i n f o
Article history: Received 5 February 2008 Received in revised form 17 March 2008 Accepted 19 March 2008 Available online 27 March 2008 Keywords: Polypropylene Biaxial orientation Oxygen permeability

a b s t r a c t
Biaxially oriented polypropylene (BOPP) films were produced by simultaneous and sequential biaxial stretching to various balanced and unbalanced draw ratios. The BOPP films were characterized in terms of density, crystallinity, refractive index, oxygen permeability and dynamic mechanical relaxation behavior. It was found that the density and crystallinity of BOPP films decreased as the area draw ratio increased. Sequential stretching led to a slightly lower density than simultaneous stretching to the same draw ratio. Moreover, sequential stretching produced lower orientation in the first stretch direction and higher orientation in the second stretch direction compared to simultaneous stretching. The study confirmed the generality of a one-to-one correlation between the oxygen permeability of BOPP films and the mobility of amorphous tie chains as measured by the intensity of the dynamic mechanical b-relaxation. Moreover, the study established the correlation for commercially important sequentially drawn BOPP films with an unbalanced draw ratio. Finally, the chain mobility in the stretch direction was found to depend on the final stress during stretching. Ó 2008 Elsevier Ltd. All rights reserved.

1. Introduction Two of the key requirements for packaging films in beverage and food applications are atmosphere control and mechanical robustness. For polypropylene, adequate properties are achieved commercially through tentering processes that enhance toughness and gas barrier [1,2]. Commercial biaxially oriented polypropylene (BOPP) films are usually produced through a sequential process with unbalanced draw ratios. In this situation, an unoriented starting sheet is first stretched uniaxially at the softening temperature and then stretched in the perpendicular direction at elevated temperature. However, recent technological advances have allowed for simultaneous biaxial drawing on a commercial scale where unoriented extrudate can be stretched in two perpendicular directions in one step, resulting in a more energy and time-efficient process [3]. As a consequence, it is of immediate interest to compare and contrast the solid state structure and properties achieved with the two methods for fabricating BOPP film.

* Corresponding author. Department of Macromolecular Science and Engineering and Center for Applied Polymer Research, Case Western Reserve University, Kent Hale Smith Building, Room 423, 10900 Euclid Avenue, Cleveland, OH 44106-7202, United States. E-mail address: ahiltner@case.edu (A. Hiltner). 0032-3861/$ – see front matter Ó 2008 Elsevier Ltd. All rights reserved. doi:10.1016/j.polymer.2008.03.033

The first step in the sequential process is uniaxial stretching in the machine direction under constrained conditions. As described ¨ by Lupke et al. [4], the initially unoriented film is transformed into a highly oriented, fibrous structure of the shish–kabob type. The crystal orientation is dominated by uniaxial c-axis orientation in the stretch direction. In the second step, the initial morphological response to the transverse stretch is separation and splaying of the close-packed shish–kabob fibers, and formation of a population of thin fibrils highly oriented in the transverse direction. As the transverse stretch increases, the shish–kabob fibers are completely transformed into a purely fibrous network with c-axes preferentially oriented in the two orthogonal stretch directions [4–6]. One study that also considered the amorphous phase found that the amorphous chains are oriented almost entirely in second stretch direction [7]. Because sequential stretching produces different fibrous structures in the first and second stretch directions, a balanced biaxial draw ratio results in significantly higher orientation in the second stretch direction [4]. It is not surprising that the stress–strain behavior is anisotropic as well. In order to obtain a good balance in properties, tentered BOPP is typically fabricated with different draw ratios, and with different stretch temperatures, in the machine and transverse directions. In contrast, simultaneous biaxial stretching produces a fibrillar network texture in a single step [8]. Isotropic orientation of the

During the first stretch. Gas transport is seen as occurring only through the amorphous regions. Specimens weighing 5–10 mg were cut from the molded sheet or the biaxially stretched film. whereas in the constrained direction. In the present study. An optimum balance in stress response and orientation was achieved for this resin at 140  C [14]. A Metricon Model 2010 Prism-Coupler was used to measure the refractive index of the oriented films at a wavelength of 1544 nm.1. the sheet was stretched in both directions to the lower draw ratio. Results and discussion 3. whereas the draw ratio in the y-direction ly was varied from 3 to 7.9. The correlation encompassed BOPP films obtained from different isotactic propylene homopolymers and copolymers [13]. the final stress in the .1 followed by strain hardening. The stress relaxed somewhat during the 0. The stress–strain curves. it was stretched further to the higher draw ratio. which arises from main chain motions in the amorphous phase. 1. with very limited data. showed yielding at a draw ratio of about 1. one report. and then increased during the second stretching in both the stretched and constrained directions due to strain hardening. and BOPP films obtained by stretching PP sheets with different thermal histories [14]. the stress relaxed slightly before some further strain-hardening occurred due to the constraint. the target draw ratio in the x-direction lx was constant and equal to 5. After a pause of 0. In simultaneous stretching to different draw ratios. A 2-propanol/water gradient column with a range of 0. Square specimens 85 mm  85 mm were cut from the compression molded sheets.6 mm were prepared by compression molding. a simultaneously stretched film with a balanced draw ratio possesses isotropic properties.4 s pause. With increasing temperature. as more crystals melted.10]. Consequently. marked with a grid pattern. In simultaneous stretching. The permeant gas stream was diluted with nitrogen to achieve a 2% oxygen concentration in order to avoid exceeding the detector capability of the instrument. the film strain-hardened further in the stretched direction.0005. 2. The measurements were performed at 23  C.42  105 g molÀ1 and Mw/Mn of 2. the sheet was partially melted. Typical stress–strain curves for simultaneous biaxial stretching are shown in Fig.95 g cmÀ3 was calibrated with glass floats with known density. It had weight average molecular weight Mw of 3. after that. Permeability was obtained from the steady flux Jo according to P ¼ Jo l=p (1) where p is the oxygen pressure and l is the film thickness. Fig. In sequential stretching. In all cases. while the film was constrained at the lower draw ratio.4 s that was imposed by the instrument. Small pieces of film (w2 mm  2 mm) were placed in the column and measurements were taken after 10 h equilibration. and biaxially ¨ stretched in a Bruckner Karo IV biaxial stretcher at 140  C at an engineering strain rate of 400% sÀ1 based on the original specimen dimensions. Unoriented sheets with a thickness of approximately 0. Stretching at lower temperatures required larger forces and often resulted in void formation. At 140  C.085% over the temperature range from À60 to 120  C with a heating rate of 3  C minÀ1. The first heating thermograms were recorded at a heating rate of 10  C minÀ1 from À60 to 190  C. In these examples. At least 3 pieces from each film were tested. which of course were essentially the same in the two directions.J. Stretching was performed either simultaneously in the two directions or sequentially. In sequential stretching. gas permeability does not exhibit a simple relationship with optical birefringence. It is not known whether the morphological differences between sequentially and simultaneously drawn films also impact the gas permeability. the stress response decreased as the crystals melted.Y. and in the y-direction as well due to the stress imposed by the constraint. Specimens cut parallel to the two stretching directions were tested in the tensile mode with a frequency of 1 Hz and a strain of 0. 2. During this stretching. 1 atm and 23  C was measured with a MOCON OX-TRAN 2/20. Polypropylene pellets were molded at 190  C using a laboratory hot press and quenched as described previously [14]. the film was stretched in the y-direction to the target draw ratio while being constrained in the x-direction. the specimen was constrained in one direction and stretched in the other direction. Oxygen flux J(t) at 0% relative humidity. The orientation process for forming BOPP film stretches and tightens the amorphous tie molecules that connect the crystals and transfer the stress. Lin et al. it was stretched further to the higher draw ratio in the y-direction. Load and displacement were recorded and the stress–strain curves were calculated from these data. which is dominated by orientation of the crystalline phase [11]. the tie chains became less effective and the amount of orientation was reduced. A dynamic mechanical thermal analyzer (DMTA) Mk II unit from Polymer Laboratories was used to obtain tan d. Recent studies of simultaneously drawn BOPP films with a balanced draw ratio found a single one-to-one correlation between the oxygen permeability and the intensity of the dynamic mechanical b-relaxation. while the film was constrained at the lower draw ratio in the x-direction. Then. Two films prepared under the same conditions were tested to obtain the average permeability. As a consequence.85–0. / Polymer 49 (2008) 2578–2586 2579 c-axes [9. Then. The density was measured at 23  C according to ASTM D1505-85. showed a correlation between oxygen permeability and Herman’s amorphous phase orientation function in the transport direction [12]. The preheat time before stretching was fixed to be 1 min. the sheet was stretched in both directions to the lower draw ratio. Correlations are sought between the oxygen permeability of the BOPP films and the amorphous chain mobility. differentiates the single step BOPP film from the sequentially stretched film with bimodal c-axis orientation. It needs to be determined if the correlation extends to the commercially important sequentially drawn BOPP film with an unbalanced draw ratio. Materials and methods The polymer used in this study was a developmental polypropylene that was prepared with a post-metallocene catalyst by The Dow Chemical Company. The sheet was preheated at 140  C for 60 s and stretched at a strain rate of 400% sÀ1. yielding occurred in the x-direction. it was constrained in the first stretch direction and stretched in the second direction. The error in the permeability measurement was about 5%. However. the film was stretched in the x-direction to a target draw ratio of 5 while being constrained in the y-direction. PP sheet is drawn sequentially and simultaneously with balanced and unbalanced draw ratios. This suggests that the morphological rearrangements during stretching lead to restricted motion of the amorphous chains. Few studies have addressed the fundamental relationships between the solid state structure of BOPP films and the gas permeability. which further distinguishes it from the sequentially stretched counterpart. The error in the density measurements was Æ0. The uniformity of the drawn specimens was determined from the even deformation of the grid pattern. the temperature used to perform the stretching. However. 3. Biaxial stress–strain behavior A thermogram of the compression molded PP sheet showed the gradual onset of melting at about 120  C and the peak melting temperature at 146  C.

and crystalline phase density. (b) stretched to 5  5. which was the preheat condition used for all the stretched films. A relatively large scatter in the DSC measurements obscured the difference between simultaneous stretching and sequential stretching that was observed in the density. It was observed that for a given biaxial draw ratio.97 MPa 2 y 3. Characterization of biaxially stretched films = 1. ra.853 g cmÀ3 and rc ¼ 0. Specimens were cut from this uniform area for further characterization.and y-direction was recorded and an average final stress was calculated. it was also noted in Table 1 that unbalanced sequential stretching to the larger target draw ratio first resulted in a film with a lower density than vice versa. respectively. 1. the heat of fusion of 100% crystallized PP [15]. Crystallinity was calculated from density according to   r r À ra Xc.and y-direction: (a) stretched to 5  3. relaxation and recrystallization during cooling were inhibited by orientation of the amorphous tie chains. sequential stretching resulted in a film of slightly lower density than simultaneous stretching. The draw ratio in the two orthogonal directions was calculated from the change in separation of the parallel grid lines. However. According to one explanation that preserves the simple two-phase model of crystalline and amorphous phases. 3.17]. 4a. it should be recalled that the film was partially melted during the preheat period and it remained partially melted during the stretching process. and (c) stretched to 5  7. Stretching reduced the density from 0. A similar discrepancy between the two crystallinity determinations is typical of polypropylene and propylene copolymers [16. where Ao is the initial area defined by the grid lines and A is the area defined by the same grid lines after stretching. amorphous phase density. i. Table 1. = 1.2580 Y. The difference disappeared when the data were plotted as a function of the area draw ratio because stretching to the larger target draw ratio first resulted in a film of slightly higher area draw ratio. sequential stretching led to a higher final average stress than simultaneous stretching. x. the center region of the stretched film was very uniform as indicated by straight. It is proposed that constraints imposed by the crystalline phase affect chain packing in the Stress (MPa) . The vertical dashed lines in (a) and (c) indicate where the film was constrained at the lower draw ratio. For the same area draw ratio. and cooled to ambient temperature without stretching was used as the control for determining the effects of stretching. parallel grid lines. The area draw ratio A/Ao was also obtained.e. which underscored the effect of stretched tie chains.9068 g cmÀ3 for the control to almost to 0. Typically. Biaxial stress–strain curves for stretching simultaneously in the x. However. the density of atactic polypropylene should not be used as the density of the amorphous phase in isotactic polypropylene [17]. and rc are the bulk density. DSC ¼ DHm  100% o DHm (3) Stress (MPa) 0 0 1 2 3 4 5 6 7 c 5 Simultaneous 5x7 4 3 2 1 0 0 1 2 3 4 5 6 7 Draw Ratio Fig. m Qualitatively. Fig. / Polymer 49 (2008) 2578–2586 a 5 Simultaneous 5x3 x-direction 4 y-direction Stress (MPa) 3 x an accurate measure of the draw ratio.29 MPa 1 0 0 1 2 3 4 5 6 7 b 5 Simultaneous 5x5 4 3 2 1 A film that was heated at 140  C for 60 s.J. The decrease in crystallinity depended on how far the film had been stretched into the strain-hardening region.9000 g cmÀ3 for the most highly drawn films. Generally accepted values of ra ¼ 0. Fig. The crystallinity calculated from the density was consistently higher than the crystallinity from heat of melting. The crystallinity was also calculated from the DSC heat of melting according to Xc. decreasing from about 48% for the preheated control to as low as 41% for the films with the highest draw ratios. Recrystallization occurred during subsequent cooling. A grid pattern was marked on the sheet before stretching in order to determine the uniformity of the deformation and to obtain where DHm is the heat of melting of the specimen and 209 J gÀ1 is taken as DHo .r ¼ c  100% (2) r rc À ra where r. all the sequentially stretched films followed the same trend regardless of the stretching sequence.936 g cmÀ3 were used for the calculation [15]. Lin et al. whether the film was stretched first to the larger target draw ratio or to the smaller target draw ratio. the DSC crystallinity followed the same trend as the density crystallinity.2. To understand the decrease in crystallinity. In the figure.

Draw Ratio.12 MPa Stress (MPa) 3 = 1. y-direction x a 5 4 Sequential 5x3 x-direction y-direction. and (c) stretched to 5  7. where nx and ny are the refractive indices in the two stretching directions and nz is the refractive index in the normal direction. (b) stretched to 5  5.0 =1.0 y = 3. given as ntotal ¼ nx þ ny þ nz (5) As the area draw ratio increased. Lin et al. Fig. Another measure of crystallinity is the total refractive index. 4a.and y-direction: (a) stretched to 5  3. 4b. y =5. DSC À rc (4) Fig. Biaxial stress–strain curves for stretching sequentially in the x. a decrease in density of the amorphous phase.J. amorphous phase and thereby increase the amorphous phase density by an amount that depends on the crystallinity. The trend was the same for simultaneously and sequentially stretched films. / Polymer 49 (2008) 2578–2586 2581 First Stretch in the x-Direction Second Stretch in the y-Direction x-direction. The effective amorphous phase density was calculated from the DSC crystallinity according to ra ¼ rc À rc ðr À rc Þ r  Xc. Fig.46 MPa 2 x 1 0 0 1 2 3 4 5 6 7 0 1 2 3 4 5 6 7 b 5 4 Sequential 5x5 Stress (MPa) 3 2 1 0 0 1 2 3 4 5 6 7 0 1 2 3 4 5 6 7 c 5 Sequential 5x7 4 Stress (MPa) 3 2 1 0 0 1 2 3 4 x 5 6 7 0 1 2 3 4 y 5 6 7 Draw Ratio. Fig. paralleled the decrease in crystallinity. 2.Y. 5 shows excellent correlation between DSC crystallinity and .

6  6.7 3.4867 1.6 4.7 94.5  7.4951 1.00 .2 61.4998 1.0 3.5 61.6 11.70 Æ 0.6 13.7  4.7 45.9042 0.4885 1.6 43.4936 1.2 6.2  5.4853 1.5012 1.8  5.2 4.4987 1.9023 0.0 91.1 94.0251 0.01 0.4842 1. Orientation of polymer chains is conveniently described by the birefringence index [11].6  6.7 95.5 nx The normal birefringence reflects the orientation with the z-direction as the reference.1 12.9006 0.5  6.7  5.67 Æ 0.5041 1.2 91.00 0.e.9 45.0267 0.902 0.4854 1.0287 0.4918 1.4933 1.0349 0.4846 1.7 32.5006 1.9 5. Comparing simultaneous and sequential stretching.6 40. i.5  7.6  4.00 0.9 13.9012 0.5015 1.0 62.9028 0.3 98.4 13.4850 1.4 62.4921 1.4907 1.7 4.0 45.2 39.7 32.9061 0.4847 1.0 12.03 0.0 12.1 13.9 46.1 45.4985 1.x Ib. As ly increased.9039 0.9039 0.0 13.7 12.4891 1.0 60.5 63.70 Æ 0.3 12.9061 0.4835 1.0269 0.73 Æ 0.0 9.4850 1.4841 1.4932 1.9018 0.1 24.62 Æ 0.4999 1.0291 0.1 12.5 13.9013 DH (J/g) 101.62 Æ 0.5  5.9 Xc.64 Æ 0. The stretching sequence also affected the final orientation of the samples.2 4.0 40. Concurrently.898 0 10 20 30 40 50 A/A0 Fig.4978 1.0 12. and lower orientation in the first stretch direction.5 27. it can be seen that ny increased and nx decreased.4 20. simultaneously and sequentially stretched films with lx ¼ 5 were taken as example.2 63.5 63.5029 1.9048 0.4 5.9043 0.1 44.75 Æ 0.01 0.4853 1.6  5.4937 1.4984 1.4903 1.6  6.4 13.2582 Y.1 90.0 27.0  5.4956 1.0 13.00 0.0 16.9 64.65 Æ 0.4866 1.1 11.3 63.4 45.4846 1.1 12.4920 1.3 12.61 Æ 0.6 59.62 Æ 0.0 6.4968 1.4973 1.4  5.02 0.9020 0.8 5.68 Æ 0.9 47.9 12.9 45.9 44.8 11.y P(O2) (Barrer) 0.2 61.4863 1.4 60.00 0.4976 1.64 Æ 0.5005 1.4988 1. 3.9045 0.4 43.0 90.6 12.6 32.1 31.8 25.4836 1.4921 1.4 4.01 0.02 0.4955 1.7  4.5 94.6 41.5 12. although the sequential 5  3 and 3  5 films ny 1. the sequentially stretched film always had higher orientation in the y-direction and lower orientation in the x-direction for the same draw ratios.0 3.8 3.00 0.5  5.4967 1.4860 1.05 0. To illustrate how the refractive index changed with the draw ratio.0188 0.3 12.0  4.7  4.0 11.6  3.906 ðDntotal Þ2 ¼ Density (g cm-3) Á2 1À Á2 1 1À ðnx À nz Þ2 þ ny À nz þ nx À ny 2 2 2 (7) 0.7 89.4975 1.0177 0.4 37.5 37.02 0.01 0.4 16.5001 1.2 7.9 62.4961 1.1 43.1 44.4956 1. nz also decreased although nz decreased less than nx.03 0.7 14.8 19.4 63.5041 1.0 12. y.0 12.7 62.4 3.2 94.01 0.and z-direction. The refractive index of the unstretched control was nx ¼ ny ¼ nz ¼ 1. Fig.55 Æ 0.1 47.9040 0.5 95.72 Æ 0.9041 0.4965 nz 1.9013 0.5  7.9 93.2 95.00 0. / Polymer 49 (2008) 2578–2586 0.4830 1.3  4.6 3.4936 1.4903 1.8 12.3 64.03 0.8 Density (g/cm3) 0.1 98.58 Æ 0.58 Æ 0.4834 1.5058 1.4861 1.4 12.0 96.05 0.4855 1. 6 to 5  3.7 Dntotal  1000 0.02 0. whereas the total birefringence measures the differences among the orientations in the x-.4952 1.DSC (%) 48.0 42.4878 1.1 3.7 45.7 24. For example.5 64.2 17.05 0.6  5.9068 0.4 47.0320 0.8 95.4861 1. 6.4935 1.5 12.5007 1.8 5.6  6.1 65.9018 0.7 30.0 15. Not surprisingly.8 A/Ao 1.3 46.9048 0. Lin et al.4 12.6 99.3 28.7 15.9 10.88 Æ 0.4832 1.8 45.02 0.9019 0.4 11.0 100.4 5.0 9.3 14.9 11.5008 1.2 60.0 91.9 43.0 12.7 43.3 12.4856 1.2 61.01 0.8 96.0327 0.6 4.0314 0.4858 1.3 13.3 64.4987 1.1 7.8 21.3  6.2 41.9 37.9034 0.00 0.0211 0.8 64.4959 0.62 Æ 0.9007 0.8 92.2 13.67 Æ 0.7 5.67 Æ 0.4954 1.0  1.4974 1.6 12.4903 1.00 0.9 12.7 43.4846 1.7 12.2 17.6 12.5 48.0 43.9054 0.6 5. For example.2 5.9 95.59 Æ 0.6 62.5028 1.0329 0.2 61.9046 0.4966 1.59 Æ 0.5 11.6  3.1 60.01 0.7  5.4958 1.9 43.4 44.91 Æ 0.0 45.9 59.1 66.3 45.5 46.4983 1.3  6.5 17.4931 1.56 Æ 0.4835 Dn  1000 0.4842 1.8 7.9 11.9 26.9028 0.r (%) 66.5  7.2 12.5026 1.4 87.7 5.00 0.0284 0.1 61.4956 1.8 42.9 29.0284 0.9 12.1 4.61 Æ 0.9 21.02 0.7  6.0 25.3 33.9 3.02 1.9020 0. sequential stretching always gave higher orientation in the second stretch direction.1 11.9035 0.2 45.0 43.9 90.75 Æ 0.8 3.4871 1.5032 1. when compared with simultaneous stretching.7 Ib.7 37.4850 1.01 0.2 91.62 Æ 0.4855 1.5 63.4964 1.1 92.67 Æ 0.1  5.6 15.0 93.5005 1.78 Æ 0. which can be expressed as the normal birefringence Table 1 Properties of BOPP films and control Real draw ratio Control Sim-3  3 Sim-3  4 Sim-3  5 Sim-3  6 Sim-3  7 Sim-4  4 Sim-4  5 Sim-4  6 Sim-4  7 Sim-5  5 Sim-5  6 Sim-5  7 Sim-6  6 Seq-3  3 Seq-3  4 Seq-3  5 Seq-3  6 Seq-3  7 Seq-4  3 Seq-4  4 Seq-4  5 Seq-4  6 Seq-4  7 Seq-5  3 Seq-5  4 Seq-5  5 Seq-5  6 Seq-5  7 Seq-6  3 Seq-6  4 Seq-6  5 Seq-6  6 Seq-7  3 Seq-7  4 Seq-7  5 1.1 65.9 3.0 13.9 12.7 62.4934 1.0259 0.70 Æ 0.4971 1.68 Æ 0.4956 1.7 12.4945 1.3 6.5 13.2 5.67 Æ 0.0294 0.4981 1.0 89.4 12.4973 1. Relationship between area draw ratio and density of biaxially stretched films. balanced orientation was achieved by sequentially stretching the film in Fig.5052 1.9028 0.4 40.4845 1.73 Æ 0.9050 0.7 21.9 96.4 33.00 0.5043 1.3 13.4  7.4975 1.5 13.2 6.6 26. the polymer chains tended to align in the direction with the highest stretch.904 0.4 85.0 27.8 98.4 15.9022 0.9 66.8 92.6  6.9 16.4 Xc.8 63.6 61.9 6.4 11.5014 1.9054 0.9027 0.0 17.J.4 44.75 Æ 0.00 0.5052 1.908 Dn ¼ nx þ ny À nz 2 (6) or as the total birefringence 0.6 12.4956.1 95.0 12.0264 0.9017 0.01 0.6  7.7 90.4848 1.4949 1.02 0.4857 1.6 17.6  6.5013 1.82 Æ 0.00 0.900 Simultaneous Sequential 0. crystallinity from ntotal especially considering that the variation in crystallinity of the BOPP films is quite small.9028 0.4917 1.

5. nx . for the stretched films.6 60 0.DSC (%) P(O2) (Barrer) 0. Relationship between the total refractive index and the crystallinity from DSC.J. have similar area draw ratios (21. Fig.872 0 5 10 15 20 25 30 35 40 45 50 A/A0 Fig.3). the 5 Â 3 film showed almost balanced orientation whereas the 3 Â 5 film had much higher orientation in the second stretch direction. According to free volume concepts of gas transport as applied to the two-phase model for crystalline polymers. 3.3.485 1.470 0 4.Y. A/A0 Fig. the crystals are considered impermeable and diffusion occurs through the amorphous phase free volume. stretching facilitated the processes of chain orientation when the film was subsequently stretched in the y-direction.880 0. These concepts readily account for the general observations that gas permeability is reduced by increasing the crystallinity and by increasing the amorphous phase density [18]. / Polymer 49 (2008) 2578–2586 2583 a 55 Simultaneous Sequential 1. nz 1.480 4.495 45 1.876 0. ny . Oxygen permeability of biaxially stretched films (g cm-3) a 0.878 0.500 Xc. Relationship between area draw ratio and oxygen permeability of biaxially stretched films.886 0. 6.475 4.4 58 4. Effect of area draw ratio on: (a) crystallinity from DSC and (b) amorphous phase density. The effect was slightly higher with sequential stretching.8 64 62 0. . It can be imagined that constrained y-direction yielding during x-direction 70 Simultaneous 68 Sequential Increasing the draw ratio of the stretched film had the effect of reducing the oxygen permeability.480 3 35 0 5 10 15 20 25 30 35 40 45 50 4 y( 5 x=5) 6 7 b 0.510 . However.882 Fig. which was consistent with the general finding that the sequential stretching produced a somewhat larger effect than simultaneous stretching at the same draw ratio.485 4. the decrease in permeability was accompanied by decreasing density. Table 1. Lin et al.DSC (%) 1. 4.490 40 1.874 0.505 Squares: Simultaneous Circles: Sequential Refractive Index 50 1.2 Simultaneous Sequential 1. Effect of ly for constant lx ¼ 5 on refractive indices of simultaneously and sequentially biaxially stretched films.7 and 20.490 10 20 30 40 50 nx+ny+nz Fig. This also could have been the origin of the anisotropic fiber morphology reported by others [4]. 7. which combined lower crystallinity (more amorphous phase) and lower 1.884 0. 7.0 66 Xc.

According to the free volume concepts of gas transport.10 Iβ = 0.02 0. Previous results on stretched films prepared from compression molded sheets of the same resin with different thermal histories [14]. / Polymer 49 (2008) 2578–2586 1. it was demonstrated that the correlation between P and nz depends on the resin [13]. A parameter that reflects the properties of the amorphous phase only is needed. some other factor or factors overrode the effects of density alone.4 1. The intensity of the b-relaxation Ib is taken as the height of the deconvoluted peak. Because the permeability measurement combined the effects of orientation in both x.and y-direction. This result appeared to be inconsistent with conventional free volume concepts of gas permeability.484 1.5 Simultaneous Sequential BOPP films with different thermal histories (ref. It was possible that stretching in the pre-melting region indeed decreased the size of nanoscale free volume holes. To obtain the intensity of the b-relaxation. the a-relaxation and the onset of melting as illustrated with a film that was simultaneously stretched to 5 Â 7 in Fig. but at the same time introduced a population of submicron voids.b). In particular.8 tan 0. previous positron annihilation lifetime spectroscopy measurements on similar films showed that the stretching conditions did not affect the free volume hole size [13]. .05 0.00 0. The former would have decreased the gas permeability. The normal birefringence reflects the orientation with the z-direction as the reference. and the thermal history of the compression molded sheet [14].0267 0. main chain mobility in the amorphous phase is associated with the dynamic mechanical b-relaxation at about 10  C.5 0.482 b 1. The two-phase transport model is appropriate for isotropic films. including a metallocene PP and a propylene/ethylene copolymer [13]. P of the stretched films decreases with increasing orientation as measured by Dn. This is understandable because n includes a large contribution from the crystalline phase orientation. diffusivity derives from the dynamic free volume.15 P(O2) (Barrer) 0. However. are included. 14) BOPP films from different resins (ref.9 Sequential a 0.00 0.20 nz 1. Table 1.490 0. whereas the latter would have decreased the density without affecting the gas diffusivity.and y-direction.00 -60 -40 -20 0 20 40 60 80 100 Temperature (°C) Fig. 0. The extrapolated oxygen permeability at zero Ib 1. Thus. It was previously found that the decrease in oxygen permeability of stretched films was due primarily to a decrease in the diffusivity [19]. Dntotal is determined primarily by the difference between nx and ny. Table 1.7 0. In polypropylene.15 tan Fig.5 -60 -40 -20 0 20 40 60 80 100 0. 0.03 0.01 0. 10.0 0. the average value of Ib was used to characterize the chain mobility. 9. For these films. Relationship between oxygen permeability and refractive index in the z-direction. but does not consider the effects of orientation. 8. 8. Lin et al.and y-direction provides the channels perpendicular to the z-direction that allow gas molecules to diffuse.05 0.6 0. Relationship between oxygen permeability and the b-relaxation intensity averaged in the x. 4a.486 0.20 0.10 Iβ = 0.J. Although this possibility could not be ruled out completely. 10. In general.04 0.2584 Y.06 I Fig.0 Simultaneous 0. 13) P(O2) (Barrer) 1. All the data fit a good linear relationship between permeability and chain mobility as reflected by Ib from DMTA.0211 0.488 1. DMTA spectra of a film simultaneously stretched to 5 Â 7: (a) the x-direction and (b) the y-direction. A better correlation is observed between P and nz. The permeability of some simultaneously and sequentially stretched films is plotted against the average Ib in Fig. 9. No general trend is found in the relationship between permeability and Dntotal. Fig. chain mobility in the x.05 amorphous phase density (higher free volume) (see Fig. A reduction in amorphous chain mobility can lead to lower diffusivity by decreasing the frequency with which connecting channels form between free volume holes.0 0. the tan d curve is deconvoluted into 3 Gaussian contributions from the b-relaxation. and results from stretched films of different resins.

oriented platelets could have contributed to the decrease in permeability. The Ib results revealed that the second stretching was also more effective than the first in stretching and tightening the amorphous chains.01 0 1 2 3 4 5 6 0. Ib was lower in the direction of higher draw ratio. For the film illustrated in Fig. However.0 Simultaneous 0. Because the permeability measurement combined the effects of stretching in both x. Thus. Clearly.and y-direction plotted separately. when compared with simultaneous stretching to the same biaxial draw ratios. and lower orientation in the first stretch direction. The result appeared to be inconsistent with conventional free volume concepts of gas permeability. Although the stress on the stretched .6 0.Y.5 0. Parallel changes in P and nz (see Fig. Although recrystallization of impermeable crystals as high aspect ratio. 8) were attributed to increasingly taut tie molecules as the process of crystalline orientation proceeded.03 0. when compared with simultaneous stretching.8 0. 11 shows the relationship between Ib and the final stress with the x. It followed that in sequential stretching to unbalanced draw ratios. However. 12 confirmed a systematic decrease in P as the film experienced increasingly higher stresses during stretching.and y-direction results plotted separately. (0. orientation also stretched and tightened the amorphous tie chains that connected the crystals and transferred the stress. orientation occurred during strain hardening by the processes of lamellar breakup and recrystallization. which reflected primarily the crystalline orientation.and y-direction.26 Barrer) was the contribution from relaxations that were active below the temperature of the b-relaxation [14].02 0. Unlike the total orientation as measured by birefringence. This suggested a relationship between the b-relaxation intensity and the stress when the film achieved the final draw ratio. Relationship between the b-relaxation intensity and the final stress when the film achieved the target draw ratio with results for the x. Average Final Stress (MPa) Fig. The extent to which the tie chains were stretched and tightened depended on the stress applied to the film. Relationship between the oxygen permeability and the final stress averaged in the x. 9 that was simultaneously stretched to 5 Â 7. The study demonstrated that the correlation extends to commercially important sequentially drawn BOPP films with an unbalanced draw ratio.and y-direction. different results were obtained depending upon whether the first stretch was taken to the larger or the smaller draw ratio. it should be useful for predicting the relative gas permeability from the knowledge of the stress applied during stretching without the need to measure Ib. the sequentially stretched films did not necessarily follow this trend. the oxygen permeability decreased with increasing area draw ratio. The result in Fig.7 I 0. the controlling factor was thought to be the reduced mobility of stretched tie chains that control the frequency with which connecting channels form between free volume holes. Despite increases in the amount of amorphous phase (decreased crystallinity) and in the amount of free volume (decreased amorphous phase density). revealed that sequential stretching always gave higher orientation in the second stretch direction. Rather.9 Sequential P(O2) (Barrer) 0. It was now possible to establish a relationship between the oxygen permeability of the biaxially stretched film and the stress on the film during stretching. Conclusions Characterization of the BOPP films revealed significant differences between simultaneous and sequential stretching. 4. which translated to lower gas permeability. Fig. 12. It may be that constrained yielding during the first stretching facilitated subsequent orientation during the second stretching. Not surprisingly. As with relationships between P and nz. Refractive index. a higher stress during stretching resulted in a lower Ib. The amount of crystalline phase orientation. the intensity of the b-relaxation is specific to the amorphous phase and therefore a single correlation applies to different resins and to different thermal histories. / Polymer 49 (2008) 2578–2586 2585 0. this was the case for all the films that were simultaneously stretched to an unbalanced draw ratio. and lower orientation in the first stretch direction. Sequential drawing always gave higher orientation in the second stretch direction. It was imagined that constrained yielding in the second stretch direction during stretching in the first direction facilitated the processes of chain orientation when the film was subsequently stretched in the second direction. Rather. the Ib was lower in the second stretch direction regardless of whether ly was larger or smaller than lx. This resulted in a systematic decrease in P as the film experienced increasingly higher stresses during stretching. depended on the stress applied to the film. and the extent to which the tie chains were stretched and tightened.4 0 1 2 3 4 5 Final Stress (MPa) Fig. the final stress was expected to depend on the resin and the thermal history of the compression molded sheet used to prepare the stretched film. the second stretch was more effective than the first in orienting the amorphous chains. Table 1. This study also tested the generality of a one-to-one correlation between the oxygen permeability of BOPP films and the intensity of the dynamic mechanical b-relaxation. the average final stress was used to test the relationship.04 Simultaneous Sequential 1. 11. In biaxial stretching. Lin et al.J.

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