THE EFFECT OF LDPE CONTENT ON HIGH DENSITY POLYETHYLENE (HDPE) FILMS FOR STRETCHED FILM TAPES

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Society of Plastics Engineers Annual Technical Conference 2008 ANTEC-0278-2008.R2 FLEXIBLE PACKAGING D44 Interactive preferred Technical n/a Lahuerta-Calahorra, Francisco; Steve Orr Ltd Orr, Philip; Steve Orr Ltd Leathem, Mark; Steve Orr Ltd Robinson, Stan; Steve Orr Ltd McNally, Gerry; Queen's University Belfast, Polymer Processing Research Centre Murphy, Raymond; Queen's University Belfast, Polymer Processing Research Centre

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THE EFFECT OF LDPE CONTENT ON HIGH DENSITY POLYETHYLENE (HDPE) FILMS FOR STRETCHED FILM TAPES
Lahuerta, F., Orr, P., Leathem, M., Robinson, S. Steve Orr Ltd, Dromore, Co, N. Ireland Mc Nally, G.M., Murphy, W.R. Polymer Processing Research Centre, Queens University Belfast Ashby Building, Stranmillis Road, Belfast, BT9 5AH, N. Ireland Abstract
A range of blown films were prepared by extruding blends of a commercial HDPE with two separate LDPEs with different densities. Narrow tapes of the films were then stretched at draw ratios of between 1:6 and 1:8 at elevated temperatures. The mechanical, morphological and tensile recovery characteristics, before and after drawing were investigated in order to determine optimum blend composition and drawing conditions for a range of polyolefin stretched tape applications. elongation to maintain the bale density and good weatherability resistance. High density polyethylene is characterized by its linear structure with little molecular branching and as such has a high degree of crystallinity, which affects processability and mechanical properties. However, low density polyethylene has a branched structure with short and long chain branching and is relatively easier to process. Hence blending of polyethylenes is a common industrial practice, with the main reason being to modify the properties of the film and improve the processability. The miscibility of different polyethylene blends has been studied in the past few years [3, 4], due to its direct impact on the processing and final properties of blends. Polyethylene blends have been reported to be either miscible, partially miscible or immiscible depending on molecular parameters such as: molecular weight, molecular weight distribution, branch content and distribution. In addition the use of polyethylene blends in film manufacturing and application for films has been reported by several authors [5-7]. Studies of un-axial and bi-axial stretched polyethylene films and correlation with the orientation measured using techniques such as FTIR, have demonstrated the strong influence that molecular orientation has on the mechanical properties of the films. However very little information is available on the effect of blending low density polyethylene and high density polyethylene on the performance of stretched film tapes using a range of different stretching conditions. Therefore in this work HDPE was blended with two different grades of LDPE at different concentrations to produce the initial blown films. In order to investigate the effect of LDPE concentration on the properties of these tapes, a range of stretched tapes was prepared from these films using different stretch ratios at two stretching temperatures. The effect of processing conditions on the tensile and the recovery properties of the stretch tapes were investigated.

Introduction
The background of this work is related to the manufacture of stretched polyolefin tapes for use in agricultural baler netwrap. The use of netwrap to wrap new generation round bales was introduced in 1970. This was due to the design of modern round balers by the Vermeer Company (USA) and the use of polyethylene stretch films for wrapping silage bales during the 1970s. Since then baler netwrap was found to be the most convenient method for securing round bales and improving the bale density. With a yearly global market of 120,000 tonnes of silage stretch film [1], the netwrap bale market size is estimated to be 700,000 rolls per year (230,000 rolls USA, 120,000 rolls Germany, 110,000 rolls UK/ROI, 70,000 rolls Australia/NZ and 170,000 rolls Europe), which represents around 21,000 ton of knitted HDPE per year. The range of agricultural nets reported by Briassoulis [2], shows that agricultural baler netwrap is based on a fabrication structure of a knitted Raschel net. This type of net is constructed with longitudinal ribbons referred to as pillars and zigzag transversal ribbons referred to as inlays. While the main function of the pillars is to ensure the longitudinal tensile strength of the netwrap, the function of the inlay is to ensure the structural integrity of the net. Both pillar and inlays, are manufactured from HDPE stretched tapes or monofilaments. These tapes are cut from high density polyethylene blown films, which are then stretched at elevated temperatures in an ISO process. Subsequently the stretched tapes are then knitted in a loom to form the netwrap. From an agricultural application point of view, the main properties the netwrap should exhibit are the following: relatively high tenacity breaking stress to resist the baling process and the bale pressure, low

Experimental
This investigation is based on a commercial high density polyethylene blended at different concentrations with two different low density polyethylene grades.

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Materials
The technical specifications of the resins used in this work are shown in Table 1. The main raw material was a commercial HDPE which exhibited relatively high extension properties. In order to enable improved miscibility, two different LDPE grades, with similar MFIs to the high density polyethylene, were blended at concentrations of 10, 20, 30 and 40%. These blends were then converted to films using blown film extrusion.

cell of 0.1kN, and a cross head speed of 127mm/min, a grip length of 50mm and no relaxation time. During the * tests the elastic recovery was determined. The permanent deformation was studied at the following extensions 5, 10, 20, 30 and 40%. With the elastic recovery values it was possible to estimate the elastic limit for each of the polymer blend concentrations, stretch ratios and stretch temperatures.

DSC analysis
Differential scanning calorimetry was used to determine the latent heat of fusion and the melting temperature of the films. Tests were performed on all films using a Perkin Elmer DSC-6. Samples were heated from 30 to 150C, cooled from 150 to 40C and heated again to 150C at a rate of 10C/min. The latent heat of fusion (H J/g) was calculated for each film.

Preparation of the films

A Killion blown film extrusion system was used to manufacture the range of films. The system comprised a Killion KN150 38mm extruder; with a general purpose screw (L/D 30 3:1 compression ratio) fitted with a 75mm diameter die and die gap of 1mm. The temperature profile used in the extruder was ramped from 200C in the feed section to 210C at the adaptor, and the die temperature was setup at 210C. The films were manufactured at a constant screw speed of 31rpm, with a target film thickness for all the blends of 50m. All the films were produced at the same blow ratio of 1:5. The films were carefully labeled and wound onto cores for subsequent cutting into tapes.

Result and Discussion

MFI analysis of the different LDPEs blends was carried out as a general indication of the miscibility of the blends. The MFI of the HDPE was 0.61g/10min and Figure 1 shows the effect of LDPE type and concentration on the recorded MFI. The results show that there is an almost linear increase in the MFI with progressive increase in LDPE1 (MFI 0.8 g/10min) content in the blend. Whereas the MFI of the blends containing LDPE2 (MFI 0.3 g/10min) decrease linearly with increase in LDPE2 content. The shrinkage (at 120C) values of films stretched at 1:4 90C is shown in Figure 2. The shrinkage values indicate the degree of orientation in the film and the results show a linear increase with increasing LDPE concentration with higher shrinkages being recorded for the lower MFI LDPE2.

Stretching process of the tapes

Tapes (5mm width) were cut from each film in the main direction, and were stretched using an Instron 4411 Universal Tensile Tester fitted with an air circulating oven. The tapes were mounted using a grip length of 20mm and operated at a crosshead speed of 250mm/min. The stretching process was carried out using oven temperatures set at 25, 60 and 90C, and stretch ratios of 1:4, 1:6 and 1:8. During the stretching process it was not possible to stretch the 40%LDPE1 tapes at the stretch ratio of 1:8 at 90C and for the stretch ratios of 1:6 and 1:8 at 60C, because the tapes broke prematurely during stretching.

Tensile properties of the stretched tapes

The results in Figure 3 and Figure 4 show the effect of low density polyethylene concentration on tensile modulus of the stretched films. Both figures show that increase in LDPE content resulted in an overall reduction in modulus. However, the films containing LDPE1 exhibited higher modulus values than LDPE2 for similar stretch ratios and stretch temperatures. The results in Figure 5 to Figure 8, shows lower elongations and stress at break for blends containing LDPE1. This behavior tends to indicate that the LDPE1 requires lower stretch ratios to obtain the same mechanical properties, which means higher deniers. This also agrees with the fact that it was not possible to stretch the 40% LDPE1 samples at low temperatures and high

Tensile analysis
The tensile properties of both the stretched tapes and the unstretched tapes were measured according to ASTM D 88297 at room temperature. The test was performed using an Instron 4411 Universal Tensile Tester, with a load cell of 0.1kN, operating at a constant cross head speed of 250mm/min and a grip length of 50mm. Tensile strength at break, yield stress and initial modulus (1% to 5% elongation) was recorded for all films, and his averages and statistical errors was calculated for all the result sets.

Recovery tests
The recovery properties after tensile deformation of the tapes which had been stretched at different stretch ratios and stretch temperatures were investigated according to the ASTM D 5459-95. These tests were carried out using an Instron 4411 Universal Tensile Tester, with a load
*

Elastic Recovery =

DE 100 (see Figure 14) AE

Elastic limit is defined as the percentage of elongation experienced by the sample after which the sample can return to its original length.

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stretch ratios. However, as it was expected, both LDPEs in Figure 3 and Figure 4 exhibit increase in modulus with increase in stretch temperature and more significantly with increase in stretch ratio. The effect of LDPE concentration and drawing conditions on the tensile stress at break is shown in Figure 5 and Figure 6 . The results show a general decrease in the stress at break values occurs with increase in the low density polyethylene content, with the LDPE1 showing a greater decrease in the stress at break values than the LDPE2. This behavior is related to the higher modulus and the lower elongations at break. In addition, with the modulus result, there is also a significant increase in the stress at break values with increase in the stretch ratio and only slight changes in the stress at break values were observed for the increase in stretch temperatures from 60 to 90C. Figure 7 and Figure 8 show the effect of blend concentration and drawing conditions on the elongation at break. The results clearly show that the most important factor influencing elongation is the stretch ratio, with significant decrease in elongations being recorded with increasing stretch ratios. Increase in stretch temperatures from 60 to 90C resulted in only slight changes to the elongation values. The results also show that higher elongations were exhibited by the blends containing LDPE2. In both cases, the results show a decrease in elongation at break with increasing concentration of LDPE. The tensile stress and strain at yield values show a similar trend as the stress and strain at break values. Nevertheless the blends containing LDPE1 show higher stress at yield values than the LDPE2 (see Figure 9 and Figure 10).

Conclusions
This work describes the effect of two grades of LDPE, blended with a commercial HDPE, on the thermal behavior and the mechanical performance of stretched film tapes. The blends extruded as films using four different LDPE concentrations, and the film tapes were then stretched at two different stretch temperatures and three stretch ratios. The mechanical properties were obtained for the different sets of stretch conditions and LDPE concentrations. The results showed that as the LDPE content increased, the modulus and stress at break of the stretched tapes decreased, and an improvement in the recovery properties was observed. Moreover the LDPE2, with the lower MFI, exhibited the superior performance in terms of higher stress and elongation at break, with the lowest modulus and higher recovery properties.

Acknowledgments
The authors would like to thank the PPRC staff and UPU staff for their technical assistance and support.

References
1. 2. 3. 4. 5. 6. 7. Dow Silage Website. www.dow.com/silage/index.htm D.Briassoulis, A.Mistriotis, D.Eleftherakis, Polymer Testing 26, 822832, 2007. Tayyab Hameed, Ibnelwaleed A. Hussein. Macromol. Mater. Eng. 289, 198203, 2004. Q. Fua, Y. Menb, G. Stroblb. Polymer 44, 19271933, 2003. Laffin, C., Mc Nally, G.M., Forristal, P.D., OKiely, P., Small SPE-ANTEC Tech. papers 143-147, 2005. Small, C.M., McNally, G.M., Murphy, W.R. and Garrett, G. SPE-ANTEC Tech. papers 3266-3270, 2003. Beagan, C.M., McNally, G.M., Murphy, W.R. SPEANTEC Tech. papers, 1998.

Recovery properties of the stretched tapes

Figure 11 and Figure 12 show the effect of LDPE concentration, stretch ratios and stretch temperatures on the elastic limit for different films. The results show an increase in the elastic limit with increase in concentration of both low density polyethylenes. However, the blends containing LDPE2 show higher elastic recovery. In addition, the results also show that higher stretch ratios exhibit higher elastic limits, whereas higher stretch temperatures leads to a decrease in the elastic limit.

Tables and Figures

Density (g/cm3) MFI Tensile break MPa % 62 650 20 390 23 580

Crystallinity and Tm
DSC analysis was carried out on all the films in order to determine the effect of LDPE content on the crystallinity of the blends, as determined by H (J/g). Figure 15 shows the change in the melt temperatures and the latent heat of fusion of the films. The results show a general decrease in the melting temperatures and the latent heat of fusion with increasing LDPE concentration. In addition, the thermograms (Figure 13) show no discernable double melting endotherm peaks, which tends to suggest some degree of miscibility of the HDPE / LDPEs blends.

(190C 2.16kg) HDPE 0.945 0.61 Dow 300E LDPE1 0.924 0.80 Dow 303E LDPE2 0.922 0.3

Table 1. Material Properties HDPE and LDPE.

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1.0

LDPE1 LDPE2

Shrinkage (%), 120C 75sec

MFI (190C 2.16kg)

75

LDPE1 1:4, 90C LDPE2 1:4, 90C

0.8

50

0.5

25

0.3

0.0 100% HDPE 10% LDPE 20% LDPE 30% LDPE 40% LDPE

0 100% HDPE 10% LDPE 20% LDPE 30% LDPE 40% LDPE

Figure 1. The Effect of LDPE Concentration on the Blend MFI.

2500 Initial Modulus (MPa) Unstretched Stretch ratio 1-6 2000 Stretch ratio 1-8

Figure 2. Effect of LDPE Concentration on the Shrinkage of 1:4 Stretch Ratio and 90C Tapes.
2500 Initial Modulus (MPa) Unstretched Stretch ratio 1-4 Stretch ratio 1-6 Stretch ratio 1-8

2000

Unstable 1:6, 1:8 40%LDPE1

1500

1500
Unstable 1:8 40%LDPE1

1000

1000

500

500

100% 10% 20% 30% 40% 10% 20% 30% 40% HDPE LDPE2 LDPE2 LDPE2 LDPE2 LDPE1 LDPE1 LDPE1 LDPE1

100% 10% 20% 30% 40% 10% 20% 30% 40% HDPE LDPE2 LDPE2 LDPE2 LDPE2 LDPE1 LDPE1 LDPE1 LDPE1

Figure 3. The Effect of Stretch Ratio at 60C on the Initial Modulus.

500 450 400 350 300 250 200 150 100 50 0 100% 10% 20% 30% 40% 10% 20% 30% 40% HDPE LDPE2 LDPE2 LDPE2 LDPE2 LDPE1 LDPE1 LDPE1 LDPE1 Stress at break (MPa) Unstretched Stretch ratio 1-6 Stretch ratio 1-8
Unstable 1:6, 1:8 40%LDPE1

Figure 4. The Effect of Stretch Ratio at 90C on the Initial Modulus.

500 450 400 350 300
Unstable 1:8 40%LDPE1

Stress at break (MPa)

Unstretched Stretch ratio 1-4 Stretch ratio 1-6 Stretch ratio 1-8

250 200 150 100 50 0

100% 10% 20% 30% 40% 10% 20% 30% 40% HDPE LDPE2 LDPE2 LDPE2 LDPE2 LDPE1 LDPE1 LDPE1 LDPE1

Figure 5. The Effect of Stretch Ratio at 60C on the Stress at Break.

1288 1162 1053 1015 973 1194

Figure 6. The Effect of Stretch Ratio at 90C on the Stress at Break.

1288 % 1162 1053 1015 973 1194

200 175 150 125 100 75 50 25 0

1147

200 175 150

1142

1025

1147

225

Strain at break Strain at break (%)

Unstretched Stretch ratio 1-6 Stretch ratio 1-8

225

Strain at break (%) Strain at break

Unstretched Stretch ratio 1-4 Stretch ratio 1-6 Stretch ratio 1-8
1142 1025 Unstable 1:8 40%LDPE1

Unstable 1:6, 1:8 40%LDPE1

125 100 75 50 25 0

100% 10% 20% 30% 40% 10% 20% 30% 40% HDPE LDPE2 LDPE2 LDPE2 LDPE2 LDPE1 LDPE1 LDPE1 LDPE1

100% 10% 20% 30% 40% 10% 20% 30% 40% HDPE LDPE2 LDPE2 LDPE2 LDPE2 LDPE1 LDPE1 LDPE1 LDPE1

Figure 7. The Effect of Stretch Ratio at 60C on the Strain at Break.

Figure 8. The Effect of Stretch Ratio at 90C on the Strain at Break.

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350 300 250

Stress at yield (MPa)

Unstretched Stretch ratio 1-6 Stretch ratio 1-8

350 300 250

Unstable 1:6, 1:8 40%LDPE1

Stress at yield (MPa)

Unstretched Stretch ratio 1-4 Stretch ratio 1-6 Stretch ratio 1-8

200 150 100 50 0

200 150 100 50 0

Unstable 1:8 40%LDPE1

100% 10% 20% 30% 40% 10% 20% 30% 40% HDPE LDPE2 LDPE2 LDPE2 LDPE2 LDPE1 LDPE1 LDPE1 LDPE1

100% 10% 20% 30% 40% 10% 20% 30% 40% HDPE LDPE2 LDPE2 LDPE2 LDPE2 LDPE1 LDPE1 LDPE1 LDPE1

Figure 9. The Effect of Stretch Ratio at 60C on the Stress at Yield.

8

Figure 10. The Effect of Stretch Ratio at 90C on the Stress at Yield.
8

6 Elastic limit %

Stretch ratio 1:6, stretch temp. 60C Stretch ratio 1:6, stretch temp. 90C Stretch ratio 1:8, stretch temp. 60C Stretch ratio 1:8, stretch temp. 90C
Elastic limit %

Stretch ratio 1:6, stretch temp. 60C Stretch ratio 1:6, stretch temp. 90C Stretch ratio 1:8, stretch temp. 60C Stretch ratio 1:8, stretch temp. 90C

6
Unstable 1:6 (60) 40%LDPE1 Unstable 1:8 (60) 40%LDPE1 Unstable 1:8 (90) 40%LDPE1

0 0% 10% 20% 30%

LDPE2%

0
40%

0%

10%

20%

30%

LDPE1%

40%

Figure 11. The Effect of the Stretch Ratio and Stretch Temperature on the Elastic Limit for LDPE2 Blends.

Figure 12. The Effect of the Stretch Ratio and Stretch Temperature on the Elastic Limit for LDPE1 Blends.

Figure 13. DSC Thermograms of the Films. Tm (C) 129.3 128.7 128.4 127.8 127.4 128.8 128.1 127.8 127.0 H (J/g) 156.7 125.4 135.0 110.5 109.7 110.6 136.3 144.8 87.1

Figure 14. Example Recovery Curve, 100% HDPE Set 1:8 and 90C at 30% Elongation. Key words: blown film tape stretch LDPE HDPE PE polyethylene blend net agricultural monofilament recovery

100% HDPE 10% LDPE1 20% LDPE1 30% LDPE1 40% LDPE1 10% LDPE2 20% LDPE2 30% LDPE2 40% LDPE2

Figure 15. The Effect of LDPE Concentrations on the Melting Temperature and Latent Heat of Fusion.