Malaysian Polymer Journal (MPJ), Vol 2, No.

2, p 58-71, 2007

Silane Grafting and Crosslinking of Metallocene-catalysed LLDPE and LDPE.
A. A. Yussuf1, E. Kosior2 and L. Alban3
1

Industrial Research Institute Swinburne (IRIS), Swinburne University of Technology, 543545 Burwood Road, Hawthorn, Vic.3122, Melbourne, Australia
2

Nextek Pty Ltd, 3 St. Thomas Street, Bronte, NSW 2024, Sydney, Australia

3

Royal Melbourne Institute of Technology, RMIT, Department of Civil and Chemical Engineering – City Campus, 124 Latrobe Street, Vic. 3001, Melbourne, Australia Corresponding author: aayussuf@gmail.com

ABSTRACT:Two grades of metallocene-catalysed LLDPE and one grade of low-density polyethylene (LDPE) have been silane grafted and crosslinked by contact with water and their performance has been compared and evaluated. The effects of vinytrimethoxysilane (VTMOS) levels on the degree of crosslinking for each grade were also studied. It was found that increasing level of silane increases the degree of crosslinking. However, no significant increase of the gel content was observed beyond 1.5 phr of silane concentration. All grades studied are shown to crosslink adequately, albeit with differing sensitivities to the level of silane, curing time and temperature. However, metallocene-catalysed LLDPE grades performed better in terms of crosslinking than LDPE, and among the metallocene-catalysed grades; EG 8150 has achieved a higher degree of crosslinking under the same level of silane concentration, and same processing conditions. The influences of curing time and temperature on the degree and rate of crosslinking were investigated, and it was observed that increasing curing time and temperature had a significant effect of increasing both the degree and the rate of crosslinking for all grades. The mechanical properties of all crosslinked samples are reported and correlated with their silane content results, which shows the increase of tensile strength and decrease of elongation at break. Keywords: crosslinking, silane grafting, metallocene catalysed LLDPE, mechanical property, gel content.

1.0

INTRODUCTION

Crosslinking is a widely used method for the modification of polymer properties. This process involves the formation of tridimensional structure-gels-causing substantial changes in material properties. In many applications there is a need to improve the properties of polyethylene, particularly with respect to heat deformation resistance, chemical resistance, stress cracking, and shrinkage. Crosslinking then is an obvious alternative to improve those properties and it is used today on a large commercial scale [1].

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-H 2 O *CH Si (OR) 3 P CH 2 CH CH 2 CH 2 CH 2 CH 2 - H CH CH 2 CH 2 CHAIN BRANCHING CH 2 CH 2 + P* H3CO Si O OCH 3 CROSSLINK BETWEEN POLYMERS OCH 3 CH 2 H3 CO Si CH 2 CH 2 (a)(OR) Si 3 H2 C CH (b) CH 2 CH 2 Figure 1: Grafting (a) and crosslinking (b) reaction mechanism [13]. the efficiency of radiation crosslinking decreases with thickness and thick sections are difficult to crosslink sufficiently. which form crosslinks via hydrolysis of silanol moieties [9-12]. On the other hand. 2007 Common methods of initiating crosslinking involve macroradical formation via thermal decomposition of peroxide [2-5]. The silane crosslinking process involves at least two stages. and favourable properties in the processed materials. a silane-grafted polymer is prepared using peroxide and vinyl alkoxysilane. the crosslinking step is normally carried out after the polymer has been shaped into product and polymer is in a solid state. gamma or electron beam [6-8]. H 2 O CH 2 POLYMER CH 2 CH 2 RO* CH 2 PEROXY RADICAL CH 2 H3 CO CH2 Si OCH 3 OCH 3 2 CH 2 CH CH 2 CH 2 CH 2 CH2 CH 2 CH * CH 2 H 2 C = CHSi(OR) CH 2 CH CH 2 CH 2 CH 2 3 (VTMOS) GRAFTED COMPOUND H3 CO Si OH OCH 3 GRAFTING CONDENSATION REACTION CATALYST. Figure 1 shows the free radical reactions producing silane grafted polyethylene (a) and mechanism of hydrolysis and crosslink formation through the condensation reaction of silanol groups (b). No. which may be done together. 2. and in the case of peroxide crosslinking. and grafting of silane groups. The grafting step may be performed while the polymer is in either solution or the molten state. and in the second stage. In the first stage. p 58-71. followed by condensation of the hydroxyl groups to form stable siloxane linkage. the silane-grafted polymer is crosslinked by exposure to hot water with catalyst. such as easy processing. low capital investment. Vol 2. high-energy irradiation. The technology of silane grafted and crosslinked polymers is being successfully exploited on a large commercial scale with polyethylene to produce XLPE for electrical cable insulation and water heating pipes [1]. The crosslinking reaction involves hydrolysis of the alkoxy groups by moisture. Silane crosslinking has become an alternative method and gained much attention in recent years because of its various advantages. 59 . speed is limited by the cure and the demands for a certain residence time in the heating zone. R-O-O-R 2 RO * 2 CH 2 CH CH 2 CH 2 CH 2 -CH 3 OH HYDROLYSIS REACTION DECOMPOSITION OF PEROXIDE TO FREE RADIAL CATALYST . In addition to that. Both radiation and peroxide crosslinking techniques require a high investment cost.Malaysian Polymer Journal (MPJ).

Vol 2. Hence. 2. Zhang et al. very few articles have been noted in the literature. the project sponsor. However. processability and good end-use performance for a variety of wire and cable applications [17]. 2. Metallocene-catalysed LLDPE are ethylene-octene copolymer.Malaysian Polymer Journal (MPJ). Sirisinha and Meksawat [19] studied the changes in properties of silane crosslinked metallocene ethyleneoctene copolymer after prolonged crosslinking time. developed from single-site INSITE metallocene catalysed technology. Sen et al. Polymer properties are tabulated in Table 1 60 . the aim of this article is to study the influence of silane concentration. dealing with very different aspects such as formulation. [18] investigated the effects of silane crosslinking of metallocene-based polyethylene on the mechanical and thermal properties and concluded that increasing silane concentrations increases tensile strength and degree of crystallinity decreases slightly with increase of degree of crosslinking. thermal and mechanical properties.1-di-tert-butylperoxy-3. Metallocene or single-site catalysts are able to produce polyethylene and polyethylene copolymers with narrow molecular distributions and uniform distribution of short chain branches. This allows the polymer researcher and manufacturer to explore opportunities that were previously unreachable with traditional polyolefins. was supplied by Kemcor Australia. This research will further extent the knowledge of silane crosslinking and will allow the potential of these materials to be evaluated as new generation materials for demanding applications such as cable sheathing. Vinyl Trimethoxy Silane (VTMOS). Shieh et al [16] have studied the heterogeneous molecular structure and morphology of the silane-grafted water crosslinked LDPE by using DSC fractionation method. As for silane crosslinking of metallocene catalysed LLDPE. [13] investigated the kinetics of silane grafting and moisture crosslinking of polyethylene and ethylene propylene rubber and concluded that both the degree and rate of crosslinking are controlled by the concentration of catalyst and moisture. Australia.0 2. Finally to compare the performances of metallocene catalysed grades to the conventional LDPE. 2007 In the literature. Trigonox 29B Peroxide (1. and also to examine the link between the molecular structures of the metallocene catalysed LLDPE and crosslinking evaluations. The successful development of metallocene catalysed LLDPE was considered to be one of the most significant achievements in the polymer history for the past 20 years [17]. in his study it was not possible to predict the sensitivity of a particular polyethylene to silane crosslinking. reaction kinetics.5-trimethylcyclohexane) and Dibutyl Tin Dilaurate (DBTDL) Catalyst. Bullen [15] studied the silane crosslinking behaviour of low-density polyethylene from different production routes and found that LDPEs can behave quite differently in their response to a standard silane crosslinking formula. were supplied by Dow Chemical Company. No. All additives. which combine the features of narrow molecular weight distribution (MWD).1 EXPERIMENTAL Materials Two grades of metallocene catalysed LLDPE’s (EG 8150 and EG 8200). curing time and temperature on the degree and rate of crosslinking. were supplied by MM cables. which was a commercial grade (LD0231). processing. Cartasegna [14] reported on the molecular and structural parameters of ethylene/propylene rubber (EPR) and low density polyethylene (LDPE) on silane grafting and crosslinking and discussed how these parameters affect the degree of crosslinking. a great number of papers on silane crosslinking have been published. while low density polyethylene (LDPE).3. p 58-71.

The grafting and crosslinking procedures were taken as follows. with residence time of five minutes and a melt temperature on exit from the die of 200°C-205°C. 2. depending on the polymer type. the higher the gel content of the sample. 2007 Table 1: Properties of metallcene catalysed LLDPE and LDPE Properties Polymer Density MFI Octene Crystallinity grade (g/cm) (g/sec) content (%) (%) MW EG 8150 0. the concentrations of silane used were varied from 0 to 2 phr (parts of reagent per hundred parts of polymer). p 58-71. The higher the degree of crosslinking. after which the sample was ready to evaluate its degree of crosslinking.84x105 2 LDPE 0. Weighed specimens (cut into a number of small pieces) were allowed to swell and the soluble portions were extracted in Toluene at 110ºC for 10 hours. The specimens were then dried to a constant weight in a vacuum oven at 70ºC for 5 hours.5 EG 8200 0. The percentage of the weight remaining. Vol 2. No.Malaysian Polymer Journal (MPJ).11x105 1. 2.4 -1 Tensile testing An Instron tensile tester (Series 4400) was used at a crosshead speed of 100 mm min using a 2-kN load cell at room temperature.2 -----43. and the die was maintained at 200°C.87 5 23 1. The pellets were then tumble blended with the requisite quantities of silane and peroxide in a stoppered flask for 15 minutes. All moisture crosslinking was conducted immediately after extrusion and was carried out by immersing the prepared sample sheets in a water bath maintained at different temperatures of 90°C.2 phr and 0. Degree of crosslinking was determined by measuring gel content or insoluble fraction of silane crosslinked samples after extraction.6 2.932 0. hopper of the Brabender extruder (type 832400). nitrogen-gasflushed. with respect to the initial weight.2 Specimen preparation techniques for grafting and crosslinking.06 phr respectively. Barrel temperatures were 150°C.868 0. gave the gel fraction or gel content. 2. In this study. Cold air was blown on to the extruded rod to chill it rapidly before granulation. the required quantity of dibutyl tin dilaurate (DBTDL) catalyst was added to the grafted material in a stoppered flask and immediately extruded generating a 2 mm thick sheet. Metallocene catalysed LLDPE and LDPE (pellets) were dried and preheated in a vacuum oven at 40°C overnight in order to minimise the moisture content of these materials. The grafted compound was transferred into a plastic bag with nitrogen gas and kept in a desiccator to prevent premature moisture curing taking place. while the concentrations of peroxide and catalyst were kept constant at 0. using dumb bell specimens according 61 . A screw speed of 50 rpm was used. 170°C and 190°C working from the hopper. The mixture was transferred to the sealed. The specimens were prepared from crosslinked sheet extruded from a twin screw extruder. For the crosslinking step.3 Gel content measurements The crosslinked and finished samples were removed from hot water and kept at ambient condition over night.5 26 3. 60°C and 25°C for different periods of time.

3 and 4 respectively. is achieved at 60ºC for four hours of curing.2 phr and 0. The effects of curing temperature and time on EG8150. it is shown that the maximum gel content of 83% has been reached after two hours of curing in hot water at 90ºC and then no further gel content increase is observed. peroxide and catalyst. 60ºC and 25ºC) in water for different time intervals (1 to 12 hours). the crosslinking reactions were carried out at different temperatures (90ºC. however takes a relatively longer time (12 hours). which means curing time of two hours at 90ºC is more than enough for this grade to reach the satisfactory degree of crosslinking. The concentrations of additives used were kept constant for all grades i. In Figure 2 for EG 8150. 2. 80%.Malaysian Polymer Journal (MPJ). 100 90 80 70 60 50 40 30 20 10 0 0 1 2 3 4 5 Gel Content ( % ) 25 Degree C 60 Degree C 90 Degree C 6 7 8 9 10 11 12 Curing Time (hours) Figure 2: The effect of curing time and temperature for EG8150 62 . EG8200 and LDPE are presented in Figures 2. and 65% in 12 hours at 25ºC. 2007 to the ISO 37 type II standard. p 58-71. Increasing temperature opens the network of polymer chain reducing density and increasing diffusion. Crosslinking at 25ºC. For other metallocene catalysed grade. and it also causes high mobility of water.1 RESULTS AND DISCUSSIONS Effects of curing time and temperature on the degree of crosslinking In order to study the effects of curing time and temperature on the degree of crosslinking. while it takes 12 hours to achieve about 72% gel content.06 phr for silane. respectively. the degree of crosslinking is lower compared to the other grade (EG 8150). the maximum gel content attained at 90ºC was 74% in two hours and 70% in four hours at 60ºC. As illustrated in these figures the degree of crosslinking is controlled by the time and temperature. Vol 2. 0. At least five specimens were tested for each batch of samples and the average of the results was taken.0 3. Almost similar gel content. No.e at 2 phr. gel content increases slightly and 50% gel content is achieved at two hours of curing. As shown in Figure 3. 3. EG 8200 (Figure 3). The degree of crosslinking increased dramatically with the increase in temperature and time of curing.

Metallocene catalysed grades have higher crosslinking performances than LDPE under the same processing conditions. 63 . Due to this LDPE requires high temperature and longer time of exposure in order to achieve higher gel content [20]. No. 2007 100 90 80 70 60 50 40 30 20 10 0 0 1 2 3 4 5 6 7 Gel content ( % ) 25 Degree C 60 Degree C 90 Degree C 8 9 10 11 12 Curing Time (hours) Figure 3: The effect of curing time and temperature for EG8200 However. Vol 2. it is clearly shown that the rate of gel formation for metallocene catalysed grades was high during the first hour of crosslinking at 90ºC water exposure. 2. For instance. From these results. 100 90 80 70 60 50 40 30 20 10 0 0 1 2 3 4 5 6 7 8 Curing Time (hours) Gel Content ( % ) 25 Degree C 60 Degree C 90 Degree C 9 10 11 12 Figure 4: The effect of curing time and temperature for LDPE. crosslinking of LDPE proceeds very slowly.Malaysian Polymer Journal (MPJ). has the lowest degree of crosslinking for all temperatures compared to the metallocene catalysed grades. This is due to different molecular structure of the resin. and in 12 hours less than 40% gel content is achieved. At ambient temperature. Metallocene catalysed grades have lower crystallinity. and maximum gel content of 70% was reached. frequent short chain branching. p 58-71. for LDPE as shown in Figure 4. for LDPE to reach the maximum gel content of 67% at 90ºC it takes four hours. while for LDPE gel content is less than 50%. and six hours at 60ºC.

All these aspects allow metallocene catalysed grades to have higher crosslinking rate than LDPE. 0. as shown in Table 1. 6 and 7 present the rate constant plots for the EG 8150. which have similar crystallinity and density. Cartasegna [14] reported a higher crosslinking speed in an ethylene/propylene rubber system than in the LDPE. 2. the higher the temperature the higher the rate constants. EG 8200 and LDPE respectively. crosslinking reactions were carried out at different temperatures (90. and the faster moisture diffusion into such a solid state structure will enable rapid moisture curing of metallocene grades. which means this grade has a higher rate of crosslinking than the other grades.2 Rate constant for crosslinking reaction For determining the rate constant for all grades. Vol 2.06 phr respectively. As shown in these figures. and hence. EG 8150 has higher molecular weight and higher octene content than EG 8200. using the slope of the straight line in dependence on the logarithm of relative gel & G ' Gt # ln $ ( ! .[23] proposed a method to characterize the rate of the crosslinking reaction. where G! is maximum gel content . Gt is gel content at time t . EG 8200. For instance. crosslinking time is plotted for all grades. due to its lower crystallinity. 64 . Since grafted silane molecules only exist in the amorphous zone. and as result. 3. EG 8150 grade has the highest rates at all temperatures. leads to a higher rate of water diffusion. By using the above method and gel content against curing time plots (section 3. peroxide and catalyst concentration of 2. This would be attributed to difference in molecular weight and percent octene content. Therefore. Also higher octene content means higher amount of amorphous phase in polymer. This result further proves and indicates that metallocene catalysed grades have better crosslinking than LDPE.1). the EG 8150 grade achieves higher levels of crosslinking than the other grade. and as expected metallocene catalysed grades have a higher rate than LDPE. Similarly.Malaysian Polymer Journal (MPJ). metallocene catalysed grades requires less time for crosslinking than LDPE under the same processing conditions. higher diffusion rate of water. Kelnar et al. 60 and 25ºC) in water using a silane. the ln of relative gel vs. and the slope is termed the “rate constant”. For instance. which have lower crystallinity than LDPE. Figures 5. All polymer grades have different rate constants. The diffusion of water is faster in the amorphous domain than in the crystalline domain [22]. It is interesting to note that the metallocene catalysed grades. The rate constants values for all grades are tabulated in Table 2.2 and 0. 2007 lower density and higher diffusion coefficient. and G0 is initial % G( ' G0 " gel content (zero). It is expected that the higher molecular weight resin will form a tighter physically crosslinked network than the lower molecular weight counterpart at similar crystallinity [21]. perform differently. No. a better silane crosslink distribution can be expected for the metallocene catalysed grades. the rate constant is controlled by temperature. p 58-71.

234x Figure 5: Linear dependence of relative gel on crosslinking time for EG 8150 0 Ln of Relative Gel -1 -2 -3 -4 -5 -6 0 0.5 1 25 Degree C 60 Degree C 90Degree C y = -0. p 58-71.5 2 Crosslinking Time (hours) Figure 6: Linear dependence of relative gel on crosslinking time for EG 8200 65 .0208x y = -2.5 2 Crosslinking Time (hours) 25 Degree C 60 Degree C 90 Degree C y = -2.185x 1. 2.4339x y = -1.Malaysian Polymer Journal (MPJ).354x -1 -2 -3 -4 -5 -6 0 0.524x y = -1. No. 2007 0 Ln of Relative Gel y = -0.5 1 1. Vol 2.

Vol 2.009 0. No.011 0.Malaysian Polymer Journal (MPJ).036 0.5 phr. it is clear that increasing silane content induces a very dramatic change on the degree of crosslinking and similar observations have been reported by Zhang et al [18]. the gel content achieved for EG 8150 was almost 60%.023 0.015 Influence of silane concentration on the degree of crosslinking Figure 8 shows the effects of the silane concentration used during grafting and crosslinking reaction on the gel content.037 0. while concentrations of peroxide and catalyst were kept constant at 0. 2007 0 Ln of Relative Gel -1 -2 -3 -4 -5 -6 0 0. i.1744x y = -0. p 58-71.6448x y = -0.5 2 Crosslinking Time (hours) Figure 7: Linear dependence of relative gel on crosslinking time for LDPE Table 2: Rate constants for crosslinking reaction of all grades Polymer grades EG 8150 EG 8200 LDPE 3. while for EG 8200 that figure was approximately 40%. On the hand. 66 .017 0.06 phr respectively. The concentrations of silane were varied from 0 to 2 phr. At lower levels of silane concentrations.5 phr) was less than 30%.007 0. increasing silane content increases the gel content for all grades. From these results it can be seen that the metallocene catalysed grades could achieve higher gel content at lower silane concentration than LDPE.e 0.8932x 1.5 phr for all grades has no significant effect of increasing the gel content.5 1 25 Degree C 60 Degree C 90 Degree C y = -0. and also the curing temperature of 60ºC was used for a period of four hours.3 Rate constant (min-1) 25ºC 60ºC 90ºC 0.003 0. It must be noted that increasing silane concentration beyond 1. 2. for LDPE the gel content at lower silane concentrations (0. Hence from these results.2 phr and 0. As shown in Figure 8. The reason for this observation is attributed to the possible homopolymerisation of the vinyl silane group reducing the effective level of silane available for grafting.

tensile strength increases gradually with increasing silane concentration from zero to 1. 34±0. The samples were prepared using different amounts of silane content. As shown in Figure 9. this is due to the extensive network and the formation of silane crosslinking structure. On the other hand.85 MPa and 27±0.5 Silane Concentrations (phr) Figure 8: Effect of silane concentration on gel content As expected metallocene catalaysed grades perform better than LDPE at lower silane content. less chain extended LDPE requires more silane grafting. The main reason for this is. All samples were immersed in hot water at 60ºC for a period of four hours. 67 . a further increase of silane concentration from 1. and reaches a maximum of 38±1.5 1 Gel Content ( % ) EG 8150 EG 8200 LDPE 1. 2. The effects of silane concentration on mechanical properties are shown in Figure 9 and 10. while the concentrations of peroxide and catalyst were kept constant at 0.2 phr and 0.0 phr has no significant influence on tensile strength.4 Influence of silane concentration on the mechanical properties. p 58-71.5 to 2. However. the highly chain branched metallocene catalysed grades can be turned into a high crosslink density network at low silane grafting levels more readily than LDPE due to the high degree of substitution on the polymer backbone. This is consistent with the influence of silane concentration on the gel content discussed in the previous section (3.0 MPa. These results indicate that crosslinking increases tensile strength of the crosslinked polymers. 3.06 phr respectively. No.9 MPa for LDPE. Vol 2. 2007 80 70 60 50 40 30 20 10 0 0 0. which is a very stable network due to the high bonding energy of the Si-O-Si crosslink. due to these facts metallocene catalysed LLDPE have higher rate and higher degree of crosslinking than LDPE.5 2 2.5 phr.Malaysian Polymer Journal (MPJ).3). EG 8150 and EG 8200 respectively. Therefore. and therefore longer crosslinking time to achieve a satisfactory network structure.

5 Figure 9: Effect of silane concentration on the tensile strength for all grades. As shown in that figure increasing silane concentration decreases elongation at break slightly. Figure 10 shows the correlation between percent elongation at break and silane concentrations for all grades. 2.5 1 1. 2007 45 40 35 30 25 20 15 10 5 0 0 Tensile Strength (MPa) EG8150 EG8200 LDPE 0.5 1 1. Vol 2.5 2 2. p 58-71.5 Silane Concentrations (phr) EG 8150 LDPE EG 8200 Figure 10: Effect of silane concentration on the percent elongation for all grades.5 2 Silane Concentrations (phr) 2. No. 1000 Elenogation at break (%) 800 600 400 200 0 0 0. 68 .Malaysian Polymer Journal (MPJ). This is unlike the peroxide crosslinking where the presence of a crosslink network generally results in a drastic decrease in elongation at break [19]. On the other hand.

Degree of crosslinking is a function of curing time and temperature.5 phr has no significant change on the degree of crosslinking for all grades. The range of rate constants for metallocene catalysed LLDPE grades from 25ºC to 90ºC are between 0. 69 . 6. Metallocene catalysed LLDPE have higher degree of crosslinking than LDPE under the same processing conditions. The performances of each grade has been evaluated and compared. E. The rate constant for crosslinking reaction is controlled by curing temperature. Benzoyl peroxide as a crosslinking agent for polyethylene. and Jafari. However. density.. the following main conclusions have been drawn: 1. Journal of Applied Polymer Science. Vol 2. 5. 1992. Among metallocene catalysed LLDPE grades.. International Polymer Science and Technology. 34:1209-1216. 5. An investigation of chemical crosslinking effect on properties of high-density polyethylene.015 min-1. molecular weight and percent octane content were found to have a significant influence over the degree of crosslinking and physical performance of the different grades of polymers used. The molecular parameters such as percent crystallinity. Applications of crosslinked polyethylene. G. S.003 to 0. H. J. 2. and Andereopoulos. A. 1987.Malaysian Polymer Journal (MPJ). 2003. Metallocene catalysed LLDPE grades have higher rate constant than LDPE at all temperatures. and percent crystallinity... level of silane concentrations. H. The higher the temperature the higher the rate constant. p 58-71. and those for LDPE are between 0. No. A. and Zelenak. M. Wagenknecht. 4.009 to 0. EG 8150 grade has higher degree of crosslinking than that of EG 8200. 2. Morshedian. 44 (15): 4301-4309. increasing silane concentration beyond 1. Increasing silane concentration was found to give the optimum degree of grafting and subsequent crosslinking. Kampouris. Polymer. 6.. From the results and discussions. The effects of crosslinking on the mechanical properties has been studied. and it was found that increasing silane concentration increases tensile strength for all grades and slightly decreases percent elongation. U. 19 (4): 72-77. Khonakdar.0 CONCLUSIONS Different grades of polymers (metallocene catalysed LLDPEs and LDPE) have been successfully grafted and crosslinked by using silane crosslinking technique. R. 2007 4.036 min-1.0 [1] [2] [3] REFERENCES Rado. P.0 ACKNOWLEDGMENTS The authors wish to express their gratitude to the MM cables an Australian leading cable company for funding this research project. 3.

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