Malaysian Polymer Journal (MPJ) Vol 3, No.

2, p 54-64, 2008

Rheological Studies of Modified Maleated Polyethylene/ Medium Density Polyethylene Blends

Moayad N. Khalaf *, Ali H. AlMowali, and Georgius A. Adam. Chemistry Department, College of Science, Basrah University, Basrah, IRAQ. *Corresponding author: Moayad N Khalaf (moayad_khalaf@yahoo.com) ABSTRACT: A modified maleated polyethylene (MAPE) was blended in a twin screw extruder with the percentage of maleation of 9%. The presence of the maleic anhydride group on the polyethylene backbone increased the ability to bonding with any surface or compound that has functional groups. The use of the maleated polyethylene as a compatibilizer in the polyblend showed high effect in the compatibility between the polymer and the sample in term of the rheological properties. This paper presents the results of an experimental study of the oscillating flow (shark skin and spurt defect) of medium density polyethylene (MDPE) with 1% maleated polyethylene (MAPE). It showed the disappearance of the sharkskin from polyethylene surface and a complete elimination of discontinuity in the flow curve of MDPE, thus disappearance of the spurt defect phenomena. Keywords: rheological properties, twin screw extruder, maleated polyethylene, blend, sharkskin 1.0 INTRODUCTION

Irregularities appearing on the surface of extrudate often limit the rate of production of polyethylene processing operations such as film blowing [1]. Manufacturers specifically wish to increase the flow rate, reduce energy cost, and minimize the occurrence of extrudate irregularities [2]. The irregularities are generally classified into two groups: (1) surface irregularities, which often occur under constant shear stress regardless of extrusion temperature, and (2) gross irregularities ( i.e. melt fracture), which occur at high shear stress[3]. Surface irregularities vary with unsteady flow conditions from loss of surface gloss shark skin to melt fracture [4-6] (see Figure 1). The rate of production in processing operations has certain limit to avoid the surface defects, since these irregularities such as melt fracture typically occur at a lower throughput [3]. A number of chemicals have been used as processing aids in an attempt to minimize surface roughness during polyethylene processing. The flow behavior of HDPE/ polyamide 11 (PA11) blends with 1% PA11 could eliminate the pressure oscillation region of the flow curve of HDPE. The test was conducting with capillary extrusion using a constant piston speed device with a plane capillary entrance of (180oC) [4], Fumed silica and carbon black, both at 7% weight filling level, completely eliminated the pressure oscillations to HDPE. At 3% weight filling, the effect of the fillers on the oscillation amplitude was insignificant [5]. The addition of hyperbranched polymers (HBPs) to LLDPE successfully eliminated surface defects under normal processing conditions for LLDPE [7]. Experiments were performed in capillary and slit rheometers to determine the effects of fluoropolymers presence at the polymer-wall interface on wall slip and extrudate distortion of a molten HDPE. Two fluoropolymers were used to modify the interface. It was found that one of the polymer had reduced the slip compared to the clean interface while, the other increased the slip [8].

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Malaysian Polymer Journal (MPJ) Vol 3, No. 2, p 54-64, 2008

(a)

(b)

(c)

(d)

(e)

Figure 1: (a) stable; (b) sharkskin; (c) slip-stick, showing alternating smooth and sharkskin regions (d) wavy, initial portion of the upper branch of the flow curve; and (e) gross melt fracture [9,10].

2.0 2.1

EXPERIMENTAL Materials

Medium density polyethylene (MDPE) SCPILEX TR-401 and Low Density Polyethylene (LDPE) SCPILEN 464 were supplied by state compan for petrochemical industry (SCPI) in Basrah, MFI=0.11 gm/10min, density=0.941 gm/cm3; MFI= 4.0 gm/10min, density= 0.9220 gm/cm3 respectively. Maleic anhydride (MA) industrial grade was supplied by Adrash Chemicals and Fertilizers Ltd., Udhna Gujorat-India. Maleic anhydride was used without purification. 2ethyl terbutyl-hexanoate peroxide (C67), peroxide content 98% was supplied by Pergon G.m.b.h Company. High purity Soltrol (130 Kerosene) was purchased from Baji refinery (Iraq), with flash point of 53 min. and aniline point between 83 87 oC.

2.2 2.2.1

Instrument Rheological Measurements

Rheological properties were carried out by using a capillary rheometer device (Instron model 3211), ASTM D-3835. The diameter of the capillary is 1.257 mm, the length to diameter (L/D) ratio of 80.9, with an angle of entry of 900. Load weighing which dropped on the polymer melts by plunger transversed from the top to the bottom of the barrel was constant (2000 kg). The constant plunger speeds ranged from 0.06 to 20.0 cm. min-1, the extrusion temperature was 2000C.

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2.2.2

Mixer Instrument

Mixer-600 attached to Haake Rhechard Torque Rheometer supplied by Haake Company. The RPM of the Mixer can be controlled depending on the shear rate. 2.2.3 Melt Indexer

The melt indexer type Dinysco 4000 supplied by Kayness polymer test system was used to measure the melt index of the prepared samples (temperatures= 190C, load= 2.160 kg). 2.2.4 FTIR-Measurements

Fourier transform infrared spectrophotometer Shimadzu FTIR-84005 was used for measuring the IR-Spectra for the samples. 2.2.5 Photomicroscope

Digital camera type CCD camera attached to Photomicroscope (wild) was used to photographing the samples. 2.2.6 Modified Twin Screw Extruder

For continuous production of the maleated polyethylene a continuous production system was developed by modifying compounding twin screw extruder with the following specifications: 1-Four heating zones. 2-Production rate = 2 ton/day 3-Length/Diameter (L/D) = 40 4- Die with 25-50 holes with 2 mm diameter was attached at the end of the extruder to get the fiber extrudate of 2 mm diameter. 5-Water bath. 6-Pelletizer. 7-A modification was added to the extruder hopper via a line to feed the peroxide solution by a dozing pump. The extruder was supplied by the Japan Steel Company and schematic diagram for the modified extruder used in the production process is shown in Figure 2.

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Figure 2: Schematic diagram of the extrusion production for the maleated polyethylene plant a) (Polyethylene pellet + maleic anhydride) storage. b) Drive. c) Sealing end. d) Feeding hub. e) Twin-screw extruder. f) Heating and cooling jacket. g) Extrusion die. h) Cutting machine. i) Peroxide storage. j) Peroxide feeding line.

2.3 2.3.1

Polyethylene (PE)-Maleic Anhydried Grafting Laboratory Preparation Method

Low Density Polyethylene (LDPE) Grade 464 was fed to a Mixer-600 attached to Haake Record meter at temperature = 150C and RPM = 64. After 5 min, maleic anhydride was fed portion wise and the peroxide was added drop wise. The modified polyethylene was characterized and evaluated via the degree of maleation (%). 2.3.2 Mass Production

For continuous production of the maleated polyethylene, the modified compounded twin screw extruder was used. The temperature of the extruder zones was adjusted to 100, 120, 140 and 160 C respectively while the temperature of the die was 100C. The addition

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of the solid materials (polyethylene and maleic anhydride) to the hopper was controlled automatically by weighing feeder according to the laboratory work (Haake mixer). The feed quantities from both components were mixed and charged into the extruder, while the peroxide solution was fed by a dozing pump through stainless steel line to the bottom of the hopper of the extruder. The peroxide amount was determined with 3% concentration based on polyethylene feed. The fibrous maleated polyethylene extrudates were cooled in the water bath then fed to a pelletizer to get pellets with size of 2x4 mm. 2.3.3 Preparation of the MAPE/MDPE Blend

Medium Density Polyethylene (MDPE) Grade TR-401 and the MAPE was fed to a Mixer-600 attached to Haake Record meter at temperature = 160OC and RPM=32, the percent of MAPE was 1% in the blend.

2.4 2.4.1

Evaluation of the Maleated Polyethylene Determination of the Degree of Maleation

Standard procedure was adopted thus [11] samples from the maleated polyethylene was dissolved under reflux in xylene at a concentration of 1% weight/volume, followed by the addition of an excess amount of 0.3M trichloroacetic acid solution in xylene. The mixture was refluxed for 90 min. to drive the ring opening reaction of epoxy with the acid to completion. The hot solution was titrated immediately with 0.05 N ethanolic KOH using three to four drops of 1% thymol blue in DMF. The deep blue color was back- titrated to a yellow end point by against 0.05 N isopropanolic HCl in the hot solution. The acid number and the grafted percentage of maleic anhydride were determined from the following relationships [13,14].

Acid Number (mg KOH / g polymer) =

ml KOH x N KOH x 56.1 Polymer (g)

Therefore MAH (%) = Acid . o 98 n 2. 6.1 5 The percent of maleation was found equal to 9%.

2.4.2

Melt Index of the Maleated Polyethylene:

The melt flow index was originally chosen for polyethylene to evaluate the melt characteristics under conditions related to it processing. The melt viscosity (melt index) was measured adopting polyethylene standard procedure commonly used for polyethylene evaluating and quality control measurement. The rate of extrusion (in 10 min.) of the polyethylene and maleated polyethylene samples were measured through a standard die. Typical results are shown in Table 1. It was observed that the melt index of maleated polyethylene decreased with respect to the base polymer. The result is in agreement with the induced ability of maleated polyethylene to increase the intermolecular forces between the polymer chain via the

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chemical and physical bonds. These intermolecular forces presence in the polymer due to polar anhydride groups, caused the flow of the polymers chains have been restricted and the melt index value decreased. Table 1: The Melt Index (MI) of base polyethylene and maleated polyethylene (MPE) Polyethylene (grade) LDPE 464 2.5 Results and Discussion MI (g/10 min) 4.0 Maleated MI (g/10 min) 1.578

In order to insert randomly single functional groups onto polyethylene chains, maleic anhydride may be considered as an appropriate unsaturated molecule. Polyethylene with over 10% grafting of maleic anhydride was quite similar in its chemical characteristics (activity) which was the copolymer of ethylene-maleic anhydride. This is common industrial product used and as curing binder between solid epoxy powder coat and polyethylene top coat. Grafted maleic anhydride and copolymers of ethylene-maleic anhydride have both similar solubility's in hot xylene and acetone i.e. the cross linked polyethylene was insoluble in both solvents. The comparison of the infra-red spectra of the pure polyethylene and the maleated polyethylene sheet, Figures 3 and 4, has confirmed the presence of maleic anhydride units on polyethylene backbones. In comparison with the infra-red spectrum of pure polyethylene, the grafted polyethylene showed very strong bonds at 1779 cm-1 and 1859 cm-1, which are characteristics of cyclic anhydride. The bond at 1221 cm-1 corresponds to C-O stretching vibrations in the cyclic anhydride [11, 12 and 14].

Figure 3: FT-IR spectra of pure polyethylene

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Figure 4: FT-IR spectra of maleated polyethylene

2.5.1

Melt Flow Instability of Medium Density Polyethylene (MDPE)

The flow behavior of MDPE was studied, Figure 5 shows in a schematic way of the two branches (discontinuity) flow curve for MDPE extruded in a capillary with an entrance angle of 900. When the flow rate is increase [at a first critical shear stress value, 1, (329.8 KPa)] the stability of the flow is disturbed and resulting in a certain level of surface roughness. Generally denoted as shark skin region, see Figure 6-b. MDPE exhibit a pulsating flow, the onset of this melt defect occurs at a second critical shear stress value 2 (442 KPa). This type of melt defect (spurt defect) is characterized by significant, largely periodical distortions of the extrudate geometry and pressure oscillation in the barrel and the die entry, see Figure 6-c .The screw distortions of the extrudate observed in the melt fracture region appear to be due to disturbances at the die inlet.

Figure 5: Flow curve of MDPE. Data based on temperature 2000C, capillary diameter 1.257 mm, (L/D) ratio 80.9, with an angle of entry is 900.

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2.5.2

Rheological Properties of Polyethylene Blend (MAPE / MDPE):

It was observed that the addition of 1% MAPE to MDPE had cause disappearance of the shark skin phenomena of MDPE (see Figure 7-a) and eliminated the pressure oscillation region of the flow curve of MDPE (see Figure 8).The disappearance of pressure oscillations resulted in a smooth extrudate surface (see Figure 7-b).The nonpolar characteristics of polyethylene often lead to poor interfacial adhesion properties with other materials such as dies surfaces. Ramamurthy had proposed that the vanishing of the instabilities was consequence of improved adhesion [2]. The adhesive strength, even under ambient conditions, is known to depend on several factors including the cleanliness of the substrate and the detailed attractive forces (dispersion, dipolar, induction, hydrogen bonding, chemical cross linking, etc.) at the interface [15]. Therefore, the blend of maleated polyethylene (MAPE) with MDPE will increase the ability of the polymer chains to bond together via the chemical and physical bond. In addition, the adhesion force between the polyethylene blend and die surface was increased, resulting the disappearance of flow instability of MDPE. The increase in adhesion force is due to the presence of the carboxyl group and hydroxyl group of the maleic anhydride on the backbone of the low density polyethylene (LDPE), thus improve of the adhesion property (see Figure. 9).

(a)

(b)

(c)

(d)

Figure 6: Photographs of MDPE surface at temperature 200 oC

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(A) 40X

16X

(B) 40X

Figure 7: Photographs for the polyethylene blend at addition 1% MAPE to MDPE, (A) Shows disappearance the shark skin phenomena at a first critical shear stress value [1]; (B) Shows disappearance the spurt defect of MDPE surface at a second critical shear stress value [2].

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Figure 8: Flow curve of polyethylene blend (MAPE / MDPE).Data based on temperature 200oC, capillary diameter 1.257 mm, (L/D) ratio 80.9, with an angle of entry is 90o.

Figure 9: Schematic representation of maleic anhydride units on polyethylene backbones, which increase the adhesion force between the polyethylene blend and die surface.

3.0

CONCLUSION

The use of modified twin screw extruder, has improved the properties polymer (polyethylene) with high percent of maleation which can be achieved with some modification attached to the extruder to control the addition of the peroxide. Particularly interesting is that the addition of 1% MAPE resulted in disappearance of the shark skin from polyethylene surface and the complete elimination of discontinuity in the flow curve of MDPE, thus disappearance of the spurt defect phenomena.

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REFERENCES [1] Hatzikiriakos, S. G. Stewart, C. W. Dealy, J. M., 1993, Effect of Surface Coatings on Wall Slip LLDPE, Int. Polym. Process; 3, 30-35. Ramamurthy, A.V. 1986, Wall Slip in Viscous Fluids and Influence of Materials of Construction, J. Rheology; 30, 337-357. Ye Hong, J. J. Cooper-White, M. E. Mackay, C. J. Hawker, E. Malmstrm, and N. Rehnberg,1999, A novel processing aid for polymer extrusion: Rheology and processing of polyethylene an hyperbranched polymer blends, J. Rheology; 43, 781793. Dospisil, D., Kubat, J., Saha, P. Pavlinek V. and Becker, J. 1998, Rheological Behaviour of HDPE/PA11 Blends, Int. Polym. Process; 13, 40-49. Dospisil, D. Kubat, J. Saha, P. Trlica J. and Becker, J. Instabilities of Filled HDPE, Int. Polym. Process.; 13, 91-98. 1998, Melt Flow

[2]

[3]

[4]

[5]

[6]

Becker, J. Bengtsson, P. Klason C. and Kubat, J. 1991, Pressure oscillations during capillary extrusion of high-density polyethylene , Int. Polym. Process.; 6,318-325. Ye Hong, Hawker, C.J. Malmstrom, E. and Rehnberg, N. 1999, A novel processing aid for polymer extrusion: Rheology and processing of polyethylene and hyperbranched polymer blends, J. Rheology; 43,781-793. Hatzikiriakos S. G.and Dealy, J.M., 1993, Effects of Interfacial Conditions on wall Slip and Sharkskin Melt Fracture of HDPE, Int. Polym. Process.; 3, 36-44. Pudjijanto, S. Denn, M.M., 1994, A stable ``island'' in the slip-stick region of linear lowdensity polyethylene, J. Rheology; 38, 17351744.

[7]

[8]

[9]

[10] Kalika, D.S. Denn, M.M., 1987, Wall Slip and Extrudate Distortion in Linear LowDensity Polyethylene, J. Rheology, 31, 815834. [11] Ghaemy, M. and Roohina, S., 2003, Grafting of Maleic Anhydride on Polyethylene in a Homogenous Medium in the Presence of Radical Intiators, Iranian Polymer Journal; 12, 21-29. [12] Doney, W.G.; US Patent 2002002880; (2002). [13] Sung Joon Oh, Jin Chul Jung and Wang-Cheol Zin, 2001, Synthesis and Surface Property Variations of Polypropylene-graft-poly(ethylene glycol), J. of Colloid and Interface Science; 238, 43-47. [14] J.M. de Gooijer, 2002, Ph.D. Thesis; Technische Universiteit. Eindhoven. [15] Minford, J.D. (editor) , Treatise on adhesion and adhesives, 1991,UK, Marcel Dekker Ltd, vol. 7, Chapter 1, p. 119.

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