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Malaysian Polymer Journal (MPJ) Vol 3 No.

2, p 39-53, 2008

Low Density Polyethylene-Nanoclay Composites: The Effect of Poly(acrylic acid) on Mechanical Properties, XRD, Morphology Properties and Water Absorption Supri A.G, H. Salmah, and K. Hazwan School of Material Engineering, University Malaysia Perlis (UniMAP), 02600, Arau, Perlis. Malaysia *Corresponding author: Supri A.G. (supri@unimap.edu.my) ABSTRACT: Effect of poly (acrylic acid) on mechanical properties, X-ray diffraction, morphology properties, and water absorption of low density polyethylene / nanoclay composites have been prepared by melt intercalation. The LDPE / nanoclay composites were produced using the melt compounding technique in an internal Z-Blade mixer at 190C and rotor speed of 50 rpm. The compatibilizer used in this study was poly(acrylic acid) (PAA). All the composites were characterized by Instron machine, X-ray diffraction and Scanning electron microscopy. The results indicate at 2.5 phr and 5.0 phr of nanoclay loading with and without PAA shows better tensile strength and modulus of elasticity compare to other composition. These enhanced properties are due to the homogenous dispersion of nanoclay in LDPE matrix, which is evidenced from the structure that evaluated using XRD and SEM in LDPE/nanoclay composites. The presence of PAA of all compositions are dramatically enhanced homogenous dispersion due to the existed of polar and nonpolar group in the poly (acrylic acid). Keywords: nanoclay, poly(acrylic acid), low density polyethylene, polymer matrix composites

1.0

INTRODUCTION

Nanocomposites have attracted attention in recent years because improved mechanical, thermal, solvent resistance and fire retardant properties compare to the pure or conventional composite materials. Therefore, much work has focused on developing polymer/clay nanocomposites using various polymers [1-2]. Depending on the clay type and chemical structure of the polymer, several methods have been developed to synthesize polymer/clay nanocomposites. The common technique to produce polymer/clay nanocomposites is by melt compounding, which is the easiest and most cost effective method to produce nanocomposite materials. The technique induces the formation of nanocomposites structure by subjecting shearing force at high temperature [3-4]. Ren et al. [4] studied poly (vinyl chloride)/compatibilizer /organophilic-montmorillonite nanocomposites by melt intercalation. They used VAc (vinyl acetate) copolymer as a compatibilizer. They succeeded in getting intercalated nanocomposites and fully exfoliated nanocomposites. Their results indicated that the clay in the composite was barely intercalated [5-6]. Therefore, there is still a need for research to address the question of how to obtain fully exfoliated nanocomposites [7-12]. This study examines the feasibility of melt intercalation for preparing better exfoliated PE/clay nanocomposites with various compatibilizers and characterizes their resulting physical properties. This article reports the effects of nanoclay content and the addition of a compatibilizer on mechanical properties, morphology properties, X-ray diffraction, and water absorption of low density polyethylene/nanoclay composites were investigated and discussed.

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Malaysian Polymer Journal (MPJ) Vol 3 No. 2, p 39-53, 2008

2.0 2.1

EXPERIMENTAL Materials

Low density polyethylene (LDPE) (melt flow index = 0.26, melting temperature = 98115C, processing temperature at 134-210C, and density is 0.91-0.94 g/cm3.) was obtained from Malayan Electro Chemical Industry, Penang, Malaysia. Nanoclay and poly (acrylic acid) were supplied by Mega Makmur Sdn. Bhd. Seberang Prai, Penang 2.2 Preparation of LDPE/Nanoclay Composites

The experiment without PAA had been prepared by referring the formulation is shown in Table 1. Blend ratios of LDPE to nanoclay composite was fixed as 100/0, 100/2.5, 100/5, 100/7.5 and 100/10. LDPE material was charged into the blade Z-Mixer mixing chamber at 1800C and a rotor speed of 50 rpm for 5 minutes. Nanoclay material was added into the blade Z-Mixer for the next 5 minutes and wait the compound became homogeneous after 10 minutes. The molten mixing was immediately removed from the mixed chamber and sheered on cold two-roll mill. The experiment with the addition of PAA had been prepared by using the formulation is shown in Table 2. LDPE was charged into the blade ZMixer mixing chamber for 5 minutes with the rotor speed of 50 rpm. After the compound became homogeneous, was added the PAA and allowed to equilibrate for 10 minutes. Mixing was then continued until a constant torque was obtained. The total mixing time was 20 min. The compound was removed from the mixer and sheeted on a cold two-roll mill.

Table 1: Formulation of LDPE / nanoclay composites without poly (acrylic acid )

Blend Composition LDPE LDPE/nanoclay 2.5 LDPE/ nanoclay 5.0 LDPE/ nanoclay 7.5 LDPE/ nanoclay 10.0 LDPE 100 100 100 100 100

Phr Nanoclay (NC) 2.5 5.0 7.5 10.0

Table 2: Formulation of LDPE / nanoclay composites with the addition of poly (acrylic acid )

Blend Composition LDPE LDPE/ nanoclay 2.5 LDPE/ nanoclay 5.0 LDPE/ nanoclay 7.5 LDPE/ nanoclay 10.0 LDPE 100 100 100 100 100

Phr Nanoclay (NC) 2.5 5.0 7.5 10.0

PAA 6 6 6 6

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Malaysian Polymer Journal (MPJ) Vol 3 No. 2, p 39-53, 2008

2.3

Compression Molding

The samples of composites were compression molded in an electrically heated hydraulic press. Hot-press procedures involved pre-heating at 180 0C for 4 min, followed by compressing for 4 min at the same temperature. Tensile tests were carried out with a Tensometric tensometer M 500. Test was done according to ASTM D638. Dumbbell specimens of 2 mm thickness were cut from molded sheets with a Wallace die cutter S6/1/4.A. Five specimens were used in each case and the median value was selected. Tensile strength, elongation at break, and modulus of elasticity were recorded directly from the digital displays at the end of each test. 2.4 Scanning Electron Microscope (SEM)

Studies on the morphology of the tensile fracture surfaces of the LDPE/nanoclay composites were carried out using a scanning electron microscopy (SEM), model Leica Cambridge S-360. The fracture ends of specimens were mounted on aluminium stubs and spotter coated with a thin layer of gold to avoid electrostatic charged during examination. 2.5 X-ray Diffraction (XRD)

Wide-angle X-ray diffraction measurement was carried out using a D8-advance Xray diffractionmeter with Cu K radiation ( = 0.154 nm) and a scanning rate of 20/min, diffraction angle from 10 and 800. Braggs equation, = 2d sin , was used to calculate the d-spacing. The specimens for XRD were 1 mm x 1mm2 cut from molded sheets with 1 mm thickness. 2.7 Water Absorption Test

Three dumb-bell samples used for tensile measurements were used in this study. Water absorption test carried out according to ASTM standard D 750-95. It involved total immersion of the samples in distilled water at room temperature, i.e., 300C. All the specimens were previously dried in an oven at 500C for 12 h and then stored in a dessicator. The water absorption test was determined by weighing the specimens at regular intervals using a balance (Mettler type AJ150) with a precision of 1 mg. The percentage of water absorption was calculated by:

Water absorption (%) =

Ww Wd x 100% Wd

(1)

Where Ww and Wd are original dry weight and weight after exposure, respectively. The average reading of three samples was taken.

3. 0 3.1

RESULTS AND DISCUSSION Tensile Properties

Figure 1 shows the effect of blend composition on tensile strength of LDPE/nanoclay composite with and without PAA. It can been seen that tensile strength for LDPE/nanoclay composite is increasing at the blend composition of clay 2.5 phr and clay 5.0 phr and decreasing at the blend composition of clay 7.5 phr and 10.0 phr. This is because the good dispersion of nanoclay is achieving with the LDPE that lead to the higher tensile strength. According to Liang et al. [12], the nano-dispersed clay with high aspect ratio possesses a higher stress bearing capability and efficiency. Stronger interaction between nanoclay

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Malaysian Polymer Journal (MPJ) Vol 3 No. 2, p 39-53, 2008

layers and polymer molecules associated with larger contact surface result in more effective constrain of the motion of polymer chain. The decreasing of the blend composition of nanoclay above 5.0phr is because the homogenous structure of nanoclay with the LDPE is difficult to achieve. According to Ardhyananta and Ismail [6], at high filler loading, the organoclay is found in the form of microscale filler due to preferred stacking of the individual silicate layer in ordered structure (tactoids). Arroyo et al. [7] also reported that low reinforcing effect is due to the formation of a conventional composite at the micro scale.

12 10 Tensile Strength (MPa) 8 6 4 2 0


LDPE LDPE/nanoclay2.5 LDPE/nanoclay5

uncompatibilizer compatibilizer(PAA)

LDPE/nanoclay7.5 LDPE/nanoclay10

Blend Composition(Wt%)

Figure 1: Tensile strength versus blend composition of LDPE/nanoclay composites with and without poly(acrylic acid). The result for the LDPE/nanoclay with poly(acrylic) acid also shows the same pattern where the tensile strength increase at blend composition of clay 2.5 phr and 5.0 phr and decrease with blend composition of clay 7.5 phr and 10.0 phr. The present of the poly(acrylic acid) in the polymer matrix composite it is believed as the main factor why the tensile strength is increasing compare with the polymer matrix composite without poly(acrylic acid). The poly(acrylic acid) substance have both, polar and non-polar group that will be interaction with the clay and the LDPE. According to Lee et al. [11] the presence of more polar group and ionic interaction between polymer chain and silicate layer increase the tensile strength of the nanocomposites. The elongation at break versus blend composition of LDPE/nanoclay composite shows a decreasing pattern for all blends composition (Figure 2). The result is same for the LDPE/nanoclay composites with the present of the poly(acrylic acid). According to Ardhyananta and Ismail [6], the reduced elongation at break is due to the formation of micro filler and poor interaction between matrix and filler. Therefore, the polymer wills loss their plastic properties due to the increased of the stiffness value. The values for nanoclay with poly(acrylic acid) shows a big different compare without the present of poly(acrylic acid). It show that the existences of poly(acrylic acid) will gradually drop the plastic properties of the composite and make the composite become difficult to elongate. The reduced elongation at break is a agreement with the increasing stiffness of LDPE/nanoclay composites with poly(acrylic acid) .

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Malaysian Polymer Journal (MPJ) Vol 3 No. 2, p 39-53, 2008

400
uncompatibilizer

350 Elongation at Break (%) 300 250 200 150 100 50 0


LDPE LDPE/nanoclay2.5 LDPE/nanoclay5

compatibilizer(PAA)

LDPE/nanoclay7.5 LDPE/nanoclay10

Blend Composition (Wt%)

Figure 2: Elongation at break versus blend composition of LDPE/nanoclay composites with and without poly(acrylic acid). Figure 3 shows the modulus of elasticity versus blend composition of LDPE/nanoclay composites with and without poly(acrylic acid). The Modulus of elasticity for nanoclay with poly(acrylic acid) is increase in all blend composition compare the nanoclay without poly(acrylic acid) and pure LDPE. The result is due to the presence of more filler and good interaction between the filler and the matrix. In addition of the LDPE/nanoclay composite sample with poly(acrylic acid) for 2.5 phr and 5.0 phr shows both increase properties for tensile strength and modulus of elasticity. According to Uhl et al. [9], the filler particles reduce the molecular mobility of polymer chains resulting in a less flexible material with a higher tensile strength and Youngs modulus.

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Malaysian Polymer Journal (MPJ) Vol 3 No. 2, p 39-53, 2008

160
uncompatibilizer

140

compatibilizer(PAA)

Modulus of Elasticity (MPa)

120 100 80 60 40 20 0 LDPE LDPE/nanoclay2.5 LDPE/nanoclay5 LDPE/nanoclay7.5 LDPE/nanoclay10

Blend Composition (Wt%)

Figure 3: Modulus of elasticity versus blend composition of LDPE/nanoclay composites with and without poly(acrylic acid).

3.2

Morphology Properties

In morphology properties, it can be seen that the effect of filler loading with the addition of poly(acrylic acid) on the tensile fracture surface micrograph for the LDPE/nanoclay composites. Figure 4 shows the tensile fracture surface micrograph of the pure LDPE as the comparison. We can see the fracture surface is soft and smooth. Figure 5 shows the tensile fracture surface micrograph of the LDPE/nanoclay 2.5 phr composite. The tensile fracture surface is smooth with high degree of fibrils and there are plastic deformations of the matrix, which indicate ductile failure mode. Figure 6 shows the micrograph of the LDPE/nanoclay 2.5 phr composite with poly(acrylic acid). It shows rougher surface compare with Figure 5, this is in agreement with the improvement of tensile strength of the nanocomposite.

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Malaysian Polymer Journal (MPJ) Vol 3 No. 2, p 39-53, 2008

Figure 4: SEM micrograph of tensile fracture surface of LDPE

Figure 5: SEM micrograph of tensile fracture surface of LDPE/nanoclay 2.5 phr composites

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Malaysian Polymer Journal (MPJ) Vol 3 No. 2, p 39-53, 2008

Figure 6: SEM micrograph of tensile fracture surface of LDPE/nanoclay 2.5phr composites with poly(acrylic acid). Figure 7 shows the tensile fracture surface micrograph on LDPE/nanoclay 5 phr composite. The fracture surface is ductile failure mode and has the surface less smooth compare with Figure 5. The presence of matrix fibrils also increases compare with the LDPE/nanoclay 2.5 phr composite. Figure 8 shows the existence of poly(acrylic acid) on LDPE/nanoclay 5 phr composite. The presences of poly(acrylic acid) make the interaction between the matrix and the filler increased, thus producing the smooth surface. It is can be show by the tear line present in the Figure 8. This corresponds to loss of plastic deformation and high tensile strength.

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Malaysian Polymer Journal (MPJ) Vol 3 No. 2, p 39-53, 2008

Figure 7: SEM micrograph of tensile fracture surface of LDPE/nanoclay 5 phr composites

Figure 8: SEM micrograph of tensile fracture surface of LDPE/nanoclay 5 phr composites with poly(acrylic acid)

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Malaysian Polymer Journal (MPJ) Vol 3 No. 2, p 39-53, 2008

Figure 9 shows the tensile fracture surface micrograph of the LDPE/nanoclay 10phr composite. As the filler loading increase, the formations of filler are founding to be difficulties to achieve homogeneous dispersion within the matrix. The lack of this homogeneous dispersion is due to excessive filler loading in the composite. It is produce lower tensile strength properties with the existence of void at the fracture surface. Figure 10 shows the SEM micrograph of tensile fracture surface of the LDPE/nanoclay 10phr composite with poly(acrylic acid). The excessive of filler loading can be seeing from the existence of void at the fracture surface.

Figure 9: SEM micrograph of tensile fracture surface of LDPE/nanoclay 10 phr composites

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Malaysian Polymer Journal (MPJ) Vol 3 No. 2, p 39-53, 2008

Figure 10: SEM micrograph of tensile fracture surface of LDPE/nanoclay 10 phr composites with poly(acrylic acid)

3.3

XRD Analysis

The XRD diffractograms for LDPE, LDPE/nanoclay 2.5 phr, LDPE/nanoclay 2.5 phr with PAA, LDPE/nanoclay 5 phr and LDPE/nanoclay 5 phr with PAA composites are shown in Figures 11-13. The d-spacing (spacing between the planes in the atomic lattice) values were calculated using the Braggs Law. An increased in the degree of coherent layer stacking of the clay would lead to peak broadening and increases of intensity in wide angle x-ray. Figure 11 shows the XRD diffractogram for LDPE. It can be seen that LDPE is partly crystalline and partly amorphous structure due to the existence of sharp narrow diffraction peaks and broad peak. The d-spacing at 2=19.8 is 4.479 . XRD diffraction for LDPE/nanoclay 2.5 phr and 5 phr composite at Figure 12 shows a crystalline pattern structure with the d-spacing value at 2=21.96 and 2=21.32 are 4.043 and 4.163 respectively. The peak shifts to a higher angle compare with the LDPE, which correspond to the distance between interlayer decreases. The lower d-spacing value is at filler loading 2.5 phr. As the filler loading increases the composite become more crystalline due to the present of sharp narrow diffraction peaks. Figure 13 shows XRD diffractogram for composite with PAA. XRD diffraction for LDPE/nanoclay 2.5 phr and 5 phr composite also shows the same pattern as Figures 12 but with the d-spacing value at 2=22.0 and 2=21.40 are 4.035 and 4.147 respectively. The interlayer distance also decreases with the increases of the filler loading. The lower interlayer value is at filler loading 2.5 phr.

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Malaysian Polymer Journal (MPJ) Vol 3 No. 2, p 39-53, 2008

1800

1600

1400

1200

Intensity

1000

800

600

400

200

0 10 12 59 61 14.1 16.1 18.2 20.2 22.2 24.3 26.3 28.4 30.4 32.4 34.5 36.5 38.6 40.6 42.6 44.7 46.7 48.8 50.8 52.8 54.9 56.9 63 65.1 67.1 69.2 71.2 73.2 75.3
75.9

77.3
78

2 theta

Figure 11: XRD diffractogram of LDPE

18000
LDPE

16000

LDPE/Nano Clay 5.0 phr LDPE/Nano Clay 2.5 phr

14000

12000

Intensity

10000

8000

6000

4000

2000

0 10 12.1 14.1 16.2 18.2 20.3 22.4 24.4 26.5 28.5 30.6 32.7 34.7 36.8 38.8 40.9 43 45 47.1 49.1 51.2 53.3 55.3 57.4 59.4 61.5 63.6 65.6 67.7 69.7 71.8 73.9

2 theta

Figure 12: XRD diffractogram of LDPE and LDPE/nanoclay 2.5 phr and 5.0 phr composites

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79.4

Malaysian Polymer Journal (MPJ) Vol 3 No. 2, p 39-53, 2008

20000
LDPE LDPE/Nano Clay 5.0 phr with PAA LDPE/Nano Clay 2.5 phr with PAA

18000

16000

14000

12000 Intensity

10000

8000

6000

4000

2000

0 10 31 52 12.1 14.2 16.3 18.4 20.5 22.6 24.7 26.8 28.9 33.1 35.2 37.3 39.4 41.5 43.6 45.7 47.8 49.9 54.1 56.2 58.3 60.4 62.5 64.6 66.7 68.8 70.9 73 75.1 77.2 79.3

2 theta

Figure 13: XRD diffractogram of LDPE and LDPE/nanoclay 2.5 phr and 5.0 phr composites with poly(acrylic acid)

The existence of PAA in the composite system is seeing to decrease the distance of d-spacing in the composite. It is an agreement that the PAA will make the interaction between the filler and the matrix become stronger and contributes to the higher tensile strength. According to Kato et al. [1], a certain amount of polar group is needed to achieve nanocomposite structure by the formation of hydrogen bonding between polar group and oxygen group of silicates. The polar group in the poly(acrylic acid) will interact with the polar group in the nanoclay while the non polar group in the poly(acrylic acid) will interact with the non polar group in the LDPE. The interactions between the polar and non-polar decrease the d-spacing in the composite and produce the composite with higher tensile strength.

3.4

Water Absorption Analysis

Figure 13 shows the effect of filler loading on the typical water absorption curves versus time of LDPE/nanoclay composites with and without poly(acrylic acid) for 64 days. All composites show a similar pattern of water absorption (except LDPE/nanoclay). As can we see the increasing of filler loading also increased the water absorption for all samples in the experiment. According to Ardhyananta and Ismail [6] the increasing of the water absorption at higher filler loading is due to the formation of agglomerate, which are hydrophilic and the difference in water absorption corresponds to the different dispersion state of silicate layers at each filler loading.

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Malaysian Polymer Journal (MPJ) Vol 3 No. 2, p 39-53, 2008

2 LDPE LDPE/nanoclay2.5 1.6 Water absoprtion (%) LDPE/nanoclay5 LDPE/nanoclay7.5 1.2 LDPE/nanoclay10 LDPE/nanoclay2.5 w ith PAA LDPE/nanoclay5 w ith PAA 0.8 LDPE/nanoclay7.5 w ith PAA LDPE/nanoclay10 w ith PAA 0.4

0 1 2 3 4 5 8 15 22 29 36 43 50 57 64 Tim e (day)

Figure 13: Water absorption versus time of LDPE/nanoclay composites with and without poly(acrylic acid). The water absorption for LDPE/nanoclay without poly(acrylic acid) will not change after some period due to the outstanding barrier properties of the layered silicates structure that are form because of the reaction between the water and the nanoclay [11]. However, LDPE/nanocaly composites with poly(acrylic acid) show more water absorption, which might be due to the polar group in the poly(acrylic acid) (-COOH groups) will interact with more hydrogen bonding from the water and make the percent of water absorption increased. 4.0 CONCLUSIONS

The optimum nanoclay loading to enhance the mechanical properties such as tensile strength, modulus of elasticity and water absorption was achieve at 2.5 phr and 5.0phr. It corresponds to the formation of nanocomposite structure. At lower filler loading, the homogeneous dispersion into nanoscale filler was difficult to achieve. Above 5 phr, the excessive of the filler loading decrease the properties of the nanocomposite due to the presence of the microscale filler. Only at 2.5 phr and 5.0 phr filler loading the properties of the PMC increase, as exhibited by the tensile fracture surfaces of the composites using a scanning electron microscope. The existence of PAA in the composite system is showed to decrease the distance of d-spacing in the composites.

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