research article ldpe/hdpe/clay nanocomposites: effects of...

Hindawi Publishing CorporationJournal of NanotechnologyVolume 2013 Article ID 138457 10 pageshttpdxdoiorg1011552013138457

Research ArticleLDPEHDPEClay Nanocomposites Effects ofCompatibilizer on the Structure and Dielectric Response

B Zazoum E David and A D Ngocirc

Departement de Genie Mecanique Ecole de Technologie Superieure (ETS) 1100 Notre-Dame Ouest Montreal QC Canada H3C 1K3

Correspondence should be addressed to B Zazoum bouchaibzazoum1ensetsmtlca

Received 26 July 2013 Accepted 16 August 2013

Academic Editor John Zhanhu Guo

Copyright copy 2013 B Zazoum et al This is an open access article distributed under the Creative Commons Attribution Licensewhich permits unrestricted use distribution and reproduction in any medium provided the original work is properly cited

PEclay nanocomposites were prepared by mixing a commercially available premixed polyethyleneO-MMT masterbatch into apolyethylene blend matrix containing 80wt low-density polyethylene and 20wt high-density polyethylene with and withoutanhydride modified polyethylene (PE-MA) as the compatibilizer using a corotating twin-screw extruder In this study the effectof nanoclay and compatibilizer on the structure and dielectric response of PEclay nanocomposites has been investigated Themicrostructure of PEclay nanocomposites was characterized using wide-angle X-ray diffraction (WAXD) and a scanning electronmicroscope (SEM) Thermal properties were examined using differential scanning calorimetry (DSC) The dielectric response ofneat PE was compared with that of PEclay nanocomposite with and without the compatibilizerThe XRD and SEM results showedthat the PEO-MMT nanocomposite with the PE-MA compatibilizer was better dispersed In the nanocomposite materials tworelaxationmodes are detected in the dielectric lossesThe first relaxation is due to aMaxwell-Wagner-Sillars interfacial polarizationand the second relaxation can be related to dipolar polarization A relationship between the degree of dispersion and the relaxationrate 119891max of Maxwell-Wagner-Sillars was found and discussed

1 Introduction

There has been growing interest in polymernanoclay nano-composites in recent years because of their outstanding prop-erties at low loading levels as compared with conventionalcomposites It has been observed that adding small quantitiesof nanoclay to some thermoplastics as a reinforcing fillerto form nanocomposite materials has not only led to moreimproved mechanical and thermal properties but also to anenhancement of the dielectric strength and partial dischargeresistance [1ndash10] However the understanding of the role ofthe interfaces of the nanofillers with the molecular mobilitymechanism is still rather unsatisfactory

Although there are different processing methods forpreparing nanocomposites themost widely used technique isthe melt-compounding method using a twin-screw extruderbecause this technique features economic benefits and eco-logical advantages The main challenge in the fabricationof nanocomposites is dispersion of the individual clayplatelets into the polymer matrix due to the incompatibil-ity of hydrophobic matrix with hydrophilic nanoclay [11]

Rendering clay platelets more hydrophobic requires a surfacetreatment which is accomplished via ion-exchange reactionswith cationic surfactants using quaternary alkyl ammoniumcations [12] For more polar polymers such as nylon asurface treatment of layered silicate with an alkyl-ammoniumsurfactant is sufficient to facilitate exfoliation of the nanofillerwithin the polymer matrix in some process conditionsHowever in the case of polyethylene it is necessary touse maleic anhydride modified polyethylene PE-g-MA as acompatibilizer to facilitate exfoliation There are two param-eters that contribute to achieving the exfoliation of layeredsilicates (1) maleic anhydride content and (2) molecularweight In general maleic anhydride modified polyethy-lene PE-g-MA possesses these two required factors and iswidely used as compatibilizer for preparing polyethyleneclaynanocomposites The most commonly used techniques forevaluating the quality of the dispersion of the nanoclaywithin the polymer matrix are scanning electron microscopy(SEM) transmission electron microscopy (TEM) and X-raydiffraction (XRD) Only few publications in this field reportthe use of dielectric methods which are able to characterize

2 Journal of Nanotechnology

the level of dispersion and can be combinedwithmicroscopicmeasurements [13ndash17]

Polyethylene is one of the polyolefins that is used mostextensively as ground-wall insulation for medium- to high-voltage applications and especially for cable insulation dueto its desirable electrical insulating properties includinglow relative permittivity 1205761015840 low dielectric loss 12057610158401015840 and highdielectric breakdown strength

Only a few works have focused on the structuredielectricresponse relationship of polyethylene blend nanocompositesThe main objective of this paper is to examine the effect ofnanoclay and compatibilizers on the structure and dielec-tric response of PEclay nanocomposites prepared by melt-compounding using a corotating twin-screw extruderand tounderstand the relationship between these two properties

2 Experiment

21 Materials Thematrix consisted of low-density polyethy-lene (LDPE LF-Y819-A NOVA Chemicals) with a melt flowindex (MFI) of 075 g10min and a density of 0919 gcm3 andhigh-density polyethylene (HDPEDGDP-6097NT 7DOW)with a melt flow index (MFI) of 105 g10min and a densityof 0948 gcm3 The compatibilizer was anhydride modifiedpolyethylene (PE-MA E226 Dupont) with a melt flowindex (MFI) of 175 g10min and a density of 0930 gcm3A commercially available masterbatch of LLDPEO-MMT(NanoMax) containing 50 organomodified montmoril-lonite (OMMT) was supplied by Nanocor

22 Preparation of Nanocomposites The blend of LDPEHDPEwas fixed at a weight ratio of 8020The LDPE HDPEPEMA and the commercial masterbatch of LLDPEO-MMTwere dried at 40∘C in a vacuum oven for a minimum of48 hrs prior to extrusion Nanocomposites were prepared byan extrusion process using a corotating twin-screw extruder(Haake Polylab Rheomex OS PTW16 119863 = 16mm 119871119863 =40) coupled with a Haake Metering Feeder to control thefeed rate The temperature profile used in this study was 170ndash180∘C from hopper to die the feed rate was fixed at 1 kghrand the screw speed was set at 140 rpm All materials weremanually premixed before introduction into the twin-screwextruder The pellets that were obtained after extrusion werepress-molded using an electrically heated hydraulic press toform thin plates (12mm thick) The molding temperatureand pressure were 178∘C and 5MPa respectively A summaryof the compositions of the PEclay nanocomposites used inthis paper is collected in Table 1

3 Characterization and Measurements

31 Differential Scanning Calorimetry (DSC) Thermalparameters (melting temperature crystallization temper-ature and crystallinity) of neat PE PEO-MMT and PEO-MMTPE-MA nanocomposites were determined using aPerkin-Elmer DSC Pyris 1 instrument The calibration ofthe DSC was performed using indium All samples had thesame weight (approximately 50mg) and the PE and its

nanocomposites were heated from 30∘C to 180∘C during eachrun at a heating rate of 10∘Cmin in nitrogen atmosphereThe endothermic and exothermic diagrams were recorded asa function of temperature

32 X-Ray Diffraction (XRD) X-ray diffraction (XRD) wasemployed in order to assess the degree of dispersion and exfo-liation or intercalation state of the nanoclay in the polymermatrix XRD patterns were identified using a diffractometer(PANalytical XrsquoPert Pro) with K120572 radiation at a wavelength120582 of 15418 A and operated at an accelerating voltage of40 kV and an electrical current of 45mA The scanning wasconducted from 2∘ to 9∘ with a scan rate of 06∘min Theintercalate spacing 119889

001was calculated using Braggrsquos law

2119889 sin 120579 = 120582 (1)

where 119889 120579 and 120582 represent the interlayer distance of theclay the measured diffraction angle and the wavelengthrespectively

33 Microscopical Observations The morphology of thesamples was examined using a Hitachi scanning electronmicroscope (SEM)The samples were first cut in amicrotome(Ultraculeika) equipped with a glass knife and then coatedwith a 2 nm thick layer of platinum in order to avoidelectrostatic charging during microscopic observations Theoperating voltage was fixed at the lowest possible voltage(5 kV) in order to prevent polymer damage and maintainhigh-resolution images

34 Dielectric Relaxation Spectroscopy Dielectric relaxationspectroscopy experiments were carried out using a Novo-control alpha-N in the 10minus2 to 105Hz frequency domain attemperatures of 30∘ 40∘ 50∘ 60∘ and 70∘CThe temperaturewas controlled using a Novotherm system with a stability of05∘C

Prior to all dielectric spectroscopy measurements thesamples measuring 40mm in diameter and 120mm inthickness were dried at 50∘C in a vacuum oven for 24 hrs andthen sandwiched between two gold-plated electrodes mea-suring 40mm in diameter to form a parallel-plate geometrycapacitor

The complex dielectric permittivity is given by

120576lowast (120596) = 1205761015840

(120596) minus 11989412057610158401015840

(120596) (2)

where 1205761015840(120596) represents the real part 12057610158401015840(120596) represents theimaginary part and 120596 = 2120587119891 represents the angularfrequency

The experimental dielectric data can be fitted into theHavrilialk-Negami equation as shown below

120576lowast = 120576infin+119899

sum119894=1

Δ120576119894

(1 + (119894120596120591119894)120572119894)120573119894

(3)

where 120576infin

represents the high frequency permittivity Δ120576119894

represents the 119894th dielectric relaxation strength 120591119894represents

Journal of Nanotechnology 3

Table 1 Sample formulation and designation

Sample designation LLDPE(wt)

LDPEHDPE(wt)

PE-MA(wt)

O-MMT(wt)

MB 50 mdash mdash 50PE mdash 100 0 0PEO-MMT 5 90 0 5PEO-MMTPE-MA 5 80 10 5

the relaxation time of the 119894th relaxation 119899 represents thenumber of relaxation processes and 120572

119894and 120573

119894(0 lt 120572 le

1 120572120573 le 1) represent the shape parameters describingsymmetric and asymmetric broadening of the relaxationspectra At low frequency the influence of the charge carrierfluctuations must be taken into consideration The complexpermittivity can then be expressed as

120576lowast = 120576infin+119899

sum119894=1

[

[

Δ120576119894

(1 + (119894120596120591119894)120572119894)120573119894

]

]

+1205900

1205760(119894120596)119904

(4)

By using (2) (3) and (4) the real part 1205761015840(120596) and theimaginary part 12057610158401015840(120596) of the complex dielectric permittivity120576lowast(120596) can be written as

1205761015840 (120596) = 120576infin+119899

sum119894=1

[

[

Δ120576119894cos (120573

119894120593119894)

times ((1 + 2 (120596120591119894)120572119894 sin(

120587 (1 minus 120572119894)

2)

+(120596120591)2120572119894 )

1205731198942

)

minus1

]

]

+120590119900120596minus119904

1205760

cos(1205871199042)

12057610158401015840 (120596)

=119899

sum119894=1

[

[

Δ120576119894sin (120573

119894120593119894)

(1+2 (120596120591119894)120572119894 sin (120587 (1minus120572

119894) 2)+(120596120591)2120572119894)

1205731198942

]

]

+120590119900120596minus119904

1205760

sin(1205871199042)

(5)

where

120593119894= tanminus1 [

(120596120591119894)120572119894 cos (120587 (1 minus 120572

119894) 2)

1 + (120596120591119894)120572119894 sin (120587 (1 minus 120572

119894) 2)

] (6)

where 120590119900represents dc conductivity and 119904 represents an

adjustable parameter In the case of pure electronic dcconductivity 119904 = 1

40 60 80 100 120 140 160Temperature (∘C)

Hea

t flow

endo

up

PEPEO-MMTPEO-MMTPE-MA

Figure 1 DSC heating thermograms of neat PE PEO-MMT andPEO-MMTPE-MA nanocomposites

4 Results and Discussion

41 Thermal Properties Differential scanning calorimetry(DSC) was used to measure the melting temperaturescrystallization temperatures and fusion enthalpy Δ119867

119865 The

degree of crystallinity was calculated as expressed by thefollowing equation

120594 = Δ119867119865

Δ1198670119865(1 minus 120593)

(7)

whereΔ119867119865represents the heat of fusion (Jg)Δ1198670

119865represents

the theoretical heat of fusion of 100 crystalline PE (293 Jg)and 120593 represents the weight fraction of O-MMT in thecomposites

The melting and crystallization curves of neat polyethy-lene and its nanocomposites are depicted in Figures 1and 2 respectively The thermal parameters derived fromthese curves are shown in Table 2 Differential scanningcalorimetry (DSC) thermograms revealed two different peaktemperatures with the first melting temperature related toLDPE and the second melting temperature related to HDPEThe melting point peak of LLDPE was not detected due tothe low concentration of LLDPE in the nanocomposites TheDSC results clearly showed that the melting temperature


Table 2 DSC data for PE and its nanocomposites

Sample LDPE(119879119898 ∘C)

HDPE(119879119898 ∘C)

LDPE(119879119888 ∘C)

HDPE(119879119888 ∘C)

Heat offusion of PE (Jg)

Crystallinity ofPE ()

PE 1094 1258 973 1135 1158 395PEO-MMT 1106 1274 974 1134 1144 411PEO-MMTPE-MA 1109 1277 988 1127 1137 408

Table 3 2120579 and 119889001 data for the different nanocomposites

Sample 2120579 (∘) 119889001 (nm)MB 313 282PEO-MMT 293 302PEO-MMTPEMA 272 325

40 60 80 100 120 140 160Temperature (∘C)

Hea

t flow

endo

up


Figure 2 DSC cooling thermograms of neat PE PEO-MMT andPEO-MMTPE-MA nanocomposites

crystallization temperature and crystallinity of PEO-MMTand PEO-MMTPE-MA are almost the same as those of neatPEThis behavior suggests that the presence of the organoclaydid not create a nucleating effect The same resultants werefound by Morawiec et al [18]

42 Wide-Angle X-Ray Diffraction (WAXD) Figure 3 showsthe X-ray diffraction spectra for the O-MMT masterbatchPEO-MMT and PEO-MMTPE-MA nanocomposites Thediffraction peak for the O-MMT masterbatch is approxi-mately 2120579 = 313∘ which corresponds to a 119889

001value of

282 nm calculated using the Bragg law (Table 3) When theO-MMT masterbatch was diluted with pure PE to createPEO-MMT nanocomposites the diffraction peak was foundto shift to a smaller angle of 293∘ indicating the increasein 119889001

spacing of the galleries of the organoclay Thisimprovement in the dispersionwas due to the processing con-ditions for the fabrication of nanocomposites For the ternary

2 4 6 8 10 122120579 (deg)

Inte

nsity

(au

)

MBPEO-MMTPEO-MMTPE-MA

Figure 3 X-ray diffraction patterns forMB and PE nanocompositeswith and without compatibilizer

nanocomposites PEO-MMTPE-MA the diffraction peakwas observed at a lower angle of 273∘ corresponding to anincrease in intercalate spacing 119889

001to 325 nm On the other

hand the reduction in the diffraction intensity accompaniedby the broadening of the basal peak in the PEO-MMTPE-MA nanocomposites suggests that the degree of dispersionof the nanoclay within the polymer matrix was improvedand that these compatibilized nanocomposites contain asignificant proportion of exfoliated nanoclay in the finalnanocompositesThis is due to the polar interactions betweenthe maleic anhydride groups in the PE-MA and the OHgroups of clay which lead to a formation of a covalent bondbetween clay and compatibilizer and help polymer chains topenetrate the galleries of the organoclay easily [6 19 20]Since PE-MA has a high molecular weight (low melt index)the shear stress was significant which led to an increase in thedelamination of the clay platelets [1 21ndash27]

43 Morphological Characterizations by SEM In order toconfirm the XRD results the morphology of the nanocom-posites was observed using a scanning electronic microscopy


(a) (b)

(c)

Figure 4 Representative SEMmicrographs for (a) neat PE (b) PEO-MMT and (c) PEOMMTPE-MA

(SEM) Figure 4 shows the morphology of neat PE (Fig-ure 4(a)) PEO-MMT (Figure 4(b)) and the ternarynanocomposites PEO-MMTPE-MA (Figure 4(c)) at a mag-nification of 5000 For PEO-MMT nanocomposites theexistence of the clay aggregates or tactoids can be seen atthe micrometer level and therefore the morphology is nothomogeneous which reveals a poor intercalatedexfoliatedstructure However when the compatibilizer was added itwas observed that the density and size of the aggregatesdecreased which indicates that the dispersion of nanoclayswithin the polymer matrix is much better This is consistentwith the higher intercalate spacing 119889

001and the reduction

in the diffraction intensity accompanied by the broaden-ing of the peak observed in the XRD results (Figure 3and Table 3)

44 BroadbandDielectric Spectroscopy Polyethylene is classi-fied as a nonpolar polymer with low dielectric permittivity Ingeneral this type ofmaterial exhibits no notable or significantionic interfacial or dipolar polarization being characterizedby low flat dielectric losses As observed from Figure 5(a)the relative permittivity (1205761015840) of neat PE remains essentiallyconstant in the 10minus2 to 105 frequency range showing asmall decrease when the temperature is increased The slightdecrease in (1205761015840) at higher temperatures can be related toa combination of water evaporation and a decrease in thedensity [17] However the dielectric loss (12057610158401015840) of neat PEat low frequency (Figure 5(b)) shows a significant increasewhich can be attributed to the contribution of charge carriers

leading to various forms of conductivity and electrode polar-ization [28] This is the so-called low-frequency dispersionAs expected no relaxation process is detected in thismaterial

For PEO-MMTnanocomposites Figure 6 shows the fre-quency dependence of relative permittivity 1205761015840 and dielectricloss 12057610158401015840at various temperatures It can be seen that the relativepermittivity 1205761015840 shows two sharp decreases (Figure 6(a))corresponding to the two peaks in the dielectric losses12057610158401015840 (Figure 6(b)) This indicates that the nanocompositesexhibited two dielectric relaxation processes It is evident thatthe 12057610158401015840 peaks observed in PEOMMTnanocomposites are dueto the addition of nanoclay because no dielectric relaxationswere observed for the neat PE The peaks of the relaxationprocesses presented in the nanocomposites were shifted tohigher frequencies as the temperature was increased Thischange shows that the relaxation processes exhibited thermalactivation behaviour

In order to clearly show the relaxation processes observedin PEO-MMT nanocomposites the dielectric loss (12057610158401015840) wasplotted as a function of the frequency and temperature ina 3D representation (Figure 7) Two relaxation modes wereobserved in the dielectric losses The first relaxation wasdetected at low frequency and it is attributable to a Maxwell-Wagner-Sillars polarization associated with the blockingof charges at the interfaces between two inhomogeneousphases with different conductivity such as the polymermatrix and the silicates filler [29ndash31] The second relaxationwhich was detected at high frequency can be attributed todipolar polarization associated with the polar characteristicof the intercalant that was used for surface treatment of


25

24

23

22

21

10minus2 10minus1 100 101 102 103 104 105

Frequency (Hz)

PE120576998400

30∘C40∘C50∘C

60∘C70∘C

(a)

0025

0020

0015

0010

0005

0000

120576998400998400

10minus2 10minus1 100 101 102 103 104 105

Frequency (Hz)

PE

30∘C40∘C50∘C

60∘C70∘C

(b)

Figure 5 Relative permittivity 1205761015840 (a) and dielectric loss 12057610158401015840 (b) versus frequency at various temperatures observed for the neat PE blend

10minus2 10minus1 100 101 102 103 104 105

Frequency (Hz)

28

27

26

25

24

23

PEO-MMT

120576998400

30∘C40∘C50∘C

60∘C70∘C

(a)

008

006

004

002

000

minus002

10minus2 10minus1 100 101 102 103 104 105

Frequency (Hz)

PEO-MMT

120576998400998400

30∘C40∘C50∘C

60∘C70∘C

(b)

Figure 6 Relative permittivity 1205761015840 (a) and dielectric loss 12057610158401015840 (b) for PEO-MMT nanocomposites versus frequency at different temperatures

montmorillonite clay in order to improve compatibility anddispersion of the hydrophilic clay within the hydrophobicpolymer matrix

The experimental data related to the dielectric loss 12057610158401015840 forPEO-MMT nanocomposites were fitted into the Havrilialk-Negami function (Figure 8) and the optimum dielectricparameters are shown in Table 4

Figure 9 shows the frequency dependence of the permit-tivity 1205761015840 (Figure 9(a)) and the dielectric loss 12057610158401015840 (Figure 9(b))

for PEO-MMTPE-MA As observed for PEO-MMT thetwo relaxation processes are also presented for these com-patibilized nanocomposites It can be seen that the relaxationpeaks are more thermally activated in PEO-MMTPE-MAthan in PEO-MMT

In order to study the temperature dependence of bothrelaxation processes for the PEO-MMT nanocompositesthe relaxation rate 119891max of the Maxwell-Wagner-Sillars anddipolar polarization processes were plotted versus inverse


PEO-MMT

Tempera

ture (∘ C)

006

005

004

003

002

001

000

Frequency (Hz)

006005005004003003002001000

Maxwell-Wagner-Sillars Dipolar relaxationrelaxation

120576998400998400

10minus2

10minus1

100

101

102

103

104

105

3040

50

60

70

Figure 7 Dielectric loss (12057610158401015840) for PEO-MMT nanocomposites versus frequency at various temperatures plotted in 3D representation

10minus2 10minus1 100 101 102 103 104 105

Frequency (Hz)

008

004

000

PEO-MMT

120576998400998400

30∘C40∘C50∘C

60∘C70∘C

Figure 8 Dielectric loss 12057610158401015840 for PEO-MMT nanocomposites versusfrequency at different temperatures with the optimum fitting curvesfor the Havrilialk-Negami equation

temperatures as shown in Figure 10 The data were found tobe in agreement with the Arrhenius equation

119891max (119879) = 119891infin exp(minus 119864119860119896120573119879) (8)

where119891infinrepresents the preexponential factor119864

119860represents

the activation energy and 119896120573

represents the Boltzmannconstant It can be seen that both processes follow Arrheniusrsquo

Table 4 Optimum fit parameters for MWS and dipolar relaxationsin Figure 8

(a)

MWS polarization119879 (∘C) 1205721 1205731 Δ1205761 1205911 (s)30 029 100 050 05640 043 100 032 01150 048 100 027 00460 049 098 026 00270 055 089 023 001

(b)

Dipolar polarization119879 (∘C) 1205722 1205732 Δ1205762 1205912 (s)30 079 087 005 260119864 minus 5

40 067 063 014 608119864 minus 5

50 062 070 018 177119864 minus 5

60 067 068 018 645119864 minus 5

70 063 081 019 235119864 minus 5

law with activation energies of 12 eV and 16 eV for theMaxwell-Wagner-Sillars and dipolar relaxation respectively

It is evident fromFigure 11 that the values of the relaxationrate 119891max of Maxwell-Wagner-Sillars are significantly influ-enced by the structure of the nanocomposites with the valuesof 119891max being higher in the well-dispersed PEO-MMTPE-MA nanocomposites than in the PEO-MMT nanocompos-ites In order to better understand the relationship betweenthe structure and the relaxation rate 119891max of the Maxwell-Wagner-Sillars relaxation process Bohning et al [14] suggest


28

27

26

25

24

23

22

21

PEO-MMTPE-MA

10minus2 10minus1 100 101 102 103 104 105

Frequency (Hz)

120576998400

30∘C40∘C50∘C

60∘C70∘C

(a)

10minus2 10minus1 100 101 102 103 104 105

Frequency (Hz)

012

010

008

006

004

002

000

120576998400998400

PEO-MMTPE-MA

30∘C40∘C50∘C

60∘C70∘C

(b)

Figure 9 Relative permittivity 1205761015840 (a) and dielectric loss 12057610158401015840 (b) for PEO-MMTPE-MA nanocomposites versus frequency at differenttemperatures

PEO-MMT

4

3

2

1

0

minus1

29 30 31 32 33

1000T (Kminus1)

Log(f

max

(Hz)

)

MWS polarizationDipolar polarization

Figure 10 Relaxation rate 119891max as a function of inverse temperaturefor the two relaxationmodes observed in PEO-MMTnanocompos-ites The solid lines represent best fits for the Arrhenius function

that 119891max is inversely proportional to the mean distance 119889between separated nanoclay layers

119891max 21198891

asymp119891max 11198892

(9)

4

3

2

1

0

minus1

29 30 31 32 331000T (Kminus1)

PEO-MMTPEO-MMTPE-MA

Log(f

max

(Hz)

)

Figure 11 Relaxation rate 119891max as a function of inverse temperaturefor the MWS relaxation rate observed in PEO-MMT and PEO-MMTPE-MAnanocompositesThe solid lines represent best fits forthe Arrhenius function

Accordingly the improvement in the degree of dispersionin PEO-MMTPE-MA nanocomposites obtained with theaddition of the compatibilizer leads to a decrease in the meandistance between the clay layers and consequently an increasein the relaxation rate 119891max for the Maxwell-Wagner- Sillarsprocess


5 Conclusion

A commercially available premixed polyethyleneO-MMTmasterbatch was used in this study to prepare PEO-MMTnanocomposites using a corotating twin-screw extruder

The quality of dispersion was improved by the incor-poration of anhydride modified polyethylene (PE-MA) asthe compatibilizer This is due to the fact that PE-MA helpspolymer chains to penetrate the galleries of the organoclayeasily No relaxation processes were observed in the neat PEbut two thermally activated relaxation modes were observedin the nanocomposite materials a low-frequency relaxationthat can be attributed to an interfacial process and a high-frequency relaxation that is related to a dipolar polarizationprocess It was observed that the relaxation rate of theMaxwell-Wagner-Sillars process increased as the degree ofdispersion increased This correlation shows that broadbanddielectric spectroscopy can be used as a macroscopic tool toevaluate the quality of dispersion in nanocomposite materi-als

Conflict of Interests

The authors declare that there is no conflict of interestsregarding the publication of this paper

Acknowledgment

Theauthors are grateful for the financial support revived fromthe National Sciences and Engineering Research Council ofCanada (NSERC)

References

[1] M Kawasumi N Hasegawa M Kato A Usuki and A OkadaldquoPreparation and mechanical properties of polypropylene-clayhybridsrdquoMacromolecules vol 30 no 20 pp 6333ndash6338 1997

[2] H Tan and W Yang ldquoToughening mechanisms of nano-composite ceramicsrdquo Mechanics of Materials vol 30 no 2 pp111ndash123 1998

[3] Y Han Z Wang X Li J Fu and Z Cheng ldquoPolymer-layeredsilicate nanocomposites synthesis characterization propertiesand applicationsrdquo Current Trends in Polymer Science vol 6 pp1ndash16 2001

[4] X Kornmann H Lindberg and L A Berglund ldquoSynthesis ofepoxy-clay nanocomposites influence of the nature of the clayon structurerdquo Polymer vol 42 no 4 pp 1303ndash1310 2001

[5] L A Utracki and M R Kamal ldquoClay-containing polymericnanocompositesrdquo Arabian Journal for Science and Engineeringvol 27 no 1 pp 43ndash67 2002

[6] S Hotta and D R Paul ldquoNanocomposites formed from linearlow density polyethylene and organoclaysrdquo Polymer vol 45 no22 pp 7639ndash7654 2004

[7] K Zhao and K He ldquoDielectric relaxation of suspensions ofnanoscale particles surrounded by a thick electric double layerrdquoPhysical Review B vol 74 no 20 Article ID 205319 10 pages2006

[8] H Awaji Y Nishimura S Choi Y Takahashi T Goto and SHashimoto ldquoToughening mechanism and frontal process zone

size of ceramicsrdquo Journal of the Ceramic Society of Japan vol 117no 1365 pp 623ndash629 2009

[9] L Chen and G Chen ldquoRelaxation behavior study of siliconerubber crosslinked network under static and dynamic compres-sion by electric responserdquo Polymer Composites vol 30 no 1 pp101ndash106 2009

[10] P Kim N M Doss J P Tillotson et al ldquoHigh energy densitynanocomposites based on surface-modified BaTiO

3and a

ferroelectric polymerrdquo ACS Nano vol 3 no 9 pp 2581ndash25922009

[11] M A Osman J E P Rupp and U W Suter ldquoTensile propertiesof polyethylene-layered silicate nanocompositesrdquo Polymer vol46 no 5 pp 1653ndash1660 2005

[12] X Zhang Z Liu Q Li Y Leung K Ip and S Hark ldquoRoutesto grow well-aligned arrays of ZnSe nanowires and nanorodsrdquoAdvanced Materials vol 17 no 11 pp 1405ndash1410 2005

[13] R D Davis A J Bur M McBrearty Y Lee J W Gilmanand P R Start ldquoDielectric spectroscopy during extrusionprocessing of polymer nanocomposites a high throughputprocessingcharacterization method to measure layered silicatecontent and exfoliationrdquo Polymer vol 45 no 19 pp 6487ndash64932004

[14] M Bohning H Goering A Fritz et al ldquoDielectric studyof molecular mobility in poly(propylene-graft-maleic anhy-dride)clay nanocompositesrdquoMacromolecules vol 38 no 7 pp2764ndash2774 2005

[15] N Noda Y H Lee A J Bur et al ldquoDielectric properties ofnylon 6clay nanocomposites from on-line process monitoringand off-line measurementsrdquo Polymer vol 46 no 18 pp 7201ndash7217 2005

[16] P J Purohit J E Huacuja-Sanchez D Wang et al ldquoStructure-property relationships of nanocomposites based on polypropy-lene and layered double hydroxidesrdquo Macromolecules vol 44no 11 pp 4342ndash4354 2011

[17] V Tomer G Polizos C A Randall and E Manias ldquoPolyethy-lene nanocomposite dielectrics implications of nanofiller ori-entation on high field properties and energy storagerdquo Journal ofApplied Physics vol 109 no 7 Article ID 074113 11 pages 2011

[18] J Morawiec A Pawlak M Slouf A Galeski E Piorkowskaand N Krasnikowa ldquoPreparation and properties of compati-bilized LDPEorgano-modified montmorillonite nanocompos-itesrdquo European Polymer Journal vol 41 no 5 pp 1115ndash11222005

[19] T G Gopakumar J A Lee M Kontopoulou and J S ParentldquoInfluence of clay exfoliation on the physical properties ofmontmorillonitepolyethylene compositesrdquo Polymer vol 43no 20 pp 5483ndash5491 2002

[20] M J Dumont A Reyna-Valencia J P Emond and MBousmina ldquoBarrier properties of polypropyleneorganoclaynanocompositesrdquo Journal of Applied Polymer Science vol 103no 1 pp 618ndash625 2007

[21] N Hasegawa M Kawasumi M Kato A Usuki and A OkadaldquoPreparation and mechanical properties of polypropylene-clay hybrids using a maleic anhydride-modified polypropyleneoligomerrdquo Journal of Applied Polymer Science vol 67 no 1 pp87ndash92 1998

[22] NHasegawa HOkamotoM Kato andA Usuki ldquoPreparationandmechanical properties of polypropylene-clay hybrids basedon modified polypropylene and organophilic clayrdquo Journal ofApplied Polymer Science vol 78 no 11 pp 1918ndash1922 2000


[23] M Kato A Usuki and A Okada ldquoSynthesis of polypropyleneoligomer-clay intercalation compoundsrdquo Journal of AppliedPolymer Science vol 66 no 9 pp 1781ndash1785 1997

[24] P Maiti P H Nam M Okamoto N Hasegawa and A UsukildquoInfluence of crystallization on intercalation morphology andmechanical properties of polypropyleneclay nanocompositesrdquoMacromolecules vol 35 no 6 pp 2042ndash2049 2002

[25] E Manias A Touny L Wu K Strawhecker B Lu and TC Chung ldquoPolypropylenemontmorillonite nanocompositesReview of the synthetic routes andmaterials propertiesrdquo Chem-istry of Materials vol 13 no 10 pp 3516ndash3523 2001

[26] P H Nam P Maiti M Okamoto T Kotaka N Hasegawaand A Usuki ldquoA hierarchical structure and properties ofintercalated polypropyleneclay nanocompositesrdquo Polymer vol42 no 23 pp 9633ndash9640 2001

[27] Y Wang F B Chen K C Wu and J C Wang ldquoShear rheol-ogy and melt compounding of compatibilized-polypropylenenanocomposites effect of compatibilizer molecular weightrdquoPolymer Engineering and Science vol 46 no 3 pp 289ndash3022006

[28] F Kremer and A Schonhals Broadband Dielectric SpectroscopySpringer New York NY USA 2003

[29] E Laredo M Grimau F Sanchez and A Bello ldquoWater absorp-tion effect on the dynamic properties of nylon-6 by dielectricspectroscopyrdquo Macromolecules vol 36 no 26 pp 9840ndash98502003

[30] H M Le Huy and J Rault ldquoRemarks on the 120572 and 120573 transitionsin swollen polyamidesrdquo Polymer vol 35 no 1 pp 136ndash139 1994

[31] D W McCall and E W Anderson ldquoDielectric properties oflinear polyamidesrdquoThe Journal of Chemical Physics vol 32 no1 pp 237ndash241 1960

Submit your manuscripts athttpwwwhindawicom

ScientificaHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CorrosionInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Polymer ScienceInternational Journal of



CeramicsJournal of


CompositesJournal of

NanoparticlesJournal of



International Journal of

Biomaterials


NanoscienceJournal of

TextilesHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Journal of

NanotechnologyHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

CrystallographyJournal of


The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014


CoatingsJournal of

Advances in

Materials Science and EngineeringHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Smart Materials Research



MetallurgyJournal of


BioMed Research International

MaterialsJournal of


Nano

materials


Journal ofNanomaterials


the level of dispersion and can be combinedwithmicroscopicmeasurements [13ndash17]

Polyethylene is one of the polyolefins that is used mostextensively as ground-wall insulation for medium- to high-voltage applications and especially for cable insulation dueto its desirable electrical insulating properties includinglow relative permittivity 1205761015840 low dielectric loss 12057610158401015840 and highdielectric breakdown strength

Only a few works have focused on the structuredielectricresponse relationship of polyethylene blend nanocompositesThe main objective of this paper is to examine the effect ofnanoclay and compatibilizers on the structure and dielec-tric response of PEclay nanocomposites prepared by melt-compounding using a corotating twin-screw extruderand tounderstand the relationship between these two properties

2 Experiment

21 Materials Thematrix consisted of low-density polyethy-lene (LDPE LF-Y819-A NOVA Chemicals) with a melt flowindex (MFI) of 075 g10min and a density of 0919 gcm3 andhigh-density polyethylene (HDPEDGDP-6097NT 7DOW)with a melt flow index (MFI) of 105 g10min and a densityof 0948 gcm3 The compatibilizer was anhydride modifiedpolyethylene (PE-MA E226 Dupont) with a melt flowindex (MFI) of 175 g10min and a density of 0930 gcm3A commercially available masterbatch of LLDPEO-MMT(NanoMax) containing 50 organomodified montmoril-lonite (OMMT) was supplied by Nanocor

22 Preparation of Nanocomposites The blend of LDPEHDPEwas fixed at a weight ratio of 8020The LDPE HDPEPEMA and the commercial masterbatch of LLDPEO-MMTwere dried at 40∘C in a vacuum oven for a minimum of48 hrs prior to extrusion Nanocomposites were prepared byan extrusion process using a corotating twin-screw extruder(Haake Polylab Rheomex OS PTW16 119863 = 16mm 119871119863 =40) coupled with a Haake Metering Feeder to control thefeed rate The temperature profile used in this study was 170ndash180∘C from hopper to die the feed rate was fixed at 1 kghrand the screw speed was set at 140 rpm All materials weremanually premixed before introduction into the twin-screwextruder The pellets that were obtained after extrusion werepress-molded using an electrically heated hydraulic press toform thin plates (12mm thick) The molding temperatureand pressure were 178∘C and 5MPa respectively A summaryof the compositions of the PEclay nanocomposites used inthis paper is collected in Table 1

3 Characterization and Measurements

31 Differential Scanning Calorimetry (DSC) Thermalparameters (melting temperature crystallization temper-ature and crystallinity) of neat PE PEO-MMT and PEO-MMTPE-MA nanocomposites were determined using aPerkin-Elmer DSC Pyris 1 instrument The calibration ofthe DSC was performed using indium All samples had thesame weight (approximately 50mg) and the PE and its

nanocomposites were heated from 30∘C to 180∘C during eachrun at a heating rate of 10∘Cmin in nitrogen atmosphereThe endothermic and exothermic diagrams were recorded asa function of temperature

32 X-Ray Diffraction (XRD) X-ray diffraction (XRD) wasemployed in order to assess the degree of dispersion and exfo-liation or intercalation state of the nanoclay in the polymermatrix XRD patterns were identified using a diffractometer(PANalytical XrsquoPert Pro) with K120572 radiation at a wavelength120582 of 15418 A and operated at an accelerating voltage of40 kV and an electrical current of 45mA The scanning wasconducted from 2∘ to 9∘ with a scan rate of 06∘min Theintercalate spacing 119889

001was calculated using Braggrsquos law

2119889 sin 120579 = 120582 (1)

where 119889 120579 and 120582 represent the interlayer distance of theclay the measured diffraction angle and the wavelengthrespectively

33 Microscopical Observations The morphology of thesamples was examined using a Hitachi scanning electronmicroscope (SEM)The samples were first cut in amicrotome(Ultraculeika) equipped with a glass knife and then coatedwith a 2 nm thick layer of platinum in order to avoidelectrostatic charging during microscopic observations Theoperating voltage was fixed at the lowest possible voltage(5 kV) in order to prevent polymer damage and maintainhigh-resolution images

34 Dielectric Relaxation Spectroscopy Dielectric relaxationspectroscopy experiments were carried out using a Novo-control alpha-N in the 10minus2 to 105Hz frequency domain attemperatures of 30∘ 40∘ 50∘ 60∘ and 70∘CThe temperaturewas controlled using a Novotherm system with a stability of05∘C

Prior to all dielectric spectroscopy measurements thesamples measuring 40mm in diameter and 120mm inthickness were dried at 50∘C in a vacuum oven for 24 hrs andthen sandwiched between two gold-plated electrodes mea-suring 40mm in diameter to form a parallel-plate geometrycapacitor

The complex dielectric permittivity is given by

120576lowast (120596) = 1205761015840

(120596) minus 11989412057610158401015840

(120596) (2)

where 1205761015840(120596) represents the real part 12057610158401015840(120596) represents theimaginary part and 120596 = 2120587119891 represents the angularfrequency

The experimental dielectric data can be fitted into theHavrilialk-Negami equation as shown below

120576lowast = 120576infin+119899

sum119894=1

Δ120576119894

(1 + (119894120596120591119894)120572119894)120573119894

(3)

where 120576infin

represents the high frequency permittivity Δ120576119894

represents the 119894th dielectric relaxation strength 120591119894represents




LDPEHDPE(wt)

PE-MA(wt)

O-MMT(wt)



119894and 120573

119894(0 lt 120572 le


120576lowast = 120576infin+119899

sum119894=1

[

[

Δ120576119894

(1 + (119894120596120591119894)120572119894)120573119894

]

]

+1205900

1205760(119894120596)119904

(4)


1205761015840 (120596) = 120576infin+119899

sum119894=1

[

[

Δ120576119894cos (120573

119894120593119894)

times ((1 + 2 (120596120591119894)120572119894 sin(

120587 (1 minus 120572119894)

2)

+(120596120591)2120572119894 )

1205731198942

)

minus1

]

]

+120590119900120596minus119904

1205760

cos(1205871199042)

12057610158401015840 (120596)

=119899

sum119894=1

[

[

Δ120576119894sin (120573

119894120593119894)

(1+2 (120596120591119894)120572119894 sin (120587 (1minus120572

119894) 2)+(120596120591)2120572119894)

1205731198942

]

]

+120590119900120596minus119904

1205760

sin(1205871199042)

(5)

where

120593119894= tanminus1 [

(120596120591119894)120572119894 cos (120587 (1 minus 120572

119894) 2)

1 + (120596120591119894)120572119894 sin (120587 (1 minus 120572

119894) 2)

] (6)



40 60 80 100 120 140 160Temperature (∘C)

Hea

t flow

endo

up





119865 The


120594 = Δ119867119865

Δ1198670119865(1 minus 120593)

(7)


119865represents





Sample LDPE(119879119898 ∘C)

HDPE(119879119898 ∘C)

LDPE(119879119888 ∘C)

HDPE(119879119888 ∘C)






40 60 80 100 120 140 160Temperature (∘C)

Hea

t flow

endo

up





001value of



2 4 6 8 10 122120579 (deg)

Inte

nsity

(au

)








(a) (b)

(c)










25

24

23

22

21

10minus2 10minus1 100 101 102 103 104 105

Frequency (Hz)

PE120576998400

30∘C40∘C50∘C

60∘C70∘C

(a)

0025

0020

0015

0010

0005

0000

120576998400998400

10minus2 10minus1 100 101 102 103 104 105

Frequency (Hz)

PE

30∘C40∘C50∘C

60∘C70∘C

(b)


10minus2 10minus1 100 101 102 103 104 105

Frequency (Hz)

28

27

26

25

24

23

PEO-MMT

120576998400

30∘C40∘C50∘C

60∘C70∘C

(a)

008

006

004

002

000

minus002

10minus2 10minus1 100 101 102 103 104 105

Frequency (Hz)

PEO-MMT

120576998400998400

30∘C40∘C50∘C

60∘C70∘C

(b)








PEO-MMT

Tempera

ture (∘ C)

006

005

004

003

002

001

000

Frequency (Hz)

006005005004003003002001000


120576998400998400

10minus2

10minus1

100

101

102

103

104

105

3040

50

60

70


10minus2 10minus1 100 101 102 103 104 105

Frequency (Hz)

008

004

000

PEO-MMT

120576998400998400

30∘C40∘C50∘C

60∘C70∘C





119860represents




(a)


(b)


40 067 063 014 608119864 minus 5

50 062 070 018 177119864 minus 5

60 067 068 018 645119864 minus 5

70 063 081 019 235119864 minus 5




28

27

26

25

24

23

22

21

PEO-MMTPE-MA

10minus2 10minus1 100 101 102 103 104 105

Frequency (Hz)

120576998400

30∘C40∘C50∘C

60∘C70∘C

(a)

10minus2 10minus1 100 101 102 103 104 105

Frequency (Hz)

012

010

008

006

004

002

000

120576998400998400

PEO-MMTPE-MA

30∘C40∘C50∘C

60∘C70∘C

(b)


PEO-MMT

4

3

2

1

0

minus1

29 30 31 32 33

1000T (Kminus1)

Log(f

max

(Hz)

)




119891max 21198891

asymp119891max 11198892

(9)

4

3

2

1

0

minus1

29 30 31 32 331000T (Kminus1)

PEO-MMTPEO-MMTPE-MA

Log(f

max

(Hz)

)




5 Conclusion





Acknowledgment


References












3and a































CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials






LDPEHDPE(wt)

PE-MA(wt)

O-MMT(wt)



119894and 120573

119894(0 lt 120572 le


120576lowast = 120576infin+119899

sum119894=1

[

[

Δ120576119894

(1 + (119894120596120591119894)120572119894)120573119894

]

]

+1205900

1205760(119894120596)119904

(4)


1205761015840 (120596) = 120576infin+119899

sum119894=1

[

[

Δ120576119894cos (120573

119894120593119894)

times ((1 + 2 (120596120591119894)120572119894 sin(

120587 (1 minus 120572119894)

2)

+(120596120591)2120572119894 )

1205731198942

)

minus1

]

]

+120590119900120596minus119904

1205760

cos(1205871199042)

12057610158401015840 (120596)

=119899

sum119894=1

[

[

Δ120576119894sin (120573

119894120593119894)

(1+2 (120596120591119894)120572119894 sin (120587 (1minus120572

119894) 2)+(120596120591)2120572119894)

1205731198942

]

]

+120590119900120596minus119904

1205760

sin(1205871199042)

(5)

where

120593119894= tanminus1 [

(120596120591119894)120572119894 cos (120587 (1 minus 120572

119894) 2)

1 + (120596120591119894)120572119894 sin (120587 (1 minus 120572

119894) 2)

] (6)



40 60 80 100 120 140 160Temperature (∘C)

Hea

t flow

endo

up





119865 The


120594 = Δ119867119865

Δ1198670119865(1 minus 120593)

(7)


119865represents





Sample LDPE(119879119898 ∘C)

HDPE(119879119898 ∘C)

LDPE(119879119888 ∘C)

HDPE(119879119888 ∘C)






40 60 80 100 120 140 160Temperature (∘C)

Hea

t flow

endo

up





001value of



2 4 6 8 10 122120579 (deg)

Inte

nsity

(au

)








(a) (b)

(c)










25

24

23

22

21

10minus2 10minus1 100 101 102 103 104 105

Frequency (Hz)

PE120576998400

30∘C40∘C50∘C

60∘C70∘C

(a)

0025

0020

0015

0010

0005

0000

120576998400998400

10minus2 10minus1 100 101 102 103 104 105

Frequency (Hz)

PE

30∘C40∘C50∘C

60∘C70∘C

(b)


10minus2 10minus1 100 101 102 103 104 105

Frequency (Hz)

28

27

26

25

24

23

PEO-MMT

120576998400

30∘C40∘C50∘C

60∘C70∘C

(a)

008

006

004

002

000

minus002

10minus2 10minus1 100 101 102 103 104 105

Frequency (Hz)

PEO-MMT

120576998400998400

30∘C40∘C50∘C

60∘C70∘C

(b)








PEO-MMT

Tempera

ture (∘ C)

006

005

004

003

002

001

000

Frequency (Hz)

006005005004003003002001000


120576998400998400

10minus2

10minus1

100

101

102

103

104

105

3040

50

60

70


10minus2 10minus1 100 101 102 103 104 105

Frequency (Hz)

008

004

000

PEO-MMT

120576998400998400

30∘C40∘C50∘C

60∘C70∘C





119860represents




(a)


(b)


40 067 063 014 608119864 minus 5

50 062 070 018 177119864 minus 5

60 067 068 018 645119864 minus 5

70 063 081 019 235119864 minus 5




28

27

26

25

24

23

22

21

PEO-MMTPE-MA

10minus2 10minus1 100 101 102 103 104 105

Frequency (Hz)

120576998400

30∘C40∘C50∘C

60∘C70∘C

(a)

10minus2 10minus1 100 101 102 103 104 105

Frequency (Hz)

012

010

008

006

004

002

000

120576998400998400

PEO-MMTPE-MA

30∘C40∘C50∘C

60∘C70∘C

(b)


PEO-MMT

4

3

2

1

0

minus1

29 30 31 32 33

1000T (Kminus1)

Log(f

max

(Hz)

)




119891max 21198891

asymp119891max 11198892

(9)

4

3

2

1

0

minus1

29 30 31 32 331000T (Kminus1)

PEO-MMTPEO-MMTPE-MA

Log(f

max

(Hz)

)




5 Conclusion





Acknowledgment


References












3and a































CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials





Sample LDPE(119879119898 ∘C)

HDPE(119879119898 ∘C)

LDPE(119879119888 ∘C)

HDPE(119879119888 ∘C)






40 60 80 100 120 140 160Temperature (∘C)

Hea

t flow

endo

up





001value of



2 4 6 8 10 122120579 (deg)

Inte

nsity

(au

)








(a) (b)

(c)










25

24

23

22

21

10minus2 10minus1 100 101 102 103 104 105

Frequency (Hz)

PE120576998400

30∘C40∘C50∘C

60∘C70∘C

(a)

0025

0020

0015

0010

0005

0000

120576998400998400

10minus2 10minus1 100 101 102 103 104 105

Frequency (Hz)

PE

30∘C40∘C50∘C

60∘C70∘C

(b)


10minus2 10minus1 100 101 102 103 104 105

Frequency (Hz)

28

27

26

25

24

23

PEO-MMT

120576998400

30∘C40∘C50∘C

60∘C70∘C

(a)

008

006

004

002

000

minus002

10minus2 10minus1 100 101 102 103 104 105

Frequency (Hz)

PEO-MMT

120576998400998400

30∘C40∘C50∘C

60∘C70∘C

(b)








PEO-MMT

Tempera

ture (∘ C)

006

005

004

003

002

001

000

Frequency (Hz)

006005005004003003002001000


120576998400998400

10minus2

10minus1

100

101

102

103

104

105

3040

50

60

70


10minus2 10minus1 100 101 102 103 104 105

Frequency (Hz)

008

004

000

PEO-MMT

120576998400998400

30∘C40∘C50∘C

60∘C70∘C





119860represents




(a)


(b)


40 067 063 014 608119864 minus 5

50 062 070 018 177119864 minus 5

60 067 068 018 645119864 minus 5

70 063 081 019 235119864 minus 5




28

27

26

25

24

23

22

21

PEO-MMTPE-MA

10minus2 10minus1 100 101 102 103 104 105

Frequency (Hz)

120576998400

30∘C40∘C50∘C

60∘C70∘C

(a)

10minus2 10minus1 100 101 102 103 104 105

Frequency (Hz)

012

010

008

006

004

002

000

120576998400998400

PEO-MMTPE-MA

30∘C40∘C50∘C

60∘C70∘C

(b)


PEO-MMT

4

3

2

1

0

minus1

29 30 31 32 33

1000T (Kminus1)

Log(f

max

(Hz)

)




119891max 21198891

asymp119891max 11198892

(9)

4

3

2

1

0

minus1

29 30 31 32 331000T (Kminus1)

PEO-MMTPEO-MMTPE-MA

Log(f

max

(Hz)

)




5 Conclusion





Acknowledgment


References












3and a































CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials




(a) (b)

(c)










25

24

23

22

21

10minus2 10minus1 100 101 102 103 104 105

Frequency (Hz)

PE120576998400

30∘C40∘C50∘C

60∘C70∘C

(a)

0025

0020

0015

0010

0005

0000

120576998400998400

10minus2 10minus1 100 101 102 103 104 105

Frequency (Hz)

PE

30∘C40∘C50∘C

60∘C70∘C

(b)


10minus2 10minus1 100 101 102 103 104 105

Frequency (Hz)

28

27

26

25

24

23

PEO-MMT

120576998400

30∘C40∘C50∘C

60∘C70∘C

(a)

008

006

004

002

000

minus002

10minus2 10minus1 100 101 102 103 104 105

Frequency (Hz)

PEO-MMT

120576998400998400

30∘C40∘C50∘C

60∘C70∘C

(b)








PEO-MMT

Tempera

ture (∘ C)

006

005

004

003

002

001

000

Frequency (Hz)

006005005004003003002001000


120576998400998400

10minus2

10minus1

100

101

102

103

104

105

3040

50

60

70


10minus2 10minus1 100 101 102 103 104 105

Frequency (Hz)

008

004

000

PEO-MMT

120576998400998400

30∘C40∘C50∘C

60∘C70∘C





119860represents




(a)


(b)


40 067 063 014 608119864 minus 5

50 062 070 018 177119864 minus 5

60 067 068 018 645119864 minus 5

70 063 081 019 235119864 minus 5




28

27

26

25

24

23

22

21

PEO-MMTPE-MA

10minus2 10minus1 100 101 102 103 104 105

Frequency (Hz)

120576998400

30∘C40∘C50∘C

60∘C70∘C

(a)

10minus2 10minus1 100 101 102 103 104 105

Frequency (Hz)

012

010

008

006

004

002

000

120576998400998400

PEO-MMTPE-MA

30∘C40∘C50∘C

60∘C70∘C

(b)


PEO-MMT

4

3

2

1

0

minus1

29 30 31 32 33

1000T (Kminus1)

Log(f

max

(Hz)

)




119891max 21198891

asymp119891max 11198892

(9)

4

3

2

1

0

minus1

29 30 31 32 331000T (Kminus1)

PEO-MMTPEO-MMTPE-MA

Log(f

max

(Hz)

)




5 Conclusion





Acknowledgment


References












3and a































CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials




25

24

23

22

21

10minus2 10minus1 100 101 102 103 104 105

Frequency (Hz)

PE120576998400

30∘C40∘C50∘C

60∘C70∘C

(a)

0025

0020

0015

0010

0005

0000

120576998400998400

10minus2 10minus1 100 101 102 103 104 105

Frequency (Hz)

PE

30∘C40∘C50∘C

60∘C70∘C

(b)


10minus2 10minus1 100 101 102 103 104 105

Frequency (Hz)

28

27

26

25

24

23

PEO-MMT

120576998400

30∘C40∘C50∘C

60∘C70∘C

(a)

008

006

004

002

000

minus002

10minus2 10minus1 100 101 102 103 104 105

Frequency (Hz)

PEO-MMT

120576998400998400

30∘C40∘C50∘C

60∘C70∘C

(b)








PEO-MMT

Tempera

ture (∘ C)

006

005

004

003

002

001

000

Frequency (Hz)

006005005004003003002001000


120576998400998400

10minus2

10minus1

100

101

102

103

104

105

3040

50

60

70


10minus2 10minus1 100 101 102 103 104 105

Frequency (Hz)

008

004

000

PEO-MMT

120576998400998400

30∘C40∘C50∘C

60∘C70∘C





119860represents




(a)


(b)


40 067 063 014 608119864 minus 5

50 062 070 018 177119864 minus 5

60 067 068 018 645119864 minus 5

70 063 081 019 235119864 minus 5




28

27

26

25

24

23

22

21

PEO-MMTPE-MA

10minus2 10minus1 100 101 102 103 104 105

Frequency (Hz)

120576998400

30∘C40∘C50∘C

60∘C70∘C

(a)

10minus2 10minus1 100 101 102 103 104 105

Frequency (Hz)

012

010

008

006

004

002

000

120576998400998400

PEO-MMTPE-MA

30∘C40∘C50∘C

60∘C70∘C

(b)


PEO-MMT

4

3

2

1

0

minus1

29 30 31 32 33

1000T (Kminus1)

Log(f

max

(Hz)

)




119891max 21198891

asymp119891max 11198892

(9)

4

3

2

1

0

minus1

29 30 31 32 331000T (Kminus1)

PEO-MMTPEO-MMTPE-MA

Log(f

max

(Hz)

)




5 Conclusion





Acknowledgment


References












3and a































CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials




PEO-MMT

Tempera

ture (∘ C)

006

005

004

003

002

001

000

Frequency (Hz)

006005005004003003002001000


120576998400998400

10minus2

10minus1

100

101

102

103

104

105

3040

50

60

70


10minus2 10minus1 100 101 102 103 104 105

Frequency (Hz)

008

004

000

PEO-MMT

120576998400998400

30∘C40∘C50∘C

60∘C70∘C





119860represents




(a)


(b)


40 067 063 014 608119864 minus 5

50 062 070 018 177119864 minus 5

60 067 068 018 645119864 minus 5

70 063 081 019 235119864 minus 5




28

27

26

25

24

23

22

21

PEO-MMTPE-MA

10minus2 10minus1 100 101 102 103 104 105

Frequency (Hz)

120576998400

30∘C40∘C50∘C

60∘C70∘C

(a)

10minus2 10minus1 100 101 102 103 104 105

Frequency (Hz)

012

010

008

006

004

002

000

120576998400998400

PEO-MMTPE-MA

30∘C40∘C50∘C

60∘C70∘C

(b)


PEO-MMT

4

3

2

1

0

minus1

29 30 31 32 33

1000T (Kminus1)

Log(f

max

(Hz)

)




119891max 21198891

asymp119891max 11198892

(9)

4

3

2

1

0

minus1

29 30 31 32 331000T (Kminus1)

PEO-MMTPEO-MMTPE-MA

Log(f

max

(Hz)

)




5 Conclusion





Acknowledgment


References












3and a































CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials




28

27

26

25

24

23

22

21

PEO-MMTPE-MA

10minus2 10minus1 100 101 102 103 104 105

Frequency (Hz)

120576998400

30∘C40∘C50∘C

60∘C70∘C

(a)

10minus2 10minus1 100 101 102 103 104 105

Frequency (Hz)

012

010

008

006

004

002

000

120576998400998400

PEO-MMTPE-MA

30∘C40∘C50∘C

60∘C70∘C

(b)


PEO-MMT

4

3

2

1

0

minus1

29 30 31 32 33

1000T (Kminus1)

Log(f

max

(Hz)

)




119891max 21198891

asymp119891max 11198892

(9)

4

3

2

1

0

minus1

29 30 31 32 331000T (Kminus1)

PEO-MMTPEO-MMTPE-MA

Log(f

max

(Hz)

)




5 Conclusion





Acknowledgment


References












3and a































CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials




5 Conclusion





Acknowledgment


References












3and a































CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials




















CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials



research article ldpe/hdpe/clay nanocomposites: effects of...

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