Research Article Ethylene-Octene Copolymers/Organoclay ... · 2. Materials and Methods.. Materials. Polymer matrices used as carrier materials were ethylene-octene copolymers: Engage

Research ArticleEthylene-Octene CopolymersOrganoclay NanocompositesPreparation and Properties

Alice Tesarikova1 Dagmar Merinska12 Jiri Kalous12 and Petr Svoboda1

1Department of Polymer Engineering Faculty of Technology Tomas Bata University in Zlin Nam T G Masaryka 275762 72 Zlin Czech Republic2Centre of Polymer Systems University Institute Tomas Bata University in Zlin Nad Ovcirnou 3685 760 01 Zlin Czech Republic

Correspondence should be addressed to Petr Svoboda svobodaftutbcz

Received 29 September 2015 Revised 8 December 2015 Accepted 10 December 2015

Academic Editor Antonios Kelarakis

Copyright copy 2016 Alice Tesarikova et al This is an open access article distributed under the Creative Commons AttributionLicense which permits unrestricted use distribution and reproduction in any medium provided the original work is properlycited

Two ethylene-octene copolymers with 17 and 45wt of octene (EOC-17 and EOC-45) were compared in nanocomposites withCloisite 93A EOC-45 nanocomposites have a higher elongation at break Dynamical mechanical analysis (DMA) showed adecrease of tan 120575with frequency for EOC-17 nanocomposites but decrease is followed by an increase for EOC-45 nanocompositesDMA showed also increased modulus for all nanocomposites compared to pure copolymers over a wide temperature rangeBarrier properties were improved about 100 by addition of organoclay they were better for EOC-17 nanocomposites due tohigher crystallinity X-ray diffraction (XRD) together with transmission electron microscopy (TEM) showed some intercalationfor EOC-17 but much better dispersion for EOC-45 nanocomposites Differential scanning calorimetry (DSC) showed increasedcrystallization temperature 119879

119888for EOC-17 nanocomposite (aggregates acted as nucleation agents) but decrease 119879

119888for EOC-45

nanocomposite together with greatly influenced melting peak Accelerated UV aging showed smaller C=O peak for EOC-45nanocomposites

1 Introduction

Polymer nanocomposites have been interesting already for alonger period of time They represent the group of systemswhere polymer matrix is mixed with a certain type ofnanofiller One of the fillers is a type from layered silicateminerals when the thickness of the individual leaves is innanometer size The most frequently used type of nanoclayis montmorillonite (MMT) [1ndash5] It is a layered mineralbelonging to a group of clay minerals with octahedral andtetrahedral nets in the ratio of 2 1 Because of the problemswith the exfoliation of its agglomerates in the polymericmatrix MMT is used not pure but modified by the processknown as organofilization or intercalation that is the inser-tion of a suitable organic compound into MMT interlayer[6ndash9] The result of this step brings a broader 119863-spacing aswell as a reduction of dispersing forces between the individualplatelets of montmorillonite The role of MMT nanoplatelets

in the polymer matrix can be considered from various pointsof views Generally the first one is the original effect of thefillermdashespecially the improvement of mechanical properties[10ndash13] The advantage of nanofillers lies in the ability tocreate this improvement by much lower loading in com-parison with common fillers Another quality of nanoleavesis their positive impact on the orientation of long thickplatelets in polymer matrix during compounding (mainlyat extrusionblowing of packaging films) where they createby their orientation a gas barrier to the gas transmissionThus the gas permeability is lower The principle of thisphenomenon is shown in Figure 1 where the imagination ofan ideal situationmdashperfect exfoliation of the filler particlestogether with the perfect orientation of all MMT platelets inpolymer matrixmdashis presented

Next to the commonly used polyethylene (PE) orpolypropylene (PP) matrices from the group of the polymeralso some a little bit special types of these polymer matrices

Hindawi Publishing CorporationJournal of NanomaterialsVolume 2016 Article ID 6014064 13 pageshttpdxdoiorg10115520166014064

2 Journal of Nanomaterials

A polymermatrix

Gas transmission

Nanofillerplatelets

Figure 1 Improved barrier properties of nanocomposites

are studied One of them can be an ethylene-octene copoly-mer (EOC) and alternatively its blends with other polymermatrices mostly PP [1ndash3]

The ethylene-octene copolymer (EOC) a new polyolefinelastomer developed byDowChemical Company (DelawareUSA) with metallocene catalysis is interesting by its prop-erties and is attracting a lot of attention from both researchand industry [14ndash16] EOC is an ethylene based elastomerso it brings an excellent compatibility with polyolefins suchas polyethylene and PP [17ndash20] The presence of the octenecomonomer in EOC causes a lower level of crystallinity and ahigher flexibility in the copolymer EOC can be consideredas an elastomeric polymer and usually the octene contentin the copolymer varies under 20wt [21 22] Blends ofPPEOC may provide enhanced impact properties and canbe used for example in extruded or molded automotiveexterior and interior parts housing appliances and otherlow-temperature applications Pelletized EOC exhibits easyhandling mixing and processability Based on these prop-erties EOC is currently being used as an impact modifier ofPP to replace ethylene propylene rubber (EPR) and ethylenepropylene diene rubber (EPDM) [19 23 24]

As it was mentioned above EOC significantly improvesthe impact strength but it causes a decrease of thetensile strength and stiffness of PP [25ndash27] ThereforePPEOCmineral filler-based composites have been studiedin order to enhance the toughness and stiffness of PPsimultaneously These systems are double-phased [23ndash25]Mineral fillers with high aspect ratio that is clay nanofillershave been found to increase stiffness and strength to thethermoplastic polyolefins they provide a greater possibilityfor energy transfer from one phase to another [28ndash31]

However comparative evaluation of the mechanical andthermal properties of composites based on PP EOC andmineral fillers is still limited

The aim of this work was to add more information aboutthe properties of EOC copolymer with clay nanofiller inorder to evaluate the influence of used nanofiller and itsconcentration on the EOC copolymer EOC matrix withnanoclay was chosen because this polymer matrix can be

considered as one of tie layers of multilayer packaging filmswith the better end of use properties

2 Materials and Methods

21 Materials Polymer matrices used as carriermaterials were ethylene-octene copolymers Engage8842 and Engage 8540 (both of DuPont DOWElastomers Europe GMBH Switzerland)mdashlinear formula(CH2CH2)119909[CH2CH[(CH

2)5CH3]]119910(see Figure 2)

To increase compatibility between the polymer matrixand the filler maleinized polyethylene (PE-MA) Priex 12043(ADDCOMPHolland BV) in 5wt concentration was used

EOC-45 (Engage 8842) is an ultralow density copolymer(see Table 1) that offers exceptional properties of an ultralowdensity elastomer with the added potential of handing thispolymer in pellet form It has excellent flow characteris-tics and provides superb impact properties in blends withpolypropylene (PP) and polyethylene (PE)

EOC-17 (Engage 8540) is a polyolefin elastomer thatis well suited for foam applications and offers excellentperformance for profile extrusion of tubing and hoses

Organically modified montmorillonite (MMT) withtrade name Cloisite 93A (Southern Clay Products Inc) wasusedThis type of nanoclay ismodified by organic branches oftype dimethyl hydrogenated tallow 2-ethylhexyl and quar-tenary ammonium methylsulfate this type is recommendedfor nonpolar polymer matrices

The quantity of the above-mentioned nanofiller added tothe polymeric matrix was 3 5 or 7wt

22 Sample Preparation Polymers with the fillers were com-pounded in twin-screw extruder Scientific LTE 20-40 screwdiameter was 20mm and 119871119863 ratio was 401 The tempera-tures of the individual heating zones and the extrusion headwere set from 170∘C to 205∘C the rotation speed of screwswas 300 rpm and the rotation speed of volumetric feedingscrew was 20 rpm The extruded strands were air-cooled andthen transferred using a knife mill back to a pelletizer ScherrSGS-50E

Specimens for measurement of properties were preparedby compression molding and cutting Blends in the formof pellets were placed between two PET sheets preventingthe contact with air and thus oxidative degradation Thematerial was pressed in a mold with size 125 times 125 times 2mm(for platelets) The pressing time was 5 minutes for platelets(thickness approximately 2mm) and 3 minutes for films(thickness about 50120583m) pellets are molded without a frameonly between two plates of the machine After that the moldwith material was placed into a water-cooled hydraulic pressand cooled down to room temperature

23 Evaluation of Prepared Samples

231 Mechanical Properties Tensile tests are among themostwidely used test methods The test specimen is deformedunidirectional until the break Tensile testing was performedon tear machines with a range of campaign Tensile test

Journal of Nanomaterials 3

Table 1 List of applied polymer materials (information from datasheets)

Name AbbreviationOctenecontent(wt)

Density(gcm3)

119879119898

(∘C)

Engage 8540 EOC-17 17 0908 104Engage 8842 EOC-45 45 0857 38

CH2CH2 CH2CH

CH3(CH2)4CH2

x

y

Figure 2The structural formula of the ethylene-octene copolymer

measures the deformation of the sample and the forcerequired for deformation

Tensile tests were measured at the Faculty of Technologyin Tomas BataUniversity in Zlin (FTTBU) On tensile testingmachine Galbadini Quasar 25 EN ISO 527-3 (64 0604) wasused for the speed of tearing 2 initial speed was 1mmminto the module 2 and then the speed was increased to100mmmin until rupture For tensile strength elongation atbreak and tensile modulus were measured and evaluated

232 DynamicMechanical Analysis (DMA) tan 120575 (tan delta)damping which is the tangent of the phase angle and theratio of 119864101584010158401198641015840 for room temperature in range 1ndash200Hz withstep 2Hz and for temperature in the range minus100∘C to +100∘Cwith at 1Hz and amplitude 50120583m were measured DMAmeasurements were performed on samples of size 20 times 5mmmade from premolded panels on the device DMA PerkinElmer in laboratories of FT UTB Zlin

233 Gas Barrier Properties (GTR) Observed nanocompos-ite molded films with the thickness of about 50120583m anddiameter 80mm at a pressure 2 bar and a temperature of35∘C were used for the measurement of N

2 O2 and CO

2

permeability on the equipment known as Julabo TW8 basedonCSN640115methodof a constant volumeThe conversionof the results according to standard ASTM D 3985-05 wasperformed

234 XRD Analysis In FT TBU laboratories X-ray diffrac-tion analysis (XRD) was also performed The instrumentdiffractometer URD 6 was used Measurements were donein the reflection mode in the 2120579 range of 2ndash30∘ at a voltageof 40 kV and 30mA with a step size of 00263∘ Informationfrom X-ray analysis complemented by TEM provides uswith information on the morphology of the nanocomposites

235 Transmission Electron Microscopy (TEM) Dispersionof the clays in polymer matrix and nanostructures wasobserved through microscopic investigations

Samples of 40 times 20mm made from molded plates weresent to IMC Prague where TEM observation was performedUltrathin sections prepared on special ultracryomicrotomeLEICA at minus100∘C were used as samples temperature of

the knife was minus50∘C and thickness was of about 50 nmTransmission electron microscopy was performed on a JEM200 CX at an accelerated voltage of 100 kV

236 Thermal Analysis Differential Scanning Calorimetry(DSC) The samples on the Mettler Toledo DSC 1 with anexternal cooling unit and purging the chamber with nitrogengas were observed The rate of cooling and heating was 20∘Cper minute and the temperature range was minus90∘C to 150∘C

237 Accelerated Weathering Test Samples about 5 times 15 cmfor accelerated UV degradation test according to EN ISO4892mdash2nd ingestion devicemdashXenotest Alpha were preparedThe measurement conditions were as defined in above-mentioned standard (temperature was 38∘C irradiance60Whm2 filters simulating daylight and RH 50) Onemeasurement cycle (46 days) simulates the degradation ofone year

238 Fourier Transform Infrared Spectroscopy (FTIR) Thetest on the FTIR spectrometer AVATAR 320 (Nicolet) whichis a standard single-beamFTIR spectrometer operating in therange of wave numbers 4000 to 500 cmminus1 was performedFTIR instrument is controlled via a PC using the softwareOmnic The measurement by the ATR (attenuated reflectionmethod) was carried out

3 Results and Discussion

31 Mechanical Properties Polymerclay nanocompositeshave been studied for longer period of time as materialsthat could be used in packaging industry Two types ofEngage (ethylene-octene copolymer)clay nanocomposites inthis paper are reported This work is particularly focused onthe mechanical barrier and morphology properties

Table 2 presents the mechanical properties of two typesof EOC with nanofiller Cloisite 93 in the polymer matrix Ascan be seen the values of the tensile strength of EOC are thesame in comparison to materials enriched by filler Cloisite93 It can be assumed that the presence of filler in samplescompared to the neat ones does not have a significant effecton the change of mechanical properties

Figure 3 illustrates tensile stress as a function of strain forpure EOC-17 (45) and EOC with 5 of Cloisite 93 in Table 2the values for filler contant 3 5 and 7wt are listed EOC-17exhibits yield point and higher values of stress This is causedby the presence of lamellar crystals Higher content of octenegroups in EOC-45 causesmuch lower presence of crystals andthe crystals are not lamellar but very small ldquospot-likerdquo [17]This unique morphology is responsible for lower modulus(higher softness) absence of yield point and better elasticity(which is illustrated in Table 2) Presence of nanoclay causedhigher stress value in case of EOC-17 during the whole testin case of EOC-45 it caused higher elongation For examplethe yield point of EOC-17 increased by addition of 5 wt ofnanoclay from 741 to 928MPa (see Figure 3(a)) During thetensile test the orientation of crystals caused increase in stressfor all samples


Table 2 Tensile tests of pure EOC-17 EOC-45 and filled EOC-17 and EOC-45 with 3 5 and 7 wt of nanoclay Cloisite 93

Composition Tensile strength (MPa) Std dev Ductility (au) 119864modulus (MPa)EOC-17 pure 30950 24 108237 2534EOC-17 + 3 Cloisite 93 26767 24 90378 2456EOC-17 + 5 Cloisite 93 28458 25 91541 2465EOC-17 + 7 Cloisite 93 25117 26 83711 2438EOC-45 pure 6950 04 185486 216EOC-45 + 3 Cloisite 93 6208 04 174329 253EOC-45 + 5 Cloisite 93 7400 03 194329 462EOC-45 + 7 Cloisite 93 5258 05 115429 343

Mechanical properties of EOC-17 (Engage 8540)

Strain ()0 200 400 600 800 1000

Stre

ss (M

Pa)

0

10

20

30

EOC-17 + 5 Cloisite 93EOC-17 pure

(a)


0

2

4

6

8

Strain ()0 500 15001000

Stre

ss (M

Pa)


(b)

Figure 3 Mechanical properties of (a) EOC-17 (Engage 8540) with 5wt Cloisite 93 and (b) EOC-45 (Engage 8842) with 5wt Cloisite 93

After the tensile test we have measured also the residualstrain EOC-45 samples exhibit better elasticity (lower valueof residual strain) The composites have only slightly worseelasticity (slightly higher values of residual strain)

Measuring distance is as follows 1198970= initial distance 119897

1

= distance at maximum extension and 1198972= distance after 24

hours of relaxation (see Table 3)

32 DynamicMechanical Analysis (DMA) Pure EOC-17 andits blends with Cloisite 93 show a linear decrease of tan delta(tan 120575) with increasing frequency The addition of Cloisite 93causes tan 120575 to drop significantly at high frequencies whereasthe low frequencies are affected only marginally

However EOC-45 is behaving differently the additionof Cloisite 93 leads to increased tan 120575 and the increaseis higher when compared to pure EOC-45 What remainsthe same is the marginal effect of Cloisite 93 within lowfrequencies andmuch stronger interaction at high frequencyAlso the percentage of Cloisite 93 does not affect final values

Table 3 Residual strain of pure EOC-17 EOC-45 and filled EOC-17EOC-45 with 5 wt of nanoclay Cloisite 93

Composition 1198970(mm) 119897

1(mm) 119897

2(mm)

EOC-17 pure 10 80 601EOC-17 + 5 Cloisite 93 10 90 605EOC-45 pure 10 140 302EOC-45 + 5 Cloisite 93 10 145 305

of tan 120575 EOC-45 possesses a high percentage of octene chains(45wt) compared to 17 wt of EOC-17 As we can see inFigure 4 the driving force for different mechanical behavioris interaction with Cloisite 93

Results and curves of tan delta versus frequency werevery similar for 3 5 and 7wt Cloisite 93 therefore weused results of the dependence on the frequency and thetemperature only for 5wt concentration level Accordingto our previous experience the 5 nanoclay filling is optimal


DMA frequency sweep EOC-17 (Engage 8540)

Frequency (Hz)0 50 100 150 200

002

004

006

008

010

012

014

016

018

EOC-17 pureEOC-17 + 5 Cloisite 93

tan 120575

(a)


Frequency (Hz)0 50 100 150 200

00

01

02

03

04

05

tan 120575


(b)

Figure 4 DMA graphs of (a) EOC-17 (Engage 8540) with 5wt Cloisite 93 and (b) EOC-45 (Engage 8842) with 5wt Cloisite 93 at roomtemperature

Table 4 Dependence of tan delta and 1198641015840 modulus on the temperature for pure EOC-17 EOC-45 and filled EOC

Composition Temperature (∘C)minus90 minus60 minus30 0 30 60 90

tan 120575EOC-17 pure 00893 00215 00626 01106 01669 01885 00579EOC-17 + 5 Cloisite 93 00312 00205 00576 00931 01482 02000 01262EOC-45 pure 01314 01370 02551 00701 00824 mdash mdashEOC-45 + 5 Cloisite 93 00742 00978 02413 00762 00987 mdash mdash

1198641015840 modulus (MPa)

EOC-17 pure 1258 1197 871 356 1476 4709 1910EOC-17 + 5 Cloisite 93 1552 1460 1078 498 2377 7731 2859EOC-45 pure 537 436 264 821 401 mdash mdashEOC-45 + 5 Cloisite 93 841 701 599 194 979 mdash mdash

tan 120575 was lower for both of the EOC filled nanocompos-ites At lower frequencies the EOC-45 andEOC-45 nanocom-posites exhibit lower value of tan 120575 (better elasticity) Thisis caused by lower crystallinity and also by defect that thecrystals are ldquospot-likerdquo while in EOC-17 there are normallamellar crystals At frequencies higher than 100Hz we foundincrease of tan 120575 for EOC-45 The test was performed atroom temperature which is rather close to melting pointThemacromolecules lose the ability to return to original shapeduring the high-frequency test The nanofiller decreases theamount of deformation therefore the tan 120575 values are lower(see Figure 4)

The dependency of 1198641015840 modulus on temperature is sim-ilar for both materials and nanocomposites (Figure 5 andTable 4) After reaching glass transmission temperature

modulus shows sharp drop and both compounds possesshigher modules in almost whole temperature range with theexception of temperature close to melting point Strengthen-ing effect of Cloisite is stronger in EOC-17 nanocompositewhen compared to EOC-45 in addition to increased mod-ulus glass transition and melting temperatures are slightlyshifted to higher temperatures

Both nanocomposites show similar behavior in tan 120575temperature dependency Cloisite 93 increases tan deltaMentioned increase is more significant at the peak positionof the curve The compound of EOC-17 with 5wt Cloisite93 loses tan delta much less compared to pure EOC-17 andwhen the temperature approaches melting point it retainssignificantly higher tan 120575 On the other hand EOC-45 withCloisite 93 loses tan delta at the same rate as pure EOC-45


DMA cryo of EOC-17 (Engage 8540)and EOC-45 (Engage 8842)

0 50 10010

100

1000

E998400

mod

ulus

(MPa

)

Temperature (∘C)minus100 minus50

EOC-17 + 5 Cloisite 93 EOC-45 + 5 Cloisite 93EOC-45 pureEOC-17 pure

(a)

DMA cryo of EOC-17 (Engage 8540)and EOC-45 ( Engage 8842)

00

01

02

03

04

05

06

tan 120575

0 50 100Temperature (∘C)

minus100 minus50

EOC-45 + 5 Cloisite 93EOC-17 + 5 Cloisite 93EOC-45 pureEOC-17 pure

(b)

Figure 5 DMA graphs temperature dependencies EOC-17 (Engage 8540) with 5wt Cloisite 93 and EOC-45 (Engage 8842) with 5wtCloisite 93 (a) log1198641015840 modulus and (b) tan 120575

but the maximal increase at peak point is higher than EOC-17 Another difference is visible when close to melting pointtemperatures the volume of side chains does change the effectof Cloisite 93 on EOC behavior

Curves can be influenced by the low thermal conductivityof polymer samples The 1198641015840 modulus values were higher forthe nanocomposites at all temperatures

With increasing temperature the 1198641015840 modulus decreasesfor all samples especially above minus50∘C nanofiller increasesthemodulus greatly at temperatures above119879

119898which is at this

graph visible only for EOC-45 (with 119879119898around 50∘C)

Figure 5(b) illustrates decrease from 05 to 039 Theposition of 119879

119892(the first peak) did not change in case of EOC-

17 nevertheless above +50∘C the presence of nanoclay sig-nificantly increased the tan 120575 value which can be interpretedas worse elasticity above this temperature for the nanocom-posites At lower temperatures the tan 120575 values are lower forthe nanocomposites which means better elasticity The worseelasticity at temperature approaching melting point is causedby a flow of the material during mechanical testing which isnot prevented by crosslinking (see Figure 5(b))Thenanofillerprevents return of the sample from elongated state at elevatedtemperatures and thus tan 120575 for the nanocomposites is higher

33 Barrier Properties As mentioned above the ethylene-octene copolymer can be used in packaging industry There-fore this study also covers the values of permeability for N

2

O2 and CO

2 which are mediums that should be prevented

from penetrating through the film for example in the caseof food wrapping In this instance films pressed on the

manual and hydraulic presses were used as the samples forthe measurement

The evaluation of gas transmission rate and oxygentransmission rate (see Table 5 and Figure 6) is shown forEOC-17 andEOC-45 copolymerclay nanocomposites As theresults show permeability pure materials (EOC-17 and EOC-45) have inferior properties compared to filled materials Thebest combination seems to be of EOC + 5 Cloisite 93

In a comparison of both used ethylene-octene copoly-mers EOC-17 shows significantly better properties for allgases This may be due to lower content of octene groups andhigher crystallinity

It can be concluded that the nanofiller Cloisite 93 canimprove the polymer matrix EOC When applied in EOCmatrix the permeability of gases decreases This may be dueto a better distribution and dispersion of filler or betterexfoliation MMT nanolayers in the polymer matrix It isknown that during the pressing of samples it is not possibleto suppose an achievement of a perfect orientation of MMTplatelets

Hot plates are pressed in a press machine into very thinfilms The thickness of the pressed film is about 50120583m andthe size of MMT platelets is on the similar level thus theorientation of MMT leaves in this case is not excluded

34 Analysis of the Morphology by XRD In order to discoverthe level of montmorillonite exfoliation in used matricesXRD patterns have been taken For easier comparison graphswith the curve of neat EOC matrix of original MMTnanofiller and their mixture have been summarized (Fig-ure 7)


Table 5 The gas transmission rate for N2 O2 and CO

2

Composition Thickness(mm)

GTR for N2

(cm3 (STP)m2sdotden 01MPa)GTR for O

2

(cm3 (STP)m2sdotden 01MPa)GTR for CO

2

(cm3 (STP)m2sdotden 01MPa)EOC-17 pure 052 509 1372 5361EOC-17 + 3 Cloisite 93 052 295 789 2765EOC-17 + 5 Cloisite 93 053 264 734 2619EOC-17 + 7 Cloisite 93 053 386 940 3541EOC-45 pure 053 3055 8060 33369EOC-45 + 3 Cloisite 93 053 1792 4265 17874EOC-45 + 5 Cloisite 93 053 1683 4113 16664EOC-45 + 7 Cloisite 93 052 2065 5391 25878

Gas transmission rate of EOC-17 and EOC-45

0

10000

20000

30000

40000

N2O2

CO2

EOC-

45+7

C

loisi

te 9

3

EOC-

45+5

C

loisi

te 9

3

EOC-

45+3

C

loisi

te 9

3

EOC-

45

pure

EOC-

17+7

C

loisi

te 9

3

EOC-

17+5

C

loisi

te 9

3

EOC-

17+3

C

loisi

te 9

3

EOC-

17

pure

GTR

(cm

3(S

TP)

m2middotd

en01

MPa

)

(a)

Oxygen transmission rate of EOC-17 and EOC-45

0

2000

4000

6000

8000

10000

OTR

(cm

3(S

TP)

m2middotd

en01

MPa

)

EOC-

45+7

C

loisi

te 9

3

EOC-

45+5

C

loisi

te 9

3

EOC-

45+3

C

loisi

te 9

3

EOC-

45

pure

EOC-

17+7

C

loisi

te 9

3

EOC-

17+5

C

loisi

te 9

3

EOC-

17+3

C

loisi

te 9

3

EOC-

17

pure

(b)

Figure 6 Barrier properties of EOC-17 (Engage 8540) and EOC-45 (Engage 8842) (a) gas transmission rate and (b) oxygen transmissionrate

According to the recorded results it is possible to observethat incomplete montmorillonite exfoliation has taken placebut as discussed below despite the incomplete exfoliationshown byXRDmeasurement a certain improvement of somequalities observed has been proved

Better results in X-ray diffraction can be observed in thecase of EOC-45 where curves of filled materials comparedwith pure EOC sample are almost identical with no signifi-cantly different peaks in the area of Cloisite 93A In contrarythe curve of a composite of EOC-17 exhibits very noticeablepeak almost the same like origin Cloisite 93A This can beconnected with the different EOC sample structure

Figure 7(a) illustrates a small shift in diffraction angletowards lower value corresponding to small increase of 119863-spacing (see Table 6) from 256 to 272 nm in case of EOC-17 nanocomposite This could be interpreted as intercalation

Table 6119863-spacing of clay and filled EOC-17

Composotion 119863-spacing (nm)EOC-17 + 5 Cloisite 93 2728Cloisite 93 2562

Quite different scenario is recorded for EOC-45 nanocom-posite in Figure 7(b) The peak has almost completely disap-peared which can be interpreted as exfoliation The presenceof a small peak at 42∘ corresponding to 119863-spacing being221 nm can be explained by a distribution of 119863-spacing inoriginal Cloisite 93 ranging from 22 to 27 nm During themelt-mixing the clay with larger 119863-spacing (23sim27 nm) gotexfoliated while small amount of clay with119863-spacing 22 nmremained


XRD of EOC-17 (Engage 8540)

2 3 4 5 6 7 8

Inte

nsity

(au

)

0

500

1000

1500

2000

2500

Diffraction angle 2120579 (deg)

EOC-17 pure Cloisite 93EOC-17 + 5 Cloisite 93

D-spacing 27nm

D-spacing 25nm

(a)


2 3 4 5 6 7 8

Inte

nsity

(au

)

0

500

1000

1500

2000



Cloisite 93

D-spacing 25nm

(b)

Figure 7 XRD graphs of EOC (a) EOC-17 (Engage 8540) with 5wt Cloisite 93 and (b) EOC-45 (Engage 8842) with 5wt Cloisite 93

100nm

(a)

100nm

(b)

Figure 8 TEM pictures of (a) EOC-45 (Engage 8842) with 5wt Cloisite 93 and (b) EOC-45 (Engage 8842) with 7wt Cloisite 93

35 Analysis of the Morphology by Transmission ElectronMicroscopy (TEM) Themixing was quite successful for bothEOCs as it comes from results of TEM analysis In Figures8 and 9 a comparison of the distribution of nanofiller ina matrix of EOC-17 with different contents of clay can beseen Distribution in both cases is about the same but imagessuggest that in the case of EOC-17with 5 and 7wtnanofillerin polymer matrix the exfoliation is worse

TEM results confirm previous conclusions from XRDindicating better exfoliation of nanofiller in case of EOC-45

The similar situation is also shown in Figure 9 Thedistribution and exfoliation of nanofiller in the polymermatrix is correct but only for 5wt Cloisite 93

According to our experience with filled polymers 5 wtnanofiller filling is optimal in the polymer matrix

This concentration leads to the exfoliation of the filler par-ticles in the polymer While when 7wt nanofiller is usednot only the exfoliation is not good but even agglomeratescan be formed

36 Differential Scanning Calorimetry (DSC) Previous testsshow that the best performance is at about 5 of nanofillerin the polymer matrix In further tests such as the DSC andFTIR the samples are compared in particular with a 5wtconcentration

DSC curve of pure EOC-17 (see Figure 10(a)) showsmelt-ing temperature of 1083∘C 5 of Cloisite causes the meltingpoint to drop slightly to 1062∘CThe peak occurring at 126∘C(after Cloisite 93 addition) could be assigned to the PE-MA


100nm

(a)

100nm

(b)


0 50 100 150Temperature (∘C)

minus50

Tm = 10834∘C

X = 3055

Tm = 10629∘C

X = 3277

minus100

05

00

minus05

minus10

minus15

Hea

t flow

(Wgminus

1)


DSC of EOC-17 (Engage 8540)mdashmelting 2

(a)


minus100 minus50

02

00

minus02

minus04

minus06

minus08

Hea

t flow

(Wgminus

1)


Tm = 4261∘C

X = 755

Tm = 4353∘C

X = 959


(b)

Figure 10 DSC graph of (a) EOC-17 (Engage 8540) with 5wt Cloisite 93mdashmelting 2 and (b) EOC-45 (Engage 8842) with 5wt Cloisite93mdashmelting 2

presence However crystallization curves differ significantlypure EOC crystallizes at 883∘C blending Cloisite 93 intoEOC leads to the higher crystallization temperature of 894∘Cand additional peak occurs at 105∘C The reason for twocrystallization peaks is a low percentage of octene unitsCloisite 93 causes a shift in crystallization peaks whichexplains two peaks of a blend compared to two peaks ofpure EOC We can speculate that Cloisite 93 can influencecrystallization ability of long base ethylene chains but doesnot affect short octene chains

The exfoliation of nanoclay in EOC-17 was not perfect(shown by XRD and TEM) and some aggregates of clayremained These aggregates acted most likely as nucleatingagents Therefore the crystallization temperature increasedabout 2∘C

This effect is much more visible in a second nanocom-posite EOC-45 with Cloisite 93 (Figures 10(b) and 11(b))mdashinthis case pure polymermelts at 435∘CCloisite 93 causes shiftpeak at 426∘C of pure EOC-45 and additional peak at 126∘Cis visible (comes probably from PE-MA compatibilizer) PureEOC-45 crystallizes at temperature 188∘C and filled at 161∘Cpeak at 120∘C (PE-MA) remains

Due to mentioned effect at crystallization and a higheroctene content of EOC-45 peak appearance could be causedby a combination of both factors Melting curves showthat similar behavior of Cloisite 93 causes forming of theadditional peak at high temperature and a slight drop in amelting temperatureThe percent crystallinity was calculatedusing a value ofΔ119867∘

119898= 290 Jgminus1 for the heat of fusion of 100

crystalline polyethylene [32]


Table 7 FTIR measurement and comparison of the peak area before UV degradation and peak area after 46 days of UV degradation

Composition Peak area1810920ndash1508135 cmminus1

Peak area 46 days1810920ndash1508135 cmminus1

Peak height at 1720 cmminus146 days (absorbance)



minus50minus100

25

20

15

10

05

00

minus05

Hea

t flow

(Wgminus

1)


Tc = 8940∘C

X = 3198

Tc = 8736∘C

X = 3161

DSC of EOC-17 (Engage 8540)mdashcrystallization 1

(a)

Tc = 1823∘C

X = 984

Tc = 1645∘C

X = 895


minus50minus100

08

06

04

02

00

Hea

t flow

(Wgminus

1)



(b)

Figure 11 DSC graph of (a) EOC-17 (Engage 8540) with 5wt Cloisite 93mdashcrystallization 2 and (b) EOC-45 (Engage 8842) with 5wtCloisite 93mdashcrystallization 2

As shown by XRD and TEM the exfoliation of nanoclayin EOC-45 was better This influenced rather broad meltingpeak and lower crystallization temperature This time therewere no aggregates that could serve as nucleating agents

37 Accelerated Weathering Test and FTIR The samplesunderwent UV degradation in the device Xenotest Alpha forthe period 46 days At the beginning of the degradation testand at the end of degradation test FTIR analysis of all themeasured samples was performed

EOC chain is composed only of CH3and CH

2groups

Typical peaks (see Figures 12 and 13) for these groups are in2962 cmminus1 for CH

3asymmetric valence (as v) 2872 cmminus1

for CH3symmetric valence (s v) and 2926 cmminus1 for CH

2

asymmetric valence (as v) 2853 cmminus1 for CH2symmetric

valence (s v)By FTIR analysis change in the area of 1810 cmminus1 to

1681 cmminus1 was monitoredThis maximum corresponds to thevibration of C=O bonds that are generated in the degradationprocesses The results show that the largest increase in thearea of the pure samples EOC-17 and EOC-45 was recorded

The higher change of EOC-17 pure was observed Filledspecimens show a smaller percentage of degradation of thematrix (see Table 7) During sample degradation probablymolecular weight decreases and leads to the breaking ofchains

Filling 5wt of the modified Cloisite 93 has improvedobserved characteristics especially in the longer term In thiscase the impact modifier can be expected during the courseof degradation

The difference between the materials in the curves maybe caused by different densities of both the EOC andvarious contents of octene groupsThe protection against UVdegradation was better in the case of EOC-45 nanocompositemost likely due to a better dispersion of clay

The presence of the filler (Cloisite 93) in the EOC-45 matrix reduces degradation of the nanocomposite incomparison to pure EOC-45 which may be due to a higherlevel of exfoliation of the MMT platelets in polymer matrixbecause these exfoliated filler particles can protect EOCrsquospolymer chain against the degradation impacts Table 7 showspeak height at 1720 cmminus1 46 days (absorbance) and Figure 13


1500200025003000

Abso

rban

ce

00

01

02

03

EOC-17 pureafter 46 days after 46 days

EOC-17 + 5 Cloisite 93

EOC-17 pure EOC-17 + 5 Cloisite 93EOC-17 pureafter 46 days

EOC-17 + 5 Cloisite 93after 46 days

Wavenumber (cmminus1)

Figure 12 FTIR graph of EOC-17 (Engage 8540) pure and EOC-17 with 5wt Cloisite 93 and details of area 1810 to 1681 cmminus1 Picture ofchange of EOC-17 pure after 46 days of UV degradation EOC-17 + 5 Cloisite 93 after 46 days of UV degradation

1500200025003000

Abso

rban

ce

000

005

010

015

020

025

030EOC-45 pureafter 46 days after 46 days







shows decrease from 0133 for pure EOC-45 to 0102 for EOC-45 with 5wt Cloisite 93

The results of FTIR confirm the tests of the DMA XRDTEM and DCS for better exfoliation of nanofiller in polymermatrix EOC-45 The perfect exfoliation of nanofiller in thepolymer matrix may be caused by higher content octeneunits

4 Conclusion

Ethylene-octene copolymer matrices with one type of com-mercial nanofiller with different concentrationwere preparedand observed Because of using mentionedmaterials for foodpackaging the mechanical properties of prepared samplesbarrier morphological thermal and UV degradation prop-erties were checked

Comparison of mechanical properties and exfoliationof the nanofiller in the polymer matrix was observedStrengthening effect of Cloisite is stronger in the EOC-45mixture when compared to EOC-17 In addition to increasedmodulus glass transmission and melting temperature areslightly shifted to higher temperatures The very good resultin the case of mechanical and barrier properties were foundespecially for EOC matrix with 5wt Cloisite 93 The EOCreaches the maximum value EOC-45 with 5wt Cloisite 93on the opposite side of the lowest values in the EOC-17 +3 Cloisite 93 for mechanical properties EOC-17 pure andits blends with Cloisite 93 show a linear decrease of tan delta(tan 120575) with increasing frequency The addition of Cloisite 93causes tan 120575 to drop significantly at high frequencies whereasthe low frequencies are affected onlymarginally

Filling 5wt of the modified Cloisite 93 has improvedFTIR observed characteristics especially in the longer termIn this case the impact modifier can be expected duringthe course of degradation Platelets of montmorillonite canoverlap andmay cause deterioration of the desired propertiesThe goal of the production of polymer nanocomposites isto achieve the full exfoliation It was found that nanofillersin polymer matrix mechanics affect polymer properties It ispossible to state that good exfoliation of fillers can improvemechanical properties of nanocomposites Nevertheless thedegree of exfoliation and orientation of the platelets is themost critical parameter

Conflict of Interests

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

Acknowledgments

This paper (specified by the fact) was writtenwith the supportby the Projects TA03010799 and IGAFT2015007 TBU inZlin

References

[1] F Bertini M Canetti G Audisio G Costa and L FalquildquoCharacterization and thermal degradation of polypropylene-montmorillonite nanocompositesrdquo Polymer Degradation andStability vol 91 no 3 pp 600ndash605 2006

[2] S P Zhu J Y Chen H L Li and Y Cao ldquoEffect of polymermatrixmontmorillonite compatibility onmorphology andmeltrheology of polypropylene nanocompositesrdquo Journal of AppliedPolymer Science vol 128 no 6 pp 3876ndash3884 2013

[3] F Lei S Yang M T Yang J Li and S Y Guo ldquoExfoliation oforganic montmorillonite in iPP free of compatibilizer throughthe multistage stretching extrusionrdquo Polymer Bulletin vol 71no 12 pp 3261ndash3273 2014

[4] L B Fitaroni J A de Lima S A Cruz and W R Wald-man ldquoThermal stability of polypropylene-montmorillonite claynanocomposites limitation of the thermogravimetric analysisrdquoPolymer Degradation and Stability vol 111 pp 102ndash108 2015

[5] X Yin and G S Hu ldquoEffects of organic montmorillonitewith different interlayer spacing on mechanical propertiescrystallization and morphology of polyamide 1010nanometercalcium carbonate nanocompositesrdquo Fibers and Polymers vol16 no 1 pp 120ndash128 2015

[6] K-B Yoon H-D Sung Y-Y Hwang S K Noh and D-HLee ldquoModification of montmorillonite with oligomeric aminederivatives for polymer nanocomposite preparationrdquo AppliedClay Science vol 38 no 1-2 pp 1ndash8 2007

[7] L B Manfredi D Puglia A Tomasucci J M Kenny andA Vazquez ldquoInfluence of clay modification on the propertiesof resol nanocompositesrdquo Macromolecular Materials and Engi-neering vol 293 no 11 pp 878ndash886 2008

[8] Z Qian S Zhang and M Yang ldquoEffect of clay modification onphoto-oxidation of polyethyleneclay nanocompositesrdquo Poly-mers and Polymer Composites vol 16 no 8 pp 535ndash546 2008

[9] X Y Meng Z Wang X H Du Y H Wang and T TangldquoExfoliation of organically modified montmorillonite drivenby molecular diffusion in maleated polypropylenerdquo Journal ofApplied Polymer Science vol 113 no 1 pp 678ndash684 2009

[10] J Soulestin B J Rashmi S Bourbigot M-F Lacrampe andP Krawczak ldquoMechanical and optical properties of polyamide6clay nanocomposite cast films influence of the degree ofexfoliationrdquo Macromolecular Materials and Engineering vol297 no 5 pp 444ndash454 2012

[11] T Kuila T Tripathy and J H Lee ldquoPolyolefin-based poly-mer nanocompositesrdquo in Advances in Polymer NanocompositesTypes and Applications pp 181ndash215 Woodhead Publishing2012

[12] F Zandi M Rezaei and A Kasiri ldquoEffect of nanoclay on thephysical-mechanical and thermal properties and microstruc-ture of extruded noncross-linked LDPE nanocomposite foamsrdquoComposite Science and Technology vol 471-472 pp 751ndash7562011

[13] P Santamarıa J I Eguiazabal and J Nazabal ldquoDispersion andmechanical properties of a nanocomposite with an organoclayin an ionomer-compatibilized LDPEmatrixrdquo Journal of AppliedPolymer Science vol 119 no 3 pp 1762ndash1770 2011

[14] R Theravalappil P Svoboda J Vilcakova S Poongavalappil PSlobodian andD Svobodova ldquoA comparative study on the elec-trical thermal and mechanical properties of ethylene-octenecopolymer based composites with carbon fillersrdquo Materials ampDesign vol 60 pp 458ndash467 2014


[15] C Grein M Gahleitner and K Bernreitner ldquoMechanical andoptical effects of elastomer interaction in polypropylene modi-fication ethylene-propylene rubber poly-(ethylene-co-octene)and styrene-butadiene elastomersrdquo Express Polymer Letters vol6 no 9 pp 688ndash696 2012

[16] R Rajeshbabu U Gohs K Naskar VThakur UWagenknechtand G Heinrich ldquoPreparation of polypropylene (PP)ethyleneoctene copolymer (EOC) thermoplastic vulcanizates (TPVs) byhigh energy electron reactive processingrdquoRadiation Physics andChemistry vol 80 no 12 pp 1398ndash1405 2011

[17] P Svoboda RTheravalappil D Svobodova et al ldquoElastic prop-erties of polypropyleneethylene-octene copolymer blendsrdquoPolymer Testing vol 29 no 6 pp 742ndash748 2010

[18] R R Babu N K Singha and K Naskar ldquoDynamically vulcan-ized blends of polypropylene and ethylene octene copolymerinfluence of various coagents onmechanical andmorphologicalcharacteristicsrdquo Journal of Applied Polymer Science vol 113 no5 pp 3207ndash3221 2009

[19] D Pizele V Kalkis R M Meri T Ivanova and J ZicansldquoOn the mechanical and thermomechanical properties of low-density polyethyleneethylene-120572-octene copolymer blendsrdquoMechanics of Composite Materials vol 44 no 2 pp 191ndash1962008

[20] M Jaziri N Mnif V Massardier-Nageotte and H Perier-Camby ldquoRheological thermal and morphological proper-ties of blends based on poly(propylene) ethylene propylenerubber and ethylene-1-octene copolymer that could resultfrom end of life vehicles effect of maleic anhydride graftedpoly(propylene)rdquo Polymer Engineering and Science vol 47 no7 pp 1009ndash1015 2007

[21] M J O C Guimaraes F M B Coutinho M C G Rocha MFarah and R E S Bretas ldquoEffect of molecular weight and longchain branching of metallocene elastomers on the properties ofhigh density polyethylene blendsrdquo Polymer Testing vol 22 no8 pp 843ndash847 2003

[22] A L N Silva M C G Rocha and F M B Coutinho ldquoStudyof rheological behavior of elastomerpolypropylene blendsrdquoPolymer Testing vol 21 no 3 pp 289ndash293 2002

[23] R R Babu N K Singha and K Naskar ldquoPhase morphologyand melt rheological behavior of uncrosslinked and dynam-ically crosslinked polyolefin blends role of macromolecularstructurerdquo Polymer Bulletin vol 66 no 1 pp 95ndash118 2011

[24] R R Babu N K Singha and K Naskar ldquoInterrelation-ships of morphology thermal and mechanical propertiesin uncrosslinked and dynamically crosslinked PPEOC andPPEPDMblendsrdquoExpress Polymer Letters vol 4 no 4 pp 197ndash209 2010

[25] X Yan X Xu T Zhu C Zhang N Song and L ZhuldquoPhase morphological evolution and rheological properties ofpolypropyleneethylene-octene copolymer blendsrdquo MaterialsScience and Engineering A vol 476 no 1-2 pp 120ndash125 2008

[26] N Tortorella and C L Beatty ldquoMorphology and mechanicalproperties of impact modified polypropylene blendsrdquo PolymerEngineering and Science vol 48 no 11 pp 2098ndash2110 2008

[27] W-Y Guo and B Peng ldquoRheology morphology and mechan-ical and thermal properties of blends of propylene based plas-tomer and ethylene1-octene copolymerrdquo Journal of Elastomersand Plastics vol 40 no 1 pp 61ndash76 2008

[28] K Wang F Addiego N Bahlouli S Ahzi Y Remond and VToniazzo ldquoImpact response of recycled polypropylene-basedcomposites under a wide range of temperature effect of filler

content and recyclingrdquo Composites Science and Technology vol95 pp 89ndash99 2014

[29] O Saravari H Waipunya and S Chuayjuljit ldquoEffects of ethy-lene octene copolymer and ultrafine wollastonite on the prop-erties and morphology of polypropylene-based compositesrdquoJournal of Elastomers and Plastics vol 46 no 2 pp 175ndash1862014

[30] I Bochkov R M Meri J Zicans T Ivanova and J Gra-bis ldquoMulti-component composites based on polypropyleneEthylene-octene copolymer and zinc oxiderdquo Engineering Mate-rials amp Tribology XXII vol 604 pp 130ndash133 2014

[31] S Bagheri-Kazemabad D Fox Y H Chen H Z Zhangand B Q Chen ldquoMorphology and properties of polypro-pyleneethylene-octene copolymerclay nanocomposites withdouble compatibilizersrdquo Polymers for Advanced Technologiesvol 25 no 10 pp 1116ndash1121 2014

[32] P Dias Y J Lin B Poon H Y Chen A Hiltner and E BaerldquoAdhesion of statistical and blocky ethylenendashoctene copolymersto polypropylenerdquo Polymer vol 49 no 12 pp 2937ndash2946 2008

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


A polymermatrix

Gas transmission

Nanofillerplatelets

Figure 1 Improved barrier properties of nanocomposites

are studied One of them can be an ethylene-octene copoly-mer (EOC) and alternatively its blends with other polymermatrices mostly PP [1ndash3]

The ethylene-octene copolymer (EOC) a new polyolefinelastomer developed byDowChemical Company (DelawareUSA) with metallocene catalysis is interesting by its prop-erties and is attracting a lot of attention from both researchand industry [14ndash16] EOC is an ethylene based elastomerso it brings an excellent compatibility with polyolefins suchas polyethylene and PP [17ndash20] The presence of the octenecomonomer in EOC causes a lower level of crystallinity and ahigher flexibility in the copolymer EOC can be consideredas an elastomeric polymer and usually the octene contentin the copolymer varies under 20wt [21 22] Blends ofPPEOC may provide enhanced impact properties and canbe used for example in extruded or molded automotiveexterior and interior parts housing appliances and otherlow-temperature applications Pelletized EOC exhibits easyhandling mixing and processability Based on these prop-erties EOC is currently being used as an impact modifier ofPP to replace ethylene propylene rubber (EPR) and ethylenepropylene diene rubber (EPDM) [19 23 24]

As it was mentioned above EOC significantly improvesthe impact strength but it causes a decrease of thetensile strength and stiffness of PP [25ndash27] ThereforePPEOCmineral filler-based composites have been studiedin order to enhance the toughness and stiffness of PPsimultaneously These systems are double-phased [23ndash25]Mineral fillers with high aspect ratio that is clay nanofillershave been found to increase stiffness and strength to thethermoplastic polyolefins they provide a greater possibilityfor energy transfer from one phase to another [28ndash31]

However comparative evaluation of the mechanical andthermal properties of composites based on PP EOC andmineral fillers is still limited

The aim of this work was to add more information aboutthe properties of EOC copolymer with clay nanofiller inorder to evaluate the influence of used nanofiller and itsconcentration on the EOC copolymer EOC matrix withnanoclay was chosen because this polymer matrix can be

considered as one of tie layers of multilayer packaging filmswith the better end of use properties

2 Materials and Methods

21 Materials Polymer matrices used as carriermaterials were ethylene-octene copolymers Engage8842 and Engage 8540 (both of DuPont DOWElastomers Europe GMBH Switzerland)mdashlinear formula(CH2CH2)119909[CH2CH[(CH

2)5CH3]]119910(see Figure 2)

To increase compatibility between the polymer matrixand the filler maleinized polyethylene (PE-MA) Priex 12043(ADDCOMPHolland BV) in 5wt concentration was used

EOC-45 (Engage 8842) is an ultralow density copolymer(see Table 1) that offers exceptional properties of an ultralowdensity elastomer with the added potential of handing thispolymer in pellet form It has excellent flow characteris-tics and provides superb impact properties in blends withpolypropylene (PP) and polyethylene (PE)

EOC-17 (Engage 8540) is a polyolefin elastomer thatis well suited for foam applications and offers excellentperformance for profile extrusion of tubing and hoses

Organically modified montmorillonite (MMT) withtrade name Cloisite 93A (Southern Clay Products Inc) wasusedThis type of nanoclay ismodified by organic branches oftype dimethyl hydrogenated tallow 2-ethylhexyl and quar-tenary ammonium methylsulfate this type is recommendedfor nonpolar polymer matrices

The quantity of the above-mentioned nanofiller added tothe polymeric matrix was 3 5 or 7wt

22 Sample Preparation Polymers with the fillers were com-pounded in twin-screw extruder Scientific LTE 20-40 screwdiameter was 20mm and 119871119863 ratio was 401 The tempera-tures of the individual heating zones and the extrusion headwere set from 170∘C to 205∘C the rotation speed of screwswas 300 rpm and the rotation speed of volumetric feedingscrew was 20 rpm The extruded strands were air-cooled andthen transferred using a knife mill back to a pelletizer ScherrSGS-50E

Specimens for measurement of properties were preparedby compression molding and cutting Blends in the formof pellets were placed between two PET sheets preventingthe contact with air and thus oxidative degradation Thematerial was pressed in a mold with size 125 times 125 times 2mm(for platelets) The pressing time was 5 minutes for platelets(thickness approximately 2mm) and 3 minutes for films(thickness about 50120583m) pellets are molded without a frameonly between two plates of the machine After that the moldwith material was placed into a water-cooled hydraulic pressand cooled down to room temperature

23 Evaluation of Prepared Samples

231 Mechanical Properties Tensile tests are among themostwidely used test methods The test specimen is deformedunidirectional until the break Tensile testing was performedon tear machines with a range of campaign Tensile test




Density(gcm3)

119879119898

(∘C)


CH2CH2 CH2CH

CH3(CH2)4CH2

x

y






2 O2 and CO

2

















Strain ()0 200 400 600 800 1000

Stre

ss (M

Pa)

0

10

20

30


(a)


0

2

4

6

8

Strain ()0 500 15001000

Stre

ss (M

Pa)


(b)




1







1(mm) 119897

2(mm)






Frequency (Hz)0 50 100 150 200

002

004

006

008

010

012

014

016

018


tan 120575

(a)


Frequency (Hz)0 50 100 150 200

00

01

02

03

04

05

tan 120575


(b)





1198641015840 modulus (MPa)








0 50 10010

100

1000

E998400

mod

ulus

(MPa

)



(a)


00

01

02

03

04

05

06

tan 120575


minus100 minus50


(b)











2

O2 and CO











2


GTR for N2


2


2



0

10000

20000

30000

40000

N2O2

CO2

EOC-

45+7

C

loisi

te 9

3

EOC-

45+5

C

loisi

te 9

3

EOC-

45+3

C

loisi

te 9

3

EOC-

45

pure

EOC-

17+7

C

loisi

te 9

3

EOC-

17+5

C

loisi

te 9

3

EOC-

17+3

C

loisi

te 9

3

EOC-

17

pure

GTR

(cm

3(S

TP)

m2middotd

en01

MPa

)

(a)


0

2000

4000

6000

8000

10000

OTR

(cm

3(S

TP)

m2middotd

en01

MPa

)

EOC-

45+7

C

loisi

te 9

3

EOC-

45+5

C

loisi

te 9

3

EOC-

45+3

C

loisi

te 9

3

EOC-

45

pure

EOC-

17+7

C

loisi

te 9

3

EOC-

17+5

C

loisi

te 9

3

EOC-

17+3

C

loisi

te 9

3

EOC-

17

pure

(b)










2 3 4 5 6 7 8

Inte

nsity

(au

)

0

500

1000

1500

2000

2500



D-spacing 27nm

D-spacing 25nm

(a)


2 3 4 5 6 7 8

Inte

nsity

(au

)

0

500

1000

1500

2000



Cloisite 93

D-spacing 25nm

(b)


100nm

(a)

100nm

(b)










100nm

(a)

100nm

(b)



minus50

Tm = 10834∘C

X = 3055

Tm = 10629∘C

X = 3277

minus100

05

00

minus05

minus10

minus15

Hea

t flow

(Wgminus

1)



(a)


minus100 minus50

02

00

minus02

minus04

minus06

minus08

Hea

t flow

(Wgminus

1)


Tm = 4261∘C

X = 755

Tm = 4353∘C

X = 959


(b)















minus50minus100

25

20

15

10

05

00

minus05

Hea

t flow

(Wgminus

1)


Tc = 8940∘C

X = 3198

Tc = 8736∘C

X = 3161


(a)

Tc = 1823∘C

X = 984

Tc = 1645∘C

X = 895


minus50minus100

08

06

04

02

00

Hea

t flow

(Wgminus

1)



(b)





2groups




2









1500200025003000

Abso

rban

ce

00

01

02

03







1500200025003000

Abso

rban

ce

000

005

010

015

020

025










4 Conclusion






Acknowledgments


References










































CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials






Density(gcm3)

119879119898

(∘C)


CH2CH2 CH2CH

CH3(CH2)4CH2

x

y






2 O2 and CO

2

















Strain ()0 200 400 600 800 1000

Stre

ss (M

Pa)

0

10

20

30


(a)


0

2

4

6

8

Strain ()0 500 15001000

Stre

ss (M

Pa)


(b)




1







1(mm) 119897

2(mm)






Frequency (Hz)0 50 100 150 200

002

004

006

008

010

012

014

016

018


tan 120575

(a)


Frequency (Hz)0 50 100 150 200

00

01

02

03

04

05

tan 120575


(b)





1198641015840 modulus (MPa)








0 50 10010

100

1000

E998400

mod

ulus

(MPa

)



(a)


00

01

02

03

04

05

06

tan 120575


minus100 minus50


(b)











2

O2 and CO











2


GTR for N2


2


2



0

10000

20000

30000

40000

N2O2

CO2

EOC-

45+7

C

loisi

te 9

3

EOC-

45+5

C

loisi

te 9

3

EOC-

45+3

C

loisi

te 9

3

EOC-

45

pure

EOC-

17+7

C

loisi

te 9

3

EOC-

17+5

C

loisi

te 9

3

EOC-

17+3

C

loisi

te 9

3

EOC-

17

pure

GTR

(cm

3(S

TP)

m2middotd

en01

MPa

)

(a)


0

2000

4000

6000

8000

10000

OTR

(cm

3(S

TP)

m2middotd

en01

MPa

)

EOC-

45+7

C

loisi

te 9

3

EOC-

45+5

C

loisi

te 9

3

EOC-

45+3

C

loisi

te 9

3

EOC-

45

pure

EOC-

17+7

C

loisi

te 9

3

EOC-

17+5

C

loisi

te 9

3

EOC-

17+3

C

loisi

te 9

3

EOC-

17

pure

(b)










2 3 4 5 6 7 8

Inte

nsity

(au

)

0

500

1000

1500

2000

2500



D-spacing 27nm

D-spacing 25nm

(a)


2 3 4 5 6 7 8

Inte

nsity

(au

)

0

500

1000

1500

2000



Cloisite 93

D-spacing 25nm

(b)


100nm

(a)

100nm

(b)










100nm

(a)

100nm

(b)



minus50

Tm = 10834∘C

X = 3055

Tm = 10629∘C

X = 3277

minus100

05

00

minus05

minus10

minus15

Hea

t flow

(Wgminus

1)



(a)


minus100 minus50

02

00

minus02

minus04

minus06

minus08

Hea

t flow

(Wgminus

1)


Tm = 4261∘C

X = 755

Tm = 4353∘C

X = 959


(b)















minus50minus100

25

20

15

10

05

00

minus05

Hea

t flow

(Wgminus

1)


Tc = 8940∘C

X = 3198

Tc = 8736∘C

X = 3161


(a)

Tc = 1823∘C

X = 984

Tc = 1645∘C

X = 895


minus50minus100

08

06

04

02

00

Hea

t flow

(Wgminus

1)



(b)





2groups




2









1500200025003000

Abso

rban

ce

00

01

02

03







1500200025003000

Abso

rban

ce

000

005

010

015

020

025










4 Conclusion






Acknowledgments


References










































CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials







Strain ()0 200 400 600 800 1000

Stre

ss (M

Pa)

0

10

20

30


(a)


0

2

4

6

8

Strain ()0 500 15001000

Stre

ss (M

Pa)


(b)




1







1(mm) 119897

2(mm)






Frequency (Hz)0 50 100 150 200

002

004

006

008

010

012

014

016

018


tan 120575

(a)


Frequency (Hz)0 50 100 150 200

00

01

02

03

04

05

tan 120575


(b)





1198641015840 modulus (MPa)








0 50 10010

100

1000

E998400

mod

ulus

(MPa

)



(a)


00

01

02

03

04

05

06

tan 120575


minus100 minus50


(b)











2

O2 and CO











2


GTR for N2


2


2



0

10000

20000

30000

40000

N2O2

CO2

EOC-

45+7

C

loisi

te 9

3

EOC-

45+5

C

loisi

te 9

3

EOC-

45+3

C

loisi

te 9

3

EOC-

45

pure

EOC-

17+7

C

loisi

te 9

3

EOC-

17+5

C

loisi

te 9

3

EOC-

17+3

C

loisi

te 9

3

EOC-

17

pure

GTR

(cm

3(S

TP)

m2middotd

en01

MPa

)

(a)


0

2000

4000

6000

8000

10000

OTR

(cm

3(S

TP)

m2middotd

en01

MPa

)

EOC-

45+7

C

loisi

te 9

3

EOC-

45+5

C

loisi

te 9

3

EOC-

45+3

C

loisi

te 9

3

EOC-

45

pure

EOC-

17+7

C

loisi

te 9

3

EOC-

17+5

C

loisi

te 9

3

EOC-

17+3

C

loisi

te 9

3

EOC-

17

pure

(b)










2 3 4 5 6 7 8

Inte

nsity

(au

)

0

500

1000

1500

2000

2500



D-spacing 27nm

D-spacing 25nm

(a)


2 3 4 5 6 7 8

Inte

nsity

(au

)

0

500

1000

1500

2000



Cloisite 93

D-spacing 25nm

(b)


100nm

(a)

100nm

(b)










100nm

(a)

100nm

(b)



minus50

Tm = 10834∘C

X = 3055

Tm = 10629∘C

X = 3277

minus100

05

00

minus05

minus10

minus15

Hea

t flow

(Wgminus

1)



(a)


minus100 minus50

02

00

minus02

minus04

minus06

minus08

Hea

t flow

(Wgminus

1)


Tm = 4261∘C

X = 755

Tm = 4353∘C

X = 959


(b)















minus50minus100

25

20

15

10

05

00

minus05

Hea

t flow

(Wgminus

1)


Tc = 8940∘C

X = 3198

Tc = 8736∘C

X = 3161


(a)

Tc = 1823∘C

X = 984

Tc = 1645∘C

X = 895


minus50minus100

08

06

04

02

00

Hea

t flow

(Wgminus

1)



(b)





2groups




2









1500200025003000

Abso

rban

ce

00

01

02

03







1500200025003000

Abso

rban

ce

000

005

010

015

020

025










4 Conclusion






Acknowledgments


References










































CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials





Frequency (Hz)0 50 100 150 200

002

004

006

008

010

012

014

016

018


tan 120575

(a)


Frequency (Hz)0 50 100 150 200

00

01

02

03

04

05

tan 120575


(b)





1198641015840 modulus (MPa)








0 50 10010

100

1000

E998400

mod

ulus

(MPa

)



(a)


00

01

02

03

04

05

06

tan 120575


minus100 minus50


(b)











2

O2 and CO











2


GTR for N2


2


2



0

10000

20000

30000

40000

N2O2

CO2

EOC-

45+7

C

loisi

te 9

3

EOC-

45+5

C

loisi

te 9

3

EOC-

45+3

C

loisi

te 9

3

EOC-

45

pure

EOC-

17+7

C

loisi

te 9

3

EOC-

17+5

C

loisi

te 9

3

EOC-

17+3

C

loisi

te 9

3

EOC-

17

pure

GTR

(cm

3(S

TP)

m2middotd

en01

MPa

)

(a)


0

2000

4000

6000

8000

10000

OTR

(cm

3(S

TP)

m2middotd

en01

MPa

)

EOC-

45+7

C

loisi

te 9

3

EOC-

45+5

C

loisi

te 9

3

EOC-

45+3

C

loisi

te 9

3

EOC-

45

pure

EOC-

17+7

C

loisi

te 9

3

EOC-

17+5

C

loisi

te 9

3

EOC-

17+3

C

loisi

te 9

3

EOC-

17

pure

(b)










2 3 4 5 6 7 8

Inte

nsity

(au

)

0

500

1000

1500

2000

2500



D-spacing 27nm

D-spacing 25nm

(a)


2 3 4 5 6 7 8

Inte

nsity

(au

)

0

500

1000

1500

2000



Cloisite 93

D-spacing 25nm

(b)


100nm

(a)

100nm

(b)










100nm

(a)

100nm

(b)



minus50

Tm = 10834∘C

X = 3055

Tm = 10629∘C

X = 3277

minus100

05

00

minus05

minus10

minus15

Hea

t flow

(Wgminus

1)



(a)


minus100 minus50

02

00

minus02

minus04

minus06

minus08

Hea

t flow

(Wgminus

1)


Tm = 4261∘C

X = 755

Tm = 4353∘C

X = 959


(b)















minus50minus100

25

20

15

10

05

00

minus05

Hea

t flow

(Wgminus

1)


Tc = 8940∘C

X = 3198

Tc = 8736∘C

X = 3161


(a)

Tc = 1823∘C

X = 984

Tc = 1645∘C

X = 895


minus50minus100

08

06

04

02

00

Hea

t flow

(Wgminus

1)



(b)





2groups




2









1500200025003000

Abso

rban

ce

00

01

02

03







1500200025003000

Abso

rban

ce

000

005

010

015

020

025










4 Conclusion






Acknowledgments


References










































CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials





0 50 10010

100

1000

E998400

mod

ulus

(MPa

)



(a)


00

01

02

03

04

05

06

tan 120575


minus100 minus50


(b)











2

O2 and CO











2


GTR for N2


2


2



0

10000

20000

30000

40000

N2O2

CO2

EOC-

45+7

C

loisi

te 9

3

EOC-

45+5

C

loisi

te 9

3

EOC-

45+3

C

loisi

te 9

3

EOC-

45

pure

EOC-

17+7

C

loisi

te 9

3

EOC-

17+5

C

loisi

te 9

3

EOC-

17+3

C

loisi

te 9

3

EOC-

17

pure

GTR

(cm

3(S

TP)

m2middotd

en01

MPa

)

(a)


0

2000

4000

6000

8000

10000

OTR

(cm

3(S

TP)

m2middotd

en01

MPa

)

EOC-

45+7

C

loisi

te 9

3

EOC-

45+5

C

loisi

te 9

3

EOC-

45+3

C

loisi

te 9

3

EOC-

45

pure

EOC-

17+7

C

loisi

te 9

3

EOC-

17+5

C

loisi

te 9

3

EOC-

17+3

C

loisi

te 9

3

EOC-

17

pure

(b)










2 3 4 5 6 7 8

Inte

nsity

(au

)

0

500

1000

1500

2000

2500



D-spacing 27nm

D-spacing 25nm

(a)


2 3 4 5 6 7 8

Inte

nsity

(au

)

0

500

1000

1500

2000



Cloisite 93

D-spacing 25nm

(b)


100nm

(a)

100nm

(b)










100nm

(a)

100nm

(b)



minus50

Tm = 10834∘C

X = 3055

Tm = 10629∘C

X = 3277

minus100

05

00

minus05

minus10

minus15

Hea

t flow

(Wgminus

1)



(a)


minus100 minus50

02

00

minus02

minus04

minus06

minus08

Hea

t flow

(Wgminus

1)


Tm = 4261∘C

X = 755

Tm = 4353∘C

X = 959


(b)















minus50minus100

25

20

15

10

05

00

minus05

Hea

t flow

(Wgminus

1)


Tc = 8940∘C

X = 3198

Tc = 8736∘C

X = 3161


(a)

Tc = 1823∘C

X = 984

Tc = 1645∘C

X = 895


minus50minus100

08

06

04

02

00

Hea

t flow

(Wgminus

1)



(b)





2groups




2









1500200025003000

Abso

rban

ce

00

01

02

03







1500200025003000

Abso

rban

ce

000

005

010

015

020

025










4 Conclusion






Acknowledgments


References










































CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials





2


GTR for N2


2


2



0

10000

20000

30000

40000

N2O2

CO2

EOC-

45+7

C

loisi

te 9

3

EOC-

45+5

C

loisi

te 9

3

EOC-

45+3

C

loisi

te 9

3

EOC-

45

pure

EOC-

17+7

C

loisi

te 9

3

EOC-

17+5

C

loisi

te 9

3

EOC-

17+3

C

loisi

te 9

3

EOC-

17

pure

GTR

(cm

3(S

TP)

m2middotd

en01

MPa

)

(a)


0

2000

4000

6000

8000

10000

OTR

(cm

3(S

TP)

m2middotd

en01

MPa

)

EOC-

45+7

C

loisi

te 9

3

EOC-

45+5

C

loisi

te 9

3

EOC-

45+3

C

loisi

te 9

3

EOC-

45

pure

EOC-

17+7

C

loisi

te 9

3

EOC-

17+5

C

loisi

te 9

3

EOC-

17+3

C

loisi

te 9

3

EOC-

17

pure

(b)










2 3 4 5 6 7 8

Inte

nsity

(au

)

0

500

1000

1500

2000

2500



D-spacing 27nm

D-spacing 25nm

(a)


2 3 4 5 6 7 8

Inte

nsity

(au

)

0

500

1000

1500

2000



Cloisite 93

D-spacing 25nm

(b)


100nm

(a)

100nm

(b)










100nm

(a)

100nm

(b)



minus50

Tm = 10834∘C

X = 3055

Tm = 10629∘C

X = 3277

minus100

05

00

minus05

minus10

minus15

Hea

t flow

(Wgminus

1)



(a)


minus100 minus50

02

00

minus02

minus04

minus06

minus08

Hea

t flow

(Wgminus

1)


Tm = 4261∘C

X = 755

Tm = 4353∘C

X = 959


(b)















minus50minus100

25

20

15

10

05

00

minus05

Hea

t flow

(Wgminus

1)


Tc = 8940∘C

X = 3198

Tc = 8736∘C

X = 3161


(a)

Tc = 1823∘C

X = 984

Tc = 1645∘C

X = 895


minus50minus100

08

06

04

02

00

Hea

t flow

(Wgminus

1)



(b)





2groups




2









1500200025003000

Abso

rban

ce

00

01

02

03







1500200025003000

Abso

rban

ce

000

005

010

015

020

025










4 Conclusion






Acknowledgments


References










































CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials





2 3 4 5 6 7 8

Inte

nsity

(au

)

0

500

1000

1500

2000

2500



D-spacing 27nm

D-spacing 25nm

(a)


2 3 4 5 6 7 8

Inte

nsity

(au

)

0

500

1000

1500

2000



Cloisite 93

D-spacing 25nm

(b)


100nm

(a)

100nm

(b)










100nm

(a)

100nm

(b)



minus50

Tm = 10834∘C

X = 3055

Tm = 10629∘C

X = 3277

minus100

05

00

minus05

minus10

minus15

Hea

t flow

(Wgminus

1)



(a)


minus100 minus50

02

00

minus02

minus04

minus06

minus08

Hea

t flow

(Wgminus

1)


Tm = 4261∘C

X = 755

Tm = 4353∘C

X = 959


(b)















minus50minus100

25

20

15

10

05

00

minus05

Hea

t flow

(Wgminus

1)


Tc = 8940∘C

X = 3198

Tc = 8736∘C

X = 3161


(a)

Tc = 1823∘C

X = 984

Tc = 1645∘C

X = 895


minus50minus100

08

06

04

02

00

Hea

t flow

(Wgminus

1)



(b)





2groups




2









1500200025003000

Abso

rban

ce

00

01

02

03







1500200025003000

Abso

rban

ce

000

005

010

015

020

025










4 Conclusion






Acknowledgments


References










































CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials




100nm

(a)

100nm

(b)



minus50

Tm = 10834∘C

X = 3055

Tm = 10629∘C

X = 3277

minus100

05

00

minus05

minus10

minus15

Hea

t flow

(Wgminus

1)



(a)


minus100 minus50

02

00

minus02

minus04

minus06

minus08

Hea

t flow

(Wgminus

1)


Tm = 4261∘C

X = 755

Tm = 4353∘C

X = 959


(b)















minus50minus100

25

20

15

10

05

00

minus05

Hea

t flow

(Wgminus

1)


Tc = 8940∘C

X = 3198

Tc = 8736∘C

X = 3161


(a)

Tc = 1823∘C

X = 984

Tc = 1645∘C

X = 895


minus50minus100

08

06

04

02

00

Hea

t flow

(Wgminus

1)



(b)





2groups




2









1500200025003000

Abso

rban

ce

00

01

02

03







1500200025003000

Abso

rban

ce

000

005

010

015

020

025










4 Conclusion






Acknowledgments


References










































CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials










minus50minus100

25

20

15

10

05

00

minus05

Hea

t flow

(Wgminus

1)


Tc = 8940∘C

X = 3198

Tc = 8736∘C

X = 3161


(a)

Tc = 1823∘C

X = 984

Tc = 1645∘C

X = 895


minus50minus100

08

06

04

02

00

Hea

t flow

(Wgminus

1)



(b)





2groups




2









1500200025003000

Abso

rban

ce

00

01

02

03







1500200025003000

Abso

rban

ce

000

005

010

015

020

025










4 Conclusion






Acknowledgments


References










































CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials




1500200025003000

Abso

rban

ce

00

01

02

03







1500200025003000

Abso

rban

ce

000

005

010

015

020

025










4 Conclusion






Acknowledgments


References










































CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials






4 Conclusion






Acknowledgments


References










































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










CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials



Documents

Research Article Ethylene-Octene Copolymers/Organoclay ... · 2. Materials and Methods.. Materials. Polymer matrices used as carrier materials were ethylene-octene copolymers: Engage