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Influence of Branch Influence of Branch Content on the Content on the
Mechanical Properties Mechanical Properties of metallocene of metallocene
LLDPEsLLDPEsAshraful Islam, Ibnelwaleed A. Ashraful Islam, Ibnelwaleed A.
HusseinHussein Department of Chemical EngineeringDepartment of Chemical Engineering
PPS 21PPS 21stst Annual Meeting, Leipzig, Annual Meeting, Leipzig, GermanyGermany
June 19-23, 2005 June 19-23, 2005
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IntroductionIntroduction Literature ReviewLiterature Review ObjectivesObjectives Experimental workExperimental work Results & DiscussionsResults & Discussions
OUTLINE
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HDPE LDPE
m-LLDPE
Schematic representation of the different classes of PE
ZN-LLDPE
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Morphology of polyethylene
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LITERATURE REVIEW
Authors Authors [Year][Year]
CommentsComments
Mandelkern & Mandelkern & Maxfield [1979]Maxfield [1979]
Studied the morphology of ZN LDPEs for two different Studied the morphology of ZN LDPEs for two different extreme crystallization modes. The thermodynamic extreme crystallization modes. The thermodynamic properties of LDPE primarily governed by BC and not properties of LDPE primarily governed by BC and not much dependent on molecular weight.much dependent on molecular weight.
Popli & Popli & Mandelkern Mandelkern [1987] [1987]
Studied mechanical properties of HDPE & LDPEs. Studied mechanical properties of HDPE & LDPEs. LDPEs showed lower yield stress compared to HDPEs. A LDPEs showed lower yield stress compared to HDPEs. A nonlinear relationship was found for Young’s modulus as nonlinear relationship was found for Young’s modulus as function of BC for ZN-LDPEs. Ultimate properties were function of BC for ZN-LDPEs. Ultimate properties were not strongly influenced by BC. not strongly influenced by BC.
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Authors Authors [Year][Year]
CommentsComments
Bensason et al. Bensason et al. [1996][1996]
Classified Ethylene-Octene copolymers based on BC. Classified Ethylene-Octene copolymers based on BC.
LITERATURE REVIEW (Cont’d)
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LITERATURE REVIEW (Cont’d)
Authors Authors [Year][Year]
CommentsComments
Simanke et al Simanke et al [1999] [1999]
Reported low strain properties of m-LLDPEs. They failed Reported low strain properties of m-LLDPEs. They failed to report high strain properties due to the sample to report high strain properties due to the sample slippage in the grips.slippage in the grips.
Walker et al Walker et al [2003] [2003]
DSC analysis of m-LLDPEs showed a progressive DSC analysis of m-LLDPEs showed a progressive increase in Tincrease in Tmm with decreasing BC. The results also with decreasing BC. The results also
showed that the ZN-LLDPEs have higher melting showed that the ZN-LLDPEs have higher melting temperature than the m-LLDPEs. temperature than the m-LLDPEs.
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LITERATURE REVIEW (Cont’d)
Summary:
1. Studied thermal and mechanical properties of different catagories of ZN HDPE, LDPE and LLDPEs.
2. Investigated the effect of Mw and thermal treatment on the various thermal transitions.
3. Examined the effect of comonomer type and BC on the different thermal transitions of ZN-LLDPEs.
4.Compared the final properties of traditional ZN-LLDPE with m-LLDPE.
5.Studied the influence of BC on low strain properties of m-LLDPEs with BC less than 20 CH3/1000C.
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Table 01: Polymer Characterization
ResinsDensity,
g/cm3
Mw,
Kg/molMI,
g/10minMWD BC
(CH3/1000C)
m-EH12 0.918 94 2.5 1.40 12.02
m-EH15 0.912 102 1.20 2.14 14.5
m-EH18 0.900 108 1.20 1.83 18.02
m-EH20 0.902 95 2.0 2.06 19.74
m-EH24 0.895 92 2.20 1.85 32.60
m-EH32 0.883 97 2.20 2.02 32.17
ZN-EH17 0.917 80 2.80 8.40 16.71
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Resin
Carver Press
Thin Sheet
Pneumatic Punch CutterDog-bone
Instron Machine
Experimental Steps (Mechanical)
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Resin Aluminum Pans
Press
Modulated DSCLNCS
Experimental Steps (Thermal)
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0
5
10
15
20
25
30
35
40
45
0 200 400 600 800 1000 1200 1400
Engineering Strain (%)
Engi
neer
ing
Stre
ss (M
Pa)
m-EH12
m-EH15
m-EH18
m-EH20
m-EH24
m-EH32
BC = 12.0
14.4
19.7 23.6
18.0
32.2
Figure 03: Stress/Strain curves for EH m-LLDPEs with different BCs.
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Table 2: Selected thermal properties of ethylene/-olefins copolymers
ResinBC
(CH3/1000C)
Melting Peak (oC)DSC Crystallinity Values
(%)
Before After Before After
m-EH1212.02 115.2 114.7 40.3 41.6
m-EH1514.50 105.7 103.0 34.9 36.0
m-EH1818.02 95.7 99.6 28.9 29.0
m-EH2019.74 45.1, 88.3 45.4, 94.7 31.1 31.5
m-EH2423.60 47.2, 90.3 43.2, 92.6 28.4 29.6
m-EH3232.17 46.4, 73.2 44.7, 80.0 22.6 25.2
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Figure 04: Avrami plot for EH m-LLDPEs (Strain rate 4.92 min-1)Figure 04: Avrami plot for EH m-LLDPEs (Strain rate 4.92 min-1)
Resins m-EH12
m-EH15
m-EH18
m-EH20
m-EH24
m-EH32
Avrami Exponent (n)
0.65 1.34 1.31 1.44 1.35 1.34
Crystallization Rate Constant (k)
1.01 0.95 0.91 0.96 0.89 0.81
-10
-8
-6
-4
-2
0
2
-8 -7 -6 -5 -4 -3 -2 -1 0 1 2 3
lnt
ln(-
ln(1
-Xt)) m-EH12
m-EH15m-EH18
m-EH20m-EH24
m-EH32
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Figure 05: Yield Phenomena at crosshead speed of 125 mm/minFigure 05: Yield Phenomena at crosshead speed of 125 mm/min
0
2
4
6
8
10
12
0 20 40 60 80 100 120 140 160 180 200
Engineering Strain (%)
Engin
eerin
g St
ress
(MPa
)
m-EH12
m-EH15
m-EH18
m-EH20
m-EH24
m-EH32
BC = 12.0
14.4
19.7
18.0
23.6
32.2
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Figure 06: Young’s modulus as a function of BC (crosshead speed 125 Figure 06: Young’s modulus as a function of BC (crosshead speed 125 mm/min)mm/min)
Y= 22621 BC-1.8644
R2 = 0.9846
0
50
100
150
200
250
0 5 10 15 20 25 30 35BC (CH3/1000C)
Youn
g's
Mod
ulus
m-EH
ZN-EH
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Figure 07: Elongation at break as function of BC (crosshead speed 125 Figure 07: Elongation at break as function of BC (crosshead speed 125 mm/min)mm/min)
0
200
400
600
800
1000
1200
1400
1600
0 5 10 15 20 25 30 35 40 45Branch Content (CH3/1000C)
Elo
ngat
ion
at B
reak
(%)
m-EH
ZN-EH
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Figure 08: Ultimate tensile strength as function of BC (crosshead speed Figure 08: Ultimate tensile strength as function of BC (crosshead speed 125 mm/min).125 mm/min).
0
5
10
15
20
25
30
35
40
45
0 5 10 15 20 25 30 35 40 45Branch Content (CH3/1000C)
Ultim
ate
tens
ile S
treng
th (M
Pa)
m-EH
ZN-EH
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Acknowledgements:Acknowledgements:
King Abdul Aziz City for Science and Technology (KACST) for financial support
KFUPM ExxonMobil, Belgium for
providing free samples
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ThanksThanks