Post on 11-Jan-2016
description
Predicting Polyolefin Predicting Polyolefin Foamability UsingFoamability Using
Melt Rheology Melt Rheology
Associated Polymer LabsAssociated Polymer Labs
Presented by Jim ZwynenburgPresented by Jim Zwynenburg
AgendaAgenda
Define Rheology Test Resulting Data Converting Data Plots Interpretations Examples Remember to Remember
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DefinitionsDefinitions
Rheology Rheo means Flow Ology means the
study of
The Study of Flow
Melt Strength Is a property of the
polymer melt which indicates its ability to withstand drawing without breaking.
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ASTM D-4440ASTM D-4440
Standard Test Method for Plastics: Dynamic Mechanical Properties Melt RheologyStandard Test Method for Plastics: Dynamic Mechanical Properties Melt Rheology
Frequency Sweep at 190C
Temperature Ramp from 140C-230C for Polyethylene
Temperature Ramp from 180C-260C for Polypropylene
Rheology Test Sensitivity Increases with Rheology Test Sensitivity Increases with Decreasing FrequencyDecreasing Frequency
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120.0 130.0 140.0 150.0 160.0 170.0 180.0 190.0 200.0 210.0
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
Temp [°C]
ta
n_
de
lta (
)
[ ]Tan delta verses Temp
C:\RSIOrche600\Data 2000\June\RSI Orchestrator Document.RSD
ISO 6721-10ASTM D4440-95a
tan_delta Tan delta v erses Temp Westlake EF606, TR 100 rads, 200-130C Westlake EF606, TR 10 rads, 200-130C Westlake EF606, TR 1.0 rads, 200-130C Westlake EF606, TR 0.1 rads, 200-130C
100 rads/sec
10 rads/sec
1.0 rads/sec
0.1 rads/sec
Rheology Lab for Solids and MeltsRheology Lab for Solids and Melts
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Typical Data from Temperature RampTypical Data from Temperature Ramp
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Temp (C) G' (Pa) G" (Pa) Tan-deltaEta* (Pa-s)
139.7 16904 14605 0.86399 3557144.0 16320 14210 0.87075 3446149.5 15503 13740 0.88627 3299154.9 14704 13290 0.90385 3156160.0 13926 12875 0.92448 3020
165.4 13127 12451 0.94848 2881170.1 12405 12046 0.97107 2754175.0 11645 11609 0.99693 2618180.0 10909 11188 1.0255 2488185.4 10093 10667 1.0568 2338190.1 9427 10242 1.0864 2217195.0 8741 9769 1.1177 2087200.4 8005 9241 1.1545 1947205.0 7430 8823 1.1875 1837210.1 6823 8343 1.2229 1716215.5 6217 7856 1.2636 1595220.0 5757 7465 1.2967 1501225.1 5256 7040 1.3395 1399230.5 4773 6603 1.3833 1297
Rheology Plot 1Rheology Plot 1
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130.0 140.0 150.0 160.0 170.0 180.0 190.0 200.0 210.0 220.0 230.0 240.0
103
104
105
103
104
Temp [°C]
G
' ()
[P
a]
G
" (
) [P
a] E
ta* (
) [P
a-s]
Best Low Density Polyethylene for Foam
G' / G" Crossover Point:(175.58,1.156x104)Data: Eta*(Temp) [1..19] (19 pts) Note: o = 4393.7 Model: Ellis Model Eqn: c1/(1+(x/c2)
(c3-1)) Fit Error: 0.9999 3 Coefficients: 4393.7 190.61 5.5729
Converted Data Converted Data
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Temp (C) G' (Pa) G" (Pa) Tan-deltaEta* (Pa-s)
Torque (g/cm)
Phase Angle
Log tan-delta
Log Eta* (Pa-s)
139.7 16904 14605 0.86399 3557 67.162 40.827 -0.063 3.551144.0 16320 14210 0.87075 3446 67.164 41.048 -0.060 3.537149.5 15503 13740 0.88627 3299 67.167 41.55 -0.052 3.518154.9 14704 13290 0.90385 3156 67.169 42.109 -0.044 3.499160.0 13926 12875 0.92448 3020 67.172 42.753 -0.034 3.480
165.4 13127 12451 0.94848 2881 56.363 43.485 -0.023 3.460170.1 12405 12046 0.97107 2754 56.366 44.159 -0.013 3.440175.0 11645 11609 0.99693 2618 56.368 44.912 -0.001 3.418180.0 10909 11188 1.0255 2488 56.371 45.722 0.011 3.396185.4 10093 10667 1.0568 2338 47.202 46.583 0.024 3.369190.1 9427 10242 1.0864 2217 47.204 47.372 0.036 3.346195.0 8741 9769 1.1177 2087 47.207 48.18 0.048 3.320200.4 8005 9241 1.1545 1947 40.223 49.101 0.062 3.289205.0 7430 8823 1.1875 1837 40.226 49.899 0.075 3.264210.1 6823 8343 1.2229 1716 40.229 50.725 0.087 3.235215.5 6217 7856 1.2636 1595 33.753 51.642 0.102 3.203220.0 5757 7465 1.2967 1501 33.756 52.362 0.113 3.176225.1 5256 7040 1.3395 1399 33.759 53.256 0.127 3.146230.5 4773 6603 1.3833 1297 28.089 54.136 0.141 3.113
Plotting DataPlotting Data
Tan-Delta (G”/G’) Converted into log.
Fractions (less than one, become negative numbers)
Plot on Linear Scale
Eta* (Complex Viscosity) converted into log.
Decimal place becomes the first number, example 4000Pa-sec is 4.0
Plot on Linear Scale
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Rheology Plot 2Rheology Plot 2
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Log tan-delta
-0.100
-0.050
0.000
0.050
0.100
0.150
0.200
3.000 3.100 3.200 3.300 3.400 3.500 3.600
Log Viscosity (Eta*)
Log
Tan-
delta
(G"/
G')
Temp (C)230225220215210205200195190185180175170165160155150145140
Rheology Plot 3Rheology Plot 3
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2.8 3.0 3.2 3.4 3.6 3.8 4.0 4.2 4.4 4.6 4.8-0.2
-0.15
-0.1
-0.05
0.0
0.05
0.1
0.15
0.2
0.25
0.3
0.35
0.4
0.45
0.5
0.55
0.6
Log Viscosity [ Pascal-sec]
Log T
an-
delta (
) [ (G
"/G
')]
Best Low Density Polyethylene for Foam
230C
140C
Low TemperatureHigher ViscosityGreater Melt Elasticity and Strength
Higher TemperatureLower ViscosityLow Melt Elasticity and No Strength
Low Melt Elasticity and StrengthLow ViscosityHigh Density Foam Only
Polystyrene AreaHigh Eleasiciaty and Melt StrengthHigh Viscosity
Important Factors; 1) Slope2) Length3) Shape
Rheology Plot 4Rheology Plot 4
3.0 3.5 4.0 4.5 5.0 5.5 6.0-0.2
-0.1
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Log Eta* [ ]
Lo
g ta
n de
lta
()
[ ]
Polyolefin Foaming Window
LDPE
LLDPE
Polypropylene
PolyStyreneHMS PP
Branched LDPE
HDPE
High Melt Strength
Low Melt Strength
Every Polyolefin has a Unique Curve
Fingerprint The Resin
Know the response of the polymer
Imagine The Possibilities
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Example 1, Using Recycled ResinExample 1, Using Recycled Resin
Recycled content appears to separate at higher temperatures
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2.8 3.0 3.2 3.4 3.6 3.8 4.0 4.2 4.4 4.6 4.8-0.2
-0.15
-0.1
-0.05
0.0
0.05
0.1
0.15
0.2
0.25
0.3
0.35
0.4
0.45
0.5
0.55
0.6
Log Viscosity [ Pascal-sec]
Log
Tan
-del
ta
()
[ (
G"/
G')]
4 PCF Foam
Log Tan-delta 4 PCF Foam 4 PCF Foam with Recycled Resin
Example 2, Blending VerticallyExample 2, Blending Vertically
To blend Polyolefins,
Use the WZ Theorem: geometric averaging of the viscosities produces the new blended viscosity.
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2.8 3.0 3.2 3.4 3.6 3.8 4.0 4.2 4.4 4.6 4.8-0.2
-0.15
-0.1
-0.05
0.0
0.05
0.1
0.15
0.2
0.25
0.3
0.35
0.4
0.45
0.5
0.55
0.6
Log Viscosity [ Pascal-sec]
Log
Tan
-del
ta
()
[ (
G"/
G')]
Blending Polymers; Equistar NA957, NA940, 75/25 Blend
Fractional MeltEquistar NA 940
Equistar NA 957
Blend 75%/25%
Blending Rule1 + 2 = 3
Example 3;Example 3; Blending is as easy as 1,2,3 Blending is as easy as 1,2,3
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2.9 3.1 3.3 3.5 3.7 3.9-0.2
-0.06667
0.06667
0.2
0.3333
0.4667
0.6
Log Eta* [Pa-s]
Log tan d
elta (
) [ ]
125% / 75%
50% / 50%
75% / 25%
PelletsLLDPE Mixed (Post Industrial)
Log tan delta LDPE 25% LLDPE 75% LLDPE Mix LDPE 75% LLDPE 25% LDPE 50% LLDPE 50% Reprocessed LDPE Virgin LDPE
Virgin LDPE
Reprocessed LDPE
Hidden Information
Remember to RememberRemember to Remember
Polyolefins viscosity is 1+2=3 Testing takes one hour Measure and Know the Resin Properties Applies to recycled, fractional melts, additives,
rheology modifiers, crosslinking agents, etc New Models are available for all thermoplastic
materials Cost Savings
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The EndThe End
I’m Grateful to share my experience and knowledge
Extra Special Thanks to Gary Wilkes
Special Thanks to Stephen Driscolle, University of Massachusetts
Jay Patel, Patel Scientific
Members of the Foams Committee for accepting my paper
Everyone present for listening
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