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Processing and Characterization of Bio-Plastics

Yanir Shaked University of Massachusetts, Lowell Shenkar College of Engineering and Design Green Plastics Technology
June 08
Thursday, June 26, 2008

Introduction
Bio-Plastics are not a single class of polymers but rather a family of products which can vary considerably A generally recognized definition of the concept does not exist Bio-Plastics consist of
Biobased plastics, based on renewable resources Biodegradable polymers, which meet all criteria of scientifically recognized norms for biodegradability and compostability
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Bio-Plastics Properties
Slow Recrystallization Moisture absorption
Hydrolytical degradation, mainly PLA above Tg Bulk imperfections for PHA

Thermal degradation
Mw reduction affecting Melt strength, Mechanical properties

Viscosity
Melt elasticity of linear polyesters
Foaming, Thermoforming, Blown Film, Blow Molding

Shear thinning effects, coupled with Mw reduction


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Processing Considerations
Implications
Drying Increased cycle time, lower line speeds (compare to polyolefines) Low processing temperatures, many times at relatively high viscosity
High Pressure, and Torque requirements

Tools design for reduced viscous heating and residence time


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Processing of Bio-Plastics

Nature Works, Jim Nangeroni, 2007 5


Thursday, June 26, 2008

Processing of Bio-Plastics

Nature Works, Jim Nangeroni, 2007 6


Thursday, June 26, 2008

Processing of Bio-Plastics

Telles, Robert S Whitehouse, 2007 7


Thursday, June 26, 2008

Processing of Bio-Plastics

Nature Works, Jim Nangeroni, 2007


Thursday, June 26, 2008

Poly Hydroxybutyrate
Poly Hydroxybutyrate, PHB, is the most common of PHA Bio-Based and Bio-Degradable Polymer Aliphatic, thermoplastic, linear, semi-crystalline polyester When copolymerized can cover a wide range of mechanical properties

0.5m

K. Sudesh et al, 2000 9


Thursday, June 26, 2008

PHB, Melt Characteristics


DSC

PP 2300c

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PHB, Melt Characteristics


Parallel Plate Rheology
Slope: -2.601X10-4

165oc 185oc

@ 300sec (5min), 26% reduction in Mw @ 1850c 5% reduction in Mw @ 1650c

Slope: -1.516X10-3

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Rheological Characterization
Tm 1700c Capillary Rheometer @ 1800C 27% MW loss

J. Zhang, et al, 2004


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PHB, Melt Characteristics


DSC

700c

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PHB, Processing
Super cooling Processing below Tm Reverse Temperature Profile

J. Zhang, et al, 2004


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PHB, Processing
Implement
Characterization Processing

T3

T2

T1

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PHB, Extrusion Rheology


Extrusion Rheology
True steady state Separate variables
Viscous heating Screw RPM and Design Residence time Screw RPM and Design Temperature Extruder and Die temperature profiles

Extensive super-cooling
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PHB, Extrusion Rheology


Apparent shear rate from flow rate

Apparent shear stress from P


L=70mm P

Apparent viscosity
W=32mm

H=1.5mm

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PHB, Extrusion Rheology


Flow Curve
1500

Pa*sec

1000

160 500 20 70 Sec-1

172

120

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PHB, Extrusion Rheology


Die melt temperature, different extruder temperatures
175

Die melt T [0C]

170

165 170 180 190

zone 3 set point [0C]


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PHB, Extrusion Rheology


Mw as a function of die set point, different RPM

Mw

30 160 170 Die setpoint 0C

50

40 180

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PHB, Extrusion Rheology


Extruder Melt temperature as a Function of RPM, different Temp. Set Point
210

205

Melt T [0C]

200

195

171c
190 30 40

177c

182c
50
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RPM
Thursday, June 26, 2008

PHB, Extrusion Rheology


Mw as a function of Melt temperature,

Mw

30

40

50

190

195

200

205

210

Melt T [0C]
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PHB, Extrusion Rheology


Parallel plate Rheology, as a function of

1700 1400

Pa*sec

1100 800
CR=3.5, T3=166c CR=3, T3=154c

500 30 40 50 60 70
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RPM

PHB, Extrusion Rheology


Extrusion well below Tm
180 165 150 135 120 120 135 150 Die set point [0C]
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Die melt T [0C]

165

180

Conclusions
Extrusion Rheology is a very powerful tool for the determination of PHB flow characteristics, and possibly other thermally unstable BioPlastics Residence time effects overwhelm temperature effect, for the evaluated range Super cooling of the melt is possible up to 1350c, ~350c below Tm Best MW retention achieved at low temperatures, short residence times, and low shear
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Conclusions
While as solid PHB resembles the behavior of other known polymers, its melt state differs substantially Loss in molecular weight during processing should be taken into account There will always be some reduction in MW down the process stream Knowing the polymers limitations will ease its implementation into existing processes The use of Bio-Plastics in large scale manufacturing is doable
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Questions

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