LOW ENVIRONMENTAL IMPACT PLASTICS Prof.Marco-Aurelio De Paoli Universidade Estadual de Campinas...
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Transcript of LOW ENVIRONMENTAL IMPACT PLASTICS Prof.Marco-Aurelio De Paoli Universidade Estadual de Campinas...
LOW ENVIRONMENTAL IMPACT PLASTICS
Prof.Marco-Aurelio De Paoli
Universidade Estadual de Campinas (UNICAMP) - Brasil
2009
Post-doctoral work at MPI für Strahlenchemie, RFA, 1975 – 1977.Alexander von Humboldt Stiftung
Introduction
Aims of our research:
• Develop thermoplastic composites with adequate mechanical properties, reduced environmental impact and good cost/benefit ratio; use of renewable resources.
•To replace short glass fibers in reinforced thermoplastics processed by injection molding; weight and environmental impact reduction.
“They (automobiles) will be
lighter and much of them will
be built of plastics developed
from farm products”.
Henry FordHenry Ford, from an article written by James Schweinehart published in The Detroit News of July, 30rd, 1942.
Introduction
Car parts made with natural fibers composite
Vegetal fibers can be used in substitution to fiber glass due to the following advantagesadvantages:
•Produced from renewable resources.
•Less abrasive to the processing equipments.
•Lower density, producing lighter composites,
•Better thermal and acoustic insulation,
•Better surface finish in injection molded parts,
Introduction
Vegetal fibers also present some challengeschallenges.
•Vegetal fibers decompose thermally above 220 oC.
•Like with fiberglass, composites cannot be mechanically recycled. They
can be recycled only by pyrolysis (however, with carbon credits),
•Vegetal fibers reinforced thermoplastics show higher flammability, thus,
the use of a flame retardant is necessary.
•Achieve a competitive cost in relation to synthetic fibers.
Introduction
dens.
Why use Curauá fibers and not the market available vegetal fibers ?
Specific density, stress, E and b for same reinforcing fibers*
1,0-1,3164-17128601,4Carbon
2,4-2,645-482140-22401,4Aramid
1,134,418002,5glass (S)**
1,028800-14002,5glass (E)*
1,3-1,76,3-14,7340-4161,5Sisal
2,4-2,541-85270-6251,5Ramie
1,8-2,118,4230-7901,5Linho
1,2-1,420,4302-5951,3Jute
4,7-5,03,4-7,9191-3981,5-1,6cotton
b / % cm3/g
E / GPa cm3/g
/ MPa /g.cm-3
Density g/cm3
fiber
* Electric insulation, ** militar applications.*- from: A. K. Bledzki; J. Gassan. Composites reinforced with cellulose based fibres. Progres in Polymer Science 24 (1999) 221-274.
stress., E e b specific for Curauá fibers
3 ± 136 ± 10 636-1000FC
b / (% cm3/g)E / (GPa cm3/g)força máx / (MPa /g.cm-3)Fiber
1,10
Introduction
HDPE, Braskem, MFI = 7 g/10 min.
PP, Braskem, MFI = 10 g/10 min.
Curauá fibers, dryed and milled in a three knives
rotary mill, Rone.
Materials used
side feederMain feeder degasing
Co-rotating interpenetrating twin-screw extruder, Werner-
Pfleiderer ZSK-26, L = 1056, D = 24 mm, L/D = 44 (Fapesp
2004/15084-6), SRS 250 – 500 rpm, side feeder 200 – 465 rpm.
Injection molding Arburg All Rounder M-250
Processing equipment
Processing equipment
Experimental: processing parameters
HDPE matrix
SRS* (rpm) Mass temperature(°C)**
Pressure(bar)
Torque(%)
Output(kg/h)
SME***(Wh/kg)
250/200 136-160 4-19 33-40 1.9 1.1
300/250 143-164 4-22 34-38 2.2 1.1
350/300 140-168 6-16 30-42 2.4 1.2
400/350 151-172 5-23 28-41 3.1 1.0
500/450 145-178 9-14 32-37 3.5 1.1
PP matrix
250/215 171-195 7-16 31-41 2.5 0,8
300/265 177-195 8-16 30-37 2.6 0,9
350/315 177-199 7-16 29-34 2.6 1,0
400/365 175-204 10-16 27-34 2.9 1,0
500/465 178-202 10-12 29-37 3.6 1,0
*Main screws/side feeder screws** polymer temperature near the dye*** Specific Mechanical Energy
Above 350 rpm, aspect ratio decreases
HDPE matrix: effect of SR on fiber geometrical parameters
Screw rotation (rpm) 250 300 350 400 500ARn 18 16 15 12 7ARw 35 34 28 20 10
ARw/ARn 2 2 2 2 1
0 20 40 60 80 100 120
0.2
0.4
0.6
0.8
1.0
CF
D
Aspect Ratio
Legend: pristine fiber () and composites processed at () 250, () 300, () 350 (), 400 and () 500 rpm
6 μm
HDPE-Fibrillation effect: MEV
50 μm
100 μm
Matriz HDPE: mechanical properties
The yield stress and Young’s Modulus show a decreasing tendency, in accordance with the
decrease in the fiber aspect ratio.
The elongation at break increases due to the decline in the reinforcement effect.
14% tensile 7% flexural
26% tensileFlexural n.v.
50%
Formulaçãoem wt %
máx./ (MPa.g/cm3)máx. (MPa)
E (MPa)/ (MPa.g/cm3)
E (MPa)
(%)/ (%)
HDPE 17.8 ± 0.1 1358 ± 152 < 100HDPE/20%FC 28.4 ± 0.2
28.1 ± 0.22501 ± 4472471 ± 447
3.7 ± 0.13.7 ± 0.1
HDPE/20%FC/
2%PEAM
30.7 ± 0.330.3 ± 0.3
2763 ± 2942730 ± 294
3.2 ± 0.53.2 ± 0.5
HDPE/30%FV* 42 - 5152 - 63
3952 - 50804900 - 6300
1.2 - 2.01.5 - 2.5
Tensile mechanical tests - ASTM D-638
*PE 30 % GF – Polyethylene 30 % Glass fiber ®, Omnexus, United States, 2007.
dCFC = 0.988 ± 0.04 g/ cm3 (15,7 % em volume)
dCFV = 1.2 - 1.28 g/ cm3 ( 1,27 g/cm3 com 15 % em volume)
HDPE
Flexural mechanical tests ASTM D-790
Formulaçãoem wt %
máx./ (MPa.g/cm3)máx. (MPa)
E (MPa)/ (MPa.g/cm3)
E (MPa)HDPE 20.9 ± 0.5 888 ± 43
HDPE/20%FC 37.5 ± 0.337.1 ± 0.3
1609 ± 981590 ± 98
HDPE/20%FC/
2%PEAM
41.4 ± 0.340.9 ± 0.3
1983 ± 1291959 ± 129
HDPE/30%FV*
42 - 5152 - 63
3952 - 45164900 - 5600
*PE 30 % GF – Polyethylene 30 % Glass fiber ®, Omnexus, United States, 2007
dCFC = 0.988 ± 0.04 g/ cm3 (15,7 % em volume)
dCFV = 1.2 - 1.28 g/ cm3 ( 1,27 g/cm3 com 15 % em volume)
HDPE
Impact resistence ASTM D-256
Formulaçãoem wt %
Resistência ao Impacto
Izod (J.g/cm3)(J/m)
Resistencia ao Impacto
Charpy (kJ/m2)
HDPE 82.3 ± 6.4 3.5 ± 0.1HDPE/20%FC 62.8 ± 2.9
62.0 ± 2.93.5 ± 0.4
HDPE/20%FC/
2%PEAM
66.0 ± 3.965.2 ± 3.9
3.4 ± 0.2
HDPE/30%FV*
48 - 6460-80
-
*PE 30 % GF – Polyethylene 30 % Glass fiber ®, Omnexus, United States, 2007
dCFC = 0.988 ± 0.04 g/ cm3 (15,7 % em volume)
dCFV = 1.2 - 1.28 g/ cm3 ( 1,27 g/cm3 com 15 % em volume)
HDPE
Changes in aspect ratio with screw rotation
PP matrix: effect of SR on fiber geometrical parameters
Legend: pristine fiber () and composites processed at () 250, () 300, () 350 (), 400 and () 500 rpm
0 20 40 60 80 100 1200.0
0.2
0.4
0.6
0.8
1.0
CD
F
Aspect ratio
PP-Fibrillation effect: MEV
PP matrix: mechanical properties
Tensile yield stress and Young Modulus show a decreasing tendency, in accordance with the variation in the fiber aspect ratio.
The elongation at break increases due to the decline in the reinforcement effect.
12.5% tensile flexural n.v.
5% tensileflexural n.v.
32%
Formulaçãoem wt %
σmáx./d (MPa/g cm -3)
σ máx. (MPa)
E (MPa)/d (GPa.g/cm3)
E (MPa)
(%)/d e (%)
PP 27,2 ± 0,5 1736 ± 112 > 300PP/20%FC 32,3 ± 0,2
31,4 ± 0,52870 ± 2542790 ± 254
1,9 ± 0,21,8 ± 0,2
PP/20%FC/2%PPAM 39 ± 0,238 ± 0,2
3393 ± 3573298 ± 357
2,2 ± 0,32,1 ± 0,3
PP/20%FV* 4345
38104000**
4,85
Mechanical tensile tests, ASTM D-638
* PP com 20 wt% de FV – Petrotene PH304, Petropol Polímeros ** Polypropylene/ 20 % Glass fibre ®, Omnexus, United States, 2007
dCFC = 0, 972 ± 0, 010 g/ cm3 (15 % em volume)
dCFV = 1,05 g/ cm3 (1,14 g/cm3 com 8 % em volume)
PP
Flexural mechanical tests, ASTM D-790
Formulaçãoem wt %
máx./ (MPa/g/cm3)máx. (MPa)
E (MPa)/ (MPa/g/cm3)
E (MPa)PP 37,1 ± 1,4 1046 ± 59
PP/20%FC 51 ± 150 ± 1
2187 ± 1002126 ± 100
PP/20%FC/2%PPAM
58 ± 156 ± 1
1913 ± 2141859 ± 214
PP/20%FV* 7680
30003000
* PP com 20 wt% de FV – Petrotene PH304, Petropol Polímeros
dCFC = 0, 972 ± 0, 010 g/ cm3 (15 % em volume)
dCFV = 1,05 g/ cm3 (1,14 g/cm3 com 8 % em volume)
PP
Impact resistence tests, ASTM D-256
Formulaçãoem wt %
Resistência ao Impacto
Izod (J/g/cm3)(J/m)
Resistência ao Impacto
Charpy (kJ/m2)
PP 17,3 ± 4,43 1,6 ± 0,2PP/20%FC 28 ± 9
27 ± 93,3 ± 0,6
PP/20%FC/2%PPAM
29 ± 328 ± 3
2,6± 0,3
PP/20%FV* 5255
-
dCFC = 0, 972 ± 0, 010 g/ cm3 (15 % em volume)
dCFV = 1,05 g/ cm3 (1,14 g/cm3 com 8 % em volume)
* PP com 20 wt% de FV – Petrotene PH304, Petropol Polímeros
PP
Developed under contract with Sabic Innovative Plastics
Car parts made with Nylon-6/curauá fibers composite
Developed under contract with Sabic Innovative Plastics
Car parts made with Nylon-6/curauá fibers composite
• Aspect ratio of the fibers in the injection molded samples is affected by the processing conditions in the extruder.
• For both polymers, the mechanical properties are affected by the fiber aspect ratio variation.
• HDPE is more affected than PP by the processing conditions.
• Final mechanical properties depend on the correct choice of processing conditions.
CONCLUSIONS
Research group
• MSc, Bárbara Mano, MSc, Bárbara Mano, • MSc, Joyce Araújo, MSc, Joyce Araújo, • Vanessa S de OliveiraVanessa S de Oliveira• Prof. Dr. Márcia AS SpinacéProf. Dr. Márcia AS Spinacé• Léa Garcia JaneiroLéa Garcia Janeiro• Filippe BernardinoFilippe Bernardino• Thais GrossiThais Grossi• MSc, Paulo Santos (SABIC)MSc, Paulo Santos (SABIC)• Karen Fermoselli (SABIC/Unicamp)Karen Fermoselli (SABIC/Unicamp)• Prof. Dr. Walter R Waldman (UENF)Prof. Dr. Walter R Waldman (UENF)
Procs.04/15084-6, 06/58342-0, 06/58343-7, 08/06503-6 e 08/06506-8.
ACKNOWLEDGEMENTS