silica-like malleable materials group 10 kristen losensky tzu-hao yen 11-16-12 1
TRANSCRIPT
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SILICA-LIKE MALLEABLE MATERIALSGroup 10
Kristen Losensky
Tzu-Hao Yen
11-16-12
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Summary: How It Works• Thermoplastics
• Flow when heated• Can be extruded shaped and molded
• Thermosetting / Cross-linked Polymers• Can not be reprocessed by heat or solvent• Dimensional stability• High-temperature mechanical, thermal, and
environmental resistance
• Make covalent links reversible• High Temperature: exchange reactions enable stress
relaxation and malleability• Low Temperature: exchanges become essentially stop,
producing a solid system• Reversible topology fixing controlled by kinetics
Montarnal, Damien, Mathieu Capelot, Francois Tournilhac, and Ludwik Leibler. "Silica-Like Malleable Materials from Permanent Organic Networks." Science 334 (2011): 965-68. Web. 11 Nov. 2012.
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Summary: Research Performed
• Synthesis of both hard and soft epoxy networks with rearrangable topology• Exchange reactions without depolymerization. • Insoluble and processable• Gradual viscosity variations
• Examination of thermal and mechanical properties
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Thermosetting Polymers
• Thermosetting materials• Irreversible• Liquid prior to curing• Good mechanical
properties• Solvent resistant• Cured by heat and
radiation
http://sp.life123.com/bm.pix/how-to-change-brake-pads.s600x600.jpg
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Cross-Linked Materials• Cross-linking
• Un-polymerized resin + Crosslinking agents• Difficult to break• Most materials when heated may degrade or burn
• Commercial plastics
http://chemistry2.csudh.edu/rpendarvis/thermoplas.GIF
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Thermoplastic Polymers• Thermoplastic materials
• Reversible • Remold and reforms• Weaker mechanical
properties• Solvent soluble• Recyclable http://images.wisegeek.com/stack-of-legos.jpg
http://chemistry2.csudh.edu/rpendarvis/thermoplas.GIF
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Reversible Malleable Material Issues
• Depolymerization-repolymerization equilibria
• Degradation of combined materials
• Unavoidable termination reactions
http://images.clipartof.com/small/1047648-Royalty-Free-RF-Clip-Art-Illustration-Of-A-Cartoon-Black-And-White-Outline-Design-Of-A-Man-
Carrying-A-Heavy-Problem-Rock.jpg
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High Silica Materials
• Amorphous silica• Thermally insulated• Inert to chemical
reagents• Resistance to organic
acids• Electrical insulation• Easily molded
http://image.made-in-china.com/2f0j00zBQTMaICHFcK/High-Purity-Silicon-Dioxide-Coating-Material.jpg
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Stress & Strain Diagram
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Previous Work
• Radical Systems• Photoinduced plasticity in cross-linked polymers• Thermally/ Photochemically induced reparability• Unavoidable Termination Reactions
• Chemical Equilibrium• Heating
• Drives equilibrium towards depolymerization• Increases rate of bond breaking/reforming
• Prevent flow by using glass transition• Increased fluidity and processability• Network is less stable and sensitive to solvents
molle.k.u-tokyo.ac.jp
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Materials and Methods
• Soft Networks• Fatty acids and Catalyst Zn(Ac)2, 2H2O heated from 100
°C to 180°C under vacuum• Diglycidal ether of bisphenol A (DGEBA) is added to
fatty acid mixture and stirred at 130°C • Mixture is poured into brass mold with anti-adhesive
silicone paper
http://chemsrv1.uwsp.edu/macrog/lab/epoxyqc.htm
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Materials and Methods
• Hard Networks• Zinc Acetylacetonate Dihydrate Catalyst dissolved in
DGEBA by heating• Glutaric Anhydride added• Poured into brass mold • Cured at 140°C for 12 h
http://www.sigmaaldrich.com/catalog/product/FLUKA/49670?lang=en®ion=US
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Results: Soft Network Synthesis • DGEBA and fatty dicarboxylic and tricarboxylic acids
• Epoxy/COOH has 1:1 stoichiometry• Zinc Acetate Catalyst Zn(Ac)2
• Complete conversion of epoxy groups
• Transesterification Reactions
Montarnal, Damien, Mathieu Capelot, Francois Tournilhac, and Ludwik Leibler. "Silica-Like Malleable Materials from Permanent Organic Networks." Science 334 (2011): 965-68. Web. 11 Nov. 2012.
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Results: Soft Network Properties• Elastomeric behavior • Modulus of 4 MPa• Elongation and stress at break 180%, 9 MPa • Number of ester links does not change with heating
Montarnal, Damien, Mathieu Capelot, Francois Tournilhac, and Ludwik Leibler. "Silica-Like Malleable Materials from Permanent Organic Networks." Science 334 (2011): 965-68. Web. 11 Nov. 2012.
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Results: Soft Network Solubility
• The network swells but does not dissolve
Montarnal, Damien, Mathieu Capelot, Francois Tournilhac, and Ludwik Leibler. "Silica-Like Malleable Materials from Permanent Organic Networks." Science 334 (2011): 965-68. Web. 11 Nov. 2012.
Fig. 2 Flow and insolubility properties of an epoxy network with 5 mol% Zn(Ac)2 catalyst. (A)Swelling during immersion in trichlorobenzene
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Results: Soft Network Malleability• Can completely relax stresses at high temperatures
• η(T) follows Arrhenius law• 100 °C relaxation time of 58 h• Room temperature relaxation time of 6 yr
• Can easily make complex shapes without mold
Montarnal, Damien, Mathieu Capelot, Francois Tournilhac, and Ludwik Leibler. "Silica-Like Malleable Materials from Permanent Organic Networks." Science 334 (2011): 965-68. Web. 11 Nov. 2012.
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Results: Hard Network Synthesis• DGEBA with glutaric anhydride
• Zinc Acetyl Acetonate Zn(AcAc)2
• Epoxy/Acyl stoichiometry is 1:1
• Transesterification Reactions
Montarnal, Damien, Mathieu Capelot, Francois Tournilhac, and Ludwik Leibler. "Silica-Like Malleable Materials from Permanent Organic Networks." Science 334 (2011): 965-68. Web. 11 Nov. 2012.
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Results: Hard Network Solubility
• Sample swells but does not dissolve• 16 h in trichlorobenzene at 180 °C
• Number of ester links does not change with temperature
Montarnal, Damien, Mathieu Capelot, Francois Tournilhac, and Ludwik Leibler. "Silica-Like Malleable Materials from Permanent Organic Networks." Science 334 (2011): 965-68. Web. 11 Nov. 2012.
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Results: Hard Network Properties• Behavior is similar to
typical hard epoxy resins• Glass Transition Tg 80 °C
• Modulus of 1.8 GPa• Stress at break of 55 MPa• Transesterification
reactions allow network to flow• Viscosity of 1.2 x 1010 Pa s• η(T) follows Arrhenius
equation
Montarnal, Damien, Mathieu Capelot, Francois Tournilhac, and Ludwik Leibler. "Silica-Like Malleable Materials from Permanent Organic Networks." Science 334 (2011): 965-68. Web. 11 Nov. 2012.
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Results: Hard Network Malleability
• Can be reprocessed• Compression molding at
high temperature• 3 min at 240 °C
• Can form complex shapes without molds
Montarnal, Damien, Mathieu Capelot, Francois Tournilhac, and Ludwik Leibler. "Silica-Like Malleable Materials from Permanent Organic Networks." Science 334 (2011): 965-68. Web. 11 Nov. 2012.
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Results: Topology• Systems with exchangeable links behave as a viscoelastic
fluid • Above Tg exchange reactions occur slowly
• Material properties depend on thermal history
• During cooling ramp:• Topology rearrangements become too slow, network appears
quenched• Further cooling freezes local monomer motion
Montarnal, Damien, Mathieu Capelot, Francois Tournilhac, and Ludwik Leibler. "Silica-Like Malleable Materials from Permanent Organic Networks." Science 334 (2011): 965-68. Web. 11 Nov. 2012.
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Results: Dilatometry Experiments• Cross-linked polymers have lower expansion coefficients• Increasing catalyst concentration increases expansion
coefficients• Topology freezing is well separated from Tg
• Topology freezing and Tg shift to higher temperatures when the heating rate is increased
Montarnal, Damien, Mathieu Capelot, Francois Tournilhac, and Ludwik Leibler. "Silica-Like Malleable Materials from Permanent Organic Networks." Science 334 (2011): 965-68. Web. 11 Nov. 2012.
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Results: Broadness of Tg
• Rate of change of η at Tg
• “Strong” Glass Formers show broad Arrhenius-like variations• Silica• P2O5
• “Fragile” Glass Formers show rapid η increase upon cooling• Organic and Polymer liquids
Montarnal, Damien, Mathieu Capelot, Francois Tournilhac, and Ludwik Leibler. "Silica-Like Malleable Materials from Permanent Organic Networks." Science 334 (2011): 965-68. Web. 11 Nov. 2012.
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Assessment• Synthesized both soft and hard polymer networks with
reversible covalent links• Transesterification Reactions• Mechanical Properties• Insoluble• Arrhenius-like variation in viscosity
• Separate topology freezing and glass transitions
Montarnal, Damien, Mathieu Capelot, Francois Tournilhac, and Ludwik Leibler. "Silica-Like Malleable Materials from Permanent Organic Networks." Science 334 (2011): 965-68. Web. 11 Nov. 2012.
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Further Research• Ability to control or fine tune temperature of topology
freezing transition
• Ability to control or fine tune glass transition temperature
• Choice of starting materials
http://www.bestchemshows.com/
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References (Pictures)1. molle.k.u-tokyo.ac.jp
2. http://chemsrv1.uwsp.edu/macrog/lab/epoxyqc.htm
3. http://www.sigmaaldrich.com/catalog/product/FLUKA/49670?lang=en®ion=US
4. http://www.bestchemshows.com/
5. http://sp.life123.com/bm.pix/how-to-change-brake-pads.s600x600.jpg
6. http://image.made-in-china.com/2f0j00zBQTMaICHFcK/High-Purity-Silicon-Dioxide-Coating-Material.jpg
7. http://images.clipartof.com/small/1047648-Royalty-Free-RF-Clip-Art-Illustration-Of-A-Cartoon-Black-And-White-Outline-Design-Of-A-Man-Carrying-A-Heavy-Problem-Rock.jpg
8. http://chemistry2.csudh.edu/rpendarvis/thermoplas.GIF
9. http://chemistry2.csudh.edu/rpendarvis/thermoplas.GIF
10. http://me.aut.ac.ir/staff/solidmechanics/alizadeh/Tensile%20Testing_files/image011.gif
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References
1. Montarnal, Damien, Mathieu Capelot, Francois Tournilhac, and Ludwik Leibler. "Silica-Like Malleable Materials from Permanent Organic Networks." Science 334 (2011): 965-68. Web. 11 Nov. 2012.
2. Callister, William D., and David G. Rethwisch. Fundamentals of Materials Science and Engineering: An Integrated Approach. Hoboken, NJ: Wiley, 2012. Print.
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Questions?