Chemistry and Physics of Hybrid Materials
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Transcript of Chemistry and Physics of Hybrid Materials
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Chemistry and Physics of Hybrid Materials
Lecture 2
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Today
• Quiz #1• Biohybrids• Tools for making hybrids
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Hybrid Organic-Inorganic materials are common in nature: composites
Nacre
Argonite (CaCO3) plates as inorganicwith protein (polyamide) as organic
Animals
Plants
phytolith
Teeth, spines in echindermsMussel shells, sponges, diatoms and corals are utilize hybrid organic-inorganic materials
Organic phase is biopolymers
Carbohydrates are the template and organic phase
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Silica - SiO2
radiolaria diatoms
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Colloidal silica in diatoms: Hierarchical structure
Silica walls are build up from ca. 5nm particles to give ca. 40nm diameter particles that are organized within the frustule.
pH ≈ 5
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What is a hierarchical structure?
In materials, a structure with different structures at different length scales: like in tendons (above)
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More Bio-Hybrids based on CaCO3: NacreArgonite (CaCO3) plates as inorganic phasewith protein (polyamide) as organic phase
Mother-of-pearl
Opalescence from light diffraction in nacre (argonite blocks height ≈ λ light)
Fracture strength is 3000 times higher than its mineral constituent CaCO3.
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The hierarchical structure of nacre
Barthelat F Phil. Trans. R. Soc. A 2007;365:2907-2919
argonitecrystalstructure
Phasemorphology
Long range order: stacked crystals
Growth rings (mesolayers)
Macromolecular
Inner surface of shell (mother or pearl)
The shell itself
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Lobster exoskelton
CaCO3
& Carbohydrate & protein
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Teeth: Enamel, dentin, and cementum
Apatite – hydrated CaPO4
Protein– collagen & others
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200 MPa yield strength 30 MPaM0.5 toughness
Apatite – hydrated CaPO4
Protein– collagenBones
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Echinoderm spine
CaCO3
Protein templating
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Phytoliths
Horsetail, banana leaves
2-3% silicon by weight
SiO2 silica
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Silica in Sponges
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Bio Hybrid Organic-Inorganic MaterialsSophisticated, highly evolved hybrids
-nominally weak, but bio-accessible minerals (eg. CaCO3)-hydrophilic, water plasticized biopolymers (eg. protein) -Integrated at nano-length scales-Phase separation templating of hierarchical structures-All water based chemistry!! The ultimate green
chemistry
Optimized to give non-additive property (synergistic effects)
Models for many research programs in hybrid materials
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Making hybrids ourselves
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Class 1 Hybrids: No covalent bonds between organic & inorganic phases
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Class 2 Hybrids: Covalent bonds between organic & inorganic phases
Life uses Class 2C approach to make biohybrids
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Tools for making hybrids• Chemical reactions– Do both inorganic and organic undergo reactions– Which reactions are first – What are the relative rates
• Physics: Changes in state or properties– Do either or both organic and inorganic change
phase due to chemistry or temperature/solvent– What is the timing of phase change relative to
chemical reactions
Together these determine if hybrid is multiphase and the size, structure, and morphology of phase(s)
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For example: chemical hybrids (Class 2A)
• Fast chemical reactions at both inorganic and organic (part of one monomer)
• Change in phase very slow compared to chemistry
Formation of hybrid networks, and thermodynamic gelation
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For example: Physical hybridsClass 1A
• Organic and inorganic phases are preassembled, then physically mixed above the melting point of the organic, then cooled
• Long range structure and morphology are affected
Formation of hybrid networks, and gelation
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Some hybrid monomers:
•Polymerize by hydrolysis and condensation (sol-gel polymerization)•Monomers 2-4 polymerize to class 2 materials•But act like class 1 in many cases.•Used for many of the other classes as the inorganic component.
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Inorganic Phases
Silica Particles
Preformed inorganic clusters
POSS
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Inorganic PhasesCarbon Buckeyballs, nanotubes and graphene
Nature Materials 9, 868–871 (2010)
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Making Hybrid Materials: Class 1A (pre-formed particles and fibers)
Physical mixing or particles
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Making Hybrid Materials: Class 1B (in situ particle growth)
No Solvent except for monomer(s)Generally uses low tg organic polymers or in polymer melts (< 100 °C).
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Making Hybrid Materials: Class 1C(Polymerizing in pores)
•Porous metal oxide•Liquid monomer (no solvent) •UV, heat, radiation
Non-porous composite material
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Making Hybrid Materials: Class 1D(encapsulation of small organics)
• Polymerize metal oxide around organic• pores must be small or leakage will occur•Solid state dye lasers, filters, colored glass
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Making Hybrid Materials: Class 1E(Interpenetrating network)
• Both organic and inorganic phases grow simultaneously•Timing is more difficult• Reproducibility is a challenge• May need to use crosslinking organic monomers to ensure solid product
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Making Hybrid Materials: Class 2A(Covalent links at molecular level)
• Organic group is attached to network at molecular level•Pendant or bridging monomers•Bridging groups can be small or macromolecule•This class also includes the organometallic polymers
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Making Hybrid Materials: Class 2B(Covalent links at polymer level)
• ligands attached to polymer • Reaction rates slow unless in sol. or melt
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Making Hybrid Materials: Class 2C(Templating) Shown here with block
copolymer
Heat polymer then cool or cast from solvent
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Classes 2D &E Covalent coupling agents
Class 2E: Attaching inorganic group onto organic polymer
For tough electrical wire coating& shrink fit wrapa
Class 2D: Attaching organic group onto inorganic material
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Have a nice week-end