Physics and Chemistry of Hybrid Organic-Inorganic Materials Lecture 5: Naturally occurring hybrids.
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Transcript of Physics and Chemistry of Hybrid Organic-Inorganic Materials Lecture 5: Naturally occurring hybrids.
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Physics and Chemistry of Hybrid Organic-Inorganic Materials
Lecture 5: Naturally occurring hybrids
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Biological hybrids: key points
• Hybrids made by plants or animals• Strong composites from very weak components
– Wet protein and carbohydrates are very soft– calcium carbonate is also weak and soft
• Multiple phases, hierarchical structures
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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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What is a hierarchical structure?
In materials, a structure with different structures at different length scales: like in tendons (above)
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The Building PlanFabrication Conditions in Living Organisms
only few elements: C, H, O, N, P, S, Ca, Si, Mg
mild pH
ambient pressure and temperature
Calcite Crystals Extracted from the Prismatic Layer of Pinna Nobilis Shells
www.cutgana.it/acquario/specie Marin et al., J. Biol. Chem., 2005, 40, 33895
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The Building Plan
Hierarchical Design – Morhpology Control on Several Levels
Interaction of an Organic and an Inorganic Component
Fabrication Conditions in Living Organisms
only few elements: C, H, O, N, P, S, Ca, Si, Mg
mild pH
ambient pressure and temperature
Incorporation of biopolymers increased fracture resistence
&
aspartate residue in peptide bond
chitin network
Nudelman et al., Faraday Discuss. 2007, 136, 9
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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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Silica (SiO2) & protein
radiolaria diatoms
Proteins act as templates for building silica architectures
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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, & cementum
Apatite – hydrated CaPO4
Protein– collagen & others
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The layered, rod structure of hydroxyapatite (a calcium phopshate) in dental enamel. Very tough for a ceramic.
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Hierarchical structure of alligator gar, a primitive fish, scales. Ganoine is mostly mineral, like enamel, with tougher bone beneath.
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Enamel and collagen
Regular Fish Scales
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Fish scale puncture resistance
fish scales are better than polycarbonate.note how they give, and then reload. This is just one scale.
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200 MPa yield strength 30 MPaM0.5 toughness
Apatite – hydrated CaPO4
Protein– collagen
Bones
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The Building Plan
Hierarchical Design – Morhpology Control on Several Levels
Interaction of an Organic and an Inorganic Component
structural optimization from the atomic to the macroscopic scale
Fabrication Conditions in Living Organisms
only few elements: C, H, O, N, P, S, Ca, Si, Mg
mild pH
ambient pressure and temperature
&
Bone
Fratzl et al., Progr. Mat. Science, 2007
Peterlik et al., Nat. Mat., 2006
Gupta et al., PNAS, 2006
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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
Templated by proteins
hierarchical structures
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Euplectella sp.
7 hierarchical levels
Stress-deflection responses of synthetic silica rod and sponge spicule in flexuretesting. (Courtesy of M. Sarikaya and G. Mayer.)
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conch shell Almost no protein 3 hierarchical levels of layers made from layers of calcite.
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Chiton Teeth
the tips of the teeth are hard magnetite (Fe3O4) with a tough fibrous calcite interior
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Metal in Spider Fangscarbohydrate fibers in a protein matrixwith zinc and magnesium ions
Politi, Y., Priewasser, M., Pippel, E., Zaslansky, P., Hartmann, J., Siegel, S., Li, C., Barth, F. G. and Fratzl, P. (2012), A Spider's Fang: How to Design an Injection Needle Using Chitin-Based Composite Material. Adv. Funct. Mater., 22: 2519–2528
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Biomaterial: Toucan Beak
(a) Toucan beak; (b) external shell made of keratin scales. Cellular materials: (a) synthetic aluminium foam; (b) foamfound in the inside of toucan beak.(Courtesy of M. S. Schneider andK. S. Vecchio.)
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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