ii -some applications of high-resolution tem to …highly absorbing material a widespread drug that...
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II -Some applications of high-resolution TEM to porous
non-conventional minerals
Alain Baronnet, Jérémie Berthonneau & Olivier Grauby
Aix- Marseille Université (AMU) Centre Interdisciplinaire de Nanosciences de Marseille (CINaM)
Fourth Winter School on Multiscale Porous Materials – January, 2017-Marseilles, France
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structural nanopores in minerals
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faujasite structure [110]
Nanostructure of the EMT zeolite (Elf Mulhouse Two) with faujasite intergrown lamellae:
an acidic catalyzer for fuel oil
"lateral" nanopore network EMT: AB stacking hexagonal structure Faujasite: ABC stacking cubic structure
please tell
the story !
JEOL 2000fx CRMCN
4.0 nm
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Palygorskite/attapulgite (Mg,Al)2Si4010(OH) -4(H2O): a nanoporous fibrous clay
Raw JEOL 3010 CINaM Fourier-filtered
Highly absorbing material A widespread drug that binds to acid and toxic substances in the stomac and digestive tract Also to treat diarrhea!!
1.27 nm Ball-and-stick model
The eternal « Maya blue » = trapped indigo molecules Cat beds
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Todorokite - A tunnel manganese oxide (K, Ca, Na) 0.5 Mn(3+,4+)
6 O12 - 4H2O
CINaM-JEOL 3010 Fourier-filtered image
Three levels of connected porosity
in polymetallic nodules on the sea floor
1.0 nm
macropores
nanopores
mean X-ray structure
25 nm
woodruffite ? ? 3 x 4 2 x 5 2 x 4
todorokite romanechite hollandite pyrolusite 3 X 3 2 x 3 2 x 2 1 x 1
Modular structures
SAED pattern
3
3
3 3 3 34 4
Woodruffite modules Todo-
rokite Todo- rokite
1.0 nm
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Synthetic imogolite Al2SiO3(OH)4 short nanotubes SWNT
in soils derived from volcanic ash
tubule: external diameter ≈ 2 nm
layers of tubules resembling panpipes (arrows)
10 nm
Used as template for synthesis of nano composites
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Chrysotile - asbestos
1 cm
Thetford Mine Québec
10 cm
“Crack – seal“ veins in a serpentinite
The longest chrysotile fibers In close-packing
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Zoom on the mid-ocean ridge
A black smoker
The hardest quench on Earth (exclusive of fulgurites)
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Chrysotile Mg3Si2O5(OH)4: a nano tubular silicate structure
Polyhedral model of the polar structure of chrysotile
0.72 nm
O T O T O T
Cross-section of a chrysotile nanotube
JEOL 3010 CINaM
A microstructural pore in the centre
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Textural nanopores
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The glue of cement:
The Calcium Silicate Hydrate (CSH)
Inside high-density CSH
An house-of-card Texture
A nanoporous
material
Compare with Emanuela’s simulations
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Opal A: a photonic, colloidal crystal amorphous SiO2
1µm
Opal structure
(courtesy
JP Gauthier)
Gilson�s synthesis of opal
1 cm
Coober Pedy, Australia!
Cabochons from Gilson �s opal!
SEM image
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A colloidal 2-D glass of serpentine nanotubes
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Nanopores in colloidal chrysotile crystals
two triangular channels bordered by Mg(O,OH)6 octahedra per one cylindrical channel bordered by SiO4 tetrahedra
A potential "two-function" molecular sieve? An UV photonic crystal
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A mosaic of colloidal crystals formed by 2-D "assemblage" of chrysotile nanotubes
Serpentinite vein Val d'Aosta Piémont Italy
100 nm
defects grain boundaries long fibers; equal size
JEOL 2000fx - CRMCN
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Repeated "Twinning" of colloidal chrysotile crystals on dense tubule planes A "supra-crystallography" at work?
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Textures of short chrysotile nanotubes: arabesques of serpentine: closer-and-closer to biological microstructures
For fun
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Biologically-controlled, Ca-carbonate biominerals are all
nanoporous organo-mineral composites
Last news
Example of mollusc sea shells
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cryofracture!Trochus nacre!
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TEM views of nacre cross sections!
Haliotis rufescens!abalone shell!
300-350 nm!
700-900 nm!
mini crack!
Trochus niloticus!sea cone! iridescent and colorful nacre!
porcelain and color fading nacre !
pores
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Ammolite as a new gem (bio) stone
Iridescent ammonite Cleoniceras (albian) Madagascar
Ammolite pendant
Metallic color changes with viewing incidence
Placenticeras Meeki Cretaceous (≈ 80 Mya) Alberta (Canada)
φ ≈ 0° ρ ≈ 20°
φ ≈ 0° ρ ≈ 50°
φ ≈ 80° ρ ≈ 20°
5 mm
50 cm
gift from J.P. Gauthier
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0.2 µm
SAED
200 nm FIB
nanopores: native or preparation damages? photonic 1-D grating of aragonite tablets
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0.2 µm Bubble-rich zone
Bubble-poor zone
Basal inter tablet boundary (vanishing organic matter)
Lateral inter tablet boundary
Empty bubbles
calcite- filled bubbles
Ammolite = a photonic crystal involving a 1D-modulated grating of bubbles?
FIB cross-section of ammolite nacre
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Nanomechanical properties of nacre Collaboration: Dept Materials Sciences and Engineering - MIT(B. Bruet & C. Ortiz) -Nano indentation of single tablets under AFM --> nano hardness balistic absorber--> inside bullet-proof vests of the GI ? Origin of the plastic deformation behaviour? Collab. B.Bruet & C. Ortiz DMSE - MIT
surface
Aragonite single-crystal pavement
Indentation AFM
0,5 µm
nano grains
Outstanding !mechanical properties:!-toughness!-strength!-stiffness!
FIB!
The sea cone
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Berkovitch 10 mN SAED patterns
Bright-Field TEM image
Micro indenter trace
400 nm
1 2
4
3
5
rotation of!nanograins! collapse of!intertablet OM!
1 2
3
4 5
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100 nm
Berkovitch indenter 5 mN
Electron diffraction!pattern just below !the indent!
Dark-field TEM image made with the tails of selected diffraction arcs
Where are rotating!grains in the tablet?!
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Extreme border of the valve (prismatic layer) of a �fresh��Pinctada margaritifera
50 µm
Petrographic microscope Crossed nicols
Palleal borderline
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Back-thinned outer surface of a single prism of Pincatada margaritifera – bright-field TEM view
Alternating sectors around the « nucleation centre »
Radial and circumferential variations of porosity In a single crystal controlled by mantle cells
2 µm
CC
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non wetting wetting
amorphous granules crystallized granules
Prism of Ostrea edulis (flat oyster)
A wetting transition before/during crystallization?
150 nm
250 nm
top view topmost layer
side view in depth
BF-TEM
PIPS FIB highly porous "single" crystal
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The sub-micron units = the biological units of calcification
200 nm
250 nm
100 nm
crystalline
amorphous
crystalline
amorphous
Arrested fronts of calcite crystallization close to the organic « mould » of prims
PIPS
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Inside the calcitic prisms
Inside the aragonitic tablets of nacre
Trochus niloticus farmed in the US -killed in liquid N2 -shell pieces Immersed in ethanol -rapid mail in air-dried parcel ( MIT-DMSE-->CRMCN) -detached µm-sized particles by shear with a diamond-coated wire saw under dry N2 -particles spread dry on a holey C-film -TEM imaging using mostly absorption contrast (transmitted beam only of a SAED without strong reflections) , and low electron dose Towards the pristine nanostructure of the shell A framework to host fibrous (silk)proteins?
Vermicular nanoporosity (3-7 nm) running inside single biocrystals
Disordered network
Ordered network
c-axis
0.8 µm
≈ 20-25 nm
≈5 nm
30 nm
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5 nm
The ultra structure of calcitic prisms of Pinctada margaritifera
A single-crystal sponge!
JEOL 3010 HRTEM; atomic resolution
<001> calcite Detached shards overhanging on a holey carbon membrane
nano pores/nano channels
vacuum
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The sponge-like, nanoscopic model of bio-calcite single crystal
Size range 0.1 nm - 100 nm percolation of a {10.4} twin plane
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Need of electron tomography to know better and quantify nanopores
Nanopore network in a geopolymer shard seen by bright-field TEM
Don’t worry, Jérémie B. will fill up this gap of knowledge tomorrow evening