lecture07 klein solgelpart1
DESCRIPTION
Glass course materialTRANSCRIPT
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Glass Processing
Advanced Fabrication: Sol-Gel Processing
Part I: February 12, 2015
Processing Steps and Chemistry
Part II:February 17, 2015
Applications, Monoliths and Thin Films
Lisa C. Klein
Materials Science & Engineering Department
Rutgers University
Piscataway, NJ
(848) 445-2096/ [email protected]
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Sol-Gel Processed Glasses Come in
Many Shapes and Sizes
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Monoliths
Xerogels
Aerogels
Hosts for Dyes
Thin Films
Composites
Hybrids
etc.
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Overview of Sol-Gel Processing:
“Bottom-up” in Liquids
•What is Sol-Gel Processing?
– Chemical route to oxides, using alkoxides, oxychlorides and soluble salts (precursors)
•What are Precursors?
– Molecules that contain the elements of the future network, and that allow its formation by chemical reactions in liquid medium, silicas, aluminas, zirconias, etc.
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Working Definition:
The Sol-Gel Process
refers to preparation of
an inorganic network
in solution.
Typically, inorganic
oxides are formed.
Sol-gel processing has
been a “nanomaterial”
process from the start.
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Global View of Sol-Gel Processing
(www.chemat.com)
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What is the sol-gel process?
• The sol-gel process can be used to produce
polymers or particles.
• A sol is a colloidal suspension of
nanoparticles dispersed in a liquid, usually
water.
• A sol exhibits Brownian motion (random walk
driven by momentum of collisions) and short-
range forces (such as van der Waals), while
gravitational forces are negligible.
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What is Sol-Gel Processing?
• Based on acid–base reactions
• Metal alkoxide salts are generally
soluble in alcohols
• Alcohols are very weak acids
– Essentially no tendency to lose H+
• Alkoxide ions are very strong bases
– React with water to form alcohol and OH–
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Chemistry of the Sol-Gel Process
• Alkane – molecule containing only carbon and hydrogen linked by a single bond, such as methane, CH4
• Alkyl – ligand created by removing one hydrogen from the alkane, such as methyl, -CH3
• Alcohol – adding one hydroxyl (OH) to an alkyl, such as methanol, CH3OH
• Alkoxy – removing a proton (H+) from an alcohol, such as methoxy, -OCH3
• Alkoxide – metalorganic compound, in which an organic ligand attaches to a metal atom, M-OCH3
• Organometallic – a compound with a direct metal-carbon bond.
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Metal Alkoxide Precursors
• Metal alkoxides are popular precursors because they react with water.
• The hydrolysis reaction goes to completion when there is excess water and catalyst.
• Alkoxy groups are replaced with OH
Si(OR)4 + 4H2O -> Si(OH)4 + 4ROH
• If there is deficit water, the system is partiallyhydrolyzed
• Two partially hydrolyzed molecules can link together in a condensation reaction, which liberates water.
• Linking monomers connect and extend to form a polymer skeleton.
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Most Common Precursor:
Tetraethylorthosilicate (TEOS)
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Ligands –functional group attached to
central metal atom
Ligands present in the complex will direct
the reactions
– Can slow down the reaction due to steric
(size and geometry) reasons
– Can stop the reaction with blocking (not
able to hydrolyze) groups
– Can yield different morphologies of
products with different ligands
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Functionality
• The number of bonds a monomer can form is called its functionality.
• The formation of a 3-D cross-linked network (polycondensation).
• Dimer Chain Ring is the progression in the polymerization process.
• Polyfunctional monomers tend to form fractalsurfaces, polymeric clusters resulting from branching and random bonding.
• If a monomer can make 2 or more bonds, it can increase its molecular size without limit.
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Simplified Chemical Reactions
of the Sol-Gel Process
Hydrolyzation| |
-Si-0-C2H5 + H20 = -Si-0H + C2H50H (1)
| |
Polymerization| | |
-Si-0-C2H5 + Si-0H = -Si-0-Si- + C2H50H (2)
| | |
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Chemical Reactions
OR
M
OR
OR
OR
H2O
OR
M
OR
OH
OR
H
OR
M
OR
OH
OR
OR
M
OR
OR
OR
OR
M
OR
O
OR
M
OR
++
+OR
OR
+ ROH
Hydrolysis
Condensation
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Possible
Hydrolysis and
Condensation
Reactions
Producing
Various Dimers,
Trimers and
Oligomers
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Partial Charge Model (Livage)
• Transformations depend upon partial charge of atoms
within a complex.
– Negative partial charge - nucleophilic species.
– Positive partial charge - electrophilic species.
• Equilibrium is achieved when all electrons of a molecule
or complex transfer from atom to atom until they all
reach the same equilibrium chemical potential.
– This is in turn related to electronegativity.
– In principle, one can predict which complex of precursor M
will exist by calculating the electronegativity of all possible
combinations of metal-ligand interactions.
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Partial Charge
• Partial Charge on atom i in complex
relates to difference in electronegativity
in the complex from some reference
electronegativity.
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0
i
0
i
i
36.1
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The electronegativity of the complex C(C)
is calculated according to:
____ ___ ___
√CSiº + N√COº + (2N-h)√CHº + 1.36(z-h)
C(C)=___________________________________________________________________
1 + N + 2N-h
√CSiº √XOº √CHº
based on electronegativities (given in Homework) and definition of partial
charge.
N (coordination number = 4)
z (valence/formal charge of Si = 4)
h (number of hydroxo ligands)
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Electronegativity of Water
• (SiO2) = 2.6
• (CH4) = 2.1
• (NaCl) = 1.6
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49.212
2
00
00
2
OH
OH
OH
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Acid Catalyzed Hydrolysis
• Sn2 type of
reaction
• Electrophilic
substitution
• Leaving group
same side as
attacking group
• Leads to polymer
formation
OR
M
OR
OR
OR
OR
OR
OR
OR
H ++
HOH
M
HOH
H+
H+
OR
OROR
OH
+ ROH
“Tangled Spaghetti”
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Base Catalyzed
• Fast hydrolysis (above pH = 7)
• Condensation mechanism (above pH=2):
ΞSiOH + OH- ΞSiO- + H2O
ΞSiO- + ΞSiOH ΞSiOSiΞ + OH-
• Nucleophilic attack: Reaction between most acidic silanols is favored.
• Form highly condensed species
• Large particles grow at the expense of small particles (ripen)
+
++
+
+
+
+
+
+
+
+
-
-
--
--
-- --
-
-
-
--
-
-
--
-
--
- -
-- -
-
--
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Base Catalyzed Hydrolysis
Sn2 type of
reaction
Leaving group
on opposite side
of attacking
group
Leads to particle
formation
OR
M
OR
OR
OR
OR
OR
OR
OR
OH -+
OH -
M
OR
OROR
OH
+ ROH
OH -
HOH
“Tumbleweeds”
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Acid vs. Base
Catalyst Acid Base
Mechanism Electrophilic Nucleophilic
Side of Attack Front Back
Rate w.r.t.
condensation
Slower Faster
Crosslinking Weak Strong
Effect of
polymerization
Small Large
Hydrolysis Complete Incomplete
Reversibility Good Poor
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Role of Water
• Water is often the solvent
– Precursors must be dissolved
– Other solvents are typically alcohols
• Water is also a reactant
• Because of its reactivity, sometimes we need
to employ sub-stoichiometric quantities
– e.g., Ti(OR)4 + 2H2O (not 4H2O)
• Water is also a product
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Getting Started…
• Measure components by volume
• Set molar ratios of alkoxide:alcohol:water
• Adjust pH of water
• Gradually add water to alcohol solution of alkoxide
• For multicomponent oxides, add alkoxides in order of increasing reactivity (e.g., Si < Al < Ti)
• Alkoxide ions gradually replaced by OH– ions
• When two (C2H5O)3SiOH encounter each other, they undergo an acid-base reaction and condense H2O
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Clear Solution Stirring with Heat
• Hydrolysis reaction
Si(C2H5O)4 + H2O (C2H5O)3SiOH + C2H5OH
• As more H2O is added:
– More alkoxide ions converted to alcohols
– More oxide linkages bridging ions
– May stay clear or become
cloudy when very fine particles
of metal oxides with residual
OH ions become suspended
in alcohol (gel-like)
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Sol-Gel Process:
Alkoxide vs Colloidal Route
Xerogel Aerogel
Alcogel Hydrogel
Solution/Sol
Sol
Cake Powder
Soluton
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Gelation
• The gel point is a transition, sol-to-gel transition
• Empirical “time-to-gel” when solution no longer flows
• t<tgel behavior is that of a fluid, described by viscosity h
• t>tgel behavior is that of a solid, described by shear modulus G
• At tgel, viscoelastic behavior,
• reflecting structure
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Role of pH
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from Iler
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Time-to-gel and Aging
• Time-to-gel – by examination, it is the time when no flow is observed when the sample is tilted
• Isoelectric point ~pH 2 gives the maximum gelation time– because of increased mutual repulsion from electrostatic
charge
• Aging – time when gel is surrounded by liquid before drying
• Effect of aging on porosity– pH<2 gives microporosity that is little effected by aging
– pH>2 gives mesoposority that can be altered by aging
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Sol-to-Gel Transition
• Hydrolysis occurs in single phase solution
• Polymerization occurs in single phase and in 2-phase gel
• Gellation leads to 2 phases, oxide skeleton plus solvent (water and alcohol in “alcogel”) where Si is surrounded by mostly bridging oxygens
• 1 phase 2 phases means creation of interface
• Solvent phase is replaced by vapor phase by natural evaporation (xerogel) or hypercritical evacuation (aerogel)
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What is a “gel”?
• A gel is a continuous solid skeletonencapsulating a liquid phase, formed from the entanglement of polymer chains or van der Waals forces between particles.
• Gelation occurs when clusters impinge and link to one another constructing a network.
• Initially, the gel is soft, until portions of the gel network move close enough together for additional condensation reactions.
• Aging results in changes in structure and properties after gelation, generally leading to shrinkage.
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Percolation
• Percolation is the study of how systems of discrete objects are connected to each other.
• More specifically, percolation is the analysis of clusters - their statistics and their properties.
• The applications of percolation are numerous: phase transitions (physics), forest fires, epidemics, fracture, etc.
• For site percolation there is a critical concentration (of occupied sites), above which a cluster exists that spans the domain, i.e. connects the left hand edge to the right hand edge.
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Generating Bond Percolation on the
Way to Percolation Threshold
• •
• • •
• •
•
• • •
• •
• • •
• •
•
• • •
“Connect the Dots”
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Drying
Xerogel
• Natural evaporation
• High capillary stresses
• Shrinkage, as much as 70% reduction in volume
• Problems with cracking
Aerogel
• Supercritical drying/CO2
exchange
• No shrinkage
• Densities less than 0.1 g/cm3
• Surface areas > 1,000 m2/g
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Drying leads to shrinkage
Sometimes the reduction in
size is close to 70%
The sample on the left (which
contains Rhodamine 6B dye)
has gelled, synerized, and is
beginning to shrink. The
shrinkage has been arrested
by sealing the container.
If the container is opened
and the sample is allowed to
shrink and dry, the sample on
the right is achieved in about
1 month.
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Size Scale: Is it Nano?
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from Ozin
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Is it Glass?
• X-ray amorphous
• Random network
• Same as conventional glass? Not yet
• Can be multicomponent
• Most glass components available in
alkoxide form
• No stoichiometric limits
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Are you paying attention?
Which of the following is an example of an
alkoxide ion ?
A. CH3OCH2+
B. CH3CH2CHO–
C. CHCOO–
D. OH–
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Sol-Gel Process:
Processing Steps
• Formulation
– Acid-addition
– Base-addition
– Dilution
• Reaction
– Hydrolysis
– Polymerization
• Gellation –
polymerization to
“no-flow” condition
• Syneresis-
spontaneous
expulsion of solvent
• Drying – removal of
pore fluid
• Shrinkage
• Consolidation
• Sintering