lecture 6 hybrid poss
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Lecture 6 Hybrid POSS. Class 1B: inorganic phase is made in-situ in organic continuous phase. in situ means “in place”. Making Hybrid Materials: Class 1B (in situ particle growth). Ideally, no Solvent except for monomer(s) - PowerPoint PPT PresentationTRANSCRIPT
Lecture 6 Hybrid POSS
Lecture 6 Hybrid POSS
Class 1B: inorganic phase is made in-situ in organic continuous
phase.
in situ means in place
Making Hybrid Materials: Class 1B (in situ particle
growth)
Ideally, no Solvent except for monomer(s)No solvent with low tg
organic polymers or in polymer melts (< 100 C) or if monomer
will is soluble in polymer.
Otherwise solvent may be used to mix before casting.
Preparation by dissolving inorganic monomer in solid organic
polymer then polymerizing to form particles
Solid Organic Polymer
Monomer must be soluble in polymer
Polymerization by:1) hydrolysis & condensation of M(OR)nWater
diffuses into membrane from air2) Reduction of metal compound. H2
or polymer itself as reducing agent3) sulfidation of cations
(H2S)4) photochemical or thermal decomposition
Inorganic Monomer (liquid) & catalyst
Organic Polymer Inorganic Monomer
Monomer polymerizes & forms particles
Preparation by mixing inorganic monomer with liquid organic
polymer & hydrolysis & condensation
Physical mixing
Very few liquid polymers, save some elastomers like
polydimethylsiloxane and low molecular weight polybutadiene or
polyisoprene
Organic Polymer Inorganic Monomer
Liquid Organic Polymer
Inorganic Monomer (liquid) & catalyst
1) Water diffuses in from outside2) Monomer polymerizes 3)
Particles phase separate
Silica-PMS materials are looked at later in lecture
Preparation by mixing inorganic monomer with solid organic
polymer and allowing particles to form
Solid Organic Polymer
Physical mixing
Solvent must be removed before polymerization
Water for hydrolysis and condensation would be diffused into dry
film from air.
Organic Polymer Inorganic Monomerin solvent
Dissolve
Organic Polymer in solvent
Evaporate solvent
Inorganic Monomer (liquid)
Organic Polymer Inorganic Monomer
Monomer polymerizes & forms particles
Silica-Nafion materialsmade this way are looked at later in
lecture
Polymers used in class 1B systems
Elastomers: silicone, polybutadiene, polyisopreneThermoplastics:
polyurethanes, polycarbonates, polyvinylalcohol, polyacrylates,
polysulfones, polyethylene oxide (PEO), polypropylene oxide
(PPO)Thermosets: epoxiesPolyionomers: Nafion
Review of polymerizations
1) hydrolysis & condensation of M(OR)nor RSi(OR)32) Reduction
of metal compound3) sulfidation of cations4) photochemical or
thermal decomposition
Hydrolysis & condensation of M(OR)n: the monomers
Silicon: Si(OR)4 or RSi(OR)3
Aluminum: Al(OR)3 or AlCl3 6H2O
Transition metals: Mz(OR)n or MzCln hH2O
z = oxidation number for metaln = number of alkoxide or halide in
monomerh = number of coordinating waters
Hydrolysis & condensation of Si(OR)4
Catalyzed by acids (HCl,HNO3) or bases (NH3 aq, NaOH) or
fluoride.
Particles from hydrolysis & condensation of Si(OR)4
Typically leads to amorphous spherical particles (not quartz) Can
template particles with ordered mesopores with surfactants Stober
synthesis from TEOS with NH3 and water gives monodisperse particles
Emulsion polymerization (water in oil) gives monodisperse particles
Other preps give polydisperse particles
Hydrolysis & condensation of RSi(OR)3
Particles from hydrolysis & condensation of RSi(OR)3
Typically leads to amorphous spherical particles Not as easy to
prepare particles as with silica Can template particles with
ordered mesopores with surfactants Stober synthesis from TEOS with
NH3 and water affords polydisperse particles Emulsion
polymerization (two step) gives monodisperse particles
Hydrolysis & Condensation of Mz(OR)n to form MOn/2
Hydrolysis: formation of monomeric MOH species
higher charge & higher pHMore reactive, but too high shuts down
condensation
Condensation: formation of oxo (neutral) M-O-M
M = Al, B, Ti, Zr, Cr, Fe..
Hydrolysis & Condensation of Mz(OR)n to form MOn/2
Olation: formation of oxo (neutral) M-O-M
olation >> oxolation
Particles from hydrolysis & condensation of M(OR)n
Particles may be amorphous or crystalline Some amorphous particles
will crystallize with time. Stober synthesis from TEOS with NH3 and
water does not work Emulsion polymerization (water in oil) gives
monodisperse particles Many more molecular clusters are available
through olation chemistry
Reduction of metals
Metal and Semiconducting Sulfides
Class 1B: in situ Silica-Nafion Nanocomposite
Solid Nafion
Physical mixing
Nafion & TEOSin ethanol
Dissolve
Nafion in Ethanol
Evaporate solvent
Si(OEt)4 (liquid)
Nafion & TEOS
Silica particles form in membrane
NafionTM
5 weight percent ex situ silica in Nafion
Class 1B: in situ Silica-Nafion Nanocomposite
In situ Silica particles
In situ filled Silica in polydimethylsiloxanes
Journal of Polymer Science Part B: Polymer Physics, 2003, 41,
16
Solid Organic Polymer
Inorganic Monomer (liquid) & catalyst
Organic Polymer Inorganic Monomer
In situ filled Silica in polydimethylsiloxanes
Highly transparent
Does not require mechanical blending
Journal of Polymer Science Part B: Polymer Physics, 2003, 41,
16
In situ filled Silica in polydimethylsiloxanes
Journal of Polymer Science Part B: Polymer Physics, 2003, 41,
16
Silver particles made in situ polydimethylsiloxanes
Templating with triblock copolymer is formally a Class 1B
material
Polymer is template. After removal, silica remains
Class 1B: In situ formation of inorganic phases in
polymers
Method for mixing at nanoscale without mechanical blending
required-less chance for aggregation and segregation to occur
(steric stabilization)Raises modulus and strength of materialsIn
situ polymerization of inorganics selectively in blocks of block
copolymers-first step to biomimetic mineralization.
*
Class 1 B materials are those in which the inorganic phase is grown
from a monomer or precursor in the organic polymer as a solvent or
template. It is done to reduce the stress of mechanical mixing
(probably not as big a problem as indicated) and to prevent
aggregation and segregation experienced during mixing. Detractions:
more expensive, time consuming, and control over particle size is
generally not as good as in Class 1A materials.
*
It is often said that the major advantage of filling a network by
this in situ approach is the avoidance of the problems associated
with mechanical blending. In this case the monomer is dissolved
into the solid polymer then reacted to make the inorganic phase.
The size if the inorganic phase is going to depend on the polymer
free volume (the space between polymer chains) and how much monomer
can be soaked into the polymer. This approach limits the processing
to thin films or fibers since diffusion in solid polymers is slow.
Polymerizations will be described later, but in several cases there
is a coreactant that must also be difused into the polymer.
Depending on reaction rates, it is possible to get gradient
structures.
*
This is the case of polymers like polydimethylsiloxane (PDMS) which
are liquids unless they are highly filled with inorganic or
crosslinked. In this case, all you have to worry about is the
misciblity of the monomer with the polymer. These are often
hydrolysis and condensation systems, though metals have been
reduced in PDMS as well. To get the water into the system, you
generally store samples in humidity chambers under 100 percent
relative humidity. The thermosets may also be in this category as
the silica may be prepared in situ in the epoxy prepolymer before
it is cured or crosslinked.
*
A lot of the theromplastics arte no going to have very fast
diffusion of monomers into them, so many researchers have resorted
to premixing everything in a solvent, then evaporate quickly and
allow the particle formation to continue. The polymerization
reaction kinetics leading to particles needs to be slow for this to
be acceptable. For hydrolysis and condensation, the fact that the
water has to come from outside, allows this to work. If you added
the water at the same time as monomer youd have problems.
*
The number of polymers is pretty extensive since people have been
studying this Class1B approach since the 80s when Jim Mark and
Garth Wilkes pioneered the field with silicones and polyethers,
respectively.
*
Lets look at little at the polymerization chemistries involved. We
have already spoken about hydroysis and condensation of alkoxides
so this will be some review and some new material to build on the
old. I will briefly introduce reduction sulfidation and
decomposition approaches.
*
In situ filling has been done with a lot of different silicon and
metal oxides, including the silica and silsesquioxanes at the top
of the list. Main group metal oxides like alumina and boron oxides
have also been looked at along with a number of transition metals.
Magnetic metal oxides (magnetite) in nanocomposites are very
popular because you can physically remove nanocomposites from
mixtures by a magnet.
*
A erview of the hydrolysis and condensation chemistry for
tetraalkoxysilanes. These monomers are reactive with water but
reaction rates are slow without catalysts. Since the water is added
to the Class 1B materials in the vapor phase, the catalyst needs to
be in with the monomer. That rules out HCl, or ammonia. One
commonly used catalyst class of catalysts are based on tin (II),
like dibutyl tin dilaurate 9which are generally liquids). Careful
around tin compounds because the dialkyl tin is toxic. So as water
diffuses into our polymer impregnated with monomer and tin catalyst
it reacts to hydrolyze the alkoxide groups which means alcohol is
liberated. The water generated by the condensation step will most
get used up by more hydrolyses. Now in the polymer, it is going to
be slow for molecules to diffuse and as they grow, it will become
even harder to move around. So much of the particle growth will be
monomer diffusing to growing clusters and eventually
particles.
*
This is a summary of sol-gel polymerization of tetraalkoxysilanes
outside of a class 1B system, but in the class 1B, the particles
will likely be spherical, amorphous and polydisperse. In many cases
people have reported larger particles (for a weight percent of
precursor) than they would see in a regular low viscosity
solvent.
*
Now with the silsesquioxane monomers, the only differences are
small increases in rates of reaction under acidic conditions and
slightly lower rates under basic conditions. The organic group, R,
acts as a steric blocking group helping make cyclics but hindering
development of networks. The only monomers suitable for in situ
polymerization in polymers are the methyltrialkoxysilane, some with
reactive functionalities on the R group, and bridged monomers with
two or more trialkoxysilane groups. Many of the simple alkyl or
aryl groups cause formation of an oily phase that plasticizes the
polymer making it weaker.
*
Again general characterisitics for organotrialkoxysilane
polymerizations. Note Stober method does not afford nice
monodisperse particles like it does for tetraethoxysilane.
*
Formation of metal oxides like TiO2, Fe2O3, Al2O3, etc. Metal
oxides can be prepared from metal salt hydrates, like AlCl36H2O, or
from metal alkoxides like Al(Obu)3. In all cases oxidized metals
are more electrophilic and generally more reactive with water than
silicon. In fact metal salts, when added to water, will lower the
pH considerably by forming oxonium species like the intermediate
shown in the hydrolysis scheme above. Since every monomer gets a
positve charge from the coordinated water, the monomers repel each
other and wont react until base is added to neutralize the acid.
Metal alkoxides have such electrohilic metals that they dont give
up the alkoxide group as a base the way sodium alkoxides would in
water. Instead, they get lone pairs from other alkoxides on other
metals or on solvent molecules to help satisfy the metals
electrophilicity. A simple transition metal ethoxide is actually an
oligomer through these tris hapto bonds. Now formaly the hydrolysis
and condensations see above are mechanistically similar to the
reactions on silicon. Just a lot faster. Usually we try and slow
the sol-gel chemistry down to prevent precipitation. So being in a
polymer with water as the limiting reagent is actually a good
thing. Now metals can have multiple oxidation states, generally,
the higher the oxidation state the more electrophilic a metal is.
However, two high and the metal grabs all of the electron density
of the oxygen making unable to participlate in condensation
reactions as a nucleophile. One way to think of these highly
oxidized metal oxides is that they have a metal oxygen double bond.
So lower oxidation states actually work out better for sol-gel. The
reason to put these metals into polymers is that the metal oxides
have high Z and high refractive indices (for optical applications)
and the metals give rise to nanocomposites that are harder and more
abrasion resistant than silicon.
*
Now this slide shows you the way that metals grab lone pairs off of
oxygens with two bonds already in place. The metals use the oxygeas
a ligand using eh lone pairs. This gives rise to a higher level,
more compact bonding that observed with silicon. Metals with their
full use of the d orbitals can easy form four atom rings whereas
silicon cannot.
*
Now metal oxides have lower barriers to crystallization than
silica. To turn amorphous silica into quartz you need high
temperatures and pressues in a hydrothermal environment. In metals
amorphous materials can crystallize at room temperature. Stober
chemistry doesnt work at all in making monodisperse particles, but
emulsion chemistry does. One thing silicon cant do is form the very
cool molecular clusters that many metal alkoxides form even before
hydrolysis. We will talk more about sol-gel chemistry throughout
the course.
*
Reduction of metals is a topic we havent broached yet. However, it
is a form of chemistry humans have been purposefully using since
Roman times. Rake a metal salt and chemical reduce it in solution
and you get metal nanoparticles. This was done in ceramics by the
Romans with gold nanoparticles that made their ceramics red. Red
stained glass from the Middle Ages is often red with gold
nanoparticles. Metal nanoparticles are electrically conducting, so
adding them to a polymer makes the polymer conducting once you
reach percolation levels. They can be made by chemical reduction
with hydrazine, hydrogen gas, hydroquinone, silyl hudrides, and
alcohols. The last reaction of the metal carbonyls is not a
reduction since the metal doesnt change oxidation state. It is a
cool way to make particles, though the metal carbonyls are
extremely toxic and, in some cases, pyrophoric (spontaneously catch
fire).
*
Metal sulfides are semiconductors and if made small enough show
quantum effects like blue shifting of the absorption and emission
bands into the visible range of light. So nanocomposites with metal
sulfides would potentially have light emitting diode applications.
You make them with hydrogen sulfide, but that is very smelly and
toxic so most use either sulfur or thioureas to sulfide metals or
metal salts.
*
Now back to class 1B materials preparation. This is some work my
group did. We were making Nafion silica class 1A materials, but
made a couple of Class 1B for comparative purposes. Always design
control and baseline experiments based on literature so that your
work can be compared with others more easily. Anyway, we wanted to
have silica particles in Nafion to see if we could reduce water
usage in fuel cells and increase ionic conductivity and thermal
stability of the sulfonated fluoropolymer membranes.
*
The membrane made by Class 1A methods is on the left, the membrane
from class 1B is on the right. We found that you could not
systematicaly control of the size of the particles with the Class
1B approach.
*
Poly(dimethylsiloxane) (PDMS) [Si(CH3)2O] is probably the most
important and the most useful high-performance elastomer, but only
when its inherent weakness is overcome by reinforcement with some
particulate filler, usually silica. Such fillers are typically
mechanically blended into the polymers before crosslinking. There
are inherent problems, however, with this type of ex situ blending
process. Some of the disadvantages of blended systems include the
time-consuming and energy-intensive nature of the blending and the
lack of control over the morphology or surface characteristics of
the aggregated filler.In a typical two-step process, a polymer
network is first formed with PDMS, tetraethoxysilane (TEOS), and
stannous octoate (STO). This crosslinked network is swollen in TEOS
for a few minutes and then placed in a solution containing acid or
base and water to precipitate silica. In this work, the unfilled
polymer network was swollen in a solution containing TEOS and a tin
salt. No water was added except as was absorbed by the sample from
water vapor in the air.
*
In a typical two-step process, a polymer network is first formed
with PDMS, tetraethoxysilane (TEOS), and stannous octoate (STO).
This crosslinked network is swollen in TEOS for a few minutes and
then placed in a solution containing acid or base and water to
precipitate silica. In this work, the unfilled polymer network was
swollen in a solution containing TEOS and a tin salt. No water was
added except as was absorbed by the sample from water vapor in the
air.
*
The strength of the silica polydimethylsiloxane polymer
nanocomposites with 0-154 wt% silica made by class 1B approach are
shown here. PDMS without filler is a very weak material. Remember
tehermoplastics have tensile strengths between 10-60 MPa. The
tensile strength of PDMS is less than 0.1 MPa. With the silica in
it, the strength went up eight fold to almost 1 MPa.
*
IN this work PDMS was filled with silver particles made with a
silyl hydride as the in situ reducing agent. The stress strain
curve shows improvement in strength but this can be misleading
since there is also some curing taking place with the reduction.
Thre are many other examples of type 1B nanocompoistes, but in the
end using the method to provide mechanical reinforcement is not a
economically feasible approach. There are other things you can do
with a Class 1B materilal however.
*
The block copolymers used to template silica, silsesquioxane or
metal oxide growth are basically a Class 1B system. They are lumped
in class 2 in this course, but in the future I will probably move
them to this lecture. The triblock above has hydrophilic and
hydrophobic phases. Unhydrolyzed monoemr will dissovle in the
hydrophobic phase but as it hydrolyzes, it becomes hydrophilic
enough that it migrates into the hydrophilic phase where it
condenses into an amorphous structure tempalted by the 3-D
structure of the surfactant. Note if you start with the metal salt
hydrates they will go into and stay in the hydrophilic phase. We
will talk more about these templated materials in the lectures to
come, because they are the closet akin to biohybrids that we have
to date.
*
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