Physics and Chemistry of Hybrid

Organic-Inorganic Materials
Lecture 6: Polymerizing
monomers to make hybrids

preassembled inorganic phase (particles, fibers) dispersed in organic phase

 Key concepts
• Reasons for making an inorganic filled organic polymer hybrid:
improve strength, abrasion resistance, modulus, hardness,
inflammability,
• Metal oxide inorganic particles can be made by sol-gel, Stober
preparation, precipitation, flame synthesis
• Organic phase: organic polymers melted or in solution
• Inorganic particles increase viscosity in polymer melt or solution
• Particle aggregation ruins hybrid effects
• smaller the particle, the greater the strength and modulus of the
hybrid
• the higher the particle concentration, the greater the strength and
modulus of the hybrid
 What are Hybrid Materials?
Composite materials mixtures of organic and
inorganic components
Metal
oxide
network

Improvement on either organic or inorganic components

Making Hybrid Materials: Class 1A
(pre-formed particles and fibers)

•Physical mixing of particles in

melt or solution
•Easiest hybrid to make
• Most common hybrids
Preparation by melting polymer and mixing
Preparation by dissolving polymer and mixing
Solid Inorganic
particles

Solid Inorganic
particles dispersed
in same solvent

Particle dispersion in solid

polymer
Reasons for making a particle-filled
polymer
• Fillers (CaCO3, Silica, Talc, wood powder) are cheaper
than some plastics-cut cost.
• Reduce Coefficient of thermal expansion of polymer
• Reduce shrinkage during thermoset curing
• Improve abrasion resistance and hardness
• Increase modulus
• Make melt more viscous or gel (thixotrope)
• Make Flame resistant
• Aesthetics – pearlesence or opalescence
 Organic polymers that have been
used:
• Thermoplastics: polystyrene, poly(methyl methacrylate),
HDPE, polypropylene, Nylon’s, polycarbonate, polyimides,
poly(ethylene oxide), polyurethanes, polyesters….

• Elastomers: silicones, polyisoprene,…

• Thermosets: epoxies,

• Polyelectrolytes: Nafion

practically every commercial polymer known.

Physically mixed hybrids are a composite material
based on an inorganic particle & an organic
polymer

Silica particle (130

nm in diameter)

5 weight percent silica in Nafion

Polymer is the continuous phase or matrix

The inorganic particles is the dispersed phase or filler
 Examples of Physically Mixed
Hybrids
• Paint – poly(vinyl acetate) + TiO2
• Pearlescent paint – polyacrylate +
TiO2 coated mica
• Make-up or cosmetics –
polyvinylpyrrolidone + metal
oxides (for color)
• Sunscreens – polyvinylpyrrolidone
or polyethers and TiO2 or ZnO
nanoparticles in water or glycerin
 Class 1 Hybrids: No covalent bonds
between organic & inorganic phases
Physically dispersed
particles in polymer

POSS in polypropylene

Generally meta-stable: particles will segregate

if given the opportunity
Sedimentation or floatation of particles
during mixing and drying

(a) (b)
 Sedimentation of particles during
mixing and drying

(a) (b)

•Solution viscosity was too low

•Particles floated to the top of the membrane
as the solvent dried
•Solved problem by evaporating solvent while
mixing until viscosity was 65 cP.
 Influence of nanoparticles on melt
viscosity

Smaller the size particle, the greater the viscosity

“Nanofillers in polymeric matrix: a study on silica reinforced PA6,” E. Reynaud, Polymer 2001, 42, 8759
 Particles in polymers: thixotropes
Particles are used to Silicone Silicone
stop liquids from flowing sealant with sealant with
until subject to shear. NO silica silica

Used in “non-running”
or “no-drip” liquid
adhesives, paints, and
lubricants.
 How to make inorganic particles
• Sol-gel “wet” synthesis

• Emulsion polymerizations (sol-gel in oil & water) microns in

diameter
• Aerosols/flame syntheses (will not make silsesquioxanes)
 Sol-gel: Stober synthesis
All particles round and same size

TEOS
Concentrations NH4OH
0.011M (0.03736g) to 0.28M (0.934g) Concentrations
0.1M to 1.2M

Hydrolysis: exchange of OEt groups with OH groups

Condensation: Reaction of OH groups to form Si-O-Si links

J. Colloid Interface Sci., 26 (1968), pp. 62–69

 Control of particle size by changing the
concentration of ammonium hydroxide with
0.28M TEOS

Rayleigh scattering
 Light scattering from
particle/polymer composites
 Other ways to make particles:
Synthesis of T8 POSS “particle”
Hybrid Hydrolysis &
monomer condensation

Yields are not always so good

 Synthesis of Phenyl T8 POSS
Hybrid Hydrolysis & breaking and
monomer condensation remaking bonds

Also works from the polymer!!!!

Best way to make POSS
 “Two-step” method to prepare
silsesquioxane particles from hybrid
monomers
Hydrolysis &
condensation

Typical recipe:
1) PhSi(OEt)3 (2.4 grams) in 12 mL anethol is
mixed with aq. HCl (0.0027 M, 3.6 mL) for 7
h.
2) This sol was added to aq. NH3 (1M, 32.4 Loy, D. A. Macromole Mater Eng. 2012, in press.
mL) and stirred for 20 h.
3) Particles isolatedA. and washed with
Matsuda et al. J. Ceram. Soc. Jap. 2007, 115, 131-135.
centrifugation.
Flame synthesis of inorganic particles

Langmuir 2004, 20, 5933

 Other inorganic fillers include
• Clays (2-D aluminosilicates)*
• Fullerene, nanotubes, and graphene*
• other aluminosilicates
• Main group metal oxides
• Transition metal oxide particles
• Alkali earth carbonates and sulfates
• Quantum dots
• Metals
*included in this lecture
POSS physically dispersed in polypropylene
How do you
characterize a
XRD of POSS
hybrid:

Particle is
crystalline

Can see if XRD of POSS in HDPE

crystals exist in
hybrid

Macromolecules, 2006, 39 (5), pp 1839–1849

 Influence of nanoparticles on melt viscosity

Micrographs of the PA-05-S

composite (left) and the PA-05-L
system (right) (MET)

Silica particles mixed into Nylon while

melted

Viscosity is higher with smaller particles

and with more particles
“Nanofillers in polymeric matrix: a study on silica reinforced PA6,” E. Reynaud, Polymer 2001, 42, 8759
Tensile modulus (stiffness) of nylon 6 nanocomposites as a
function of SiO2 content
More inorganic: higher modulus

Less inorganic: lower modulus

No inorganic, just nylon: lowest modulus

.

Modulus increases as inorganic content increases

Composites Part B: Engineering Volume 39, Issue 6 2008 933 - 961

Tensile strength of nylon 6 nanocomposites as a
function of SiO2 content & surface modification
using coupling agent

With surface modification

Without surface modification

If surface tensions at surface are too different, poor wetting results in

weaker materials. Modify surface to match surface tension –
increase in strength.
 Polymer-clay composites

montmorillonite

Exfoliated montmorillonite clay

2-Dimensional inorganic phases provide incredible reinforcement

 Polymer-clay composites
• Clay: 2-D sheets of alumino-silicate with metal
cations in between
• Replace metal cations with cationic
surfactants
• Replace surfactants with polymers
(melted or in solution)-intercalation
• Heat and apply shear – exfoliation
• Stronger, fire resistant, less permeable
Process for forming clay polymer composites

clay with Na
counterions clay with surfactant
counterions organic polymer
intercalated into
clay

polymer exfoliated clay:

No stacking of
aluminosilicate
sheets
Detecting intercalation and exfoliation

X-ray diffraction

From Giannelis et al., Adv. Polym. Sci., 118 (1999)

Tensile strength of non-covalently integrated
clay-polystyrene-co-acrylate nanocomposites

Mechanics of Composite Materials 2006, 42, 45.

 Carbon Spheres (Buckyballs) &
Nanotubes & graphene as inorganic
fillers

High modulus
Strong
Stable

Macromolecules, 2006, 39 (16), pp 5194–5205

Nature Materials 9, 868–871 (2010)
 Fullerenes as inorganic particles in
polymers

The curves of uniaxial deformation of the LDPE films with different fullerene
content: 0 (1), 1 (2), 3 (3), 5 (4) and 10 wt% (5)

J. Mater. Chem., 1997,7, 1097-1109

 Summary: Physical mixing of
inorganic in organic polymer
• Made by solvent or melt mixing
• Particle aggregation will ruin any positive influence from
the inorganic particles
• Nature of non-bonding interactions will affect strength &
modulus trends
• But generally, modulus and strength increases with
decreasing particle size
• Modulus and strength increases with increasing weight
percent particle
• Clay –polymer composites best properties of hybrids so far
 Study Guide

• Name Naturally occurring hybrids and describe what they are made of: Nacre
(argonite and protein), bone (apatite and protein), enamel (apatite and proteins),
dentin (apatite and proteins), echinoderm spines (calcium carbonate and
proteins), lobster chitin (Mg, Ca, proteins, carbohydrate), spider fangs(Mn, Zn,
proteins, carbohydrate), phytoliths (silica-carbohydrate), sponges (silica-protein).
• Hierarchical material – different structures at different length scales
• Physical mixing of hybrids: in melted polymer or adding dispersed particles to
polymer solution then evaporating solvent
• Clay polymer composites are made by intercalation and exfoliation
• Common inorganic particles – carbon black, silica, titanium dioxide, clay, calcium
carbonate, fullerenes and carbon nanotubes
• What are nanocomposites- A nanocomposite is a two phase hybrid with one or
both phases having structural dimensions in the 1-100 nanometer length scale.
Paint, glue, and cosmetics are examples.