Nanopatterned Polymer Coatings for Marine Antifouling Applications
Lecture 1 Overview of polymer coatings (paint and other ... · Latex coatings. Viscosity and...
Transcript of Lecture 1 Overview of polymer coatings (paint and other ... · Latex coatings. Viscosity and...
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Overview of polymer coatings (paint and other coatings)
Pigment volume concentration (PVC and CPVC)
Rheology
Crosslinking and film strength
Powder coatings
Latex coatings
Viscosity and colloidal stability
Emulsion polymerization
Particle morphology
Polymer Coatings
Mitchell A. Winnik, CHM1303, fall 2010
Lecture 1
How latex particles form films:
Drying, deformation, and contact (and VOCs)
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Latex Coatings and Latex Film Formation
Polymer diffusion and development of mechanical strength
Brief introduction to ET (non-radiative energy transfer)
Brief introduction to SANS (small angle neutron scattering)
Polar membranes in latex films
Moisture and humidity effects
Lecture 2
Required reading will be posted on the course web site.
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Polymer Coatings (paint)
SOLVENTRESIN
PIGMENTS
curing agent
basefunctional hiding extender
thixotropescatalysts film
forming aids
ADDITIVES
COATING
The resin is a glue holding the paint together cohesively and providing adhesion to the substrate.
The resin is always a polymer.
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Nanomaterials used in coatingsThe coatings industry is the largest producer and consumer of
nanoparticles in the world.
Monodisperse polymer particles, d = 80 nm to 400 nm
(megatons per year)
TiO2
Pigmentd = 450 nm
Al2 O3 shell
Hollow PS-PMMA crosslinked beads
d = 450 nm
d = 450 nm
Rhopaque
Examples:
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Varnish (clear coat) has no pigment.
“100% solids” has no solvent.
Lacquers are high M polymers dissolved in a solvent. They dry to leave an entangled plastic film.
VOC (volatile organic content) : wt/unit volume of most organic compounds with bp
250 C.
Protective coatings: The primary function of these coatings is to protect the underlying substrate. At the very high-tech end are automotive recoat paints.
Decorative coatings: The primary function is to hide the surface or previous coating. Interior house paints are the most common example.
some terms:
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pigment
resin
Pigmented coatings
Pigments provide opacity and color to a coating.
The TiO2 particle size is chosen to give the maximum scattering of visible light.
It is the normally the most expensive component in the coating.
TiO2(nD 2.66)
acrylate polymer(nD 1.48)
450 nm
TiO2 SiO2
The TiO2 used as a pigment in coatings is covered by a thin layer of silica (or alumina) to prevent photo- oxidation of the matrix.
In paper coatings, clay and calcium carbonate are commonly used in coatings. The volume fraction of pigment is much higher than in paints.Other pigments in smaller amounts
give color to the coating.
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30 40 50 60
gloss
blisteringcorrosion
permeability
PIGMENT VOLUME CONCENTRATIONC
OA
TIN
G F
ILM
PR
OPE
RTI
ES
CPV
C
PVC and film properties
At PVC > CPVC, the film contains voids.
PVC (pigment volume concentration)
CPVC (critical PVC): the concentration of pigment at which the pigment becomes continuous and there is just enough binder to fill the interstitial spaces.
pigment
resin
High gloss coatings have low PVC.
C.H. Hare, Protective Coatings, Technology Publishing, 1994
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settling occurs at ultra low shear rates
sagging and leveling at low
shear rates
good stirring consistency at medium shear
rates
paint application at
high shear rates
shear rate (s-1)
visc
osity
(Po
ise)
visc
osity
(Po
ise)
Thixotropic flow is a special type of pseudoplastic flow typical of most coatings. As shear rate is increased, the viscosity drops. As the shear rate is decreased back to zero, the viscosity builds more slowly. The time to regain full structure (sec to hr) is vital to coating rheology because it relates to properties such as sag resistance, film build, flow and leveling.
Coating Rheology
viscosity as a function of shear rate
A variety of soluble polymers are added to
the paint formulation as rheology modifiers.
C.H. Hare, Protective Coatings, Technology Publishing, 1994
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9Graessley, 1974; taken from Tonelli, AE Polymers from the Inside Out, Wiley, 2001 p 139
ENTANGLEMENTS -- Review
polymer chains cannot cross
a polymer chain moves among obstacles
obstacles
The confining effect of the surrounding chains
act like a confining tube.
For many polymers, it has been observed that above a critical
molar mass (Me ), the melt viscosity increases as M 3.4. This
behavior is attributed to the effect of entanglements.
Me
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film strength as a function of molar mass
(for polystyrene)Definition of tensile strength and fracture
energy
G1c
from R. Wool, Polymer Interfaces, 1997
there is an increase in strength associated with entanglements
Cohesive strength of a coating
Solutions of polymers with M >> Me have very high viscosity and have
to be applied at low solids.
The initial slope is the modulus.
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Thermoset coatings
Many coatings that cure are low M polymers with reactive groups dissolved in a solvent. They dry to form a weak plastic film that undergoes crosslinking on the substrate.
• Oxidative cure: alkyds• Moisture cure: alkoxy silanes,
silicates• “2-pack” (“2K”): epoxy + curing
agent, urethane• Baking systems: melamine, N-
methlyol acrylamide + acid
film of linear chains too short to be entangled
after crosslinking, the entire film becomes a single
interconnected molecule
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Thermoset coatings
Crosslinked coatings have better solvent resistance, better acid and base resistance.
They have improved hardness and tensile strength, often at the expense of brittleness.
Parameters characterizing crosslinked coatings.
1. gel content (1 - sol content)2. crosslink density (mean chain length
Mc between crosslinks)3. Swell ratio when exposed to a solvent
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bake time
POWDER COATINGS
powder on the substrate
powder melts and begins to fuse
fused coating
Powder coatings melt (soften and flow) when they are heated, and crosslink as the particles fuse into a film.
These are pigmented coatings.
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object to be coated
by electrostatic sprayby fluidized bed process
The bed can be charged from an overhead electrode. The object (grounded) within the cloud of electrostatically charged powder is more uniformly coated.
Electrostatically charged beds eliminate the need for pre-heating the object and reduce the quantities of powder needed.
POWDER COATINGS
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Adhesion and cohesion in multilayer coatings
Automotive coatings:clear coat (gloss, UV
protection)basecoat (pigment)primer
examples of paint failure
C.H. Hare, Protective Coatings, Technology Publishing, 1994
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LATEX COATINGS
Latex particles consist of polymer molecules of any molar mass (typically 5000 to 1 x 106.
Latex dispersions maintain low viscosity for high solids even
for high M polymers.
A latex is a colloidal dispersion (suspension) of polymer particles in
water.10-2
100
102
0.50 0.750.25
visc
osity
(Po
ise)
vol. fraction solids
Steric (entropic) stabilization
Coulombic (charge) stabilization
Colloidal stability is either coulombic or steric in origin.
m
shear rate
low
high
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from D Urban, K Takamura, Eds. Polymer Dispersions and their Industrial
Applications.Wiley-VCH 2002
Aqueous polymer dispersions by class
other, 5%
acrylate, 30%
styrene-butadiene, 37%
vinyl acetate, 28%
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--
- -
-
--
-
--
-
- -
-
--
-
-
Coulombic repulsion
Electrostatic Stabilization
water
entropic repulsion
osmotic repulsion
Steric Stabilization
all solvents
MECHANISMS FOR COLLOIDAL STABILITY
Aqueous dispersions must maintain colloidal stability
during storage but lose this stability at some key point
during the application.
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surfactant micelle
EMULSION POLYMERIZATION
monomer
water
surfactant
initiatormonomer droplets
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Typical acrylate monomers
O
O O
O
O
O
O
O
methyl methacrylate (MMA)
butyl methacrylate (BMA)
butyl acrylate (BA)
2-ethylhexyl acrylate (EHA)
In North America, the most common latex for paints are
copolymers of BA with MMA or BA with vinyl acetate (VAc).
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SDS
C12H25-SH
monomer
droplets
surfactantinitiator
EMULSION POLYMERIZATION
S-BACOO(-)
COO(-)
S-BACOOH
COOHlow pH pH > 6
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growing polymer particles
surfactant micelle
EMULSION POLYMERIZATION
Stage 1: Particle nucleation (homogeneous or micellar)
Stage 2: Particle growth fed by monomer from the monomer droplets
(Transport of the monomer through the aqueous phase is critical.)
Stage 3: Particle growth after disappearance of the monomer droplets
monomer molecules in
water
monomer droplet2 to 10 m
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growing polymer particles
surfactant micelle
EMULSION POLYMERIZATION
monomer molecules in
water
monomer droplet2 to 10 m
Initiation occurs in the water phase.
Polymerization occurs in the water phase and in the particles.
When oligomers formed in the water exceed their solubility, they are “swept
up” by the growing particles.
For most monomers
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ingredient amount, gvinyl acetate 16.0
dibutyl maleate 4.0
poly(vinyl alcohol) 10% 10.0
NaHCO3 0.200
H2O 69.8
KPS 0.200
“Protective Colloid”
The grafted polymer is called a steric stabilizer. In the old literature, the polymer itself is referred to as a
“protective colloid.”
When emulsion polymerization is carried out in the presence of a water- soluble polymer, the polymer becomes
grafted to the particle surface.
*OH O
H3C
O
When the polymer at the particle surface is a polyelectrolyte, the particle is said to be “electro-
sterically stabilized.”
PVOHpartially
hydrolyzed PVAc
(-) (-)(-)
(-)
(-)
O-O O O-
Na+Na+
P(VAc-DBM)
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EMULSION COPOLYMERIZATION
If the reactivity ratios are unfavorable, the composition changes throughout the reaction, and phase separation occurs.
Example: VAc-BA copolymerization (rVAc
0.02; rBA
3) The VAc radical prefers to add BA, and the BA radical also prefers to add BA. The BA monomer is used up first, followed by the VAc.
VAc-rich matrix
Overall conversion (%)M
onom
er c
onve
rsio
n (%
)
0 20 40 60 80 1000
20
40
60
80
100
VAc
BA
4:1 w/w VAc/BA -- J. Oh 2003
BA-rich occlusions
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EMULSION COPOLYMERIZATION
When the reactivity ratios are unfavorable, particles with uniform polymer compositions can be prepared by seeded semi-continuous
emulsion polymerization under “monomer-starved” conditions.
Con
vers
ion
(%)
Dia
met
er (n
m)
0 50 100 150 200 2500
20
40
60
80
100
Polymerization time (min)0 50 100 150 200 250
100
150
200
Globalconversioncalculated
Con
dens
erInitiatorsolution
MonomerMixture
Pre-emulsionVAcBA
C12 -SHwaterSDS
NaHCO3
waterKPS
instantaneous conversion
J. Oh 2002
VAc/BA 4:1 w/w
seed particles, ca. 3 to 5 wt % solids
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EMULSION COPOLYMERIZATION
If the second stage monomer is different than the first, one can
obtain structured latex particles.
core-shell
half moon(Janus)
These morphologies can be very useful for obtaining unique properties: crosslinked core, hard core-soft
shell, soft core-hard shell
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Questions
1. Imagine that you have a sample of monodisperse PMMA particles with a diameter of 200 nm and the polymer has Mn = 100,000, Mn / Mw = 3. On average, how many polymer molecules are there per particle?
2. Imagine that you have a sample of monodisperse polystyrene with Mn = 20,000,000 and that you can emulsify them to produce particles containing a single molecule. What would be the diameter of the particles? How does the particle radius compare to the unperturbed radius of gyration of PS? What would you expect to happen if you melt-pressed a film of these particles and annealed them at T >> Tg (PS)?
1
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Environmental factors are causing major changes in the coatings industry.
• replacement of solvent-borne coatings by water- borne coatings (low VOC)
• removal of all solvent from waterborne coatings (e.g., 15 wt% organic solvent)
WATERBORNE COATINGS
Most waterborne coatings involve latex dispersions.
A latex is defined as a dispersion of polymer nanoparticles in water.
80 to 250 nm
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LATEX FILM FORMATION
PROCESS solids content 40 to 50 wt%
particles in contact
void-free solid
mechanically coherent film
water evaporates
polymer diffusion
particles deform
T > MFT
latex in water
drying
diffusion
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wet dry
wet
the last spot to dry
How latex dispersions dry on a substrate
Water evaporates most rapidly at the dry/wet boundary. There is a flux of water and particles toward the edge of the film.
wet dispersion drying boundarydry film
1.5 mm 15 mm
film
substrate
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LATEX FILM FORMATION
Drying
The polymer modulus must be less than 107 Pa
Deformation precedes contact
107
108
109
105
106
- 50 50 1000
Tg = 0 oC Tg = 75 oC
temperature
stor
age
mod
ulus
E’ glass
rubbery
flow
The MFT is the minimum
temperature at which the latex will form a transparent
film on drying.
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Drying
cells
LATEX FILM FORMATION
Forces associated with drying deform latex spheres into space-filling polyhedral cells.
Capillary forces, surface tension….
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LATEX FILM FORMATION
rhombic dodecahedra
If the particles in solution form a colloidal crystalline phase, with fcc packing, isotropic
deformation will lead to rhombic dodecahedra.
biaxial
isotropic
Isotropic compression should lead to shrinkage in the x,y plane.
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LATEX FILM FORMATION
rhombic dodecahedra
Isotropic deformation of fcc packed particles will lead to
rhombic dodecahedra.
PBMA d = 337 nm20 h at 36 oC
Freeze-fracture TEM images of a poly(butyl methacrylate) latex film.
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36PBMA 337 nm20 h at 36 oC
Cohesive fracture after annealing.
Freeze-fracture TEM images of a poly(butyl methacrylate) latex film.
rhombic dodecahedra
Interfacial fracture in the new film.
2 h, 80 C
surfactant (SDS) crystals.
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LATEX FILM FORMATION
Drying
The polymer modulus must be less than 107 Pa
Plasticizers lower Tg and decrease the
modulus.
OH
OO
HO O O C4H9
HO O C4H9
TMP (Texanol)
butyl cellosolve
butyl carbitol
volatile plasticizers (VOC)
If an organic solvent is added to the latex and dissolves in the
particles, it will act as a plasticizer.
, ,
1 pol solv
g g pol g solv
w wT T T
Fox equation
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LATEX coatings
Drying
The polymer modulus must be less than 107 Pa
107
108
109
105
106
- 50 50 1000
Tg = 0 oCTg = 45 oC
temperature
stor
age
mod
ulus
E’ glass
Volatile solvents added to the dispersion, lower the modulus of the polymer in the particles.
OH
OO
HO O O C4H9
TMP (Texanol)
butyl carbitol
volatile plasticizers (VOC)
After the paint dries on the substrate, the solvents evaporate and the Tg of the polymer increases.
But this releases VOCs into the atmosphere.