PigmentsandFillers Pigments and Fillers

Mike Diebold
DuPont de Nemours, Inc
DuPont TitaniumTechnologies DuPont Titanium Technologies
michael.p.diebold@usa.dupont.com
Important Properties of Small Particles
Particle size and shape
Surface Area
Surface Energy
Friction and Bulk Flow
P ki dD it Packing and Density
Surface Charge
Interactionwithlight Interaction with light
Absorption
Scattering
Surface area
Depends on particle size and shape.
Increases linearly with particle size decrease. y p
Typical values as a function of size:
A (
2
/ )
*
Area (m
2
/g)
*
1 mm 0.003
10 i 03 10 microns 0.3
1 micron 3
10 nm 300
*
Assumes density of 2 g/cc
Origin of Surface Energy
Magnitude of Surface Energy
D d hi Depends on two things:
Amount of surface
Chemical state of the surface atoms
Consequences of Surface Energy
Particles are attracted to other surfaces.
Particlessticktogether Particles stick together
Particles stick to bin walls, etc.
Particlesaredifficult todisperseinliquids Particles are difficult to disperse in liquids
V d W l f ti
r
1
r
2
Van der Waals force equation:
( )
( )
(
(

=
2 1
2
) (
r r W
F
at t r act i on
L
( )
(

+
2 1
2
) (
r r
L
at t r act i on
W = Constant
Friction and Bulk Flow
Friction is a surface phenomenon:
proportional to amount of contact between two surfaces
(i. e. surface area).
proportional to strength of contact between two
surfaces(i e surfaceenergy) surfaces (i. e. surface energy).
Friction is a very significant force for small
particles particles
Because of friction, the flow of particles (moving
particles past one another) is difficult. p p )
Friction between Small Particles
Small particles: Small particles:
are very light
havehighsurfaceareas have high surface areas
O i l h ld One particle can hold up
1,000,000 others!
Wall Pigment Bed
Particle Packing
Depends on particle shape
Roundparticlespackthemost densely Round particles pack the most densely
acicular (rod-like) particles pack least densely
Depends on particle size
L ti l kth t d l Large particles pack the most densely
Small particles pack least densely
Effect of Particle Shape on Packing
Effect of ParticleSizeonPacking Effect of Particle Size on Packing
Material Particle Size True Density Bulk Density Void Fraction
SiO
2
Sand 1,000 2.6 g/cc 1.6 g/cc 38%
TiO
2
0.25 4.1 g/cc 0.8 g/cc 80%
fumed SiO
2
0.015 2.2 g/cc 0.05 g/cc 98%
2
80%
100%
c
t
i
o
n
40%
60%
80%
V
o
i
d

F
r
a
c
0%
20%
40%
P
a
c
k
i
n
g

0.01 0.10 1 10 100 1000
Particle Size (microns)
SurfaceChargesinPowder Surface Charges in Powder
Static Electricity
Excess electrical charge on a particle will accumulate on
the particle surface.
If h i hi h i l l h f If charge is too high or particles are too close, the surface
will discharge (~10,000 volts/cm).
Maximumchargedensity(coulombsper area) is Maximum charge density (coulombs per area) is
independent of particle size.
Therefore, the amount of excess charge in a pound of material
increasesastheparticlesizedecreases increases as the particle size decreases.
Electrostatic forces from static charge become relatively more
important for smaller particles.
Formationof SurfaceCharge Formation of Surface Charge
in Slurries
H
+
H
+
++
OH
--
OH OH
H
+
H
O
-
OH
-
+ H
2
O
Acid (Low pH)
Positive Charge
Base (High pH)
Negative Charge Positive Charge Negative Charge
Surface Potential
40 0
60.0
(mv)
Basic Solid
Acidic Solid
pH
0 0
20.0
40.0
TiO
2 ZnO
6.0
-20.0
0.0
2.0 4.0 8.0 10.0 12.0
-60.0
-40.0
Some Solids are Both Acidic and Basic
O
-
O
-
O O
Si Si
H
O
O

Si Si
H
O
O
O OH
2
+
Al Al
H
O
O
O
Al Al
H
Al Al
O
O
O OH
2
+
Al Al
O
O
O
Si Si
O
O
O
H
Si Si
O
O

H
O
-
O
-
Some Solids are Both Acidic and Basic
Negative Faces
PositiveEdges Positive Edges
Kaolinite
House of Cards
Important Properties of p p
Pigments and Fillers
Particle size and shape
CPCV
Tinting properties
S f Ch i CPCV
Oil Absorption
Surface Chemistry
Dispersion
Density / Bulking Value
HidingPower / Opacity
Surface Charge
Influenceonfilmdurability Hiding Power / Opacity Influence on film durability
Manufacture
Effect of ParticleSizeonPaint FilmProperties Effect of Particle Size on Paint Film Properties
Film Properties
Gloss, DOI
Degree of
Dispersion
Optimal for
Light Absorption
Optimal for
Light Scattering
0.1 1.0 0.5 5.0 0.2 2.0
Diameter (microns)
0.01 0.05 0.02
( )
Effect of Particle Shape on Paint Film Properties
Shape affects packing characteristics.
Rod shaped particles improve film strength (like reinforcing
b ) bars).
Rod shaped particles can hurt gloss (if the protrude from the
surface) but improvetooth inprimers. surface) but improve tooth in primers.
Platy particles overlap and make penetration by water, light
more difficult (c. f., roof shingles).
Round particles have lesser effects on film strength,
permeability, etc.
FactorsDeterminingCPVC Factors Determining CPVC
Particle Porosity
Diatomaceous Earth
an empty sphere
CPVC = 0.18
Fumed Silica
very open structure
CPVC = 0.23
Oil Absorption (OA) Value
Grams linseed oil required to form a paste from
100 gram pigment. g pg
Oil first coats surface and fills voids; excess
neededtoturnmoist solidintoliquid needed to turn moist solid into liquid.
Depends on:
S f / P ti l i (lik CPVC) Surface area / Particle size (like CPVC)
Packing - presence of voids / porosity (like CPVC)
bili Wettability
Oil Absorption vs. Surface Area p
TiO
2
Grade Surface Area Oil Absorption
(m
2
/g) lbs/100 lbs ( g)
R-700 9.6 12
R-706 11.4 14
R-900 13.5 16
R-960 14.2 19
R-902 15.2 17
R-931 42.1 37
Effect of White Pigment on Tint
strong scattering
short path length
weak scattering
long path length
Effect of Pigment Flocculation on Tint
If the white pigment flocculates:
Color darkensbecausepathlengthof light Color darkens because path length of light
increases.
If thecoloredpaint flocculates: If the colored paint flocculates:
Color lightens because flocculated particles do
not absorb light as efficiently as dispersed ot abso b g t ase c e t yasdspesed
particles.
Surface Chemistry
Hydrous oxide surfaces tend to be
hydrophilic. y p
Pure oxide surfaces are marginally
hydrophilic hydrophilic.
Organic surfaces (carbon black, organic
pigments) tendtobehydrophobic pigments) tend to be hydrophobic.
Surface Modification - Theory
O it dC l b lk t Opacity and Color - bulk property
Refractive index
Absorption coefficient
Particle size
dispersibility, dispersion stability, bulk
h dli h l i i i f handling, photocatalytic activity, rate of
incorporation into polymer resin:
ALL ARE SURFACE PROPERTI ES
ModifyingPigment Surfaces Modifying Pigment Surfaces
1. Surface Deposition
TiO
2
Slurry Treated TiO
2
Soluble Oxide
Precursor
Change in
Conditions
NaAlO
2
Al
2
O
3
nH
2
O
H
+
Na
2
SiO
3
SiO
2
nH
2
O
H
+
Surface Deposition
Modifying Pigment Surfaces
2 SurfaceOxidation
Mild oxygenation creates -OH and -O
2
H
2. Surface Oxidation
yg
2
moieties on the surface of organic pigments.
COOH
OH
CO
oxygensource
COO
-
H
+
HOOC
COOH
COOH
OH
CO
oxygen source
COOH
OH
Modifying Pigment Surfaces
3 OrganicSurfaceTreatment
Two forms:
3. Organic Surface Treatment
Small, high functionality molecules
e. g., TMP, AMP
Grafted alkanes
e. g.,
Si-R
X
X
X
Decrease surface energy
G ll i di ibilit
X
Generally increase dispersibility
Dispersion of Pigment
Particles have a natural attraction to one another
(Van der Waals attraction).
To keep them separated, must force them to repel
one another (electrostatic charge).
Repulsion must be large enough to overcome
attraction:
Particle size Charge need for stability
0.25 micron > 20 mv (or < -20 mv)
001micron >80mv(or <-80mv) 0.01 micron > 80 mv (or < -80 mv)
Dispersion Process
Wetting
[SurfaceEnergy/ Chemistry]
ParticleSeparation
[Surface Energy / Chemistry]
Particle Separation
[Van der Waals Attractions]
Stabilization
[Surface charge]
Formation of Surface Charge
H
+
OH
H
+
++
--
OH OH
O
-
H
+
OH
-
+ H
2
O
H
Acid (Low pH)
Positive Charge
Base (High pH)
Negative Charge Positive Charge Negative Charge
Surface Potential
f
40 0
60.0
(mv)
Area of stability
0 0
20.0
40.0
TiO
2 ZnO
Zone of i nstability
6.0
-20.0
0.0
2.0 4.0 8.0 10.0 12.0
-60.0
-40.0
Area of stability
pH
Formation of Surface Charge
H
+
OH
-
H
+
OH OH O
-
H
+
OH
-
+ H
2
O
H
Acid (Low pH) Base (High pH)
dispersant
O
dispersant
Influence of Pigment on Film Durability
Major problem is UV component of sunlight
Energetic enough to break chemical bonds
Organic binder reacts with oxygen and water to
eventually give CO
2
+ more H
2
O
Inorganic pigments tend to be inert (high
thermodynamic stability)
Organic pigments can fade easily
TiO
2
has complex role on film durability
TiO
2
and Paint Durability
TiO
2
is an EXCELLENT UV light absorber
Oneparticle(0.25microns) absorbs>99%of One particle (0.25 microns) absorbs 99% of
UV from sunlight.
TiO
2
thereforePROTECTStheorganic TiO
2
therefore PROTECTS the organic
binder in a paint
HOWEVER TiO cantransformsomeof HOWEVER, TiO
2
can transform some of
the UV light energy into chemical energy in
theformof reactiveradicals the form of reactive radicals.
Binder Protection by TiO
2
Pure Binder Pure Binder
Pigmented
Binder
Radical Reactions
TiO
2
+ UV light e
-
+ hole
+
e
-
+ hole
+
TiO
2
+ heat
e
-
+ O O
-
hole
+
+ OH
-
OH

e + O
2
O
2
O
2
-
+ OH

+ (-CH
2
-) intermediates
O
2
-
+ OH

+ intermediates CO
2
+ H
2
O

UV light + O
2
+ (-CH
2
-) intermediates
UV light + intermediates CO + H O UV light + intermediates CO
2
+ H
2
O
Improving TiO
2
Durability
Surface of TiO
2
is reactive on exposure to
UV light. g
Solution - encapsulate surface with inert
material (silicaor alumina) material (silica or alumina)
TiO
2
Titanium Dioxide Pigments Titanium Dioxide Pigments

Type I
Anatase
Type I I
Rutile
Type I I I
Rutile
Type I V
Rutile Anatase Rutile Rutile Rutile
Product Name
TiO
2
min.%
LW
94
R-900
92
R-900, R-901
80
R-960
80
Chalking

Surface treatment
free

none
medium
resistant
Al
2
O
3

medium
resistant
SiO
2
+Al
2
O
3

medium
resistant
SiO
2
+Al
2
O
3


Chalking: loose pigment particles form on the surface from the
More complete encapsulation to protect TiO
2
from UV free radical reaction
g pg p
erosion of the binder as a result of photodegradation.
Conclusions
Pigment and filler particles are PARTICLES.
Particlesobeythesamephysical lawsaswe Particles obey the same physical laws as we
do, but the relative importance of these laws
isdifferent - particlesaredominatedby is different particles are dominated by
surface forces; we are dominated by volume
forces(weight) forces (weight).
Many particle properties translate directly to
pigment / filler properties pigment / filler properties.