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Latex film formation Mechanism

Water
Evaporation
(Depends (Depends
on
Humidity)
Particle Driven by capillary
Deformation
y p y
forces as final water
evaporates
Polymer Diffusion Polymer Diffusion
Rarely Fully
Achieved
Note: Particle deformation and polymer diffusion usually require coalescing solvents
to achieve hard films with good mechanical properties. Too high humidity can result in too
much coalescent evaporation before the water evaporates.
Minimum Film Formation
Temperature (MFFT, MFT)
Important Factors Controlling MFFT
 Tg
Pl i i (C l )  Plasticizer (Coalescent)
 Water Plasticization
P ti l i  Particle size
 Particle size distribution
S f T i  Surface Tension
 Interfacial Tension
 Capillary forces
 Double layer
Visschers, et al.,
J CT (2001) J CT (2001)
Film Formation – Analytical Tools
 MFFT BAR  MFFT BAR
 SAN
SAX  SAX
 AFM
 Fluorescence
Measurements of Polymer Diffusion
D i L t Fil F ti During Latex Film Formation
AFM
6 Lin, F.; Meier, D.J . Langmuir 1996, 12, 2774-2780
Courtesy of Cheng-Le Zhao, BASF
Persistance of Particle Boundary
G. Kanig, D. Distler et al. (1975, 1978)
and Fracture through Bulk
7 D. DistlerandG. Kanig, Colloid & PolymSci. 1978, 256, 1052-1060
Courtesy of Cheng-Le Zhao, BASF
The Autohesion or Self-Sticking Concept
of S.S. Voyutskii y
S.S. Voyutskii et al. (1957, 1958)
Delamination
Resistance,
g/cm
Contact Time hr Contact Time, hr
8
Courtesy of Cheng-Le Zhao, BASF
Measurements of Polymer Diffusion
During Latex FilmFormation
Non-Radiative Energy Transfer
During Latex Film Formation
9
C.L. Zhao, Y.C. Wang, Z. Hruska and M.A. Winnik, Macromolecules 1990, 23(18), 4082-4087
Y.C. Wang, C.L. Zhao and M.A. Winnik, J . Chem. Phys. 1991, 95(3), 21432153
Courtesy of Cheng-Le Zhao, BASF
Effect of Polar Comonomer
on Latex Film Mechanical Properties
A li L t ith 0 C MFFT d2 5% li id
Acylic Latex with 0 C MFFT and no polar groups
Film Formation: RT / 2 weeks
Tensile Strength: 2.46 N/mm
2
El ti t B k 588%
Acylic Latex with 0 C MFFT and 2.5% acrylic acid
Film Formation: RT / 2 weeks
Tensile Strength: 7.52 N/mm
2
Elongationat Break: 485%
10
Elongation at Break: 588%
Elongation at Break: 485%
C.L Zhao & W. Heckmann
Proceedings of the 27th International Waterborne, High-Solids & Powder Coatings Symposium (2000), 119-133
Effect of Polar Comonomers
P i t P ti
5000
05AA
on Paint Properties
4000
0.5 AA
3000
0.5 AM
u
b

c
y
c
l
e
s
1000
2000
2.5 AM
2.5 AA / 1.5 AM
s
c
r
u
00 05 10 15 20 25 30 35 40 45
0
1000
2.5 AA
1.5 AA / 1.5 AM
11
0,0 0,5 1,0 1,5 2,0 2,5 3,0 3,5 4,0 4,5
Sum of Comonomers
S. Porzio, S. Kirsch et al. Presentation at ICE 2000
Kan, J CT (1999)
Film Formation Studied by AFM (SPM)
Eff t f C l i A t Effect of Coalescing Agent
Film Formation Conditions:
1 hr @ 40°C + 1 week above MFFT
MFFT of neat polymer: 37 °C
Coalescent:
1 %EB
EB: Ethylene Glycol Monobutyl Ether
1 % EB
10 % EB
14
Courtesy of Cheng-Le Zhao, BASF
Coalescents
 Hoy (J PT 1973)  Hoy (J PT, 1973)
 Solvent Tg effect
 Fox equation to determine Tg of swollen polymer q g p y
 Sovent Partitioning between water and latex
polymer
 Taylor and Klots (PCI, 2002)
 Tg of a large number of solvents
 Relative evaporation rates
Tg of Copolymers (Non-Block) & Blends g p y ( )
W W
2 1
2 1
1
g
T
W
g
T
W
g
T
+ =
Fox Equation
2 1
2 1
| |
g g g
T T T + = Gordon-Taylor Equation
 Fox equation can be used to estimate Tg of
random and alternating copolymers
 Gordon-Taylor equation is used with
compatible polymer blends
Tg of Plasticized Films
2 1
1
T
V
T
V
T
+ =
2 1
g
T
g
T
g
T
1
V V o
2
2
1
1
1
g
T
V
g
T
V
g
T
o
+ =
(
(

2 1
1
1
V V o
(
(
(
¸

¸
+ =
2
2
1
1
1
g
T
g
T K
MFT
K = MFT / Tg
Coalescent
Di ib i i L Distribution in Latex
Distribution Coefficient (D) = C
w
/ C
p
C
w
= Coalescent concentration in water
C
p
= Coalescent Concentration in polymer
“Estimating the effectiveness of latex coalescing aids”, K. Hoy, J ournal of Paint
Technology, 45(579), 51 (1973)
Waterborne 2K Systems y
 Competition between cross-linking and  Competition between cross-linking and
film formation
P t lif ti  Pot life versus cure time
Film Formation Vs Cross-Linking
(J CT, 1998)
Film Formation Vs Cross-Linking
 Acetoacetate-Amine  Acetoacetate Amine
 Feng et al. (J CT, 1998)
 Rapid reaction rates p
 Cross-linking preceded film formation
 (Guerink et al., POC, 1996)
 Performance deteriorated during pot-life
 Poor coalescence and increased water sensitivity
Film Formation Vs Cross-Linking
 Epoxy-Amine Epoxy Amine
 Geurts et al. (1990, POC)
 Tg and MW of copolymers affected film formation
H
O
HO
O
R
HO
R N
H
+
R
R N H
R
R
R N
R R
HO
Epoxide
Film Formation Vs Cross-Linking
 Epoxy-Amine (Galgoci, et al., J CT, 1999)
Film Formation Vs Cross-Linking
(Galgoci, et al., J CT, 1999)