Escolar Documentos
Profissional Documentos
Cultura Documentos
CLIFFORD K. SCHOFF
PPG Industries Inc., Allison Park, PA (U.S.A.)
Contents
1 Introduction, 189
2 Review of rheology of coatings, 190
2.1 Introduction, 190
2.2 Different types of viscosity behavior, 190
2.3 Viscosity measurement and plotting, 192
2.4 Other considerations, 194
3 Rheology of high solids coatings, 194
3.1 Introduction, 194
3.2 Viscosity-solids-molecular weight relationships, 194
3.3 Use of low viscosity, possibly reactive solvents, 197
3.4 Resin-solvent interactions, 198
3.5 Erickson’s equation, 200
3.6 Effect of pigmentation, 201
3.7 Viscosity-temperature relationships, 202
3.8 Fiow control: prevention of sagging, 204
4 Conclusion, 207
References, 208
1. Introduction
*
Portions of this paper were presented at the University of Detroit Conference,
Advances in Coating Science and Technology, May 17, 1976, and at North Dakota State
University’s 16th Annual Coatings Symposium, Energy Savings Through Reactive Coat-
ings, June 2,1976.
190
paint manufacturers are striving for. High solids coatings include a large num-
ber of different materials. They range from pigmented linseed oils through
the more conventional high solids polyesters, alkyds, and acrylics (some of
which are curable by U.V_ or high energy radiation) to polyester/styrene gel
coats and poly(viny1 chloride) plastisols.
Only a small amount of solvent can be incorporated in or added to a
high solids coating. The fact that 80% volume solids corresponds to 85 - 88%
weight solids shows how little this amount is. Because of the low solvent
content, high solids formulations are more sensitive to resin molecular
weight and flexibility and to resin-solvent interactions than are convention-
al coatings. This means that a high solids system must be very carefully
designed if it is to have acceptable viscosity characteristics. In this paper I
shall discuss some of the methods used to control the rheology of high
solids coatings.
2.1 Introduction
It should be useful at this point to review the principles of rheology as
they apply to coatings. Rheology is the science of flow, which is a phenom-
enon found in every coatings operation. The study of rheology covers a num-
ber of different measurements and parameters. The one we are most con-
cerned with is that of dynamic or absolute viscosity, Q, which may be defin-
ed in the following manner. Consider a force per unit area T which causes a
layer of liquid at a distance x from a fixed boundary wall to move with a
velocity u. The viscosity is defined as the ratio between the shear force or
stress, T, and the velocity gradient, dv/dx (which is also the shear rate G), i.e.
q=r/dv=r/j
z
This means that viscosity is a measure of a material’s resistance to flow.
If a given shear stress produces sluggish flow, i.e. the shear rate is low, then
the viscosity is high. The material is resistant to flow. If the same shear
stress gives a high shear rate, then the viscosity is low, and the material flows
easily.
16,
\-.’
14 -
Vinyl
plastisd
VlSCOSll
12 _ ( 10 ‘1
‘j;
$ 10 _
2 a_
!3
‘5
2 6_
z
B
l+i
4_
2_
01 1 I I I I
0 20 40 60 80 100
coats. The vinyl plastisol shows an increase in viscosity as shear rate increases.
This fairly unusual behavior is called shear thickening or dilatancy.
Figure 2 illustrates another form of behavior, thixotropy, in which the
viscosity decreases with time at a given shear rate. Due to the time it takes
the instrument to reach a maximum reading, the viscosity-time’ plot gives a
characteristic peak. Eventually the viscosity becomes constant. When the
Thlxotroplc material Y
Shearing out
D
5
3
Non thuolropic Non -thixotropic -
8
&i &
. I
0 Time Time
* If
Shearing begins Shearing stopped
shearing action is stopped, the viscosity recovers. For comparison, the viscos-
ity-time behavior of a non-thixotropic coating is also shown in Fig. 2. Thi- .
192
Shear rale, $
The slope is equal to the viscosity. The plastic (Bingham) material produces
a straight line having an intercept (yield point or yield stress) on the shear
stress axis. The plot for the pseudoplastic/thixotropic material also has an
intercept, but is a curve. It shows a thixotropic loop, indicating that once
the material is subjected to high shear it gives a lower shear stress response
to a given shear rate. The size of the thixotropic loop is a measure of the
thixotropy of the sample. A non-thixotropic fluid would not give a loop at
all, only a single curve..
A more useful plot in terms of establishing application, processing, and
flow parameters is the Casson plot. It may be generated from Brookfield
data through the use of a computer program [ 4 3 or from Rotovisco or other
variable shear rate viscometer data. Casson’s original equation 171, 7% = k, +
kl+“, was rearranged by Asbeck [l] to give ql/a= 75 + ~g+-‘/‘. The square
root of viscosity, qS, is plotted against the reciprocal of the square root of
the shear rate G-X, as shown in Fig. 4. In a Casson plot a Newtonian fluid
gives a straight, horizontal line. A pseudoplastic material produces a sloped
line. A thixotropic fluid tends to give two lines with a common intercept
when it is measured before and after shearing. The sheared material should
have a lower slope.
S Dilalant . 1
-G
i
5
s
PseudoplastIc
thixotropic
Newtonian
Fig. 4. Casson plots, based on the equation 71% = 772 + 7.” %-“.
The various straight line plots are easily extrapolated to <-1’2 = 0 (+ = m).
The intercept is qz where qoo is the viscosity at irfinite shear. The slope is
7g where 7. is the yield point mentioned previously. Q_ and ~c are very
useful parameters. The infinite shear viscosity is a measure of the ease of
application of a coating. It approximates the viscosity at the high shear rates
(up to 40,000 set-‘) of spraying, brushing, roller coating, and some disper-
sion processes. For good sprayability, vrn should be within the range of 0.4
194
3.1 Introduction
In high solids systems it is necessary to control atomization and flow
without employing large amounts of solvents. Sagging must also be prevent-
ed. How is this done?
(1) By using low molecular weight resin or oligomers.
(2) By using a low viscosity solvent, possibly one that is reactive so that
it acts both as a solvent and a monomer.
(3) By mir.imizing resin-solvent interactions.
(4) By using heat to reduce the application viscosity.
(5) By using thixotropes or other additives to prevent sagging.
age chain length, 2,. Below 2, (which was in the region of 2, = lOUO), the
dependence was between 1 and 2, usually about 1.75. It is obvious that in
order to achieve application viscosities with only small additions of solvent,
low molecuiar weight resin must be used in the formulation. If high molecu-
lar weight is needed for good film properties, the molecular weight building
must occur in the applied film.
The effect of molecular weight on viscosity-solids curves is shown in
Fig. 5 which is taken from a paper by Mercurio and Lewis [9] . It includes
plots for a thermoplastic acrylic poIymer (MW - lOO,OOO), a thermosetting
1 I I , I
o.20
20 LO 60 80 100
ld-
A,
I 1 1 I
20 LO 60 60 100
Polymer solids (wt. %)
Fig. 6. Isoviscosity molecular weight-polymer solids plots. (Data from Mercurio and
Lewis 193)
1OL
5-
z
.L”
s -
z
.Y
;:
.-:: l- _
>
05 -
0.2’ I
10’ 5x10‘
solids. The factor x in 7) = K(MW)” ranged from 1.7 to 3.3 over the three
solids levels considered. This again shows the considerable effect of molec-
ular weight on viscosity.
197
i.
10
~5
dl
O.
o
v.J
LQ
1.0
O.5
1 Adipate plasticizer"
2 Ohgomerlc- BA
3 Oligomeric- BM~,
z. O l i g o m e r i c - M M A •
0,I I I I I I
50 60 70 80 90 100
Polymer solids {wt.°lo)
t i o n , o l i g o m e r - M M A is m o r e v i s c o u s t h a n o - B M A , w h i c h is m o r e viscous
than o-BA. This trend toward higher viscosity correlates with the increasing
glass t r a n s i t i o n t e m p e r a t u r e s o f t h e o l i g o m e r s a n d is an i n d i c a t i o n of their
relative s t i f f n e s s . T h i s w o u l d i n d i c a t e t h a t o p t i m u m f l e x i b i l i t y as w e l l as
l o w m o l e c u l a r w e i g h t is n e c e s s a r y f o r l o w v i s c o s i t y at h i g h s o l i d s . Hardening
m u s t b e carried o u t in t h e f i l m a f t e r it is a p p l i e d .
tive this measure is, since there is so little solvent present. A lower viscosity
solvent could be used to bring the viscosity of a high solids system down to
a good application level in a borderline situation, but could not be used for
gross reduction of solution viscosity.
A more effective method of keeping a low viscosity at increased solids
would be to include a reactive solvent that acts as a monomer or crosslinker:
The diluent is incorporated as a nonvolatile material in the final film. Using
reactive solvents to increase solids has to be done carefully, because the dil-
uents may degrade desired properties such as hardness, strength, and sag
resistance. An example of a very effective reactive solvent is styrene, which
is incorporated into polyester gel coats. Some reactive diluents are not sol-
vents, but are low molecular weight, low viscosity resins such as the polyols
used in certain polyurethanes [ 111 and the melamines used to crosslink
acrylics and polyesters.
0 10 20 30 LO 50
Interaction variable, I,
Fig. 9. Relationship between apparent intrinsic viscosity, [q] , and the interaction
variable, Iv_ (From Erickson [ 191)
where n, qo, [‘l)]a, and C are as noted above, and qP is the oligomer viscosity.
The equation can be used to determine solution viscosities at-various oligo-
mer concentrations, the concentration necessary for optimum solution
viscosity, the effect of reducing qo, etc. Using data generated from the equa-
tion, Fig. 10 shows the effect on ln(q/qo) of reducing the apparent intrinsic
viscosity [19]. At ‘[Q] = 9, the maximum oligomer concentration at a spray-
able viscosity is 0.5. By reducing [r/l to 5, C can be increased to 0.64, a 28%
increase in oligomer content. In addition to being an example of the use of
Erickson’s equation, this plot shows the sort of viscosity reduction and sol-
ids increase obtainable when resin-solvent interactions are reduced.
8-
Oligomer concentration. c
Fig. 10. The use of Erickson’s equation to predi& the increase in oligomer concentration
with a decrease in apparent intrinsic viscosity. Relationship between ln(a/s,) and oligo-
mer concentration at various apparent intrinsic viscosities. (From Erickson 1193)
201
35 - \
\ - - - - Cone/Plate
\ - Plate/ Plate
\ 35% PVC
\ , TiOx
30 -
.
0
O20 50 too 200 500 1000 2000 5000 10,000
Shear rate (sec.‘j
fig. 11. Viscosity-shear rate relationships for linseed oil pigmented with various levels of
TiO2. (From Princen and Stolp [ 261)
PVC (0 - 15%), shear thinning was not seen until high shear rates (-4000
set- * ) were reached. The degree of shear thinning increased fairly sharply
with increased pigment loading. In another investigation [9 1, the same pig-
ment dispersed in a high solids acrylic/melamine resin (45% TiOz on solids,
64% volume solids total) showed Newtonian behavior. These results indicate
that both pigments and resins are important in determining viscosity behav-
ior.
Hansen [203 has shown that solubility parameters can be determined
for pigments, not in terms of solubility, but in terms of suspension stability,
which is a function of the surface properties of the pigment. Those solvents
which suspend a given pigment define a volume of interaction for the pig-
ment much in the same way that a solubility volume for a polymer is defin-
ed. Therefore a pigmented coating will have two solubility volumes, one for
the resin, the other for the pigment. For good pigment dispersion, the bind-
er should adsorb onto the pigment; This will occur when the resin and pig-
202
ment volumes overlap. The solvent should not absorb on the pigment and
should not interfere with pigment-binder interactions. It appears that the
ideal situation is to have a reasonably good solvent for the resin, with the
center of the resin solubility volume placed between the solvent point and
the center of the pigment interaction volume [ 203. Viscosity minima for
printing ink formulations were found to correspond to this situation [18],
but no date appear to be available on high solids coatings. This would be an
interesting area for future work.
120 -
?OO-
m
2
:
)tylo -
N
‘c
-s -
In
2
‘,-
InCO -
a
s
Y
*20 -
,
0’
I I ‘
60 60 100 120 140 160 180 200
Temperature (‘F)
I
20 30 40 50 60 70 80 90 _
Temperature (‘C)
Fig. 12. Viscosity-temperature relationships for two similar high solids polyester enam-
els at different solids. (From Ransburg Corporation 127 1)
coating sprayed well at 44 “C (110 “F), but that a similar coating at 80%
solids had to be raised to about 70 “C (160 “F) to be sprayable [27]. These
curves are representative of the viscosity-temperature relationships found
for most coatings. Figure 13 presents data in a different manner [9]. It
shows plots of the weight and volume percent spray solids for an acrylic/
melamine enamel as a function of temperature. The data points represent
the temperatures at which samples at given solids contents reached a vlscos-
ity of 25 set on a No.4 Ford cup. The results indicate that 80% volume
application solids could be achieved at a spraying temperature of about 82 “C
(180 OF)- In a recent paper, Gott [ 283 described polyester/melamine enamels.
203
601 I L
20 30 40 50 60 70 60 SO
Temperature (‘C)
Fig. 13. Relationship between application solids at a spray viscosity of 25 set (No.4 Ford
cup) and temperature. (From Mercurio and Lewis [9])
that were sprayable (35 - 40 set, No.4 Ford cup) at 80% volume solids at
49 - 54 “c (120 -130 OF)-
Molecular weight is important here also, since the lower the molecular
weight, the greater the reduction in viscosity with increasing temperature.
Figure 14 illustrates this with viscosity-temperature plots for two polyester
I I I I ‘
‘60 70 00 120 130
I Temp%ature “‘(“F) ‘lo
20 30 50
Temperatrrre fi:,
Fig. 14. Viscosity-temperature relationships for two polyester solutions: Solution A con-
tained 25% 20,000 MW polymer end solution B contained 90% 1500 MW polymer.
(From Antonelli [ 1 O] )
204
-_______
High sollds enamel (almost M lhlxolropy!
1. = 37 dynes/cm
0 1
0 0.1 0.2 0.3 0.L 0.5 0.6 0.7
Fig. 15. Casson plots for two high solids coatings, a polyester/styrene gel coat and a
polyester appliance enamel (25 “C).
pseudoplastic, although the appliance enamel only shows this at high shear
rates. The gel coat is highly thixotropic, whereas the appliance enamel exhib-
its almost no thixotropy at all. Gel coats are thick coatings. They are not
normally baked, but they mu,st be applicable at thicknesses up to 25 or 30
mils without sagging. Unwanted flow is prevented by the addition of 1.5 -
3.0% pyrogenic silica [ 33 J to the formulation to give yield points in the
region of 100 dynes/cm’. This also leads to rapid viscosity recovery with
time, as shown in Fig. 16.
The amount of thixotrope added to a coating is critical. Too much
givessuch a high yield point that the material is difficult to pump and spray,
and leveling is affected. Too little thixotrope can give too low a yield point
to prevent sagging, yet sometimes will be enough to raise the infinite shear
viscosity to such a level that pocr atomization results. The degree of disper-
sion of a thixotrope is also very important. Yield point usually increases
with improved dispersion. This is why post-grind additions of thixotropes
can be dangerous. It is possible for additional dispersion to occur in the
pump or spray gun which will lead to undesirable bodying of the coating.
Thixotropes or other thickeners prevent sag on heating by one or both
of two mechanisms. One involves raising the yield point to such a high level
that heating cannot lower it enough for sag to occur. The other mechanism
involves resin-solvent-thixotrope interactions such that the temperature
Fig. 16. Viscosity recovery for a gel coat after shearing out at 20 t-pm on a Brookfield
viscometer (25 “C).
dependence of the viscosity and yield point are reduced. The appliance ena-
mel in Fig. 15 does not sag when baked at 191 “C (375 “F). It appears that its
viscosity behavior is adequate for sag resistance. It should be pointed out
that considerable solvent is lost on spraying and flash-off afterwards, so the
viscosity of the coating on the surface is higher and more pseudoplastic than
shown in the Casson plot. The thickener in the applied coating is more effec-
tive than might be expected from its concentration in the original formula-
tion. On baking, the viscosity and yield point drop, but not enough to cause
sagging. It is interesting to examine a Rctovisco flow plot for this coating
generated over a fairly wide shear rate range (Fig. 17). It shows a classic
example of pseudoplasticity, including a constant plastic viscosity (nP = (T -
me)/ 5) above about 1000 see-‘.
Another approach to the prevention of sagging in high solids coatings is
the use of two-pack compositions, where the two components are low viscos-
ity, low molecular weight resins which cross-link with each other rapidly
after mixing [34 - 361. Examples include epoxies and polyol-polyisocyana-
te and acrylic-oxazoladine urethanes. These coatings may be cured at much
lower temperatures than other high solids coatings. This tends to minimize
sagging. Two-pack coatings have their own problems, however, and many
users dislike them.
One method of viscosity control that appears to work well with high
solids acrylic-based and other urethanes is the incorporation of low viscosity
cellulose acetate butyrate (C.A.B.) *h the coating [37,38]. The C.A.B. per-
mits rapid transport of the solvent through the coating, resulting in faster
solvent release and formation of a film prior to cure. It also acts as a reac-
tive diluent, cross-linking with the isocyanate on heating. It should do the
207
Fig. 17. Flow plot (shear stress-shear rate) for a high solids polyester appliance enamel
(25 “C).
same thing with melamines. Unlike other cellulosics, low viscosity C.A.B.
has little effect on the solution viscosity of the formulated coating. There-
fore, high volume solids can be maintained. From the number of recent pat-
ents which specify C.A.B. modification for high solids thermosetting ena-
mels 139 - 423, it appears that this method will be popular, particularly for
automotive topcoats. Presumably C.A.B. is added mainly for its reflow pro-
perties, but its good solvent release and reactivity undoubtedly are impx-
tant as well.
4. Conclusion
High solids systems offer a great deal of promise as high quality reduc-
ed pollution coatings. It is not easy to control the viscosity of these mate-
rials to provide good application, flow, and film properties. Through a better
understanding of the principles involved, this is being achieved. Recently
discovered relationships put us in a better position to design high solids
coatings with the necessary viscosity characteristics.
208
References