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Progress in Organic Coatings, 4 (1976) 189 - 208 189

0 Eisevier Sequoia S.A., Lausanne - Printed in the Switzerland

RECENT ADVANCES IN THE RHEOLOGY OF HIGH SOLIDS


COATINGS*

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

In order to reduce solvent emissions, many paint users are turning to


high solids coatings. In theory, the term high solids refers to coatings with
greater than 80% nonvolatiles by volume. In practice, 60% volume solids
probably is the lower limit. However, since the higher figure is the level
necessary for exemption under air pollution legislation, it is the goal that

*
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. Review of the rheology of 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.

2.2 Different types of viscosity behavior [I - 61


Figure 1 shows plots of Brookfield viscosity vemus spindle speed for
three coatings. It will be noted that the behavior of each coating is different.
The viscosity of the high solids enamel is independent of speed and, there-
fore, of shear rate. This is Newtonian or ideal flow behavior. It is common
for solvents, resins, varnishes, and many industrial coatings. The latex paint
viscosity decreases as shear rate increases. This is called shear thinning and is
due to plastic (Bingham) or, more commonly, to pseudoplastic behavior.
Shear thinning is common in pigment pastes, trade sales coatings, and gel
191

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

Viscomeler speed ( rpm 1

Fig. 1. Viscosity-Brookfield speed relationships for three coatings.

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

Fig. 2. Viscosity-time relationships for thixotropic and non-thixotropic materials.

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

xotropy is often confused with pseudoplasticity. It should be remembered


that the former is time-dependent, the latter shear-dependent.
A combination of thixotropic and pseudoplastic behavior is formulated
into trade sales paints, gel coats, and certain other coatings to give lcw vis-
cosity at the high shear rates of processing and application, followed by a
viscosity recovery when the shearing stops. This recovery should be slow
enough to allow flow and leveling, but fast enough (and to a sufficiently
high level) to prevent noticeable sagging even where film thickness is fairly
high.

2.3. Viscosity measurement and plotting [I - 5, 71


Coating viscosities are often measured with efflux or cup type viscome-
ters such as the No. 4 Ford or No. 2 Zahn. The cup is filled with the coating
and the time for the fluid to run through the orifice is measured. These
viscometers should be used only for Newtonian materials. Since viscosity is
determined at a single shear rate, viscosity cups and a number of other vis-
cometers are unable to reflect the viscosity characteristics of a non-Newton-
ian fluid. For such a material, viscosity readings must be taken at several dif-
ferent shear rates. The Brookfield Synchro-Lectric rotating disc viscometer
probably is the most commonly used multipoint instrument. Its main draw-
backs are that it does not give absolute viscosities and it has a limited shear
rate range (roughly 0.5 - 100 set-l for the RVT model).
A useful research instrument with a very wide shear rate range (lo-” -
4 X 104 set-‘) is the Haake Rotovisco RV - 3 concentric cylinder viscome-
ter. This instrument gives a type of viscosity plot that is often seen in the
literature, the shear stress-shear rate or flow plot. Examples are shown in
Fig. 3. The Newtonian sample gives a straight line passing through the origin.

Shear rale, $

Fig. 3. Flow plots (shear stress-shear rate).


193

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

to 1.5 poises, aRhough some thick coatings spray at up to 4 - 5 poises. Brush-


ing infinite shear viscosities for trade sales products range from 0.6 to 3.0
poises.
The yield point is a measure of the degree of pseudoplasticity and the
sag resistance. From it we can caiculate the maximum wet film thickness, h,
that will hold without sagging on a vertical surface. The equation is ~0 = pgh.
For p - 1.2 (- 10 lb/gal), h - ~~/3 (h in mils, r. in dynes/cmz)_ It should be
pointed out that loss of solvent during spraying and flash-off can drive vis-
cosity and yield point far above the application values. Therefore, h can be
much larger than the yield point of the liquid coating would indicate.
Other uses of infinite shear viscosity and yield point include prediction
of processability. Limits are sometimes difficult to set, but knowledge of vLo
and 7. can give an idea of the ease of mixing, dispersing, pumping, machine
dispensing, etc. for a coating or pigment paste.

2.4 Other considem tions


The viscosity of a coating is highly dependent on temperature. Sample
temperature should be controlled carefully during viscosity measurements
and the temperature should always be reported. Viscosity drops sharply on
heating, which explains why many coatings sag on baking. This viscosity-
temperature relationship has proved useful in the application of high solids
coating, however, and will be discussed in more detail later.
A tool that is exceedingly helpful in the study of rheology is a good
microscope. I feel that it is as necessary as a viscometer. Use of the microsco-
pe often enabIes a scientist to explain the viscometer data. He can see phe-
nomena that affect viscosity characteristics, e.g. flocculation, phase separa-
tion, dispersion quality, particle size, etc.

3. Rheology of high solids coatings

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.

3.2 Viscosity-solids-molecular weight relationships


Viscosity is dependent on molecular weight. Fox and coworkers [S]
found that above a certain critical chain length, Z,, the viscosity of polymer
melts and concentrated solutions varied as the 3.4 power of- the weight aver-
196

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 TIP acrylic (mw-100,000)


2 T/S acrylic (mw-25.0!30)
3 OF polyestertmw- 6,GOO)
L Adqate plastlozer(mw-1 500)

1 I I , I
o.20
20 LO 60 80 100

Polymer solids (wt. ‘A)

Fig. 5. Viscosity-polymer solids relationships at different molecular weights. (From


lMercurio and Lewb [ 91)

acrylic polymer backbone (MW - 25,000), an oil-free polyester (MW -


6000), and a “polymeric” adipate-based plasticizer (MW - 1500). These
data may also be plotted as a series of isoviscosity molecular weight-percent
solids curves (Fig. 6). It is obvious that the higher molecular weight poly-
mers could not be used in high solids coatings. Assuming an application vis-
cosity of 0.5 poise, the only one of these materials that could be applied at
high solids would be the 1500 MW adipate plasticizer. In order to get an
approximate determination of the viscosity-molecular weight relationship
that exists in this group of polymers, the data from Fig. 6 were plotted in
log-log form as viscosity versus-molecular weight (Fig. 7). The plots vary
with polymer solids, tending to show curvature and increasing slope at higher
196

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‘

Fig. 7. Viscosity-molecular weight relationships at different solids levels. (Data from


Mercurio and Lewis [9] )

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

The R o h m and Hao_.~ Company has developed several acrylic oligomers


in the molecular weight range 1 0 0 0 - 1 5 0 0 which have very narrow molecu-
lar weight distributions ( M w / 1 1 4 , "~ 1.2) [ 9 ] . Such a distribution appears to
be necessary for good performance. Small amounts of relatively high molec-
ular weight polymer can lead to poor application properties such as webbing
[ 1 0 ] . Figure 8 shows viscosity-solids plots for a series of the R o h m and
Haas o l i g o m e r s a l o n g w i t h t h a t o f t h e a d i p a t e p l a s t i c i z e r m e n t i o n e d previ-
o u s l y [ 9 ] . The acrylic oligomers are considerably more viscous than the
adipate plasticizer, even though all have similar molecular weights. In addi-
50,
Increasing Tg

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)

Fig. 8. Viscosity-polymer solids relationships for materials with similar molecular


weights, but different, glass transition temperatures. (From Mereurio and Lewis [g ] )

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 .

3 . 3 Use o f l o w viscosity, p o s s i b l y reactive s o l v e n t s


L o w viscosity solvents are c o m m o n l y e m p l o y e d to reduce overall vis-
cosity in conventional coatings. However, the higher the solids, the less effec-
198

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.

3.4 Resin-solvent interactions


The effect of resin-solvent interactions on viscosity is more difficult to
deal with than the other relationships discussed, and certainly is not as im-
portant an influence as molecular weight. However, a wise choice of solvent
may enable the formulator to increase the level of solids without affecting
the application viscosity.
Possible resin solvent interactions include forces such as hydrogen bond-
ing, dipole-dipole interactions, and dispersion effects. Solubility parameters
[12 - 151 may be used to measure these interactions. Under Hansen’s system
[14], solvents and polymers have three-dimensional solubility parameters
whose coordinates correspond to the three forces listed above. A polymer
is characterized by a volume of solubility formed by all the solvents dissolv-
ing it. The polymer itself is a point at the center. It appears that the greatest
resin-solvent interaction occurs when the solvent and polymer have the
same solubility parameter [ 121. At this point it is expected that the polymer
molecules will have uncoiled to the maximum, and the highest viscosity will
be obtained. This has been shown to be true for intrinsic viscosities [16,17].
However, it does not hold for solution viscosities of moderately concentrated
solutions (- 25 wt.% ) of high molecular weight polymers [17, IS] such as
those found in conventional coatings.
Erickson [19] studied oligomers (1000 - 3000 MW) at the high concen-
trations used in high solids coatings. He determined that an apparent or high
concentration “intrinsic viscosity” (on which solution viscosity was depen-
dent) showed a relatively high value at the center of the solubility volume
and a minimum well outside of the center. He related the apparent intrinsic
viscosity (which I will label as [a] ) to an interaction variable, I,. This
variable was determined from the difference between the solubility para-
meters of the solvent and the oligomer when this difference was weighted
by the square root of the molar volume of the solvent. In equation form
these relationships are
rla [q],al;=As(MV)N
199

where q is the solution viscosity; [v] ,


I,and MV are described above; A6 is
the distance between the coordinates of the polymer’s threedimensional
solubility parameter and those of the solvent. ‘I’his distance = [4 (DP- DJ2 +
(PIJ - W2 + (HP - m21 ‘h, where D, P, H are the three solubility coordinates
and “P” and “s” stand for polymer and solvent, respectively [20]. Figure 9
shows the relationship between [q] and 1, tha<. Erickson found. The appar-
ent intrinsic viscosity was at a minimum at I, - 32. The solvent-oligomer

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)

interaction component of [q] was considered to be zero at this point. The


solvent or blend of solvents that gives 1, = 32 will depend on the particular
oligomer or polymer used. Erickson’s relationship worked well for the sin-
gle-resin solutions tested. It remains to be seen whether it will hold for the
multi-resin formulations actually used in high solids coatings.
Erickson’s minimum [_~l]= occured roughly halfway between the center
of the polymer solubility volume and the edge. It was not in the phase sepa-
ration region. However, there is considerable evidence to show that tlnis
borderline solvency area (or beyond) can also be used to produce low visco-
sities. For example, a non-aqueous dispersion or NAD [21 - 251 has a much
lower viscosity for a given level of solids than does the same resin in solution.
At 50% weight solids a non-aqueous dispersion may have a viscosity of 5 -
100 centipoises as opposed to 5000 centipoises for a corresponding polymer
solution [ 253. NAD systems usually are at 50 - 60% weight solids, but higher
levels are possible. Since NAD coatings are suspensions, high molecular
weight resins may be used without producing high viscosities. This is an
important advantage over other high solids coatings.
200

3.5 Erickson ‘s equation


Erickson [19] also developed an equation relating the solution viscosi-
ty to the solvent and oligomer viscosities, the intrinsic viscosity, and the
oligomer concentration. He provides several forms of the equation in his
paper. The basic one is
c 1
=- +kC
W77h0) b71a

where q is the solution viscosity, p0 is the solvent viscosity, C is the weight


fraction of oligomer in the solution, and [qla is the apparent intrinsic viscos-
ity discussed previously. [g] a is unitless and about 100 times larger than
normal intrinsic viscosity. It is determined from a plot of C/h (v/vu) versus
C, which gives a straight line with K as the slope and l/[n] as the intercept.
A more useful form of the equation is
hl,c
Wt;,l?lo) =
cr13, _-l
1+c
( Wr),h0) 1

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-

“0 0.2 0.4 0.6 0.6 1.0

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

3.6 Effect of pigmentation


The discussion so far has centered mainly on non-pigmented resin solu-
tions, which tend to be Newtonian. However, most high solids coatings are
pigmented and many are non-Newtonian. Much of their viscosity behavior
comes from the pigmentation, which consists of fillers, extenders, and thixo-
tropes as well as colored pigments. These additions may introduce shear
thinning, as shown in Fig. Il. The data is taken from a study by Princen and
Stolp [26] on the rheology of linseed oil pigmented with TiOz. At lower

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.

3.7 Viscosity- tempem ture relationships


One of the most promising routes to very high solids is the use of high
application temperatures. Figure 12 indicates that a 65% solids polyester

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

60 80 :oo 120 140 150 180 200


Temperature (OF)

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

solutions [lo]. Solution A was a 25% solids solution of a 20,000 molecular


weight polyester in methyl ethyl ketone and ethylene glycol monoethyl
ether acetate (1:l). Solution B was a 90% solids solution of a 1500 molecu-
lar weight polyester in ethylene glycol monoethyl ether acetate
The same viscosity-temperature relationships that are so useful in
applying a coating can cause serious problems during baking. The viscosity
of the uncured paint film drops sharply as its temperature rises to that of
the oven. During the time period before molecular weight begins to increase,
the film can sag or flow off non-horizontal surfaces. Since the volatile sol-
vent/high molecular weight polymer approach cannot be employed to con-
trol sagging in high solids coatings, the formulator must rely on other tech-
niques: thixotropes, fast acting catalyst, pigment flocculation, thickeners,
etc. Some of these will be described in the next section.

3.8 Flow control: prevention of sagging


Most sagging problems occur during baking, but in thick coatings
sagging can occur at room temperature as well. We cannot prevent sag by
using a higher molecular weight polymer and still maintain high solids. How-
ever, there are a number of other ways to tackle the problem. It is not neces-
sary to stop downward flow completely; in fact, some flow is needed for
good leveling. If the sag velocity is low enough, the coating will cure before
noticeable sagging can occur. Sag velocity can be reduced without sacrific-
ing leveling by introducing both pseudoplasticity and thixotropy into the
system. Pseudoplastic coatings are, in a sense, sag-resistant by definition.
They have yield points, and unless the gravitational shear stress exceeds the
yield stress, no flow will occur. In addition, pseudoplastic materials tend to
have low sag velocities due to their high viscosities at low shear rates. Level-
ing and sagging appear to be in mutual opposition, i.e. leveling requires low
viscosity, whereas sag prevention requires high viscosity. However, these
conditions do not have to be met simultaneously, and should be achieved
consecutively in a well-formulated paint [2]. This is where thixotropy
comes in. The viscosity of a “good” coating remains at a low level long
enough for adequate flow and leveling, then recovers to a high level to pre-
vent sagging.
Thixotropy and pseudoplasticity may be introduced in any of a num-
ber of ways [29 J , including the addition of inorganic thickeners such as
bentonite clays and pyrogenic silica [30], various proprietary organic thixo-
tropes [31,32], polyethylene wax dispersions, high pigment loadings, con-
trolled pigment flocculation after the pigment is well dispersed, and use of
gelling agents such as aluminum stearate. The method best suited for a given
coating depends on the resin-solvent system and the degree of thixotropy/
pseudoplasticity required. The latter will depend on the extent of the drop
in viscosity on heating, the amount of flow and leveling necessary after ap-
plication, and the coating thickness desired. The Casson plots of two coat-
ings, a gel coat and a high solids appliance enamel (Fig. 15) show variations
in viscosity behavior that achieve the same end, a lack of sagging. Both are
205

-_______
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

(Shear rate. $I-” .(sec~)

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

Shear rate (SC-‘)

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

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