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PROGRESS

IN ORGANIC
COATINGS
ELSEVIER

Progress in Organic Coatings 31) (1997) 141-158

Rheological behaviour of latexes in-can and during film drying


F. M o l e n a a r a'*, T. S v a n h o l m b, A. T o u s s a i n t c
:'TNO Centre./or Coatings Research, P.O. Box 6034, NL-2600 JA De!l?. Netherlands
bYK1, P.O. Box 5607, S-114 86 Stockhohn, Sweden
cCoatinj4s Research Institute (CORD, Av. P. Hol(~?, B-1342 Limelette, Belgium

Received 15 July 1996: received in revised form 14 August 1996; accepted 26 August 1996

Abstract
In-can rheology was studied for sixteen model acrylate latexes and a commercial vinyl/acrylate copolymer latex. Following the model of
Quemada, the shear thinning behaviour, the effects of latex neutralisation and the copolymer composition could be described. Furthermore,
the rheological effects of coalescing agents and thickeners (a cellulose and hydrophobically modified types thereof (HEC and HMHEC), as
well as associative urethanes (HEUR)) were studied. A special apparatus (the TNO Filmviscometer) was shown to be suitable to follow the
theological changes during drying of latex films. Effects of binder type, coalescent and thickener were investigated. The rheological effects
of coalescents during drying could be related to the evaporation kinetics and latex particle swelling, while the effects of thickeners reflect
the initial in-can rheology. The rheological changes during drying correlate to sagging and levelling behaviour and to the adsorption
behaviour of associative thickeners onto latex particles. 1997 Elsevier Science S.A.

Keywords." Rheology in-can; Rheology during drying; Acrylate latexes; Coalescing agents: Associative thickeners (HMHEC, HEUR);
Adsorption of thickeners onto latex: Film drying; Evaporation kinetics; Sagging/levelling

1. Introduction

It is well known that latexes and waterborne dispersion


coatings have rheological properties that are quite different
from those of the traditional paints, such as solvent-borne
alkyds. Commercial latexes generally show non-Newtonian
behaviour and they are strongly shear thinning, which
means that the viscosity is substantially reduced under
shearing forces. Also, during drying the theology of latexes
is different from that of solvent-based coatings: they generally suffer from a lower extent of levelling, so that the
brush marks do not completely level out after application.
Furthermore, gloss can be impaired due to insufficient levelling, although pigment flocculation contributes as well. Due
to the typical rapid rise of viscosity of latexes when increasing the volume fraction of the latex particles, which actually
occurs by water evaporation during film drying, the open
time of latex paints is still an important challenge for
improvement. Generally, when formulating a latex paint,
it is more difficult to achieve an optimum viscosity profile
than in case of solvent-borne paints.
To gain more insight into the various parameters that
* Corresponding author.

I)300-9440/97/$17.00 ~ 1997 Elsevier Science S.A. All rights reserved


P l l S0300-9440(96)00681 9

affect the in-can theology of latex coatings, a wide systematic series of model acrylate latexes and a commercial vinyl/
acrylate latex were studied. It was, furthermore, investigated whether the results could be interpreted according to
the theological model of Quemada. The pure latexes were
studied by measuring flow curves to evaluate the effects of
the shear stress applied, the neutralisation of the latexes
(pH) and the copolymer composition of the binder. Subsequently, the effects of different types of coalescing agents
and thickeners were investigated. This concerns both hydrophilic, volatile coalescents and hydrophobic, slowly evaporating coalescents. The thickener types studied were a
representative hydroxyethyl cellulose (HEC), two hydrophobically modified hydroxyethyl cellulose thickeners
(HMHEC) and four hydrophobically modified ethoxylated
urethanes (HEUR).
In understanding practical paint properties that are related
to rheology (sagging, levelling, open time), often the rheological changes which occur during film formation (drying)
are overlooked, or not measured due to the experimental
difficulties when studying freely evaporating, drying latex
films. An apparatus specially developed to follow these
theological changes during drying was used in this study
(TNO filmviscometer, Section 4). The effects of different

142

F. Molenaar el al. /Progres's in Organic Coatin<gs 30 (1997) 141 15~'

Table I

Tablc 3

Binder compositions (percentages by weighil and characteristics: temposition of the model acrylate latices

Characteristics of the waterbased alkyd emulsion

Code

Co nlOllonlel's a
BMA

BA

MFFT
St),

MMA

AA

MAA

(CI

31
33
33
34
32
35
4O
27
23
23
23
25
29
29
28
28
28

B 108
B75
B76
B77
B78
B79
BSO
B125
BI26
BI27
B 128
B129
BI3I
B135
B137
B138
B139

100
99
97.5
95
99
97.5
95
39
54
69
84
91.5
39
54
69
84
91.5

In general

Solids content: 39~tlC.; b.w.


pH: 2.0
Enmlsifier: ilonylphenol elhoxylatcd (EO<~) snllale (I .7c))
on polymer wcighl)

1.0
2.5
5.0
1.0
2.5
5.0
2O

15
10
5
2,5
20
15
I(I

5
2.5

40
30
20
10
5
40
30
2(I
1(I
5

~%bbrexiations: AA. acrylic acid: BA. n-butyl acrylate: BMA, n-bttyl


methacrylate: MAA, methacrylic acid: MMA. metbyl methacrylatc; Sty,,
styrene.

binder types, the aforementioned categories of coalescents


and thickeners were studied during fihn drying.
Practical coating properties were determined for the latex
formulations (sagging, levelling, drying time) and compared with the initial in-can rheology (flow curves and
dynamic rheology) and the rheological changes as measured
during drying.
In addition, to gain more insight into the effects of coalescing agents, the evaporation kinetics of the aqueous
Table 2
Binder compositions (percenlages by ,.,,eight) and characteristics: COlnposition of the vinyl versatatetacrylale latex (VVtAcryl)

Component/properly

q" (by' ,,veighl)

Methyl inethacrylale
2-ethyl hexyl acrylate
VeoVa 9
Acrylic acid
Anionic sur factanl
Non-ionic surfactant
Biocidc Proxcl XL 12

18
2(1
60
2
0.5
1.0
0.001

Solids content
MFFT
pH
Mean particle size

46
26C
S.5
126 nm

Characteristic

Type of alkyd
Solids content
pH
Mean particle size

based on soybean fatty acids


60% ib.w.)
4.5
370 nm

phase and the swelling of latex particles due to coalescents


were studied.
The investigations concern pure latexes, binder/coalescent systems, binder/thickener systems and latex formulations containing both coalescent and thickener, while they
were optionally pigmented.

2. Experimental
2. I. Materials

The materials and the abbreviations used in this article


are summarised in the corresponding tables (latexes: Tables
1 3; coalescing agents: Table 4; thickeners: Table 5).
2.2. Methods
2.2.1. Flow curves and dynamic rheology
The flow curves were determined with a stress controlled
rheome,c; ~Carri-Med CSL 100) at 25C. The applied stress
was increasing linearly with time, corresponding with a
shear rate range of 0 - 6 0 0 0 s I. The dynamic measurements
were performed in the linear viscoelastic region with the
same rheometer (25C). In all cases a cone and plate geometry was used.
2.2.2. Zeta-polential
To study the adsorption behaviour of thickeners onto
latex particles, the zeta-potentials of the pure and thickened
VV/Acryl latexes were determined using laser Doppler
effects in light scattering with a Malvern Zetasizer 4 apparatus. Interpretation was based on the Smoluchowski equation. The latexes were diluted to a solids content of 0.5%,
Table 4
Over~icw of the coalescing agents studied
Abbreviation
Hydrophilic. volatile
EB
Ethylene glycol inono n-butyl ether
PnB
Propylenc glycol i]lono n-butyl ether
PM
Propylcnc glycol mono methyl ethel"
Hydropbobic. slowly evaporating
TEX
2.2.4-Ti-mlethyl-l.3-pentancdiol inono isobutyrate
HPV
Hydroxy propyl versatate
Aliph. HC
An aliphatic hydrocarbon (boiling point: 246-264C)

F. Moh,naar el oI. / Progres~ in Orgcnic Coating.s 30 (1997) 141-15~

Table 5
Overview of the thickeners studied
Abbreviation/
thickener type

Description

Remark

HEC

Hydroxy Ethyl Cellulose

Representative comlnercial product


Hydrophohe length: CI,:
MW,,: 36000
Hydrophobe length: C>:
MW,,: 27 000
Hydrophobe length:
C~, CH" based on PEO
and aliphatic diisocyanate
Hydrophobe length:
CL,-CH, based on PEO
and aromatic diisocyanate

HMHEC- l '

Hydrophobically
Modilied
Hydroxy Ethyl Celhflose
HMHEC-2"
Hydrophobically
Modified
Hydroxy Ethyl Cellulose
Aliphatic HEUR Hydrophobically Modified
Ethoxylated URrethane
Aromatic HEUR Hydrophobically Modified
Ethoxylated URrethane
HEUR-U1
HEUR-U2

Urea modified HEUR


Urea modified HEUR

esp. suitable at higher


shear rates

~'Experimenta[ product.
the pH was adjusted to 9 and the ionic strength was 0.01 M
(NaCI). The zeta-potentials were measured as a function of
thickener level. In special cases extra emulsifier was added
to the latex.

143

The determinations were carried out in 12-fold (two series of six). The latexes were applied by an applicator with a
clearance of 150/,m on tin-plated steel strips.
2.2.3.5. Sag resistam'e. The latexes were applied horizontally in narrow (6 ram), parallel and equidistant (6 mm)
streaks on degreased glass plates using a block shaped
applicator. The applicator clearance varied from 50 to
200 /,m. The coated substrate was positioned vertically l
rain after application. The sag resistance is defined as the
maximum applicator clearance that does not lead to
coincidence of the corresponding streak with an adjacent
streak.
2.2.3.6. Levelling. According to A S T M D 2801-69. This
standard is analogous to the sagging method described
above, however, it makes use of different dimensions of
the applicator geometry, and the full drying occurs
horizontally; scale: 0 means very poor flow and 10 is
excellent levelling.

3. Rheology of in-can latexes


3. I. Introduction

2.2.3. Film/brmation
2.2.3.1. hi general. All film formation experiments (TNO
Filmviscometer, weight loss measurements, sagging,
levelling, etc.) were carried out in a climate room (50%
RH, 23C).
2.2.3.2. TNO fihm'iscometer. The experimental method to
follow the viscosity change of a drying film as a function of
drying time, is described in Section 4 and references [ 1-31.
The air speed velocity above the film was 5 cm/s. The angle
of the coated panel and the diameter of the steel ball used
per individual case, are mentioned in Section 4. The
substrate was degreased tin plated steel (20 x 20 cm) and
the applicator clearance was 150/,m.
2.2.3,3. Weight loss meclmtrements. The gravimetric
determinations were carried out in the measuring box of
the TNO fihnviscometer at an air speed above the coated
panel of 5 cm/s (23C, 50% RH) after the same application
procedure as mentioned for the Fihnviscometer experiments.
2.2.3.4. Do'ing time and opelt time. These properties were
determined with a standard BK drying recorder (Mickle
Laboratory Engineering Co,. UK). The drying time is
characterised at the moment the scratching tip of the
needle starts to cause film wrinkling in a V-shaped
pattern. The open time is taken as the time after which
the trace of the moving needle is becoming visually
much more apparent due to insufficient flow.

In this section several aspects of the rheological in-can


behaviour of different waterborne binder types are
described. The results are presented in terms of the rheological model according to Quemada [4,5 I.
The study on pure latex binders includes the effect of:
The shear rate
Shear thinning behaviour is characteristic for commercial
waterborne latex systems. The viscosity profile is essential
for coating application purposes. For example, at high shear
rates which occur during paint application processes like
brushing (approximately 10~ s ~), the viscosity is not
allowed to be too low for sufficient film layer build-up
and can not be too high because of ease of applicability;
on the other hand, at low shear rates (approximately 10 -'10 ~ s -~) the viscosity must not be too low to prevent excessive sagging during film drying, and cannot be too high for
the requirements on levelling (see Section 3.2.2.1).
Neutralisation
The latexes were neutralised, from a pH of approximately
2 to a value of 9, which is representative for commercial
acrylate type latexes. The pH is relevant since neutralisation
induces electrostatic forces in the latex system (see Section
3.2.2.2).
The copolymer composition
The copolymerised acid type and level, and the hydrophobic/hydrophilic nature of the acrylate copolymer were
varied (see Section 3.2.2.3).

144

F. Molenaar et al. / Progress in Organic Coatings 30 (1997) 141 158

Next to the various effects occurring in pure binder systems, the rheological effects of the addition of different
types of coalescing agents and thickeners, as used in paint
formulation, were studied. In Section 3 only the effects in
the can are described, while the theological effects occurring during film drying and as observed in dried films, are
described in Sections 4 and 5.

with k.05m = 2 and

k - ko + k~(q,/~,c)
1 + ('~/~'cY'

(2)

in which: ~r = relative viscosity of the latex = (them/


rtconti..... pha~), q~= volume fraction of the dispersed phase,
0,,, = maximum packing volume fraction of the dispersed
phase, k = structural intrinsic viscosity (a function of
the shear rate and 05), k~ = structural intrinsic viscosity
at infinitely high shear rate, k0 = structural intrinsic viscosity at infinitely low shear rate, 3' = shear rate (s-~),
~c = critical shear rate above which rupture of the latex
structure is favoured over its build-up, p = a fitting parameter.

3.2. P u r e b i n d e r s - a c r y l a t e l a t e x e s

3.2.1. Quemada's model


Several models have been developed to describe the
theological behaviour of latexes as a function of the
volume fraction of latex particles (Mooney [6J, KriegerDougherty [7-9], Quemada [4,5,1 01). According to Quemada's model the relative viscosity of a dispersion is given
by:

Table 6
Rheologieal parameters according to the Quemada model for non-neutralised (*pH = 2) and neutralised latices (pH = 9)
Latex

4~,.,o

0 .....

ko

k~

'~c

B75
B75
B76
B76
B77"
B77
B78 ~
B78
B79'
B79
B80"
B80

0.435
0.394
0.406
0,406
0.391
0.391
0.404
0.398
0.394
0.393
0.403
0.393

0.894
0.690
0.856
0.653
0.888
0.581
0.899
0.719
0.864
0.770
0.873
0.791

4.60
5.08
4.92
4.92
5.12
5.12
4.95
5.07
5.08
5.09
4.97
5.09

2.24
2.90
2.34
3.06
2.25
3.44
2.22
2.78
2.32
2.60
2.29
2.53

0.61
0.65
0.58
0.55
0.48
0.61
{).59
0.52
0.56
0.55
0.56
0.53

193
83.4
72.9
23.5
34.0
3 I. 2
66.4
39.6
74.4
47.5
06.5
62.0

B 125 ~
B 125
B 126*
B 126
B 127~
B 127
B 128*
B 128
B 129'
B 129
B 131"
B 131
B 135
B 135
B 137
B 137
B 138
B 138
B 139 ~
B 139

0.411
0.425
0.425
0,383
0,426
0,425
0,425
0,424
0.411
0,410
0,425
0.404
0.410
0.418
0.427
0.425
0.425
0.434
0.425
0.426

0,772
0.756
0.769
{I.763
0,783
0.710
0.800
0.683
0.770
0.707
0.877
0.854
0.799
0.742
[).976
0.845
{).826
0.758
0.857
I).761

4.87
4.70
4.70
5.21
4.69
4.70
4.70
4.71
4.86
4.88
4.70
4.95
4.88
4.78
4.68
4.70
4.70
4.61
4.70
4.69

2.59
2.64
2.60
2.62
2.55
2.81
2.50
2.93
2.60
2.83
2.28
2.34
2.50
2.69
2.05
2.37
2.42
2.64
2.33
2.63

0.46
0.55
0.44
0.52
0.43
0.46
0.37
0.52
0.41
0.50
0.52
0.57
0.50
0.62
0.51
0.45
0.47
0.53
0.38
0.52

23.3
18.6
17.9
49.8
37.7
16.1
6.4
32.5
16.3
16.3
43.7
23.6
9.7
12.9
159
21.2
7.3
14.4
4.5
24.3

VV/Acryl

0.47

215

~Not determined.

F. Molemmr et al. /Pro,~ress in Organic Coatings 30 (1997) 141 158

3.2.2. Results and discussion


The results of the flow curves for the acrylate latexes
B75-80 and B125-139 (Table 6) show, according to the
Quemada model, the following aspects.

145

below). However, in non-neutralised latexes this effect


does not occur as the acid comonomers ionise only to a
minor part at pH = 2, thus contributing only to a very low
extent to the electrical charge density of the anionically
stabilised latex particle surface.

3.2.2.1. Effect gfshear rate. A comparison of ~bm.0and qSm~


shows that the maximum packing factor 4)m increases
strongly with increasing shear rate. This implies the
existence of large and loose aggregates of latex particles
and the formation of structures at low shear rates and at
rest. The extent of the structure build-up at rest and low
shear rates is very similar for all model latexes considering
the close values 4~m.0(Table 6). The degree of structure for
these latexes is even independent of the pH (4~,,,.0 is about
0.40-0.42).
The structure of latex particles is readily destroyed. The
destruction predominates over the build-up ['or shear
rates above typically 10-70 s ~. At high shear rates, e.g.,
during paint application at approximately 104 s-I, all latex
agglomerates and aggregates can be assumed to be
destroyed, so that all particles are in their state of fundamental entities.
It can be remarked that the shear thinning behaviour of
latexes is generally caused by the above-described mechanism of shear-dependent structure formation/destruction and,
on the other hand, by the arrangement of latex particles into
two-dimensional arrays along the shearing planes at higher
shear rates (laminar flow). Obviously, both contributions
facilitate flow and lead to lowered viscosities upon higher
shear rates.
The shear thinning effect is also reflected, next to the
model acrylate latexes, in the vinyl/acrylate (VV/Acryl)
latex. The critical shear rate 3g. is moderate (Table 6),
while showing that the particle structure in the VV/Acryl
latex is destroyed somewhat less readily than in case of the
model acrylate latexes.

3.2.2.2. Effect ofneutralisation. The observation that qS,,,~


values of the neutralised latexes (pH = 9) are significantly
lower than those for the non-neutralised latexes (pH = 2;
Table 6), shows that the apparent hydrodynamic volume
increases upon latex neutralisation (by addition of
ammonia). The particle diameter of these latexes was
shown to be independent of pH using photon correlation
spectroscopy (PCS by Forbairt), i.e., no swelling was
measured upon a pH shift from 2 to 9 with ammonia.
Therefore, the increase of effective particle volume is due
to a secondary electroviscous effect. This means that the
negative charges on the latex particle surface induce an
electrical field around the particles which enlarges the
effective volume experienced by each individual particle
when approaching a neighbouring electrostatically repelling particle.
In neutralised latexes (pH = 9) an increase of hydrodynamic volume as a function of the level of copolymerised
acid (methacrylic acid or acrylic acid) is observed (see

3.2.2.3. Effect of copolymer composition on the hydrodynamic volume


3.2.2.3.1. Non-neutralised latexes. In non-neutralised
latexes (pH = 2) the hydrodynamic volume of the
particles is essentially independent of the content and
type of the copolymerised acid, as explained above. The
structural intrinsic viscosity k= varies between 2.22 and
2.64 and is close to 2.5, which is the Einstein theoretical
value for rigid undeformable spheres. The deviation of k=
from the Einstein value allows the calculation of the
increase of the effective particle radius (A), according to:
k=
2.5

q ~ e n _ l + _3A
_
4)
R

(3)

Calculation for the latexes B125-139 shows that this ratio


varies between 1.01 and 1.04, the average value being
1.027. Since the mean particle size of this series of model
latexes is 196 nm (PCS carried out by Forbairt), this corresponds to an average increase of effective radius (A) of
0.88 nm. This is in ['act about one-third of a fully extended
emulsifier molecule (nonylphenyl ethoxylated (EOg) sulphate). The very small increase of the effective particle
size found here agrees well with the previous findings of
Quadrat et al. [11], and implies that the electrical double
layer of the latexes studied is strongly compressed.
3.2.2.3.2. Neutralised latexes. Upon neutralisation
(pH = 9) the effect of the copolymerised acid level and
type on the hydrodynamic volume is large, in contrast to
the non-neutralised latexes. The higher the acid content, the
higher the hydrodynamic volume. At equal acid
comonomer contents, the hydrodynamic volume of the
acrylic acid containing latex is substantially higher than
the methacrylic acid counterpart. In the series B75-77
the increase of effective particle radius A is 5.3 nm
(5.3%), 7.4 nm (7.5%) and 12.3 nm (12.5%) for
respectively 1%, 2.5% and 5% acrylic acid comonomer.
If non-neutralised, these increases are only 0.5%. These
findings reflect the secondary electroviscous effect, as
mentioned above, and they can be well related to the
electrical charge density measured for the respective latex
particles with a polyelectrolyte titration using the streaming
potential technique (see Section 4.2.1).
In order to evaluate the effect of the hydrophobic/hydrophilic nature of the latex copolymer (excluding the effect of
acid comonomer) on the hydrodynamic volume of neutralised latexes, the results can be compared for the following
latexes, each containing 1% acrylic acid:
1. B125-129, containing the hydrophobic comonomer
styrene at different contents

F. Molenaar et al. /Progress in Organic Coatings 30 (1997) 141 158

146

2, B75, containing butyl methacrylate (intermediate hydrophobicity)


3. B131-139, containing the hydrophilic comonomer
methyl methacrylate at different levels
The (averaged) increase of the effective hydrodynamic
radius is moderate and moreover comparable in these
three groups of latexes: 1.3%, 5.3% and 1.6%, respectively.
This suggests that the increase of effective particle size is
not or slightly dependent on the hydrophobicity of the latex
copolymer.

3.3. Binder~coalescent systems: effect of coalescent


The effect of the addition of coalescing agents to pure
latexes resulted in an increase of the viscosity for all combinations of latex type and coalescent investigated, when
comparing the data at equal experimental conditions.
This is anticipated, since the total volume of the latex
particles will increase by the amount (in volume) of the
coalescing agent that diffuses into the particles. This
increase of volume obviously leads to a higher viscosity
(see, e.g., the Quemada equation, eqn (1)). The volume
increase can be calculated theoretically when the following

parameters are known: the added amount of coalescent, the


solids content of the latex and the distribution coefficient,
representing the partitioning of the coalescent over the
water and polymer phase (which can be determined with
gas-chromatography after ultracentrifugation [12]).
The volume increase of the individual latex particles due
to coalescent addition will also be reflected in the increase
of the hydrodynamic volume and, equivalently, in the
decrease of the maximum packing volume at high shear
rate (4~m.=). The increase of volume, thus calculated fi'om
the flow curves and the resulting Quemada theological data,
is compared with the value expected when assessing the
distribution coefficient of the respective coalescing agents.
Table 7 confirms that coalescent addition leads to a higher
hydrodynamic volume (a lower ~m.~) and shows that the
increase of volume as calculated from the rheological
data, agrees reasonably well with the volume increase
expected from the distribution coefficient.
However, the agreement is not valid in some cases, particularly for PM and for TEX and hydroxypropyl versatate
(HPV) at the higher levels. The stronger increase of hydrodynamic volume for the latter two coalescents, which are
highly hydrophobic, might be attributed to their very low
distribution coefficient combined with a substantial increase

Table 7
Effect of coalescing agents on the maximum packing fraction at high shear (6,,,.+.-) for neutralised laticcs (pH = 9)
Latex

B125

Coalescent

no (Rel)
DBA a
PnB
HPV ~
TEX
aliph. HC ~
PnBA ~
PM

B131

no (Refi
DBA a
PnB
HPV L"
TEX
aliph. HC r
PnBA ~
PM

Level (%b.w))

(J.....

Volume increase
Rheology h

Ultra-centrifugation '

0
5
10
10
5
5
10
5
I0
10
10

0.756
0.732
0.722
0.698
0.739
0.722
0.668
0.721
0.700
0.681
0.696

3.2
4.7
8.3
2.3
4.7
13.2
4.6
8.0
11.0
8.6

4.5
8.7
8.2
5.0
4.9
9.2
5.9
I 1.2
8.7
4.4

0
l0
II)
I0
5
10
10
10
10

0.854
0.780
0.766
0.722
0.805
0.708
0.763
0.751
0.781

9.5
I1.5
18.3
6. I
20.6
I 1.9
13.7
9.3

8.7
8.4
9.2
5.0
10.5
11.2
9.0
1.5

"% by weight, based on polymer weight.


bExperimental increase of hydrodynanfic volume based on rheological data ( = (4~,,,.~,- 4~,,,.~.(Ret))/g~m.,+(Ref)),in which 4,,,,.~(Rel') refers to the reference latex
without coalescent added.
CExperimental increase of volume fraction based on calculation using the distribution coefficient of the coalescent, determined for the specific latex with GC
analysis after ultracentrifugation / s e e [ 12] ).
aDBA, diethyleneglycol butyl ether acetate.
~HPV, Hydroxypropyl versatate.
~aliph. HC, aliphatic hydrocarbon, high boiling type.
gPnBA, propy[eneglycol n-butyl ether acetate.

F. Moh'mmr et al. /Progres,s in Orgt l ic Coatin,%s 30 (1997) 141 158

of the free volume of the polymer due to the presence of the


plasticiser. The explanation for the deviation in volume
increase for PM is unclear.

147

!04

10'~

n'

G', G"

(Pa.s)

(14.=-2)

3.4. In-can rheology of binder~thickener systems

10a

10a

The viscosity as a function of shear stress was measured


for the vinyl versatate/acrylate copolymer latex (VV/Acryl)
containing four different types of HEUR thickeners (the
aliphatic and aromatic HEUR and two urea modified
HEURs, HEUR-U1 and HEUR-U2). The same latexes, as
well as the alkyd emulsion with the aliphatic HEUR and a
urea modified HEUR thickener (HEUR-UI), were characterised with dynamic rheology, measuring in the linear viscoelastic region (by CoRI).
In this section, mainly the dynamic results are discussed.
The results of the flow curves support the dynamic data and
they are briefly summarised in Section 4.2.3, when discussing the theological changes observed during film drying.
3.4. I. Elficiency and mechanism of associative thickeners
Fig. 1 gives an excellent overview on how the relatively
low viscosity of an associative thickener premix can be
combined with the too low viscosity of a pure latex binder
to result into a very effectively thickened latex with a viscosity profile which approaches paint formulation requirements. The synergy in thickening is demonstrated as a
viscosity increase of about one decade with respect to the
pure latex and of approximately three decades with respect
to the thickener premix solution.
The synergy in thickening originates from the additional
junction points provided by thickener adsorption onto the

102

102

.A

/ /

" ,o,"Ao....o~...

10~

to~
-o..~

10;-2

, ,,,,,.

, ,. .............

iO-t

,0o

i0

13 I

Frequency (Hz)
Fig. 2. Dynamic properties of thc VV/Acryl latex thickened with the aromatic HEUR (0.2c)} by weight based on water phase). O: ~1'; D: G': A: G".

latex particles [13]. The relatively small particle size of the


VV/Acryl latex (diameter: 126 nm) and the high hydrophobicity of the copolymer are likely to further increase the
thickening efficiency.
3.4.2. Vinyl versatate/acrvlate latex
The pure VV/Acryl latex is relatively high-viscous and
shows strong pseudoplastic behaviour (see, e.g., Fig. 1) as
well as a high level of elasticity. Thixotropy could not be
observed in flow curves. The yield stress was 1 Pa (calculated with the Casson equation). The dynamic properties of
the 0.2% (b.w. on water content) thickened latexes are sum-

i0 s
ZOS

Visccsity

(Pa s)

'0 2
-

104

iL.o-o,,
I

+~

t04
G', G"

10~
+'x o

(?as)

+..0~

\ b%,0,
,

0'

103

I01

*.,'o.
%"0,

(Nra-2)
AI "~

103

.+x o

10c

10

102
\+

[C -i

lC-:

I0i

10.2

:0-2

&
gL

10-i0-1

10c

&

10:
10~
shear rate (s-i)

Fig. I. Flow curves of the thickened VV/Acryl latex, showing the synergy
in thickening efficiency when combining an aqueous solution of an associative HEUR thickener with a latex. : solution of the aliphatic HEUR
thickener (0.5%): DI: VV/Acryl latex: + : VV/Acryl latex with 0,2% aliphatic HEUR (5~ b.w. based on water phase): O: VV/Acryl latex with
0.4% aliphatic HEUR (% based on water weight).

',;%

V'"
'

.....

I0

....

i0o

.....

?0t0

Frequency (Hz)

Fig. 3. Dynamic properties of the VVtAcryl latex thickened with the


aliphatic HEUR (0,2 and (].4(/( by weight based on water phase). O:
r/(0.2%); O: r/(0.4%1: [Z]: G' i0.2~2/i; " : G' (0.4g(): A: G" (0.2%); it:
G" (0.4g~).

k. Moh,,aar el al. /Progress in Org~ nic Coatings 30 (1997) 141 158

148
104

lO 4

n'

(N.m-2)
(Pa.s)
103

t0 3

10 2

I0 2

101

IC i

10c
10-2

. . . . . . . . . . . . .

lO-1

, .....

i0 o

qO 0

10r

Frequency (Hz)

Fig. 4. Dynamic properties of the VV/Acryl latex thickened with H E U R UI (0.2 and 0.4% by weight based on water phase). @: r/(0.2%): 0 :
r/(().4%): E: G ' (0.2%): a : G' (11.4%): & : G " (0.2%); i,: G " (0.4%).

marised in Figs 2-5. Although all latexes are viscoelastic,


they show quite different bebaviour when compared with
each other. The latex thickened with the aromatic HEUR
(Fig. 2) shows viscoelastic behaviour which is predominated by the viscous component of the complex modulus
over the whole frequency range studied (0.01-10 Hz). The
latexes thickened with the aliphatic HEUR (Fig. 3) and the
two urea modified HEURs (see HEUR-UI, Fig. 4), on the
contrary, show a cross-over point of the storage modulus G"
and the loss modulus G" curves (between ca. 0.02 and 0.04

Hz for 0.2% thickener content) below which the viscous


component prevails (tan6 > 1) and above which elastic
behaviour dominates the viscous behaviour (tan6 < 1).
The values of tan6 for the four different HEUR thickeners
are shown in Fig. 5. The aromatic HEUR is by far the most
viscous system, while the two urea modified HEURs and the
aliphatic HEUR are much more elastic. Considering the
relative order of viscous versus elastic behaviour, there is
a strong dependency on frequency. As a general rule of
thumb, it can be concluded from Fig. 5 that the aromatic
HEUR will be probably the thickener of choice if maximum
levelling (0.01 Hz) and minimum spattering during roller
application (high frequency) are desired. The strongest tendency to level out could indeed be confirmed experimentally for this HEUR type thickener when used in the VV/
Acryl latex.
In Section 4.2.3 it will be shown that the storage modulus
G', as well as G" and tan& measured for the four different
HEUR thickeners, can be directly related to the adsorption
tendency of the respective thickeners onto the latex particles
(determined with zeta-potential measurements). The
adsorption of associative thickeners strongly contributes to
the physical network formation and, therefore, to the elastic
and viscous properties.

3.4.3. Alkyd emulsion


The dynamic rheological properties of the alkyd emulsiom thickened with the aliphatic HEUR and the urea modified HEUR-U 1 thickener respectively (0.4% b.w. on water

103

10 3

103

103

10 2

Gt, G"
102

102
(N.rn ~)
(Pas

" ,.l~

tO~

tan 5
10i

tO 1

1,0o - . '

,, - u,

tO

z
j3""
10

"~Q~----o~o...

.~'

i0

"-~-.I --- ~

.....

r'" j / "
t

:i;-~

. . . . . . . . . . . . . . .

lo-'

'M

-]

Frequency (Hz)

10-1

10 -2

.......................
10 -I
Frequency

I0 0

logo 1

(Hz)

Fig. 5. Loss factor tan 6 of the VV/Acryl latex thickened v/ith different

types of HEUR thickeners, measured as a function of the frequency. This


shows that the aromatic HEUR has by far thc most pronounced viscous
(less elastic) behaviour over the whole frequency range measured. Thickener level: 0.29~ b.w. based on the water phase. + : aromatic H E U R : O:
aliphatic H E U R : ~: H E U R - U I : A: H E U R - U 2 .

Fig. 6. Dynamic rheological propcrties of the alkyd emulsion thickened


with two different types of HEUR thickeners. A comparison with the VV/
Acryl latex ( x ) shows that the thickening efficiency of HEUR thickeners
is strongly dependent on the binder type (see text). The thickener level was
in all cases 0.4% (b.w. on water content). Alkyd emulsion: all symbols
except x : O: rt'(HEUR-U1L O: r / ( a l i p h a t i c HEUR)" 13: G' (HEUR-U1);
I1: G' (aliphatic HEUR); &: G " ( H E U R - U I ) ; A: G " (aliphatic H E U R ) , x :
G ' (aliphatic HEUR in VVIAcryl).

149

F. Molenaar el al. /Progress in Organic Coatings 30 (1997) 141 158

tan

tO 3

lo 3

1'32 i

lOa

lower, see Fig. 7), the viscosity 07') of the VV/Acryl latex is
much higher (roughly one decade) and the G" is 10-100times as high. Realising that G' can be related to the structure build-up of associative thickeners in latex systems, it
can be concluded that the aliphatic HEUR and the urea
modified HEUR-U1 are much more effective in the hydrophobic VV/Acryl latex than in the hydrophilic alkyd emulsion. It can be assumed that the surface of the emulsion
droplets contains a lot of polar groups (hydroxy and/or carboxylic) and a high amount of surfactant molecules. These
polar moieties are unfavourable for interaction with the
thickener hydrophobes via adsorption. Furthermore, the
total surface area of the alkyd emulsion droplets is smaller
than that of the VV/Acryl latex particles (the particle diameters are 370 and 126 nm respectively, while the solids
contents are comparable; Tables 1-3).

<5
101

101

_-4D.

l
o

0~i

]0 - 2

......

o .o

,,i

qll.

......

10 -!

...... q O -i

10

Frequency

10:

(Hz)

4. R h e o l o g y

Fig. 7. Colnparisonof the loss factor tan6 between the alkyd emulsionand
the VV/Acryl latex when thickenedwith HEUR thickener((I.4% on water
content). The thickenedalkyd emulsionis much more viscous(less elastic)
in nature than the thickened VV/Acryl latex. : VV/Acry[ latex with
aliphatic HEUR; O: alkyd emulsion with aliphatic HEUR; D: VV/Acryl
latex with HEUR-UI" i : alkyd emulsion with HEUR-U1.

content), are shown in Figs. 6 and 7, including a comparison


with the corresponding vinyl versatate/acrylate latex.
Over almost the complete frequency range measured
(0.01-10 Hz) the viscous behaviour dominates over the
elastic behaviour for both the aliphatic and the urea modified HEUR (HEUR-UI) in the alkyd emulsion (tan6 > 1).
At 7 - 1 0 Hz, the cross-over point of G' and G" is reached.
Comparing the alkyd emulsion with the VV/Acryl latex, it
can be concluded that the correspondingly thickened VV/
Acryl latex is much more elastic (tan& approximately 1 or

of drying

latex films - filmviscometer

results
4. l . M e t h o d

The TNO Filmviscometer was especially developed to


measure the viscosity changes of a drying paint film [ 1 3]. The method is based on the principle of a rolling ball.
The velocity (v) of a steel ball, rolling through a drying film
which is supported by a rotatable substrate under an adjustable slope (a), is continuously measured during drying
using an IR detection beam. An apparent viscosity (rl) can
be calculated according to [1 ]:
k . g .p R 3 sino~

(4)

=
V

where k = a function of the layer thickness and determined


using a Newtonian oil as a calibrating standard,

V i s c o s i t y in Pa,s
100

90

2]

80
70
60
50
40
30
20

i,, , ~ , , ~ - , ~
60

,r~, ,~,...... 7-....... ,,.,, m ~ ......... ~ i ~ ~ r ~ % J "

120

180

240

300

360

420

480

540

600

-660

720

Drying time (seconds)

Fig. 8. Change of the viscosity (Pa.s) o1' the pure B75 latex (neutralised at pH = 9) as a function of the drying time Is), as measured with the TNOFilmviscometer(conditions:23C, 50% RH; rolling ball diameter: 1.5 ram; slope: 15).

150

F. Molenaar et al. / Progress in Organic Coaliplgx 30 (1997) 141 158

Table 8
Comparison of initial viscosities measured witl~ a conventional stress controlled rheometer (measured by CoRI, at 10.3 s i) and with the TNO
Filmviscometer (in a drying fihn, extrapolated to time zero): the formulations contain the latex B I25~ a HEUR thickener, titanium dioxide at 9.9
and 18% PVC, respectively, and the coalescents indicated (level: 10cA
based on binder weight)
PVC

Coalescent

9.9c7~

PnB
EB
TEX
PnB
EB
TEX

18%

Viscosity (Pa.s)
fihnviscometer
2,0
1.5
3.0
2,0
1.7
4.0

Viscosity (Pa.s)
conventional
2.4
1.9
2.7
1.8
1.4
4.5

g = constant of gravity, p = the density of the ball, R = the


radius of the ball.
The external drying conditions can be controlled (usually:
23C, 50% RH: air speed above the rotating substrate: 5 c n f
s).
The apparent viscosity of the freely evaporating film is
determined as a function of the drying time (see Fig. 8 as an
example). A key parameter is generally used, t('q..... ), which
is the time to reach the maximum viscosity measurable
under the conditions chosen. Normally, t(~,~) was determined as the mean of 5 or 6 independent measurements. The
method is discriminative: e.g., different effects could be
clearly detected when varying the thickener type at a level
of only 0.1% (on total weight: as will be shown in Table 12
and Table 13).
Depending on the ball diameter used (0.5-3.0 mm) and
the slope of the coated panel (15-45 ) and, obviously, the
latex formulation used, the drying period prior to reaching
the viscosity peak ranges from about 2 to 10-15 min. Based
on weight loss measurements on similar flms in parallel
experiments under the same drying conditions, the volume
fraction reached at t(rh,~,0 is roughly 45-57%. These values
thus calculated are inherently values that have been averaged over the surface area of the drying film and also over
the film layer thickness. Considering the above mentioned
volume fractions, the filmviscometer is assumed to measure
at the stages prior to the onset of coalescence, since the
volume fraction in case of random packing of equally
sized hard particles is 64% and in case of densest packing
74% by volume. Theoretically, this conclusion may be
incorrect when a strong gradient of packing has already
been formed in the drying film on the time scale of the
measurement (see below).
The apparent viscosity measured with the rolling ball
correlates well with viscosities measured with conventional
rheometers at the relevant shear rates (see Table 8). At the
onset of the measurement with the rolling ball, the effective
shear rate was approximately 0.4-20 s ~ (for all types of
binders studied) and typically about 10 s ~. During the

experiment, as drying proceeds, the effective shear rate


will decrease.
Especially the measurements of binder/coalescent systems (non-thickened; see Section 4.2.2) show that the
TNO filmviscometer measures more than only an equivalent
value for the initial (in-can) viscosity, but it detects complex
rheological changes in the film during drying, which are
governed by physical changes induced by the evaporation
process.
A rapid increase of the apparent viscosity is generally
measured (for the non-thickened model acrylate latexes).
This increase is at an earlier stage and faster than expected
regarding, on the one hand, the overall volume fractions
measured gravimetrically, and, on the other hand, the relevant theological equations, such as the Quemada equation
(eqn ( I )). These equations express the (relative) viscosity as
a function of the volume fraction. Presumably, three contributions to the earlier and steeper than expected increase
of apparent viscosity can be mentioned.
(1) As coagulation and coalescence start at the surface of
the latex film, the volume fraction across the layer thickness
will not be homogeneous. Thus, the volume fraction at the
top layer will be higher than in the bulk of the coating,
forcing the rolling ball to slow down relatively fast. In
case of a semi-dried top layer this agrees with the model
of Croll 114] and in case of skin formation, this is in line
with the observations and modified model of Eckersley and
Rudin [ 151.
(2) It was observed that the drying of the (emulsifier
containing) latext's starts at the edges of the film, or possibly
at film irregularities. The drying advances towards the center of the film. When the drying front across the surface area
passes the rolling ball, the local volume contraction of the
latex film is accelerated. This obviously leads to a steep
increase of the viscosity.
The occurrence of an accelerated drying process in and
near the drying front was observed by Forbairt in this
BRITE/EURAM project using non-contact film thickness
measurements. This phenomenon has also been incorpoTable 9
TNO Fihnviscometer resuhs of the acrylate latices B75 80 containing
increasing levels of acrylic acid (AA) and methacrylic acid (MAA) comonomer, measured at 23~C and 50c/c RH (ball diameter: 1.5 ram: slope: 15:
dry layer thickness: approx. 40 ,am)
Latex

Acid

Level

t(rt,~,,~,~) (s)

l0 ~4.o-"

B75
B76
B77
B78
B79
B80

AA
AA
AA
MAA
MAA
MAA

I c7~
2.5',;~
5eli
1C4
2.59~
5~,/~

680
660
520
630
640
590

2.9
4.3
8.8
2.2
2.2
3.4

;'o. Surface charge density: the number of electrical surface charges on the
latex particles per m 2, determined with polyelectrolyte titration using the
streaming potential method after three months of storage of the neutralised
latices.

F. Moh, naac el al. /Pro,k, re~s in Organic Coating.s 30 f1997) 141

4.2. Results and discussion

Table I0
TNO Fihnviscometer results of several latices (binder/coalescent systemsl
showing the effect of coalescents at a level of 49;, on total httcx weight
(t('~lll~lX): time to reach ball fixation (in seconds): differences between par
cntheses h)
Coalescent

B76
B79
B 125
VVtacryl
BMAIAA BMA/MAA Sts/acryl vinyl/acryl

No (reference)
TEX

660
590
(+70) ~
630
(+30)
650
(+10)
670
i-10i

PnB
PM
EB

151

158

640
520
(+1201
580
(+6(})
68(I
(40)
700
1-60i

380"
420
(-4(I)
470
(-90)

580
1-160)

Hydroxy propyl
versatate
High boiling
aliphatic hydrocarbon

230"
160
(+70}
310
(80)
300
(-7(1)
360
1-1301
280
(50)
200
(+30i

Measuring conditions: 23C, 50~k RH: ball diameter, slope o< B76, B79:
1.5 ram, 15: B125:2.5 Illri], 15: VVtAcryl latex: 2.0 ram, 20 c.
Difference of l(~nla\j between latices without and with coalescent: +, acceleration; , delay of the viscosity peak.

rated in the drying model recently proposed by Winnik and


Feng [16].
(3) As a result of the shear thinning behaviour (pseudoplasticity) of latexes, the apparent viscosity measured with
the filmviscometer will increase at a higher rate than
expected for Newtonian coatings, since the rolling ball continuously slows down its velocity during the measurement.
This implies that the effective shear rate at which the viscosity is measured, decreases from typically 10 s i down to
roughly 0.1 s i. In latex systems this change of shear rate
can typically lead to a viscosity increase of roughly one
decade.

4.2.1. E~/bct of binder b'pe


The effect of the latex type on the viscosity behaviour
during film drying was observed by changes in the shape of
the viscogram and the time at which the viscosity peak is
reached (t(r/ ..... ); see Tables 9 and 10).
All model acrylate latexes (neutralised to pH = 9)
showed, after a relatively long period of low and almost
constant viscosity, a sudden and very steep increase of viscosity ( B 7 5 - 8 0 and B 125 139: typical example: Fig. 8). The
vinyl/acrylate copolymer latex (VV/Acryl) showed a much
lower t(rh,,,0 value (Table 10), while the viscosity increase
during drying is much more gradual (Fig. 9).
In contrast to latex systems, the alkyd emulsion studied
showed a very different behaviour. When measuring under a
steep slope of the coated panel (30 or 45 ) and with a large
ball diameter (3.0 ram), a gradual viscosity increase is
detected and after about 6.5 rain drying time a plateau or
in many cases a maxirnum followed by a minimum occur,
prior to the very steep rise of viscosity to values well above
1000 Pa.s (see Fig. 10). The occurrence of the viscosity
plateau or maximum can presumably be assigned to a
phase inversion: the coating changes from an oil-in-water
to a water-in-oil emulsion. Upon further drying the steep
viscosity peak is reached.
Returning to the acrylate model latexes B75-80, it is very
interesting to compare the t(r/ ......) values as a function of the
content of acrylic acid and methacrylic acid comonomer
respectively (see Table 9). This shows that increasing levels
of acid as a comonomer in neutralised latexes leads to an
acceleration of the occurrence of the viscosity peak. The
effect is larger for acrylic acid than for methacrylic acid.
The reduction of t('qm,O within the series of one particular
acid comonomer type, can be related to the charge density
on the latex particles as measured with the streaming poten-

Viscosity in Pa.s
350
300
250
200
15o

/'
10o
t

/
I

5O
O

60

120

180

240

300

Drying time (seconds)


Fig. 9. Change of the viscosity {Pa.s) of the pure vinyl versatate/acrylate latex (VVtAcryl) as a function of the
Filmviscometer Iconditions: 23C, 5t)9~ RH: rolling ball dialneter: 2.0 nlnl; slope: 20%.

drying time

(s), as measured with the TNO-

152

F. Molenaar et al. /Progress in Organic Coatings 30 (1997) 141-158


V i s c o s i t y in Pa.s
1.000

-{7

900

800
700

600

500

400
I

300

200

//

100
0
0

60

120

180

240

300

360

420

480

540

600

D r y i n g time ( s e c o n d s )

Fig. 10. Change of the viscosity (Pa.s) of the pure alkyd emulsion as a function of the drying time (s), as measured with the TNO-Fihnviscometer (conditions:
23C, 50% RH; rolling ball diameter: 3.0 ram: slope: 45).

tial method. This reflects the occurrence of a secondary


electroviscous effect in these latexes, leading to higher viscosities at constant volume fraction for increasing surface
charge density or higher acid levels, as it has been observed
and discussed earlier in the framework of the Quemada
rheological model applied for the in-can latex systems
(see Section 3.2.2.3).

4.2.2. Effect of coalescing agent


4.2.2.1. Binder~coalescent systems. Upon

addition of
coalescing agents to the pure latexes, the slopes of the
viscosity increase remain roughly unchanged. However,
the effects of coalescent expressed as t(r/m,0, are large
(see Table 10 and Fig. 11).
Viscosity in Pa.s
l no coalesent

=PM<EB

The t(r/max) values for non-thickened binder/coalescent systems are not mainly determined by the initial in-can viscosity (see Table 11). This can be best shown by comparing
the data for TEX with those for EB. At the shear rates close
to those relevant to the filmviscometer at the onset of the
measurement ( 1 0 - 2 0 s ~) the TEX containing latexes B76
and B79 have a much lower viscosity than the EB counterparts. If the initial viscosity were the determining para-

The viscosi b, (Pa.s) of the coalescent containing latices B76 (BMA/AA)


and B79 (BMA/MAA), shown as a function of shear rate

300 t ' Tex


I

-~ P n B
250

TEX<PnB<

Table I 1

35O

It was generally found that, for the BMA/AA latex (B76),


the B M A / M A A latex (B79) and the vinyl versatate/acrylate
latex (VV/acryl), TEX leads to a reduction of t(rtm,x) and EB
to an increase as compared to the pure binder. PnB and PM
are intermediate. The general order for t(r/ma,) found is:

j ,, EB

200 q

Latex

shear
rate (s a)

B76

5
10
50
100
200
5
I0
20
50
100
200

150
i

100

B79
50

60

120

180

240

300

360

420

480

540

600

Drying time (seconds)

Fig. I1. Effect of addition of coalescing agents to the latex B125 on the
viscosity (Pa.s) as a function of the drying timc (s), as measured with the
TNO-Fihnviscometer (conditions: 23C, 50% RH: rolling ball diameter:
1.5 mm: slope: 15; coalescent level: 10% b.w. on solids).

PM

PnB

EB

0.0227
0.0127
0.0105
0.0093
0.0420

0.0150
0.0120
0.0110
0.0099

0.0960

0.0132
0.0098
0.0081
0.0071

TEX

O.029O
0.0200
0.0130
0.0131 0.0110
0.0091 0.0094
0.0829
0.0337
0.0149
0.0098

HPV

0.0220
0.0160
0.0175
0.0219
0.0216

0.0114
0.0110
0.0084
0.0076

0.0130
0.0100
0.0088

The values discussed in the text are in italics and show that the viscosity at
the lower shear rates is substantially lower for the TEX than for the EB
containing latices, in spite of the much stronger latex particle swelling by
TEX.

F. Molemmr et al. / P r o w e s s in Organic Coatings 30 (1997) 141 15~?

meter for t(%,~,O, then TEX should lead to the highest


t(rlm~0. However, the reverse was fkmnd. So, at least one
other parameter plays a determining role for the t(rl ......)
values.
It was possible to explain the relative order of t(rl,,,~,~) for
PM, PnB and EB in non-thickened, and also in thickened
and pigmented latexes, by assuming that the evaporation
kinetics of the continuous phase (i.e., a mixture of predominantly water and coalescent) play a very important role.
Based on thermodynamic calculations using computer
programmes the following rates of evaporation of mixtures
of water and coalescents were predicted at 50% relative
humidity and moderate levels of coalescent (e.g., 5-10%,
which are values below the respective pseudo-azeotropic
concentrations):
PnB > PM > EB
This predicted order of evaporation rates agreed well with
the relative order of the t(~lm~,0 values and the weight loss
measurements of the latex films containing the respective
coalescents.
The effect of TEX on t(rlm,,~) is probably due to the very
low distribution coefficient, resulting in a strong reduction
of the T~ of the latex particles, from above to below the
experimental temperature (T~(VV/acryl): 32C; ~(B76):
33C; T~(B79): 36C: values measured by CoRI, after conditioning at 22C and 98% RH). Apparently, at higher
volume fractions which are reached during the evaporation
process, the interaction of the rubbery ('sticky') particles
containing TEX increases relatively strongly, and, therefore, the viscosity rises and tO/ ......) is relatively low.
However, in the styrene/acrylate binder B125 (having a
lower T~, i.e., 28C (CoRI, after conditioning at 22C and
98% RH)), addition of TEX does not result into a decrease
Viscosity in Pa.s
350

--i ~> T e x + H E U R

300

' - PnB+HEUR

,!

153

Table 12
Comparison of TNO Fihnviscometer results (t(~,,,,~O) with in-can viscosity
measurements at a shear rate of 1 s ~ (rlr(t = 0): see text) and dynamic
viscosity results (at 0.1 Hz) for the thickened VV/Acryl latices (thickener
level: 0.1% b.w. on total weight: 0.2% on water content)); also, the tendency of thickener adsorption onto the latex particles is indicated
Addition

t(rl,,,~J ~/,
(see) ~ (t = 0)

Dynamic theology Adsorption


(0.1 Hz)
tendency
(~- potential) b
~1' (Pa.s) G" (Pa)

Pure
+ 5% Water (RefS)
HEC
Aliph. HEUR
Arom. HEUR
HMHEC-I
HMHEC-2
HEUR-UI
HEUR-U2

370
470
380
300
450
520
500
310
430

38
16
<l
< 1
26
l0

88.0
17.1

61
4.0

46.4
34.7

43.7
35

+ + + +
++
+
+
+ + +
+ + +

"Conditions: rolling ball diameter, 3.0 ram; slope 45 , 23C. 50%RH.


hTendency of thickener to adsorb onto the VV/Acryl latex particles,
determined with zeta-potential measurements; see text.
"Diluted to the same solids content as the thickened latices.

of t(rtm~), although the relative order for the respective coalescents is the same for this binder (Fig. 11). It is possible
that the degree of sintering of the latex particles during the
drying process, on the time scale of the measurement with
the filmviscometer, also plays a role according to the drying
mechanism proposed by Winnik and Feng [16]. This means
that the lower Tg particles (of B125 containing TEX)
deform to a larger extent in the region close to the drying
front, which leads to narrower capillaries between the latex
particles resulting in a lower rate of water transport and a
lower rate of evaporation. Due to this contribution, the overall effect of TEX in B 125 apparently results into a delay of
the viscosity peak, i.e., an increased t(rlm~x) as compared to
the pure latex.
4.2.3. Effect of thickener

* EB+HEUR
250

iI
200
150
1 O0

,>4

50

i'

,/

.,

,'
j

[
I

. .,,.~..~/%

0
0

60

120

180

240

300

360

420

480

Drying time (seconds)

Fig. 12. Effect of addition of the aliphatic HEUR Ihickener and additionally different coalescing agents to the latex B 125 on the viscosity (Pa.s) as
a function of the drying time (s), as measured with the TNO-Filmviscomeler (conditions: 23C, 50% RH: rolling ball diameter: 2.5 mm; slope:
15 " coalescent level: 10% b.w. on solids: thickener level: (I.5% on total
weight).

4.2.3.2. Binder~thickener systems. The effect of thickener


addition to a latex as detected with the TNO Filmviscometer is generally very large: t(rl ..... ) is substantially
lowered and, moreover, the shapes of the viscograms
change dramatically. The viscosity increase, as a function
of drying time, is much more gradual than in case of pure
binders or binder/coalescent systems (Fig. 12).
The more gradual viscosity increase due to thickener
addition applies to all binder/thickener systems investigated. This includes seven thickeners, of the types hydroxyethyl cellulose (HEC), hydrophobically modified
hydroxyethyl cellulose (HMHEC) and hydropbobically
modified ethoxylated urethane (HEUR) associative thickeners, applied in two model binders (the BMA/AA latex
B76 and the BMA/MAA latex B79) as well as the commercial vinyl versatate/acrylate latex (VV/Acryl). When assessing these binder/thickener systems at equal thickener

f'. Molenaw" et al. /Progress in Organic Coatings 30 (1997) 141 158

154

AA

0 &

-i0

-.~0

oa

-50

o
70

90-

-ll0

0,0

o:2

o:4

o18

t,o

concentration of thickener (g/l)


Fig. 13. Adsorption behaviour of differcnl types of thickeners onto the VV/Acryl latex, as a function nf the thickener content (g/l). The strongest adsorption
onto the latex particles is obscrved lk)r the aliphatic HEUR, which is reflected by the strongest decrease nf the absolute value of the zeta-potential at low
thickener concentrations. The aromatic HEUR shows the lowest adsorption tendency concerning the four HEUR types. The only non-adsorbing thickener is
HEC (see text). + : HEC; O: HMHEC-I: : HMHEC-2: :~: aliphatic HEUR; I1: aromatic HEUR: [Z]: HEUR-UI: i : HEUR U2.

concentrations (0.1% on total weight), the associative


urethane thickeners were in several cases more effective
in reducing t(rl ..... ) than the HEC, while the two HMHEC
thickeners studied, showed in case of the vinyl versatate/
acrylate latex (VV/Acryl), no thickening effect considering
t(rt ......), at the level used (Table 12). Table 12 shows that the
t(rI......) values for the vinyl/acrylate latex could be well correlated with the initial viscosities determined from flow
curves and expressed as the relative viscosity rt, (= rl (thickened system)/rl(non-thickened latex). The viscosity at a
shear rate of 1 s ~ is considered here, since this is roughly
the rate for the filmviscometer experiments. It must be noted
that the correlation found between t(r/m~O and the initial
viscosity rl(t = 0) for the thickened VV/Acryl latex is in
contrast to the results for binder/coalescent systems. Also,
the dynamic rheological results (see Section 3.4.2) agree
well (Table 12), when considering the values at 0.1 Hz, as
this frequency is roughly most relevant for the filmviscometer experiments. Thus, the higher the dynamic viscosity
r/', which is related to viscous flow, and the higher the storage modulus G'(at 0.1 Hz), which is related to the elasticity
of the system, the lower t(rl.n,~,) fl)r the four HEUR associative thickeners studied.
The interrelations discussed so far can be further
extended to the adsorption behaviour of the thickeners
onto the latex particles under consideration. Zeta-potential
measurements can be used to study thickener adsorption
onto dispersed particles [ 17]. A rapid decrease of the absolute value of the zeta potential measured as a function of the
concentration of non-ionic thickener, suggests adsorption of
the thickener, since thickener adsorption causes the plane of
shear to be moved outwards fi'om the particle. Any desorption of anionic emulsifier due to thickener adsorption
would further increase the effect on the zeta potential,

The following order of decreasing tendency to adsorb


onto the VV/Acryl latex particles was found by YK1 (Fig.
13):
Aliphatic HEUR > H E U R - U 2 , H E U R - U 1
> aromatic HEUR, H M H E C - 1 H M H E C - 2 >> HEC
Fig. 13 shows that all thickeners do adsorb in this latex
(under the conditions applied in the zeta-potential measurement, e.g., at the (low) polymer solids content chosen (0.5%
b.w.)), except the HEC thickener. The linear increase of the
absolute value of the zeta-potential for HEC is presumably
due to the invalidity of the Smoluchowsky equation in this
particular case leading to erroneous zeta-potential values for
the HEC thickener.
When studying competitive adsorption by adding extra
emulsifiers, it appears that all four HEUR type thickeners
are able to compete with model emulsifier types, which are
comparable with those used in the VV/Acryl latex. However, the HMHEC thickener does not adsorb. Therefore,
taking into account the sensitivity to surfactant concentrations, a more general ranking for the thickener adsorption
tendency is:
Aliphatic HEUR > H E U R - U 2 , H E U R - U I
> aromatic HEUR > HMHEC >> HEC
As the additional junction points of hydrophobic moieties
which are generated at the latex particle surface by thickener adsorption, contribute very strongly to the transient
physical 3-dimensional network of associative interactions
(see Section 3.4.1 ), it can be expected for the four HEUR
type thickeners considered here, that the aliphatic HEUR
gives rise to the highest storage modulus G', the aromatic

F. Moh'nam" el al. /Pro~,,re~~ m 0 ",wmic Coaling.s 30 (1997) 141 1.58


Table 13
Filmviscometer restills sl*~o,a,ing the time period rc'quired to reach a high
viscosity of 8411 P:.t.s for the thickenecl alkyd cnlulsions, as c o m p a r e d to the
VVfAcryl latex ( 0 . 1 q b.w. of Ihickcncr on total v, cight)
Thickener

I(840 Pa.s) (s~


Alkyd e m u l s i o n '

t ~]lfltK ) (S)
VV/Acr,,I latex'

Pure
+ 5qf waler i' Reference

8(10
990

370
47(1

HI:.("
HMHEC I
HMHEC-2
Aliphatic H E U R
Aromatic H E U R
HEUR UI

630
931)
720
910
,821)
,850
,830

3,8(1
52(1
51)(1
30(}
450

HELIR-U2

310

43()

~'Measurin,_,+ condilit'n'~s: __
v3 :~C. 5 0 q RH: ball d i a n l e t e r = 3 . 0 ram. slope = 45 ~
hDihlted with ,aater to the same solids contcnl as the thickened binders.

HEUR to the lowest and the two urea modified HEURs are
intermediate in this series. This was indeed measured (see
Table 12).
in smnmary, the thickening efficiency did not change
during fihn drying and could be related to the initial rheological behaviour of the thickened latexes.
In the case of an alkyd emulsion, HEC. and to a lesser
extent, the HMHEC (i.e. HMHEC-2) were found to reduce
t(r/ ......) substantially more strongly than the HEUR associative thickeners (Table 13), which is in contrast to the acrylate or vinyl/acrylate type latexes. This is due to the
difference of thickening mechanism combined with the
hydrophobic/hydrophilic nature of the binder particles: the
associative thickeners are more efficient in case of hydrophobic and snlall size binder particles Ithe alkyd emulsion
droplets arc relatively polar and signilicantly larger),
whereas the HEC acts ~ia the continuous water phase via
hydrogen bridges, coiling and chain entanglements,
mechanisms which are principally independent of the nature
of the surface of the polymer particles.

period, it does not change the characteristic effect on the


viscosity changes during drying which is typical for the
coalescing agent used. This means that the relative order
of t(r/ ......) found for TEX, PnB and EB m thickened latexes
was generally the same as in case of the corresponding
binder/coalescent systems for all binder systems studied
(the B M A / A A binder B76. the B M A / M A A binder B79,
the styrene/acrylate binder B125 and the vinyl versatate/
acrylate binder VV/acryl; see Fig. 12):
TEX < PnB < EB
Also, in titanium dioxide pigmented thickened latex
systems the same trend was observed for /('qmax) (at
10c4 and 18% PVC), for the coalescents studied (see Fig.
14).
This agrees with the explanations given in Section
4.2.2.

4.2.4.5. Comparison q[ the ~1~bcts of coalescent and


thickener
In the case of thickened, coalescent containing latexes the
t(r/ ......) value is determined, to a large extent, by the thickener, i.e., by the initial in-can rheology. The thickener, when
added at usual levels, generally has a higher impact on
t(rh,,, D than the coalescents, as expected. If the thickener
type and level, used in the same latex binder type, are constant, while varying the coalescent type. then the observed
significant differences in t{rl......) are determined by the coalescent. This should be related to differences in evaporation
kinetics, latex particle swelling and particle interactions due
to the interference of coalescents. Thus, a coalescent can be
used as a theology modifier, in addition to thickeners,
because of its significant effect on t(rl ......) and on levelling
and sagging (see Section 5).
Viscosity in Pa s

,1

350

300

i
,I

250

4.2.4. E~but.s o/ the comhitwd I,U.veme Of coalescent and


thickener

155

,k

,i

200
150

4.2.4..?. E~bct of thickener. The efliect of the thickeners


investigated, on binder/coalescent systelns as determined
with the TNO fihnviscometer, is comparable with the
corresponding coalescent flee systems: llr/,,~,~) is lowered
substantially and the viscosity increase upon drying time, is
much more gradual than in case of pure binders or binder/
coalescent systems. The value of t(r/,~,~,) was lowered most
strongly for the urea modified HEUR (HEUR-U2 studied
for the B M A / M A A latex B79) and more strongly for the
aliphatic HEUR than for the HMHEC-2.

100

j,
,P
,,1'

50

Tex

I PnB
EB
T

6O

120

180

240

300

360

420

480

I~

"

540

600

Drying time (seconds)

4.2.4.4. E~,ct qf coalescent. Although the addition of

Fig. 14. Efiecl of the addition of coalescing agents to a pigmented, thickencd formulation based on the latex B I 2 5 . on Ihe viscosity (Pa.s) as a
function of the drying time {s), as measured with the T N O - F i l n w i s c o m e t e r
(conditions: 2 3 ' C . 5(I<A RH: rolling ball diameter: 2.5 ram: slope: 15;
pigment: titaniuln dioxide. I(YA PVC: thickener: the aliphatic HEUR,
1.29k b.w. based on tile water phase: level of coalescents: 109i on binder

thickener shifts the viscosity peak to tin earlier time

"a cigh! I.

F. Molenaar el al. /Progress in Organic Coatings 30 (1997) 141 158

156

5. Implications on sagging and levelling


5.1. Relation between t(~,,,,O and levellingAagging
behaviour
A qualitative relation between t(rl ......) and levelling/sagging was generally observed within an analogous series of
experiments, in which, e.g., only the coalescent or thickener
type is varied (assuming that the shapes of the viscograms
and the initial viscosities are comparable). A simple rule of
t h u m b is used: the higher t(rtn,~,O, the more time is available
for levelling and sagging and, as a consequence, the higher
the extent of levelling and the lower the sag resistance.
The correlation between sagging/levelling results and
t(r/,,~) was generally much better than with weight loss
m e a s u r e m e n t s or drying time and open time results as determined with a standard drying recorder (Table 14).

5.2. Effect q[ coalescents


Regarding the effect of coalescents, a trend for sagging/
levelling can be observed which agrees with the ranking
found for t(rh~,0 for both clear and p i g m e n t e d formulations.
In order of decreasing t(rl ..... ), extent of flow and (undesired)
sag tendency the ranking is:
EB > PnB > TEX
In general, EB enlarges t(rl,,,~) for all types of systems
investigated (binder/coalescent, binder/coalescent/thickener, binderlcoalescent/thickener/pigment/dispersant systems) and increases the tendency to level out and to sag
(see the summarising Table 15).
T E X lowers t(rl,,~,~) strongly, in'espective the presence of
a thickener and/or pigment (studied up to 18% pigment
v o l u m e concentration in case of the styrene/acrylate latex

Table 14
Practical coating properties for thickened latex formulations (based on the
BMA/MAA latex B79:0.2~,4 thickened, on water phase weighl) demonstrafing the gnud correlation between sagging/levelling and ti~,,,~,), as
opposed lo the findings for the drying time and open time as measured
with a standard drying recorder, which seem contradictory to the sagging/
levelling data: also, coalescents are shown to act as rheology modifiers
Thickener Coalescent Drying Open z(rl,,,~,,! Sag
Levelling
time
time (s)
tvsistance (ASTM)"
(sl
(s)
(#m)
HMHEC-2
TEX
PnB
EB
HEUR-U2
TEX
PnB
EB

1630
1610
1290
1320
1150
1480
1I 10
1040

h
l l(I
1010
430
950
710
740
680
i,
<150
1250
290
56[)
400
690
490

175
>200
175
75
>200
>200
>200
175

~Ranking: 0 - very poor levelling: 10 - excellent flow.


"Experimentally difficuh to quantif3..

9
7
10
10
0
0
I
3

Table 15
General trends observed for the effects of coalescing agents on acrylate
and vinyl/acrylate latex furmulations (see text).
Coalescent
EB
PM
PnB
TEX

Relative
t07,,,~0
evaporation rat&
Slow
Medium
Fast
Variable

>
+
_+
<

Levelling
+
_+
_+
-

Sag
resistance
-_+
+

~*Relativeevaporation rate from films of the formulated latices, determined


with weight loss measurements and, tior the volatile coalescents (except
TEX), being in agreement with thermodynamic calculations.

B125). T E X tends to improve the sag resistance and to


detract from levelling, although this was demonstrated for
the styrene/acrylate formulations (B125) in a less pron o u n c e d way than for the B M A / M A A (B79) systems and
the vinyl versatate/acrylate (VV/Acryl) latex systems.
Regarding t(r/max), sagging and levelling, PnB and PM are
intermediate when compared with EB and T E X (Table 15).
The aforementioned trends are exemplified in Table 14.

5.3. Effect o f thickeners


As expected, the thickeners were shown to have a strong
effect on levelling and sagging.
With respect to the effect of thickeners (in binder/coalescent/thickener systems), the same general trend was found:
the lower t(r/m,~x), the lower the extent of flow/levelling and
the better the sag resistance.
These trends were found for all systems studied (based on
the B M A / M A A latex B79, the styrene/acrylate binder B 125
and the vinyl versatate/acrylate latex (VV/Acryl)), although
in a somewhat less p r o n o u n c e d way for the styrene/acrylate
system.
The effect of the four different H E U R type thickeners on
the levelling behaviour of the VV/Acryl latex could be
related to the in-can d y n a m i c rheology. The latex/thickener
system having the lowest storage modulus G" and the highest loss factor (tan6) due to the most moderate adsorption
tendency of the thickener onto the latex particles (i.e., the
aromatic HEUR) was shown to level most readily (see Table
12, Section 4.2.3 and Section 3.4.2 (Fig. 5)).

6. Conclusions
6.1. Rheology in-can
6.1.1. Pure latexes
The Q u e m a d a model is very suitable to describe and
interpret the rheological in-can behaviour of latex systems.
A wide systematic series of acrylate c o p o l y m e r latexes was
studied (T,~: 2 4 - 4 1 C, stabilised with one fixed type of anionic emulsifier at a constant level). It was shown that the

k. Molenuar el al. / Proqu'evs in Organic ('oaling.s 30 119971 141 15~'>'

shear thinning behaviour and, more specifically, the latex


particle structure, was only slightly dependent on the copolymer composition, with respect to both the acid comonomer type and level, and the hydrophobicity/hydrophilicity of
the copolymer. The particle structure was shown to be
slightly dependent on the pH (i.e., pH = 2 versus 9 after
neutralisation). However, due to neutralisation to pH = 9.
the viscosity at high shear rates and, associated therewith,
the hydrodynamic volume of the latex particles increase
substantially. This is especially found when the acid comohomer content increases. The effect is stronger for acrylic
acid than for methacrylic acid. As no panicle swelling was
detected upon neutralisation (with photon correlation spectroscopy (PCS)), this behaviour can be assigned to a secondary electroviscous effect. This agrees with the electrical
surface charge density of the latex particles, which was
measured with the streaming potential method.
Concerning the neutralised model latexes, the effect of
the hydrophobicity/hydrophilicity of the copolymer, at
equal acid comonomer level and type, on the viscosity at
high shear rate and, equivalently, on the apparent hydrodynamic volume was shown to be very moderate.
6.1.2. Eff~ct of coalescing agents
Addition of coalescing agents to latexes leads to higher
viscosities. The increase of the effective hydrodynamic
volume of the latex particles is generally roughly equal to
the volume increase that can be calculated based on the latex
formulation and the experimentally determined distribution
coefficient of the coalescent.
6.1.3. Effi~ct o f thickeners
Associative thickeners of the HEUR type, were shown to
efficiently thicken waterborne systems to a viscosity profile
that approaches paint formulation requirements. Furthermore, it was demonstrated that different types of HEUR
thickeners can lead to substantially different dynamic viscoelastic properties and that the thickening efficiency
depends on both the thickener and the binder type.
The thickener efficiency could be related to the adsorption behaviour of the respective HEUR thickeners onto the
latex particles, as found with zeta-potential measurements.
For the thickening efficiency, the contribution of the adsorption onto the particles is more important than the generation
of a transient physical network of thickener hydrophobes in
the continuous water phase. The latter contribution concerns
the formation of micelles or aggregates of thickener hydrophobes, possibly with interference of surfactant molecules.
The associative interactions between HEUR thickeners
and dispersed binder particles are enhanced in case of a
higher hydrophobicity of the particle surface and for smaller
particle size binders. This was exemplified by a comparison
between a hydrophobic, relatively small particle size vinyl
versatate/acrylate copolymer latex and an alkyd emulsion
characterised by a relatively hydrophilic particle surface and
a relatively large particle size.

157

6.2. Rheological changes during drying and sagging/


levelling behaviour

The TNO filmviscometer was shown to be very suitable


to follow the theological changes in a freely evaporating,
drying latex film. Effects of the binder type, including the
above mentioned secondary electroviscous effect, different
types of coalescing agents and thickeners (HEC, HMHEC,
HEUR) can be detected during drying.
Practical coating properties were determined for the latex
formulations (sagging, levelling, drying time, open time)
and compared with the initial in-can rheology (flow curves
and dynamic theology) and the theological changes as measured during drying with the TNO filmviscometer. A general trend was found for latex systems within a systematic
series of formulations, in which, e.g., the coalescent or the
thickener type was varied (while having comparable initial
viscosities): the larger the time to reach the viscosity peak
during drying, the better the levelling and the lower the sag
resistance. This rule of thumb for sagging/levelling behaviour correlated in many cases much better than weight loss
data and the drying time and the open time, as determined
with a standard drying recorder.
The effect of thickeners on sagging and levelling could be
related to both the theological behaviour during fihn drying,
as concluded above, and to the in-can theology. The in-can
rheology correlates to the adsorption behaviour of the associative thickeners onto the latex particles, as studied with
zeta-potential n~easurements.
Coalescing agents have a significant to large effect on
the theological behaviour during drying and the levelling
and sagging properties. The characteristic theological
effects of different coalescing agents are preserved upon
addition of thickener and pigment. Concerning volatile coalescents, these effects can be related to the evaporation
kinetics of the formulated latex, as determined with weight
loss measurements on films and as predicted with thermodynamic calculations. For a non-volatile hydrophobic coalescent the behaviour was attributed to mainly the swelling
of the latex particles, due to the absorption of coalescents
combined with a reduced effective ~, and the resulting
enhanced panicle-particle attractive interactions at the
lower shear rates.
The rheological changes during drying due to different
coalescents could be monitored with the TNO filmviscometer. However, it was not possible to deduce these
effects from the initial in-can viscosity. As coalescents
change the rheology during drying, typically due to evaporation, one cannot merely rely on the determination of
the in-can rheology when optimising, e.g., sagging and
levelling behaviour. Then rheological measurements as
a function of drying time are essential. When studying the
effects of thickeners in coalescent free systems, however,
the characterisation of the in-can rheology is useful, since
thickeners cannot - as opposed to coalescents - change
the continuous phase composition by evaporation of itself

158

F. Molenaar et al. /Progress in Or,~anic Coatings 30 (19971 141 158

or modify the effective latex particle T,g by absorption/desorption. In these systems the in-can theology is relatively
preserved during drying.

Acknowledgements
The investigations were carried out in the framework of a
BRITE/EURAM programme (PL41911. We gratefully
acknowledge the support of the European Union, the Swedish National Board for Industrial and Technical Development (NUTEK), and each of the 21 sponsoring companies
from all over Europe. We have appreciated the intense and
pleasant cooperation and many constructive discussions
with the EU, especially with Prof. C. Kiparissides and Dr.
C. Tokamanis, the project partners (CoRk Forbairt, PRA,
TNO, YKI), and the participating companies. With respect
to the rheology work presented here, the authors like to
mention the valuable contributions of Mr I. Szigetvari
(CoRI), H. van Bracht, R.M. Meertens, P. Vink (TNO)
and Dr. M. Boutonnet Kizling (YKI).

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