Drying of Alkyd Emulsion Paints

Drying of Alkyd Emulsion Paints

P.K. Weissenborn*† and A. Motiejauskaite*—Institute for Surface Chemistry*
and Royal Institute of Technology†

INTRODUCTION

T The drying and film formation of long oil alkyd

he development of alkyd emulsion-based coat-
ings has resulted, like many other waterborne
and powder coatings, from the harmful effects of emulsions was investigated with emphasis on loss
organic solvents used in solventborne coatings on the
environment and paint users.1 The first generation of of dry upon storage. The main reason for loss of
alkyd emulsion and waterborne paints in general were dry was adsorption of the cobalt (drier) on pig-
inferior to their solventborne counterparts, mainly due
to changes in binder chemistry, high levels of surfactant,
ment surfaces as a precipitated hydroxide. Tita-
lack of additives, and inexperience of the formulators. nium dioxides with alumina surface treatment
This resulted in criticism of waterborne paints which, and organic pigments were most detrimental to
unfairly, still remains today. In fact, the myth that
solventborne alkyds are “best” still exists despite the drying. Acrylate- and phosphate-based dispers-
latest generation of alkyd emulsion paints having better ants also deactivated the cobalt, presumably due
performance properties.2 This unfortunate history has
contributed to solventborne alkyds still having a signifi- to complexation and precipitation of the cobalt.
cant share of the total alkyd paint market, especially in Emulsions prepared with an emulsifiable cobalt
the industrial sector where alkyds of shorter oil length
are used. However, the even stricter legislation currently drier containing 2,2’-bipyridyl (complexing agent
being introduced in some countries has meant that the for cobalt) showed the best resistance to loss of
use of solventborne coatings, high-solids coatings, and
even some waterborne coatings (e.g., latex dispersion dry. Atomic force microscopy of films formed
paints based on high Tg latexes) is becoming very re- from the emulsions showed that the emulsifier
stricted. This trend towards zero volatile organic com-
pound content, high performance coatings, especially
migrated to the film surface which, when washed
for indoor application, favors paints based on alkyd with water, leaves holes or pits in the film. The
resin emulsions. pits were arranged in a hexagonal pattern char-
To further increase the acceptance of alkyd emulsions
in the industrial and do-it-yourself sectors, research on acteristic of Bénard cells, which form due to sur-
the drying properties of alkyd emulsions is required. face tension and/or temperature gradients gener-
Drying of alkyd resin based paints (solvent- and water-
borne), which rely on autooxidation, usually have very
ated in the film during evaporation of water.
good drying times shortly after they have been pre-
pared, due to the addition of cobalt carboxylate driers spite this experience being known to industrial users of
which catalyze autooxidation. However, after a period alkyd paints and drier manufacturers, little research has
of aging (6 to 24 months in the sealed can), the drying been published in an effort to better understand this
time often increases by several hours or the paints do not problem (for a brief review, see Bergenståhl et al.3). Drier
dry at all, which can be very annoying and expensive if manufacturers have developed driers to help prevent
the paint has already been applied to the substrate. De- “loss of dry” upon storage. These driers contain a chelat-
ing agent, which help maintain the catalytic activity of
the drier.4 An even larger threat to the drying time and
*Box 5607, SE-11486 Stockholm, Sweden, E-mail: peter.weissenborn stability of alkyd paints comes from European health
@surfchem.kth.se.
†Department of Chemistry, Surface Chemistry, SE-100 44, Stockholm, legislators taking steps to minimize or stop the usage of
Sweden. cobalt in paints. Hence, there is a clear need to under-

Vol. 72, No. 906, July 2000 65

P.K. Weissenborn and A. Motiejauskaite

stand the reasons for the loss of dry in current and future PIGMENTS: The pigments added to the LO83 long oil
generations of alkyd emulsion paints. alkyd emulsions and tested for their effect on drying
Ongoing research on alkyd emulsion paints is follow- time and loss of dry are listed in Table 1. The titanium
ing a similar route to that of latex dispersion paints. In dioxide pigments were supplied by Tioxide Europe Ltd.,
addition to investigations on the drying properties of England. The colored pigments were supplied by Jotun
alkyd emulsions, research is also being carried out on A/S, Norway.
the film formation of alkyd emulsions with the aim of OTHER REAGENTS: All other reagents and solutions were
reducing water sensitivity. Much of the work that has prepared from AR grade solids or solutions of KOH,
been carried out on latex dispersions can also be applied HCl, NH4OH, and NaCl. Double distilled water was
to alkyd emulsions. In this paper, results from a system- used in all experiments.
atic investigation on the loss of dry upon storage of long
oil alkyd emulsions are presented, along with some pre-
liminary results from a study on the film formation of Methods
long oil alkyd emulsions.
ALKYD RESIN EMULSIFICATION:
Driers added to alkyd prior to emulsification: The drier
EXPERIMENTAL was added directly to the LO83 alkyd resin. Cobalt con-
centration was typically 0.05% w/w per alkyd. If neces-
Materials sary, the drier/alkyd mixture was heated (under nitro-
gen) to aid dissolution/dispersion of the drier. An equal
ALKYD R ESINS: A long oil alkyd resin based on weight of water containing the emulsifier (pre-dissolved)
pentaerythritol, isophthalic acid, and tall oil fatty acids was added. The mixture was stirred gently and the pH
was used for the investigation on the drying properties increased to ~7 with a 50% solution of KOH (4-5 drops
and loss of dry upon storage of alkyd resin emulsions. required per 150 mL of alkyd/water mixture). The mix-
The oil length was 83%, and the acid value was between 6 ture was stirred (magnetic stirrer bar), heated to the
and 9 mg KOH/g alkyd. For further reference in the text, emulsification temperature, usually between 50 and 60°C,
this resin will be designated LO83. The alkyd resin used and introduced into a high pressure homogenizer
for the film formation study was based on pentaerythritol, (Microfluidizer TM-120 from Microfluidics). Emulsifica-
phthalic anhydride, and tall oil fatty acids. Oil length tion was carried out for a period equivalent to about
was 70% and the acid value was between 5 and 10 mg three passes of the total sample through the homogeni-
KOH/g alkyd. For further reference in the text, this resin zation cell (the length of time was dependent on sample
will be designated LO70. volume, which usually was about 150 mL). The tem-
perature was measured immediately after homogeniza-
EMULSIFIERS: Conventional surfactants were used for tion and droplet diameter, pH, and Brookfield viscosity
the emulsification of the alkyd resins. The LO83 resin within 24 hr.
was emulsified with a fatty alcohol ether sulphate
(C12EO30-SO4-Na2) used as a 32% active aqueous solu- Large batches of emulsions (up to 1.5 L) with either
tion or a fatty alcohol ethoxylate (C12/C14EO30) used as cobalt neodecanoate or cobalt caprioate were prepared
a 65% active aqueous solution. for the work with the additives and pigments. The same
batch of emulsion was used for all the tests.
D RIERS: Cobalt (II) chloride hexahydrate, cobalt
Driers post-added to emulsions (emulsifiable cobalt drier
caprioate, cobalt neodecanoate, and a water emulsifiable
and cobalt chloride only): Large batches of emulsions were
cobalt drier were used for the surface drying time and
prepared as previously mentioned, but with alkyd, wa-
loss of dry upon storage tests. The water emulsifiable
ter, and emulsifier only. The emulsifiable cobalt drier or
cobalt drier consists of cobalt neodecanoate, surfactants,
cobalt chloride were post-added to the emulsion with
and 2,2’-bipyridyl in a mineral spirits carrier. Driers
vigorous shaking from a vibrating test tube shaker
were supplied by OMG Europe GmbH, with the excep-
(Vibrax). The cobalt chloride was added as a concen-
tion of cobalt chloride (Merck, pro analysi, 1.02539).
trated aqueous solution (volume <1 mL).
DISPERSANTS: A wide range of dispersants were tested
ADDITION OF DISPERSANTS TO LO83 ALKYD EMULSIONS:
for their effects on the drying and loss of dry upon
Dispersants were post-added dropwise (as supplied)
storage of the LO83 emulsions. Details of dispersants are
with shaking to small aliquots (~20 g) of emulsion. The
given in the Results and Discussion section.
emulsion was shaken vigorously for two minutes on a
vibrating test tube shaker, transferred to a
Table 1—Pigments Used for the Loss of Dry Upon Storage Tests
shaking or rotating table, and gently shaken
2 -1
for 24 hr before measuring the drying time.
Pigment Type / Surface Treatment Surface Area (m g )
Dispersant concentration was 2.0% w/w per
Red ........................... Organic 17 emulsion. Since no pigment was present, this
Blue ........................... Phthalocyanine 36 concentration represents a large excess of free
Black ......................... Carbon black 30 dispersant (non-adsorbed). In a real formula-
Brown ....................... Iron oxide 9
TiO2 - 1 ...................... 4.6% alumina, organic coating 15 tion, the free dispersant concentration would
TiO2 - 2 ...................... 1.9% silica, 5.5% alumina, organic coating 17 be much less, however, the aim of this work
TiO2 - 3 ...................... 9.5% silica, 4.5% alumina 30 was to establish and exaggerate which dis-
TiO2 - 4 ...................... 99.5% TiO2 , no treatment 8 persants cause loss of dry.

66 Journal of Coatings Technology

 Drying of Alkyd Emulsion Paints

ADDITION OF PIGMENTS TO Table 2—Composition of Pigment/Alkyd Mixtures

LO83 A LKYD E MULSIONS :
Addition of the pigments Total Pigment
Pigment Pigment (wt%) Dispersant (wt%) Alkyd (wt%) Water (wt%) Surface Area (m2)
to the alkyd emulsions was
carried out in two steps. Red organic ................... 21.2 1.0 23.8 ~52 180
First the pigment was dis- Blue organic ................... 10.0 1.0 23.8 ~63 180
Carbon black ................. 12.0 1.0 23.8 ~61 180
persed in dispersant solu- Brown iron oxide ............ 40.0 1.0 23.8 ~33 180
tion using a Dispermat CV TiO2 - 1 ............................. 24.0 1.0 23.8 ~49 180
laboratory dissolver with TiO2 - 2 ............................. 21.2 1.0 23.8 ~52 180
either a dissolver impeller TiO2 - 3 ............................. 12.0 1.0 23.8 ~61 180
or bead milling accessory TiO2 - 4 ............................. 22.5 1.0 23.8 ~51 90
(plus ceramic beads), and Balance is emulsifier (1.2 wt%) and cobalt drier. Dispersant was an anionic block copolymer. Water concentration is
approximate. Total sample weight was 50.0 g.
second the alkyd emulsion
was mixed in with the pig-
ment slurry using the dissolver impeller at slow speed to BK DRYING TESTS: Beck-Koller drying tests were car-
avoid shear destabilization of the alkyd emulsion drop- ried out using a standard BK drying recorder from Mickle
lets (pre-checked by measuring droplet size distribu- Laboratory Engineering Co. Before sampling the emul-
tion). Finally, the mixture was allowed to shake approxi- sions, they were shaken for two minutes with a vibrat-
mately 24 hr on a shaking or rotating table to ensure ing test tube shaker. Films of wet film thickness 60 µm
good mixing before measuring the drying time. The first were applied to a glass plate using a six-holed film
step of producing a stable pigment dispersion was diffi- applicator and automated bar coater, which pushed the
cult and a trial and error approach was used to produce applicator along the glass plate at a uniform and con-
the best possible dispersion. For some pigments this was trolled speed. Surface drying time was measured in a
not possible and pigment flocculation resulted. All pig- room thermostated at 23±1°C and 50% relative humidity
ment/emulsion mixtures were shaken daily with a Vibrax (RH). Surface dry was taken as the time at which the
test tube shaker to ensure good mixing and contact be- needle started to lift out of the bulk film and skimmed
tween the pigment, alkyd droplets, and solution. Par- along the surface leaving a faint and irregular trace. At
ticle size analysis indicated that some pigments were this time, the surface was also finger touch dry. In some
well dispersed, however, these pigments flocculated cases, it was difficult to determine the exact surface
upon storage, suggesting that the dispersant concentra- drying time, hence, times should be taken as approxi-
tion was too low. The instability of the pigment disper- mates and at best to within ± 0.5 hr (30 min). To improve
sions was mainly due to the choice of the experimental accuracy, all measurements and readings of surface dry-
design which was optimized to allow comparison of the ing times were carried out by the same person, and all
effects of the pigments on loss of dry. For example, samples were measured in duplicate and the times were
optimization of dispersant concentration and correct sol- averaged.
ids level would have resulted in more stable disper-
sions. EMULSION CHARACTERIZATION: Emulsions were charac-
terized in terms of droplet size, pH, and viscosity. Drop-
The pigment concentration was chosen so that the let size was measured using a Malvern MasterSizer MS20.
total pigment surface area in the emulsion was the same This requires dilution of the emulsion (50 to 100 times)
for all pigments, hence, the potential adsorption surface so that scattering of laser light is sufficient for signal
area for cobalt was approximately the same (assuming detection but without saturation. Viscosity was mea-
the coverage of dispersant and any free emulsifier was sured using a Brookfield LVT viscometer at a speed of 30
the same). This approach was preferred over using a rpm.
constant weight percent of pigment which would result
in a wide range of adsorption surface areas and biased FILM FORMATION STUDIES: The alkyd emulsions were
comparisons between the influence of pigments on loss applied to cleaned glass cover slips using a 60 µm cube
of dry. The dispersant was an anionic block copolymer applicator, hence, after drying, the film thickness was
and the concentration was kept constant at 0.5 g per 180 ~30 µm. The films were dried in a controlled tempera-
m2 of pigment. Table 2 summarizes the composition of ture and humidity room (23°C, 50% RH) under open
the pigment/alkyd mixtures. cover to avoid contact with dust. After at least 24 hr
drying, the cover slip was cut to size (about 10 × 10 mm)
STORAGE STABILITY AND LOSS OF DRY TESTS: The drying to allow it to fit in the atomic force microscope (AFM)
time and pH of the emulsions were measured within 24 sample chamber. AFM images of the dry alkyd film
hr after preparation (fresh), and after approximately 7, were obtained using a Digital Instruments Nanoscope
14, and 35 days of storage at 50°C. For emulsions con- IIIa multimode atomic force microscope in the “tap-
taining additives and pigments, the fresh drying time ping” mode and under ambient conditions. Topography
was measured after the 24 hr mixing step (aged one day and phase images were obtained from three to five areas
at room temperature). After 35 days, the droplet diam- distributed over the film. The Z-height and XY scan size
eter was measured. All samples were stored in tightly were varied for each area. A 20 × 20 µm scan size usually
sealed glass vials filled almost to the top. Before sealing gave the most informative images. Washing of the dry
the vial, nitrogen was blown over the sample. These film was carried out under a stream of water (from a
steps were taken to decrease any possible uptake of water bottle). The film was rinsed with approximately
airborne oxygen by the emulsion. 10-20 mL of water and blown dry with nitrogen. Images

Vol. 72, No. 906, July 2000 67

P.K. Weissenborn and A. Motiejauskaite

boxylic acids. The pH decrease can be minimized by use

of isophthalic acid instead of phthalic anhydride during
the synthesis of the alkyd resin.3 To simulate if any
decrease in pH of the alkyd emulsion upon storage can
influence drying time, the pH of the emulsions was
deliberately adjusted over the pH range of 4 to 9. Since
this is not the normal mechanism by which the pH is
lowered, the results only show the potential effect of any
decrease in pH due to resin hydrolysis. Figures 1 and 2
show the results for emulsions prepared using an an-
ionic and a non-ionic surfactant. The emulsions were
aged, and the pH changes monitored.
The results clearly show that an increase in pH causes
a decrease in surface dry time. These results can be
explained by the work of Östberg et al.5 who showed
that cobalt concentration in the alkyd droplets increases
with pH. Their results indicated that higher cobalt con-
Figure 1—Effect of pH and aging at 50°C on loss
centrations in the alkyd phase decreased surface dry
of dry and surface drying time for emulsions
prepared using LO83 alkyd resin, 5% C12EO30- time.
SO4-Na2 w/w per alkyd, and 0.05% Co as cobalt The effect of aging on surface drying time was similar
neodecanoate w/w per alkyd. The fresh pH over the pH range investigated (pH 4 to 9). After 35 days
was 6.89 and droplet diameter d(0.1) = 0.21, of aging at 50°C, the surface dry time increased by ap-
D(0.5) = 0.38, D(0.9) = 0.66 µ m. proximately one and a half to two hours for both emulsi-
fiers. This is not a significant increase and only slightly
greater than the experimental error in surface dry time.
of the washed films were obtained at least 1.5 hr after
washing. Comparison of the results for the two emulsifiers
implies that the non-ionic surfactant gives better drying
at increasing alkaline pH values. This is possibly due to
differences in free cobalt concentrations in the water
RESULTS AND DISCUSSION phase. Since the anionic surfactant contains Na+ as
counter ions to the SO42- group, it is postulated that they
are replaced by Co2+. This would lead to a higher cobalt
Drying Properties of Pure Alkyd Emulsions concentration in the water phase as pH is increased due
to the precipitation of Co(OH)2. Precipitation of Co(OH)2
EFFECT OF EMULSION PH: Storage of alkyd emulsions
from a 0.05% Co2+ aqueous solution (0.008 mol L-1) is
often results in a steady decrease of the pH from about
expected to start at approximately pH 7.5 - 8.0.6
neutral down to about 4-5. This is due to the acid hy-
drolysis of ester linkages and formation of weak car- EFFECT OF COBALT FORM AND LOCATION: For solventborne
alkyd resins, the cobalt is usually added as a carboxylate
salt with carbon number ranging from 6 to 18. In a
waterborne system, the compatibility with water be-
comes a problem and, hence, self-emulsifiable cobalt
carboxylates are used. These can be post-added to the
emulsion and form small droplets in the water phase.
The stability of the drier droplets was not investigated,
but simple experiments in water showed that they would
coalesce and phase separate upon standing for a few
days. The separated phase could easily be re-emulsified.
Since the location of the cobalt in the water phase and its
state as small droplets may inhibit drying time, a series
of tests were developed where different forms of cobalt
were either added directly to the alkyd resin prior to
emulsification or post-added to the emulsion. Results
are shown in Figures 3 and 4.
Figure 3 shows the surface drying time and loss of dry
for the emulsifiable cobalt drier, cobalt chloride, and
Figure 2— Effect of pH and aging at 50°C on cobalt neodecanoate, each added to the alkyd phase
loss of dry and surface drying time for emulsions prior to emulsification (ensuring the maximum possible
prepared using LO83 alkyd resin, 5% C12/ cobalt concentration in the alkyd droplets). The cobalt
C14EO30 w/w per alkyd, and 0.05% Co as co- neodecanoate gave slightly faster drying times but
balt meodecanoate w/w per alkyd. The fresh showed some loss of dry. On average and considering
pH was 7.05 and droplet diameter d(0.1) = 0.22, the experimental error in drying times, the performance
D(0.5) = 0.39, D(0.9) = 0.67 µ m. of the three driers was similar.

68 Journal of Coatings Technology

 Drying of Alkyd Emulsion Paints

Figure 3— Effect of aging at 50°C on loss of Figure 4— Effect of aging at 50°C on loss of dry
LO83 alkyd emulsions prepared using 5% of LO83 alkyd emulsions prepared using 5%
C12EO30-SO4-Na2 w/w per alkyd and contain- C12EO30-SO4-Na2 w/w per alkyd and contain-
ing either the emulsifiable cobalt drier, cobalt ing either the emulsifiable cobalt drier or co-
neodecanoate or cobalt chloride added to balt chloride post-added to the emulsion. The
the alkyd resin prior to emulsification. The co- cobalt concentration was 0.05% w/w Co per
balt concentration was 0.05% w/w Co per alkyd. alkyd.

The comparison in Figure 4 between the emulsifiable The method of resin neutralization prior to emulsifi-
cobalt neodecanoate and cobalt chloride post-added to cation was also investigated by comparing potassium
the emulsion (i.e., cobalt in water phase), where the hydroxide and ammonium hydroxide. Use of ammo-
cobalt neodecanoate exists as droplets stabilized by sur- nium hydroxide showed an immediate effect and in-
factant and the cobalt chloride exists as a dissolved salt creased drying time by about one to three hours relative
solution, shows that the emulsifiable cobalt drier gave to potassium hydroxide. This was presumably due to
slightly faster drying times and less loss of dry. The the formation of the cobalt hexamine complex, which
difference of about one to two hours is not considered deactivated some of the cobalt.3 The emulsifiable cobalt
significant and was surprisingly small given that the drier was least affected by the use of ammonium hy-
cobalt chloride was expected to be relatively easily hy- droxide.
drolyzed and deactivated. There was no significant dif- Aging of the emulsions with a range of cobalt driers
ference in drying time for cobalt added either to the was extended beyond one month at 50°C, in an attempt
alkyd prior to emulsification or post-added (compare to induce loss of dry in the pure alkyd emulsions. All
Figures 3 and 4). emulsions suffered from loss of dry after about six months
These results suggest that location or form of cobalt of storage at 50°C, and either had drying times greater
has no significant effect on drying time or on loss of dry. than 12 hr or did not dry. Droplet stability of the emul-
To confirm this possibility, some key questions must be sions was excellent with no change in droplet size distri-
answered. First, does the form of cobalt influence the bution. The pH had decreased to approximately 5.0-5.5,
distribution of cobalt between the alkyd and water suggesting that hydrolysis of the alkyd had occurred.
phases? Second, how does homogenization influence The decrease in pH may explain the loss of dry, how-
cobalt distribution? If cobalt distribution is independent ever, the stability of the cobalt drier after such prolonged
of cobalt form at fixed pH, and equilibrium is estab- aging must also be questioned.
lished very rapidly (<24 hr), then the results in Figures 3
and 4 are for the same and constant ratio of cobalt in
alkyd to cobalt in water. It may also be that the cobalt Drying Properties of Emulsions Containing
adsorbs at the interface. Cobalt distribution and adsorp- Pigment Dispersants
tion studies are necessary to answer these questions. It
also remains to be tested if these results apply to rate of The effects of six commonly used dispersing agents
hardness development for other alkyd resins. Emulsions on surface drying time and loss of dry are shown in
of medium or short oil alkyds may favor cobalt in the Figures 5 and 6. The first three dispersants (Figure 5,
alkyd phase because cobalt in the water phase may not graphs 2-4 from the top) had very little effect on loss of
be able to diffuse into the viscous alkyd droplets during dry and increased drying time slightly relative to the
film formation. reference emulsion containing no dispersant (top graph
in Figure 5). Film appearance was glossy, smooth, and
OTHER VARIABLES: The effect of surfactant type and transparent.
concentration was briefly investigated. Priority was given
to obtaining a stable emulsion and optimizing the sur- The effect of the second three dispersants (Figure 6) on
factant concentration at the sacrifice of drying time. Non- drying time was already evident in the fresh emulsions
ionic surfactants having long ethylene oxide (EO) chains (i.e., immediate deactivation of the cobalt). In the worst
used in excessive concentrations were detrimental to cases there was no surface dry and even after a few days
drying time. Crosslinkable anionic surfactants based on the films were still tacky. The emulsifiable cobalt drier
amide functionality gave good drying times but suf- was the only drier which resisted complete deactivation,
fered from loss of dry. Anionic surfactants gave good but still had surface drying times more than double the
drying and films, but the risk of some loss of dry upon times for the reference emulsion containing no dispers-
storage increased. ant.

Vol. 72, No. 906, July 2000 69

P.K. Weissenborn and A. Motiejauskaite

For the acrylate-based polymers with either sodium 10-35 and is insoluble in water, which supports formation
or ammonium as counter ions, a possible explanation for of a pseudo cobalt metaphosphate precipitate.
the deactivation of cobalt is exchange with the sodium Since the free dispersant concentration in fully for-
or ammonium ions to form cobalt acrylates. Visual evi- mulated alkyd emulsion paints should be much lower
dence that some form of reaction had taken place was than 2.0% w/w per emulsion, the effect of dispersant
the slight pink color of the emulsions and a cloudy dry may be significantly less dramatic than shown in Figure
film, suggesting that some type of precipitate had formed. 6. However, based on the results shown, the commonly
For the ammonium form, there is the additional possi- used acrylate- and phosphate-based dispersants should
bility of reaction with ammonium ions to form hexam- be carefully tested before using them in a final alkyd
ine complexes.3 This also explains the slightly better paint formulation. At the very least, the dispersant and
drying times for the sodium form. pigment should be added to the emulsion before the
In the case of the sodium hexametaphosphate (SHMP), drier to avoid high free dispersant concentrations and
there is most likely a reaction between the cobalt cations potential immediate deactivation of the cobalt drier. This
and polymeric phosphate anions to form a pseudo co- means that the emulsifiable cobalt driers (or cobalt chlo-
balt metaphosphate precipitate. This is consistent with ride), which can be post-added to the emulsions, should
the observation of a pink precipitate in the emulsions be used and added to the alkyd emulsion after the
after seven days of storage and a cloudy dry film. Cobalt dispersant(s) and pigment(s).
(II) phosphate is pink and has a solubility product of 2 × Comparison between the cobalt forms shows that the
emulsifiable cobalt drier and cobalt chloride gave shorter
surface dry times. This cannot be interpreted as better
resistance to deactivation since the cobalt concentration
was double that used for the cobalt caprioate and

Figure 5—Effect of dispersants on surface dry-

ing time and loss of dry after aging at 50°C of Figure 6—Effect of dispersants on surface dry-
LO83 alkyd emulsions prepared using 5% C12/ ing time and loss of dry after aging at 50°C of
C14EO30 w/w per alkyd. The dispersant con- LO83 alkyd emulsion prepared using 5% C12/
centration was 2.0% w/w per emulsion. Emulsi- C14EO30 w/w per alkyd. Dispersant concentra-
fiable cobalt drier and cobalt chloride used tion 2.0% w/w per emulsion. Emulsifiable cobalt
was 0.10% w/w Co per alkyd. Cobalt caprioate drier and cobalt chloride used at 0.10% w/w
and neodecanoate was used at 0.05% w/w Co per alkyd. The cobalt caprioate and
Co per alkyd. neodecanoate was at 0.05% w/w Co per alkyd.

70 Journal of Coatings Technology

 Drying of Alkyd Emulsion Paints

neodecanoate. The cobalt concentrations used were based did not affect drying time or loss of dry. Its concentra-
on earlier studies on the effect of cobalt concentration for tion was not optimized and kept the same for all pig-
each drier on drying time of pure alkyd emulsions. As ments. Instead, pigment concentration was kept con-
shown in the top graph in Figure 5, the emulsifiable stant in terms of adsorption surface area allowing direct
cobalt drier and cobalt chloride had slightly shorter dry- comparison between the pigments.
ing times than cobalt caprioate and neodecanoate. In The effects of four titanium dioxide pigments and
hindsight, it would have been better to test all driers at four colored pigments on surface drying time and loss of
the same cobalt concentration to allow a valid compari- dry are shown in Figures 7 and 8. Pigmented fresh emul-
son between the different types of cobalt. Nevertheless, sions had slightly longer surface drying times than the
one way of overcoming loss of dry is to use higher cobalt non-pigmented emulsions (compare with the top graph
concentrations such that not all of the cobalt will be in Figure 5). For all but one of the pigments, aging of the
deactivated. emulsions caused longer surface drying times, and, for
the first time, the anticipated gradual loss of dry was
Drying Properties of Emulsions Containing Pigments observed. The colored pigments showed slightly more
or earlier loss of dry than the TiO2 pigments. Carbon
The high molecular weight anionic block copolymer black and red organic had the greatest effect on loss of
was chosen as the dispersant for the pigments because it dry. The suspension pH during aging decreased from

Figure 7—Effect of titanium dioxide and sur-

face treatment on surface drying time and loss Figure 8—Effect of colored pigments on sur-
of dry after aging at 50°C of LO83 alkyd emul- face drying time and loss of dry after aging at
sions prepared using 5% C12/C14EO30 w/w per 50°C of LO83 alkyd emulsions prepared using
alkyd. Constant pigment surface area was 180 5% C12/C14EO30 w/w per alkyd. Constant pig-
m2 in sample suspension except TiO2 (4) which ment surface area was 180 m2 in sample sus-
had 90 m2. Pigment dispersant was the anionic pension. Pigment dispersant was the anionic
block copolymer from Figure 5 used at the block copolymer from Figure 5 used at the
concentration of 0.5 g per 180 m2 of pigment (1 concentration of 0.5 g per 180 m2 of pigment (1
wt%). The emulsifiable cobalt drier and cobalt wt%). The emulsifiable cobalt drier and cobalt
chloride was 0.10% w/w Co per alkyd. The chloride was 0.10% w/w Co per alkyd. The
cobalt caprioate and neodecanoate was cobalt caprioate and neodecanoate was
0.05% w/w Co per alkyd. 0.05% w/w Co per alkyd.

Vol. 72, No. 906, July 2000 71

P.K. Weissenborn and A. Motiejauskaite

between 7.0-6.5 to between 6.0-5.5, similar to that of the tant role, since the treatment is usually based on either
non-pigmented emulsions. polyols, amines, or silicone derivatives which could also
The emulsifiable cobalt drier had the least loss of dry, interact with the cobalt. Pure titanium dioxide clearly
and after 35 days aging at 50°C still gave reasonable showed that a titanium dioxide surface also causes loss
surface drying times. Note, however, that its concentra- of dry, however, since commercial titanium dioxide pig-
tion was double that of the cobalt caprioate and ments have some form of surface treatment, the level of
neodecanoate. Comparison between the emulsifiable co- titanium dioxide exposed to aqueous solution would be
balt drier and cobalt chloride shows that the former very small or zero.
suffered from less loss of dry presumably due to pres- The deactivation of cobalt in the presence of pigments
ence of the 2,2’ bipyridyl complexing agent. is proposed to be due to interaction with the pigment
The results for TiO2 pigments reveal that at an ap- surface and is most probably based on specific adsorp-
proximately constant level of alumina surface treatment tion (chemisorption) of cobalt. The exact form of the
(4.5 to 5.5%), the loss of dry decreases as silica concentra- adsorbed cobalt and adsorption mechanism will be de-
tion is increased from 0 to 1.9 to 9.5%. This suggests that pendent on solution pH, cobalt concentration, and pig-
a silica surface helps minimize loss of dry upon storage. ment surface. For metal ion adsorption on oxide surfaces
The type of organic treatment could also play an impor- in general, the favored model is interfacial precipitation
of the metal hydroxide, which due to interfacial effects,
can occur at pH values below bulk precipitation in solu-

10

15 X 5.000 µm/div 0.5

Z 10.000 nm/div
µm
1.0
11121505.001

1.5 X 0.500 µm/div

Z 5.000 nm/div
µm
03291737.001

10

15 X 5.000 µm/div
Z 10.000 nm/div 0.5
µm
11161402.001
1.0

Figure 9—AFM topographic surface images of 1.5 X 0.500 µm/div

dry films formed from the LO70 alkyd resin dis- µm
Z 5.000 nm/div

solved in mineral spirits (top) with an average 11201512.001

surface roughness (Ra) of 0.214 nm and LO70
alkyd resin emulsified with conventional surfac-
tant (bottom) with average surface roughness Figure 10—AFM topograhic surface images of
(Ra) of 0.216 nm. Ra values measured on a films shown in Figure 9 which have been washed
selected region of the film excluding spikes, with water, dried, and re-scanned. Top is
peaks and pits (i.e., on defect free). Alkyd solventborne alkyd film with average surface
concentration of 50 wt% and drier was the roughness (Ra) of 0.19 nm. Bottom is alkyd emul-
emulsifiable cobalt neodecanoate used at sion film showing holes or pits of diameter 0.2 to
0.10% Co w/w per alkyd. Note exaggerated z- 0.3 µm and with Ra (excluding the holes/pits) of
scale. 0.30 nm.

72 Journal of Coatings Technology

 Drying of Alkyd Emulsion Paints

tion.6-9 Cobalt has shown some anomalous behavior for film (Figure 11) shows many pits, which are concen-
adsorption on MnO2.9 Our own zeta potential studies on trated in a hexagonal pattern grooved about 10 nm be-
concentrated TiO2 pigment dispersions have shown that low the surface. Such hexagonal patterns have been ob-
cobalt shifts the isoelectric point (iep) of the pigments to served earlier in films cast from solventborne paints and
higher values, even for the pure TiO2 pigment, which arise due to surface tension and/or temperature gradi-
had an iep of 2.2.10 This suggests specific adsorption of ents generated during solvent evaporation. Formally,
cobalt ions, which at a higher pH (above 5-6) precipi- they are known as Bénard cells and are considered a film
tates as the hydroxide. Loganathan et al.11 have obtained defect which can lower gloss and cause pigment flota-
similar results for cobalt adsorption on MnO2. tion.16 The size of the hexagonal cells would be expected
The time dependence of loss of dry due to cobalt to be related to film viscosity (drying) and reach their
interaction on pigments has not been investigated. The terminal size at a critical alkyd viscosity related to the
fact that surface drying time gradually decreases over 35 onset of crosslinking. Further research into this phenom-
days at 50° suggests a very complex mechanism whereby enon is necessary to help understand the mechanism of
the cobalt distribution between alkyd, alkyd/water in- surfactant migration in alkyd films.
terface, water, and water/pigment interface is continu- The film formation studies are ongoing and will be
ally changing, driven by the adsorption affinity and complemented with measurements of film properties
capacity of the cobalt on the pigment surface. In practice, (e.g., water absorption). Investigation of additive migra-
to maintain drying activity of the cobalt, it is necessary tion and attempts to overcome any detrimental effects
to prevent or slow down precipitation of cobalt hydrox- will be made in an effort to further improve the perfor-
ide. This is achieved, in part, by complexing the cobalt mance properties of alkyd emulsion paints.
with a chelating agent such as 2,2-bipyridyl, present in
the emulsifiable cobalt neodecanoate. An excess of 2,2-
bipyridyl (in terms of complexing all cobalt and to ac-
count for possible interaction with other species or dis- Flatten
20.0 10.0 nm
solution) should provide adequate protection of the co-
balt over the expected storage lifetime of the alkyd emul-
sion paint. 5.0 nm

Film Formation 0.0 nm

10.0
The formation of a dry hard film from an emulsion
involves evaporation of water, coalescence of emulsion
droplets, oxygen uptake, and crosslinking. The
crosslinking mechanism of alkyd resins has been thor-
oughly researched12,13 compared with the actual process
of forming a water free flat alkyd film. Beetsma2 and 0
0
10.0 20.0
Beetsma and Hofland14 have proposed a general mecha-
nism for film formation of alkyd emulsions based on Flatten
50.0 50.0 nm
visual observations. They proposed that the emulsion
phase inverts at a critical water concentration to form an
alkyd continuous phase and water droplets. The water 25.0 nm
continues to evaporate and the alkyd resin flows to-
gether to give a flat film. The phase inversion point, its 0.0 nm
occurrence, and flattening depend on droplet viscosity 25.0
and onset of crosslinking. The effect of various surfac-
tants and additives has not been investigated.
In this study on film formation of alkyd emulsions,
films were formed from an alkyd (LO70) emulsion con-
taining a conventional surfactant and from the same 0
alkyd (LO70) dissolved in mineral spirits. Atomic force 0 25.0 50.0
microscopy images of the dry films are shown in Figure µm
9. Both films appear flat and smooth. The film from the
11201538.001
emulsion had some very small but distinct peaks (few
nanometers high). The films were washed with water,
dried, and re-scanned. Figure 10 shows that the Figure 11—AFM top-view topographic images
solventborne alkyd film was not affected by washing, of washed alkyd emulsion film from Figure 10
whereas the alkyd emulsion film had distinct pits or bottom. Top image 20 x 20 µ m showing pits or
holes in replace of the peaks. It is most likely that the holes in the film (dark circles) concentrated in
a Y shaped pattern. Bottom image shows an
peaks in the unwashed film were surfactant which had
enlarged view (50 x 50 µm) of a hexagon
migrated to the surface and which was washed away to shaped groove, approximately 10 nm deep, in
leave the pits/holes. Similar results have been obtained which surfactant had migrated during film for-
for latex dispersions.15 A larger top view of the washed mation and drying.

Vol. 72, No. 906, July 2000 73

P.K. Weissenborn and A. Motiejauskaite

SUMMARY AND CONCLUSIONS Arbetslivsforskning) is thanked for its financial support

of our alkyd emulsion research over the past several
Loss of dry upon storage of long oil alkyd emulsions years. The following companies are also thanked for
was due to the presence of pigments. At the pH of their sponsorship and participation in the consortium
normal alkyd emulsion paints (pH 6-8), the cobalt is projects: Alcro-Beckers, Akzo Nobel, DSM Resins, FINA
precipitated as a hydroxide, and its catalytic effect on Research (Sigma Coatings), Jotun, OMG Europe,
autooxidation is diminished. Titanium dioxide pigments Tikkurila Paints, and Uniqema (ICI Surfactants).
having silica surface treatment had the least effect on
drying time and loss of dry. Emulsions without pig-
ments showed much less loss of dry, however, drying References
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acrylate- and phosphate-based dispersants. This was ob- Challenge: Recent Developments in Architectural Coatings,” Sur-
served for fresh emulsions and was an instantaneous face Coat. Aus., 35, No. 8, 14 (1998).
(2) Beetsma, J., “Alkyd Emulsion Paints: Properties, Challenges and
deactivation of cobalt relative to the gradual increase in Solutions,” Pig. Resin Tech., 27, No. 1, 12 (1998).
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sion pH and resin neutralization with ammonium hy- Emulsions,” in Polymeric Materials Encyclopedia, Salamone, J.C.
droxide also influence drying time and their effects were (Ed.), Vol.1 A-B, CRC Press, Boca Raton, FL, 154-160, 1996.
already apparent in fresh emulsions. These results led to (4) Middlemiss, R.G. and Olszanski, D.J., “New Catalysts for High-
Solids Coatings, Part 1,” Amer. Paint Ctg. J., 78, No. 17, 35 (1993).
the general conclusion that the effect of additives on (5) Östberg, G., Bergenståhl, B., and Sörenssen, S., “Distribution of
drying time of non-pigmented emulsions are observed Driers between the Alkyd and Aqueous Phase in Alkyd Emul-
relatively quickly (24 hr) compared to pigmented emul- sions and its Relation to Drying Properties,” JOURNAL OF COATINGS
sions which show a gradual loss of dry upon long-term TECHNOLOGY, 64, No. 814, 33 (1992).
(6) James, R.O. and Healy, T.W., “Adsorption of Hydrolyzable Metal
storage. Ions at the Oxide-Water Interface, I. Co (II) Adsorption on SiO2
Loss of dry is also dependent on the type of drier. and TiO2 as Model Systems,” J. Colloid Interface Sci., 40, 42 (1972).
Conventional cobalt carboxylate driers used in (7) James, R.O. and Healy, T.W., “Adsorption of Hydrolyzable Metal
Ions at the Oxide-Water Interface, II. Charge Reversal of SiO2 and
solventborne alkyd paints performed relatively poorly TiO2 Colloids by Adsorbed Co (II), La (III), and Th (IV) as Model
in alkyd emulsions, in terms of preventing loss of dry. Systems,” J. Colloid Interface Sci., 40, 53 (1972).
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tained 2,2’-bipyridyl as complexing agent, showed the Ions at the Oxide-Water Interface, III. A Thermodynamic Model
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(9) Hunter, R.J., Zeta Potential in Colloid Science: Principles and Applica-
chloride also gave good drying times, but was more tions, Academic Press, London, 326-334, 1981.
susceptible to loss of dry. Location of the cobalt (added (10) Weissenborn, P.K., Sjöberg, M., and Neminuschaya, G., unpub-
to alkyd or added to water) does not appear to influence lished work.
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pH on the Sorption of Co2+, Zn2+ and Ca2+ by a Hydrous Manga-
The formation of a dry film from a long oil alkyd nese Oxide,” Soil Sci. Soc. Am. J., 41, 57 (1977).
emulsion made from a conventional surfactant appears (12) Muizebelt, M.J., Donkerbroek, J.J., Nielen, M.W.F., Hussem, J.B.,
to suffer from the migration of the surfactant to the film Biemond, M.E.F., Klaasen, R.P., and Zabel, K.H., “Oxidative
Crosslinking of Alkyd Resins Studied with Mass Spectrometry
surface. Washing the dry film leads to holes or pits in the and NMR Using Model Compounds,” JOURNAL OF COATINGS TECH-
film which are distributed in a hexagonal pattern (Bénard NOLOGY, 70, No. 876, 83 (1998).
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tants cause sufficient surface tension and/or tempera- Unsaturated Fatty Acids Studied with Mass Spectrometry,” J.
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(15) Lam, S., Hellgren, A-C., Sjöberg, M., Holmberg, K., Schoonbrood,
H.A.S., Unzué, M.J., Asua, J.M., Tauer, K., Sherrington, D.C., and
ACKNOWLEDGMENTS Montoya Goni, A., “Surfactants in Heterophase Polymerization;
A Study of Film Formation Using Atomic Force Microscopy,” J.
Appl. Poly. Sci., 66, 187 (1997).
This work has been carried out as part of government (16) Pierce, P.E. and Schoff, C.K., “Coating Film Defects,” Federation
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74 Journal of Coatings Technology