Drying of Alkyd Emulsion Paints

P,K, Weissenborn*t a n d A, Motiej(susk(site*--Institute for Surflsce Chemistry*

and Royal Institute of Technologyt

INTRODUCTION
he development of alkyd emulsion based coat

T ings has resulted, like many other waterborne

and powder coatings, from the harmful effects of
organic solvents used in solventborne coatings on the
T h e dr}/in g [Link] qf long oil alkyd
e?mdsions was investigated with e?nplu~sis on loss
qf dr}/ upon storage. The main [Link] loss qf
environment and paint users. 1 The first generation of
alkyd emulsion and waterborne paints in general were dr}/was adsorption qf the cobalt (dr&r) on pig
inferior to their solventborne counterparts, mainly due
to changes in binder chemistry, high levels of surfactant,
merit surfaces as a precipitated hydroxide. Tita
lack of additives, and inexperience of the formulators. n i u m dioxides with alumina surface treatme~zt
This resulted in criticism of waterborne paints which, and organic pigme~zts were most detrime~ztal to
unfairly, still remains today. In fact, the myth that
solventborne alkyds are "best" still exists despite the dr}ring. Acr}/late and phosphate based dispers
latest generation of alkyd emulsion paints having better ants also deactivated the cobalt, presumably dtte
performance properties. 2 This unfortunate history has
contributed to solventborne alkyds still having a signifi to complexation and precipitation qf the cobalt.
cant share of the total alkyd paint market, especially in Emulsions prepared with an e?mds!fiable 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) sho~ed the best resistance to loss qf
use of solventborne coatings, high solids coatings, and
even some waterborne coatings (e.g., latex dispersion dr}/. Atomic .force microscopy [Link] .formed
paints based on high Tg latexes) is becoming very re from the e?mdsions showed that the e?mds!fier
stricted. This trend towards zero volatile organic corn
pound content, high performance coatings, especially migrated to the film surface which, whe~z 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 hexago~u~l pattern c]u~
To further increase the acceptance of alkyd emulsions
in the industrial and do it yourself sectors, research on acteristic qf BdJzard cells, which form dtte to su~
the drying properties of alkyd emulsions is required. face tension and~or te?nperature gradients ge~e~
Drying of alkyd resin based paints (solvent and water
borne), which rely on autooxidation, usually have very
ated in [Link] during evaporation qf 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 Bergenst~hl 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
*B,z,:,: s SE 11486:3t,z,,zkholn7 Sw~,3~n E rn,zlil: p~t~r w~iss~nb,z,rn stability of alkyd paints comes from European health
~Jsurf,zh~rn Lth s~
tD~p,zlrfrn~nf ,z,f Ch~rnisfry Surf,x~ Ch~rnisfry SE 100 44:3f,z,,zkholrn legislators taking steps to minimize or stop the usage of
cobalt in paints. Hence, there is a clear need to under

Vol. 72, No. 906, July 2000 65

P.K. W e i s s e n b o r n and A. Motiejauskaite

stand the reasons for the loss of d r y in current and future PIGMENTS: The p i g m e n t s a d d e d to the LO83 long oil
generations of alkyd emulsion paints. alkyd emulsions and tested for their effect on d r y i n g
O n g o i n g research on alkyd emulsion paints is follow time and loss of d r y are listed in Table 1. The titanium
ing a similar route to that of latex dispersion paints. In dioxide p i g m e n t s were supplied by Tioxide Europe Ltd.,
addition to investigations on the d r y i n g properties of England. The colored p i g m e n t s were supplied b y Jotun
alkyd emulsions, research is also being carried out on A/S, Norway.
the film formation of alkyd emulsions w i t h the aim of O~IER REAGENTS:All other reagents and solutions were
reducing w a t e r sensitivity. M u c h of the w o r k that has prepared from A R g r a d e solids or solutions of KOH,
been carried out on latex dispersions can also be applied HC1, NH4QH, and NaC1. Double distilled water w a s
to alkyd emulsions. In this paper, results from a system used in all experiments.
atic investigation on the loss of d r y u p o n storage of long
oil alkyd emulsions are presented, along w i t h s o m e pre
liminary results from a s t u d y on the film formation of Methods
long oil alkyd emulsions.
ALKYD RESIN EMULSIFICATION:
Driers added to alkffd prior to emulsification: The drier
EXPERIMENTAL w a s a d d e d directly to the LQ83 alkyd resin. Cobalt con
centration w a s typically 0.05% w / w per alkyd. If neces
Materials sary, the d r i e r / a l k y d mixture w a s heated (under nitro
gen) to aid dissolution/dispersion of the drier. A n equal
ALKYD RESINS: A l o n g oil a l k y d resin b a s e d on w e i g h t of water containing the emulsifier (pre dissolved)
pentaerythritol, isophthalic acid, and tall oil fatty acids w a s added. The mixture w a s stirred gently and the p H
w a s used for the investigation on the d r y i n g properties increased to N7 w i t h a 50% solution of K Q H (4 5 drops
and loss of d r y u p o n storage of alkyd resin emulsions. required per 150 m L of a l k y d / w a t e r mixture). The m i x
The oil length w a s 83%, and the acid value w a s between 6 ture w a s stirred (magnetic stirrer bar), heated to the
and 9 m g K O H / g alkyd. For further reference in the text, emulsification temperature, usually between 50 and 60~
this resin will be designated LO83. The alkyd resin used a n d i n t r o d u c e d into a h i g h p r e s s u r e h o m o g e n i z e r
for the film formation study w a s based on pentaerythritol, (Microfluidizer T M 120 from Microfluidics). Emulsifica
phthalic anhvdride, and tall oil fatty acids. Oil length tion w a s carried out for a period equivalent to about
w a s 70% ancl the acid value w a s between 5 and 10 m g three passes of the total sample through the h o m o g e n i
K O H / g alkyd. For further reference in the text, this resin zation cell (the length of time w a s d e p e n d e n t on sample
will be designated LQ70. volume, which usually w a s about 150 mL). The tern
perature w a s m e a s u r e d immediately after h o m o g e n i z a
EMULSIFIERS: Conventional surfactants were used for
tion and droplet diameter, pH, and Brookfield viscosity
the emulsification of the alkyd resins. The LQ83 resin w i t h i n 24 hr.
w a s e m u l s i f i e d w i t h a fatty alcohol ether sulphate
(C12EO30 SO4 Na2) used as a 32% active aqueous solu Large batches of emulsions (up to 1.5 L) w i t h either
tion or a fatty alcohol ethoxylate (C12/C14EO30) used as cobalt neodecanoate or cobalt caprioate w e r e prepared
a 65% active aqueous solution. for the w o r k w i t h the additives and pigments. The s a m e
batch of emulsion w a s used for all the tests.
DRIERS: Cobalt (II) chloride h e x a h y d r a t e , cobalt
Driers post added to emulsions (emulsifiable cobalt drier
caprioate, cobalt neodecanoate, and a w a t e r emulsifiable
and cobalt chloride onlff): Large batches of emulsions were
cobalt drier were used for the surface d r y i n g time and
prepared as previously mentioned, but w i t h alkyd, w a
loss of dry u p o n storage tests. The w a t e r emulsifiable
ter, and emulsifier only. The emulsifiable cobalt drier or
cobalt drier consists of cobalt neodecanoate, surfactants,
cobalt chloride were post a d d e d to the emulsion w i t h
and 2,2'~ipyridyl in a mineral spirits carrier. Driers
v i g o r o u s s h a k i n g from a v i b r a t i n g test tube shaker
were supplied by Q M G Europe G m b H , w i t h the excep
(Vibrax). The cobalt chloride w a s a d d e d as a concen
tion of cobalt chloride (Merck, pro analysi, 1.02539).
trated aqueous solution (volume <1 mL).
DISPERSANTS:A w i d e range of dispersants w e r e tested
ADDITION OF DISPERSANTS TO L O 8 3 ALKYD EMULSIONS:
for their effects on the d r y i n g and loss of d r y u p o n
Dispersants w e r e post a d d e d dropwise (as supplied)
storage of the LQ83 emulsions. Details of dispersants are
w i t h shaking to small aliquots (N20 g) of emulsion. The
g i v e n in the Results and Discussion section.
emulsion w a s 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
s h a k i n g or rotating table, and gently shaken
for 24 hr before m e a s u r i n g the d r y i n g time.
Pigmenl Type / Surface Trealmenl Surface Area (m2g -~)
Dispersant concentration w a s 2.0% w / w per
Red ........................... Organic 17 emulsion. Since no p i g m e n t w a s 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
1i02 1 ...................... 4.6% alumina, o r g a n i c c o a l i n g 15 tion, the free dispersant concentration w o u l d
1i02 2 ...................... 1.9% silica, 5.5% alumina, o r g a n i c c o a l i n g 17 be m u c h less, however, the aim of this w o r k
1i02 3 ...................... 9.5% silica, 4.5% a l u m i n a 30 w a s to establish and exaggerate which dis
1i02 4 ...................... 99.5% 1i02, no l r e a l i n e n t 8 persants cause loss of dry.

66 Journal of Coatings Technology

 D r y i n g of A l k y d E m u l s i o n Paints

ADDITIONOF PIGMENTSTO Table 2 - - C o m p o s i t i o n of P i g m e n t / A l k y d Mixtures

L O 8 3 ALKYD EMULSIONS:
Addition of the p i g m e n t s Total Pigmenl
Pigment Pigment (wt%) DJspersant (wt%) Alkyd (wl%) Water (wl%) Surface Area (m 2)
to the alkyd emulsions w a s
carried out in two steps. Red o r g a n i c ................... 21.2 1.0 23.8 -52 180
First the p i g m e n t w a s dis Blue o r g a n i c ................... 10.0 1.0 23.8 -63 180
C a r b o n b l a c k ................. 12.0 1.0 23.8 -61 180
persed in dispersant solu Brown iron oxide ............ 40.0 1.0 23.8 -33 180
tion u s i n g a D i s p e r m a t CV TiO2 1 ............................. 24.0 1.0 23.8 -49 180
laboratory dissolver w i t h TiO2 2 ............................. 21.2 1.0 23.8 -82 180
either a dissolver impeller TiO2 3 ............................. 12.0 1.0 23.8 -61 180
TiO2 4 ............................. 22.5 1.0 23.8 -51 90
or bead milling accessory
(plus ceramic beads), and Bolonc~ is~n =ulsifi~r( 12 wfS0 arid C,i,bolt drier DisF,~GOnt was on oni,i,ni,: hi,i,,2k ,2,i,p,i,Iyrli~r Water ,:,:,r,: ~ritroti,:,n is
approxirllat~ T,:r san =pl~w~ight was ~1]11]1g
second the alkyd emulsion
w a s m i x e d in w i t h the pig
meLt slurry u s i n g the dissolver impeller at slow speed to BK DRYING TESTS: Beck Keller d r y i n g tests were car
avoid shear destabilization of the alkyd emulsion drop ried out using a standard BK d r y i n g recorder from Mickle
lets (pre checked b y m e a s u r i n g droplet size distribu Laboratory Engineering Co. Before s a m p l i n g the emul
tion). Finally, the mixture w a s allowed to shake approxi sions, they were shaken for two minutes w i t h a vibrat
mately 24 hr on a shaking or rotating table to ensure ing test tube shaker. Films of w e t film thickness 60 ~tm
good m i x i n g before m e a s u r i n g the d r y i n g time. The first were applied to a glass plate u s i n g a six holed film
step of producing a stable p i g m e n t dispersion w a s diffi applicator and a u t o m a t e d bar coater, which p u s h e d the
cult and a trial and error approach w a s used to produce applicator along the glass plate at a uniform and con
the best possible dispersion. For some p i g m e n t s this w a s trolled speed. Surface d r y i n g time w a s m e a s u r e d in a
not possible and p i g m e n t flocculation resulted. All pig room thermostated at 23_+1~ and 50% relative h u m i d i t y
m e L t / e m u l s i o n mixtures were shaken daily with a Vibrax (RH). Surface d r y w a s taken as the time at w h i c h the
test tube shaker to ensure good m i x i n g and contact be needle started to lift out of the bulk film and s k i m m e d
tween the pigment, alkyd droplets, and solution. Par along the surface leaving a faint and irregular trace. At
ticle size analysis indicated that some p i g m e n t s w e r e this time, the surface w a s also finger touch dry. In s o m e
well dispersed, however, these p i g m e n t s flocculated cases, it w a s difficult to determine the exact surface
u p o n storage, s u g g e s t i n g that the dispersant concentra d r y i n g time, hence, times should be taken as approxi
tion w a s too low. The instability of the p i g m e n t disper mates and at best to within _+0.5 hr (30 rain). To i m p r o v e
sions w a s mainly due to the choice of the experimental accuracy, all m e a s u r e m e n t s and readings of surface d r y
d e s i g n w h i c h w a s optimized to allow comparison of the ing times were carried out b y the same person, and all
effects of the p i g m e n t s on loss of dry. For example, samples were m e a s u r e d in duplicate and the times were
optimization of dispersant concentration and correct sol averaged.
ids level w o u l d have resulted in more stable disper
sions. EMULSIONCHARACTERIZATION:Emulsions were charac
terized in terms of droplet size, pH, and viscosity. Drop
The p i g m e n t concentration w a s chosen so that the let size w a s m e a s u r e d using a Malvern MasterSizer MS20.
total p i g m e n t surface area in the emulsion w a s the s a m e 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 w a s approximately the same ( a s s u m i n g detection but w i t h o u t saturation. Viscosity w a s m e a
the coverage of dispersant and any free emulsifier w a s sured u s i n g a Brookfield LVT viscometer at a speed of 30
the same). This approach w a s preferred over u s i n g a rpm.
constant w e i g h t percent of p i g m e n t w h i c h w o u l d result
in a w i d e range of adsorption surface areas and biased FILM FORMATIONSTUDIES: The alkyd emulsions w e r e
comparisons between the influence of p i g m e n t s on loss applied to cleaned glass cover slips u s i n g a 60 ttm cube
of dry. The dispersant w a s an anionic block copolymer applicator, hence, after drying, the film thickness w a s
and the concentration w a s kept constant at 0.5 g per 180 N30 ~tm. The films were dried in a controlled tempera
m 2 of pigment. Table 2 s u m m a r i z e s the composition of ture and h u m i d i t y room (23~ 50% RH) under open
the p i g m e n t / a l k y d mixtures. cover to avoid contact w i t h dust. After at least _9_4hr
drying, the cover slip w a s cut to size (about 10 x 10 ram)
STORAGESTABILITYAND Loss of DRY TESTS:The d r y i n g to allow it to fit in the atomic force microscope (AFM)
time and p H of the emulsions w e r e m e a s u r e d within 24 sample chamber. A F M i m a g e s of the d r y alkyd film
hr after preparation (fresh), and after approximately 7, were obtained u s i n g a Digital Instruments Nanoscope
14, and 35 days of storage at 50~ For emulsions con IIIa m u l t i m o d e atomic force microscope in the "tap
taiLing additives and pigments, the fresh d r y i n g time p i n g " m o d e and under ambient conditions. T o p o g r a p h y
w a s m e a s u r e d after the 24 hr m i x i n g step (aged one d a y and phase i m a g e s were obtained from three to five areas
at room temperature). After ~ days, the droplet d i a m distributed over the film. The Z height and XY scan size
eter w a s measured. All samples were stored in tightly were varied for each area. A 20 x 20 ~tm scan size usually
sealed glass vials filled almost to the top. Before sealing g a v e the most informative images. W a s h i n g of the d r y
the vial, nitrogen w a s b l o w n over the sample. These film w a s carried out under a stream of w a t e r (from a
steps w e r e taken to decrease any possible uptake of water bottle). The film w a s rinsed w i t h approximately
airborne o x y g e n by the emulsion. 10 20 m L of water and b l o w n d r y w i t h nitrogen. I m a g e s

Vol. 7 2 , No. 906, July 2 0 0 0 67

P.K. Weissenborn and A. Motiejauskaite

boxylic acids. The p H decrease can be m i n i m i z e d b y use

of isophthalic acid instead of phthalic anhydride d u r i n g
9 fresh [ the synthesis of the alkyd resin. 3 To simulate if any
decrease in p H of the alkyd emulsion u p o n storage can

! !i!ii!!!i: influence d r y i n g time, the p H of the emulsions w a s

deliberately adjusted over the p H range of 4 to 9. Since
this is not the normal m e c h a n i s m by w h i c h the p H is
lowered, the results only s h o w the potential effect of any
decrease in p H due to resin hydrolysis. Figures 1 and 2
s h o w the results for emulsions prepared u s i n g an an
ionic and a non ionic surfactant. The emulsions w e r e
aged, and the p H changes monitored.
I I I i I
The results clearly s h o w that an increase in p H causes
4 5 6 7 8 9 10 a decrease in surface d r y .time. These results can be
pH explained by the w o r k of 9 et al. 5 w h o s h o w e d
that cobalt concentration in the alkyd droplets increases
w i t h pH. Their results indicated that higher cobalt con
Figure l--E ffect of pH and aging at 5ff C on loss
centrations in the alkyd phase decreased surface d r y
of dry and surface drying time for emulsions
prepared using L083 alkyd resin, 5% CTzEO30- time.
S04-Na w/wper alkyd, and 0.05%Co as cobalt The effect of a g i n g on surface d r y i n g time w a s similar
neodecanoate w / w per alkyd. The fresh pH over the p H range investigated (pH 4 to 9). After 35 days
was 6.89 and droplet diameter d(O. 1) = 0.21, of a g i n g at 50~ the surface d r y time increased b y ap
D(0.5) = 0.38, D(0.9) = 0.66 !xm. 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 w a s h e d films were obtained at least 1.5 hr after
washing. C o m p a r i s o n of the results for the two emulsifiers
implies that the non ionic surfactant gives better d r y i n g
at increasing alkaline p H values. This is possibly due to
differences in free cobalt concentrations in the water
RESULTSAND DISCUSSION phase. Since the anionic surfactant contains N a + as
counter ions to the S9 group, it is postulated that they
are replaced by Co 2+. This w o u l d lead to a higher cobalt
Drying Properties of Pure Alkyd Emulsions concentration in the w a t e r phase as p H is increased due
to the precipitation of Co(9 Precipitation of Co( 9
EFFECT OF EMULSIONPH: Storage of alkyd emulsions
from a 0.05% Co 2+ aqueous solution (0.008 reel L 1) is
often results in a steady decrease of the p H from about
expected to start at approximately p H 7.5 8.0. 6
neutral d o w n to about 4 5. This is due to the acid hy
drolysis of ester linkages a n d formation of w e a k car EFFECT OF COBALT FORM AND LOCATION: For solventborne
alkyd resins, the cobalt is usually a d d e d as a carboxylate
salt w i t h carbon n u m b e r r a n g i n g from 6 to 18. In a
waterborne system, the compatibility w i t h water be
9 fresh
comes a problem and, hence, selGemulsifiable cobalt
carboxylates are used. These can be post a d d e d to the
9 aged8 days
emulsion and form small droplets in the w a t e r phase.
9 aged 14 days
The stability of the drier droplets w a s not investigated,
9 aged 36 days
but simple experiments in water s h o w e d that they w o u l d
coalesce and phase separate u p o n standing for a few
days. The separated phase could easily be re emulsified.
Since the location of the cobalt in the w a t e r phase and its
state as small droplets m a y inhibit d r y i n g time, a series
of tests were developed w h e r e different forms of cobalt
w e r e either a d d e d directly to the alkyd resin prior to
I i I I i i emulsification or post a d d e d to the emulsion. Results
4 5 6 7 8 9 10
are s h o w n in Figures 3 and 4.
Figure3 s h o w s the surface d r y i n g time and loss of d r y
for the emulsifiable cobalt drier, cobalt chloride, and
Figure 2-- Effect of pH and aging at 5ff C on cobalt neodecanoate, each a d d e d to the alkyd phase
losso f dry and surface drying time for emulsions prior to emulsification (ensuring the m a x i m u m possible
prepared using L083 alkyd resin, 5% C7:/ cobalt concentration in the alkyd droplets). The cobalt
C74E030 w / w per alkyd, and 0.05% Co as co- neodecanoate g a v e slightly faster d r y i n g times b u t
bait meodecanoate w/w per alkyd. The fresh s h o w e d s o m e loss of dry. O n average and considering
pH was 7.05and droplet diameter d(0. 1)=0.22, the experimental error in d r y i n g times, the performance
D(0.5) = 0.39, D(0.9) = 0.67!xm. of the three driers w a s similar.

68 Journal of Coatings Technology

 Drying of Alkyd Emulsion Paints

[] emulsifiable~ chloride9 n~decanoate/ [] emulsifiable[] chlodde~ 8

~8 ~~
d e dd a ito emulsionp ~ 6

82

!o fresh aged7-8days aged 14 days aged 35 days fresh aged 7-g days aged 14 days aged85days
Figure 3-- Effect of aging at 56TC on loss of Figure 4-- Effect o f aging a t 50- C on losso f dry
L083 alkyd emulsions prepared using 5% of L083 alkyd emulsions prepared using 5%
CTzEO30-SO4-Na: w/w per alkyd and contain- CTzEO30-SO4-Na 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 a d d e d to bait chloride post-added to the emulsion. The
the alkyd resin prior to emulsification. The co- cobalt concentration was 0.05% w / w Co per
bait concentration was 0.05%w/w Co per alkyd. alkyd.

The comparison in Figure 4 between the emulsifiable The m e t h o d of resin neutralization prior to emulsifi
cobalt neodecanoate and cobalt chloride post a d d e d to cation w a s also investigated by c o m p a r i n g potassium
the emulsion (i.e., cobalt in water phase), w h e r e the hydroxide and a m m o n i u m hydroxide. Use of a m i n o
cobalt neodecanoate exists as droplets stabilized by sur n i u m hydroxide s h o w e d an i m m e d i a t e effect and in
factant and the cobalt chloride exists as a dissolved salt creased d r y i n g time b y about one to three hours relative
solution, s h o w s that the emulsifiable cobalt drier g a v e to potassium hydroxide. This w a s p r e s u m a b l y due to
slightly faster d r y i n g times and less loss of dry. The the formation of the cobalt hexamine complex, w h i c h
difference of about one to two hours is not considered deactivated some of the cobalt. 3 The emulsifiable cobalt
significant and w a s surprisingly small g i v e n that the drier w a s least affected b y the use of a m m o n i u m h y
cobalt chloride w a s expected to be relatively easily hy droxide.
drolyzed and deactivated. There w a s no significant d i g A g i n g of the emulsions w i t h a range of cobalt driers
ference in d r y i n g time for cobalt a d d e d either to the w a s extended b e y o n d one m o n t h at 50~ in an attempt
alkyd prior to emulsification or post a d d e d (compare to induce loss of d r y in the pure alkyd emulsions. All
Figures 3 and 4). emulsions suffered from loss of dry after about six months
These results s u g g e s t that location or form of cobalt of storage at 50~ a n d either had d r y i n g times greater
has no significant effect on d r y i n g 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 m u s t be sions w a s excellent w i t h no change in droplet size distri
answered. First, does the form of cobalt influence the bution. The p H had decreased to approximately 5.0 5.5,
distribution of cobalt b e t w e e n the alkyd a n d w a t e r suggesting that hydrolysis of the alkyd had occurred.
phases? Second, h o w does homogenization influence The decrease in p H m a y explain the loss of dry, h o w
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 a g i n g m u s t also be questioned.
lished v e r y rapidly (<24 hr), then the results in Figures 3
and 4 are for the s a m e a n d constant ratio of cobalt in
alkyd to cobalt in water. It m a y also be that the cobalt Drying Properties of EmulsionsContaining
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 c o m m o n l y used dispersing agents
hardness d e v e l o p m e n t for other alkyd resins. Emulsions on surface d r y i n g time and loss of d r y are s h o w n in
of m e d i u m or short oil alkyds m a y favor cobalt in the Figures 5 and 6. The first three dispersants (Figure 5,
alkyd phase because cobalt in the w a t e r phase m a y not g r a p h s 2 4 from the top) had v e r y little effect on loss of
be able to diffuse into the viscous alkyd droplets d u r i n g d r y and increased d r y i n g time slightly relative to the
film formation. reference emulsion containing no dispersant (top g r a p h
in Figure 5). Film appearance w a s glossy, smooth, and
OTHER VARIABLES: The effect of surfactant type and transparent.
concentration w a s briefly investigated. Priority w a s g i v e n
to obtaining a stable emulsion and optimizing the sur The effect of the second three dispersants (Figure6) on
factant concentration at the sacrifice of d r y i n g time. N o n d r y i n g time w a s already evident in the fresh emulsions
ionic surfactants h a v i n g long ethylene oxide (E9 chains (i.e., i m m e d i a t e deactivation of the cobalt). In the w o r s t
used in excessive concentrations w e r e detrimental to cases there w a s no surface d r y and even after a few d a y s
d r y i n g time. Crosslinkable anionic surfactants based on the films w e r e still tacky. The emulsifiable cobalt drier
a m i d e functionality g a v e good d r y i n g times but suf w a s the only drier w h i c h resisted complete deactivation,
fered from loss of dry. Anionic surfactants g a v e good but still had surface d r y i n g times more than double the
d r y i n g and films, but the risk of some loss of d r y u p o n 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-s-~and is insoluble in water, which supports formation
or ammonium as counterions, 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 plaoa 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 thatsome 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) This also explains the slightly better paint formulation. At the very least, the dispersant and
drying ~nes 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 potenfialimmediate 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).
(11)phosphate is pink and has a solubility product of 2 x 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 caorioate and

r r,nl,, W, ' - ,,-.I ' up Ill. b 9 ml

. ~ 9 -~

m .:.:,, m :.:.., m :.:.

~--,-~- ~ p ~,Tdi~"
~, ",,-

m -,,' . rn , -*l ', I. I', - , -

" ! k--'
rld~. Ih,.,- ~1 " , i ,, ,m In, h- ,I, ~ll,lld~l

:,. , ...
",."'~ :, 9 :-":,.. 9
9 ..,..-
~':':~:
,:.:. ,, f8':
,::.:: :,,
9 ....., 9 ,,.,..s
-- -- ~ ,,-,- m ,~,,=,, 9
:.-,,
.:.~,,,,, mm ~.~, , m
.:.:,,.,,, ,,,~,
:.:~, 9 m ,'.".,
,:.:.,,,' |
,lllm ',11~11 N ,I,' .,I L ,

,,, ~ ...@, ;:::.:; ,,' ".'/

i I.,L,I Illl ,I l,~- ,d lh, ,,~ .*la , , l l h I ,IN I
= ~ -.: ., ~
.. m :.;..- m ::.,.:
:.:.: :
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.. ,, '..:~b ,,
"" ~
~..~-,, l ""
~.,-, l ..~,
'" -,
,,.,~ ~. .'.;
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:.'r .':.':',
,-,.:-. ~I ..:.,-,, ~.-. I
m m n
m .~' " 9 " q"~" i -%J
m - - ' ,-- "".: - ;';" ,. _.".Z
' r--- '
9" ~" m . ",.,:,:
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'hlJ, h i ,~[Link] ,iH, fl ,

, IIIHI~, 9 ,i,I iIa I , Ii ,'h iIh dml ~," IIn~ *,dl .-::~. ~.;: .x- I:::,
..:..,:, 9 :.:.:, 9 .:.:, ::~
:.:.,, :.. , .:.:.. ,,..~
:':"
9 " " :::::: :i:i'
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9 @. :.:.).-
':'l~:f.. '. ~ ", _,: ;-;- - " - "~_--_. ,...~., ~...,
1

F@ure 5--Effect of ,J/~'per~',~nfi" on surf,~c e cb'- ]

ing time ,:~n,J /@'~"o f cb' after ,:@ing a t 5{~C o f F/gure c,--Effec t ,of ,Jspers,s~nts ,on surtace d@'-
LOSS ,:dky,~emuk,-/,gn,prep,s~re,J u~'/ng .,;~ ~"" C ~ / i'ng tl'n'~e ,:ynd loss of dry ,:y~er ,:G'~/n@,:it {C~ O of
C~,,EC,t]O w'lw" per ,:dkvd. The @'~'per~',y~t ,=on- LO~ ,J~.}',J erTiu@'or~ prep,~re,J us~r@.,~%OrS
c entr,~t/on ~,',~"2,0% w / w per emul~'/on, Err~ul~'i- C~E030 w'lw" per as d, D~'per~'ant ,=on,= entr,~-
f/,v~b/e ,:ob,vXt drier ,:~nd ,:ob,vXt ,:h/ori,~e u~'ed t/on 2, 0% w / w per emu6"/on, Emul~'/fiable c oh,Jr
w',s~sO, 10% w'lw' Co per,~/kv,J, Cob,Jt,:,s~prio,s~te drier ,~n,J ,=ob,sdt,: hlor/,J e u, e,J ,7~tO, 10% ~,'/~,"
and neodec,~no,~te was used a t 0,05% ~,,/~,, Co p e r alkyd, The cob,~lt ,:apr/o,~te a n d
Co p e r ,:dl.:v,J, neodec,~no,~te u,',~',~tO,05% w / w C o per,~l~.}'d,

70 Journal of Coah rigs Technology

 D r y i n g o f A l k y d E m u l s i o n 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 &ier 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 Conlaining Pigmenls 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

" ,,,iq - I~.llnl, Ir ~ql

[5

9_,_,, 9 ,
~ ~5-'

","," "
L 9 I
. ,",;,,, 5~?, ,,
m
i%"q, 9

I .-.-I
.%"~
j,
I
-

!.il ' 11 ~.'.~._~. ~ ,

I ~ ,:

,-.',~.. ~ , v.'.. '1

;..
?,!: -: i i
,.%~ 9

'""
"!
i ] I1-11 . . . . i 4 , i,iiillLllJ -,111111. ,J iJi i1.1~ i,
ilia % n I

:! . ,- .tll d Jl ,.,,.
9 ,,, , EE , 9 ,I EE ~ ,...
",'e
,,,~h hL , ,

9 ,. ;,.:

:.:.~ " ,:
-:.:,. I ,...,, i ,...,-
| ','d!"_' .' .
ii
F@ure 7--Effe,=t of t/t,sn/um [Link] ,sad sur-
f,s,=e tre,stment on surf,s,=e dry~ass time and loss F@ure 8--Effe,=t of ,=o/ored p/gments on sur-
of dry after ass~ass ,st 5(~ C of k08S ,slbr'd emu/- f,~,=e drv/n~ time and loss of dry after , ~ / n ~ at
s/ons prepared us~ass5% C~JC~4EOt~,O~,'/~,"per 5(~C of k08S ,~s emu/sions prepared usin~
,Jkv d, Const, snt p@ment surf,sc e area s/as 180 5% C~JC~4EOt~,O ~,'/~,' per ,Jbr'd, Const,~nt p@-
m:/n sample suspens/on e.x,=ept T/C,:I 4'~ ~,'h/,=h
hacl ~9 rn:, P 9 was the anionic is~ension, P 9 ,Jispers,~nt was the anionic
b/o,=R ,=opo/vmer from Ft'gu@ 5 usecl at the b/ocR ,=opo/vmer from Fiou@ 5 used ,~t the
,=,~r~,=er~tr,~tl',~r~of O,5 ~ per 180 rr7 of p/gmer~t l 1 c-onc-entr,~tion ofO, g o per 180 rr7 of p 9 c1
~,~'~, The emuls/fi,~b@ ,=oh,Jr clrier ,~ncl ,=oh,Jr ~,~'~, The emuisif/,~bie ,=oh,Jr clr/er anti ,=oh,Jr
,=h/or~tie ~,'as 0, 10% ~,'/~," Co Is,er ,~/br'd, The ,=h/ofic~e ~,~s 0, 10% ~,'/~,' C'o per ,~/br'd, The
,=ob,~lt c,~prio,~te anti neoclec,~no,~te was ,=ob,~R ,=apfio,~te a n d neoc~e,=,~r~o,~te ~,',~s
0,05% ~,'I~; O~ per ,~@r'd, 0,05% ~,'/~,' C'o per ,~/~,~r'd,

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-pi~nted emulsions. polyols, amines, or silicone derivatves w h i c h could also
The emulsifiable cobalt drier h a d the least loss of dry, interact with the cobalt9 Pure titanium dioxide clearly
a n d after 35 days aging at 50~ still gave reasonable s h o w e d 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 w a s d o u b l e that of the cobalt caprioate a n d ments have some form of surface treatment, the level of
neodecanoate. Comparison between the emulsifiable co- titanium dioxide exposed to aqueous solution w o u l d be
balt drier a n d cobalt chloride s h o w s that the former very small or zero.
suffered from less loss of dry presumably due to pres- The deactivation ofcobaltin the presence of pigments
ence of the 2,2' bipyridyl complexing agent. is proposed to be due to interaction with the p i g m e n t
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 cobalt9 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 EH, cobalt concentration, and pig-
a silica surface helps minimize loss of dry u p o n storage. ment surface. For metal ion adsorption on oxide surfaces
The type of organic treatment could also play an impor- in general, the favored m o d e l is interfacial precipitation
of the metal hydroxide, w h i c h due to interfacial effects,
can occur at EH values below bulk predpitation in solu-

-,' .

..- ,~ '~.~, , ~ ,#
.., 9 ~',.,",7,~. --~- ~ ;' " i . "~-'~'~ . ~ ;,.~.-.,
...~.'--'. ~,~.-
, ~4", ,"
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-~. 9 L " -

.,'

.." .,, ".'4

9 i ~ to ,,-
, -, I ~_ h- ,I

1,. I' I~

__.~.,- , ~--,,
~i ~=< . ~ , ' '~ -.Z

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bl 9 9

~,._-~, ,i ; j ~ . - ~ . -y
~,--~ . ~r/T,. ~ -. -

i '1 .

%" ~ ql""

i_1 .i. ,i

r i ,,i im i,
F~@ure o - - , 4 F M top,~n~phic surf,~,=e images of 9 I I ,,.

city films f,~rrne,J frorr~ t h e LOT0 ,:A/..v,:~ resin cl~> I , II'1, il

sob'e,J in rrdner,~l spirits I top'~ w'ith ,~n ,:~v'erc~ge

.+uff,~,=e roughness I fib'~ of 0.214 nrn an,J LO70
,Jkv,J re.+in ernuldfied w'ith ,=,y~v'enfi,y~,J.+urt;~,= -
F~ure IO--AFM top,~r,~hic surface images of
IF.B'~ o f 0.21o ore, F.B v',Jues m e , ~ s u @ d o n ,~ fffrr~sshow'r~inF~ure9 wtd,=h h,s!v'e b e e n w',:Jshed
s e l e c t e d r e g i o n o f t h e flirts e.x,=/udir~g spires. w'ith w a t e r , clriecl. ,sncl re-s,=,sr~necl. Top is
pe,~k~ a n d pits (i,e,. o n d e f e c t free'~, ,41Lvd sob'er~tborr~e ,~lkvcl film wdth ,~v'en~ge ~rf,~,=e
,=,gr~,=er~#,~h',gr~ o t 50 ~,~{ ,y~,J drier ~,',~s f&e roughr~ess IF.B'~of O, 19 nrn, Bottorr~ is alkv cl ernul-
emul~'ifi,:Je,le ,=oh,Jr ne,~,:~e,=,~no,~te u.+e,:~ ,~t don film show'ing holes or pits of cli,~rneterO,2 to
O. 10% Co w'/w'per ,Jkvd. Note e.x,:Jgger,:Jted z- 0,3 I~rn a n d w'ith F.B I [Link]/udir~g the holeslpits'~ of
~,2 ,J~_ . 0,30 nrn.

:'~..
= Journal of Coati n!qs_Technology
 Drying of Alkyd Emulsion Paints

tion. ~-9Cobalt has shown some anomalous behavior for film (Figure 117 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 TiO2pigment 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.x' 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 B6nard cells and are considered a film
tates as the hydroxide. Loganathan et al.~ have obtained defect which can lower gloss and cause pigment flota-
similar results for cobalt adsorption on MnOs. tion .1oThe size of the hexagonal cells would be expected
The ~me 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 mechanismwhereby 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-
T ,,,
count for possible interaction with other species or dis-
solution) should provide adequate protection of the co-
balt over the expected storage lifetime of the alkyd emul-
sion paint.

Film Formalion
The formation of a dry hard film from an emulsion .... ;.,.r -,
involves evaporation of water, coalescence of emulsion , ' "~.,, .~. ,-," ,-.,_
droplets, oxygen uptake, and crosslinking. The
crosslinking mechanism of alkyd resins has been thor- - ,L l~,~%" ~i "
oughly researched~2,~scompared with the actual process
of forming a water free flat alkyd film. Beetsma ~ and . ,, , ',i
Beetsma and Hofland ~ahave proposed a general mecha-
nism for film formation of alkyd emulsions based on
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

continues to evaporate and the alkyd resin flows to-
gether to give a flat film. The phase inversion point, its
occurrence, and flattening depend on droplet viscosity
ml I,L
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
alkyd (LO70) dissolved in mineral spirits. Atomic force l

microscopy images of the dry films are shown in Figure

9. Both films appear flat and smooth. The film from the
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 F@ure 1 I--AFM tlsp-v'/ew topossrlsphic /mlSs'~e~"
solventborne alkyd film was not affected by washing, of w,~he,3 ,~f~#',3 erylu@'on fl'fryl from Fl'~ure 10
whereas the alkyd emulsion film had distinct pits or 8,offor~, To/c,irn,~e -'0 .x -'0 ~rn ~ho~,'ing Ic,it~"or
holes in replace of the peaks. It is most likely that the h,Jes in fhe film r circ@s'~ conc enfr, sfecl in
peaks in the unwashed film were surfactant which had en/,s@e,J view r .x 50 prr/~ of ,~ he.x,s@Dn
migrated to the surface and which was washed away to a~h,~pe,3gn~ov'e. ,~ppn~.x/rn,~fe/v lO nrn ,3eels/n
leave the pits/holes. Similar results have been obtained wh/ch a~uM~,sf,~nfh,~,3 rn@r,~fe,3 ,Jut/rig film for-
for latex dispersions, is A larger top view of the washed r~,~h'on ,y~cl cl6,'/ng,

Vol 72, No 9,0d,, July 2000 7,3

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 u p o n storage of long oil alkyd emulsions years. The following companies are also thanked for
was due to the presence of pigments. A t 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 C o a t i n g s ) , Jotun, Q M G E u r o p e ,
autooxidation is diminished. Titanium dioxide pigments Tikkurila Paints, and U n i q e m a (ICI Surfactants).
h a v i n g silica surface treatment had the least effect on
drying time and loss of dry. Emulsions w i t h o u t pig
ments showed m u c h less loss of dry, however, drying References
time was increased to > 24 hr by addition of "free" (1) de Hok, H., ZaBol,K.H., and Geuriilk,P.J.A., "Acceptingthe VOC
acrylate and phosphate based dispersants. This was ob Challenge:Recent Developmentsin ArchitecturalCoatings,"Szm
served for fresh emulsions and was an instantaneous f~'e Coat. Aus., 35, No. 8, 14 (1998).
(2) Beetsma,J., "Alkyd EmulsionPaints: Properties, Challengesand
deactivation of cobalt relative to the gradual increase in Solutions,"Pig. Resit~ Tech., 27, No. 1, 12 (1998).
drying time observed for p i g m e n t e d emulsions. Emul (3) Berg~stfihl, B., Hofland,A., Ostberg,G., and Larsson,A., "Alkyd
sion p H and resin neutralization w i t h a m m o n i u m hy Emulsions," in Polymeric Materials Eta:yclopedia, 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 Catalystsfor High
Solids Coatings,Part 1," Amen Pait~t Ctg. J., 78, No. 17, 35 (1993).
the general conclusion that the effect of additives on (5) Ostberg, G., Berg~stfil~, B., and SOrenss~, S., "DistriButionof
drying time of non p i g m e n t e d emulsions are observed Driers betwe~ tho Alkyd and Aqueous Phase in Alkyd Emul
relatively quickly (24 hr) compared to p i g m e n t e d emul sions and its Rolationto Drying Properties," JOTTpNAL,Z,PC'ZATING3
sions which show a gradual loss of dry u p o n long term TECHN'Z'L'Z"~r, 64, NO. 814, 33 (1992).
storage. (6) James,KO. and Healy,T.W., "Adsorption of HydrolyzableMetal
Ions at file Oxide Water Interface, I. Co (II) Adsorption on SiQ
Loss of dry is also dependent on the type of drier. and TiO~as ModolSystems,"J. Colloid h~ter/~'e Sci., 40, 42 (1972).
C o n v e n t i o n a l c o b a l t c a r b o x y l a t e d r i e r s u s e d in (7) James,KO. and Healy,T.W., "Adsorption of HydrolyzableMetal
solventborne alkyd paints performed relatively poorly Ions at file Oxidc~WaterInterface, II. Charge Reversalof SiQ and
TiO2Colloidsby AdsorBed Co (II), La (III), and Th (IV) as Modol
in alkyd emulsions, in terms of preventing loss of dry. Systems," J. Colloid h~terface Sci., 40, 53 (1972).
The emulsifiable cobalt neodecanoate drier, which con (8) James,KO. and Healy,T.W., "Adsorption of HydrolyzableMetal
tained 2,2' bipyridyl as complexing agent, showed the Ions at the Oxidc~WaterInterface, III.A Thermodynamic Modol
best resistance towards loss of dry. Surprisingly, cobalt of Adsorption," J. Colloid h~terface Sci., 40, 65 (1972i.
(9) Hunter, R.J.,Zeta Pote t~tiaI it~ Colloid Sciet~ce: Prit~'iples at~d AppI~'a
chloride also gave good drying times, but was more tlotas,Academic Press, London,326 334, 1981.
susceptible to loss of dry. Location of the cobalt (added (io) Weissenborn, P.K., SjOberg,M., and Neminuschaya, G., unpuB
to alkyd or a d d e d to water) does not appear to influence lished work.
drying time. (ii) Loganaffian,P., Burau, R.G.,and Fuerst~au, D.W., "influenceof
pH on file Sorption of Co2+,Zn~+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) MuizoBelt,M.J., DoilkerBroek,J.J., Nielen, M.W.F., Hussem, J.B.,
to suffer from the migration of the surfactant to the film Bi~mond, M.E.F., Klaas~, R.P., and ZaBol, K.H., "Oxidative
Crossinlking of Alkyd Resins Studied with Mass Spectrometry
surface. W a s h i n g the dry film leads to holes or pits in the and NMR Using Modol Compounds," J,Z,TTpNAL,Z,FC'ZATING3TEC~
film which are distributed in a hexagonal pattern (B6nard N';'LO';r, 70, No. 876, 83 (1998).
cells). This suggests that water evaporation and surfac (13) MuizoBelt,M.J. and NioM~,M.W.F., "Oxidative Crosslhlkingof
tants cause sufficient surface tension a n d / o r tempera Unsaturated Fatty Acids Studied with Mass Spectrometry," J.
ture gradients in the film for the formation of B6nard Mass Spectrometry, 31,545 (1996).
(14) Beetsma, J. and Hofland, A., "Alkyd Paints: From the Ease of
cells. Orgaidc Solventsto file Difficultiesof Water," Pait~t Resit~ h~t'I.,
68, 15 (1996).
(15) Lam, S., Hollgren,A C., SjOBerg,M., Holmberg,K., Schoonbrood,
H.A.S., Unzu6,M.J.,Asua, J.M.,Tauer, K., Sherrington, D.C., and
ACKNOWLEDGME NTS Montoya Goid, A., "Surfactants in Heterophase Polymerization:
A Study of Fthn Formation Using Atomic Force Microscopy," J.
AppI. Poly. Sci., 66,187 (1997).
This work has been carried out as part of g o v e r n m e n t
(16) Pierce, P.E. and Schoff, C.K., "Coating Film Dofects," Federatiots
and industrially sponsored consortium projects. The Series ors Coatitzgs Techtmlo~3y, Federation of Societiesfor Coatings
Swedish Council for W o r k Life Research (R~det f6r Tedmology, Philadelphia,13 14, 1988.

74 Journal of CoatingsTechnology