PROGRESS Ng!

g&
ELSE?lER

prexn~rbep~gme~~tlpolymerpackingwillassume configuration a, the UPVC.

itsdensest

Latex systems do not nonnaliy promote the agglomeratmn

The critical concentration &s. pigment volume conce.mrauon (CPVC) of of pigment particles. To avoid coagulation of the latex partic&during significantly storage, freezing and& on. enough surf&m is provided that the addition of tbe pigment usually doer not deplete the smfactant already adsorbed on the at least, we latex panicle surfaces. As a first approximation, coating systems has been defined as ~bat ptgmem volume at which there is just sufficient binder present of the packing characteristics of the in the dry paint film to till the voids between Pigment panIt is a function coating fomwlation. In emulsion-based paints, tie binder IS mmally composed of discrete polymer particles. These coalesce to form a more or less continuous polymer matrix as the paint dries. This II why the CPVC of emulsion-basedcoatings basdifferentchilrthan lhosc of solvent-based &ints (I-10,. The

can assume Lbat the pigment particles in fbe latex systems are not severely agglomerated. These systems will then have a high packing density of pigment and polymer panicles and therefore they are essentially near the UPVC. Below, wc explam CPVC tehaviour by considering Ihe latex and pigment to be components of a packed system of spheres in which the pigment is generally fairly well. but oerfectlv. disoersed. There arc several papers which consider and evaluate
I..

&ris,ic*

key difference irthatemulsionparticlesand~igmentpanicles

both share the close packed &ray that forms as the water evap+~aes, before the polymer particles coalesce. In salventbased syswm~s,by contrast, the pigment particles are always dispersed in an essentially continuous solution or polymer matrix. The ultimate pigment volume defined [IO] concentration (PVC) was

apparently not
in

the methods for exoerimental derermination of the CPVC coatings

[ l-6,9]. The properties of lbc paint undergo

(i)

a change at this pant. transition can bc stain remowl. block

asthelimitingormarimumvalueoftheCPVC, arc assumed to he

The propenles *at change at the CPVC divided inm three groups: electrical resistance): (il) mechanical properties wst.we.

that pertains to Ihe condition where tbe particles are all completely dispersed. Since no agglomeraas

tmnsporf properties (i.e. permeability, (i.e.

tensile svength,

densay, scrub resistance);

(iii)

opticalproperties (i.e. specular gloss. opacity, tin1

acceptance) Different gradually approxbed

propertics may change

a3

relaucly

the cnticrd pigment volume (7).

cmcentration is
Polymerisations reactorcwtenl~ were carried out in a stirred 1

sharply ormnre

This hes been explained on the basis of do not necessarily coincide one

I reactor

flaciuarions in packing densny and because endpoints of vaious measurements ofCPVC [h.g.IO.II]. Some authors have compared methods to detemune the CPVC I Ialex coaungs wth anothcrsincethercmethodrmeawrediffereatpropenies

fitted with an overhead condenser. The temperature of the was maintained at 80C by partially immersbath. The reactor ing the reactor in a thermostated wtcr for 30 min. The pre-emulsion feed was composed of monomers (vinyl acetate and n-butyl acrylate 8915 tent (sodium bicerbonale) dodecylbenzene sod deioaised (ammonium wt.%) mixed withsurfacbuffer (sodium was sulfonale).

charge wes healed in the water bath end purged with nitrogen

[ I.2,4.6]. II has been reported _

that

tic endpaint measured by changes in specular gloss is not very sharp and that experiments relying on changrs in gloss we imprr&al. In

thispaper

we show, however. that the

water. The pre-emulsion persulfate)

CPVC value given bv soecular eloss can be a valid method m latex systema, under the proper expenmenlal conditions. Since the polymer is initially and the pigment participate particulate in nature, both it in the packing process, which

stirred during tbc 5e.1 period. The initiator was added in two stages. The first stage was in the form of a batch addition just prior to the beginning of the addition of the pre-emulsion. During the second stage e concentrated sohnion was added to the reactor concurrently with the monomers ac P constant rate. using a syringe pump. The pre-emulsion was added in two stages. The first stage was after the initiator batch addition, in the form of a preemulsion batch. where the pre-emulsion had all the ingredients except the buffer (NaHCO,). The second stage started 30 min later. The pre-emulsion. with buffer, was fed to the

occurs during drying prior to the onset oi latex coJescence. 7his paper shows how this packmg model is applicable to explain the effects of iatex particle size on the CPVC.

2 Research programme
Monodisperre (vinyl acetate-co-n-butyl acrylate) latexes

reactor using an FM1 Lab pump model RP-sy. beginning at slowrateandincreasingthefeedrateeach30min,butalways maintaining a starved feed condition (i.e. no reflux was and ini60 observed). After the total addition of pre-emulsion min at 80 C for complete conversion [ 121. Table

were made at several particle sizes using a process described below. Then, simple psints were made at different pigment volume concentrations (TiO,), (%PVC) with only one pigment latex and other components of latex paint formula-

tiator, the reaction mixture was heated for an additional

tions. These paints were applied on n Rat glass plate, dried and lcstcd for smcular e!oss. From these data. CPVC values were calculated and th~relauonship latex pemcle size was found. Conwast ratio (hiding method power) The w&s evaluated es a second paint formulations were to get the CPVC. between ;he CPVC and

I shows

the reaction quantities for the semibatch

reaction, along with the resulting latex particle sizes. Seeded reactions were used to make large latex particle sizes. The procedure follows the samelatexpreparsriongiven above, butaseedlatexofknownpafiiclesiEewasinrheinitial reector change. see Table 2. The latex particle size and size distribution weremeasured using an ICXoyce Lo&e1 disk centrifuge. The output was recorded by a Brookhaven tem. Wate;was Instrument DCP-1000 data sysused as the spin fluid and the density grad& The rotational sped

adjusted to obtain dry pant

films with constant weight of

pigment per unit area. The paints were applied on opacily testing chats. dried and chxacterised. However, reliable CPVC values could not be calculaled fmm these contrast is calour redo measurements. Another allemalive difference. method LOobtain the CPVC The colours of the dry while paint films were

wes produced using methanol. The density of the latex was taken as 1.17 g cn-.

of the disk wan

measured. but no significant differences were found. Therefore another set of paints wes prepared by adding 0.67 wt.% of phthzlo blue pigment to the same white paint fomulation. along with some hydraxyethyi cellulose thickener. The colvalues

selected so that the particles passed the detector in a period after 2-5 min of spinning [ 13.14], 3.2. Painrprepararion 3.2.1. Pi,mwnr (Ti02J Awhi~ebase(Table3) &r wasweighedanddirpersedat12JD was measured and gauge valuers rpm for I5 min with a Cowles-tylrestirrer with a bladediamof 2 inches. The fineness of-grinding

our difference was recorded and the data showed a tendency from which the CPVC can be calculated. TbcaeCPVC at an incrdence angle of 85. Because we worked with monodisperse lawxes, we can consider the latex and TiOl pigmerd both as spheres in the bchaviour packing process and design a model for CPVC wth rcspec~ to latex particle size. are similar to those obtained by specular gloss measureroenl~

showed very good dispersion with Hegman

close to 5. That means the fineness of grinding is less than IO ~.rm in the pigmem base. The white base showed good flow

mow&es , .

and was stable. maintainine the same bodv and iii-

this value wirh that ofasmooth index (Eq. (I)) [15,16].

black tileofknownreflective

same Hegman fineness during three months storage. To keep the proportion

(surfactant/latex) consm,. I.2

wm edded to

wt.% of non-ionic surfactant (Rexal 251407)

(1)

each latex. The paints were made by mixing proportions of latex with white base, using a magnetic stirrer, for IO min.

The paint was applied using a Bird film applicator with 3

mil gap (equal to 775 Mm) and X.5 inches wide, cm a Rat glass surface OT a contrast ratio chart. Three replicate drawdowns were made each time. 3.2.3. Drying condirions Just after the application, the sample were put in a closed drawer until dwinp. was comdete. This is to avoid air Row while the film is &ying. The room temperature was 72 F (22.2 C), and tlte humidity was nor measured. Because it is difficult tocontrol tbe humidity, theexperiments werecarried out in winter, hoping to have more or less the same humidity. We know that the humiditv affectr film fonoation: therefore. we did all the draw-downs size. for each latex in one day. in or&x for each latex particle to have tbe same drying conditions

Specular gloss, which is a measure of brightness of a reflected image, was ohtamed from the dry paint film at three different incidence angler (Zk about 20 measwements 60 and 85). Fcr each aagte were mnde. The mean value i3

reported as the specular gloss at the spwific angle.

The contrast ratio method for the measurement of opacity

is descrtbed m several published lest methcds (AS?M 2805-80. TAPPI T425).and uses tberatiooftbereflectcc D

of the dried films over a white backing to that of the sample aooiied owr a black backbaa il71.
L.

..

The contrast ratio \YBS obtained for each dry paint tilm coated on opacity testing charts at different pigment volume concentrations, calorimeter. (whiteness) using a Hwterlab model D25A tristimulur The contrast ratio is measured by the Y value on the white backing,compared to Y valuemeas-

wed on the black backing.

The specular gloss was measured

using a BYK model 4524. Gardner

each dry paint film Inc. Reflectornew Micro-Tti-Gloss

for

(2)
In order to obtain the fame amount of pigment per area at different pigment volume concentration. two basic formulas. A and B. were made for each latex:

Specular gloss involves measuring tbe ratio of!he intensity of refle~ted/specular beam of light (P) from the dry paint film,totheintensityoftbeincident beam (l),andccmparing

FLX?ll!d~A

White base (Table 3 j Latex PVC = 22.7% Formula B While base (Table 3) Latex Dewnissd water PVCB = 70.98

37.5 wt.8 62.5%

38.86 wt.% 5.18% 55.95%

Both fomm1a.s have Ihe same emounl of pigment per unit obimc of liquid paint. Tbe swpa in the PVC ladder were calculated as follows: (3)

where X.=percent of paint A in the mixture: PVC,,,= pigmenl volume concentration expected: PVC*. PVC?= $meni volumeconcenuation of p&A and B. respectively. Because of the low viscosity of most of the paints. some Row to tbe edges was observed during drying and wnsequently the dry film was not uniform. showing an uneven pigmentation. In order to prevent this problem a constant &mum of tbicknener sol&on (2.5 WI:% of hydroxyelhyl cellulose (HE0 in water) war added to all sets of aaims. The revised paint fom&ion includes 27.2% of &thicknener solution. After the increase of viscosity, the dry paint films were uniform and did not evidence any Row during the Elm formation.

Since the presence of air in a dry paint film affects the scatreriog efficiency of the TiO*. a change in colow is also observed when tinter is present [ 181. Measuring colour involves the knowledge of the three basic compunenu of calour: sources of light, object illuminated and observer. There are international standards for source of light and observers and colow scales have been pmposed baxdontbcopponent-colowtbeory ofvision [ 191. scales most used in matching colour are CD3 lab and CIIiXyZ which are based on the CLB standard observer. Thespecihcarionofcolourisgivenbytristimulusvalues,and thesevalues can beconvenedfromonecolourscaleloanother using tbe appropriate conela:ian functions. In our case, only the CIEZ uistimulus value for lighmesswhiteness was found to be useful to determine CPVC, in a pigmented system described below.

The colour

The paint formulation wasmodificd pigment L7080 (BASF) tinter. TiO,:Phtbalo

by adding phthalobluc tinter weighhr ratio

Tbe

Blue pigment was 149: I, and the rest of the for the white base is shown in

ingredients were the same as in Table 5. The tinted formulation Table 5. Again, because of the low viscosity of the pants. we used the same thickened formulation (27.2%). as was used for the contrast ratio method, using the same amount of thickener sol&m

4. Resullr and diwussion

The specular glass for different pigment volume concentrations was measured. The specular gloss versus PVC plots go through minima. as seen in Figs. I and 2. The reason for the inidal decrease of specular gloss wrth increase of PVC (before a minimum) is explained by the optical theory of specular glass for perfecdy smooth surfaces (malilied Fresnel equation) and the deviation due to surface equation). micro-mughnex when the WC (m~xlilied Rayleigh-Toporets

inxeases. the average refractive index of index. The refracdvc index of

thepaintincreasesbecauseoftheaddilionofpigment(TiO,), which has a high refractive

polyvinyl

acetate and

of polybutyl

nce~c

is the

fame and

cquak

1.46 whde lhal of TiO,

is 2.71. Al the same time.

pigment addition would tend 10 increase the roughness dry paint film.

o:the

The roughness of a coaung can be considered 10 be of Iwo types, namely macro-roughness and mrro-roughness. Macro-roughness aable less. If a pant film exhibk only macro-roughness. the specular gloss will bc lower than expected since some of the light which should have been reflcclcd in the mirror-image direction is disvibuted away from peak reflectance value. Macroroughness surface defect to rheological the paint. The micro-roughness particles (0.2-0.4 pm). is a result of very small surf.??e in srze la litanium isductodlffracmm dioxide which Here the decrease oi specularly defects. whrch are comparable reflected lighlwith increasingPVC BIG relatively large and are related The correcdon factor due to micro-roughness by the modilied Raykigh-Toporets C=G,exp[-(4~ cosilh)*l is predicted equation 1201: (5) problems such es poor fl3w and levclling of is Ihe rcsuk of surfail. dcfccts of the order of light and

of 1 wrn or more in hex&t. whereas micro-roughness 1sattribto defects of the order of the wwelenglh

where i = angle of incidence A = light wavelength. (T = mot mean square deviation of the surface from the mean level of reflectiw surface (roughness). G=real G,=tbeoretical secular gloss (Fresnel equation).

occurs a~ Ihe surface of the coaling and is a very fine scale of light scaxerod al the surface. When specular gloss was measured at several points in the film, we found that the deviabons WCPZ small. We assume tirn that the macro-roughness is constant for each drawgives homogeneous films on down, and the film applicalion

specular gloss.

See Fie. 4. which is bas:d on a model in which the disuibulion oflbe heights of surface variations is assumed to be Gaussian. By using these two equalions together, wean roughness. estimate the s~~pcularglorschangefarngivenmeasuringangleandsurface

lhis scale of measurement. When the reflecting surface is oplica#tly smooth rhe modified Frcrncl cquarion predicts the intensiry of reflected/

[ 15)

specular beam of light (I)

nggainst the incidence angle (ij 87 Gloss. In the case of measurements at an incidence surfaces is almost constant in the range of of 1.5-2.7 (Fig. 3). Thus when the

and :he refractive index of the malerial (n). s =(i.s{(:a;~;:~~~~~~~~~)

angle~f85,wecanreetharthetheoretical(Fresncl)speeular glosr for smwlh coalingrefractiveindexes +(%ST} Fig. 3 IL a plot of Eq (4). perfectly smooth surface. (4) 11shows how the magnitude of the

PVC is increased. the refractive index increases, and the 85 specular gloss should be more or less constant. However, the measuremen,s show that the real specular gloss decreases, indicating fhal the dry film is increaskg in roughness. light. so the measured @as\ increases with the measuring angle. I. for a The glossmeter dDes not use monochromatic

correction factor. which is alsoa fucction of light wavelength

(Eq. (5)),

indicates a range

of roughnessforcach

incidence

angle. At85inc1dence 0.550

angle.thecorrecnon

facuxform~~obe

roughness a higher roughness values 10 rhe range 0.30~ wrn is quite large. and the specular gloss will severely affected, adversely affectmg reproducibility. 60 Gloss. In the case of 00 incidence angle of 60. the theoretical (Fresnel) index of 1.5-2.7
10

specularglossfortberangeofrefraciive (Fig. due we find a

should mcressc more than two-fold gloss

3~.bu~thecorrectionfactor~Ra~lei~h-Toporels.Fi~.4~ roghess

afrecisIhe

more. Ti&ero~,

decrease in real specular gloss with increasing PVC. At 60. the correction factor for micro-roughness is large, when Ihe roughness value (0) is greater than O.IMM 150

Sm. 20 Gloss. In the cast of an incidence angle of 20. the measured gloss follows range where (approx. the same pauem as at 60. but the dommares II smaller and speculu gloss at 600 and at 85 acwally increases as seen in Figs. I and 2. A possible explanation of such increases in sp-ecular gloss at higher PVCe is because our dnw-downs impermeable As we can see. the values obtained for micro-roughness al 85 are no, the same as those for 60. and rhe explanalion could be tba, the surface defects have a large effect at 60, and B lesser effect at 85. (The ratio 0r the express100 in Eq (5) for cos 6Oand cos 85. is 1.51.) When for CPVC other authors f4.61 used large pigment panicle notsuitable charts). and the mobile componexs were made on formulation (sursubstrates (glass and coated opacity testing the micro-roughness

devwion

from the mean level = 0.050 gm),

the specular &Jss is highly aoomximatelv

dre.3ed. so wecannot see any

uml.

difference if the surface roughness soffcrr changes at values

..

the size ofthe oiement (0.2-0.4

ha! is

of the

factants. defoamer, dinpersants. etc.), arenot adsorbed by the pigment (TiQ) or the subsmale. Therefore. at low amowns of laier. when lhe paint film is drying, these compounds go 10 the surface, where lhey promote levelling, by a referee is that- the increase ily of TiO, in the absence of latex. Al:hough there is no apparent theoretica! reas.00 for lids (i.e. occurs I coincidcncc, if ~urnsouttharthcminimumspeculargloss with a net decrease of micro-rouehnesa. Another exolaoalion orowsed in spec~lw gldss at PVC > CPVC mav have to do with the oackineand

sizes.theyfouodthalthespecularglosrat60w~r

mea~~remeots. because rhe measured specular lowvalucs.Thisagreeswrlhourresul~s.

reflecriv-

gloss decreased rapidly and remained low as the PVC was increased fmminitial

41.2. Specular gloss behmiourar

At PVC>CPVC

PVC,? higher rban CPVC

maximum in estimated surface micro-roughness) the CPVC. menu of the CPVC. described below.

air oores are oresent in the dr

as shown by coincidence with another measure-

new third phase, and these air voids increase in

&berwtb

film as a

fonber increase in PVC. When the aid voids appear the dry film will show a decrease in its refmcdve index. because the air is replacing the latex. which has a higher rerraclive index than air. This should cause a fwtber decrease in g!oss (from Es. (4) 1. Consider now that the maximum volume concentrauon Tbe va!oes of CPVC from the minimum in specular gloss ohtnmed using an incidence angle of 60 was observed not 10 be the same as lhat for 85. When the latex particle size is greater than 0.200 @n, the CPVC value at 6O is higher than the CPVC value at 85. When d&ding which incidence angle is better for CPVC cstimatlons. we have to consider two factors. The specular gloss BL60 is highly sensitive to roughness (Fig. 4). We can see that when cr (roughness) is greater than 0.100 pm. the specular gloss value is small. This point does not necessarily denoteaminimum,becauseIheroughness(cr)couldincrcase wthoo! producing any considerable When the paint is made from a latex (0.45C-O.700 difference in gloss. size

that the pigmenl could have in clusesl packing is some value (approx. 63% by volume). We can lhen estimate the refractive index of the dry film as a rimction of PVC. Then we calculate the theoretical

specular gloss. and usingexperiaen-

tal data, we can esrimnte the me.^a micro-roughness, 600 indicate that the micro-rowhness ion goes through P maximum &h &me&in at PVCs>

with

results as shown in Fig. 5. The exl erimentzl data al 85 and estimated in this fashmcreasing PVC.

To exolain this we must consider two effects. Firstly. the refractive index with increased IT void c&11 CPVC oauses P decrease in theoretical (Fresnol : Secondly, the surface roughness decreases

ofmedium panicle

,mam)specular gloss at 60 is low over a wide

specular gloss.

interval of PVC, which means that the roughness is large and there is no minimum point (e.g. Fig. 6).

after a certain PVC and II the major effect ~0 that the tin+

the~tilecrystal and itsparticlesize (0.2-0.4q). Thelight scattering efficiency of Ti02 also depends on the particular spacing uf lhe pa&&s in a paint film. When the centre-tocentre diLtanra or spacing between particles is equal to one full wavelength oflight, then each particle isamosteffective light scanerer. Sincc the diameter of the particles ofTi0, is about half the wavelenglh of light, on the average. the marimum scatwing efficiency will occur when the pigment particles (Ti02) are separated by another half wavelength of visible light. That occurs when muticles arc soaecd bv a ing conditkm results in poorer &wring efficiency. It has been calculated 161 that TiO, has iu maximum scattering efficiency at 10% pigment wlume. concentration. As rhe PVC increz.es above 10%. the Darticles of titanium dioxide become spaced closer and &&, until atCPVC they are spaced as clcse as they can he. (Note that Hcsler [6j regards the CPVC as equal to the clasest packing configwadon of the pigment.) At PVCs above the CPVC. insufticient vehicle solids volume is available to bind the pigmentandair voids begin to become incorporated into the dry paint film. his postulated that scattering efficiency willhegintoincrease due to the incorporation of sir and subsquent dry hiding, The condition ceded for measurement of the CPVC by contrast ratio is a constant weight of pigment pa unitarea of dry film. Ihe latter is reached using the basic fomwlas A and El mentioned earlier. Our expcrimenlal results are plotted in Fig. 9. As can be observed, the change in con@ast ratio is smaller than the experimental error. Fig. 9 shows data for three sets of paints corresponding to three latex particle sizes. All the latexes showed the same tendency. The inability of this contrast ratio experiment to permit CPVC mcaswcmcnts may be because the assumption drat the CPVC indicates the closest packing of !he pigment is nm always true for latex-paint systems. when the latex panicle size is varied. If we use a Ia~cx with a large panicle size, the pigrnenldoesnol~~hitsElaaeslin~erpanicledis~~ce.while at CPVC. when we use a very small latex particle size. the

On tie other hand. in the refractive index interval of use here, the theoretical specular glass value at 85 is almost constanl (Fig. 3). so we can canc!ude that this specular gloss IS a measure of the surface roughness. If was concluded, therefore. thalspecularglosspl85incidencr.and~ isthebcst measure for CPVC analyses. For illustration. the specular gloss at 85 incidence angles is reported agains the PVC in Figs. 7 and 8. The error bars correspond 10 f 2.5 units of gloss. The applicability of the specular gloss method to measure CPVC in commercial paints has a bmnauon. This is the presence of large particle size ( 1-3 pm) extendcn or fillers commonly added to the systems. It is known that the amount and height of the surface roughness affects the gloss. Tke largeparticle size additives producesurfaces with highroughnesses, which makes the specular gloss method not sensitive enough for detecting CPVC in real systems.

711~method used was proposed by Herler and is based on light scattering efficiency. The light scsuering abilby of TiOz IS dewed from both the high refractive index (2.7 I ) of

I61

closest pigment CPVC.

packing

may happen at lower values of oanicles. This is shown in the blueness calour valuesthat are not reproduced here. for conciseness. Fig. 11 shows CPVC values from colow difference. as coincidence We conclude that the measured by Z values. and 85O gloss dam. I%

Various

colour measuremen,

parameters

were plotted
(Fig. IO). and.

is eood for th;r t-me of detwmination.

against PVC but the only parameter that permitted an objective. measure of an endpoint was the CIEZvalue The Z value relater the L value (lightness-whiteness) the chance ofZvalue Tbhest&ht linctity in c&w with the oresenceofairvoids

inllcction points in 85 gloss measurements that were interpreted as CPVC data were indeed such. 4.4. Proposed c.rpkmation part. cle size CPVC

in our system, lhe blueness. In Fig. IO, it is possible to &ate (CPVC). Tlw lines in Fig, 10 were fitted 10 tie data assuming change below and abwe the CPVC.

fir the dependenceof 1are.r

of acrylic latex paina Bowcll

Usmg data for ths CPVC 1211 kand X=4.25.6 the following

intersections on Pig. 10 are. distinct enough to provide areliable detetination lat.%. At higher PVCs, binder (latex) agglomeration of phthalo blue pigment cccurs. This does not happen at lower PVCs because the competesin the packing whiledryinganddoes of rhe phthalo blue pigment not permit the agglomeration except for Ihe very small panicle size

relationship. (6)

where: X= number of latex particles [ number of pigment panicles

at 1.
v&es

CPVC

This simple model Iits our CPVC

also.

Using the CPVC vales obtained by 89 gloss and the corresponding panicles dianetax. the X and Y experimental values were calculated. Our X5 specular gloss data give: X=l.437YN (7)

specular

BowelI reported that the 2.61 exponent is Ihe same for all latexes and that the precxponential coefficient differs fordifferent latex bases. tie didnot ent results are the repon the contidence limits on vinylhis data, but he worked with polydisperse systems. fix pres-

first tobe reported for mcmcdispene

acrybc ,arex p&MS. The agreement with Bowells equation

is excellent.

In order to explom

the ohmned

hehavinur we propose that and the the

Bydefinition

lhcCPVCisthatwhenall

thepigmcntprescnt 10 visualise particle the the

in lbc dried. uncoalcsccd latex. the pigment ptiiclcs maximum packiog conligoralion WC mw since walr consrder three steps m drying !22] IS present. Ifthis

IS just covered and the voids am tilled by Ihe latex particles. So, usmg a two-dnncnsional arrangement at CPVC approach around one pigmem

I~tcres pa~nlcles are arranged 10 produce approximarely

In lbc first

bchaviour shown in Fig. I3 was obtained. This trend is simdar to the experimental dam for CPVC (Fq. II). The same type of approach should be valid for three dimensions. Fig. 14 shows the porosity of mixtures of LWO types of monodisperse spheres as a function of volume fraction ofthe smaller species and the ratio of the diameter of the smaller to the larger spheres. I% curve is obtained theoretically From considerations of reladve sires and numbers of soheres in a packing. II is based on work by Wise ,231 andkagcndijk 1241. The review of Trocdec and Dodds 1251 is a leadine reference to the literature in this field and is tie basis for the following Eqs. (6) discussion. the experimental relationship expressed in and (7) the focus is not an the coalesced film but To explain

drymg stage the pigment and the latex pamcles can move, proasn takes enough lime. it is valid lo constder that the system may approach the maximum packmg denwy. Then, the second drying step suns and the et the polymer-polymer interface may latex panicles deform and coalesce, sod finally, m rbe third step, mterdiffusion pigment panicles. Because the particles (pzgment and latex) are well dispersed in Ihe firs1 drying step, il is reasonable to bebeve lbal the packing here determines the CPVC of the syswr. 1; order-lo visualise the volume amount of latex panicles required to cover a pigment parwle. let us work lirst in two is a sphere dimensions. Assume the pigment particle (TLI,) form a more or less continuous polymer matrix with trapped

witb a diameter of one unit. When the latex panicle size decreases, the numher of panicles which can contact tiepigmenl sphcrc increases (see Fig. 12).

rather on the maximum packing of the pzgment panicles and undeformed latex spheres. At the condition of minimum porosity the assembly consists of pigment particles, larcx particles and voids (pores).

me numbers of ptgment and latex particlcr arc dctcrmincd as nr and a,, respectively. and are calculaied from the volurn~ fraction of small spheres at minimum porosity using the COTresponding diameter ratio. The scmxpondmg porosity is equal to the volume fraction of votds. and IS gwen by the appropriate cuwc in Fip. 14. This volume can be expressed ~the~quivalent of an additional number, n;, of I& pancles, .which would have the total volilme of the votd fractmn. The minimum porosity condition is de&bed then by the ratio X where

(%)

If the polymer latex can dcfonn dunng CoalCsccncc 10 fill the voids, then this will correspond to the CPVC. Any different volume fraction of smaller spheres leads 10 a condaion of higher porosity in the dried rmxture of pigment and undeformed latex particles. For our calculations, the Ti02 pigment is assumed to be spherical. with a monodisperse diameter equal LO0.3 m_ With any given latex the diameter ratio of pigment to latex particles is known f y) and with <he minimum porosity and volume fraction of small spheres from Fig. 14, X, is then estimated usmgEq. (8). Fromlhiscalculation,theexprrssion obtained forX against Y is: X= I.lSYz4 (9)

fix bard sphcrc model employed here IS based on the assumption that gaps in the packing are randomly dispersed. It may be expected that the real mixtures of dIfferem sned particles will exhibit higher porosity limits than shown at the minima in Fig. 14. Addition of a constant porostty factor to the minima in Fig. I4 does not change the exponent significantly. However. it is imponant to note that if one supposes that the system does notreach minimum poroc~ty lev& then the calculations for X will give different values for the exwnent. Depending on the de&lion assumed from the &imum level. one can obtain regression lines wrth exponents lviw between 2.3 and 3.0. The experimental observed Y& 01 2.66 for the X-Y&&n in dried films (see Re. 15) ~resumably reflects the wxurmnce of somewhat le& than perfect packing of the pigment and latex particles. The agreement ofthis study (monodisperse systems) with ,ha,ofBowe,, 12, (polydispersesystcms) suggcsuthatthc relationship of latex particle size on CPVC could be valid in a typical paint formulation.

while wnh smaller latex panicle sizes. the behaviour is close to logarithmrc. Two optad methcds (specular gloss at incidence angleof 85 and colour difference) gave coincident results for CPVC va!uec for a simple paint formulation. An explanation for the specular gloss data was proposed based on film surface roughness. The pigment and polymer both paniclpate in the packing process which explains the effects of latex particle size on the CPVC. The exponential relation between the CPVC and latex particle size could be explained using the assumption of minimum porosity in packing. before the latex coalesces. The relationship given here in Eqs. (6) and (7) can be used to quanufy the effects of latex particle size on binding capacity in water-based paints. The model used here implies that the packing of the pigmented composition in the first drying stage determines the CPVC of the system. It follows that any factors which restrict pigment mobility. such as larger sizes of non-spherical shapes. will reduce the CPVC of a given latex. This interpretation is consistent with all past work showing that latex paint CPVC values trnd to be higher than solvent coatings of equal pigmmPn!ation and identifies a lack of pigment mobility and latex size as controlling factors. This picture is consistent with the model presented by Fishmanet al. [26].

Acknowledgements We acknowledge financial s~ppon from CONACYT (Consejo Nacmnaide Ciencia y T&hnology) and the Coatings Industry Education Fund of the Federation of Societies for Coatmg; Technology, and helpful discussions with G.P. Bicrwgen.

5. conclusiollr Some authors have shown that the relationship between the CPVC and latex panicle size is Imeu. but others have reportedthattherelationshipislogarithmic Weobserved .>?I CPVC behaviour against latex particle six is neither linear nor logarithmic. Nevertheless, in a medium latex particle snze r:-;.p (0.3-0.7 pm) the behaviour appears linear.

I I I.