Comparison of Meth,

Assess Pigment Disp

Sang T. Van,** Bhaskar V. Velamakanni,t and Ronald R. Adkins-3M Corporation*

Tmo inks made with different led pigme**ts were evaluated by. common mettvods to assess the &give of pigment dispelsion, cT~wpigment
is ?rvoredifficult to dsperse than the other its the vehicle used. The five ttsettwds that could detect &anges in dispersion with each pass
over a three-roll mill weir" a light scattering pa~ticle size distribution analyze,, a NPiRI fi,ze?zess of gi~nd gauge, gloss, contrast ratio
measurements, a~ut rheology. The gloss a~M contrast ratio measu,~?iwnts could detect changes with ead~ pass ovo" a three roll mill only
with a significant reduction fl~ pigment particle size.

INTRODUCTION troscopy (UAS), 12 centrifugal sedimen-
tation measurements, :3 or "ink finger-
The dispersion of a pigment plays a ma~ printing <4 although t h e y are all avail-
jor rote in the properties of the final fihn able to us. W e a p p l i e d the noted meth-
formed b y an ink, paint, or any other ods to two red pigments in a m o d e l
pigmented coating. The pigment par- vehicle for screen printing inks that corn
t i d e size distribution has an effect on rained no dispersion agents. One pig-
the color strength and s h a d @ opacity m e n t is considered b y us to be more
and transparency, 2 gloss, 3 and outdoor difficult than the other to disperse in
weatherability ~in the final film. The p a > this vehicle. W e were curious as to w h y
ticle size distribution has art effect on this is so and if the conmson m e t h o d s
the coating in the liquid state on its rhe noted p r e v i o u s l y w o u l d give us some
ology s and, for fluids of tow viscosity, insight.
on how stable a system will be against There are n u m e r o u s types of fine-
pigment settling. ness of grind gauges used in the indus-
This s t u d y takes a look at some com- try. is We prefer a National Prmting Ink
mon methods to assess the pigment dis- R e s e a r c h I n s t i t u t e (NPIRI) one~mil
persion within a system. Those meth- g r i n d o m e t e r for a fineness of grind
ods are fineness of grind, contrast ratio gauge as o p p o s e d to a Hegman or PC
m e a s u r e m e n t s ~ for opacity and trans gauge. The NPIRI grindometer is used
parency, color strength and shade de routinely in the printing ink industry
velopment, gloss, particle size measure- and is more able to detect particle sizes
ment b y light scattering, rheology, and near the lower linfit of detection than
optical microscopy. We limited our in- the H e g m a n or PC gauge. The printing
vestigations to these methods as these industry needs finer particle sizes be
are the most c o m m o n l y used in the in- cause of the thinner films in printing as
dustry. We d i d not investigate less cons- opposed to painting. A grind gauge is
m o n l y used m e t h o d s such as scanning easy to use, reproducible, and gives an
electron microscopy (SEM) and irons indication of large particles in a pig-
mission electron microscopy (TEM) of a mented system but gives no indication
d r i e d p a i n t film section7 quasi-elastic of the distribution of the majority of
light scattering (photon correlation spec- smaller particles in the dispersed sys-
troscopy)/" image analysis, '~ h y d r o d y - tem3 ~,17It is generally assumed that the
n a m i c chromatography, ~~ back-scatter- decrease in size of the largest particles
ing studies, n ultrasonic attenuation spec- corresponds to an improvement of the
overall dispersion of pigments in the sys
tern. This has been noted in the litera-
Prvs~nle d a t ch e 7 sth A nn ,.,al M ~eI~n< of lh e F ~d ~r alton o f ture for some time, 1:; The smallest par-
6o,:le*les forCo,stlngsI~chndogy, on, J,:l~c,~r 1620, 2ru)u. in ticle size that can be detected b y a fine-
ch , : a ~so.I[
*~2ommer,:~al Graph~,_-sD~vrs~on, 2(~7-glq-(~!: 3M C~ni~r, ness of grind gauge is around 10 mi-
SI Paul, MN 55144 crons according to Lawrence t~ and Hall
t!:M Coris,ora> Prc~:es~T~,:l-nol,a,~y Ce-,l~r. :'~.~1 01 3M
C~nt~. ~"1 Pm,k MI'155t 44
et a l l-~ but Patton is w o u l d suggest that
* * R.etrr~d from 3M Corp b~for~ p,.,b[~,:,~t~on the lower limit is t w o to five microns.
The particle sizes of pigments thai give
the best performance are much smaller
than this. Further, there are those who
feel that the action of drawing the pig-
mented liquid d o w n the gauge can dis-
perse the pigment inore than it is in the
undisturbed state. Still, the fineness of
grind gauge, or grind gauge, is used
extensively in the industry.
A relationship between the degree of
pigment dispersion and the color devel-
opment properties of a pigment, irtctud-
ing the opacity and transparency, has
been noted for some time by Mie.21 Later,
Brockes ~: and Chromey 23 applied spe
cificatly to pigments of all shapes Mie's
theory of spheres. The Mie theory states
that for a given pigment, m a x i m u m color
development is achieved once that pig-
ment is dispersed below a n ~ s i m m n size.
This m i n i m u m size is around 0.10 mi
cron for a moderately absorbing p i ~
ment and 0.05 micron for a strongly ab-
sorbing pigment. Further, the m a x i m u m
opacity of a pigment is reached at a di
ameter of around t~alf the wavelength
of visible light or at around 0.25 micron, z
As the particle size is decreased further,
a decrease in opacity with a subsequent
i n c r e a s e in t r a n s p a r e n c y a n d color
strength is obtained '-~as shown in Figure
1. For many, but not all pigments, there
is a change in shade 1,3,24> with a change
in the particle size distribution. There~
fore, the o p a c i t y / t r a n p a r e n c y and the
color strength and shade of a pigment
can give an indication of its degree of
dispersion.
It should be noted from Figure I that
there is a decrease in opacity with an
increase in particle size above 0.25 mi-
cron. This indicates that any change in
particle siz e from flocculation can lead to

Vol. 73, No. 923, December 2001 61

S.T. Van, B.V. Velamakanni, and R.R. Adkins
~. ................ColorStrength
o _
I
/ ber and type of light source(s) and the
t t
( I . . : I ,_
0 0.I 0.5
ParticleSize,micron
fl' f-Colo;str ng;#
opacity versus particle size.
a significant decrease in opacity. It should
be stressed that this change of o p a c i t y /
transparency with particle size ca~t
in the liquid dispersion or with the dry-
ing or curing of the liquid after applica-
tion. Figu~f 1 indicates also that
strength can be a practical method for
assessing particle size distribution for the
finest of pigment dispersions. The change
in color with dispersion will be d e p e n
dent on the particle shape. The theory
d e v e l o p e d b y Mie w a s for spheres,
Felder3~ has noted that it is the minbmon
dimension of a nonspherical particle that
has the greatest effect on determining
color strength.
Gloss has been Mlown to be an indi-
cator of the degree of pigment disper
sion)S 31-34Normally, the gloss will in
crease with a decrease in the p i g m e n t
particle size. Guenthert et a13 and Carr 1,3r
have noted that the specular gloss of a
film cast h~crease until the mean particle
size is around 0.30 micron. There is no
apparent change in specular gloss with
mean particle sizes smaller than 0.30 mi-
cron, but Carr ~did note in his s t u d y that
there w a s a decrease in haze as the mean
particle size was decreased to about 0.12
micron. This was the smallest size that
could be detected inhis study. Guenthert
et aL noted that a small fraction of par-
ticles with sizes exceeding 0.50 micron
can cause a significant reduction in gloss,
Therefore, gloss can be a sensitive
method to give an indication of the dis-
persed state of a system.
The measurement of particle size b y
light scattering is based on the Mie
theory. A particle will scatter light ac-
cording to the particle diameter, its re
tractive index, and the wavelength of
the light source(s). A schematic of a light
scattering instrument is presented in Fig~
ure 2. The angle of the light that is scat~
tered off a dilute dispersion is detected.
62 Journalof Coatings Technology
From this, a particle size distribution can
be calculated. This method assumes for
the calculations that the particles are
spherical, In order for the method to be
of value, one must be sure that what is
b e i n g m e a s u r e d is a r e p r e s e n t a t i v e
sample of the dispersion and that there
is no change in the dispersion of the
system upon dilution for measurement.
The values one obtains w i l l d e p e n d upon
the algorithm used in the calculations
and instrument factors such as the n u m -
n u m b e r of detectors. Js,3~ Further, the
particle sizes calculated are from allpos-
I
t.O sible orientations of the particles. The
particle size information that one ob~
rains might or might not correspond to
what is actually present in the dispersed
'L state.
| A discussion of the theology of dis
persions is beyond the scope of this in-
troduction. The rheology of a dispersed
system, though, wilt changewith a change
inthe particle size distribution? 7-39In gen-
occur eral, as the average particle size becomes
smaller, the total surface area of the pig
merit increases, which results in more
color vehicle being adsorbed. This adsorption
normally causes the yield value, viscos~
ity, and the dynanfic elasticity of a dis-
persion to h~crease and the compliance
(creep) 4~ to decrease.
Optical microscopy is a valuable in-
strument that is often ignored b y coat-
ing scientists. The microscope can be used
to obtain a particle size distribution ac
cording to several established test pro~
cedures. 4L'-44 The practicalresolvingpower
of an optical microscope is d e p e n d e n t
on the numerical aperture of the objec
tive and the wavelength of the light
source. For oil immersion lens w i t h a
numerical aperture of 1.30 and ush G
white light, the lowest possible limit of
resolution is 0.20 micron. ~ The practical
lower limit without the use of oil immer
sion of the objectives w o u l d be around
0.50 micron. The microscope could be
used to determine the absolute sizes or
dimensions of particles greater than this.
~aa-tother use w o u l d be to confirm that all
particle size dimensions are less than 0.50
micron which can be concluded if no
individual p article can be resolved, I f so,
r~
d Figure 2-Schematic of a light scattering particle size analyzer.
this particle size distribution w o u l d be
adequate for most applications. Again,
as with the dynanfic light scattering in-
strument, the application of the optical
microscope requires that the sample be-
ing investigated be representative of the
pigment dispersion and that there be no
change in particle size distribution with
dilution. It should be noted that refer~
ences 43 a n d 45 refer to ASTM lest
method E20. This test method was dis~
continued as of 1994.
EXPE RIMEN TAL
Two red pigments were studied in a con
ventional solvent based acrylic vehicle
for a screen printing ink. One pigment
studied -was a perylene red (PR 224)and
the other was the Irgazh~TM DPP red BO
(PR 254) b y Ciba Specialty Chemicals
Corp., Newport, DE. The perylene pig-
ment is considered b y us to be n~ore
difficult to disperse in the vehicle used in
this study.
The vehicle in this study consisted of
a blend of a poly(methyl methacrylate)
(PMMA) resin and a PMMA copolymer
resin at a 3:5 solids ratio at 42.40 wt%
total solids in EB acetate solvent. The EB
acetate solvent was chosen to l~0inimize
the solvent loss on a three-roll mill while
still resulting in a vehicle of acceptable
solids loading and acceptable Newtonian
viscosity (71.2 poises at 25.0~C).
The millbases were prepared with 20
wt% p i g m e n t in the vehicle b y p o w e r
mixing with a Cowles 4' blade at high
shear at 3000 r p m for 40 rain and then
passing over a three roll mill at pres
sures (feed r o l l e r / a p r o n roller) once at
100/150 psi and the remaining times at
200/250 psi. Samples of the millbases
were taken to make inks after each pass
over the three roll mill. The percent solids
of each rnillbase were measured after ev
ery pass to determine if any solvent loss
h a d occurred during milling. If so, the
solvent loss was compensated for when
making inks. The hlks were made b y
n~xing 55.20 wt% of the millbase with
44.17 wt% of the vehicle and the rest
(0.63 wt%) was a silicone flow agent. The
final inks had 11.04 wt% of pigment.
~etectofs d~'~ ~ ; 1 0 r r,c a 1 1 ~ ' ~ l I~;~| rsallem
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