TE

Effect of Extenders with Narrow and Broad Particle

CH
N
FO OLO
RU G
Effect of Extenders with Narrow M Y
and Broad Particle Size Distributions
on the Properties of Coatings
Rüdiger Werner—OMYA-Plüss-Staufer AG*

Extenders are manufactured in a wide range of finenesses enabling paint formulators to influence specific properties of the finished paint.
It is necessary to know the “granulometry” or particle size distribution of the extender to select the appropriate one to achieve the desired
properties.
Two extenders with practically the same top cut, but one with a broad particle size distribution curve, and the other one with a narrow
or “steep” particle size distribution curve, were compared in four different coating systems. The extender with a narrow particle size
distribution offered some advantages over the finer one with a broader particle size distribution.
The technical advantages of using such extenders over those with broad curves but similar finenesses, are in particular: ease of
dispersion, higher opacity, haze-free gloss, shortening of the drying time, and spacing properties for titanium dioxide.

E
xtenders are manufactured in a An additional property is the “steep- ultra-fine). It represents a convention-
wide range of finenesses and are ness” of a particle size distribution ally manufactured, very fine extender.
used in the paint industry to ful- curve, defined by the “steepness fac- An extender with a narrow particle
fill specific requirements in different tor” (SF).1 This is the quotient of the size distribution curve contains particles
coating systems. Products that are used d50 and the d20 values (corresponding within a smaller size range. Ideally such
in the coatings industry range from very to the size of particle such that 20% by an extender would be monodisperse or
fine powders in the sub-micron range weight of those present are finer). The iso-diametric, i.e., all particles would be
up to 7-mm chips. To cover the varying SF defines certain properties in the of the same size. In the following text, an
requirements of paint manufacturers, a finished paint. extender with a very high proportion of
large number of extender grades are The SF can be calculated from the particles within a very narrow particle
manufactured. particle size distribution curve of the rel- size range will be described as CaCO3-
Why are there so many different ex- evant extender as shown in Figure 1 us- ID (for iso-diametric).
tenders? The paint chemist can influ- ing the following equation: The most important fineness data
ence a wide range of properties, e.g., together with the oil absorption and
rheology, density, mechanical and op- d
SF = 50 (1) specific surface area of two fine cal-
tical properties, corrosion resistance, d20 cium carbonate extenders are summa-
and durability, by correctly selecting ex- rized in Table 1. Figure 2 gives the par-
tenders with the appropriate chemical 0.85µm
SF = = 1.89 (2) ticle size distribution curves of CaCO3-
composition and granulometry. The 0.45µm UF and -ID, representing fine extend-
granulometry or particle size distribu- ers with broad and narrow curves, re-
tion of an extender is characterized in A curve with the SF greater than 2 is spectively.
general by the particle size distribution described as “broad,” and those with
curve illustrated in Figure 1. The most the factor of less
important points are the “top cut” (d98), than 2 as “nar-
which gives the diameter of extender row” or “steep.”
particle so that at least 98% of the par- In other words,
ticles by weight are finer, i.e., in prin- a fine extender
ciple the coarsest particle present, and with a broad
the “median particle size” (d50), which particle size dis-
represents the size of particle so that tribution curve
50% of the particles by weight are contains a wider
coarser or finer. range of differ-
These terms are of particular impor- ent size par-
tance when considering fine extenders. ticles, e.g., from
under 0.1 to 3
Revised version of a paper presented at 1998 FSCT µm. Such an ex-
Annual Meeting Technical Program, October 14–16,
1998, New Orleans, LA. tender will be re-
*Technical Services Laboratory, Paints & Surface ferred to in the
Coatings, CH-4665 Oftringen/Switzerland.
following text as
Contact in the USA: OMYA, Inc., Alpharetta, GA
CaCO3-UF (for Figure 1—Particle size distribution.
30022.

Vol. 72, No. 903, April 2000 71

R. Werner

ticles of the right size. The parameters

Table 1—Fineness Data of CaCO3-UF and -ID
which influence light scattering power
CaCO3-UF CaCO3-ID are particle diameter, particle size distri-
bution, and refractive index. For high
Oil absorption opacity, Burri and Mitton2,3 calculated
(Rub out - method, ISO 787/5)g/100 g ............................ 20 21 that a narrow particle size distribution
Specific surface
(BET - method, ISO 9277) m2/g .............................. 16 7
with a median diameter between 0.6 and
Top cut (d98) µm .............................. 3 4 0.8 µm should be the target. All particles
Mean particle size (d50) µm .............................. 0.44 0.90 having the same size would be ideal.
Particle size (d20) µm .............................. 0.17 0.60 The second effect is due to the cre-
d
Steepness factor = 50 .............................. 2.6 1.5 ation of tiny empty spaces between the
d 20
particles. These can either be filled by
air, which increases the opacity, or by
the fine pigment particles present. Since
the CaCO3-ID contains virtually no par-
Table 2—Formulation (C 344) of a Practical Interior Emulsion Paint ticles below 0.2 µm, these spaces are filled
Formulation Pt. Wt. Lb/100 Gal (U.S.) Gal (U.S.) with air. This is called “dry hiding“ in
the literature.4 Using an isodiametric ex-
Binder 50% tender increases the volume of air in the
(vinyl acetate, VeoVa, acrylic ester) ... 105.0 138.0 15.32 film markedly. This can be deduced from
Rutile TiO2 ......................................... 60.1 79.0 2.31 the oil absorption and the specific sur-
Co-extender face area (SSA) values given in Table 1
(5 µm median particle size) ............... 320.0 420.7 18.67 and measured using the rub-out method.
CaCO3 test extender The SSA of CaCO3-UF is 16m2/g, double
(density 2.7) .................................... 124.9 164.2 7.29
Water + additives ............................... 390.0 512.5 56.43
that of CaCO3-ID (7 m2/g), due to the
much higher content of ultra-fine par-
1000.0 1314.4 100.02 ticles.
Data
Pigment volume concentration (PVC) ............... 81.5%
Oil absorption is a measure of the
Density of the liquid paint .............................. 13.14 lb/gal amount of linseed oil adsorbed onto the
Volume solids ............................................... 38.2% surface of the extender particles plus the
Weight solids ............................................... 61.5% amount needed to fill in the micro-voids
between the particles. The higher SSA of
CaCO3-UF results in greater oil adsorp-
tion, but the larger number of ultra-fine
EXPERIMENTAL EXAMPLES The paints were made using a high particles present in CaCO3-UF fill many
speed disperser and allowed to age for of the micro-voids, reducing the amount
Opacity of a Heavily Filled about 16 hr. They were applied to black of oil needed for this purpose. These
Interior Emulsion Paint and white opacity charts using a draw two opposing effects cancel one another
bar with a gap of 150 µm. After 24-hr out resulting in virtually identical oil
The comparison of the optical perfor- drying time, the optical properties of the absorption values.
mance of the ultra-fine CaCO3-UF with dried films were measured. The results The critical PVC of paints made us-
the iso-diametric CaCO3-ID was made are given in Table 3. ing CaCO3-ID is lower than those made
in a practical interior emulsion paint for-
Virtually no differences between the with CaCO3-UF at constant PVC, so more
mulation (Table 2). The pigment compo-
two extenders were detectable regard- air is entrapped in the dry film, leading
sition consisted of about 6 wt% titanium
ing brightness, yellowness index, and to a higher dry opacity.
dioxide and 32 wt% of a co-extender
low angular sheen. But the contrast ratio
with a mean particle size of 5 µm and in
was increased by almost one percentage
each case 12.5 wt% of the fine extender Manufacture of Eggshell and
point, although CaCO3-ID has a higher
under test. The pigment volume con-
median particle size diameter (MPD) of High-Gloss Oil-Bound Paints
centration (PVC) of both paints was
0.9 µm than CaCO3-UF (MPD 0.44 µm). Using a High Speed Disperser
81.5%.
This difference is
High speed mixers are being increas-
clearly visible to
ingly used to manufacture the whole
the human eye.
range from eggshell to high-gloss syn-
This surprising thetic binder-based paints. The aim of
result is attributed saving time and costs can only be
to the following achieved when easily dispersible pig-
properties high- ments and extenders are available. The
lighted in Figure 2: CaCO3-ID is easier to disperse than the
CaCO 3 -ID con- conventional ultra-fine calcium carbon-
tains a high pro- ate because it contains less particles finer
portion of particles than 0.2 µm. It is these particles that are
between 0.6 and strongly attracted due to Van der Waals
1.2 µm—about forces and so form hard agglomerates
55% by weight that are difficult to break up.5 This is
compared to 22% illustrated in the following eggshell
for CaCO 3 -UF— alkyd paint with a PVC of 34% (Table 4).
Figure 2—Particle Size Distribution of CaCO3-UF hence, a large
and -ID (Sedigraph 5000). number of par- A high speed mixer with a saw-
toothed disc was used. The peripheral

72 Journal of Coatings Technology

 Effect of Extenders with Narrow and Broad Particle

speed was deliberately kept low at 9.5

m/s (30 ft/s). The fineness of grind was
determined using a grindometer accord- Table 3—Brightness, Opacity and Sheen (Gloss
ing to ISO 1524, comparable with the at 85° Angle)
Hegman gauge. The results, compared
CaCO3-UF CaCO3-ID
to a formulation containing only tita-
nium dioxide as a reference, are given in Brightness Y (%) ......................... 89.6 89.5
Table 5. Yellowness index ....................... 4.0 3.5
Contrast ratio (%) ....................... 95.7 96.6
The paints with a PVC of 34% were Sheen at an angle of 85° (%) ...... 3 3
applied to glass panels using a drawbar
with a gap of 150 µm. The films were
allowed to dry for four weeks at 23°C
and 50% relative humidity (RH). The
60° gloss was 48% for CaCO3-UF and
75% for CaCO3-ID.
The iso-diametric CaCO3-ID with a Table 4—Formulation (Q 160) of a White Eggshell Alkyd Paint
narrow particle distribution curve, more-
over, shows excellent dispersion charac- Formulation Pt. Wt. Lb/100 gal (U.S.) Gal (U.S.)
teristics, comparable to a very easily dis-
persible titanium dioxide. The outstand- Mill base Long oil soya alkyd 70% .......... 209.2 241.5 30.50
TiO2 (Kronos 2059) ................. 235.6 271.9 7.96
ing dispersion properties of CaCO3-ID CaCO3 extender (density 2.7) .. 235.6 271.9 12.09
also explain the markedly smoother film Anti-skinning agent .................. 5.4 6.3 0.82
surface and the much higher gloss val- Solvent ................................... 51.6 59.5 9.16
ues compared to CaCO3-UF.
Let down Long oil soya alkyd 70% .......... 201.9 233.0 29.43
Solvent + additives .................. 60.7 70.1 10.04
Gloss and Gloss Retention of
............................................. 1000.0 1154.2 100.0
CaCO3-ID in a Blue Industrial Data
Metal Finish Pigment volume concentration (PVC) ........................ 34.3%
Density of the liquid paint ....................................... 11.54 lb/gal
Air-drying maintenance paints used Volume solids ....................................................... 58.4%
to coat machinery parts and equipment Weight solids ....................................................... 77.5%
usually contain small amounts of extend-
ers. These act as bulking agents and also
help to lower raw material costs. The
extenders must not cause hazing and
must be easy to disperse.
Interesting results were obtained Table 5—Results of the Dispersion Trials
when ultra-fine CaCO3-UF was com- after Eight Minutes
pared with iso-diametric CaCO3-ID,
with a steep particle size distribution High speed dispersion (ISO 8780-3)
curve, in a fast-drying blue machine 9.5 m/s (30 ft/s) Fineness of Grind
paint. The formulation and data are
given in Table 6. Extender: ISO 1524 Hegman (NS)

The machine paints were made using CaCO3-UF .................. 40 µm 4.5 - 5.0
a high speed disperser (HSD). The ph- CaCO3-ID .................. 10 µm 7.0 - 7.5
thalocyanine blue pigment was made For comparison:
into a paste concentrate separately us- Titanium dioxide ......... 10µm 7.0 - 7.5
ing a three-roll mill.
The HSD was run for 10 min with a
peripheral disc speed of 18 m/s (60 ft/
s). The results are given in Table 7.
The superior dispersion properties of Table 6—Formulation (Q 161)—Blue Industrial Metal Finish
this iso-diametric extender compared to
CaCO3-UF, which contains many ultra- Formulation Pt. Wt. Lb/100 Gal (U.S.) Gal (U.S.)
fine particles that tend to form agglom-
Medium oil alkyd resin (55%) ............. 653.1 601.4 76.71
erates, are evident.
Phthalocyanine blue .......................... 14.2 13.1 0.95
In Table 8, the gloss and gloss reten- Titanium dioxide, rutile ...................... 141.2 130.0 3.90
tion after four-weeks’ drying at 23°C and CaCO3 test extender (density 2.7) ...... 57.6 53.1 2.36
50% RH are given. Haze was also as- Solvents + additives .......................... 133.9 123.4 16.10
sessed after 10-weeks’ drying time by 1000.0 921.0 100.2
using visual standards graduated from Data
0 (no haze) to 10 (very hazy). Pigment volume concentration (PVC) ............... 17.0%
The 20° gloss was measured 24 hr Density of the liquid paint .............................. 9.21 lb/gal
after application to the glass panels (start- Volume solids ............................................... 42.3%
Weight solids ............................................... 59.6%
ing values) and after four-weeks’ dry-
ing. The loss of gloss was about 14 per-

Vol. 72, No. 903, April 2000 73

R. Werner

centage points for CaCO3-UF and only 4

Table 7—Results of the Dispersion Trials for CaCO3 -ID.
after 10 Minutes
This can be explained by the shrink-
High speed dispersion (ISO 8780-3) age of the film as the last traces of sol-
18.0 m/s (60 ft/s) Fineness of Grind vents evaporate. The surface of the paint
film takes up the contours of the under-
Extender: ISO 1524 Hegman (NS) lying pigment and extender particles.
CaCO3-UF ................. 25 - 30 µm 6.0 As already noted, the CaCO3-UF con-
CaCO3-ID .................. <10 µm 7.5 tains more, larger agglomerates than
CaCO3-ID resulting in a “rougher” sur-
For comparison:
face. Paints manufactured with the easy
Phthalocyanine blue
paste concentrate ..... <10µm 7.5 dispersible CaCO3-ID have not only a
high initial gloss but also superior gloss
retention. This makes such an extender
of particular interest to the paint indus-
try, including manufacturers of glossy
filler-surfacers for automotive OEM coat-
Table 8—Gloss, Gloss Retention, and Hazing of a Blue Indus- ings and glossy powder coatings. In the
trial Metal Finish
latter case, the easy dispersion of CaCO3-
CaCO3-UF CaCO3-ID ID helps to disperse the white and col-
ored pigments during the extrusion pro-
Gloss 20° Angle cess.
(%) Start ................................. 66 79
4 weeks ............................ 52 75 Two additional examples illustrate
the advantages offered by an extender
Gloss 60° Angle with a steep particle curve such as
(%) Start ................................. 84 87 CaCO3-ID; further interesting properties
4 weeks ............................ 79 87
of a steep particle size distribution curve
Hazing (visual standards)a .......................... 6 3 become evident.
10 weeks .......................... Marked Slight
(a) 0 = no haze; 10 = very hazy. Drying Time of
Waterborne Coatings
The speed of drying such systems
depends on the ease with which water
molecules can escape to and evaporate
Table 9—Formulation (I 145) Use of CaCO3-ID in a Road Marking Paint from the surface of the coating. This is
one of the most important criteria in
Formulation Basis (pt. wt.) CaCO3-ID (pt. wt.) physically drying waterborne road
Styrene acrylate emulsion 40% ............... 223.0 223.0 marking paints.
Titanium dioxide, rutile .......................... 148.0 100.0 When the extenders contain ultra-fine
CaCO3 5 µm ....................................... 189.0 189.0 particles, these block the micro-capillar-
CaCO3 15 µm ..................................... 377.0 377.0 ies hindering the passage of water mol-
CaCO3-ID (test extender) ....................... — 48.0
Water + additives ................................. 63.0 63.0
ecules. In contrast, the CaCO3-ID does
not contain such particles leaving the
1000.0 1000.0 micro-capillaries free. This phenomenon
Data
is comparable to the passage of water in
Pigment volume concentration ................ 73.8% 74.1% trees from the roots to the crown or with
Density of the liquid paint ...................... 15.52 lb/gal (U.S.) 15.37 lb/gal (U.S.) the flow of liquid wax in the wick of a
Volume solids ....................................... 63.1% 63.4% burning candle.
Weight solids ....................................... 80.3% 80.3% The partial replacement of titanium
dioxide by an iso-diametric extender can
reduce the drying time of a road mark-
ing paint by 50% as shown in Table 9.
The simple addition of CaCO3-ID can
Table 10—Formulation (L 131) of a Short-Oil Baking Enamel shorten the drying time of a waterborne
road paint from 17 to 7 min, a reduction
Formulation Pt. Wt. Lb/100 Gal (U.S.) Gal (U.S.) of more than 50%. This was measured
under ambient conditions using the dry-
Short-oil castor oil alkyd 60% .................. 432.8 455.0 53.45 ing-time-wheel according to ASTM D
Highly reactive melamine resin 55% ........ 146.0 153.5 19.16
Rutile titanium dioxide, enamel quality ...... 294.5 309.5 9.05
711.
Additives + solvents ............................... 126.7 133.2 18.34 Shortening the drying time of water-
reducible paints offers further opportu-
1000.0 1051.2 100.0
nities for CaCO3-ID, especially in prim-
Data ers. In wood primers, the fibers swell
Pigment volume concentration (PVC) .................... 19.4% less since there is less time for them to
Pigment:binder (100% solids) .............................. 0.87:1 absorb water. In anti-corrosion primers,
Alkyd:melamine resin ratio .................................. 76:24 it reduces the risk of flash-rusting dur-
Baking conditions .............................................. 30 min/120°C ing the drying process.

74 Journal of Coatings Technology

 Effect of Extenders with Narrow and Broad Particle

CaCO3-ID as a Spacing Extender

for the Partial Replacement Table 11—Results—Dispersion, Gloss, and Hazing
of TiO2 TiO2 (%) ................................. 100.00 93.75 87.50
CaCO3-ID (%) ......................... 0 (basis) 6.25 12.50
In North America, the paint industry
used about 775,000 tons of TiO2 in 1997.6 Fineness of grind
Assuming that perfect dispersion and ISO 1524 (0 - 25 µm) ......... < 10 µm < 10 µm < 10 µm
optimum formulation allows a saving of Hegman (NS) ..................... 7.5 7.5 7.5
10%, then 78,000 tons of this valuable, Gloss at 25° angle
expensive raw material could have been Goniophotometer ................ 99% 97% 97%
saved. Evidently it is of great impor-
Hazing (visual standards)a ........ 0 0 1
tance to the paint industry to use the
None None Virtually none
technical properties of this raw material
to the utmost by optimizing the formu- Gloss reduction after overbaking
lation. (60 min at 150°C)
Percentage points ............... 10 11 11
Which factors inhibit the perfect use
of TiO2? What can CaCO3-ID do to im- (a) 0 = no haze; 10 = very hazy.
prove its efficacy? These questions can
be answered by the following example
of the partial replacement of TiO2 in a
white baking enamel. The most impor- Table 12—Results—Brightness and Opacity
tant factors that hinder the optimum ef-
ficacy of TiO2 in a paint system can be Volume Replacement of TiO2 Brightness (%)
summarized as follows7: incomplete dis- TiO2 : CaCO3-ID RX Ry Rx
persion of TiO2 agglomerates during the (%) (%) (red) (green) (blue) Opacity (%)
mixing process; flocculation caused by
incomplete wetting of TiO2 and unsuit- 100.00 : 0 (basis) 92.6 92.4 90.4 98.8
able stabilization; and imperfect spac- 93.75 : 6.25 92.5 92.2 90.4 98.7
87.50 : 12.50 92.4 92.2 90.4 98.4
ing of the TiO2 particles in the dry film
due to too high a TiO2 volume concen-
tration and crowding caused by shrink-
ing of the film during drying, which ultra-fine particles below 0.2 µm. This of the drying time, especially of water-
forces the TiO2 particles to pack too is anther example of the excellent dis- borne systems, due to the capillary ef-
closely together. persion properties of CaCO3-ID with fect; and partial replacement of titanium
What can a suitable extender do to a fineness of grind of under 10 µm dioxide by spacing and preventing re-
improve the optical efficiency of titanium measured using the 25 µm gauge. This agglomeration.
dioxide?8 The main requirements are: ease of dispersion is comparable to
good dispersion to break up TiO2 ag- that of a top quality titanium dioxide
glomerates and hinder flocculation dur- which is sold for the manufacture of
ing drying9,10; suitable separation of TiO2 industrial enamels using a high speed ACKNOWLEDGMENTS
in particular in the dry film (also re- disperser.
ferred to as spacing11; any single particle The author wishes to express his grati-
There was scarcely any difference in tude to the following colleagues for their
of a 0.8 µm spacing extender (e.g., the brightness, gloss, gloss retention af-
CaCO3-ID, replaces 64 particles of a 0.2 contributions: Martin Merz for technical
ter over-baking, or hazing compared to review and calculations, Anthony C.
µm TiO2 on an equal volume basis12); the original formulation that contained
and good dried film appearance (i.e., Page for his conscientious translation of
only titanium dioxide. the manuscript, Peter Faganello for the
maintain the gloss of the dried film and
not cause hazing). The values given in Table 12 show preparation of graphs and figures, and also
that virtually identical optical proper- to OMYA-Plüss-Staufer AG, Oftringen,
The results of trials with CaCO3-ID ties were achieved even when up to 12.5 Switzerland for permission to publish this
as a partial replacement of titanium di- vol% of the titanium dioxide was re- work.
oxide are given in the following example. placed on a volume basis by CaCO3-ID.
The trials were carried out in a critical,
short-oil baking enamel; the formulation References
is given in Table 10. (1) Strauch, D., Belger, P., Hofer, H., and
SUMMARY
The partial replacement of titanium Merz, M. (to Plüss-Staufer AG), U.S.
The examples given have shown that Patent 4,767,464 (Aug. 30. 1988).
dioxide was carried out in two steps: on
“still finer” does not necessarily mean (2) Burri, P., Spielmann, D.C., Naydowski,
a volume basis, 6.25% and in a second C., and Swanson, E.T., “From Theory to
step, 12.5% of the titanium dioxide was “still better.” Fineness as defined by top
Practice —Use of Classical Theory to De-
replaced. The enamel was made using a cut and median particle size must be sign a Pigment with Improved Optical
high speed disperser with a saw-tooth supplemented by the steepness factor Properties,” TAPPI Conference, Nash-
disc. It was dispersed for 15 min and the (SF) of the particle size distribution ville, TN, May 16-18, 1996, TAPPI Tech-
peripheral speed of the disc was 11 m/s curve. A narrow particle size distribu- nology Park, P.O. Box 105113, Atlanta
(36 ft/s). The results are given in Tables tion extender (SF 1.5) – offers the follow- GA.
11 and 12. ing advantages over a product with a (3) Mitton, P.B., Vejnoska, L.W., and
broad particle size distribution (SF 2.6): Frederick, M., “Hiding Power of White
The outstanding results can be ex- improved opacity of emulsion paints; Pigments: Theory and Measurements,
plained by the narrow particle size easier dispersion; higher gloss and no Part II,” Official DIGEST, 34, No. 444, 73,
distribution curve with practically no (1962).
hazing in oil-bound systems; shortening

Vol. 72, No. 903, April 2000 75

R. Werner

(4) Stieg, F.B. and Ensminger, R.I., “The Pro- (8) Vaidya, V.S. and Nato, V.M., “Simulta- (10) Fitzwater, S. and Hook, J.W., “Depen-
duction and Control of High Dry Hid- neous Assessment of Influence on Hid- dent Scattering Theory: A New Ap-
ing,” Official DIGEST, 34, No. 38, 92 (1961). ing Power by Several Compositional Fac- proach to Predicting Scattering in
(5) Crocker, J.C. and Grier, D.G., MRS-Bul- tors: Taguchi Approach,” JOURNAL OF Paints,” JOURNAL OF COATINGS TECHNOL-
letin 23, 24-31 (1998). COATINGS TECHNOLOGY, 64, No. 811, 63 OGY, 57, No. 721, 39 (1985).
(6) Kline & Co., Extender and Filler Minerals, (1992). (11) Debnath, N.C. and Kotkar, D.D., “Theo-
North America 1998, Vol. 2, Kline & Co., (9) Cutrone, L. and Becherel, D., “Interac- retical Studies of Light Scattering
Little Falls, NJ. tion Between Fine Particle Size Extend- Power,” Eur. Coat. J., 4/98, 264 – 269.
(7) Cremer, M., “Eigenschaften von ers and Titanium Dioxide in Paints,” (12) Stieg, F.B., “Effect of Extenders on
Titandioxidpigmenten in Abhängigkeit Tioxide-Technical Service Report D9202 Crowding of Titanium Pigment,” JOUR-
vom Herstellungsverfahren,” Farbe und GC. Report freely available from Tioxide, NAL OF COATINGS TECHNOLOGY, 61, No. 778,
Lack, 98, No. 8, 597 (1992). England. 67 (1989).

76 Journal of Coatings Technology