MNL17-EB/Jun.
1995
Black Pigments
by Frank R. Spinelli 1
BLACKPIGMENTSFALLINTOthree classes [1 ] (Table 1). The first
two classes derive their color characteristics from the ele-
ment carbon, the third class from ferrous oxide, Fe304. Class
1 blacks are carbon blacks, which are composed of 90% or
more of elemental carbon. Class 2 blacks may be referred to
as "carbonaceous pigments," which range from 8 to 88% ele-
mental carbon.
CARBONACEOUS PIGMENTS (CLASS 2)
This class of blacks, perhaps the least important for paints
and coatings, is composed of two main types:
Mineral Blacks
Mineral blacks are finely ground derivatives of coal and
shale and are mixtures of carbon, aluminum silicates, silica,
and iron oxides. They can be characterized as having poor
jetness, very low tinting strength, low oil absorption, very
brown undertone, and poor dispersibility. Consequently, they
are rarely used in the paint industry.
Bone Blacks
Bone blacks are made by destructive distillation of solvent-
extracted cattle and sheep bones and contain only from 8 to
17% carbon with the remainder mostly calcium phosphate.
During the "calcination" (8 h at 800~ the organic matter is
decomposed and the resulting carbon forms a thin, porous
film on the surface of the mineral network, creating a large
carbon surface area per unit of weight. Consequently, they
have high color and great adsorptive ability, but very weak
tinting strength. Oil absorption is quite low, and aqueous
dispersibility is excellent. Bone blacks are used only in spe-
cialty finishes where high color with low oil absorption is
essential.
IRON OXIDE BLACKS (CLASS 3)
Naturally occurring as the mineral magnetite, these blacks
are synthesized by reacting ferrous sulfate, FeSO4, with alkali
and then oxidizing to ferrous oxide, Fe304 (black magnetic
oxide). Having the highest density as well as excellent light
~Technical consultant for Cabot Corporation, Special Blacks Divi-
sion, 157 Concord Rd., Billerica, MA 01821.
Copyright9 1995 by ASTM International
i
fastness and chemical resistance, they are used in the paint
industry chiefly in metal-protective primers. It should be
noted that black iron oxide, Fe304, will oxidize at high tem-
peratures to red or brown ferric oxide, Fe203. Iron oxide
blacks have very poor color and strength properties com-
pared to carbon blacks.
CARBON BLACKS (CLASS 1)
Carbon black is the most important black pigment for
paints and coatings. This unique, strictly manmade material
offers great versatility in end use performance. Through vari-
ation in key properties, by careful control of manufacturing
conditions, a broad range of grades is commercially avail-
able. To provide a better understanding of carbon black as a
pigment in paints and coatings, the effects of carbon black
property variations on its optical functioning in dispersed
media are herein defined. This involves some discussion of
how carbon black is formed as well as identification of its key
parameters. Following is an elucidation of the mechanisms of
carbon black optical function and how they are influenced by
variations in each of the key parameters. Based on this
knowledge, certain guidelines for selection of a grade of
carbon black are enumerated. As a corollary, the subjects of
achieving optimal quality dispersion and its importance to
end use performance are addressed. Finally, techniques of
measurement of carbon black coating's optical performance
properties are outlined with reference to the appropriate
ASTM tests where applicable.
Carbon Black Optical Function
General Nature of Carbon Black
1. Principles of Formation--The formation of carbon black
requires the application of thermal energy to a hydrocarbon,
usually by incomplete combustion (limited oxygen supply),
which results in the rupture of C - - H bonds [2]. This first
stage is often called "cracking" (Fig. 1A). The reaction prod-
ucts are aromatic radicals and dicarbon radicals, highly reac-
tive species, which combine to form hexagonal lattices in a
planar configuration. Several "layer planes" then tend to stack
to form crystallites (Fig. 1B). These crystallites tend to form
spherical prime particles that continue to grow, forming pri-
mary aggregates, the characteristic units of carbon black (Fig.
2). Both prime particle and primary aggregate distributions
are typically broad since a great number of layer planes and
179
www.astm.org
 180 PAINT AND COATING TESTING MANUAL

TABLE 1--Classification of black pigments.

Type Source Specification Color Index and Name
Class 1: Carbon Blacks
(a) Furnace Oil ...
(b) Channel Gas D 561 77226; pigment black 7
(c) Lamp Oil D 209 77226; pigment black 7
(d) Thermal Oil and gas ...
(e) Acetylene Gas ...
Class 2: Carbonaceous Pigments
(a) Mineral Coal
(b) Bone Bones D 210 77267; pigment black 9
Class 3: Iron Oxides
(a) Synthetic Copper D 769 77499; pigment black 6
(b) Natural Ore ... 77499; pigment black 6
NOTE: From ASTM Paint Testing Manual, Black Pigments 2.8.4; 13th ed., 1972.

(AROMATIC (DICARBON
RADICAL) RADICAL)
c ~ C H 3 6 *~,'~* *
CH4 + CRACKI~* ' ~. / ~ f9' * "4" C2 "~" H 2

A
T ~

INTERACTIO~NOF
REACTIVE SPECIES

(HEXAGONALLATTICE
LAYERPLANE) B

(NUCLEATIONOR
CRYSTALLITEFORMATION)
FIG. 1-Formation of carbon black. Asterisks indicate active sites.

crystallites are going t h r o u g h the described processes, b u t
not in phase. Those particles a n d aggregates which b e g a n
f o r m a t i o n sooner w o u l d have longer growth times a n d w o u l d
be larger. By choice of h y d r o c a r b o n feedstock a n d careful
control of r e a c t i o n conditions, the key p r o p e r t i e s of p r i m e
particle size, p r i m a r y aggregate size, porosity, structure, a n d
surface c h e m i s t r y are varied to create the s p e c t r u m of com-
mercial c a r b o n blacks.
2. Types~Processes [ 3 ] - - T h e r e are five types of industrial
carbons which fall in the general category of c a r b o n black.
I n c l u d e d are l a m p b l a c k , channel black, furnace black, ther-
mal black, and acetylene black. E a c h of these is m a d e b y a
different process and, consequently, has some unique p r o p e r -
ties (Table 2).
L a m p b l a c k Process. Oils or resins are b u r n e d in shallow
p a n s in a n enclosure with restricted air supply, a n d the smoke
 CHAPTER 20--BLACK PIGMENTS 181

This process can produce carbon blacks of particle sizes rang-

CRYSTALLITE ~ , , g P - - PRIME PARTICLE
/
PRIMARYAGGREGATE
FIG. 2-Growth to particles and aggregates.
is passed through settling chambers prior to venting (Fig. 3).
Carbon black deposited on the cool walls of the chambers is
subsequently scraped off by motor-driven ploughs. The prin-
cipal feedstocks are coal tars or petroleum residual oils.
Lampblack's major usage in the coatings industry is as a
tinting pigment. It exhibits excellent antiflocculation proper-
ties and an extremely blue undertone. Though lampblacks
have been replaced by furnace blacks to some extent on a
tinting strength basis, substantial quantities are still pro-
duced for special applications.
Channel Process. Until about 1975, this process was the
leading source of carbon blacks for the coatings industry. Its
demise was brought about by two principal factors: (1) the
escalating cost of natural gas and (2) the increasing
stringency of air pollution regulations.
The process (Fig. 4) involves partial burning of natural gas
with insufficient air. Small fan-shaped flames from gas
burner tips (2000 or more) are housed in sheet metal build-
ings or "hot houses" and are arranged so that they impinge on
channel irons suspended above hoppers. Using scrapers and
a reciprocating action of the channel irons, the deposited
carbon is collected in the hoppers and passed through the
collection system. Yields are characteristically very low,
reaching a m a x i m u m of about 5% with the coarser grades.
ing from about 30 to less than 10 nrn. The resultant blacks
have typically higher volatile contents (chemisorbed oxygen
complexes on the surface) because of the presence of oxygen
during formation. Though channel blacks have virtually dis-
appeared from industry, a variant called roller process
blacks, made from feedstocks other than natural gas, are still
produced in limited quantities in Germany.
Furnace Process Blacks. These are made by partial com-
bustion of a hydrocarbon in a closed reactor (or furnace)
under well-defined conditions. The precursors of m o d e r n oil
furnace blacks were the gas furnace blacks, which are no
longer produced.
Oil Furnace Process. A hot flame is first created by burning
gas with air inside a closed furnace, and then a liquid hydro-
carbon is atomized into the hot flame zone. Furnace designs
and reactor configurations vary considerably, but the princi-
ple is the same (Figs. 5a and 5b). The feedstock is usually a
medium-molecular-weight aromatic oil that must be heated
to 200 to 250~ to have sufficient fluidity. Yields are high (30
to 60%), air pollution is virtually nil, and it offers superior
process control capability. Blacks ranging in prime particle
size from 100 down to about 10 nm, with variations in struc-
ture level (degree of aggregation of prime particles), can be
produced by varying furnace conditions, feedstock proper-
ties, residence times (time in hot zone), and quench distances
(how far downstream the cooling sprays are introduced into
the furnace).
Oil Furnace Carbon Blacks. These essentially satisfy all re-
quirements of industrial blacks and account for 95% of all the
carbon black produced today.
Thermal Cracking or Thermal Decomposition--A final cate-
gory of carbon black processes uses thermal cracking or ther-
mal decomposition of a gaseous hydrocarbon in the absence
of flame. This includes thermal blacks and acetylene blacks,
which are not used in the coatings industry.
M e c h a n i s m s o f Interaction with Light [4]
Since coatings vehicles are usually transparent resin solu-
tions, the function of a pigment in rendering the coating
opaque and imparting a desired color is to intercept and
modify incident visible light. Carbon black accomplishes this

TABLE 2--Typical analyses of carbon black grades from five different processes.

Type: Furnace Thermal Channel

Symbol: HAF MT FT EPC Lampblack
Property ASTMNo.: N-330 N-990 N-880 Acetylene $300 Lb
Average particle 28 500 180 40 28 65
diameter, nm
Surface area (BET), m2/g 75 47 13 65 115 22
DBPA, mL/100 g 103 36 33 250 100 130
Tinting strength, % SRF 210 35 65 108 180 90
Benzene extract, % 0.06 0.3 0.8 0.1 0.00 0.2
pH 7.5 8.5 9.0 4.8 3.8 3.0
Volatile material, % 1.0 0.5 0.5 0.3 5 1.5
Ash, % 0.4 0.3 0.1 0.0 0.02 0.02
Composition, %
C 97.9 99.3 99.2 99.7 95.6 98
H 0.4 0.3 0.5 0.1 0.6 0.2
S 0.6 0.01 0.01 0.02 0.20 0.8
O 0.7 0.1 0.3 0.2 3.5 0.8
NOTE:From Encyclopediaof ChemicalTechnology,Vol. 4, 3rd ed.
182 PAINT AND COATING TESTING MANUAL

translates to about 2 to 3% carbon black by weight in most

vehicle systems. Loadings of carbon black above the opacity
loading level will not further enhance the color (blackness).
2. Light Scattering [5]--Another factor that contributes to
carbon black's appearance is its relatively weak light-scatter-
ing ability. When dispersed in a vehicle, individual aggregates
of carbon black are much too fine to be efficient scatterers [6].
Nevertheless, light scattering plays a significant part in the
details of carbon black optical performance.

Carbon Black Parameters Affecting the Optical

FIG. 3-Old plant for lampblack manufacture.
by means of two mechanisms: light absorption and light scat-
tering.
1. Light Absorption--By nature of its quasigraphitic micro-
structure, carbon black strongly absorbs visible light across
the spectrum. In dispersed media, because of its relatively
fine particle size and high surface area, it is an extremely
efficient light absorber and thus appears black. To achieve
opacity, it is necessary to have a sufficient number of carbon
black aggregates distributed throughout the resin matrix to
intercept virtually all of the incident light (Fig. 6). This condi-
tion is often referred to as the opacity loading level and
Function
General Principles
When dispersed in a transparent vehicle, the primary ag-
gregates of carbon black are the optically functional units.
Thus, the optical function is affected by variations in the two
key carbon black parameters which determine aggregate size:
prime particle size and structure.
As primary aggregates decrease in size, the specific surface
area increases and incident light must penetrate more car-
bon, which results in increasing light absorption. Both ab-
sorption and scattering efficiencies (per unit weight of carbon
black) increase with decreasing aggregate size (Fig. 7) down
to a size equal to about one third the wavelength of the
incident light, D (about 180 nm for "white light"). Further
decreases in aggregate size show a leveling off of absorption
efficiency and a decrease in scattering efficiency.
The size of the prime particle determines the size of the
primary aggregate at a fixed level of aggregation. The level of
aggregation is known in the carbon black industry as struc-
ture. It is a parameter that not only indicates the average
number of prime particles composing a primary aggregate,
but also the degree of anisometry, branching and chaining or
shape irregularity (Fig. 8). The higher the structure, the
greater the void space within and around a primary aggre-
gate. In fact, the extent to which a carbon black absorbs oil or

8" ='
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'I'" Tip<-" il'~/Carbon black/~
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Screw conveyor discharge black

FIG. 4-Channel process for carbon black manufacture.

dibutylphthalate (DBP), which fills the void spaces, is a com-
m o n industry measure of its structure.
Jetness
The industry term for degree of "blackness" is "jetness,"
which increases with decreasing aggregate size for two rea-
sons: (1) increasing light absorption efficiency and (2) de-
creasing light-scattering efficiency. As primary aggregates be-
come smaller, incident light must penetrate more carbon,
resulting in more light absorption per unit weight of black.
Also, despite the individual variations of absorption and scat-
tering efficiencies per unit weight shown in Fig. 7, the ratio
[4] of absorption efficiency to scattering efficiency, A/S, es-
sentially increases continuously with decreasing aggregate
size. Thus, both mechanisms, absorption and scattering, are
synergistic with respect to jetness, and the degree ofjetness is
controlled by the A/S ratio. The smaller the aggregate, the
higher the A/S ratio and the jetter the black.
Structure can also be a measure of aggregate size for a
given prime particle since it reflects the number of prime
particles composing a primary aggregate. In this sense it is
also an indicator of scattering efficiency. Low-structure
blacks have smaller primary aggregates, exhibit less scatter-
ing, and have higher A/S ratios. High-structure blacks have
larger primary aggregates, exhibit more scattering, and have
lower A/S ratios. Given two carbon blacks of comparable
prime particle size, the black of lower structure (smaller,
more compact primary aggregates) will show the higher
jetness because of a higher A/S ratio.
Tinting Strength
Carbon black's primary tinting application is to make gray
colors by blending with a white pigment. Addition of a fixed
amount of a number of different carbon blacks to a titanium
dioxide, TiOz, dispersion, for example, will result in various
depths of gray color. The darkest gray will represent the car-
bon black highest in tinting strength. Since even a dark gray
surface reflects a great amount of light relative to a black
surface, the increment of light scattered by the carbon black
is insignificant. For this reason, the controlling mechanism in
tinting strength is light absorption [7]. Finer primary aggre-
gate size, which favors increased absorption, will enhance
tinting strength (Fig. 9). As the primary aggregate size is de-
termined both by prime particle size and structure, higher
tinting strength is favored by fine-particle-size, lower struc-
ture blacks. However, as shown in Fig. 7, at an aggregate size
Water Quench
"'X AA, A/ ......
gasair,,~.,.. 2100 - 3 0 0 0 ~ F
feedstock ~/~___.w~,"
Yield: 30 - 6 0 %
FIG. 5a-Oil furnace reactor.
CHAPTER 20--BLACK PIGMENTS 183
equal to one third the wavelength of incident light, the ab-
sorption efficiency, and consequently tinting strength, levels
off and becomes independent of further decreases in size.
This phenomenon can be seen in Fig. 9 as well.
Opacity
The extent to which a coating will cover or "hide" a sub-
strate is a function of the nature of the pigment and its
loading level. As mentioned earlier, the opacity loading level
of carbon black in a coating system is usually 3% by weight or
less for normal paint film thicknesses (around 1.0 mil). With
much thinner films, higher loadings would be required to
achieve opacity. In other words, there must be a sufficient
number of primary aggregates dispersed throughout the film
to prevent any significant amount of incident light from pass-
ing through.
Carbon black creates opacity through the two mechanisms
cited earlier, absorption and scattering of visible light. In fact,
opacity of carbon black can be considered as being directly
proportional to the sum of_the absorption coefficient and the
scattering coefficient, (A + S). This means simply that light
that is either absorbed or scattered is not transmitted through
the film. From this relationship, it is also possible to predict
that optimum opacity, as a fixed loading, would be rendered
by blacks having an aggregate size close to one third the
wavelength of incident light (in short, blacks in the regular to
medium color categories for white light of 180 nm, as per Fig.
7).
One convenient way to express the opacity of films is to use
the parameter called optical density. This is a function of the
percent of incident light transmitted as follows:
Optical Density = - LOG10T~
where
Tx = Transmitted light/incident light, and
h = Wavelength of incident light.
An optical density of 1.0 would indicate a transmission of
1% (0.01), 2.0 would indicate a transmission of 0.1% (0.001),
etc. Since T will vary somewhat with wavelength, it is neces-
sary to use the subnotation to denote the wavelength of the
incident light. Further, there is a logarithmic relationship
with film thickness (expressed as weight of coating per unit
area) for a fixed carbon black loading, i.e.
Optical Density -- - In (grams/m 2)
(
PRODUCTS
CARBON BLACK
-,, 400 ~ F /
CO 2
\
CO
H~
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H20
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System Recovery Compartments
System
FIG. 5b-Oil furnace plant.
 CHAPTER 20--BLACK PIGMENTS 185

Light
Absorption ////
/////l Lig
HT

~ Scattering
Low
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I o 9 9 ~ P a i n t Film Qo9
MEDIUM

FIG. 6-OPTICAL FUNCTION OF CARBON "1

BLACK. This diagram is an oversimplification of
how carbon black functions in that primary ag-
gregates are depicted as spherical and of
roughly the same size. In reality, the aggregates
are irregular in shape and occur as a distribution
of sizes, which complicates the optical function-
ing considerably. However, the fundamental
processes as shown still represent the theoreti- HIGH
cal basis for more complete treatments of the
subject.

Undertone
In the carbon black industry, blacks are visually character- FIG. 8-Structure comparison.
ized as having a blue or brown undertone or some gradation
in between when dispersed in a coating system. In a black
coating it is called mass tone and in a gray it is called tint
tone. The phenomenon of undertone results from the fact
that both scattering and absorption efficiencies of carbon
black vary with wavelength [8]. Preferential absorption of
blue light tends to make the unabsorbed light reaching the
observer favor the red end of the spectrum (browner tone).
The degree of preferential absorption/scattering of the blue 300 ' '1''1 I " ' I '
end of the spectrum increases with decreasing aggregate size.
Thus, in a gray finish, where the absorption mechanism is in
20O
Absorption ~-3
I
I S- ~ ~% g 100

so
b.
Scattering * D•
V zo , ,J, , I I , , I'~
High Color Medium Color RegularColor Low Color 50 75 100 200 500 750
Blacks Blacks Blacks Blacks
Da(nm)
AGGREGATE SIZE
FIG. 7-CARBON BLACK OPTICS. *D M3 = An aggregate Particle Size
size equal to one third the wavelength of the incident light. FIG. 9-Tinting strength of a range of carbon blacks.
186 PAINT AND COATING TESTING MANUAL
control, the finer the aggregates the browner the tint tone. In
mass tone we have the more complex situation where both
preferential scattering and preferential absorption, each with
a separate wavelength dependency, contribute to undertone.
Gloss
The term gloss is generally taken to mean the specular
reflectance of a surface measured at some specific angle (for
example, 60~ As with any pigment added to a transparent
vehicle, the gloss of the dried film will be influenced by the
loading and the properties of the carbon black. Starting with
an unpigmented coating having optimal gloss in the dried
film and adding a given carbon black incrementally (assum-
ing excellent dispersions), a point will be reached where gloss
begins to deteriorate until eventually the finish becomes flat.
Since it is the resins in the dry film which create the smooth
surface for reflection, the addition of particulate substances
such as pigments or fillers in significant concentrations can
only interfere with the "smoothness" of the surface.
The properties of carbon black that affect the gloss of a
coating are: aggregate size, structure, and surface chemistry.
Other factors being constant, the finer the aggregate size the
less the effect on surface texture. The finer aggregate blacks
tend to give coatings with higher gloss when properly dis-
persed.
Higher structure, which means more void space and there-
fore higher oil absorption, tends to work against gloss. This is
because more vehicle is "tied up" for a given loading of black
in comparing a higher structure with a low structure black.
Once again we must emphasize the importance of quality of
dispersion. Since higher structure blacks are somewhat eas-
ier to disperse, the effect of structure can only be properly
observed in cases where optimal dispersion has been
achieved.
Surface chemistry generally refers to the amount of volatile
content or chemisorbed oxygen complexes on the surface
(that is, hydroxy|ic, carboxylic, quinonic, or lactonic groups).
Carbon blacks often are chemically oxidized after formation
(aftertreatment) to increase volatile content. While this is
usually done to improve rheological properties (for example,
flow, viscosity), it normally creates improved gloss as well.
The volatile content acts as a built-in dispersing agent, ser-
ving to reduce the amount of vehicle needed to completely
wet the surface of the black.
The Effect of Dispersion Quality
General Principles
The influence of the key carbon black parameters on dis-
persibility must first be defined [9]. As the primary aggregates
of carbon black become finer, dispersion becomes more diffi-
cult for two reasons: (1) higher energy needed to "wet" the
higher surface areas and (2) greater attractive forces between
aggregates because more particles per unit weight of carbon
black means smaller interaggregate distances.
Structure plays a key role as well. Low structure blacks
allow closer "packing" (higher density), which results in
smaller interaggregate distances and stronger attractive
forces or more difficulty in dispersion, ttigher structure
means more void space (lower density), which reduces
interaggregate attractive forces and provides greater accessi-
bility to vehicle penetration or greater ease of dispersion.
While lower structure blacks are more difficult to disperse
ultimately, they contain less occluded air (lower density) to
be displaced so that they incorporate or "wet-out" more read-
ily.
Surface chemistry can be a factor in dispersion both as
volatile content or simply as adsorbed moisture. Higher vola-
tile content, acting as a built-in dispersing agent, tends to
favor easier dispersion. Adsorbed moisture, present in all
carbon blacks in proportion to surface area and ambient
conditions in limited amounts, has proven to be beneficial to
dispersion in liquid systems.
Density and physical form of carbon black also influence
dispersibility. Carbon black as produced is extremely "fluffy"
and must be substantially densified (removal of occluded air
by agitation), usually to over 10 lb/ft 3 for handling purposes.
When the densification is done by rotary agitation in drums,
either wet or dry, the result is spherical pellets, which offer
ease of handling and reduced dusting. Densification packs
agglomerates more closely, increasing interaggregate attrac-
tion and making dispersion more difficult. Pelletization adds
the dimension of pellet hardness which must be overcome
prior to actual dispersion. However, pelleted blacks "wet-out"
very quickly and are thereby suitable for certain types of
equipment (Table 3).
Optimal dispersion of carbon black can be defined as that
condition in which all agglomerates are broken down into
their constituent primary aggregates; each aggregate is sepa-
rated from the others, and the surface of each is completely
covered by resin. Primary aggregates are the characteristic
units of carbon black and are not broken down under normal
dispersion conditions. The steps involved in the dispersion
process are:
1. Incorporation (Wetting)--This step involves the displace-
ment of occluded air and covering the surface of agglomer-
ates with vehicle, yielding a workable dispersion mix.
Sometimes this is referred to in the coatings industry as pre-
mixing.
2. Pellet Breakdown--When pelleted black is used, Step 1,
Incorporation, is easier since initial mixing causes little, if
any, pellet fracture. Thus, at the worst, larger pellet fragments
need to be "wetted" by vehicle. Pellet breakdown must then be
accomplished by the application of additional energy (for ex-
ample, longer mixing) after Step 1.
3. De-Agglomeration--This is the principal step in achiev-
ing optimal dispersion and the one that consumes most of the
applied energy. Interaggregate attractive forces must be over-
come to break down agglomerates into their constituent pri-
mary aggregates.
TABLE 3--Preferred form of carbon black.
Preferred Form
Equipment Fluffy Pellets
Two-roll mill X
Three-roll mill X
Steel ball mill X
Attritor X
Disk disperser X
Sand/shot mill X X

4. Stabilization--At this stage, in order to stabilize the
deagglomerated aggregates, each of the aggregates must ad-
sorb sufficient vehicle to completely deactivate its surface.
This process can often be facilitated by the use of dispersing
agents.
To function efficiently in an optical sense, carbon black
must be optimally dispersed. The primary aggregates which
characterize carbon black must be separated from one an-
other and distributed fairly uniformly throughout the vehicle
matrix to be most efficient at intercepting incident light.
Choosing a grade with high surface area for high color appli-
cations, for example, must be combined with designing an
effective dispersion system to ensure full color development.
Mill base formulations, grade selection, physical form of car-
bon black (fluffy or pellets), and premixing as needed all play
a part in ensuring quality dispersion. Perhaps the most im-
portant factors in mill base formulation are: (1) providing
sufficient vehicle solids to accommodate the carbon black
surface (Table 4) and (2) adjusting viscosity to a level suitable
for the chosen dispersion equipment.
Dispersion Mechanisms
Available liquid system dispersion equipment utilizes ei-
ther or both of the two main dispersion mechanisms: (1)
shearing force and (2) collision of agglomerates with each
other and with dispersion media particles. These mecha-
nisms describe the manner in which energy is applied to
carbon black agglomerates during the dispersion process.
For example, disk disperses and three roll mills use shearing
force while ball mills, sand mills, and attritors rely on colli-
sions.
Dispersion Quality Testing
It is possible to stabilize carbon black dispersions at vari-
ous levels of deagglomeration. The term macrodispersion is
applied to very moderate levels of deagglomeration at which
only the larger agglomerates are fractured. Microdispersion,
on the other hand, refers to levels of deagglomeration ap-
proaching the ideal of single primary aggregates.
The most accurate way to measure dispersion quality is
microscopically. Using X100 optical micrographs, it is possi-
ble to set up a classification system. However, it is costly and
time consuming and somewhat impractical for production
control. More commonly used in the coating industry is the
grind gage (Hegman gage, paint club gage, etc.). These de-
vices do not measure microdispersion. Since it is mi-
crodispersion that largely determines color performance, it is
possible to have two identical mill bases, both "off-scale" on a
grind gage, one of which is significantly poorer in dispersion
quality. The better dispersed system would be blacker (jetter)
and glossier. This leads to the most practical indirect method,
TABLE 4--Suggested vehicle solids to carbon black ratios for mill
base compositions.
Suggested Ratio,
Nitrogen Surface Vehicle Solids/Carbon
Type Area, m2/g Black
High color 230-560 3.5/1 to 4.5/1
Medium color 200-220 2.5/1 to 3.0/1
Regular color 45-140 1.5/1 to 2.0/1
Low color 25-40 1.0/1
CHAPTER 20--BLACK PIGMENTS 187
that is, using color and/or gloss development, which are ex-
tremely sensitive to small variations in degree of mi-
crodispersion.
Selecting a Grade o f Carbon Black for Coloring
Black Coatings
For coloring purposes, a grade of carbon black should be
selected that is as low as possible in surface area, but consis-
tent with end use color specifications. This enables the for-
mulator to take advantage of the greater ease of dispersion
and lower cost associated with the lower surface area. The
desired structure level would be high enough to give accept-
able dispersibility, but not so high as to adversely affect gloss
or rheology. In some cases the use of aftertreated grades will
give an edge in dispersion and gloss as well as protect the
rheology at higher loadings. Normally, at opacity level load-
ings, rheology is only a problem when more concentrated
mill bases are used.
Implicit in the selection of a grade of carbon black is the
choice of the fluffy or pelleted form. The choice is usually
made on the basis of dispersion equipment available or on
ease of incorporation or both. Listings of preferred forms for
best results with each of the major pieces of equipment are
helpful (Table 3). Regarding ease of incorporation, if, for
example, a steel ball mill which is a very effective disperser is
to be used, the edge in dispersion provided by the fluffy form
is not really needed, so it is wise to consider the pelleted form
which will "wet in" quickly and which creates less dust on
handling.
Candidate grades must be dispersed in the specific formu-
lation in which they are intended to be used. Keeping in mind
the sensitivity of color and gloss development to dispersion
quality, it is useful to evaluate jetness and gloss both at the
end of the prescribed grind cycle and again after an extended
cycle. This technique not only identifies which of the candi-
dates will provide the color and gloss levels needed, but also
indicates whether or not full color value from a given grade
will be achieved under the prescribed dispersion conditions.
The factors of carbon black cost and dispersibility must be
weighed against desired color and gloss levels in making a
final decision. Some commonly used oil furnace grades for
the coatings industry are listed in Table 5.
Black Tinted Coatings
While selecting a black for tinting purposes involves the
principles mentioned earlier under General Natures of Carbon
Black on mass tone color, some key points need emphasis.
The selection depends upon required tinting strength (see
Table 5), tint tone, and relative ease of dispersion.
Tint tone (see under Carbon Black P a r a m e t e r s Affecting
the Optical Function the section on Undertone) refers to the
color undertone in tinting. If very blue undertone is needed,
grades such as LCF 2 and LCF 3 are suggested. Sometimes it
is necessary to sacrifice some tinting strength by going to
grades with larger aggregate size in order to maximize blue
tint tone (for example, going from LCF 1 to LCF 2). High-tint-
strength blacks tend to give browner undertone, which is
desirable in some applications.
Finally, where dispersion stability (that is, flocculation re-
sistance) is critical, aftertreated blacks can be helpful. MFF
188 PAINT AND COATING TESTING MANUAL

TABLE 5--Oil furnace black color grades for coatings.

DBP
Absorption, Tinting Volatile Density,
Surface Particle cc/100 g lb/ft3
Jetness Area (BET), Size, Strength, Content,
Grade Index~ m2/g nm Fluffy Pellets % % Fluffy Pellets

ASTM Test N/A D 3037 N/A D 2414 D 3265 D 1620 D 1513

High HCF 3 60 560 13 90 80 100 9.0 17 27
color HCF 2 64 560 13 100 90 100 9.5 16 25
HCF i 69 340 16 105 100 116 9.5 11 24

Medium MCF 4 70 230 15 70 64 120 2.0 14 29

color MCF 3 74 220 16 112 105 122 1.5 8 21
MCF 2 73 210 17 74 68 120 1.5 15 28
MCF 1 78 200 18 122 117 118 1.5 9 19

Flow Long flow, LFF 83 138 24 60 55 112 5.0 15 32

grades Medium flow, MFF 84 96 25 72 69 112 3.5 14 30

Regular RCF 4 83 112 24 65 60 116 1.0 15 31

color RCF 3 84 94 25 70 65 110 1.0 19 28
RCF 2 87 80 27 85 72 104 1.0 13 29
RCF 1 90 85 27 100 .-. 92 1.0 12 ...

Low color LCF 4 93 43 37 95 ... 80 1.0 11 ...

grades LCF 3 95 42 41 ... 121 62 1.0 ..- 22
LCF 2 96 35 50 ... 90 60 1.0 -.. 27
LCF 1 99 25 75 72 64 58 0.5 18 33
aBased on Nigrometer scale values so lower numbers indicate higher jetness.
NOTE: Above data typical of commercial grades representative of the indicated categories [11].

( m e d i u m flow furnace) black, for example, exhibits excellent 10,000 I - I I 1 I I I --

stability and high tinting strength and is often used for tinting 6,000
9 Oil-type rubber blacks
in p o o r e r wetting vehicles. 6,000 I - O Gas4ype rubber blacks /s
5'000 I - O Oil-type color blacks /
4,000 I - + Gas-type color blacks

Measuring Appearance Properties of Carbon

Black Coatings
A black coating p i g m e n t e d with c a r b o n black at the opacity
2,000[
0,< 3,000 r

level (less than 3% by weight) will probably reflect only ab o u t

1% of the light incident u p o n it. This presents s o m e u n i q u e
p r o b l e m s in trying to m a k e absolute i n s t r u m e n t a l m e a s u r e -
me nt s since the sensitivity of available i n s t r u m e n t s is simply
not adequate. F o r this reason, it has been traditional in the
c a r b o n black industry and even a m o n g end users to d e p e n d 300 o ~r~
u p o n visual j u d g e m e n t s of a p p e a r a n c e properties in m a n y +4-
cases. While no one challenges the incredible sensitivity and
versatility of the h u m a n eye, it has the d r a w b a c k of not being
able to quantify its observations. Nevertheless, using special
100| I I I I I
techniques, it is possible to obtain quantitative measure- 50 60 70 80 90 100 110 120
me nt s on all a p p e a r a n c e properties as outlined below. Nigromater value
FIG. 1 0 - N i g r o m e t e r values versus particle size for a range of
Jetness carbon blacks.
Jetness or blackness is a function of B E T surface area, i.e.,
inversely p r o p o r t i o n a l to aggregate size (Fig. 10). Tradition- nates [10] to quantitatively m e a s u r e jetness an d mass tone as
ally, the industry assigned n i g r o m e t e r "scale" values, w h i ch well.
are a direct function of the a m o u n t of light reflected by
dispersed samples (coatings, plastics, etc.). S m a ll e r "scale"
values indicated jetter carbon blacks. However, the m o d e r n Undertone
a p p r o a c h is to m e a s u r e the spectral reflectance of a black The mass tone is m e a s u r e d as described above in the sec-
dispersion, w h i c h is m a d e possible by the e n h a n c e d sensitiv- tion on jetness. This is an i m p o r t a n t tool b ec a us e visual
ity of cu r r en t instrumentation. The spectral reflectance ratings of jetness are usually influenced by u n d e r t o n e varia-
curves can then be converted to H u n t e r L, a, b; or CIE coordi- tions a m o n g blacks being rated.

Tint tone, on the o t h e r hand, can n o r m a l l y be m e a s u r e d
directly via absolute reflectance (versus a white s t a n d a r d )
using a s p e c t r o p h o t o m e t e r o r a colorimeter. However, com-
m o n practice is to m e a s u r e against a gray s t a n d a r d (ASTM
D 3265: Test M e t h o d for C a r b o n Black-Tint Strength).
Tinting Strength
As illustrated in Fig. 9, tinting strength increases with de-
creasing particle size. The differential m e a s u r e m e n t tech-
nique, d e s c r i b e d above, is u s e d to assign tinting strength
values. The procedure, ASTM Test D 387-86, Test M e t h o d for
Color a n d Strength of Color Pigments with a Mechanical
Muller, involves dispersing c a r b o n b l a c k together with a
white p i g m e n t in a wetting oil or other suitable vehicle. The
refectance of this d i s p e r s i o n versus a s t a n d a r d gray tile or
gray vitreous e n a m e l is t h e n a m e a s u r e of its tinting strength.
While it was c u s t o m a r y in the c a r b o n b l a c k i n d u s t r y for m a n y
years to r e p o r t tinting strength as a p e r c e n t of a reference
black (for example, IRB No. 4), some suppliers are n o w using
an i n d e p e n d e n t tinting strength index, allowing strength
c o m p a r i s o n s only within their own p r o d u c t lines.
Gloss
Clearly, this p r o p e r t y a n d the m a n n e r in w h i c h it is mea-
sured is not u n i q u e for c a r b o n black coatings. W h e t h e r the
p i g m e n t a t i o n is black o r any o t h e r color, the test (for exam-
ple, for 60 ~ gloss) is the same.
SUMMARY
Individual key c a r b o n black p a r a m e t e r s have b e e n viewed
from the s t a n d p o i n t of their influence on the optical function.
It is i m p o r t a n t to emphasize, however, that these p a r a m e t e r s
do not o p e r a t e separately. The effect on optical functioning,
a n d therefore on p i g m e n t a r y properties, is a c o m b i n e d one.
E a c h p a r a m e t e r w h e n varied influences the o t h e r p a r a m e -
ters, w h i c h are also varying. Thus the situation is d y n a m i c
a n d complex.
CHAPTER 20--BLACK PIGMENTS 189
Dispersion quality and its i m p o r t a n c e in realizing the full
optical potential of a given grade has also been addressed.
Therefore, in the grade selection process, the physical f o r m of
c a r b o n black as well as key p a r a m e t e r s m u s t be c o n s i d e r e d in
light of the chosen d i s p e r s i o n technique.
REFERENCES
[1] Spengeman, W.F., ASTM Paint Testing Manual, Black Pig-
ments, 2.8.4, 13th ed., 1972.
[2] Boonstra, B. B., "A, B . . . . Z of Carbon Black," an internal publi-
cation of Cabot Corporation.
[3] Dannenberg, E. M., "Carbon Black," Encyclopedia of Chemical
Technology, Vol. 4, 3rd ed., Wiley-Interscience, New York, 1978,
pp. 631-666.
[4] Donoian, H. C. and Medalia, A. I., Journal of Paint Technology,
Vol. 39, 1967, p. 716.
[5] Mie, G., Annalen der Physik, Vol. 25, No. 4, 1908, p. 377.
[6] Kubelka, P. and Munk, F., Zeitschrift f~r Technische Physik, Vol.
12, 1931, p. 593.
[7] Medalia, A. I. and Richards, L. W., "Tinting Strength of Carbon
Black," Journal of Colloid and Interface Science, Vol. 40, 1972, p.
233.
[8] Donnet, J. B. and Voet, A., Carbon Black, Marcel Dekker, New
York, 1976.
[9] Cabot Corporation, Special Blacks Division, Technical Report
S131, 1989.
U0] Judd, D. B. and Wyszecki, G., Color in Business, Science, and
Industry, 3rd ed., Wiley, New York, 1975.
{11] Cabot Corporation, Special Blacks Division, Technical Report
S136, 1988.
NOTE: References 2, 9, a n d 11 are Cabot C o r p o r a t i o n inter-
nal publications copies of which are available from:
Cabot C o r p o r a t i o n
Special Blacks Division
157 Concord R o a d
Billerica, MA 01821
Phone: 800-462-2313, Fax: (508) 670-7035
TLX: 947119