Carbon Black

Professor Joe Greene

CSU, CHICO

Carbon Black
Reference: Rubber Technology, Chapter 3
Phenomenon of carbon black reinforcement was discovered in early 1900s
Physical and chemical attachments are capable of giving reinforcement effects by
increasing the tensile strength and modulus of the rubbery phase
Carbon black and vulcanization generates a 3-D network

Carbon black
Range of physical and chemical attributes
Particle size, surface area, structure, surface activity

Gas-furnace blacks: Thermal black process: 3% of current carbon black

Initially made using gas as the source of carbon and the fuel source
Carbon black had small particles and were acidic
Worked well with natural rubber
Large amounts of air pollution was generated and expensive

Oil furnace black (1943) is the current manufacturing method: 97% of black
Low grade petroleum feedstock was cheaper, less polluting, and flexible process
Higher structure and more alkaline than gas furnace (channel) blacks
Improved significantly the properties of SBR polymers

Carbon Black Manufacture

Manufacture and Morphology
Typical oil furnace reactor, Figure 3.1
Refractory lined tube that can be horizontal or vertical.
Feedstock oil, natural gas, or other fuel, and air are preheated and injected
into the combustion zone at specific rates for the carbon black
Burning generates a very hot, turbulent atmosphere for cracking the feedstock
oil.
90% of the feedstock is based on refinery heavy bottom oils.
Chemical reactions to convert the aromatic feedstock to elemental carbon are
not well understood and complex
Collision of particles in a liquid-like state produces aggregates of spherical
particles fused together in a random grape-cluster configuration, Fig 3.2
The carbon is formed in aggregates with a distribution of sizes

Water quench is used to rapidly reduce the temperature and terminate the
reaction.
The smoke exiting the reactor is a mixture of carbon black aggregates,
combustion gases, and moist air.
The smoke preheats the feedstock and air, and generates steam for plant use.
Fluffy black and gases (tail gas) are separated by filtration, and the loose
3 black
is pulverized to a 325 mesh and then pelletized

Carbon Black Manufacture

Manufacture and Morphology
Wet-pelleting process is used
A rotating, pin-studded shaft mixes the loose black with water and binder to
produce small beads or pellets.

Wet pellets are fed into a rotary drier heated by combustion of the
tailgas from the earlier step in the process.
Steam that is generated is removed and replaced with air that oxidizes the
carbon black, which influences the chemical properties of the carbon black
and, in turn, the cure rate and properties of the vulcanizates.

The pelleted black is screened for uniformity and passed over

magnetic separators to remove metallic contamination that may
have gotten in the product stream.
Finished product is packaged and shipped
Furnace black categories
Reinforcing: hard, tread. Have a smaller particle size and lower yields and
more expensive than semi-reinforcing.
Semi-reinforcing: soft, carcass.
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Carbon Black Properties

Physical and Chemical Properties
Particle size can be measured by electron micrographs, Figure 3.3
Average diameter is 19 to 95 nm (nanometers or 10-9 m)
Particles are measured manually or with image analysis software

Particle size can be measured by tint strength test (ASTM D3265)

Carbon black sample is mixed with zinc oxide and a soybean oil epoxide to
produce a black or gray paste.
Paste is spread to produce a suitable surface for measuring the reflectance of
the mixture with a photoelectric reflectance meter.
Reflectance is compared to the reflectance of paste containing the
Industry Tint Reference Black (ITRB) prepared in the same manner.
Tint test is affected by the structure as well as the particle size of the
black.
For a given particle size, the higher structure blacks have a lower
tinting strengths.
Average particle size can be estimated from statistical equations
that relate tint strength and structure to particle size as measured
from electron micrographs.
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Carbon Black Surface Area

Surface Area
Very important in carbon black because it defines how much
surface is available for interactions with other materials present in
a rubber compound.
Small particle-size black will have higher surface area, but the texture or
nature of the surface area can also influence the surface area.
BET method (ASTM D3037) to determine surface area
Adsorption of a gas, usually nitrogen, on the surface.
Surface area can be measured from electron micrographs

Standard rubber grade black (nitrogen surface area of less than 130 m2/g)
are nonporous
Non-specialty furnace blacks give good inverse correlation between
nitrogen surface area and the particle size measurements.
Specialty furnace blacks require a devolatilization step to remove residual
oils present on the surface of the blacks

Volume of void space between aggregates per unit weight of

carbon black increases with the number of particles per aggregate
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Non-spherical particles pack differently from spheres

Carbon Black Chemical Properties

Chemical Properties
Chemical nature of a carbon black is variable
Evidence for the presence on the surface of at least four oxygen containing
groups, carboxyl, phenol, quinone, and lactone.

Elastomers are polar in nature, neoprene or nitrile rubber

Will react more strongly with fillers with dipoles, OH, COOH, or Cl

Chemical surface groups affect the rate of cure with many

vulcanization systems
Physical adsorption activity of the filler surface is of much greater overall
importance for the mechanical properties of the general-purpose rubbers than
the chemical nature.

Oxygen content influences the cure rate

Increased oxygen gives longer scorch period, a slower rate of cure, and a
lower modulus at optimum cure.
Amount of oxidation during the pellet drying operation can affect the cure
rate and modulus of rubber compounds.

Carbon blacks are generally electrically conductive because of the

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highly conjugated bonding scheme in crystalline regions

Carbon Black Nomenclature

Nomenclature
First digit following the letter indicates the particle size range
Lower numbers for smaller particle-size blacks

Last two digits are arbitrarily assigned by ASTM

Table 3.1
ASTM
Old Name
Properties
ASTM D1765

N110
N220
N330
N358
N660
N762

SAF (Super-abrasion furnace)

ISAF (Intermediate Super-abrasion furnace)
HAF (High abrasion furnace)
SPF (Super processing furnace)
GPF (General-purpose furnace)
SRF (Semireinforcing furnace)

Carbon Black Properties

Properties
High surface area and high structure carbon blacks are associated with increased
reinforcement
Particle size affects abrasion resistance, heat build-up (resilience), tensile strength,
and tear strength.
Structure has more of an effect on modulus, hardness, and extrudate swell.

Four carbon blacks are shown to demonstrate the effects of varying surface area,
structure, and black loadings on various compound properties.

Structure Differences
N339 vs N356
N650 vs N660

Both pairs have

Equivalent surface N2 surface area
Large differences in structure from

N339
N356
N650
N660

Nitrogen DBP
Void
Tint
Surface
Absorption Volume
Strength,
area m2/g cc/100g
cc/100g %ITRB
98.9
118.4
69.2
108.8
100.1
160.2
77.7
103.2
38.8
123.7
57.4
52.7
39.3
89.7
44.5
59.2

DBP absorption and void volume data

N339 and N356 vs N650 and N660 shows large difference in

surface area
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Carbon Black Properties

Three compound recipes based upon different
polymers enable the observation of changes in
carbon black effects from one polymer to another
Table 3.3

EPDM Compound
EPDM
100 phr
Naphthenic oil
12
Zinc oxide
5
Stearic acid
1
Processing aid
2
Sulfur
1.5
MBT
0.5
TMTD
3
Carbon black 0 to 80phr

SBR Compound
SBR-1500
100 phr
Aromatic oil
5
Zinc oxide
3
Stearic acid
1.5
Sulfur
1.75
CBS
0.85
DPG
0.28
Carbon black
0 to 80phr

NR Compound
Natural Rubber
Highly aromatic oil
Zinc oxide
Stearic acid
Antioxidant
Antiozonant
Sulfur
CBS
Carbon black

100 phr
15
5
2.5
2
2
1.5
1.6
0 to 80phr

Figures 4 through 12
Mechanical properties for Different concentrations (loading
10
levels) of carbon black

Carbon Black Properties

Compound Property Group 1
Viscosity, modulus, hardness, extrudate swell
Measures the degree of stiffening that carbon contributes
High structure and an increase in the amount of carbon black surface
available for attachment to the polymer result in the rubber compound to be
more viscous and less elastic

Viscosity, modulus, hardness, extrudate swell, Figures 3.4, 3.5,3.6

Increases with increased amount of carbon black for all three recipes, SBR,
EPDM, and NR
The N356 carbon black (highest N2 surface area) had the highest viscosity,
modulus at 200% elongation, and hardness; and the least amount of extrudate
swell.
The higher the N2 surface area the higher the viscosity, modulus at 200%
elongation, and hardness; and the lower amount of extrudate swell.
The N660 carbon black (lowest N2 surface area and lowest void volume) had
the lowest viscosity, modulus at 200% elongation, and hardness; and the most
amount of extrudate swell.

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Carbon Black Properties

Compound Property Group 2
Abrasion resistance, tear strength, and tensile strength
Measures the resistance to failure under several types of stress
Strength related properties enhanced by carbon black surface area and
increased black loading up to a limiting value that is dependent on the
packing characteristics (morphology) of the carbon black aggregates.
High structure and an increase in the amount of carbon black surface available
for attachment to the polymer in the rubber compound.
Asblack loading in increased to maximum level, the carbon aggregates are no
longer adequately separated by polymer which weakens the rubber composite

Abrasion Resistance, Figures 3.8a, 3.8b, 3.8c

Abrasion resistance is most affected by surface area and loading
Lower surface area GPF blacks (N650 and N660) contribute small
improvements in abrasion, regardless of carbon black loadings
Higher surface area HAF blacks (N339 and N356) contribute better
improvements in abrasion, depending on carbon black loadings.
Higher structure N356 black reach maximum abrasion resistance at lower
loadings than N339, but N339 ultimately gives higher abrasion resistance

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Carbon Black Properties

Compound Property Group 2
Tear-strength, Figures 3.9a and 3.9b
As carbon black is increased, the tear strength increases up to a peak, then
decreases after that.
Structure causes a shift in the strength curve to the left (lower limiting value
for strength because of the effect of higher structure on packing)

Tensile strength, Fig 3.10a

Unfilled EPDM rubber compound has very low tensile strength.
Tensile strength is increased dramatically as carbon black is added until a
maximum tensile strength is attained.
Higher surface area HAF blacks give improved tensile strength compared to
GPF blacks, but not significantly difference due to structure.
NR compound has inherently higher tensile strength in the unfilled natural
rubber due to its crystallizing ability.
Carbon black causes less of a change in NR
Tensile strength reaches a maximum at relatively low carbon black loadings (240 phr) and shows a decreasing tendency as the black loading is increased.

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