Orion What Is Carbon Black
Orion What Is Carbon Black
Orion What Is Carbon Black
Fo c u s e d. I n n o v a t i v e. R e s p o n s i v e.
Contents
1 Introduction
1.1 About Orion Engineered Carbons
1.2 What is Carbon Black
4
4
7
2 Manufacturing Process
2.1 Raw Materials
2.2 Thermal-Oxidative Processes
2.2.1 Furnace Black Process
2.2.2 Degussa Gas Black Process
2.2.3 Lamp Black Process
2.2.4 Channel Black Process (historical)
2.3 Thermal Decomposition Processes
2.3.1 Thermal Black Process
2.3.2 Acetylene Black Process
2.4 Carbon Black Dispersions, Compounds,
Plastic and Rubber Masterbatches
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12
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4 Handling
38
5 Product Safety
5.1 Toxicology
5.2 Safety-Related Properties
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6 Applications
6.1 Rubber Carbon Blacks
6.2 Specialty Carbon Blacks
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3 3
1 Introduction
1.1 About Orion Engineered Carbons
Who We Are?
Orion Engineered Carbons (OEC) is one of the worlds
leading suppliers of Carbon Black. We offer standard
and high-performance products for coatings, printing
inks, polymers, rubber and other applications. Our
high-quality Gas Blacks, Furnace Blacks and Specialty
Carbon Blacks tint, colorize and enhance the performance of plastics, paints and coatings, inks and toners,
adhesives and sealants, tires, and manufactured rubber
goods such as automotive belts and hoses.
With 1,360 employees worldwide, Orion Engineered
Carbons runs 14 global production sites and 4 Applied
Technology Centers, focusing on quality supply and
collaborative partnerships with customers. Common
shares of Orion Engineered Carbons are traded on the
New York Stock Exchange under the symbol OEC.
Our Vision
We are the premium supplier of Carbon Black.
We generate long-term benefits for stakeholders while remaining committed to responsible
business practices with a focus on team culture, reliability and sustainability.
Reliable Partner
Key Figures
Sales 2014
14
Employees
1,360
Active in
1.4 million t
Locations
1) USA, Borger
Orion Engineered Carbons LLC
9440 FM 1559, Hwy 136
Borger, TX 79007, USA
2) USA, Kingwood (Regional Headquarters)
Orion Engineered Carbons LLC
4501 Magnolia Cove Drive
Suite 106
Kingwood, TX 77345, USA
3) USA, Orange
Orion Engineered Carbons LLC
1513 Echo Road
Orange, TX 77632, USA
4) USA, Belpre (Plant)
Orion Engineered Carbons LLC
11135 State Route 7
Belpre, OH 45714-9496, USA
4) USA, Belpre (Technical Center)
Orion Engineered Carbons LLC
2730 Washington Blvd. Suite 2
Belpre, OH 45714, USA
5) USA, Ivanhoe
Orion Engineered Carbons LLC
7095 Highway 83
Franklin, LA 70538, USA
6) Brazil, Paulnia
Orion Engineered Carbons Ltda.
Av. Antonio Fadin, 1300
Paulnia, SP, CEP 13147-030, Brazil
7) Brazil, So Paulo
Orion Engineered Carbons Ltda.
R. Maestro Cardin, 1293
So Paulo, SP, 01323-001, Brazil
8) Luxembourg
(Global Corporate Headquarters)
Orion Engineered Carbons S.A.
6 Route de Trves
2633 Senningerberg, Luxembourg
9) France, Ambs
Orion Engineered Carbons SAS
Lieu Dit Saint Vincent
BP 3, 33810 Ambs, France
1 Introduction
History of Orion Engineered Carbons
July 2014
July 2014
2013
2013
Orion installs a new Rubber Carbon Black
production line in Yeosu (South Korea)
December 2013
2011 - 2014
Orion Engineered
Carbons
Operates as
Standalone
Business
September 2012
May 2013
2011
Evonik aquires full ownership of Algorax
Port Elizabeth (South Africa) Joint Venture
2010
Evonik converts rubber lines into mainly
Specialty Carbon Black production at
Belpre (Ohio, USA) and Malm (Sweden)
2009
Evonik converts rubber line into Specialty
Carbon Black
2007
2011 - 2014
Established as
Standalone
Business
1998 - 2010
Repositioning
Towards
Specialty Carbon
Black
2008
Evonik installs two oxidation units for Specialty Gas Black at Cologne (Germany)
2002
2000
1986 - 2002
1994
International
Expansion
July 2011
Separation of Evonik`s Carbon Black business into a new standalone business called
Orion Engineered Carbons
2002
1999
Degussa acquires plants in Bupyeong
(Korea) and Yeosu (Korea)
1997
Degussa aquires plant in Sines (Portugal)
1988
1986
1958
1938
1956
1932 - 1958
Historical
Backdrop
1932
Degussa enters the Carbon Black business
through the acquisition of a significant
share in August Wegelin AG
December 2013
Orion consolidates all German R & D activities in a single facility (Cologne), thereby
creating a global center of excellence
Acquisitions
1936
Degussa forms a Joint Venture with Deutsche Gasruwerke GmbH & Co. KG (the
German Joint Venture) with German tire
producers
Management
Initiatives /
Joint Ventures
Capacity
Expansions /
Conversions
Small particle size Carbon Blacks fulfill these requirements. Coarser Carbon Blacks, which offer a more
brownish undertone, are commonly used for tinting
and are indispensable for obtaining a desired gray
shade or color hue.
In the polymer industry, fine particle Carbon Black is
used to obtain a deep jet black color. A major attribute
of Carbon Black is its ability to absorb detrimental UV
light and convert it into heat, thereby making polymers, such as polypropylene and polyethylene, more
resistant to degradation by UV radiation from sunlight.
Specialty Carbon Black is also used in polymer insulation for wires and cables. Specialty Carbon Black also
improves the insulation properties of polystyrene,
which is widely used in construction.
In the printing industry, Carbon Black is not only used
as pigment but also to achieve the required viscosity
for optimum print quality. Post-treating Carbon Black
permits effective use of binding agents in ink for optimum system properties. New Specialty Carbon Blacks
are being developed on an ongoing basis and contribute to the pace of innovation in non-impact printing.
1 Introduction
With a yearly production volume exceeding ten million metric tons, the most important Carbon Black
manufacturing process is the Furnace Black method.
More than 98 % of the worlds annual Carbon Black
production is manufactured through this process.
Nevertheless, other manufacturing methods are also
used in the commercial production of Carbon Black,
e.g., for fabrication of Gas Blacks, Lamp Blacks, Thermal
Blacks and Acetylene Blacks.
Figure 1:
Roman Fresco, Pompeii
2a)
Area
Application
Rubber
Printing Inks
Coatings
Plastics
Fibers
Pigmentation
Paper
Construction
Power
Metal Carbide
Fireproofing
Insulation
Table 1:
Major Carbon Black
applications
2c)
2b)
Figure 2:
Description of Carbon Black production process in De Architectura by Vitruvius
a) Medieval manuscript
b) Latin text
c) English translation
2 Manufacturing Process
Pine resin proved an ideal raw material for Carbon Black used in
printing inks, and Germanys Black Forest region soon became
the epicenter of a thriving industry. Special settling chambers
made it possible to conveniently produce large quantities of
Carbon Black (Figure 5).
Figure 4:
Ancient Lamp Black process
as described in Diderots
Encyclopdie (Paris 1770/80)
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Chemical Process
Manufacturing Method
Thermal-Oxidative
Decomposition
Thermal Decomposition
Figure 5:
Processing pine resin to create pitch, tar and Carbon Black
11
2 Manufacturing Process
2.1 Raw Materials
The preferred feedstock for most Carbon Black
production processes, especially the Furnace Black
process, is heavy oil with a high content of aromatic hydrocarbons. The aromatic form of carbon
gives the greatest carbon-to-hydrogen ratio, thus
maximizing the available carbon, and is the most
efficient in terms of Carbon Black yields. Theoretically, the greater the aromaticity the more efficient
the process is. Unfortunately, as the number of
combined rings increases the substances move from
viscous liquids to solid pitches.
Figure 6:
Gas Black manufacturing apparatus as depicted
in German patent application DRP 29261
12
The yield of Carbon Black depends on the aromaticity of the feedstock. It was commonly measured
by BMCI (Bureau of Mines Correlation Index) value.
However, BMCI is only applicable to feedstocks
derived from petroleum. In the case of carbochemicaloils the BMCI may not reflect the true aromaticity of
the product. For this reason the carbon-to-hydrogen
ratio is favored for carbochemical products. However,
as this measurement is also superior to BMCI, even
for petrochemical products, the carbon-to-hydrogen
ratio and the carbon content are becoming the preferred criteria for all Carbon Black feedstocks.
a)
b)
Figure 7:
a) Furnace Black reactor, German patent DRP 50605 of 1899
b) Furnace Black reactor, US patent 1,438,032 of 1922
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2 Manufacturing Process
Figure 8:
Scheme of a Furnace Black
reactor
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Figure 9:
Furnace Black production
installation
Figure 10:
Furnace Black reactor
(section)
15
2 Manufacturing Process
Figure 11:
16
* see 3.1
1) Furnace Black, fine primary particle size
Figure 13:
OEC Carbon Black plant
in Cologne (Kalscheuren)
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2 Manufacturing Process
Figure 14:
Scheme of Gas Black
production process
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Figure 15:
Electron microscope view
of Gas Black particles
(COLOUR BLACK FW 285)
Figure 16:
Scheme of Lamp Black
production process
In order to separate the solids, process gases containing Carbon Black are passed through a filter after the
cooling stage. Onward processing is similar to that of
the Furnace Black method described in section 2.2.1.
Although different types of Lamp Blacks were produced
in the past, the method was eventually standardized
to yield only one type of Specialty Carbon Black and
one type of Rubber Carbon Black. These Carbon Blacks
are characterized by a broad primary particle size
distribution ranging from approximately 60 to over
200 nm (Figure 17) and are widely used in special
applications.
Figure 17:
Electron microscope view
of Lamp Black particles
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2 Manufacturing Process
Figure 18:
Scheme of Channel Black
production process
Figure 19:
Historic view of a Channel
Black production
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Figure 20:
Scheme of Thermal Black
production process
Figure 21:
Electron microscopeview
of Thermal Black particles
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2 Manufacturing Process
2.3.2 Acetylene Black Process
At higher temperatures, exothermic decomposition
of acetylene yields carbon and hydrogen, forming the
basis of the Acetylene Black process. Hydrocarbons are
usually added to acetylene in order to prevent reactor
temperatures from rising due to the exothermic reaction. Once the reaction mixture has cooled down, the
Carbon Black is separated from the hydrogen.
Figure 22:
Electron microscope view
of Acetylene Black particles
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Properties
Aqueous Dispersions
Pre-Dispersions
Pastes
Chips
Plastic Masterbatches
Rubber Masterbatches
Oil Pellets
Table 3:
Carbon Black compounds
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Particle Surface
Ether
Carboxyl
O
O
O
OH
Peroxide
O
HO
Phenol
Lactone
Hemiacetal
OH
Quinone
acidic
24
O
O
O
Ketone
O
Anhydride
alkaline
Figure 23:
The surface of Carbon Black
can bind oxygen in the
form of acidic or alkaline
functional groups.
that are of primary significance when it comes to characterizing Carbon Blacks and defining their suitability
for specific applications:
The specific surface area (m2/g) of Carbon Black is
a function of primary particle size. Looking at geometric proportions, we can determine that smaller
Carbon Black primary particles have a higher specific
surface area.
The structure designates the three-dimensional
arrangement of primary particles in the aggregate.
Extensive interlinking or branching characterizes
a high structure, whereas less pronounced interlinking or branching indicates a low structure.
Electron microscopy combined with X-ray structural
micro-analysis, shows that these primary particles
consist of concentrically arranged, graphite-like crystallites. By partially fusing together, the graphite layers
are often twisted into each other, exhibiting a disordered state. A single primary particle can contain up
to 1,500 of such crystallites.
Element
Content (% of wt.)
Carbon
96 99.5
Hydrogen
0.2 1.3
Oxygen
0.2 0.5
Nitrogen
0 0.7
Sulfur
0.1 1.0
Residual Ash
<1
Table 4:
Typical elemental Carbon
Black composition
Figure 24:
Scanning electron microscope view of a Carbon Black aggregate consisting of fused primary particles
(magnification: x 120,000)
25
1018
1016
1014
1012
26
1010
108
106
104
102
100
01
01
52
PRINTEXL
PRINTEX45
Figure 25:
Specific volume resistance
curves for filled HD polyethylene samples relative
to Carbon Black content
Content in ppm
Antimony
< 10
Arsenic
< 10
Barium
< 10
Cadmium
<1
Chrome
<5
Cobalt
<5
Copper
<5
Lead
< 10
Nickel
< 10
Mercury
<1
Selenium
< 10
Zinc
< 10
Table 5:
Typical concentrations of
trace metals
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ECORAX Blacks
4th stage
New technology Blacks
DBP
absorptionstructure
Iodine number
specific
surface area
2nd stage
1st stage
1950
28
3rd stage
1960
1970
2000
Figure 26a:
Furnace Black history
Figure 26b:
Scanning tunneling
microscopy (STM)
Higher surface roughness for ECORAX black due to smaller crystallites and more disordered arrangement of crystallites
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Figure 27:
Test methods
1) Determination of toluene extract
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ISO
ASTM
DIN
Surface Area
Iodine Adsorption
Nitrogen Surface Area/STSA
1304
4652/18852
D 1510
D 6556
66132
Structure/Rheology
OAN
COAN
Oil Absorption
4656
4656
787/5
D 2414
D 3493
Colorimetry
Jetness
Tint Strength
5435
D 3265
1125
787/2
787/18
D 1506
D 1509
D 1514
D 7724
D 4527
D 1618
D 1512
Chemical Analyses
Volatile Components
Ash Residue
Moisture
Sieve Residue
Non-Dispersible Matter
Toluene Extract
Transmittance of Toluene Extract
pH
External Appearance/Texture and Handling
Properties
Pour Density
Individual Pellet Hardness
Pellet Size Distribution
*)
55979
6209
3858
787/9
1306
8511
D 1513
D 3313/D 5230
D 1511
53552
53586
*)
*)
*)
**)
Table 6:
Carbon Black test methods.
*) DIN EN ISO method
**) DIN ISO method
Figure 27:
Test methods
3) Measurement of oil absorption capability (OAN)
31
32
Blackness value MY
290
280
270
260
250
240
10
15
20
25
Figure 28:
Primary particle size and
jetness
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Figure 29:
Control room of a
Carbon Black plant
34
105
OAN [ml/100g]
102
99
96
93
Time
Figure 30:
Process control chart
35
determine the quantity and size of the primary particles, which then yields the number of specific diameter clusters.
Figure 31 shows the primary particle size distribution
curve for each of the main production methods. Fine
Carbon Blacks (Gas Blacks) for instance are clustered in
a relatively narrow primary particle size range. Coarser
Carbon Blacks exhibit flatter curves.
Thermal Decomposition
Lamp Black
Gas Black
Furnace Black
Thermal Black
Acetylene Black*
m /g
16 24
90 500
15 450
6 15
approx. 65
Iodine Adsorption
mg/g
23 33
n. a.
15 450
6 10
approx. 100
nm
110 120
10 30
10 80
120 500
32 42
OAN
ml/100 g
100 120
n. a.
40 200
37 43
150 200
200 220
230 300
210 300
170 190
225
Jetness MY
Tint Strength
20 35
90 150
50 160
approx. 20
n. a.
Volatile Matter
1 2.5
4 24
0.5 6
0.5 1.0
0.5 2,0
69
46
6 10
79
5 8*
pH **
Table 7:
Carbon Black variances for different production processes
* Pressureless process
** Treated Carbon Blacks may have a pH as low as 2
Frequency (% by wt.)
90
80
70
60
50
40
30
20
10
0
02
10
03
Gas Black
COLOUR BLACK FW 1
36
04
05
06
07
08
09
0
Primary Particle Diameter (nm)
Furnace Black
CORAX N 339
Lamp Black
LAMP BLACK 101
100
110
120
130
140
Figure 31:
Distribution curves for primary
particle diameters
37
4 Handling
Figure 32:
Carbon Black packaging
1) FIBC
38
2) Paper bags
One aspect to keep in mind is that wet-pelletized Carbon Black is usually characterized by a greater pellet
hardness than dry-pelletized or oil-pelletized Carbon
Black. The appropriate conveying system must be
chosen depending on the pellet hardness, considering
the strength of the pellets against the applied forces.
Figure 33:
Carbon Black handling
and shipping
1) Pneumatic conveyor system for Carbon Blacks
2) Truck containers
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5 Product Safety
5.1 Toxicology
Human Experience
In decades of Carbon Black production and processing
using a variety of methods, no significant hazardous
effects have been registered.
Acute Toxicity
Carbon Black has an acute (oral) toxicity LD50 of
> 8000 mg/kg bw. Carbon Black applied on the intact
skin and to the eye of the rabbit does not cause irritating or corrosive effects. Carbon Black did not induce
skin sensitisation effects in guinea pigs (OECD guideline 406). In humans, no cases of skin or respiratory
allergies have been reported.
Chronic Toxicity
In the early 1990s, extended long-term inhalation
studies with rats showed lung fibrosis and tumor
development in the case where the lungs were overloaded with Carbon Black particles. Mice and hamsters
did not develop lung tumors under similar testing
conditions. Although the significance of effects seen in
rats under overload conditions for human risk assessment is today still controversially discussed.
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Ecotoxicology
Carbon Black is an inorganic water insoluble substance. For this reason its bioavailability for aquatic
organisms is very low. In acute tests according to
OECD test guidelines with fish, daphnia and algae,
nominal concentrations of 1.00 mg/l showed no
effects. Based on the physicochemical and acute
toxicological data, no chronic effects and no bioaccumulation are to be expected in aquatic organisms. The
general guidelines for the examination of the biodegradability of substances (OECD, EEC-guidelines) can
be used only for organic substances. Carbon Black is
an inert inorganic substance with the structural formula C and is not biodegradable by microorganisms.
The German commission for the evaluation of water
polluting substances has classified Carbon Black as a
not water endangering substance (KBwS-No: 1742).
Special Requirements
Many Carbon Blacks fulfill the governmental standards for additives that are used in articles that
come into contact with food, drinking water and
toys. For more detailed information, please contact
the Product Stewardship and Health Department:
Orion Engineered Carbons GmbH
Hahnstrae 49
60528 Frankfurt am Main
Germany
phone +49 69 36 50 54 - 165
fax
+49 69 36 50 54 - 784
[email protected]
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6 Applications
Once you consider its possible uses you will find that
there are many answers to the question
What is Carbon Black?.
Indeed, the physical and chemical properties discussed so far hint at a broad spectrum of applications.
The high degree of light absorption, for instance, is
one aspect that makes Carbon Black so useful in the
coatings, plastics and printing industries.
42
The following widely acknowledged typology of Carbon Blacks based on reinforcing properties has stood
the test of time:
Hard Blacks:
High reinforcing capability, fine Carbon Blacks, tire
tread blacks (primary particle size: 1 30 nm)
Soft Blacks:
Semi-reinforcing capability, carcass Carbon Blacks
(primary particle size: 31 200 nm)
Thermal Blacks:
Minor reinforcing capability, high filling rates (primary
particle size: >200 nm)
N100
121 150
N200
100 120
N300
70 99
N500
40 49
N600
33 39
N700
21 32
N900
< 10
Table 8:
ASTM Rubber Carbon Black
typology (excerpt)
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6 Applications
6.2 Specialty Carbon Blacks
Specialty Carbon Blacks have a number of advantages
compared to black organic dyes:
Color stability
Solvent resistance
Acid and alkaline resistance
Thermal stability
High hiding power
These Carbon Blacks are used for a variety of applications in the printing, paints, coatings, plastics, fiber,
paper and construction industries. Here also the
industry works with a widely accepted typology based
on particle size. Although not considered an international standard, it serves as the main reference for
most manufacturers.
The classification system identifies four groups:
High Color (HC), Medium Color (MC), Regular Color
(RC) and Low Color (LC). The third letter refers to the
manufacturing process: (F) for Furnace Black and (G)
for Channel or Gas Black. Treatment is indicated by the
suffix (o).
New Specialty Carbon Blacks developed on an ongoing basis, are sustaining and driving the pace of innovation in the area of non-impact printing methods.
Today, the Specialty Carbon Black manufactured
according to the Degussa Gas Black method is at the
forefront of the industry.
Furnace Blacks
Range of Median
Primary Particle Size*
(nm)
HCG
HCF
10 15
MCG
MCF
16 24
RCG
RCF
25 35
LCF
> 36
10 17
MCG (o)
18 24
RCG (o)
> 25
Table 9:
Specialty Carbon Black classification
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45
6 Applications
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Fo c u s e d. I n n o v a t i v e. R e s p o n s i v e.
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Carbons group companies including Orion Engineered Carbons SA), its agents and/or affiliates give no warranty with respect thereto, including but not limited
to any results to be obtained or the non-infringement of any proprietary right. Use or application of such information or statements or the material or systems
described herein is at users sole discretion and risk, and consequently user acknowledges that Orion Engineered Carbons GmbH (as well as all other Orion
Engineered Carbons group companies including Orion Engineered Carbons SA), its agents and/or affiliates shall bear no responsibility or liability for same.
Nothing herein shall be construed as a license of or recommendation for use, especially with concern to the potential infringement of any proprietary right.
All sales are subject to the respective Standard Terms & Conditions of Sale issued by Orion Engineered Carbons GmbH or - as the case may be - another Orion
Engineered Carbons group company, including but not limited to the Limited Warranty clauses contained therein.
2015 Orion Engineered Carbons GmbH
OEC-06/2015