Inorganic pigments

using the Laux process

2
 
 
  

The LANXESS pigments business has been committed for manufacture dyestuffs,
many years to sustainable production processes as one of its the iron oxide byprod-
core competencies. The Laux process in Krefeld-Uerdingen uct could not be put to
  

 -           
 
duction method for iron oxide pigments.
The method is exemplary in that it fully exploits the heat pro-
duced by the chemical reaction to generate steam and hot wa-
1914 to use the resulting iron oxide as a colorant, but the
quality of the iron oxide was not adequate for pigment appli-
cations. It took another eleven years before Dr. Laux, a chem-
ist, succeeded in optimizing the process and obtaining iron
  
 

     

  
 !
 "  #
The Laux process is the key to the special properties of
LANXESS’s yellow, black and red shades. Particularly with the
reds, a very broad range of hues can be produced, from reds
with a yellow to reds with a blue undertone. The red shades
with a blue undertone are quite unique compared with other
iron oxide reds available on the market because they display
only a slight color shift even under intense milling conditions.
 
1926, one year after its discovery, iron oxide production was
launched in Krefeld.
Since then, iron oxide production at the Krefeld plant has un-
dergone remarkable development. After starting out with a ca-
pacity of roughly 1,000 metric tons in 1926, production has
steadily increased. At present, 280,000 metric tons of iron
oxide pigment are produced at the plant, two-thirds of that
by the Laux process. In other words, LANXESS operates the
world’s largest production plant for synthetic iron oxide pig-
 
        - ments in Krefeld.
trobenzene with metallic iron to aniline and iron oxides, was
implemented on an industrial scale as far back as 1911 at
the Krefeld-Uerdingen site. While the aniline was needed to

2

 

In the Laux process, nitrobenzene is reacted with cast iron pigments cannot be obtained directly by these means; they
borings. Depending on the reaction conditions and the control are produced by subsequent calcining of the black paste un-
chemicals, a suspension of black or yellow iron oxide results, der oxidative conditions.
which subsequently is washed, concentrated and dried. Red

Nitrobenzene Cast iron 

2 Fe + C 6 H 5 - NO 2 + 2 H 2 O
Reaction Aniline 2 FeO(OH) + C 6 H 5 - NH 2

Fe3O4 FeO(OH)
9 Fe + 4 C 6 H 5 - NO 2 + 4 H 2 O
Black Yellow
3 Fe 3 O 4 + 4 C 6 H 5 - NH 2
Reaction

2 Fe 3 O 4 + 0,5 O 2
Fe2O3 Mixture
Red Brown 3 Fe 2 O 3

Fig. 2: Diagram of the Laux process

Fig. 1:
Basic patent
on the Laux
process

3
 The basic reaction in the Laux process, i.e. the reaction of ni-
trobenzene with cast iron, is extremely exothermic. After vari-
ous process and plant optimizations, LANXESS has succeed-
ed in exploiting virtually all the heat of reaction to produce hot
water and steam for use in downstream processing steps. This
4
reduces primary energy demand by 28 % and cooling water
output by as much as 56 %, making the Laux process one
of the most ecologically compatible and resource-conserving
processes for the production of iron oxide pigments.
One raw material in the Laux process is nitrobenzene, ob-
tained by the nitration of benzene with nitric acid. The second
raw material, cast iron borings, is a byproduct from the ma-
chining of cast iron parts in various industries, such as auto-
motive manufacturing.
 One unique advantage of the Laux process is its ability to
Pigment properties produce red shades with a blue undertone. Significant differ-
ences exist in this area between the Laux process and others,
!
In the Laux process, all three basic iron oxide colors - red, yel-
low and black - are available in a relatively broad color spec-
trum. Due to the scattering power of iron oxides, the particle
size has a direct influence on the shade.
Red
When it comes to red, the smaller the particles, the more pro-
because the other manufacturing processes have difficulty ob-
taining the required particle sizes.
Black
In the case of black, the shade of the pigment likewise depends
on the size of the primary particles, ranging from the bluish
Bayferrox® 306 to the high-tinting-strength Bayferrox® 330.
$
 
      
  &
 "  
nounced the yellow undertone, while larger particles produce size. The larger the primary particles, the bluer the undertone of
more of a blue undertone. The difference in prevailing particle the shade. However, this effect is obtained at the cost of tinting
size spans a rather wide range, from 0.09 μm for Bayferrox® 105      
M to 0.7 μm for Bayferrox® 180 M.
Bayferrox® 318 Bayferrox® 306

Bayferrox® 110 M Bayferrox® 140 M Bayferrox® 180 M

Particle size Increasing

Tinting strength Decreasing
Shade Brownish Bluish

Fig. 3: The Laux process produces red pigments with a bluish undertone Fig. 4: Particle size affects
that set it apart from other processes. the shade.

5
 Yellow
Lightfastness of Bayferrox® 920, 420 and Colortherm® 10
With yellow, the range of shades achieved in pigments manu- (Blue Wool Scale, level 8)
factured by the Laux process is narrower. By selecting the 3.0
right raw materials, the Laux process also can produce yel- 'E*ab
low pigments that nearly rival precipitated pigments. Bayfer- 2.5
rox® 3420 is the micronized version of Bayferrox® 420 and
2.0
frequently selected as an alternative to precipitated yellow in
paint and coating applications. The yellow grade, Bayferrox 1.5
415, is mainly used to color building materials on account of
1.0
its darker, bluer shade.
0.5
"
 
0.0
Iron oxide pigments are lightfast thanks to their chemical and Bayferrox® 920 Std‘03 Bayferrox® 420 Std‘99 Colortherm® Yellow 10
physical properties. In practical pigment applications, however,
Test conditions: Xenotest 150 S/ca. 160 h until wool sample 8 fades
the interface between pigment and binder is a critical factor, this
being particularly evident in coloring laminates yellow. A distinct
Fig. 5: Differences in lightfastness
difference in color shift can be observed when using a yellow
iron oxide pigment produced by the precipitation process (Bay-
ferrox® 920), one by the Laux process (Bayferrox® 420) and a
post-treated yellow pigment (Colortherm® Yellow 10).

UV radiation at the interface of the pigment/binder matrix pre- case of Colortherm® Yellow 10, the inorganic post-treatment
sumably leads to partial reduction of the resin, expressed by a             -
green shift. This may be attributable to catalytic effects. In the ening catalytic degradation and greatly reducing color shift.

6
Laminates increasingly are used in outdoor applications,
a trend that tightens quality requirements on the lightfastness of    &
the decorative papers.  !" '$
(to DIN-EN 12877-2 Method B)

6
(!   
Colortherm® Red 110M
In terms of temperature stability, Laux pigments again offer dis- 5
Precipitated Red
tinct advantages over precipitated iron oxide pigments. 4

#$%
Limit to DIN-EN 12877 Part 2
3
Although red as hematite (Fe2O3) is heat-stable thanks to its
chemical structure, the various iron oxide reds nevertheless 2
display remarkable differences attributable to the production 1
process.
0
200 °C 220 °C 240 °C 260 °C 280 °C 300 °C 320 °C
The red iron oxide pigments produced by the Laux process are
(! )
heated to as high as 800 °C during calcining and therefore
characterized by high temperature stability. Thermal stability is
Fig. 6: Thermal stability of various red pigments
of particular importance in coloring plastics, because the elevat-

  
 
less color change versus red precipitated pigments.

7
 In contrast to Laux red pigments, precipitated red iron oxide Similarly, Laux yellow pigments are more stable than precipitated
pigments often have some water bound in the crystal lattice, products because of the manufacturing process. The post-treated
which evaporates at high temperatures. This results in a de- Laux products Colortherm® Yellow 10 and Colortherm® Yellow 20
crease in weight and a change in shade. are particularly stable.

    '$

(to DIN-EN 12877-2 Method B)
100 °C 500 °C
18
Calcined red: Decrease in weight: 0.11 % Decrease in weight: 0.31 % 16 Bayferrox® 420

'<= = 0.1 '<= = 0.3 Colortherm® Yellow 20

Bayferrox® 920
14
Max. level according to the European standard

12
Calcined red, Decrease in weight: 0.15 % Decrease in weight: 0.45 %
#$%

yellowish: '<= = 0.1 '<= = 0.3 10

Precipitated red: Decrease in weight: 0.33 % Decrease in weight: 1.85 % 6

'<= = 0.2 '<= = 2.4
4

2
Precipitated red, Decrease in weight: 0.51 % Gewichtsverlust: 2.57 %
yellowish: '<= = 0.1 '<= = 3.5 0
200 220 240 260 280 300

(! )

Fig. 7: Moisture content and color change as a function of temperature Fig. 8: Thermal stability of various yellow pigments

8
+"  
Sintering occurs during the calcining step of the Laux process,
with the primary particles forming larger agglomerates. These
are hard and must be broken up by intensive milling to ensure
good dispersibility in the end application.
As a result, Laux reds are much more stable than precipitated
red pigments when exposed to any additional milling or other
high shear forces in a customer application. For instance, the
shade of Laux red pigments changes much less during bead
milling than that of precipitated red pigments. The bluer the
undertone of the red pigment, the more pronounced the differ-
ence between these two production processes.
Pigment comparison:
The very strong shear forces prevailing in concrete applications
bring out the advantages of Laux pigments. Even Bayferrox®
130 shows better color consistency in the application than a
precipitated red iron oxide pigment. The darker the shade, the
more pronounced the difference.
* 
Because of the needle structure of yellow iron oxide pig-
ments, their viscosity behavior is a very critical parameter.
In general, the more pronounced the needle structure, the more
problematic the viscosity behavior.
+"  -.
 #%/!

;<
(Olbrich shaker: Binder: Alkydal F48, PVC 10%)

10
9
8 Calcined red Bayferrox® 420 Bayferrox® 415
7 Precipitated red
6
#%

5
4
3
2
1
0
10“ Dissolver 5“ Shaking 15“ Shaking 30“ Shaking 60“ Shaking

Dispersing time


  
 

  Fig. 10: Prismatic particle structures are characterized
to strong shear forces by low viscosity

9
 Compared to the distinct needle shape of Bayferrox® 420,
the primary particles in Bayferrox® 415 are more prismatic.
Pigment preparations of Bayferrox® 415 therefore have a sig-
nificantly lower viscosity than those of Bayferrox® 420, a prop-
erty that becomes most evident in pigment suspensions for
the building industry. Bayferrox® 415 permits a significantly
higher solids content.
For concrete manufacturers, it is important to minimize the
influence of a color pigment on the consistency of the
concrete as much as possible, because more water other-
wise may have to be added to achieve the same workability.
More water, however, translates into lower concrete strength.
Yellow Laux pigments therefore have less of an influence on
concrete consistency than yellow pigments produced by other
methods.

Viscosity in universal paste after production

5.0

4.5 Bayferrox® 420 Std. 99

Bayferrox® 415 Std. 83

4.0
Viscosity [P a*s]

3.5

3.0

2.5

2.0

1.5

1.0

0.5

0.0
0 200 400 600 800 1000 1200 1400 1600 1800 2000

Shear rate [1/s]

Fig. 11: Viscosity in universal paste after production

10
  &&
? !" $'
105 M A red shade with a yellow undertone for the paint and coatings industry
110 (M)
120 N(M)
120 (M)
130 (M)
Bayferrox® The shade exhibits an increasingly blue undertone as the number increases
130 B(M)
140 (M)
160 (M)
180 N(M)
180 (M) A red shade with a blue undertone for the paint and coatings industry
? !" $@A
415 Low-viscosity yellow pigment primarily for the building materials industry
Bayferrox® 420 Standard yellow pigment
3420 Micronized variant of Bayferrox 420
? !" EF
306 Black shade with a blue undertone
316
318
Bayferrox® 318 M Iron oxide black for the paint and coatings industry
320 Black pigment for the building materials industry
330 Very high-tinting-strength black pigment for the building materials industry
340 Black pigment for the building materials industry
 G H  !" 
Yellow 10 Heat-stabilized yellow pigment for the paint and coatings industry
Colortherm® Yellow 20 ?  "!
   
 @  J
Black 318 Heat-stabilized black pigment with high tinting strength for all common plastics applications

11
Health and Safety Information: Appropriate literature has
been assembled which provides information concerning
the health and safety precautions that must be observed
when handling the LANXESS products mentioned in
this publication. For materials mentioned which are not
LANXESS products, appropriate industrial hygiene and
other safety precautions recommended by their manu-
facturers should be followed. Before working with any of
The manner in which you use and the purpose to which
you put and utilize our products, technical assistance and
information (whether verbal, written or by way of produc-
tion evaluations), including any suggested formulations
and recommendations are beyond our control. There-
fore, it is imperative that you test our products, technical
assistance and information to determine to your own
satisfaction whether they are suitable for your intended
these products, you must read and become familiar with  
     
the available information on their hazards, proper use
and handling. This cannot be overemphasized. Informa-
tion is available in several forms, e.g., material safety data
sheets, product informa-tion and product labels. Consult
your LANXESS representative in Germany or contact
the Regulatory Affairs and Product Safety Department of
LANXESS Germany or – for business in the USA – the
LANXESS Product Safety and Regulatory Affairs Depart-
ment in Pittsburgh, Pennsylvania.
Regulatory Compliance Information: Some of the end
uses of the products described in this publication must
comply with applicable regulations, such as the FDA,
BfR, NSF, USDA, and CPSC. If you have any questions
on the regulatory status of these products, please con-
sult your LANXESS representative in Germany or contact
the Regulatory Affairs and Product Safety Department of
 &  
must at least include testing to determine suitability from
a technical as well as health, safety, and environmental
standpoint. Such testing has not necessarily been done
by us. Unless we otherwise agree in writing, all products
are sold strictly pursuant to the terms of our General Con-
ditions of Sale and Delivery. All information and technical
assis-tance is given without guarantee and is subject to
change without notice. It is expressly understood and
agreed that you assume and hereby expressly release us
from all liability, in tort, contract or otherwise, incurred in
connection with the use of our products, technical assis-
tance, and information. LANXESS Deutschland GmbH
Business Unit
Any statement or recommendation not contained in this
brochure is unauthorized and shall not bind us. Nothing
Inorganic Pigments
herein shall be construed as a recommendation to use 47812 Krefeld

    GERMANY
LANXESS Germany or – for business in the USA – your as patents covering any material or its use. No license is Tel.: +49 2151 88-8814
LANXESS Corporation representative, the LANXESS implied or in fact granted under the claims of industrial Fax: +49 2151 88-8090
Regulatory Affairs Manager in Pittsburgh, Pennsylvania. property rights such as patents. Edition 11/2011
www.lanxess.com
®
Bayferrox is a registered trademark of Bayer AG, Leverkusen, Germany. www.bayferrox.com
Colortherm® is a registered trademark of the LANXESS Group, Leverkusen, Germany. www.colortherm.com