Challenges and Developments with the Upcoming
BAN OF PFOA
 By Tobias Niederleitner, Global Technical Segment Manager, BL Advanced Surface
Solutions, Clariant, Gersthofen, Germany
T
he coatings industry as well as other
industries have been challenged to
find new solutions for some of their
well-established raw materials. Due to
the properties, its chemical nature and its long-
lasting behavior, PTFE is a common choice for
many coatings formulations. On the other hand,
short-chain fluorinated substances within PTFE
show persistence in nature, which REACH and
EPA regard as a worrying.
The European Union has put forth a regula-
tion requiring a limitation of no more than 25
parts per billion (grams per thousand tons) of
Per Fluoric Octanoic (PFOA) in PTFE micro-pow-
der, effective July 4th, 2020. The requirements
TABLE 1 v Correlation particle size and
PFOA content.
PFOA Content PTFE PFOA Content PTFE
Mean Particle Size (µm)
1 (ppb) 2 (ppb)
~ 500 ~ 75 ~ 26
~8 ~ 1,200 ~ 570
38 SEPTEMBER 2020 • W W W . P C I M A G . C O M
of the REACH legislation pose a challenge to the
coatings industry, as many possible raw materi-
als will be banned. Although there is already
an exemption for thermal-treated or irradiated
PTFEs for another two years, there will be a need
to reformulate or to make the formulation PFOA
REACH-compliant or completely PTFE-free for
the future.
Suitable Methods to
Measure PFOA
But how can it be assessed that the PFOA
limit is not exceeded? Unfortunately, it is not
enough to make sure that no PFOA is used
in the production of PTFE because PFOA
can be generated unintentionally during the
production process or in the after treatment.
The only way is to measure the final PTFE
product. And here comes another challenge.
The limit of 25 ppb is very low and quite
close to the detection limit of some analytical
devices. In addition to that, there is no official
analytical method published by REACH. The
most common or established method in
the industry is the liquid chromatography
followed by mass spectroscopy analysis (LC/
MS). However, an important issue is the
sample preparation or the extraction step for
the measurement. The analysis shows different
results when used with critical PTFE sources
with a higher surface area.
Table 1 shows the differences of the same
PTFE raw materials after micronization to a finer
particle size, which results in an increased sur-
face area. The increasing PFOA content is thus
not only limited to the pure raw material, but
also to its application. The purpose the mate-
rial is used for is important and must therefore
be determined. One example are PTFE fine
powders in coatings and inks where the PFOA
content could be potentially increased due to
higher surface area, e.g. 3 mill-roller, which is
commonly used in the industry as well. Further-
more, the extraction method is quite important
and unfortunately not defined in the REACH
legislation. As long as this is not yet defined it
is difficult to find a common set up to compare
the results. Coating and ink producers should
consider that different PTFE additive suppliers
might use different analytical and extraction
methods that might not be comparable. Clari-
ant has developed a detection method using
the LC/MS technology, obtaining a detection
limit of 2 ppb. Accordingly, the risk that REACH-
compliant Clariant additives generate detect-
able quantities of PFOA during the coatings
production process is minimal.
Clariant has analyzed the whole Ceridust®
additives portfolio containing PTFE and even
launched further products containing only
REACH-compliant PTFE with a level of <25 ppb.
These additives enable coating and ink produc-
ers to be prepared for the upcoming REACH
ban of PFOA immediately.
Typical Applications for PTFE
Micropowders Where Coatings
Require Good Scratch Performances
or Low Coefficient of Friction
In the powder coating area, it is quite difficult to
achieve uniform and repeatable matte, fine-tex-
ture finishes. PTFE micropowders are the standard
to achieve this surface modification. As described
already, the PTFEs must be compliant with REACH,
otherwise formulators are not allowed to use
them in the production process.
Clariant recently launched two new
products that help to overcome this challenge.
The well-controlled PTFE balance in the
PE/PTFE blends of Ceridust 3942 F and
Ceridust 3943 F enables a uniform and ideal
distributed texture appearance. The different
PTFE concentration in the products gives
customers the flexibility to adjust the texture
from a smooth to a sandpaper character.
The polyethylene wax source in the blends
decreases the friction during the extrusion
process and improves the milling performance.
Figure 1 provides an indication of the textured
FIGURE 1 v Ceridust 3942 F and
Ceridust 3943 F allow formulators to control
and adjust the textured appearance of
powder coatings.
1% Ceridust 3943 F
1% Ceridust 3942 F Without wax
PAINT & COATINGS INDUSTRY • 39
Challenges and Developments with the Upcoming Ban of PFOA

1% Ceridust 3943 F
FIGURE 2 v Powder coating structures in
comparison: the texturing of the coating on
top left was achieved with PTFE (Ceridust
3943 F), while for the bottom left panel, a
maleic anhydride-modified polyethylene wax
(Licocene PE MA 4351) was applied. The magni-
1% Ceridust 3942 F Without wax
fication (20 times) of the structure on the right
shows that the coating gets smoother and
forms more beads and seems to be glossier.
appearance in a standard polyester system at
the same concentration. The products are not
only limited to polyester systems; they can
also be used in hybrids or epoxy systems.
PTFE-Free Solutions as
Next Milestone
Clariant is now even going one step further by
making completely PTFE-free solutions for the
market. For PTFE, it is very challenging to have a
1:1 replacement, as it has very particular proper-
ties. The maleic anhydride-modified polyethylene
grade from Clariant, Licocene® PE MA 4351, works
in combination with titanium dioxide or barium
sulfate in certain concentrations as a structuring
agent. It is not limited to fine textures; also glossy,
slightly structured surfaces are possible, depend-
ing on the concentration level of the wax and
TiO2 or BaSo4 (Figure 2). Typical fine structures

CoF in solvent-based flexo ink

0.40
0.35
0.30
0.25
0.20
0.15
0.10
0.05
0.00 At ChemQuest Technology
Without Micronized Ceridust PE/PTFE PE/PTFE
wax Licocare RBW 8330 1 2 Institute, we help our clients
break through barriers to expedite
product development in specialty
Color difference E in solvent-based flexo ink
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8.0 Led by our diverse team of industry
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40 SEPTEMBER 2020 • W W W . P C I M A G . C O M
can be achieved by adding around 30% of TiO2,
which is more effective than BaSO4, and around
2% to 4% of Licocene PE MA 4351. The solution is
especially suitable for light colors like those used
in appliances such as air conditioners, washing
machines and dish washers.
Additionally, the typical increased viscosity
during the extrusion process, when PTFE is used,
cannot be seen. And the worse grindability with
the addition of structuring PTFE is also elimi-
nated, which means that Licocene PE MA 4351
can also be used as a processing aid to increase
throughput (milling and extrusion). The solution
can also act as a dispersant of fillers and pig-
ments due do its low melt viscosity paired with
high crystallinity. The excellent flow properties
can improve the high edge coverage to provide
better protection to the substrate, e.g. in the
agricultural, construction equipment markets.
Renewable-Based Solutions to
Become the Premium Choice
PTFE is not only limited to structuring effects. It
has other features like very low surface tension,
chemical inertance and high temperature resis-
tance. One of PTFE’s most important features
when used in coatings is its capability to lower
the coefficient of friction. Mostly blends of poly-
ethylene and PTFE are used for this purpose. The
mixtures with polyethylene should also contain
PTFE sources that are fully REACH-compliant.
This is quite critical because in such blends quite
often recycled PTFEs are used. The PE/PTFE
blends that we currently have available were
already screened internally and confirmed to be
REACH-compliant.
Of course, also in liquid coatings there are
possibilities to totally replace PTFEs. As already
mentioned, the low coefficient of friction is a
PAINT & COATINGS INDUSTRY • 41
 0.30
0.25
0.20
Challenges and Developments with the Upcoming Ban of PFOA
0.15
0.10
0.05
0.00
Without Micronized Ceridust PE/PTFE PE/PTFE
FIGURE 3 v Coefficient of friction in a FIGURE wax 4 Licocare
v Performance
RBW 8330 of PTFE
1 replace-
2
solvent-based flexographic ink by addition of ments in a solvent-based packaging ink; wax
different wax additives. additive dosage 0.5%.
CoF in solvent-based flexo ink Color difference E in solvent-based flexo ink
0.40
8.0
0.35
7.0
0.30 6.0
0.25 5.0
0.20 4.0
0.15 3.0
0.10 2.0
0.05 1.0
0.00 0.0
Without Micronized Ceridust PE/PTFE PE/PTFE Without Micronized Ceridust PE/PTFE PE/PTFE
wax Licocare RBW 8330 1 2 wax Licocare RBW 8330 1 2

key feature that must be checked. Typical waxes classical PE/PTFE blends in a solvent-based pack-
like PE waxes reducethe coefficient of fric- aging ink. The color difference value DE indicates
Color difference E in solvent-based flexo ink
tion
8.0
already. But if the level is not low enough, how strong the printing ink is. The lower the
blends
7.0 with other materials can be used. Promis- value, the better the protection. Here, Ceridust
ing
6.0 results are achieved even with renewable- 8330 demonstrates excellent color retention.
based
5.0 materials that do not show typical wax
4.0
behaviors. Clariant developed solutions derived Conclusion
3.0
from crude rice bran wax. This is a by-product Coming back to the headline regarding the chal-
2.0
from
1.0 the production of rice bran oil. lenges of the upcoming PFOA ban: yes, there
0.0It is important for both the coatings and the are challenges, but also chances and possibilities
Without Micronized Ceridust PE/PTFE PE/PTFE
printing ink industry
wax to protect
Licocare RBW 8330 surfaces
1 during
2 to develop new solutions. And as shown in this
production and in the use phase. PTFEs normally article, solutions are already available. z
lower the coefficient of friction, and the particles
act like a buffer between the surface and the For more information, visit www.clariant.com.
forces that could eventually destroy the surface.
Similar to liquid coatings, Clariant is offering solu- Disclaimer: The performance of a product depends on the condi-
tions that can replace PTFE or PE/PTFE blends. tions of use. Users should always determine the suitability of a
The lowering of friction can be realized with our product for its particular application prior to use.
renewable rice bran-based solutions. Figure 3
shows the influence of the dynamic coefficient
of friction in a solvent-based packaging ink.
­Clariant test results of the micronized rice bran Follow PCI on Facebook
waxes (Licocare RBW) such as Ceridust 1060 Vita www.facebook.com
even demonstrated that these products can
on Twitter
outperform standard PE/PTFE blends in terms of
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slip performance. Last but not least, protection
is important. Test results show in Figure 4 that and on Linkedin
materials like micronized RBW or the partially www.linkedin.com
renewable blend Ceridust 8330 can outperform

42 SEPTEMBER 2020 • W W W . P C I M A G . C O M