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PFPE-Greases: modern trends and perspectives

Conference Paper · April 2018

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PFPE-Greases: modern trends and perspectives

Alexander Grechin1, Verena Schott1, Rachel Kling2

1
Setral Chemie GmbH, 82402 Seeshaupt, Germany
2
Setral S.a.r.l, 67310 Romanswiller, France

Lubricating greases based on perfluorinated polyether (PFPE) have been predestined for a
long time as niche products, providing long-life lubrication at temperatures above 200°C, in
aggressive chemical environments, in vacuum devices or as an inert media to lubricate and/or
protect sensitive materials like plastics and elastomers. This group of specialty greases is now
becoming also competitive in a range of applications where less expensive and less-
performing lubricants are normally used. Modern PFPE greases can offer both performance
advantages and a lower total cost of ownership (purchase price + the costs of operation). The
lubrication of different devices in traditional and electric cars has proved to be one of the
successful uses of PFPE greases. This paper will overview and discuss the new possibilities in
the development and application of PFPE greases.

1. Introduction

Lubricating greases based on synthetic perfluoropolyethers (PFPE) as base oils and

polytetrafluorethylene (PTFE) or inorganic thickeners are usually classified as specialty
lubricants for high-tech industrial applications under extra high/extra low-temperature
conditions and for lubrication under the influence of aggressive chemicals like liquid oxygen,
halogens, mineral acids or molten mineral bases [1].
PFPEs used as base oils for greases cover a broad range of viscosities (22-1200 cSt at 40°C),
have operating temperature range from -75 to over 300°C and long-term thermo-oxidative
stability, excellent lubricating properties, and an inert behavior towards most of elastomers
and metals. Nevertheless, several performance and economic issues like incompatibility with
conventional lubricants and higher average pricing can cause the customers some
understandable confusion regarding correct application and economic benefits of using PFPE
lubricants.

In the present paper, we discuss actual developments and perspectives of applications of PFPE
greases in the context of the total cost of ownership (TCO) approach. This allows a more
correct evaluation of the overall lubrication performance, based on different cost effects,
some of which are usually not or not sufficiently taken into account.

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2. Experimental Part

2.1 Materials

All base oils, additives and thickeners used in this work were commercial technical grade
products. Grease samples were prepared using a conventional laboratory grease making
machines by blending the base oil with the thickener system and additives at room
temperature. The resulting greases were homogenized on a triple-roll mill.

2.2 Test methods

The greases in this study were characterized by using a number of standard tests that are
common to the lubricating grease industry. Base oil viscosity was measured on Anton Paar
SVM-300 Stabinger Viscosimeter. Consistency of the greases was determined using the
automated Normalab NPN TECH penetrometer. Dropping points were measured on Mettler-
Toledo DP70 Dropping Point System. Rust tests were run with a REBA Elektro-Apparatebau
device according to the SKF-EMCOR method and Shell-Roll Stability tests using a Stanhope-
Seta roll stability tester.

To evaluate the long term ageing thermal stability of greases the evaporation/thermal
destruction weight loss at 200°C was measured. The grease samples were spread on
aluminium plates to get a constant thickness layer, and placed in a ventilated Memmert UFE
500 oven for >2700 hours. The weight loss was repeatedly determined by using a Sartorius
R300S precision balance. The lubrication life at given temperature was estimated as a period
up to the moment when the grease begins to dry out and its typical buttery texture is
destroyed.

Rheological properties of complex viscosity, storage (G’) and loss (G’’) moduli, and loss factor
(G’/G’’) were evaluated with the oscillation shear mode of the Anton Paar MCR 302
rheometer. The rheometer was equipped with a T-PTD-200 ball-on-three-plates tribology cell
in combination with a Peltier temperature control hood H-PTD 200. This setup was used for
the investigation of the friction coefficient and the wear scar in a wide temperature range
under controlled sliding speed and normal force.

Extreme-pressure and anti-wear properties of the greases were evaluated by using the SKF 4-
ball weld load test machine operated at room temperature. Bearing performance tests were
run at 200°C with angular contact ball bearing units on the FE8 test machine.

The compatibility of greases was studied by mixing two different greases at room temperature
and monitoring the homogeneity and texture of the grease mass.
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3. High-temperature PFPE greases (220-300°C).

Most of commercially available PFPE greases are typically composed of a non-functional PFPE
base oil and polytetrafluorethylene (PTPE) as a thickener. They can include also anti-corrosion
(sodium nitrite, disodium sebacate etc.) and EP additives allowing operating in chemically
corrosive environments or under high load [1]. By changing the base PFPE oil and the
thickener(s) one can create customized products for different applications including extra
high/low temperature bearing greases, high/low-speed bearing greases, greases for the
lubrication of sliding surfaces in plastic injection molding tools, high-vacuum greases, H1 food
grade greases or greases for devices with gaseous and liquid oxygen. In Table 1 two high-
temperature PFPE greases (A and B) are presented as an example.

One more special formulation developed recently is the PTFE-free H1 food grade extra-high
temperature grease suitable for lubrication of the telescopic driver rails in domestic and
industrial baking ovens [2]. The customer’s requirements for this grease included a long-term
lubrication performance at 250-300⁰C, a PTFE-free formulation, smooth running slides in the
oven, no squeaking, low water/dishwashing detergent wash out, no emission of dangerous
products (formaldehyde, benzene etc.) at high temperatures and H1 food grade certification.
The suggested grease is thickened with a combination of an inorganic high-temperature
thickener and a corresponding binder, which allows forming a stable solid-liquid lubricating
coating on the metal surface. This customized solution has proved to be successfully providing
18000-24000 running cycles in a domestic oven (slides move in - move out) at 200°C with 7.5
kg load and 5 wash cycles with detergent in a dishwasher. The grease has also passed a long-
time emission testing at 305°C.

4. PFPE greases for the operating temperature gap 150° - 220°C.

In spite of many performance advantages of the conventional PFPE greases in comparison to

other synthetic and mineral oil based greases, there is still a need for improvements. PFPE
greases are not compatible with both mineral oil based and synthetic oil based lubricants.
Because of the inertness of perfluoropolyether molecules, no common additives can be used
in such formulations due to extremely low solubility. Typical additives have also insufficient
thermal stabilities to match the stability of the PFPE oil. For example, an effective corrosion
protection with PFPE based lubricants containing no additives may be a problem.

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 Table. 1: Setral PFPE greases with mono- and bifunctional thickeners.

Test method Grease A Grease B Grease C Grease D

Thickener type / PTFE inorganic bifunctional bifunctional
Base oil type / PFPE oil PFPE oil PFPE based PFPE based
oil oil
Food grade / none H1 none H1
ASTM
NLGI grade D217/DIN 2 2 2 2
ISO 2137
Base oil viscosity, ASTM D7042 500 510 460 460
40°C, cSt
Dropping point, °C IP 396/02 none none >300 >300
Unworked ASTM D1403- 274 268 288 290
penetration, 25°C 10
Worked ASTM
penetration 60 D217/DIN 274 277 280 293
strokes, 25°C 51350-2
Four-ball wear ASTM
scar, 1500 N load, D2266/DIN 0,9 0,8 1,0 1,0
1 min, mm 51350-2
Four-ball weld ASTM
load, N 2596/DIN 6000 4000 4800 4800
51350-4
Tribocell friction MCR
coeff., 200°C Rheometer 0,11 0,13 0,08 0,08
test
Tribocell wear scar, MCR
200°C, mm rheometer 0,30 0,29 0,40 0,42
test
Roll stability, 50h ASTM D1831 -21 -12 -18 -11
at 80°C
Cu corrosion, 24h, DIN 51811 grade 2 grade 2 grade 0 grade 0
100°C
EMCOR dest. DIN 51802 grade 2 grade 4 grade 0 grade 0
water, cotation
EMCOR salt water, DIN 51802 grade 4 grade 5 grade 2 grade 2-3
cotation
Ageing thermal House >2500 >2500 >2500 >2500
stability, 200°C, h method
Flow pressure, DIN 51805 650 600 1450 750
-35°C, hPa
4
Another point is that fully fluorinated oils like PFPE are one of the most expensive synthetic
base oils in the grease industry.
To minimize the abovementioned disadvantages several so-called hybrid PFPE greases have
been suggested [3-7]. Hybrid greases containing a mixture of PFPE and ester oils and a
thickener based on diurea or greases based on chemically modified PFPE oil thickened with a
special lithium soap are commercially available. Grease formulations comprising a mixture of
two greases with fluorinated and non-fluorinated base oils, metal soap complex and PTFE
thickeners have been developed.
Chemical modification of PFPE polymers result in a range of functionalized partly fluorinated
products. Functionalized PFPE derivates containing functional end-groups (triazole etc.) are
used as additives to improve the thermal stability and wear resistance of the non-functional
PFPE oils. Partly fluorinated (per)fluoropolyether-polyoxyalkylene glycol (PFPE-PAGs)
polymers have been suggested as base oils and as additives for fully fluorinated PFPE greases
showing improved anti-wear properties [8]. Liquid PFPE–TFE copolymers forming a gel
structure in PFPE oils can be an alternative to the solid PTFE thickeners in greases for
lubricating precision mechanical instruments and for reducing noise. [9]. Some phosphorous
compounds are soluble or form stable dispersions in PFPEs. They have proved to be effective
anti-corrosion high-temperature stable additives preventing rust in continuous service at
≥200°C [10].
At high operating temperatures (120-300°C), there is a gap region at 150°C to 220°C where
non-fluorinated synthetic greases are pushed to the limit of their capabilities and the
conventional PFPE greases bring unusable over-performance and a higher price (Fig. 1). We
have reported recently about a new family of PFPE greases based on bifunctional thickener
systems with an improved price/performance value as an economical alternative to commonly
used PTFE/PFPE greases [11].

Fig. 1: Operation temperature gap for the application of bifunctional PFPE greases.

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The results of grease testing are presented in Table 1. As an example, two new PFPE greases
based on bifunctional thickener systems, Grease C and Grease D, are compared with a PFPE
grease thickened with PTFE, Grease A.
The lubrication properties of greases were evaluated using three different model tribometers:
4-ball-tribometer, ball-on-three-plates setup of the Anton Paar tribology cell and FE8 testing
machine.
As follows from the data in Table 1, high weld load, low wear, and low friction parameters
characterize the new bifunctional greases, and are in most cases similar to the corresponding
parameters of the PTFE/PFPE based grease.

Fig. 2: Rheometry strain sweeps at 25°C.

Outstanding bearing performance of Grease D at 200°C was confirmed in the FE8 test
performed according to DIN 51819 Part 2. (Table 2). The test run reached 500 h test time
without any failure. The test specimens showed a low level of wear and a friction torque after
a certain running-in time was constant at 20 Nm (Fig. 3). As shown in Table 3, the wear weight
loss is about 40 mg on balls and lower than 2 mg on cages.
As can be seen from Table 1, better grades in the EMCOR rust test and the Cu corrosion test
are determined for the bifunctional greases compared to those of the PTFE/PFPE grease.

6
Table 2: Parameter FE8 testing according to DIN 51819 Part 2.

Parameter Value

Testload 80 kN

Rotational speed 7.5 min-1

Temperature 200°C

Duration of testing 500 h

Test samples angular contact

ball bearings
7312 B

Table 3. Bearing wear (FE8 test).

Weight loss

in mg

Bearing 1 Bearing 2

Outer ring 5 6

Inner ring 4 6

Cage <2 <2

Balls 47 33

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Fig. 3: Friction torque and bearing temperature as a function of time (FE8 test).

Mixing tests have shown very good compatibilities of the bifunctional greases with common
PFPE based greases as well as with polyurea greases.

The new bifunctional greases are priced approx. 20 to 30 % lower compared to conventional
PFPE/PTFE greases, still showing very good performance in severe industrial applications. One
is to lubricate different types of mechanical sealing rings in mixer or stirring units. In this case
a H1-registration was necessary to lubricate the mechanical sealing ring fixed on a hollow
shaft. The shaft was running at 500 to 700 rpm, and exposed to an actual working temperature
from 120°C up to 140°C. According to the re-lubrication interval, the prescribed period of
minimum 1500 operating hours has been achieved without using an expensive conventional
PFPE grease. A bifunctional grease is now the new standard here.
In plastics processing industry lubrication of the main bearing of a rotational mold system was
equipped with a bifunctional grease to cover the high temperatures of 200°C under the
additional influence of aggressive PVC fumes. The achieved lifetime was as long as with
conventional PFPE greases but for a much more reasonable price.
PFPE greases are now successfully used for fill-for life lubrication of brake calipers, lock
switches, electric throttles, AGR valves, compressors, fuel pumps and other devices in
traditional and electric cars.

8
5. The Total Cost of Ownership (TCO) approach for PFPE greases.

Industrial equipment is being designed to achieve higher production levels with increased
energy efficiency and lower total cost of ownership [12]. Lubricating greases as construction
elements, may have a significant impact on the costs of operation. It depends mainly on the
performance of the grease under operating conditions. Mineral based and conventional
synthetic greases can become lower performing products in the most demanding areas of
application with higher operating temperatures and stresses. Their overall cost/performance
profile under such conditions is reflected in shorter relubrication intervals, higher energy costs
and an increased risk of failure of the equipment [13]. High-performance lubricants could
potentially provide a lower total cost of ownership (purchase price + the costs of
operation/maintenance). The total cost of ownership concept (TCO) for advanced lubricants
was introduced recently by Shell [14], reacting on a general lack of customer’s understanding
about how lubrication affects the reliability and productivity of their equipment. According to
Shell estimations, at least $43 million TCO savings were achieved in 2011-2015 by mining
customers through lower maintenance costs, reduced equipment downtime and productivity
improvement [15].

It is well documented that PFPE greases outperform petroleum based and conventional
synthetic greases both at high and low temperatures as well as under high load. Several recent
examples of switching from less effective mineral-oil lithium thickened grease or from
synthetic hydrocarbon grease to a PFPE grease demonstrate extended re-lubrication intervals,
lower maintenance costs, spare parts costs and substantial decrease in unexpected bearing
failures.

It was shown, that operating costs savings can achieve more than 40% or $6 million for a pulp
and paper manufacturer with PFPE grease lubricated pulp dryer and electric motors over a six-
year lifetime period [16]. The higher initial cost for the PFPE grease is more than compensated
through the lower operation and maintenance expenses.

Another representative example: A metal plates manufacturer has successfully replaced a

mineral oil lithium thickened grease used in transport line bearings with a standard PTFE/PFPE
grease. The transport line contained 260 plain bearings operating at 250°C (measured) in
contact with hot (1500°C) metal plates. Switching to PFPE grease reduced the re-lubrication
frequency from 210 (every day) to 16 times p.a. and completely eliminated the bearing
failures. Maintenance costs, parts costs, and production downtime have been reduced
accordingly. Despite a large difference in the grease prices, TCO savings with a best-
performing PFPE grease are far beyond any savings related to the purchasing price of the
grease itself.

9
Getting the quantitative operation and maintenance data from the customers is not always
possible. In these cases, TCO calculation can be performed using a model approach based on
relative prices, consumption and re-lubricating intervals for PFPE and non-PFPE lubricants and
making an estimate for the contributions to the operation/maintenance costs.

6. Conclusions

Friction points for which PFPE greases are the best and most economical lubrication solution
exist in almost every industry.
Modern flexible approaches to formulation of PFPE greases allow offering optimal products
for traditional and new applications.
Bifunctional PFPE greases can successfully replace commonly used PTFE/PFPE greases in
applications with operating temperatures not exceeding 220°C (up to +250°C short-term).
Good compatibility with other PFPE greases and with some non-PFPE greases, improved rust
prevention, high mechanical and structural stability and a better cost/performance ratio make
them the products of choice for the operating temperature gap (150-220°C).
Long-life/fill-for-life lubrication with PFPE greases is an example for lower total cost of
ownership of the equipment compared to lubrication with less-performing mineral oil based
and other synthetic based lubricants due to extremely long re-lubrication intervals,
maintenance-free operation, increased energy efficiency and extending equipment life. It
indicates that the market volume of PFPE greases can be much higher than usually assumed.

7. Acknowledgements

We thank Jürgen Rigo, Tribology Center at the Mannheim University of Applied Sciences, for
performing FE8 tests and Setral Chemie GmbH for the permission to present this work.

8. List of References

1. Synthetics, Mineral Oil and Bio-Based Lubricants. Chemistry and Technology, Ed. L. R.
Rudnick, CRC Press, 2013.
2. Setral Chemie GmbH. Patent Application WO 2017/029287 A1.
3. Ausimont S.p.a. Patent EP 0657524 B1.
4. Klüber Lubrication München KG Patent US 6265362 B1.
5. NSK Ltd. Patent US 7196042 B2.
6. M. Egami, M. Asao, T. Goto: Hybrid Grease NA204F for automotive electrical
instruments and auxiliary device, NTN Technical Review No.73. 2005, P. 66-71.
7. NOK Klüber Co. Ltd. Patent EP 2341121 B1.
8. Solvay Specialty Polymers Italy S.P.A. Patent Application, WO 2016/020232 A1.
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 9. G.Boccaletti, S.Rovinetti, M.Avantaneo, E.Di Nicolo. PFPE-TFE copolymer: the new
frontier of fluorinated lubricants, NLGI Spokesman, 2013, 77(5).
10. J.Howell, S.Johnston, H.C.Walther, S.Bossler, T.Blunt, E.Siegfried. New High
Temperature Soluble Additives for Perfluoropolyethers. GfT-Meeting 2016.
Conference Paper, Göttingen, Germany.
11. V.Schott, A.Grechin, R.Kling, K.-H.Hensel. PFPE-Greases based on bifunctional
thickeners. OilDoc 2017, Conference Paper, Rosenheim, Germany.
12. D. M. Pirro, M. Webster, E. Daschner. Lubrication Fundamentals, Third Edition,
Revised and Expanded: CRC Press. 2016.
13. F. Held. Investition in die Wirtschaftlichkeit. Klüber Lubrication München KG.
Tribojournal 2/2008, P. 4-5.
14. The Cost Reduction Game. Shell Lubricants White Paper. 2016.
15. Unlocking Efficiency in Mining. Shell Lubricants. 2015.
16. T. Blunt, C. Walther. PFPE Lubrication Helps End Premature Bearing Failures. Machine
Design. July 2016, P. 50-55.

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