See discussions, stats, and author profiles for this publication at: https://www.researchgate.
net/publication/297470678
The Future of Aluminium Complex Greases
Conference Paper · February 2016
CITATIONS READS
0 2,599
3 authors, including:
György Pölczmann
MOL-Lub Plc.
98 PUBLICATIONS 164 CITATIONS
SEE PROFILE
All content following this page was uploaded by György Pölczmann on 08 March 2016.
The user has requested enhancement of the downloaded file.
The Future of Aluminium Complex Greases
Peter Baladincza, György Pölczmannb, József Tótha
a
MOL-LUB Ltd., Fő str. 21, Almásfüzitő, H-2931, Hungary
b
University of Pannonia, Egyetem str. 10, Veszprém, H-8200, Hungary
Introduction
The grease thickener components not only transform the liquid lubricant into consistent
lubricant, but also alter their properties. The gelling component of greases are mostly soaps
(fatty acid salt - normal or complex), but they can be different chemical structure materials
too (organic and ionic-non ionic polyureas, organoclay, well-dispersed silica acid, etc.) [1].
Aluminium complex greases began to appear in the mid-1960s, and a number of patents
were issued over the next several years covering various modifications. Most of the efforts
were in the areas of improved water resistance, and thermal and mechanical stability. Out of
the aluminium complex greases one type is currently dominant in the world, which contains
aluminium stearate and benzoate (Figure 1). The importance of the aluminium complex
greases shows a trend to decline in the past decades. However, there were attempts for better
understanding of the soap formation and to broaden the application areas.
Figure 1
Aluminium stearate and –benzoate complex
Main properties of the aluminium complex greases include high dropping point and thus high
maximal application temperature; excellent water resistance with a slight hardening of
consistency in the presence of water; good working, mechanical and shear stability; very good
oxidation stability; excellent pumpability and thus easy handling and applicability in central
lubrication systems and bulk storage; wide operating temperature range; chemical resistance;
good compatibility with a wide range of other greases. Its reversibility or ability to retain
consistency after repeated heating and cooling, is unique as well [2][3].
Moreover, high quality aluminium complex greases can be formulated relatively easily on
different types of base oils, which is being a current development focus.
These properties enable their application in steel mill applications. In addition, their
non-toxicity also enables their applicability in the food industry (NSF category H1 grease may
be produced), as well as in the formulation of biodegradable, environmentally sound
-1-
lubricating greases or any other highly specialized areas which require the use of lubrication
by greases [4].
There are different methods to produce aluminium complex greases. In case of 2 step
process method is known (Figure2). This is a more complex and long process which may be
difficult to handle/manage. In the first step, an aluminium containing compound which is a
reaction product of aluminium and isopropyl alcohol is reacted with fatty acid thus aluminium
and long carbon chain containing material is formed. In this step, the alcohol component of
the feedstock is released, so ventilation of the system is essential. In the second step, the
reaction product of the first step is reacted with benzoic acid to make the aluminium complex
grease.
Figure2
Aluminium complex grease production via 2 step method
In case of the 1 step aluminium complex grease production procedure, the thickener agent
feedstock is easy to handle (only slight pre-warming may be necessary), and it is a relatively
short and easy to handle process as well (Figure 3) [5]. In the process the aluminium thickener
is reacted with benzoic acid and aluminium complex soap is formed. Because there is only a
trace or no amount of alcohol is in the precursor, there is no need for ventilation of the
system, which can also mean cost reduction.
Figure 3
Aluminium complex grease production via 1 step method
-2-
Because of the increasing need for better performance, there is a growing need for high
performance, specially designed and formulated lubricants based on special base fluids. This
is already changing the lubrication market and thus the lubrication industry itself. If the
lubricant manufacturers would like to keep up with the trends, they have to find and offer
solutions for these needs for the benefit of their customers. However it lags behind a bit when
it is about change, this tendency also applies for the grease industry, too.
Experimental
Objectives
Our main objective is the continuous development and to meet the challenges of the future.
Therefore we continuously explore the possibilities of lubricating greases and grease
thickener formulation for special needs and applications, based on paraffinic base oils and
based on biodegradable base oils. We are experimenting continuously to find the optimal
maximum yield vs. maximum performance combinations in the formulation of aluminium
complex lubricating greases. On the course of this, we investigated the possibilities of the
formulation of excellent performance aluminium complex greases on different oil bases, from
Group I. to Group V. and vegetable oils as well.
Feedstocks
During the experiments, we used different types of base oils, such as mineral oils with
different characteristic (naphthenic, Group I. to Group III.), different synthetic bases (ester,
polyalphaolefin, polyisobuthylene) and organic oil (rapeseed oil), too.
As thickener component we used aluminium containing thickener agent which contained
approximately 50w/w% aluminium stearate thickener dissolved in Group I. base oil. To make
the aluminium complex structure, technical grade benzoic acid was used.
Sample production
The samples were produced in a laboratory scale open grease kettle. The whole quantity of
base oil mixture was poured into the kettle. After that stirring and heating has been started. At
about 60°C, powdered benzoic acid and in some cases excess fatty component was added.
After the acids were dissolved, the pre warmed thickener component had been added at 70–
80°C. After this the mixture has been heated to 150°C at first, for saponification. Then the
temperature has been increased to the maximum of about 200–220°C, mainly depending on
the type of base oil used. After reaching the maximum temperature, the grease has been
-3-
cooled immediately. After cooling, finishing operations, such as milling and deaeration had
been done.
Analytical methods
The analytic methods used for determining the properties of the grease samples were
standardized (ISO, DIN, ASTM) methods commonly used in the grease industry.
Results and discussion
Formulation on different base oils
In the first stage of our experiments the effect of changing the base oil types were
investigated. During this our goal was to formulate greases with NLGI grade 2 consistency
greases on different types of base fluids.
It can be seen on Figure 4, that for the formulation of NLGI grade 2 grease in case of
different base oils, different amount of soap (thickener and benzoic acid) were needed.
405 Naphthenic BO 405
Group II. BO
385 Group I. BO (X) 385 Group III. BO
Group I. BO (Y) Group IV. BO (PAO)
365 365
Group V. BO (PIB)
Worked penetration, 0.1 mm
Worked penetration, 0.1 mm
345 345
325 325
305 305
285 285
NLGI 2 NLGI 2
265 265
245 245
225 225
205 205
6 7 8 9 10 11 12 13 14 8 9 10 11 12 13 14 15 16
Amount of thickener in the formula, m/m % Amount of thickener in the formulation, m/m %
a, b,
405
Group V. BO (SynE)
385 Vegetable oil (RO)
X – SN base oil with medium viscosity, high paraffin content, low
365 naphthenic aromatic content
Worked penetration, 0.1 mm
345
Y – SN base oil with higher viscosity, higher naphthenic and
325 aromatic content;
305
PAO – Polyalphaolefin;
285 NLGI 2
PIB – Polyisobuthylene;
265
245 SynE – Synthetic ester;
225 RO – Rapeseed oil
205
16 17 18 19 20 21 22 23 24 25 26
Amount of thickener in the formulation, m/m %
c,
Figure 4
Worked penetration of the grease samples formulated on different types of base fluids
as a function of the necessary amount of thickener agent
Thickener component has approx. 50w/w% active material content
-4-
Table 2
Formulation of NLGI 2 lubricating grease on Group I. and Naphthenic base oils
Sample name 1 2 3
Type of base oil Naphthenic Group I. (X) Group I. (Y)
Molar ratio (Al stearate:BA) 1:1 1:1 1:1
Type of thickener mineral oil based mineral oil based mineral oil based
Amount of thickener, % 8 10 10
Visual yellow-brown yellow-brown yellow
Penetration at 25°C, 0.1 mm ISO 2137 277 269 266
Worked penetration at 25°C, 0.1 mm ISO 2137 282 283 274
Penetration change after 10,000 double strokes, 0.1 mm ISO 2137 44 49 36
Penetration change after 100,000 double strokes, 0.1 mm ISO 2137 66 68 71
Water wash out, % ASTM D 1264 0.5 2 0.7
Flow pressure at -30°C, mbar DIN 51805 1463 over 2100 over 2100
Oil separation at 100°C over 24h, % IP 121 6.8 6.9 3.2
Thickener component has approx. 50w/w% active material content
X – SN base oil with medium viscosity, high paraffin content, low naphthenic aromatic content; Y – SN base oil with higher viscosity,
higher naphthenic and aromatic content; BA – Benzoic acid
In case of applying naphthenic base oil only 8% of thickener component was enough to
reach NLGI 2 grade. In case of Group I base oils 10% was needed. But when applying highly
paraffinic (or similar structure) Group II-V. base oils to reach the required grade 13-14% of
thickener had to be applied. Furthermore working with synthetic ester and vegetable oil, the
thickener component had to be applied above 20%.
Table 3
Formulation of NLGI 2 lubricating grease on Group II.-IV. base oils
Sample name 4 5 6
Type of base oil Group II. Group III. Group IV. (PAO)
Molar ratio (Al stearate:BA) 1:1 1:1 1:1
Type of thickener mineral oil based mineral oil based mineral oil based
Amount of thickener, % 14 12 14
Visual yellow yellow light yellow
Penetration at 25°C, 0.1 mm ISO 2137 258 272 245
Worked penetration at 25°C, 0.1 mm ISO 2137 269 298 280
Penetration change after 10,000 double strokes, 0.1 mm ISO 2137 41 60 55
Penetration change after 100,000 double strokes, 0.1 mm ISO 2137 77 82 71
ASTM D
Water wash out, % 0.9 1.5 1.9
1264
Flow pressure at -30°C, mbar DIN 51805 2043 over 2100 872
Oil separation at 100°C over 24h, % IP 121 0.9 4.8 2.8
Thickener component has approx. 50w/w% active material content
PAO – Polyalphaolefin; BA – Benzoic acid
These results are shown in Table 2-4 also, with alongside further properties which had
been measured.
The results shown in Figure 4-5, and also in Table 2-4 show that by increasing the soap
content, the desired consistency grade with acceptable properties can be made. However in
-5-
case some of the utilized base fluids, this increase of the soap components is not too
economical because of the relatively high price of the components.
Table 4
Formulation of NLGI 2 lubricating grease on Group V. and vegetable oil
Sample name 7 8 9
Type of base oil Group V. (SynE) Group V. (PIB) Rapeseed oil
Molar ratio (Al stearate:BA) 1:1 1:1 1:1
Type of thickener mineral oil based mineral oil based mineral oil based
Amount of thickener, % 14 22 20
Visual yellow-brown light yellow yellow-brown
Penetration at 25°C, 0.1 mm ISO 2137 252 268 245
Worked penetration at 25°C, 0.1 mm ISO 2137 291 281 297
Penetration change after 10,000 double strokes, 0.1 mm ISO 2137 -38 61 -43
Penetration change after 100,000 double strokes, 0.1 mm ISO 2137 -25 73 -36
Water wash out, % ASTM D 1264 0.5 2.1 0
Flow pressure at -30°C, mbar DIN 51805 1055 over 2100 over 2100
Oil separation at 100°C/24h, % IP 121 1.2 1.4 0.9
Thickener agent has approx. 50w/w% active material content
PIB – Polyisobuthylene; SynE – Synthetic ester; BA – Benzoic acid
400
Penetration Worked penetration
Penetration change after 10,000 strokes Penetration change after 100,000 strokes
350
300
Penetration, 0.1 mm
250
200
150
100
50
-50
Figure 5
Penetration and mechanical stability
Thickener agent has approx. 50w/w% active material content; X – SN base oil with medium viscosity, high paraffin content, low naphthenic
aromatic content; Y – SN base oil with higher viscosity, higher naphthenic and aromatic content; PAO – Polyalphaolefin; PIB –
Polyisobuthylene; SynE – Synthetic ester
Changing the molar ratio
In the second stage of our experiments the effect of changing the molar ratio of the
feedstocks were investigated. Because of the special structure (one cyclic and one paraffin
-6-
component) of the aluminium complex grease, it can be tailored for different base oils
relatively easily.
Table5
Modification of the molar ratio of the soap components
Sample name
6A 6B
Type of base oil
PAO PAO
Molar ratio (SA:Al:BA)
1:1:1 1.2:1:0.8
Type of thickener
mineral oil based mineral oil based
Amount of thickener, %
14 10
Amount of excess stearic acid, %
- ~1
Visual yellow yellow
Penetration at 25°C, 0.1 mm ISO 2137 245 266
Worked penetration at 25°C, 0.1 mm ISO 2137 280 289
Penetration change after 10,000 double strokes, 0.1 mm ISO 2137 55 66
Penetration change after 100,000 double strokes, 0.1 mm ISO 2137 92 105
Water wash out, % ASTM D 1264 1.9 1.6
Flow pressure at -30°C, mbar DIN 51805 2.8 8.8
Oil separation at 100°C over 24h, % IP 121 872 787
Thickener agent has approx. 50w/w% active material content
PAO – Polyalphaolefin; SA – Stearic acid; Al - Aluminium, BA – Benzoic acid
Based on this idea the molar ratio of the cyclic component (benzoic acid) and the paraffin
component (carbon chain of the stearic acid) has been changed to produce a more paraffin
heavy grease structure. Based on the results (Table 5) it was determined that with the
modification of the molar ratio with lower amount of thickener similar grease can be
produced. This means that the thickener can be tailored well to the applied base oil, and not
only with the use of excessive amount of thickener, but only with a small amount of excessive
fatty acid, which is much cheaper. Thus this formulation method can mean economical benefit
and can lead to extra profit.
Utilization of different fatty acids
As it was presented above, with the use of a small amount of excessive fatty acid, the
desired consistency grade grease can be produced with such good performance as with
increasing the soap content. In the third stage of our experiments the effect of the use of
different fatty acids were investigated.
The results are shown in Table 6-8 and Figure 6. It was investigated that if the different
chemical formulas (ligand, unsaturation etc.) and the excess of the fatty acids had effect to
grease properties. In these experiments we applied different amounts of excess fatty acids,
namely distilled stearic acid (mixture of highly saturated C16 and mainly C18 carbon chains),
12 hydroxystearic acid (widely used in grease production) and oleic acid (unsaturated C18
chains).
-7-
Table 6
Formulation with excess stearic acid
Sample name 6A 6C 6D
Type of base oil PAO PAO PAO
Type of thickener mineral oil based mineral oil based mineral oil based
Amount of thickener, % 14 12 10
Amount of excess fatty acid, % - 0.7 1.4
Type of excess fatty acid - DSA DSA
Visual yellow yellow yellow
Penetration at 25°C, 0.1 mm ISO 2137 245 248 270
Worked penetration at 25°C, 0.1 mm ISO 2137 280 287 293
Penetration change after 10,000 double strokes, 0.1 mm ISO 2137 55 33 39
Penetration change after 100,000 double strokes, 0.1 mm ISO 2137 92 87 110
Water wash out, % ASTM D
1.9 0.5 1.1
1264
Flow pressure at -30°C, mbar DIN 51805 2.8 4.8 5.6
Oil separation at 100°C over 24h, % IP 121 872 894 950
Thickener component has approx. 50w/w% active material content
PAO – Polyalphaolefin; DSA – Distilled stearic acid
Table 7
Formulation with excess 12 hydroxystearic acid
Sample name 6A 6E 6F
Type of base oil PAO PAO PAO
Type of thickener mineral oil based mineral oil based mineral oil based
Amount of thickener, % 14 12 10
Amount of excess fatty acid, % - 0.7 1.4
Type of excess fatty acid - 12HSA 12HSA
Visual yellow yellow yellow
Penetration at 25°C, 0.1 mm ISO 2137 245 257 295
Worked penetration at 25°C, 0.1 mm ISO 2137 280 278 330
Penetration change after 10,000 double strokes, 0.1 mm ISO 2137 55 57 61
Penetration change after 100,000 double strokes, 0.1 mm ISO 2137 92 154 138
Water wash out, % ASTM D
1.9 0.8 2.1
1264
Flow pressure at -30°C, mbar DIN 51805 2.8 5.6 3.4
Oil separation at 100°C over 24h, % IP 121 872 878 935
Thickener component has approx. 50w/w% active material content
PAO – Polyalphaolefin; 12HSA – 12 hydroxystearic acid
It was concluded that applying the thickener component in 10-12% with applying different
types of excess fatty acids, proper NLGI 2 grade greases could be produced with relatively
same, very good performance levels. This means that the performance of the grease is not
necessarily depends on the price or availability of the utilized fatty component.
-8-
Table 8
Formulation with excess oleic acid
Sample name 6A 6G 6H
Type of base oil PAO PAO PAO
Type of thickener mineral oil based mineral oil based mineral oil based
Amount of thickener, % 14 12 10
Amount of excess fatty acid, % - 0.7 1.4
Type of excess fatty acid - OA OA
Visual yellow yellow yellow
Penetration at 25°C, 0.1 mm ISO 2137 245 255 244
Worked penetration at 25°C, 0.1 mm ISO 2137 280 278 264
Penetration change after 10,000 double strokes, 0.1 mm ISO 2137 55 70 51
Penetration change after 100,000 double strokes, 0.1 mm ISO 2137 92 116 101
ASTM D
Water wash out, % 1.9 0.9 1.3
1264
Flow pressure at -30°C, mbar DIN 51805 2.8 2.5 2.7
Oil separation at 100°C over 24h, % IP 121 872 995 934
Thickener component has approx. 50w/w% active material content
PAO – Polyalphaolefin; OA – oleic acid
400 Penetration Worked penetration
Change in penetration after 10,000 strokes Change in penetration after 100,000 strokes
350
300
250
Penetration, 0.1 mm
200
150
100
50
0
14% Thickener 12% Thickener, 10% Thickener, 12% Thickener, 10% Thickener, 10% Thickener, 12% Thickener,
0.7% DSA 1.4% DSA 0.7% 12HSA 1.4% 12HSA 1.4% OA 0.7% OA
Figure 6
Penetration and mechanical stability of grease as a function of
the applied amount of thickener and excess fatty component
Thickener component has approx. 50w/w% active material content; DSA – Distilled stearic acid;
12HSA – 12 hydroxystearic acid; OA – oleic acid
Conclusions
It can be concluded that the aluminium complex lubricating grease have a bright future in
special areas, where there is a need for high dropping point, high water resistance, wide
operating temperature range and chemical resistance. Such areas are steel industry, food
industry, any application which requires lubrication and a chemically active environment.
During our experimental work, we determined that aluminium complex greases are easily
made in a one step process with the utilization of aluminium stearate containing thickener
-9-
compositions and moreover it is relatively easy to formulate lubricating greases, even
specialities on different base oil types with excellent properties.
References
[1] Qvist, S.: „Greases”, Tekniskafdeling, 2013. February 28.
[2] S. K. Sharma, P. Vasudevan, U. S. Tewari: „High temperature lubricants – oils and greases”, Tribology
International, Volume 16, Issue 4, 1983, 213-219
[3] A. T. Polishuk: „Physical and chemical properties of complex soap greases”, Lubr. Eng., 1963, 19, 76-
87
[4] Lubricants and Lubrication. 2nd Ed. Edited by Th. Mang and W. Dresel, 2007, WILEY-VCH Verlag
GmbH & Co. KGaA, Weinheim, ISBN: 978-3-527-31497-3, pp. 894.
[5] MOL-LUB: “KOMAD 8400, a lubricating grease thickener”
-10-
View publication stats
