Transcript Trends in the global grease and base oil production: Heavy

Use of Super Heavy Naphthenics
in Lubricant Formulations
Luis Bastardo-Zambrano, PhD
Nynas Naphthenics AB
Nynashamn, Sweden
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Outline
 Introduction: Base Oil Market Overview
 Bright Stocks
 Super heavy naphthenic oil (Naphthenic 4000) and Polyisobutenes:
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•
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Film Strength
Thickening Effect
Tackiness
Shear Stability
Base Oil Market Overview
 Base stock supply is estimated at 931000 barrels/day more
than half Group I
 Global demand may increase by 6% by 2010 (34% of it in the
Asia/Pacific region)^
 Shift to higher quality oil worldwide (Group II and Group
III)
 Detriment of Group I production, especially bright stocks
Naphthenics
9%
Group III
5%
*
Group II
20%
Group I
66%
 Bright stocks output fell by 8% between 1995-2005. Group I
shut downs, will bring down bright stocks production by 10%
in the next 10 years.*
*Tocci, L. High stakes for base oils. Lubes´n´Greases. Vol.13 (1). 2007.
^ DeMarco, N. Total’s Take on Base Oil Balances. Lube Report. February 2007.
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Bright Stocks
 High viscosity base oils refined from paraffinic crude
 Mainly use is:





Marine oils
Monograde motor oils
Gear oils
Greases
Other products
 Possible substitutions:
 PIB (Polyisobutene)
 PAO (Polyalphaolefins)
 Heavy Naphthenics
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Super Heavy Naphthenic Oil
 The Super Heavy Naphthenic Oil used in this work (Naphthenic 4000) is a product with a very high viscosity (4800 cSt at 40°C) and excellent
solvent power (aniline point 80°C)
 Naphthenic 4000 can be used as additive in gear oils, metalworking fluids, greases and oil treatment as well as in blends with lower viscosity
naphthenic oils to obtain naphthenic bright stocks
 It displays interesting properties such as
 Very good shear stability
 High film strength
 High tackiness
 Very low carbon residue (<0.10%)
Characteristics Density @
15oC, kg/m3
Test method
D4052
ASTM
T 4000
0.968
Naphthenic 4000
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Viscosity @
40oC, mm2/s
D445
Viscosity @ Flash point Pour
Aniline
o
2
o
o
100 C, mm /s PM, C
point, C point, oC
D445
D93
D97
D611
VGC
CA %
D2501
D2140
4800
41
0.882
15
238
12
80
Tests on Naphthenic 4000
The super-heavy naphthenic oil Naphthenic 4000 was compared with several commercial PIBs
presenting different molecular weight
The following properties were tested




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Film strength
Thickening effect
Tackiness
Shear stability
Main Properties of the PIBs Tested
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Characteristics
Method
PIB A
PIB B
PIB C
PIB D
Number average molecular weight
GPC
1000
1050
1600
2300
Viscosity @ 40°C (cSt)
ASTM D 445
4650
7750
21000
48000
Viscosity @ 100°C (cSt)
ASTM D 445
190
230
725
1500
Density @ 20°C (g/cm3)
DIN 51757
0.890
0.890
0.900
0.900
Pour point (°C)
ASTM D 97
-9
-3
-4
0
Flash point (°C)
ASTM D 92
180
210
215
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
Film strength: Ability of a lubricant to withstand the effects of
load

Method used: ASTM D2783 (Four-Ball Test). Upper ball
under load and rotating (speed 1760 ± 40 rpm)

Film strength given by initial seizure

Materials tested: Naphthenic 4000, PIB A and PIB D
Initial Seizure Load (N)
Film Strength - Method
800
700
600
500
400
300
200
100
0
Naphthenic
4000
PIB A
Naphthenic 4000 Film Strength = 2 x PIB A Film Strength
Naphthenic 4000 Film Strength 50% higher than PIB B’s
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PIB B
Thickening Effect - Method
 Increasing amounts of Naphthenic 4000 and the PIB having the
same viscosity (PIB A) were added to the naphthenic oil Base oil
400
 Treating rates of 10, 20, 30, 40, 50, 60, 70, 80 and 90% were
used
 After each addition, the viscosity of the blend was measured by
ASTM D 445
 A viscosity curve was obtained for each thickener
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Thickening Effect – Results and Discussion (1)
5000
Viscosity at 40°C (cSt)
4500
TNaphthenic
4000
4000
PIB A
4000
3500
3000
2500
2000
1500
1000
500
0
0
10
20
30
40
50
60
70
80
Treatment rate of thickener (wt-%)
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90
100
Thickening Effect – Results and Discussion (2)
 The PIB A has a more marked thickening effect compared to the Naphthenic
4000
 The difference in viscosity becomes evident at additions above 30% treating
rates
 The difference is most pronounced at high treating rates (> 60%)
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Tackiness - Method
 Tackiness is defined as the resistance to flow in
extension and is a combination of cohesivity and
adhesivity
 The tackiness was measured in a filament break-up
rheometer
 The test fluid is placed between two cylindrical test
fixtures (rheometer plates) and is submitted to an
axial step-strain applied generating the formation of
an elongated liquid thread
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The Capillary Break-Up Extensional Rheometer: Filament Formation
Axial
strain
D
d0
D
df
D
Axial
strain
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D
Tackiness Tests – Experimental Conditions
 Naphthenic 4000 and four PIBs were added to the naphthenic oils Base oil 400 and Base oil 110
 Treating rates of 0.5 % and 1.5 % were used
 The time evolution of the filament diameter for the pure and additivated oils was followed
 The final gap between the rheometer plates was set to 8 mm for the tests performed on Base oil 400
and to 6 mm for the tests carried out on Base oil 110
 The final gap between the plates must be kept constant through a series of experiments as it is
directly correlated to the deformation to which the material is submitted during the test
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Tackiness Tests on Base Oil 110 with 1.5% Treating Rate
Normalized Diameter []
1
Base Oil 110
Base Oil 110+1.5% Naphthenic 4000
Base Oil 110+1.5%Polymer A
Base Oil 110+1.5%Polymer B
Base Oil 110+1.5%Polymer C
Base Oil 110+1.5%Polymer D
0.1
0.01
0
0.02
0.04
0.06
0.08
Time [s]
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0.1
0.12
0.14
Tackiness Tests – Results and Discussion
Naphthenic 4000 gave a tackiness increase equal to that given by the PIB B (having a viscosity at
40°C of 7750 cSt)
Increasing the treating rate has a positive effect both for Naphthenic 4000 and the PIB B. The effect
is more marked with Base oil 110.
As expected, the tackifying effect of the PIBs increases with increasing molecular weight.
Nevertheless, the higher the molecular weight of the PIBs, the higher the sensitivity to shearing
forces.
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Shear Stability Tests - Method
 Method used: CEC L 45-A-99 (Viscosity shear stability of
transmission lubricants – Tapered roller bearing rig)
 The viscosity of the fluid before and after the test was measured
using the method DIN 51562. The result: % of viscosity lost by
the fluid
Viscosity lost (%)
 The bearing is loaded axially with 5000 N, rotated at 1475
rev/min and maintained at a temperature of 60°C.
30
25
20
15
10
5
0
Naphthenic
4000
PIB B
PIB C
PIB D
The polymer molecules break when
submitted to high shear stresses
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Conclusions
 Worldwide production of base oils is shifting to higher quality products, Group II and III base oils
 These changes may cause shortage of Bright Stocks in the market
 Heavy naphthenic oils and PIBs are alternatives available right now
 The super heavy naphthenic oil Naphthenic 4000 outperforms PIBs in properties such as film strength
and shear stability
 Conversely, the thickening effect of PIBs is higher than that of the Naphthenic 4000
 The impact on tackiness of Naphthenic 4000 is comparable to that of the medium molecular weight
PIBs, while high molecular weight PIBs show a more marked tackifying effect
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