The Application and Use of Soltex
Products in Hydrocarbon Lubricants
and Lubrication Systems –
Lubricant Market Segments
1
Base-Stocks
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Base-stock constitutes about 90-95% of the
lube formulation
Non-Synthetic
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Long chain hydrocarbon products derived from
naturally occurring hydrocarbon mixtures, particularly
from various crude oil fractions, by refining techniques
such as distillation and solvent extraction
Synthetic
•
Long chain hydrocarbon products made by
polymerization or oligomerization of small molecules
(monomers). Do not occur naturally, “man made”.
2
Non-Synthetic
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American Petroleum Institute (API) classification based
on method of refining and purity;
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Group I
Group II
Group III
Relatively broad distribution of hydrocarbon compounds
with physical properties that reflect the average of the
distribution
Not a single compound, hundreds of compounds of every
carbon number
3
Non-Synthetic - API Group I
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Refined by distillation, freezing, filtration and
solvent extraction
To adjust viscosity (distillation)
Remove waxes (freezing, extraction, filtration)
Specifications;
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Greater than 0.03% sulfur
Viscosity Index (VI) 80 -119
Saturates < 90%
Being phased out
4
Non-Synthetic - API Group II
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Refined by distillation and hydrotreating
Hydrotreating is reaction with hydrogen
Removes waxes, non-saturates, sulfur,
improves VI
Specifications;
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< 0.03% sulfur
> 90% saturates
VI 80 – 119
Most common
5
Non-Synthetic - API Group III
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Refined by severe hydrotreating,
hydrocracking and hydroisomerization
Removes waxes and improves VI
Changes molecule??
Specifications;
• < 0.03% sulfur
• > 90% saturates
• VI > 120
6
Hydrocarbon Relationships
Group I, II, III Base Oils
7
What is Viscosity Index (VI)
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Viscosity is a fluid’s resistance to flow
Thick oils have a high viscosity, thinner oils have a lower
viscosity
Viscosity is a function of temperature; at higher
temperatures viscosity is lower; at lower temperatures
viscosity is higher
VI is the rate of change of viscosity with temperature
Low VI means a relatively large change of viscosity with
temperature and conversely high VI means relatively little
change with temperature
High natural VI is desirable
8
Synthetic- API Group IV
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Polyalphaolefins (PAO) by definition
PAO are made by the oligomerization of
an alpha-olefin such as decene-1(C10)
Increasing PAO grades, i.e.; 4, 6, 8 10
are increasing units of decene-1
Each unit of decene-1 increases the
chain length by 10 carbons
9
PAO Production Process
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The catalytic oligomerization of decene-1 to
produce PAO gives a certain distribution of
oligomeric units of decene but the distribution
is much narrower than the carbon number
distribution in Group I, II and even Group III
base-stocks
Further the oligomeric units can be separated
by distillation to give very narrow carbon
number fractions
The final products are hydrogenated to very
low residual unsaturation (bromine no.)
10
PAO Properties
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Since PAO are synthesized they are in effect almost
single chemical compounds
This unique structure allows PAO to have very low pour
(no wax) points, very high flash points (no lights) and
high VI compared to comparable viscosity grades of
Group I and Group II base-stocks
However, because of the narrow carbon distribution, PAO
have poor solubility for standard lube oil additives and
can adversely affect engine and equipment seals
PAO are often blended with other base-stocks,
particularly esters (i.e. Mobil 1, to improve additive
response and seal swell properties
Expensive, 3-5 times the cost of Group I, II base-stocks
11
PAO Chemical Structure
12
PAO Oligomer Distribution
C Number
PAO Grade
2
4
6
8
Dimer
20
98
0
0
0
Wt %
Trimer Tetramer
30
40
2
85
30
5
0
13
47
48
Pentamer+
50+
0
2
23
47
13
Synthetic - API Group III
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Said earlier that Group III are non-synthetic because that
occur naturally in nature.
However, it has been claimed that because the Group III
oils have been so severely hydrotreated and
hydrocracked, they no longer resemble their natural state,
they thus can be classified as synthetic.
This claim was upheld in court (Mobil v Castrol)
Because of lower cost of Group III this decision resulted
in loss of synthetic market share for PAO
14
Group III vs. PAO Performance
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The biggest drawback to Group III vs. PAO is
pour point.
However, maybe by addition of the right kind of
viscosity modifier (VM) and/or VI improvers this
problem can possibly be mitigated
Work in progress with Ciba R&D using new
Soltex line Of S-Flow VII and VM as additives
for Group III to replace PAO
Particularly applicable to 75W90 and 75W140
gear oils
15
Synthetic – API Group V
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All other potential base-stocks not in
Group I,II, III or IV
Doesn’t denote performance, can be
good or bad
Synthetic or non-synthetic
Includes esters, polyglycols (PAG),
alkylate, PIB, aromatic oils, napthenic
oils
16
Polybutene (PB) - Conventional
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Made from raffinate streams that contain mixed
butylenes but isobutylene is more reactive and
therefore incorporated at about 85-90% in the
polymer chain
One olefin group per chain but not on the end
Low reactivity
Used mainly in industrial applications
Molecular weights from 300 daltons (Soltex
PB4) - 4,000 daltons (Soltex PB28)
17
Polyisobutylene – High Reactive
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HR PIB is made from high purity isobutylene
streams
Polymer chain contains only isobutylene
groups
One olefin group per molecule, located either
alpha or beta to the end of the polymer chain
High reactivity
Manufacture of fuel and lubricant additives or
other derivatives where chemical reactivity is
important.
18
Terminal Olefin Isomer Groups in
Polybutene and Polyisobutylene
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Industry confusion over terminology and
structure
• E-PIB, HR-PIB, Conventional PIB
19
PB Physical Properties
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For applications not involving reactivity PIB and PB can
be used interchangeably
PIB has a highly branched molecular structure
High viscosity for a given molecular weight, good
thickening power
Economical viscosity modifier
Very clean burning, no smoke, no residue, no metal
staining
Shear stable comparable to conventional base oils and
PAO but superior to other polymers
High VI, especially for the higher grades
20
PB Applications in Lubes
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Two –cycle engine oils
• Clean burning
• Low smoke, meet JASO FD specifications
• No engine deposits
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Gear Oils and hydraulic Oils
• Shear stability
• Thickening efficiency
21
PB Applications in Lubes
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Metalworking fluids
• De-polymerize at high temperatures
• Clean surface
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Compressor oils
• Oxidation resistance
• Low deposit formation
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Engine oils
• HR-PIB maleic derivatives
22
PIB Disadvantages
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High inherent pour point. Doesn’t
respond to VI or PPD additives
Low VI at low molecular weight in the
range of lube base-stock
Low flash point at low molecular weight
in the range of lube base-stock
Moderate cost
23
Components
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Problem
Chemical Class/Compound
Function
Soltex Products
24
Antifoams
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Foam reduces efficiency of the lube oil and can
result in lube oil loses
Silicone polymers and organic siloxane
copolymers. Also PAG, mineral oils
Reduces bubble surface tension to prevent
(antifoam), reduce or eliminate foam
(defoamer). Used at low ppm levels.
Low molecular weight PB, i.e. PB 4, 8
25
Antioxidants
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Oxidation of lube oil increases acidity causing
chemical breakdown of the oil and reduces life
of the oil. Depletes add pack.
Aromatic amines, hindered phenolic
compounds. In conjunction are synergistic
Oxidation is a free radical mechanism.
Antioxidant scavenges free radicals. Geometric
progression
Soltex FS 310 (aromatic amine), Ciba hindered
phenolics.
26
Anti-Wear and EP Additives
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High loads can cause breakdown of the oil layer between
moving metal surfaces causing an increase in wear.
These loads are found to some extent in crankcase but
largely in gears
Compounds that contain the elements of P, S, Zn,
sometimes Mo.
React with the metal surface to form new harder metallic
compound on the metal surface. High load bearing
capability. Some initial wear to activate.
Zinc dialkyldithiophosphate. Zn, P, S in one molecule.
Sulfurized olefins. Contained in Soltex PCMO, DEO and
THF additive packages (PCA products)
27
Zinc Dialkyldithiophosphate
28
Detergents
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Oxidation can cause breakdown of lube oil and build up of
sludge and varnish on engine or machine parts
Ca and Mg sulfonates, phenates, salicylates
The organic metallic salts have non-polar hydrocarbon tail
and polar head group. The polar head group has affinity
for dirt particles and the non polar tail helps disperse the
attracted dirt particle in the lube oil matrix so it can be
removed by filtration
Soltex NeutralCal 10, PCA 400.
(Note: Neutral sulfonates are better detergents compared
to over-based, more active ingredient per molecule.)
29
Dispersants
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Oxidation of oil can cause sludge and varnish formation
PIB succinimides, succinic anhydrides, succinic esters.
Detergents and dispersants are sometimes the same
compound and/or can do both functions
Dispersants help disperse dirt, sludge and varnish
particles in the lube oil matrix so they can be removed by
filtration. Work in conjunction with detergent.
Soltex PCA 9050 (PIBSA), PCA 9070 (PIBSI-950), PCA
9070 (PIBSI-2300)
These are ashless dispersants and can be used alone as
ashless detergent/dispersant
30
Emulsifiers
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Many metalworking fluids, particularly
cutting fluids are oil-in-water emulsions.
The oil, containing wear and anticorrosion additives, provide lube
function, water removes heat
PIB succinic anhydrides
Emulsify oil in water.
Soltex PCA 9050 (PIBSA-950)
31
Friction Modifiers (Boundary
Lubricants)
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Break down of oil film at moderate loads can
result in metal to metal contact between
moving parts and increase wear
Organic fatty acids, esters and amides
Polar head group attaches to metal surface,
long hydrocarbon tail provides lubricity
Tall oil fatty acid, Soltex PCA 9050 (non-acidic)
Ashless
32
Performance Boosters
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Oxidation of oil can cause build up of
acidic products. Also use of high sulfur
fuels can increase acidity of lube oil.
Results in increased corrosion and wear.
Over-based Ca, Mg salts of sulfonic
acids
High alkalinity (TBN) neutralizes acid
Soltex PCA 400
33
Pour Point Depressants (PPD)
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Group I, II, III base-stocks contain wax impurities. At low
temperatures wax crystals form and separate from the oil
causing the oil to thicken and eventually not be able to flow.
This is called “the pour point”, but is approached gradually.
Polymethylmethacrylates (PMMA) most effective
PMMA interferes with the wax crystal growth and prevents
crystallization and wax separation.
(Note: base-stocks that do not contain wax and have inherent
pour points, i.e. PIB,PAO, do no respond to PPD.
Soltex S-Flow PMMA products; S-Flow P750, P711, P811,
P821
S-Flow P821 is most general purpose. Also refer to TDS and
Ciba presentation
Mixtures of S-Flow and Group III to compete with PAO
34
Viscosity Modifiers (VM)
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Base oils alone have relatively low viscosity and require
thickeners to achieve specifications esp. for gear oils
PMMA, PIB, olefin copolymers (OCP)
Increase viscosity of the base oil and improve VI, also know as
VI improvers.
PMMA are most effective, PIB is most shear stable, OCP are
most economical.
Soltex S-Flow V1201(PMMA); BSR 900, PB 124, 128 (PIB)
Soltex OCP 25, 35, 50 liquids. Concentration is about 9-10% in
Group II base oil. Number refers to Shear Stability Index (SSI).
The lower SSI products are more shear stable, but are lower
molecular weight and require higher use levels. API approved
Soltex OCP 2400, 2500 solids. SSI 45. OCP 2500 is API
approved.
35
Tackifiers
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Gear oils and greases require components that allow the
lubricant to better adhere to the metal surface.
High molecular weight PIB, 50,000 to 4,000,000 daltons.
Dissolved in Group II oil. FDA approved products are
dissolved in white mineral oil or PAO. Concentration in
range of 5 – 10%.
Provides tackiness
Soltac 922 (general purpose), Soltac 222 (for grease,
NSF approved), Soltac 428 (for gear, NSF approved)
Undiluted PB 124, 128 also used.
36
Other Components
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Demulsifiers – aids in removing water from hydrocarbon
fuels and lubricants
Metal deactivators – Inhibits corrosion effects of oxygen
and decrease metal interaction with oxygen compounds
Surfactants – Provides enhanced friction reduction and
allows oil to spread over metal surfaces
Seal swell agents – Increases volume of elastomeric
seals to counteract seal shrinkage characteristics of some
synthetic oils and base-stocks
Soot control – Keeps soot in suspension in diesel oils.
Soot comes from contamination from the combustion
chamber and incomplete diesel fuel combustion
37
Surface Active Agents (Surfactants)
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Boundary lubricants, EP additives, detergents, dispersants work by
similar mechanism; polar head group reacts with the metal surface (or
dirt particle), non-polar tail extends into the lubricant matrix
38
Additive Packages
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Components are combined into
complete packages that provide the
formulator with all requirements for
finished lube
Two-cycle engine oil (2-T)
Passenger car motor oil (PCMO)
Diesel engine oil (DEO)
Tractor hydraulic fluid (THF)
39
Two-Cycle Engine Oil
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JASO requirements
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Low Ash
Power sports including motorcycles, snowmobiles, air
cooled engines
Higher value market
ISO requirements
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Corresponds to JASO
NMMA requirements
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Marine, water cooled engines
Ashless
Lower value market
40
JASO Performance Classification
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The performance level of two cycle oils is classified into
three categories, FB,FC, FD from lowest to highest
performance
Tests measure lubricity, initial torque, detergency,
exhaust smoke, exhaust system blocking
FC is low smoke two cycle oils superior to FB in terms of
exhaust smoke and exhaust blocking
FD is improved version of FC in terms of detergency
performance at high temperatures
Must also meet physio-chemical property requirements
for viscosity, flash point, sulfated ash
41
Performance Equivalents
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JASO FB, FC, FD corresponds to ISO-L-EGB,
ISO-L-EGC, ISO-LEGD
JASO is Japanese Standards Organization.
Developed JASO standards originally for
improved motorcycle oils
ISO is International Organization for
Standards. Classification system developed to
correspond to JASO testing.
Testing can be done at SwRI, Lube Tech (?)
42
NMMA Requirements
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Current performance classification is TCW3
Testing includes bench tests for fluidity,
lubricity, viscosity
Engine testing for ring sticking and carbon
build up on pistons
Engine tests include one BRP 40 hp, one
Johnson 70 hp, and two consecutive Mercury
15 hp tests and two lubricity tests.
Performance based qualifications program.
Conducted by sanctioned lab, expensive.
43
PCA 9055
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Ashless additive package for formulated for
low smoke two cycle motor oils
Meets or exceeds NMMA TCW3 performance
requirements
Meets or exceeds JASO FD and ISO-L-EGD
performance requirements
Treat rate of 15 – 20 % in Group II base oil.
Use with PB 24 in place of brightstock to
assure low smoke performance
44
Typical Low Smoke Two-Cycle
Formulation
Component
Group II 300
PB 18
Kerosene
PCA 9055
S-Flow P8122
Wt%
37.9
30.0
13.3
17.8
1.0
Property
KV @ 40 deg C
Viscosity Index
Pour Point
Value
35.0 – 40 cSt
> 140
< -40 deg C
45
Passenger Car Motor Oil
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Performance criteria by established by
American Petroleum Institute (API)
S designation is for “spark ignited engines,
such as gasoline or propane fueled engines
Alphabetical designation supersedes previous
letter, i.e. SJ, Sl, SM
Testing is done according to series of API
Sequence Tests
SwRI, Lubrizol, Afton certified test facilities
Very expensive
46
PCMO API Service Categories
Obsolete
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SA, older engines
SB, older engines
SC, model year 1967 and older
SD, model year 1971and older
SE, model year 1979 and older
SF, model year 1988 and older
SG, model year 1993 and older
SH, model year 1996 and older
47
PCMO API Service Categories
Current
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SJ, for 2001 and older engines
SL, for 2004 and older engines
SM, for all cars currently in use. Introduced in
November 2004. Improved oxidation
resistance, improved deposit protection, better
wear protection and better low temperature
performance over the life of the oil
Reference; api.org/eolcs
48
Diesel Engine Oil
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Performance criteria by established by
American Petroleum Institute (API)
C designation is for compression ignited
engines such as diesel engines
The latest category usually, but not always,
include properties of earlier category
Testing is done according to series of API
Sequence Tests specific to service class
SwRI, Lubrizol, Afton certified test facilities
Very expensive
49
DEO API Service Classifications
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CA, CB, CC, CD, CD-II, CE, are obsolete
CF, introduced in 1994 for off road indirect
injected diesel engines using fuel with greater
than 0.5% S. Can be used in place of CD oils
CF-2, introduced in 1994 for severe duty two
stroke diesel engines. Can be used in place of
CD-II oils
CF-4, introduced in 1990. For high speed four
stroke natural aspirated and turbocharged
diesel engines. Can replace CD and CE oils
50
DEO API Service Classifications
Continued
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CG-4, introduced in 1995, for high speed four stroke
diesel engines using fuel with less than 0.05 % S. Can
replace CD, CE, CF-4 and CG-4 oils
CH-4, introduced in 1998, for high speed four stroke
diesel engines designed to meet 1998 emissions
standards. Can use in place of CD, CE, CF-4 and CG-4
CI-4, introduced in September 2002, for high speed four
stroke diesel engines designed to meet 2004 exhaust
standards using fuels with sulfur up to 0.5 % Formulated
for durability where engine gas recirculation (EGR) is
used. Can be used in place of CD, CE, CF,-4, CG-4 and
CH-4 oils
51
Soltex PCA 2877
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Multifunctional lube oil additive package used to formulate
high quality mono-grade and multi-grade gasoline and
diesel engine oils with properties similar to a wide range
of API classifications.
Contains detergents, dispersants, antioxidants, friction
modifiers, rust and oxidation inhibitors
Non-detergent VI improvers required to meet multi-grade
viscosity classifications
Performance boosters required to meet high TBN (>10)
specifications
52
Soltex PCA 2877 Treat Rates
in Group I, II Base Oils
Wt %
Perf. Equiv.
PCA 2877
SM
4.20
SL
4.81
CH-4/SJ/SH
5.88
SJ/SH
4.80
SG/SD/CF-4
6.20
SG/SF/SE/CD
4.00
SE/CC
3.21
SD/CC
3.10
SC/CC
2.29
SB/SC/CB
2.19
PCA 400
0.40
PCA 9070
1.50
0.82
53
Soltex PCA 2886
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Multifunctional lube oil additive package used
to formulate high quality mono-grade and
multi-grade gasoline and diesel engine oils
with properties similar to a wide range of API
classifications.
Less active than PCA 2877, contains Mo
Contains detergents, dispersants, antioxidants,
friction modifiers, rust and oxidation inhibitors
Non-detergent VI improvers required to meet
multigrade viscosity classifications
54
Soltex PCA 2886 Treat Rates
in Group I, II Base Oils
Perf. Equiv.
SM
SL
SJ
SH
SG
Wt %
10.0
9.5
9.3
9.1
9.0
55
Soltex PCA 2861
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High performance diesel engine oil additive package for
high speed turbocharged engines operating on fuel
containing up to 0.5% S
Contains ashless dispersant, ZDDP, metallic detergents.
Meets are exceeds the requirements of API, ACEA, and
major engine manufacturers including, Cummins, Global
DHD-1, Mack and Volvo
Non-detergent VM with SSI of 20 – 40 recommended for
multigrade oils
56
Soltex PCA 2861 Treat Rates
Perf. Equiv.
CI-4,CH-4,CG-4
CF-4,CF/SL, SJ
SAE
15W40
Base Oil
Group I, II
Wt%
12.0
CI-4,CH-4,CG-4
CF-4,CF/SL, SJ
10W30
Group II
12.0
CG-4, CF-4, CF-2
CF, Sl, SJ
30/40/50 Group I, II
8.4
CF,-4, CF, Sl, SJ
10W/20W Group I, II
8.4
CF Only
5.8
57
Soltex PCA 5715
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Economy grade tractor hydraulic fluid
Safely used in most sump-type agricultural
equipment including John Deere, Case and
New Holland, Massey Ferguson and Ford
Provides gear wear protection, maintains
hydraulic system performance and prevents
oxidation to prolong fluid life.
Treat rate is 4.0 wt% in Group I,II base oil.
58