© INFINEUM INTERNATIONAL LIMITED 2015. All rights reserved. INFINEUM CONFIDENTIAL INFORMATION VISCOSITY AND VISCOSITY MODIFIERS
© INFINEUM INTERNATIONAL LIMITED 2015. All rights reserved.
INFINEUM CONFIDENTIAL INFORMATION
VISCOSITY AND VISCOSITY MODIFIERS
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OUTLINE
• Viscosity – Definition & Terminology
– Temperature Dependence
• Viscosity Modifiers – Function
– Thickening Efficiency
– Shear-Thinning
– Types/Chemistry
• Pour Point Depressants
• SAE Viscosity Grades
• Appendix – Viscosity measurement methods
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VISCOSITY
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VISCOSITY
• Viscosity is resistance to flow of a fluid – Analogous to
• Friction coefficient • Electrical resistance
Area = A
SeparationShear rate =
Velocity=
h=
v
Shear stress =Force
Area A=
F=
Velocity = vForce = F
Separation = h
h
Units of viscosity
Pascal-seconds = Pa-s
mPa-s = 1/1000 Pa-s = cP = CentiPoise
Unit = Pascals = Pa
Unit = 1/seconds = s-1
Velocity / Gap=
Force / Area
Av
Fh=
Shear StressViscosity =
Shear Rate=
=
Newton’s
Law
Area = AArea = AArea = A
SeparationShear rate =
Velocity==
h=
v
Shear stress =Force
Area A=
F= =
Velocity = vVelocity = vForce = FForce = F
Separation = h
h
Units of viscosity
Pascal-seconds = Pa-s
mPa-s = 1/1000 Pa-s = cP = CentiPoise
Units of viscosity
Pascal-seconds = Pa-s
mPa-s = 1/1000 Pa-s = cP = CentiPoise
Unit = Pascals = PaUnit = Pascals = Pa
Unit = 1/seconds = s-1Unit = 1/seconds = s-1
Velocity / Gap=
Force / Area
Av
Fh=
Shear StressViscosity =
Shear Rate=
=
Newton’s
Law
Area = AArea = A
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WHAT IS THE OPTIMAL VISCOSITY?
• Metal on metal contact leads to high energy losses and surface wear
• Oil film between metal surfaces reduces energy losses – Oil provides less resistance to movement than metal
• Right amount of viscosity is needed to form an oil film tailored to meet the needs of different application
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MOLECULAR ORIGINS OF VISCOSITY
• Molecules in adjacent layers of oil interact, preventing layers from sliding past each other
• The higher the interaction the higher is the resistance to the flow (viscosity)
• Interacting Forces:
Flow direction
Molecules interact with surface, resist flow
Molecules interact with each other, resist flow
Van der Waals
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VISCOSITY OF LIQUIDS
Substance Viscosity at room temp
(mPa-s or cP)
Peanut butter 250,000
Clover honey 190,000
Ketchup 100,000
VM Concentrate 40,000
Molasses 8,000
Maple syrup 3,000
SAE 40 motor oil 350
SAE 30 motor oil 200
Olive oil 80
Group III base oil Yubase 4 45
Mercury 2
Water 1
Gasoline 0.5
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TERMINOLOGY
• Rheology – Study of viscosity
• Study of deformation and flow of matter
• From Greek, rheos, flow
• Kinematic Viscosity (KV) – Defined as Absolute (Dynamic) Viscosity (cP) divided by density of fluid
– Common Unit: CentiStoke (cSt) = mm2/s
– Other Units:
• Saybolt Universal Seconds (SUS)
– Used for base stock nomenclature (i.e. neutral number)
– SUS equals approximately 4.6 x cSt at 40C
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VISCOSITY DEPENDS STRONGLY ON TEMPERATURE
200
180
160
140
120
100
80
60
40
20
0 0 20 40 60 80 100 120
Temperature, Celsius
Kin
em
atic
Vis
cosi
ty, m
m2/s
Double Exponential
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VISCOSITY INDEX
• VI = A measure of the viscosity-temperature dependence
• Historical Development (1936)
– Pennsylvania crude = 100
– Gulf Coast crude = 0
– Defined in ASTM D 2270
• Higher VI means lower temperature dependence
Temperature, Celsius
300
250
200
150
100
50
0
Kin
em
atic
Vis
cosi
ty, m
m2/s
30 40 50 60 70 80 90 100 110
Same at 100°C
0 VI –20 VI
120 VI
100 VI
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VISCOSITY MODIFIERS
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VISCOSITY MODIFIERS
• Viscosity modifiers (VM) are used to decrease Viscosity-Temperature dependence of lubricants – Also known as Viscosity Index Improvers (VII)
• Viscosity modifiers in crankcase lubricants are polymers
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VISCOSITY MODIFIERS
• Polymeric Viscosity Modifier occupies large volume of solution
• Viscosity modifier increases viscosity proportionally to volume that polymer occupies
• Volume of Viscosity Modifier is almost independent of temperature
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FUNCTION OF VISCOSITY MODIFIERS
• Base oil viscosity has double exponential temperature dependence
• Thinner base oils (Oil B) provide good low temperature properties but cannot provide protection at high temperatures
• Thicker base oils (Oil A) provide protection at high temperatures but have insufficient pumpability at low temperatures
Temperature
Log (
Vis
cosity)
Oil B
SAE 5W
Oil A
SAE
30
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FUNCTION OF VISCOSITY MODIFIERS
Temperature
Lo
g (
Vis
co
sity)
Engine Operation
Cold Starting
Oil B
SAE 5W
Oil B + VM =
SAE 5W-30
Oil A
SAE 30
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THICKENING EFFICIENCY
• Thickening Efficiency or TE is related to amount of viscosity increase per % polymer
• TE is highly dependent on Molecular Weight and chemistry
– Higher MW = Higher TE
– Less Branching = Higher TE
Thickening Due to 1% Polymer B
Vis
cosi
ty
Base Oil
Base Oil
Thickening Due to 1% Polymer A
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SHEAR-THINNING: TEMPORARY AND PERMANENT VISCOSITY LOSS
• Viscosity loss due to shear:
Permanent Viscosity Loss: This measures loss of viscosity after 30 cycle KO test.
Reversible Non-reversible
Rupture of coil under shear forces
Quiescent polymer coil in oil solution
Orientation of coil under shear forces
Smaller cross- section gives less thickening which equals lower viscosity
Lower molecular weight gives less thickening which equals lower viscosity
Temporary Viscosity Loss
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SHEAR STABILITY INDEX (SSI)
• Shear Stability Index (SSI) measures loss of polymer added kinematic viscosity after 30 cycle Kurt Orbahn
• The higher the SSI the more viscosity loss upon oil shearing
• SSI is usually measured in a reference oil that represents polymer behavior in SAE 15W-40 grade
• SSI depends on polymer chemistry, molecular geometry and molecular weight
– Higher MW = less shear stable VM
Vis
cosi
ty
Base Oil
Base Oil
Thickening due to polymer
before shear
Viscosity loss
Fresh Oil Used Oil after 30 cycles
Shear Stability Index (SSI) = Viscosity loss Thickening due to polymer
X 100
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NEWTON’S LAW AND SHEAR THINNING (TEMPORARY VISCOSITY LOSS)
• Newton’s Law of Viscosity:
viscosity = shear stress / shear rate
• Newtonian Fluids = viscosity is a constant; does not change with shear stress or shear rate
• Fluids that do not obey this are called Non-Newtonian
• The most common type is Shear-Thinning
– Viscosity decreases with increasing shear rate
– Viscosity modified fluids fall into this category
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Shear Rate, sec-1
TYPICAL SHEAR RATES
Hundred Million
25
20
15
10
5
0 102 103 104 105 106 107
Vis
cosi
ty, m
Pa-s
Idle Highway Redline
Journal Bearing, piston rings, valve train
Non-Reversible
Shear-Thinning
Oil pump
Pouring oil
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Kinematic Viscosity
Shear Rate
SHEAR RATE AND SHEAR-THINNING
VM
Th
icke
nin
g
Newtonian Viscosity is constant at all shear rates
Non-Newtonian Viscosity decreases with shear rate
Low Shear Viscosity of Engine Oil
Temporary Viscosity
Loss
Ring Zone Bearings, Valve Train
Shear Rate
102 103 104 105 106 107
Shear Rate, sec-1
15
10
5
0
Vis
cosi
ty, m
Pa-s
Oil with VM
Thickening due to additives other
than VM
Bas
e St
ock
s
High Temperature High Shear (HTHS)
Shear Rate
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VISCOSITY MODIFIER TYPES
• Common Types
– Polymethacrylate (PMA)
– Ethylene-Propylene Co-polymer (OCP)
• Semi-crystalline
• Amorphous
– Styrene-Isoprene Co-polymer
• Factors that need to be considered when selecting VM
– Cost – Thickening Efficiency
– Shear Thinning Properties
– Low Temperature Properties
• Other performance harms/credits
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VISCOSITY MODIFIER CHEMISTRY
Ethylene-Propylene: (Olefin Co-Polymer)
(OCP)
Polymethacrylate: (PMA)
Styrene-Isoprene: Linear Polymer
Loose physical association due
to polarity differences
Chemically bonded together
Styrene-Isoprene: Star Polymer
O O O O O O
R R R
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PERFORMANCE COMPARISON TE VS. SSI
Thic
ken
ing
Effi
cien
cy
0 10 20 30 40 50 60 SSI
Semi-Crystalline OCP
Amorphous OCP
PMA
Styrene-Isoprene Star Polymers
Styrene-Isoprene Linear Polymers
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POUR POINT DEPRESSANTS
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POUR POINT DEPRESSANTS
• Pour Point Depressants – Commonly referred to as PPDs
– Also know as Lube Oil Flow Improvers (LOFIs)
• Break up regularity of wax crystals – Prevent large crystal sheets from forming
– Encourage small crystals - easier flow
– Minimize low-temperature viscosity and yield stress
• Types: – Fumarate Vinyl Acetates (FVA)
– Polymethacrylates (PMA)
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+ PPD
WAX CRYSTAL MODIFICATION BY PPD
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SAE VISCOSITY GRADES
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6200 at -35°C 6600 at -30°C 7000 at -25°C 7000 at -20°C 9500 at -15°C
13000 at -10°C – – – – – – – – –
0W 5W 10W 15W 20W 25W 8 12 16 20 30 40 40 50 60
SAE Grade
CCS mPa-s, Max
– – – – – –
<6.1 <7.1 <8.2 <9.3
<12.5 <16.3 <16.3 <21.9 <26.1
60 000 at -40°C 60 000 at -35°C 60 000 at -30°C 60 000 at -25°C 60 000 at -20°C 60 000 at -15°C
– – – – – – – – –
MRV mPa-s, Max w/No Yield
Stress Min
Kinematic Viscosity mm2/s
Max
– – – – – – 1.7 2.0 2.3 2.6 2.9 3.5(1) 3.7(2) 3.7 3.7
HTHS @ 106 Sec-1 mPa-s, Min
3.8 3.8 4.1 5.6 5.6 9.3 4.0 5.0 6.1 6.9 9.3
12.5 12.5 16.3 21.9
(1) For 0W, 5W, 10W Multigrades – Changed from 2.9 in 11/2007 (2) For 15W, 20W, 25W Multigrades and SAE 40 Grade
SAE J300 ENGINE OIL VISCOSITY GRADES (Issued Jan 2015)
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High
Low
Low
High
Low
High
Low
High
Kinematic Viscometer
Cold Cranking Simulator (CCS)
Mini-Rotary Viscometer (MRV)
Tapered Bearing Simulator (TBS) Tapered Plug Viscometer (TPV) Multi-Cell Capillary (MCC)
Oil Consumption Quality Control
Cold Starting
Cold Pumping
Wear/Fuel Economy
Temp Shear Instrument Performance
D 445
D 5293
D 4684
D 4683 D 4741 D 5481
ASTM Method
VISCOSITY MEASUREMENT METHODS
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SAE VISCOSITY GRADES
Straight Grades
Some common viscosity grades for engine oils
• SAE 0W-X grades typically need synthetic base stocks
25W-60
20
30
40
50
0W
0W-20
0W-30
0W-40
0W-50
5W
5W-20
5W-30
5W-40
5W-50
10W
10W-20
10W-30
10W-40
10W-50
15W
15W-20
15W-30
15W-40
15W-50
20W
20W-20
20W-30
20W-40
20W-50
25W
25W-30
25W-40
25W-50
60 0W-60 5W-60 10W-60 15W-60 20W-60
0W 5W 10W 15W 20W 25W
‘Winter’ Grade
20
30
40
50
60
‘Su
mm
er’ G
rad
e
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SAE J300 ENGINE OIL VISCOSITY GRADES
• Correct
– SAE 10W-30
• Incorrect
– 10W-30
– SAE 10W/30
– SAE 10W30
– SAE 10w-30
• Labeling
– Must label as the lowest ‘W’ grade
• An oil that meets 5W also meets 10W, 15W, etc.
– Oils with VM must be labeled as Multigrades
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SUMMARY
• Viscosity is a measure of a fluid’s resistance to flow
– It depends strongly on temperature – And it can depend on shear rate
• Viscosity modifiers in lubricants:
– Are used to decrease the temperature dependence of lubricant viscosity
– Chemical structure and molecular weight affect performance and efficiencies
– Exhibit temporary and permanent viscosity loss due to shear
– Three common types: OCPs, Styrene-Isoprene, PMAs – Oil formulators must balance viscometric requirements, engine performance
and cost
• Viscosity grades are defined by SAE J300
– Oils containing VM must be labeled as Multigrades
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VISCOSITY AND VISCOSITY MODIFIERS
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APPENDIX: VISCOSITY MEASUREMENT METHODS
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KINEMATIC VISCOSITY
• Kinematic viscosity = viscosity/density
• Principle – Measure time for known volume to
flow through capillary tube
• Driving force: gravity (mass of fluid)
• Low shear rate
– Units
• mm2/s
• CentiStokes = cSt (discouraged)
• Saybolt Universal Seconds (SUS) (obsolete)
Start
Stop
Capillary
Timing marks
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COLD CRANKING SIMULATOR
• Viscosity range
Shear rates
Shear stress
- 500 to 200,000 mPa-s
- 104 to 106 sec-1
- 50,000 Pa
CCS cross-section
Oil
Stator
Rotor
• Rotor/stator system
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MINI-ROTARY VISCOMETER
• Low shear rate/shear stress measurement
• Measurements – Yield stress
(min. stress to cause flow)
– Viscosity @ 525 Pa stress)
• Relationship to pumpability failure mechanism – Yield stress/air-binding
– Viscosity/flow-limited Rotor
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HIGH TEMPERATURE HIGH SHEAR
Capillary Increase
pressure to increase
shear rate
Laminar fluid flow
profile
Constant speed
Gap controls shear rate
Rotational
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