CME3036 Process and Product Engineering CME3036/SJB/2011

Additive structure and

performance
• Examples considered:
– Antiwear (EP additives)
– Detergents
– Dispersants
– Friction modifiers
– Antioxidants
CME3036 Process and Product Engineering CME3036/SJB/2011

Extreme Pressure Additives

• Used in heavy duty applications (high contact

load, slow speed, etc)
• Usually based on organic molecules
containing sulphur or phosphorus
• Mainly used to prevent scuffing (local
adhesion when lubricants fail leading to
severe adhesive (or abrasive) wear)
• High temperatures at contacting asperities
promote chemical reactions to produce
friction-reducing, low shear strength films
CME3036 Process and Product Engineering CME3036/SJB/2011

Antiwear additives

• A very widely used anti-wear additive is zinc

dialkyl dithiophosphate (ZDDP or ZDTP)
• This reacts with the metal surface to produce
a durable, self-healing film with low shear
strength

RO S S OR R=C4H9 or
P Zn P C5H11 usually
RO S S OR
CME3036 Process and Product Engineering CME3036/SJB/2011

Structure of ZDTP antiwear film

Multiple levels of defence against wear

Fluid lubricant Low viscosity fluid

Alkyl phosphate precipitates High viscosity fluid

Increasing
Partially complexed phosphates
resistance to
penetration

Increasing shear
Compacted phosphate matrix
strength
Solid
Solid sulphide/oxide layer Scuffing resistance
Metallic substrate

Structure can be modified by other additives, e.g. detergents and dispersants

CME3036 Process and Product Engineering CME3036/SJB/2011

Metal Detergents
Colloidal dispersion of base, solubilised by metal soap

5nm Base
soap

Base ： CaCO3 ， MgCO3 ， Metal ： Ca ， Mg ， Ba

Soap ： salicylate ， sulphonate ， phenate
Functions ： Neutralise acids ， keep surfaces clean ，
antioxidant （ salicylate ， phenate ）
CME3036 Process and Product Engineering CME3036/SJB/2011

Detergent structure

Typically a divalent metal with two long chain aromatic organic acids:
CME3036 Process and Product Engineering CME3036/SJB/2011

Ashless dispersants

• Typical manufacture
O O
O
R +
R
Polyamine
R
N NH
Etc.
O O NH NH2

O O
O

PIB MALA PIBSA PIBS

PIB – Polyisobutene
MALA – maleic anhydride
PIBSA – polyisobutene succinic anhydride
PIBS - polyisobutenyl succinamide
CME3036 Process and Product Engineering CME3036/SJB/2011

Soot in diesel engines

• Soot = carbon particles with a variety of
functional groups on the surface
• Primary particle size depends on engine
operation (up to 100nm)
• Typical of diesel combustion
• Retarded ignition gives more soot
• Very high soot concentration in some new
engines
• Causes oils thickening and impilcated in
valve train wear
CME3036 Process and Product Engineering CME3036/SJB/2011

Soot in diesel engines (2)

CME3036 Process and Product Engineering CME3036/SJB/2011

Ashless dispersants and soot

CME3036 Process and Product Engineering CME3036/SJB/2011

Metal-containing friction
modifiers
• Typically organomolybdenum compounds
– E.g. molybdenum dithiocarbamates

R S
O O S
S R
N C S Mo Mo S C N
R S R

• Layered structure of MoS2 important in their

function
• Work in combination with ZDTPs
• Also function as secondary antioxidants
–
CME3036 Process and Product Engineering CME3036/SJB/2011

Some types of additive

interaction
• Hydrogen bonding X, Y =O, N, S
e.g.
RXH
Phenol and amine
R- X- H + Y – R’  R – X – H ····· Y – R’ antioxidants
YR’
Ester base fluids

• Metal complexes
M=Zn, Mo, Ca, Mg…
X=O, N
X X
M + X X e.g. ZDTPs, Mo FMs
X X M
Ca & Mg detergents
X X Polyamine
dispersants
CME3036 Process and Product Engineering CME3036/SJB/2011

Cross-linking interactions
• When additives have several active
groups, cross-linking may occur

• Such reactions lead to gel formation

(filter blocking) or viscosity increase
• Avoid by careful choice of compatible
additives with balanced concentrations
CME3036 Process and Product Engineering CME3036/SJB/2011

ZDTP/dispersant interaction
O
R
N NH Example of structure
NH NH2
O S S
- others occur
Zn
S
S

Effects include:
• Dispersancy reduced (but only slightly due to
relative concentrations)
• Increases thermal stability of ZDTP but can
reduce its oxidation resistance
• Complex effects on antiwear performance
CME3036 Process and Product Engineering CME3036/SJB/2011

Effects of interactions

• Amount of dispersant available to

disperse soot