Bench Screening of Novel Anti-Wear Alternatives to ZDDP Victor Bakunin, Trade and Technical representative, CIS Moscow, Russia Cyril Migdal, Director, Petrochemical Additives Middlebury, CT, USA

CHEMTURA – a new brand at the Oils and Additives market The chemical company of the future

Our History Textile machinery, dyes, polymer additives, lubricants, agricultural chemicals, urethanes…. Specialized chemicals Rubber, rubber components, industrial rubber products, footwear, tires, synthetic rubber, agricultural chemicals Bromine, bromine derivatives, combustion inhibitors, agricultural chemicals, polymer additives, pool chemicals, household chemicals, fluorine derivatives, optical monomers Carbon for tires, plasticizing agents, stearates, stabilizers, silicones … Specialized chemicals (Crompton Corporation) Kaufmann Holdings was acquired in Ester lubricants – ester polyols + ready- to-use synthetic fluids Ordinary and specialized phenolic antioxidants Phosphates – non- combustible fluids (formerly Ciba)

Our Additives Trademarks Naugalube® and Naugard® antioxidants; Calcinate, Hystrene® and Industrene® anti-wear agents; Lobase®, Hybase® and Petronate® sulfonate detergents; Synton® high-viscosity polyalphaolefins (PAO); G-2000 high-quality lubricants; Durad® additives based on organic phosphates; Reolube® non-combustible lubricants and fluids (phosphates); Reomol® and KP-140® special additives (phosphates); ANDEROL®, AOSyn®, PQ® special lubricants; Hatcol® esters and ester lubricants (ready-to-use and basestocks); Royco® aircraft lubricants.

EUROPE StandardApproval Date Euro 1October 1993 Euro 2October 1996 Euro 3October 1999 Euro 4October 2005 Euro 5 Октябрь 2008 October RUSSIA

Zinc is the base for the formation of tribolayers (Zinc Polyphosphate) ZDDP is an antioxidant ZDDP is a synergist for Mo-containing additives Zinc dialkyldithiophosphate (ZDDP) - more than simply anti-wear protection Willermet et al, Trib. Inter., 5/95

Cumylhydroperoxide ( CHP )

Effect of CHP on anti-wear properties of engine lubricants (four-ball test machine) Ди, мм ASTM D 4172

Effect of CHP on anti-wear properties of engine lubricants (Cameron-Plint) Ди, мм

Ashless P-containing additives

Phosphorus-free additives (All contain sulfur - SOx, sulfate ash)

New anti-wear additives Imidazolidine thion Cyclic thiourea Oxamide Hydrazide of succinic acid Imidazolidine thion

Silicon-containing compounds: Silanes/Siloxanes Octyltriethoxysilane Bis-(triethoxysilyl) ethane Bis-(truethoxysilyl) propyl disulfide

Anti-wear properties of engine lubricants containing silanes (Cameron-Plint) Max. fin wear depth (uм) Silanes & ZDDP synergy!

Anti-wear additives based on esters MLA-2837 –Ashless, no S & P –Synergism with ZDDP –Free-flowing clear liquid –Non-corrosive

Sulfur-containing anti-wear additives MLA-2877 Thiocarbamate derivative 12 % S Free-flowing yellow liquid Non-corrosive MLA-2871 S-containing heterocycle Synergism with ZDDP 22 % S Free-flowing yellow liquid Non-corrosive

Four-ball friction machine ASTM D additives weight % (or as stated) Ди, мм 63x 73x 14x Max. fin wear depth (uм)

Cameron-Plint tribometer 1 additives weight % (or as stated) Fin wear depth (uм) 91x 12x 57x

Selection criteria Use conditions Activation temperature/ pressure Price/Quality Corrosive power Volatility Color Solubility Compatibility with sealants Smell Physical condition Toxicity Compatibility with packaging Duration of action Multifunctionality AO; AF; contribution to EP

Conclusions As an anti-wear catalytic agent, CHP reliably distinguishes among lubricants with respect to anti- wear qualities in tests on a four-ball friction machine and the Cameron-Plint tribometer. By screening various compounds, it was possible to identify several quality classes of potential anti-wear additives for engine lubricants as replacements for zinc dialkyldithiophosphate: Heterocycles with Sulfur/Nitrogen atoms Esters with Nitrogen atoms (CHON) Silanes/Siloxanes