EAL for marine applications Overview of EPA regulations and future technologies Ichiro Minami Luleå University of Technology, Sweden 8 October, 2015 Tribodays 2015 in Nynäshamn

Contents  Introduction MARTEC II ArTEco The task of LTU  EPA VGP-2013 Outline Lubricants  Strategy and design Environmentally acceptable lubrication systems Lubricant maintenance based on condition monitoring The concept of green chemistry  Summary and prospects

MARTEC II ArTEco  Abbreviation: Arctic Thruster Ecosystem  Coordinator:VTT, Finland.  Partners:Wärtsilä, Tampere U. Tech. (IHA & Material Science), ATA Gears, Armeka, Katsa, LTU, SKF, Tech. U. Dresden, Klingelnberg  Period:1 January 2015 – 31 December  Total budget:≈7.4 M€

Task of LTU: Environmentally acceptable lubrication systems  Lubricant candidates as mineral oil alternatives. EPA VGP-2013 certification Type of base oil and acceptable additive package  Sustainable lubricants for hydraulic systems. Physical properties under elevated pressures Feasibility of synthetic fluids  Lubricant maintenance. Advanced condition monitoring Extended lifetime of lubricants

EPA VGP-2013  United States Environmental Protection Agency  Vessel General Permit for discharges incidental to the normal operation of Vessels  Became effective on December 19, 2013 and expire at midnight December 19,   194 pages document regulation of waste discharge for vessels greater than 79 feet (≈ 24 m) in length in areas less than 200 nm (≈370 km) from any US shore. Additional regulations for each state and The Great Lakes.  How to manage and how to report wastes (after cleaning operation, foods, oils, etc.).  All vessels must use an EAL in all oil to sea interfaces, unless technically infeasible.

EPA VGP-2013  EAL (Environmentally acceptable lubricants) means lubricants that are “biodegradable” and “minimally-toxic” and are “not bioaccumulative.”  Products labeled by labeling programs: Blue Angel, European Ecolabel, Nordic Swan, the Swedish Standards SS and , OSPAR, and DfE.  Lubricant has to contain at least 90 mass% of biodegradable; up to 5 mass% may be non-biodegradable (but not bioaccumulative) while the remainder must be inherently biodegradable.  Grease has to contain at least 75 mass% of biodegradable; 25 mass% may be either inherently biodegradable or non-biodegradable, but may not be bioaccumulative.

EPA VGP-2013  Biodegradable: within 28 days according to the defined procedures.  Inherent biodegradability: after 28 days according to the defined procedures.  Non-bioaccumulative the partition coefficient in the marine environment is log KOW 7 using test methods OECD 117 and 107, molecular mass > 800 Daltons, molecular diameter >1.5 nanometer, BCF or BAF is <100 L/kg, using OECD 305, OCSPP or OCSPP , or a field-measured BAF or polymer with MW fraction below 1,000 g/mol is <1%.  Only stated substances present above 0.10% shall be assessed.

Lubricant design  Base oils; biodegradable synthetic fluids (esters, hydrocarbons) and plant oils are well studied. Short term  “Non-biodegradable” additives less than 5 mass% are feasible.  “Non-bioaccumulative” additives are challenging Polymers or macromolecules? Enhanced functions per molecule according to an exemption of “only stated substances present above 0.10% shall be assessed.” Midterm  Synergism of additives (combination of the approved chemicals)

Additives Base oilsMaterial Long term lubricant design (Tri-synergism) Interface chemistry A smart protocol for large-matrix experiments

Long term lubrication systems (Lubricant maintenance) J. Japan Petroleum Institute, 52(6), (2009). Extended lifetime with less amount of additive

Future requirements: 12 principles of green chemistry 1.It is better to prevent waste than to treat or clean up waste after it is formed. 2.Synthetic methods should be designed to maximize the incorporation of all materials used in the process into the final product. 3.Wherever practicable, synthetic methodologies should be designed to use and generate substances that possess little or no toxicity to human health and the environment. 4.Chemical products should be designed to preserve efficacy of function while reducing toxicity. 5.The use of auxiliary substances (e.g. solvents, separation agents, etc.) should be made unnecessary wherever possible, and innocuous when used. 6.Energy requirements should be recognized for their environmental and economic impacts and should be minimized. Synthetic methods should be conducted at ambient temperature and pressure. 7.A raw material or feedstock should be renewable rather than depleting wherever technically and economically practicable. 8.Unnecessary derivatization (blocking group, protection/deprotection, temporary modification of physical/chemical process) should be avoided whenever possible. 9.Catalytic reagents (as selective as possible) are superior to stoichiometric reagents. 10.Chemical products should be designed so that at the end of their function they do not persist in the environment and break down into innocuous degradation products. 11.Analytical methodologies need to be developed further to allow for real-time in-process monitoring and control prior to the formation of hazardous substances. 12.Substances and the form of a substance used in a chemical process should be chosen so as to minimize the potential for chemical accidents, including release, explosions, and fires. P.T.Anastas, J.C.Warner: "Green Chemistry Theory and practice“ 1998.

Summary and prospects  EPA-VGP2013 Definition of EAL Non-Bioaccumulative compounds  Future technologies (also lubricants for other applications) Synergism of each component Lubricant design and maintenance with the concept of green chemistry  Presentations “Lubricants conformed to the concept of green chemistry” International Colloquium Tribology, (Esslingen, Germany), 13 January “Lubricant maintenance based on condition monitoring” STLE Annual Meeting & Exhibition, May, 2016.