2016 ILMA Annual Meeting

Metalworking Fluids Committee

October 17, 2016

3:00PM-4:30PM

TRibological Innovative Advancements for General Energy-

efficiency (TRIAGE)Carlton Reeves, Ph.D.

Technology to Market Advisor

Advanced Research Projects Agency – Energy

U.S. Department of Energy

Washington, DC

Independent Lubricant Manufacturers Association Annual Meeting, Scottsdale, AZOctober 17, 2016

ARPA-E Directive

Goals: Ensure America’s

• Economic Security

• Energy Security

• Technological Lead in Advanced Energy Technologies

Mission: To overcome long-term and high-risk technological barriers in the development of energy technologies

Means:

• Identify and promote revolutionary advances in fundamental and applied sciences

• Translate scientific discoveries and cutting-edge inventions into technological innovations

• Accelerate transformational technological advances in areas that industry by itself is not likely to undertake because of technical and financial uncertainty

3

Reduce Emissions

Improve Energy

Efficiency

Reduce Energy Imports

Measuring ARPA-E’s Success

• New Companies formed (Public, Acquired, or Private)

4

‣ Over $1.25 Billion in Private Sector Funding

‣ Follow-on Funding from Other Government Agencies

If so, Where?

1 Quad = 1018 Joules

5

Can Tribology Save a Quad of Energy ?

Program Conception

• $30 Million• ~10 Projects• 3 Years• Engage Industry, Academia, & Gov’t

• Ground Transportation• Power Generation• Aviation• Manufacturing & Metal Working• Functional Fluids & Lubricants• Simulation Technologies

6

Materials

Coatings

Lubricants

Transportation

7

Breakdown of Passenger Car Energy Consumption

33% Friction Losses

Reduces Exhaust & Cooling Losses

Potential Technologies

• New and Nano-materials • Coating Technology• Surface Treatments• Novel Lubricant Base Stocks/Lower Viscous Oils• Enhanced Additives • Ionic Liquids• Graphene/Graphane• Lamellar Solids

Could these improve efficiency, promote longer life, increase output, and ensure reliability?How much energy could be reduced? Can this be measured?

8

9

https://arpa-e.energy.gov

9

Thank You

Carlton Reeves, Ph.D.Technology to Market AdvisorAdvanced Research Projects Agency – EnergyU.S. Department of EnergyCarlton.Reeves@hq.doe.gov

ILMA 2016 Annual Meeting Metalworking Fluids

Committee

Chemical Salts UpdateJohn K. Howell, Ph.D., GHS Resources Inc., and

James Eggenschwiler, Esq., The Redstone Group

Chemical Salt Update

• Topics:– ILMA 2015 testing results

–Corfree M1

–Chemical salt survey results

–Alternate salt compositions

–Canada Schedule 5, Schedule 6 testing requirements

–Discussion

ILMA 2015 Chemical Salt Testing Results

Salt CAS Number

Estimated SubstanceClassification,Eye (BCOP)

Estimated Substance Classification, Skin Irritation

Estimated Acute Toxicity Classification

TEA + dibasic acids

1078712-94-3

Not classified, not an eye irritant

Uncategorized, not a dermal irritant

GHS Acute Tox 5 or unclassified (OSHA)

DGA + dibasic acids

292849-36-6

Not classified, not an eye irritant

GHS Cat 3 mild dermal irritant or unclassified (OSHA)

GHS Acute Tox 5 or unclassified (OSHA)

AMP + tall oil fatty acids

67701-21-7

Mild eye irritant, GHS Eye Cat 2B

GHS Category 1C skin corrosive

GHS Acute Tox 5 or unclassified (OSHA)

TEA + isononanoic acid

67801-51-8

Moderate eye irritant, GHS Eye Cat 2A

Uncategorized, not a dermal irritant

GHS Acute Tox 5 or unclassified (OSHA)

MEA + isononanoic acid

67801-50-7

Severe eye irritant, GHS Eye Cat 1

GHS Cat 3 mild dermal irritant or unclassified (OSHA)

GHS Acute Tox 5 or unclassified (OSHA)

Corfree M-1 Possible Substitutes

• Corfee M-1 CAS #: 72162-23-3, Nitric acid, reaction products with cyclododecanol and cyclododecanone, by-products from, high boiling fraction

• Possible substitutes: Cathay Industrial Biotech Pure Mix II; Emery Oleochemicals Emerox 1199, 1185, 1175, 1112– Note: producers of possible substitutes describe their product’s

compositions in terms of dibasic acid component percentages, not by manufacturing process

• Corfree M-1 composition(from Invista Technical Brochure)– Sebacic acid, CAS 111-20-6, 5 – 10%– Undecanedioic acid, CAS 1852-04-6, 30 – 45% – Dodecanedioic acid, CAS 693-23-2, 30 – 45%– C4 – C9 dibasic acids, < 10%– Other acids, < 6%– Water, 0.3%

Chemical Salt Survey Results, August 19, 2016

• 13 respondents (not every respondent answered every question): “a small but likely significant group of MWF formulators”

• Question 1. Which countries/jurisdictions are important to your MWF product line?– United States – 12 respondents, #1; 1 respondent, #11– Canada – 8 respondents, #2; 2 respondents, #3; 1 respondent,

#5; 1 respondent #11– EU – 3 respondents, #2; 2 respondents #3; 2 respondents, #4; 1

respondent #6; 2 respondents, #11– China – 3 respondents, #3; 5 respondents, #4; 1 respondent, #9;

1 respondent, #11– Japan; South Korea; Australia; New Zealand; Philippines; Taiwan

– lower levels interest/support

Chemical Salt Survey Results, August 19, 2016

• Question 2. If you are considering another organic acid product (or products) as a partial or complete replacement for Corfree M-1, what alkanolamines would you use or are you using in combination with that organic acid product or products?– Triethanolamine (TEA), 10 responses = 71%

– Ethanolamine (MEA), 9 responses = 64%

– 2-amino-2-methyl-1-propanol (AMP), 9 responses = 64%

– Isopropanolamine (MIPA), 8 responses = 57%

– 1-(2-aminoethoxy)ethanol (DGA), 6 responses = 43%

– Any others? Butylethanolamine, MDEA

Chemical Salt Survey Results, August 19, 2016

• Question 3. Of the above alkanolamines, which two would be your top choices?– TEA, MEA– MIPA, AMP– TEA and AMP 95– MEA, TEA– AMP– MIPA, DGA or MEA (undecided)– AMP, MIPA; AMP, TEA– TEA, DGA– MIPA, TEA– MEA, AMPNote: each of eleven respondents chose a different combination of amines as their “preferred top 2.” TEA was chosen in combination with another alkanolamine by many (6) but not by all respondents

TEA Dibasic Acid Salt Compositions/CAS Nos.

CAS Number Name

Dibasic

Acid

Carbon

Chain

Length

Precursor

Acid

Contained

in Emerox

1199

Precursor

Acid

Contained

in Emerox

1185

Precursor

Acid

Contained

in Emerox

1175

Precursor

Acid

Contained

in Emerox

1112

Precursor

Acid

Contained

in Pure

Mix 2

68833-70-5 Azelaic acid, compd. with 2,2',2"-nitrilotriethanol 9 X X X X

85030-05-3 Azelaic acid, compd. with 2,2',2"-nitrilotriethanol (1:2) 9 X X X X

70103-35-4 Decanedioic acid, compd. with 2,2',2"-nitrilotriethanol 10 X

85030-07-5 Undecanedioic acid, compd. with 2,2',2"-nitrilotriethanol (1:2) 11 X X

85050-08-6 Dodecanedioic acid, compd. with 2,2',2"-nitrilotriethanol (1:2) 12 X X X

Canada Schedule 5 (1,000 kg/year; not on NDSL)

• Physical/chemical:– Melting point– Boiling point or decomposition temperature– Water solubility– Biodegradablility

• Animal Tox:– OECD 437 Bovine Eye Opacity– OECD 405 Eye irritation– OECD 404 Skin Irritation– OECD 402 Dermal Acute Toxicity Class Determination– OECD 471 Bacterial Reverse Mutation Test (Ames Test)

• Ecotox:– OECD 201 LC50 Algae

Canada Schedule 6 (10,000 kg/year; not on NDSL)

• In addition to tests required for Schedule 5:• Physical/chemical:

– Infrared spectrum or liquid chromatography – mass spec– Adsorption-desorption screening test data– Hydrolysis rate as a function of pH (likely not an issue with salts)

• Animal Tox:– Info to assess skin irritation potential (OECD 404 should be sufficient)– Skin sensitization, such as OECD 429 Local Lymph ode Assay– OECD 410 28-day dermal toxicity– Mammalian in vitro mutagenicity test such as OECD 487 in vitro mammalian

cell micronucleus test– An in vitro mammalian test for chromosomal aberrations such as OECD 473 in

vitro chromosomal aberration test

• Ecotox:– OECD 202 daphnia magna LC50

– OECD 203 fathead minnow LC50

Phosphorus Concerns in the Great Lakes Region

John Burke

Houghton International

GLWQA• U.S. and Canada addressing issue under Great

Lakes Water Quality Agreement (signed in 1972, amended several times)

• Provides a framework and outlines principles, approaches, and objectives to accomplish goals of pollution abatement and prevention

• Canada/U.S. agreed to target reductions to achieve a 40% reduction in phosphorus levels (compared to 2008)

• Implementation plans by February 2018– Mayors of impacted cities (through Great Lakes and St.

Lawrence Cities Initiative) called on U.S. and Canada for more prompt action

Lake Erie Panel • EPA’s Science Advisory Board – Lake Erie Phosphorus Objective

Review Panel reviewed a draft report last week regarding the development of reduction targets

• Independent advice to EPA consistent with Federal Advisory Committee Act

• “The SAB agrees that the 40% reduction in total phosphorus load to the Western and Central Basins of Lake Erie recommended by the Task Team will improve Lake Erie water quality and reduce harmful algal blooms. However, even with this reduction, blooms are still likely to occur relatively frequently, perhaps even routinely, in the western arm of the western basin in Maumee Bay. Ultimately, greater load reductions may be necessary to achieve the desired thresholds.”– Full report can be reviewed here:

https://yosemite.epa.gov/sab/sabproduct.nsf//MeetingCalBOARD/150AB78DDAB990B5852580180076194A?OpenDocument

State Level Activities

• Ohio and other Midwestern states looking to address issue on state level too

• Ohio crafted state plan with similar goal (40% reduction), but seeks to achieve goal by 2025

– No such deadline under GLWQA

– Draft plan calls for several proposed actions within 12-36 months (if finalized)

State Level Activities • Ohio EPA will publish two-year Water Quality Milestone

for each county and priority watershed• Ohio EPA will coordinate with local authorities to

conduct monitoring of nutrient discharge levels• Other actions planned from Ohio Dept. of Natural

Resources, Ohio Lake Erie Commission, Dept. of Health • Mainly focused on agricultural, livestock, and failed

septic tanks, but one potential key area of focus as plan finalized: NPDES permits

• It was noted in comments: over 700 entities in Lake Erie Basin that have NPDES permits (from Ohio EPA) to discharge wastewater containing phosphorus (over 80% have no limit on phosphorus)– Something to watch

NTP – TRIM ® VX

NTP – TRIM® VX

• ILMA and Master submitted extensive comments and participated in peer review panel in February 2016– Panel voted to adopt NTP’s recommended conclusions

(two incidents of clear evidence of carcinogenicity and two incidents of equivocal evidence of carcinogenicity under conditions of study) subject to certain limitations

• Submitted three sets of comments after the meeting

• The final technical report should be published around the end of 2016/start of 2017– ILMA and Master anticipate it will be inclusive of the

limiting language that the results cannot be extrapolated to other MWFs.

Chlorinated Paraffins Update

Recent Activities ILMA continued to work with the following Coalition:

American Chemistry CouncilChlorinated Paraffins Industry Association

American Wire Producers AssociationIndustrial Fasteners Institute

Center for the Polyurethane Industry National Association of Manufacturers

Auto Alliance Global Automakers

Vinyl Institute Aerospace Industry Association Adhesives and Sealants Council

Motor and Equipment Manufacturers Association

Recent Activities

• ILMA members met with SBA Office of Advocacy during NAM Summit in June 2016– Attorney in that office continues to be heavily

involved

• ILMA published a “Status Update” in July 2016 due to regulatory misinformation – Mid-2017 date to cease domestic production and

foreign importation is illusory and has no legal or regulatory effect in ILMA’s opinion

• Regular meeting with Coalition members throughout the summer

Risk Assessments

• Sent in submission that outlined the impact of TSCA reform on risk assessments– requirements of §26(h)and(i) to use “best available

science” and make decision based on “weight of scientific evidence”

– Statute instructs EPA to prioritize and address chemicals on 2014 update to TSCA Work Plan (MCCPs/LCCPs on list)

• ILMA and Coalition continue to push EPA to peer review the risk assessments for MCCPs and LCCPs– No response yet, but hopefully soon

ILMA 2016 Annual Meeting MWF Committee

Canada: Boric Acid UpdateJohn K. Howell, Ph.D., GHS Resources

Inc.

Canada: Boric Acid Update

• July 23, 2016, Environment Canada published Draft Boric Acid Screening Assessment initiating 60-day comment period– Includes boric acid, borax, sodium tetraborate but not

boric acid amides

– “The draft screening assessment proposes to conclude that boric acid, its salts and its precursors are harmful to the environment as set out in section 64 (a) of CEPA 1999. It also proposes to conclude that boric acid, its salts and its precursors are harmful to human health as set out in section 64 (c) of CEPA 1999.”

Proposed Rule 1430

John Burke

Houghton International

Mike Pearce

W.S. Dodge Oil

ILMA 2016 Annual Meeting MWF Committee

Formaldehyde/Biocides UpdateStephan Baumgärtel, Ph.D., German Lubricant

Manufacturers AssociationJohn K. Howell, Ph.D., GHS Resources Inc.

Formaldehyde Status

• 1999: approx. 100 active substances/biocides available• Today: 25• 12 of 25 are formaldehyde release agents• As of 2016, formaldehyde is now classified as CMR 1B• Customers now hesitant to use formaldehyde release

biocides although formaldehyde concentration is far below threshhold

• Impact on formulators?

Note: CMR = Carcinogen/mutagen/reproductive toxin

Formaldehyde / other chemicals

• 1999: approx. 100 active substances/biocides available

• Today: 27

• 7 of 27 are formaldehyde release agents

• As of 2016, formaldehyde is now classified as CMR 1B

• Customers now hesitate to use formaldehyde releasing biocides although formaldehyde

concentration is far below threshold.

• Alternative technology: high pH products, sometimes based on dicyclohexylamine.

• BHT / Benztriazole: CoRAP list of potential SVHC substances, suspected endocrine disruptors

• Boric acid reaction products: still used, but declining.

Remaining Biocides &

Fungicides (D)Chemistry Addition Primary

Efficacy

Issues

Formaldehyde

Releasers

conc &

tankside

bacteria formaldehyde

Pyridinethione conc &

tankside

fungi Iron complexing

Thiocyanobenzo-

thiazole

tankside fungi sensitizer

Isothiazolones

•BIT

•CMI/MIT

tankside

tankside

both

both

Corrosive,

sensitization potential,

formulating into

concentrates difficult,

short lifetime. BIT: not

against Pseudomonas

OPP conc &

tankside

bacteria environmental