MW MillingMW Milling LLCLLC

San Diego, CaliforniaSan Diego, California

Metal Flake Technologies Metal Flake Technologies LLCLLC

Nashville, TennesseeNashville, Tennessee

&&

TMTM

Might We Already Have A Sensible

Antifouling Alternative…..

and Not Even Realize It ??

Hiding in Plain Sight

What Are We Fighting?What Are We Fighting?

A Flurry Of ActivityA Flurry Of Activity• The “Gold Standard”The “Gold Standard” Tri-Butyl TinTri-Butyl Tin *Banned *Banned

By International Maritime Organization By International Maritime Organization *Banned Individually By Most Maritime Countries*Banned Individually By Most Maritime Countries

• The “Replacement”The “Replacement” CopperCopper *Banned or Max Leaching Rates Imposed in Many Countries *Banned or Max Leaching Rates Imposed in Many Countries

*IMO Concern and Dialogue Growing *IMO Concern and Dialogue Growing *California Imposed Outright Ban in Impaired or Sensitive Areas *California Imposed Outright Ban in Impaired or Sensitive Areas *History and Political Inertia *History and Political Inertia Indicate Severe Restrictions In Near FutureIndicate Severe Restrictions In Near Future

• ““Copper-Free”Copper-Free” Foul Release, Algaecidal Foul Release, Algaecidal *Durability Concerns Remain *Durability Concerns Remain *Launchable Time, Special Application Equipment??? *Launchable Time, Special Application Equipment??? *Does My Cleaning Frequency Go Up? *Does My Cleaning Frequency Go Up? *How Much Did You Say That Was???????? *How Much Did You Say That Was????????

• ““Exotics”Exotics” Metallizing, Ceramic, Slip Liner Metallizing, Ceramic, Slip Liner *Industry Needs Retraining and Education About The *Industry Needs Retraining and Education About The Process Process *Very High Implementation Costs *Very High Implementation Costs

High Tech and Ultra Engineered High Tech and Ultra Engineered CoatingsCoatings

• Self-polishing copolymer, an elegant formulation that Self-polishing copolymer, an elegant formulation that controls biocide delivery and extends coating controls biocide delivery and extends coating effective lifespan.effective lifespan.

• Ablative formulations either hard or soft constantly Ablative formulations either hard or soft constantly slough off to expose active biocide.slough off to expose active biocide.

• Low surface energy formulations take advantage of Low surface energy formulations take advantage of slickness to deter fouling growth without the use of slickness to deter fouling growth without the use of biocides.biocides.

• Chemical biocides as primary agent or in Chemical biocides as primary agent or in combination with another agent.combination with another agent.

• Hybrid systems use combinations of all of the above.Hybrid systems use combinations of all of the above.• Thermal Spray coatings.Thermal Spray coatings.

Who Am I?Who Am I? • I have been in the paint industry for 100 years.I have been in the paint industry for 100 years.

• Billions of dollars are saved every year because of me.Billions of dollars are saved every year because of me.

• Everybody knows how to use me.Everybody knows how to use me.

• I am cheaper than many of my peers.I am cheaper than many of my peers.

• I am not currently banned or restricted. *I am not currently banned or restricted. *

• I am already used throughout the marine industry.I am already used throughout the marine industry.

• I provide fantastic cathodic protection.I provide fantastic cathodic protection.

• Data has shown me to be a good anti-fouling Data has shown me to be a good anti-fouling substance if used correctly.substance if used correctly.

* California has established some localized TMDL’s* California has established some localized TMDL’s..

ZincZinc

but in the form of a flakebut in the form of a flake

CA Regional Water Quality Control BoardCA Regional Water Quality Control BoardChollas Creek Chollas Creek

CMC (Criteria Maximum Concentration)CMC (Criteria Maximum Concentration)

CopperCopper 13 ug/l 13 ug/lZincZinc 120 ug/l120 ug/l

CCC (Criteria Continuous Concentration)CCC (Criteria Continuous Concentration)

CopperCopper 9 ug/l 9 ug/l ZincZinc 120 ug/l120 ug/l

So Who Says Zinc Works?So Who Says Zinc Works?

• US Army Corps of EngineersUS Army Corps of Engineers…………ZMR-2-15 Nov. ZMR-2-15 Nov. 19941994

• Marine Environmental Research…Marine Environmental Research…Two Surprises From Inorganic Zinc-rich Silicate Coating, C. William Anderson, EPA Publishing

• United States Patent 4835050United States Patent 4835050

US Army Corps of EngineersUS Army Corps of EngineersZebra Mussel Research Program Black Rock Lock November 1994

T. Race and Dr. A. Miller

Goal: Evaluate the efficacy of antifouling coatings as a function of metal leaching rate.

Test Structure: Determinations of in situ test panel performance and in vitro panel leach rate.

Duration: 15 months

Conclusion about zinc:

““zinc coatings would offer a significant zinc coatings would offer a significant advantage in terms of cost and simplicity advantage in terms of cost and simplicity over other antifoulants.”over other antifoulants.”

Marine Environmental ResearchMarine Environmental ResearchTwo Surprises From Inorganic Zinc-rich Silicate Coating

Dr. C. William Anderson

Publisher: U.S. EPA Office of Research and Development

Research Summary: The interface between any surface and an ionic solution (seawater) has an inherently electrochemical character. This study examined an antifouling approach that exploited this electrochemistry.

Results: While the initial suspicion was that the charge applied to the coating was the principal antifouling factor,…..it became clear that the zinc it became clear that the zinc had profound effects on the larval metabolism had profound effects on the larval metabolism (especially on the charged polymer glue) in (especially on the charged polymer glue) in barnacles. barnacles. Dr Dan Rittschof….Duke UnivDr Dan Rittschof….Duke Univ..

United States Patent 4835050• 1986 Patent claiming1986 Patent claiming:: “A non-toxic composition of matter capable of providing long-“A non-toxic composition of matter capable of providing long-

lasting suppression of the growth of fouling organisms in an aquatic environment…. such that lasting suppression of the growth of fouling organisms in an aquatic environment…. such that said composition is capable of generating a voltaic current.” said composition is capable of generating a voltaic current.”

• Concept:Concept: This invention relates to paints which store a voltage in a composition consisting This invention relates to paints which store a voltage in a composition consisting of a large multiplicity of very small (zinc) particles capable of producing an emf and thus a of a large multiplicity of very small (zinc) particles capable of producing an emf and thus a potential difference. The mechanical mixture of metal powders when incorporated in a potential difference. The mechanical mixture of metal powders when incorporated in a suitable vehicle makes a good antifouling paint. When it is applied to a Zinc coated steel suitable vehicle makes a good antifouling paint. When it is applied to a Zinc coated steel surface or a wood surface it will, when immersed in an electrolyte such as sea water, provide surface or a wood surface it will, when immersed in an electrolyte such as sea water, provide millions of small individual batteries that act to prevent the attachment of marine animals millions of small individual batteries that act to prevent the attachment of marine animals such as Barnacles, Tunicates, Oysters, Clams and other organisms and also will serve to such as Barnacles, Tunicates, Oysters, Clams and other organisms and also will serve to retard vegetation growth on the panels exposed at antifouling stations for months or years at a retard vegetation growth on the panels exposed at antifouling stations for months or years at a time. Most of the miniscule antifouling batteries were included in a non-leachable vehicle time. Most of the miniscule antifouling batteries were included in a non-leachable vehicle suitably diluted with solvent. suitably diluted with solvent.

• Results:Results: All of the samples gave most encouraging results, but in this test two were All of the samples gave most encouraging results, but in this test two were outstanding: the 50--50 Zinc Tin and the 90% Zinc and 10% Graphite. Both outstanding: the 50--50 Zinc Tin and the 90% Zinc and 10% Graphite. Both samples were completely free of all growth, both animal and vegetative and there samples were completely free of all growth, both animal and vegetative and there was no slime giving them a rating of 10. Most of the other samples were almost free was no slime giving them a rating of 10. Most of the other samples were almost free of barnacles, and if there were barnacles they were very tiny especially in of barnacles, and if there were barnacles they were very tiny especially in comparison with barnacles growing on the wooden frames which were on average comparison with barnacles growing on the wooden frames which were on average about 20 times as large. The combination of zinc with a non-metal was striking and about 20 times as large. The combination of zinc with a non-metal was striking and further validates the voltaic cell principle.further validates the voltaic cell principle.

The Corrosion The Corrosion AdvantageAdvantage

Two Birds With One Stone?Two Birds With One Stone?

NewCo Paint

ZFLAKE Top and

Bottom

Anti-Corrosion/Anti-fouling

Marine Coating

Move Over Dust… Move Over Dust… Zinc Flake Does The Job Better Zinc Flake Does The Job Better

and At Less Costand At Less Cost• Corrosion Control At 40% Lower Loading RatesCorrosion Control At 40% Lower Loading Rates

• Less Weight In Dry FilmLess Weight In Dry Film

• Improved Pot LifeImproved Pot Life

• Improved Application CharacteristicsImproved Application Characteristics

• Proven Salt Spray PerformanceProven Salt Spray Performance

• No Change In Binder ChemistriesNo Change In Binder Chemistries

• Environmental Impacts Already Known Environmental Impacts Already Known

Why Will My Loading Rates Drop?Why Will My Loading Rates Drop?

Does Particle Shape Mean Something?Does Particle Shape Mean Something?

• A sphere has the smallest surface area of A sphere has the smallest surface area of any shape that encloses a given volume.any shape that encloses a given volume.

• A sphere encloses the largest volume of A sphere encloses the largest volume of any shape with a given surface area.any shape with a given surface area.

• A flake has 3 times the surface area of an A flake has 3 times the surface area of an equivalent volume of a sphere.equivalent volume of a sphere.

Graphic courtesy of ZRC WorldwideGraphic courtesy of ZRC Worldwide

Physical Comparison of Dust vs. FlakePhysical Comparison of Dust vs. Flake

• Area = 201 sq um (r = 4 um) Area = 201 sq um (r = 4 um)

• Tap Density = 7 gm/cm3Tap Density = 7 gm/cm3

• Typical Loading Rate = 75-90% Typical Loading Rate = 75-90%

• 11-17 lbs into a paint vehicle11-17 lbs into a paint vehicle

• Weight of 75 um dry film solvent Weight of 75 um dry film solvent based coating = 185g/m2 based coating = 185g/m2

• Salt Spray = 2000+ hours Salt Spray = 2000+ hours @ 15um DFT@ 15um DFT

• Area = 684 sq um (125 x 45 x1)Area = 684 sq um (125 x 45 x1)

• Tap Density = 2 gm/cm3Tap Density = 2 gm/cm3

• Typical Loading Rate = 35-50%Typical Loading Rate = 35-50%

• 6-10 lbs into a paint vehicle6-10 lbs into a paint vehicle

• Weight of 75 um dry film Weight of 75 um dry film solvent based coating = 53g/m2solvent based coating = 53g/m2

• Salt Spray = 2000+ hours Salt Spray = 2000+ hours @ 15um DFT@ 15um DFT

Dust Particle – 8 um sphere 8um sphere made into flake

Sphere to flakeSphere to flake

Scanning electron micrograph of zinc dustScanning electron micrograph of zinc dust Scanning electron micrograph of zinc Scanning electron micrograph of zinc flake made from dust on leftflake made from dust on left

Zinc Dust Coating After 900 Hrs Salt SprayZinc Dust Coating After 900 Hrs Salt Spray

Zinc Flake Coating After 900 Hrs Salt SprayZinc Flake Coating After 900 Hrs Salt Spray

Zinc FlakeZinc Flake• Anti-Fouling Capability EstablishedAnti-Fouling Capability Established• Industry Already Educated In It’s UseIndustry Already Educated In It’s Use• Lower Cost Than Other Active IngredientsLower Cost Than Other Active Ingredients• Corrosion Control At 40% Lower Loading RatesCorrosion Control At 40% Lower Loading Rates• Less Weight In Dry FilmLess Weight In Dry Film• Improved Pot LifeImproved Pot Life• Improved Application CharacteristicsImproved Application Characteristics• Proven Salt Spray PerformanceProven Salt Spray Performance• No Change In Binder ChemistriesNo Change In Binder Chemistries• Environmental Impacts Already Known Environmental Impacts Already Known

What Needs To Be Done?What Needs To Be Done?

Implement longer term evaluation to establish service Implement longer term evaluation to establish service life expectationlife expectation

Field test a vessel with trial coating to prove durability Field test a vessel with trial coating to prove durability and identify hull cleaning scheduleand identify hull cleaning schedule

Contact Metal Flake Technologies!Contact Metal Flake Technologies!

Thanks!Thanks!