BIOCIDES AND PAINTSmy.americanchemistry.com/download/Presentation... · et.al., Int’l...

ANTIFOULING BIOCIDES AND PAINTS

Presented by

ACC Biocides Panel and

NPCA Marine Antifoulants Committeeto

USEPA Antimicrobial Division8 June 2005

2

Presenters

National Paint and Coatings AssociationJohn Kelly

International Paint

ACC Biocides PanelJames Hagan

Rohm and Haas Company

3

Agenda

• Antifoulants (AF) – What and Why

• What is Fouling?

• AF Biocides

• AF Paint Chemistry

• Commercial and Pleasure Craft Ship Painting

• Regulations Impacting AF Paints

• Industry Safety Programs

• Applying AF Paints

• Commercializing Antifoulants and AF Paints

• Conclusions

4

Agenda



• AF Biocides







• Conclusions

5

Antifouling Paints Industry

• Commercial Industry (cargo and military ships)

– ~ $ 80 Million annually– Predominantly marine

• Pleasure Craft– ~ $ 40 – 50 Million annually– Marine and freshwater

6

Fouling is an ancient problem

• 500 BC - 1800 AD copper sheets over wood planking

• 1800’s copper sheets over iron (boats often sank)

• 1850 -1960 coatings with oxides and other compounds of Cu, Hg, As, Pb (worker exposure problems with Hg, As and Pb)

http://www.abc.se/~m10354/pic/mar/olympias.jpg

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• 1960 TBT with Cu, major improvement in paint properties and antifouling performance, allowed the phase out of Hg, As and Pb.

• 1980’s Damage to shellfish and fish noted, TBT control measures begin

• 1990’s Japan bans TBT and develops alternatives based on replacement of TBT with booster biocides.

Cu continues to be the major antifouling solution.

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• 2001 IMO treaty banning TBT application effective 1 Jan 2003

• 2003 4 Leading paint companies stop use of TBT AF paints globally

Cu and TBT alternative actives

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FOULING PREVENTION THE NEED

• ALL SHIPS MUST CONTROLFOULING ON UNDERWATERHULL TO:

•• ATTAIN OPTIMAL SPEED:2% - 12% SPEED LOSS.

•• MINIMIZE OPERATING EXPENSES:6% TO 45% INCREASE IN FUEL

• FOULING PREVENTION IS DIFFICULT BECAUSE ORGANISMS INCLUDE: ANIMALS, PLANTS, ALGAE, BACTERIA, etc.

ANIMALS PLANTS OTHERBARNACLES ALGAE BACTERIATUBEWORMS SPONGESMOLLUSKS

10

The Cost of Not Using Antifoulants

Economics• antifoulants save ~ $4 Billion annually

• reduced fuel usage

• less frequent dry-docking, reduced maintenance costs

• maintains structural integrity

Environmental• antifoulants reduce consumption of oil

• reduce pollution

• Reduce CO2 production (~ 200 million tons annually)

• Reduce SO2 production (~ 5 million tons annually)

• protects local and endangered species by control spread of invasive species

11

The Ideal Antifoulant

• Efficacious

• Rapid degradation or deactivation in the environment

• Limited bioavailability to marine organisms

• Minimal toxicity to marine organisms atconcentrations present in the environment

• Minimal bioaccumulation of toxicologically significant compounds

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What is Fouling?

Large ocean-going vessels

Small pleasure craft

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Major Fouling Organisms

Slime Formers Soft Fouling Hard Fouling

Bacteria Hydroids Barnacles

Diatoms Tunicates Mussels

Algae Bryozoans Tubeworms

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Soft Fouling: Up to 10% drag increase

Enteromorpha (“Marine Grass”)

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Hard Fouling: Up to 40% drag increase

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Importance of Roughness (Fouling)

% FUEL PENALTY vs. INCREASED ROUGHNESS

0.0%2.0%4.0%6.0%8.0%

10.0%12.0%

200

250

300

350

400

450

500

550

600

650

700

750

800

850

900

950

1000

Roughness (microns)

“Fuel Economy due to Improvement in Ship Hull Surface Condition”,R.L.Townsinet.al., Int’l Shipbuilding Progress, 33 (383), 1986, 127-130.

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Controlling Fouling

Antifouling Active Ingredients – Past

• Elbow Grease – manual scraping• Pitch• Copper• Metal Ships—Galvanic Effects• Creosote• Arsenicals• Organotins

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International Maritime Organization (IMO) TreatyOctober 18, 2001

International Convention on the Control of Harmful Anti-fouling Substances on Ships, 2001

• Effective 1 January 2003 - ships shall not apply or re-apply organotin which act as biocides in antifouling systems

• Effective 1 January 2008 - ships shall not bear organotins which act as biocides in anti-fouling systems on their hulls

Will enter into force with 25 countries with 25% of the worlds Tonnage

US and Europe key in ratification process because of ship traffic

Treaty has been ratified by 10 countries with 10.18% of the worlds tonnage (12/31/2004)

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Controlling Fouling

Antifouling Active Ingredients – Present

• Copper Family» Cuprous Oxide» Cuprous Thiocyanate» Metallic Copper

• Zinc Omadine• Irgarol• Isothiazolone

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Agenda



• AF Biocides







• Conclusions

21

Antifouling Paint Chemistry

• Antifoulant active ingredient and polymer in the paint formulation are critical

• Main function of antifouling paints is to keep hull bottoms smooth and clean to minimize drag

• Paint performance is dependent on long term, consistent control of the active ingredient release

• Consistent protection = Consistent antifoulant release

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AF Coating Types

•• Continuous ContactDiffusion controlledVinyl-rosin based

• AblativeMechanical erosionMetal resinates

• Self PolishingHydrolyzing binderAcrylate based

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AF Coating Types



• Self PolishingHydrolyzing binderAcrylate

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Continuous Contact Coatings

Controlled DepletionRate controlled by solublecomponent (rosin)

Depletion layer develops reducing efficacy.

Scrub depletion layer to rejuvenate efficacy

Fresh Coating (t0)

In-use Coating (t1)

“Rejuvenation” (t2)

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Continuous Contact Coatings

• Typically 2 years service

• Biocide: Copper and perhaps another biocide

• Rosin is more soluble at high pH causing release of the biocide from coating

• Coating develop depletion layer at water interface

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AF Coating Types




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Ablative Coatings

Freshly Coated (t0)• Release controlled by physical erosion

• Biocide primarily released during ship movement In-use coating (t1)

Nearing end of life (t2)

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Ablative Coatings

• Typically ~ 3 year service life

• More homogenous film composition than controlled depletion coatings

• Less biocide required than controlled depletion coatings

• Direct release of biocide from coating – no waiting for dissolution

• Less tendency to develop a depletion zone

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AF Coating Types




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Self-Polishing Coatings

Biocide release via hydrolysis of resin in water

t0

t1Hydrolyzable polymercontaining biocide

Pigment for color

t2

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•• Typically 3-5 year service life

• Practically continuous release

• Direct release of biocide from coating

• Utilizes copper and cobiocide

• Little tendency to develop non-functional leach layer (essentially no antifouling active)

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Ship with self-polishing paint after 2 years in service

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Agenda



• AF Biocides







• Conclusions

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Commercial Ship Building and Maintenance

• ~ $ 80 million AF Paints• Ship Building

Bath, MA

Philadelphia, PA

Newport News, VASan Diego, CA

Mobile, AL

Pascagoula, MS

Avondale, LA

Lockport, LA

Homer, LA

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Commercial Ship Building and Maintenance

Ship Dry Docking (Maintenance)

Boston, MA

Norfolk, VA

Charleston, SC

Tampa, FL

Jacksonville, FL

Puget Sound, WA

Portland, OR

San Francisco, CA

San Diego, CA

Pearl Harbor, HA

Mobile, AL

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Pleasure Craft Painting Industry

• 12,850,000 Registered Boats in the United States (2003)(Each State Defines the Size of Boats for Registration Purposes)

• 72,000,000 Recreational Boaters (2003)

• 5,500,000 Water-skiing Enthusiasts (2003)

• 500-600,000 Gallons of Antifouling Paint Sold Annually in US

• $40 - $50,000,000 Antifouling Paints Sold Annually in the US

• Applicators: Estimated 50% DIYs and 50% Boatyard or OEM Professionals

• Majority of DIY paint in marinas or boatyards

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AF Paint — Manufacturing

• Raw Materials Pumped or Poured Into Vessel

• Vessel Closed

• Materials Blended by High-speed Dispersion

• Specified Level of Dispersion Obtained

• Material Pumped into Let-down Tank

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• Solvent Added

• Blended by Slow-speed Mixing

• Sampled for Quality Control Checks

• Batch Adjusted As Required

• Filled-off Into Required Pack Sizes

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• Typical Batch Size → 700 - 900 Gallons

• Batch Frequency → by Product Line and Color (2-20)

• Major Colors → Red, Brown, Black (Commercial)Black, Blue, Green (Pleasure)

• Batch Processing Time → Eight (8) Hours

• Raw Material Loading Time → Two (2) Hours

• Active Ingredient Addition Time → 15 Minutes

• Limited Opportunity for Operator Exposure

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AF Paint — Health and Safety

• Highly Trained Operators (1 to no more than 3)

• Review Hazardous Materials Identification System Codes for Raw Materials

• Comply With OSHA Regulations

• Comply With USEPA FIFRA Label

• Operator Wears Personal Protective Equipment [PPE]to Prevent Chemical Exposure As Stipulated on Production “Batch Ticket”

• Gloves, Safety Glasses / Goggles, Coveralls, Safety Shoes and Appropriate Respirator

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Pleasure Craft AF Paint Types

• Erosion: Oldest Technology – Soft Rosin-basedCopper-based

→ For Work Boats or Low-to-Moderate Fouling

→ Advantages = Low Cost

→ Disadvantages =1) Out-Of-Water Cracking 2) Limited Fouling Control 3) Limited Life

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• Hard Film: Generally Vinyl, Acrylic or Epoxy Resin-based

Copper-based→ For General Use, Racing Hulls or Low-to-Moderate Fouling

→ Advantages = Hard Finish / Easily Burnished for Smoothness

→ Disadvantages =1) Heavy Build-up2) Must be Removed Every 5-to-7 Yrs3) Disposed in accordance to

local regulations

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Sanding a Hull Prior to Painting

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• Ablative: Modified Rosin, i.e., Vinyl, Acrylic, Polyamides(Copper With and Without Boosting Biocides)

• For All Waters and All Hulls → Advantages =

1) Excellent Performance

2) Film Wears Away With Speed and Time

3) Minimal Build-up

→ Disadvantages =

1) Wear-rate Difficult to Control

2) Wearing Films; Not Smoothing

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• Self-Polishing Copolymer: Unique Polymer Chemistry§

Usually Acrylic

Typically copper with or without boosting antifoulant

• For All Waters and All Hulls

→ Advantages =

1) Controlled Wear-rate2) No Build-up3) Smooths on Micro-level to Reduce Hull Friction and

Drag

→ Disadvantages = Can be more expensive

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AF Biocides and Functionality

• Copper Compounds: Cuprous Oxide, Cuprous Thiocyanate and Metallic Copper→ Best for Control of Hard Fouling, e.g., Barnacles, Tube

Worms, Zebra Mussels, Mussels, etc.

→ Activity = Ionize to Cu Species / Rate determined by Chlorine in water with lower rate in freshwater

• Organic Cobiocides: Zinc Omadine, Irgarol, Isothiazolone

→ Ideal for Soft Fouling, e.g., Algae and Slime

→ Activity = A Function of Water Temperature

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Agenda



• AF Biocides







• Conclusions

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AF and AF Paint — EPA and State Registrations

• Federal Registrations:→ New End-use Product = New Biocide(s)→ New End-use Product = Existing Biocide(s)→ End-use Product Registration Amendments

1) Revised Formula(s)2) Additional Color(s)3) Label Changes

→ Notifications = Change Brand Name→ Maintenance of Existing Registrations

• State Registrations:→ New Products Previously Registered with Federal

EPA→ Section 24c Registrations, i.e., “Special Needs”→ Maintenance of Existing Registrations

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AF and AF Paints Regulations

• California Pesticide Registration• California “Volatile Organic Compound”

[VOC] Emissions1) State CARB2) Regional Air Quality Management Districts:

Some Variances by District;Some Exemptions by-Volume-by-District.

3) Applies to Paints, Strippers, Cleaning Compounds,and Wipe-down Solvents

• California “Maximum Incremental Reactivity” [MIR]→ Currently Aerosols Affected by This Protocol

50

AF Paints Government Regulations

• Clean Water Act→ National Pollution Discharge Elimination System

[NPDES]1) Restrictions on Power Washing Hull Bottoms;2) Restrictions on Release of Wash-water into Streams.

→ National Surface-water Quality Criteria1) Establishes Thresholds for Pollutants in Fresh and Salt Water;2) Pre-cursor to Present State and Regional Limits on Zinc, Copper,

etc.

• National Emissions’ Standards For Hazardous Air Pollutants [NESHAP]→ 180 Chemicals Affected by This Protocol→ Fiberglass Boat Construction / Styrene Emissions→ Aluminium Boat Construction / All Paints and Coatings→ Miscellaneous Metal and Plastic Parts

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AF Paints Government Regulations

• Clean Air Act

• Airborne Particulate = PM-10 (Inhalant Less than Ten (10) Microns)→ Affects Sanding Dust Limits and Proper PPE

• OSHA→ http://www.osha.gov/SLTC/shipbuildingrepair/i

ndex.html

• Montreal Protocol→ Bans on Halogenated Hydrocarbons / Ozone-depleting

Substances

52

AF Active Ingredient and AF Paint Registration

Registration is a Global Effort• Canada• European National Authorities – European BPD• Japan• Malaysia• Australia• New Zealand• Mexico – antifoulant active ingredient

53

Agenda



• AF Biocides







• Conclusions

54

Industry Product Safety Programs

Going Beyond the Regulations

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NPCA – Coatings Care

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Program Structure/Resources

• Participation a condition of membership in NPCA

• Program focus/intent is to:– Foster effective health, safety and environmental (HSE)

management– Integrate HSE activities with corporate planning and

operations

• No third party certification requirements

• Compatible with ISO 14000, Responsible Care®

and Responsible Distribution ®

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58


S&W CC Pres. Jan 2001 Slide # 8

Policy Statements

Promote efforts to protect employees, customers, the public and the environment;Provide relevant information on the safe use and disposal of industry products to customers, and make such information available to the public on request; Make protection of health, safety and the environment an early and integral part of the organizational planning process;Comply with all legal requirements which affect operations and products; Be responsive to community concerns;Assist governments in the development of equitable and attainable standards.

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ACC – Responsible Care®

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Responsible Care®

• Responsible Care® is the American Chemistry Council’s (ACC’s) comprehensive environmental, health, safety and security performance improvement initiative.

• ACC member companies required to implement a Responsible Care Management System (RCMS ®) to manage their operations and products and respond to stakeholder concerns across the entire value chain.

• ACC member companies must achieve third-party certification (starting 2005).

• The ACC’s RC “Guiding Principles” (Policy) serve as the ethical foundation for the way members do business.

• Comparable to Coatings Care® , ISO 14000, and Responsible Distribution ®

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Responsible Care®

TransportSafety

RCMS

EnvironmentHealth &

SafetyProduct

Stewardship

EmergencyResponse

Security Outreach

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Sign and Commit to Guiding Principles

Public reporting of progress

Seek and incorporate public input

Produce safe products

Focus on health / safety / environment / security

Notify of hazards and pursue protection

Safe operations

Support education and research

Resolve past problems

Work for responsible public policies

Sharing & offering assistance

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Responsible Care® Guiding Principles

• To seek and incorporate public input regarding our products and operations.

• To provide chemicals that can be manufactured, transported, used and disposed of safely.

• To make health, safety, the environment and resource conservation critical considerations for all new and existing products and processes.

• To provide information on health or environmental risks and pursue protective measures for employees, the public and other key stakeholders.

• To work with customers, carriers, suppliers, distributors and contractors to foster the safe use, transport and disposal of chemicals.

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Responsible Care® Guiding Principles

• To operate our facilities in a manner that protects the environment and the health and safety of our employees and the public.

• To support education and research on the health, safety and environmental effects of our products and processes.

• To work with others to resolve problems associated with past handling and disposal practices.

• To lead in the development of responsible laws, regulations and standards that safeguard the community, workplace and environment.

• To practice Responsible Care® by encouraging and assisting others to adhere to these principles and practices.

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Agenda



• AF Biocides







• Conclusions

66

AF Paint – Shipyard Application (Commercial Professionals)

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AF Paint – Shipyard Application (Commercial Professionals)

• Applied Primarily by Airless Spray by Professionals in Shipyards and Dry Docks

• Applicator Wears Appropriate PPE to Prevent Chemical Exposure in accordance with hazard review and in compliance with the FIFRA label

• Application Done Generally On 1 – 5 year cycles

• Typically One (1) or Two (2) Coats at 3 - 5 Mils DFT/coat following the label instructions

68

AF Paint – Boatyard Application (professionals)

• Maximum workload in a shipyard involved with maintenance and repair of ships would be for an applicator to spray apply antifouling paint for 8 hours/day, 2 days/week, 100 days/year

• In a newbuilding yard, typical workload would be to spray apply antifouling for 8 hours/day, 20 days/year

• Actual Exposure Risk Slight due to of PPE worn

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• Applied Primarily by Roller and Brush in Boatyards

• Very Limited Application by Air Spray by Professionals in Boatyards in accordance with hazards and in compliance with FIFRA label

• Applicator Wears Appropriate PPE to Prevent Chemical Exposure

• Application Done Generally Once Per-season

• Typically One (1) or Two (2) Coats at 2.0-2.5 Mils DFT/coat following label instructions

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Roller Application

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• Typical PPE:1. Respirators as appropriate2. Head Cover3. Safety Glasses / Goggles4. Coveralls or Tyvek Suit5. Chemically resistant Gloves6. Safety Shoes7. Barrier Cream for Exposed Facial Skin

• FIFRA Label Review• OSHA-compliant Material Safety Data Sheets

are Supplied

72


• Typical Boatyard Paint Applicator in the South Applies Antifouling for 12 working hours in working week

• Typical Boatyard Paint Applicator in the Northeast Applies Antifouling for 12 working hours in a working week During Painting Season (4 months each year)

• Actual Exposure Risk Reduced significantly because of PPE worn

73

Antifouling Paint – Do-It-Yourself [DIY]

• Pleasure Crafts Range in Size from 14' to 30'

• Paint Applied once Annually or Less

• Application Primarily by Brush and Roller, niche use of aerosol

cans for outboard motors

• Normal Application = One (1) or Two (2) Coats

• PPE stipulated on product label may include Gloves, Eyewear,

Long-sleeved Cotton Shirt, Long Pants, Hat, Mask/respirator

• PPE available at point of sale

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Agenda



• AF Biocides







• Conclusions

75

Registration Data Requirements

• Amount of data (tox, efate, efficacy, exposure)– AD data “needs” (coming soon Part 158 Sub W)

• Time commitment for generating data– Toxicology Testing (3-5 years) – Environmental Fate Testing (4-6 years)

• Costs of the antifouling active ingredient data– ~ $5 – 7 Million

• AF Paint Data (tox, efficacy, exposure,)– ~ $100,000

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AF Paint Screening Procedure

Five rods per formulation (8 mm dia. x 11 cm fiberglass rods)

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AF Paint Screening Procedure

7 Months Exposure Results

Neg. Control

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AF Paints on Australian Navy Ship After 2 Years

Cu & Co-Biocide Paint

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AF Paints on Australian Navy Ship After 4.5 Years

Cu & Co-Biocide Paint

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AF Paint Testing Program

• Investigate antifoulant active in laboratory (1-2 years)

• Efficacy testing (1-2 years)

• Toxicology and Environmental Fate testing (5-6 years)

• USEPA Registration

• AF Paint Exposure testing (1-2 years)– Rods or panels

• USEPA Registration

• Ship Patch testing (1-5 years)

• Test Ships (1-3 years)

• Commercialization (full maintenance cycle qualification) 10+ years

81

Agenda



• AF Biocides







• Conclusions

82

Conclusions

• AF antifoulants and AF paints are essential to:– fuel conservation,– reducing maintenance costs and time, – reducing emissions, – protecting local and endangered species

• AF industry invests significant time and effort to:

– test and register products– ensure safety of products for people and the

environment

• Approval of a new antifouling biocide / paint can take many years, it is a global effort

83

Conclusions

• Many regulations impact the use of antifoulant actives and AF paints

• Coatings Care and Responsible Care Programs “regulate” industry beyond the regulations

• Industry and AD have a key role in enabling the availability of the newest and safest AF technologies for the consumer, the shipping industry, and the US Navy

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Questions

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