vocs in marine coatings a technical regulatory overview ... 11:… · vocs in marine coatings – a...

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VOCs in Marine Coatings – A Technical

Regulatory Overview David Mather IPPIC Nov 2012

Marine & Protective Coatings All products supplied and technical advice or recommendations given


1. VOC legislation and why it is needed

2. Why VOC (solvent) is required in marine coatings

3. Challenges of low VOC

• Waterbased

• High Solids/Solvent Free

4. Prognosis for further VOC reductions

Agenda



Why are VOCs a problem?

• VOC’s are lost from the coating during drying and rise

into the air.

- Other sources – Industry, forests…

• VOC’s mix with other air pollutants in the atmosphere

• Other pollutants

from vehicle exhausts and

factory stacks etc

- Oxides of Nitrogen (NOx)

- Oxides of Sulphur (SOx)

• React together in presence of sunlight

NOx + SOx + VOC’s →UV→ → O3

http://images.google.co.uk/imgres?imgurl=http://keetsa.com/blog/wp-content/uploads/2007/08/smog2.jpg&imgrefurl=http://keetsa.com/blog/pollution/now-japan-has-smog-problems/&usg=__xcuTa9OiFg-iR-mTw-0RNkygf_E=&h=294&w=500&sz=32&hl=en&start=15&tbnid=QwzKA-szXYQ-uM:&tbnh=76&tbnw=130&prev=/images?q=smog+pollution&gbv=2&hl=en&sa=G



Why are VOCs a problem?

• At high enough concentrations, low level ozone causes

health problems in humans such as asthma.

• Also damages vegetation e.g. agricultural crops and forests.

O3 + Particulates → SMOG

In 2008 this was a big

problem for China when

they hosted the Olympics in Beijing. It occurs in many large

cities which have high industry and high average sunlight.

http://images.google.co.uk/imgres?imgurl=http://daac.gsfc.nasa.gov/oceancolor/locus/images/LA-smog-2.jpg&imgrefurl=http://daac.gsfc.nasa.gov/oceancolor/locus/amateur_guide_for_air_quality_000.shtml&usg=__kQBk9vTjDwKzkTfUh2FPgERwuCI=&h=224&w=400&sz=9&hl=en&start=5&tbnid=DFwZWTQIsjySMM:&tbnh=69&tbnw=124&prev=/images?q=smog&gbv=2&hl=en&sa=G



SMOG…

London 1952

London - after

Los Angeles

China- Beijing

http://images.google.co.uk/imgres?imgurl=http://i.dailymail.co.uk/i/pix/2008/08/01/article-1040437-0215ADE400000578-460_468x286_popup.jpg&imgrefurl=http://www.dailymail.co.uk/news/worldnews/article-1040437/Beijing-smog-cut-athletes-performances-20.html&usg=__T7dQ6abPD2KXmrzW89r2CSzMBdk=&h=624&w=964&sz=68&hl=en&start=12&tbnid=PAQD40euOsNDiM:&tbnh=96&tbnw=148&prev=/images?q=beiijing+smog&gbv=2&hl=en&sa=G

http://images.google.co.uk/imgres?imgurl=http://upload.wikimedia.org/wikipedia/commons/b/ba/Downtown_Los_Angeles_skyline.jpg&imgrefurl=http://commons.wikimedia.org/wiki/File:Downtown_Los_Angeles_skyline.jpg&usg=__VjRRG_L_0cWHq94OSZ2GQ8mwVXo=&h=752&w=1274&sz=226&hl=en&start=17&um=1&tbnid=jiutNbzwuIUmaM:&tbnh=89&tbnw=150&prev=/images?q=los+angeles+skyline&um=1&hl=en&sa=N



VOC legislation – 2 methods favoured by regulators

• USA approach

• Well defined coating categories with maximum

VOC limits

• Up to paint manufacturers to make sure coatings

they supply are compliant for customers

• Compliance can be challenging for paint

manufacturer

• EU Approach

• Averaging approach

• Up to shipyard to demonstrate compliance

• Compliance less challenging

• Combination of high and low VOC containing

coatings



VOC legislation impacting Marine Coatings

Averaging

Categories and Limits

USA

EU

Hong Kong

China

1

So Korea



USA – Categories and levels

Marine Vessels Bay Area

Rule 8-43

Mohave

Desert Rule

1106

San Diego

Rule 67-18

South

Coast

Rule 1106

Ventura

County

Rule 74.24

USEPA

NESHAPS

Main

Categories

Status Last

Revised

Oct 16,

2002

Last

Revised

Oct 23, 2006

Last

Revised

May 15,

1996

Last

Revised

Jan 13,

1995

Last Revised

Nov 11, 2003

CTG Aug

1997

Anti-foulant 400 400 400 400 400 400

General coating (air-

dried) 340 340 -- 340 340 340

High gloss (air-dried) 340 340 420 340 420 420

Inorganic zinc coating 340 340 340 (650 air

dried)

340 340

Organic zinc coating -- 360 340 -- 340 360

Military exterior

specialty topcoat 340

340 340 -- 340 340

Specialty interior 340 340 340 -- 340 340

Weld-through

preconstruction

primer

-- 340 -- -- -- 650



Option 1 – Capture/Filter

Fugitive

emissions

Emissions

in waste gases

Stack

material purchased

recovered

ship stores

spillages

waste

>15Tonnes VOC/annum. Target Emission

<27.3% Average VOC in wet paint

EU – Averaging Industrial Emissions Directive 2010/75/EU

Option 2 – Solvent Reduction Scheme

OR






• Waterbased



Agenda



Why is VOC (solvent) required in marine coatings?

• Reduce viscosity to aid application through standard

equipment

• Aid manufacture eg control rheology such as sag resistance

• Aid film forming properties (flow and levelling)

• Can effect drying time

• For 2pack systems, controls reactivity



Shipyard Requirements (vary….)

Korea

• Limited space for construction of new shipyards or

expansion of existing facilities

• High labour rates

• Biggest driver is production efficiency

• Fast drying

• Rapid access

• Short recoat windows

• Winter workable



Climatic Conditions – MinimumTemperatures

0

5

10

15

20

25

30

JAN FEB MAR APR MAY JUN JUL AUG SEP OCT NOV DEC

Te

mp

ara

ture

/ º

C

Month

Average Daily Minimum Temperature

Houston

Newcastle

Busan

Shanghai

Singapore



Climatic Conditions – Maximum Temperatures

0

5

10

15

20

25

30

35

40


Te

mp

ara

ture

/ º

C

Month

Average Daily Maximum Temperature

Houston

Newcastle

Busan

Shanghai

Singapore



Climatic Conditions – Average Humidity

0

10

20

30

40

50

60

70

80

90

100


Rela

tive

Hu

mid

ity %

Month

Average Relative Humidity

Houston

Newcastle

Busan

Shanghai

Singapore






• Waterbased


4. Current technologies

• Universal primers

• Biocidal Antifoulings

• Finishes


Agenda



Key Challenges for Water Based Coatings for

Marine applications

Issue Commentary

Environmental

conditions

Temp, RH, & airflow all affect use of WB coatings

Typical usable conditions: T +10oC to +40oC; RH 20-80%; min

airflow >0.1 ms-1

Underwater resistance Full immersion is currently a challenge for Water Based

Early Water Resistance Development of fast early water resistance

Cost vs Performance vs

VOC Attaining customer confidence from Water Based coatings

VOC Water Based not necessarily solvent free

Coalescing solvents = VOC



Key Challenges for Solvent Free Coatings

for Marine applications

Issue Commentary

Environmental

conditions Minimum application temperature often 5-10ºC

Environmental

conditions

Use of low MWt amines lead to carbamation under high RH

conditions

Application

Equipment Specialist equipment often needed eg twin feed, heated lines

Thickness Control Difficult to achieve 1x125µm wft

H&S Issues Use of low MWt resins generally have higher risk profiles

Drying Times Drying times often long, reduction in productivity

Pot life Dissipation of heat more difficult w/o solvent - exotherms

Flexibility High resin content, more brittle, potential to crack

O/C Intervals Overcoating intervals often short



Pot Life – Dry Time Conundrum

• Fast reactions required to compensate for slower drying in high solids

• For 1K application need to manipulate the chemistry

Time

Exte

nt

of

reacti

on

High solids

Fast reacting

↓ Short pot life

Rapid dry

Twin feed

Low solids

conventional system

↓ Long pot life

Slow reaction

Solvent provides lacquer dry effect

Ideal high

solids system

↓ Long pot life

Rapid dry






• Waterbased



Agenda



Universal Primers – typical information

• 80% VS - maintain properties to allow efficient application

• Overthickness has less effect on drying time for HS systems

• >90% - compromises needed

60% 70% 80% >90%

Resin Type Solid or

Semisolid

Semisolid or

Liquid

Liquid or Liquid

& diluent

Liquid &

diluent

Curing

mechanism

Vitrification &

curing

Vitrification &

curing Curing Curing

Typical D/T @

5ºC 8hrs 10 hrs 14 hrs 46 hrs

Typical Max

O/C 14 days 14 days 14 days 5-10 days

Typical Pot life

@25ºC 2½ hrs 1½ hrs 1 hr ½ hr



Universal primer

• Coatings which have lower VOC content but adequate

pot life under development by industry

• Any new developments likely to have increased cost



Biocidal Antifoulings

• Based on high molecular weight, non-crosslinked thermoplastic

polymers... solvent required for usable solution viscosites

• Biocides generally solid pigments and large proportion of the

paint volume...solvent required to disperse effectively and reduce

paint viscosity

• Application critical low hull roughness low emissions

...solvent required to give good application properties

• 400g/L is possible

Further reductions lead to restriction in application properties

• Large reductions possible only with change in technology and

production methods



Finishes

• Based on relatively old technology – solids generally ~50%

• Finishes have different performance requirements

• Application critical aesthetic requirement (good flow

and levelling)

• solvent required to give good application properties

• Unlike Antifoulings, no fuel savings – purely aesthetic

• Many owners do not want to pay more for better

performance

• Newer technologies can achieve high solids, but generally

also high performance and therefore higher cost

• Low VOC target for finishes will make yards uncompetitive

with current technologies



Conclusion

• Two approaches regulators choose to restrict VOC

content of marine coatings

• USA approach - categories and limits

• EU approach – averaging

• VOC content still required in marine coatings of the

future

• Application aid

• Drying in cold temperatures

• Water based technology facing challenges

• Solvent free technology introduces application, stability,

drying problems

• Legislators will set future VOC targets on best

available technology

• Products still have to be acceptable to the market



Questions……

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