Deniz Boyaları

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Chalmers University of Technology


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Lars Nordstierna

Lars NordstiernaApplied Surface ChemistryChalmers University of Technology

Formulation research in theMarine Paint Programme


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ANTIFOULANTS

Current biocides are not effective

WHY?

Lars Nordstierna


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PROBLEM

Biocide small molecule

Paint polymer network

Lars Nordstierna


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PROBLEM

Rapid leaching of biocides-> excessive use of biocides

Reduced life-time

High concentrations influencepaint and coating properties

Lars Nordstierna


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PURPOSE

To prevent fouling on ship

hulls while minimizing theenvironmental footprint

Lars Nordstierna


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OBJECTIVE

To deliver a concept for commercially

and environmentally optimized marineantifouling paint using a formulationof efficacious biocide mixture thatefficiently release the biocides

Lars Nordstierna


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THE MARINE PAINT PROGRAMME

Lars Nordstierna

Fundamentals

Optimisa-

tion

Special Focus Project

Formula-

tion

Perfor-

mance

Recipes for commercially

and environmentally

optimised marine paints


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THE MARINE PAINT PROGRAMME

Lars Nordstierna

Fundamentals

Optimisa-

tion

Special Focus Project

Formula-

tion

Perfor-

mance

Recipes for commercially

and environmentally

optimised marine paints


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Chalmers University of TechnologyLars Nordstierna

FORMULATION

RESEARCH


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Objective

To optimize the release ofbiocides from the paint

Strategies

Binding to paint polymers

Binding to nanoparticles

Microencapsulation of biocides

Lars Nordstierna

FORMULATION RESEARCH


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Idea

Interactions between medetomidine and binder

Polymer binder, immobile anchor in the coating

Medetomidine imidazole functionality

Methods

FTIR spectroscopyNMR spectroscopy, relaxometry and diffusometryQCM-DSPREPRab initio calculations

Lars Nordstierna

BINDING TO POLYMERS


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Results

Strong binding betweenmedetomidine and:

- carboxyl groups of long-chainalkyd resin

- sulfonate groups of modified

polystyrene polymers

- Cu2+ and Zn+ ions coordinated to imidazole-methyl methacrylate copolymers

Lars Nordstierna

BINDING TO POLYMERSShtykova et al.

Prog. Org. Coat.51 (2004) 125.

Shtykova et al.J. Appl. Polym. Sci. 99 (2006) 2797.

Handa et al.Prog. Org. Coat.57 (2006) 376.

Fant et al.

J. Phys. Chem. B110 (2006) 21808.

Andersson et al.J. Phys. Chem. A114 (2010) 13153.

Andersson et al.Colloid Polymer Sci.289 (2011) 1361.

Andersson Trojer et al.Vib. Spec. 61 (2012) 38.


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Idea

Interactions between biocides and metal oxide nanoparticles

Particles, immobile anchor in the coating

Prevent premature depletion of the biocide

Methods

HPLCFTIRBETNMR spectroscopyField tests

Lars Nordstierna

BINDING TO NANOPARTICLES


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Results

Biocides: Medetomidine, Chlorothalonile, Dichlofluanid,Diuron, Irgarol, Seanine, Tolylfluanid

Oxide nanoparticles: Al2O3, CuO, MgO,SiO2, TiO2, ZnO

Strong adsorption of medetomidinecompared to other biocides

Efficient release from CuO and ZnO

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Shtykova et al.Prog. Org. Coat.64 (2009) 20.

BINDING TO NANOPARTICLES


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Idea

Two-phase compartment

Main release mechanism

from micro-reservoirinto coating matrix

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MICROENCAPSULATION OF BIOCIDES


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ADVANTAGES

Prevents early depletion

High biocide concentration

All possible biocides

Protection from paint solvent

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PREPARATION

Lars Nordstierna

Emulsion

O/W emulsion

Suspension

Evaporation of volatile solvent

Collection by sedimentation,filtration, or centrifugation

Loxley & VincentJ. Colloid Interf. Sci.208 (1998) 49.

Nordstierna et al.Prog. Org. Coat.69 (2010) 49.


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PAINT AND COMPATIBILITY

Physically/chemically stable

Re-dispersable

In paint system

Compatible

Non-destructive

Promising paint additive

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Proof of concept

Free vs encapsulated biocideformulated into paints

14C-labelled biocides leaching fromcoating into water

water-based paintfree biocide

water-based paintencapsulated biocide

oil-based paintfree biocide

oil-based paintencapsulated biocide

RELEASE STUDIES

Nordstierna et al.Prog. Org. Coat.69 (2010) 45.

Lars Nordstierna

d i


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INDUSTRIAL PRODUCTION

Dichloromethane

Regulations and legislation

Not commercially interesting

Idea

Enable industrial production of microparticles for paint

Replace dichloromethane with a less toxic solvent

Lars Nordstierna

Nordstierna et al.J. Dispersion Sci. Technol.32 (2011) 310.

Nydn et al.PCT Int. Appl. WO 2010133548 A2 20101125

C f

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Chalmers University of TechnologyLars Nordstierna

APPROACHES

Core-shell particles

Microcomposites

Replacement of hazardousdichloromethane

and much more in thenext presentation

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Models

Physical diffusion model

High quality data (release, size)needed

Prediction

Surface flux of biocide

Lifetime of paint protection

Lars Nordstierna

MODELS AND PREDICTION HULL

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Field test

ASTM standard D3623Standard Test Method for Testing Antifouling

Panels in Shallow Submergence

Methods

OptimizationLaboratory release resultsPredictions->FormulationPainted panels->Field tests

Lars Nordstierna

PERFORMANCE

Ch l U i it f T h l

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IdeaPredicted near-surface concentrations,sufficiently high for complete antifoulingactivity during a certain time of period

ResultsPrediction methodology verified

Encapsulated biocides, superior antifouling activity

over a longer time than free biocides

Effective mixtures of DCOIT, medetomidine (and CuPt, Cu2O)

Lars Nordstierna

PERFORMANCE

Chalmers Uni ersit of Technolog

Lars Nordstierna


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PEOPLE & ACKNOWLEDGMENTS

Controlled release researchAdele Khavari, Alberta Mok, Alireza Movahedi,Helena Andersson, Jonatan Borg, Lars Nordstierna,Magnus Nydn, Markus Andersson, Matias Nordin,Ye Li

FundingMistra (The Foundation for Strategic Environmental Research)The Swedish Research Council FormasVINNOVA (The Swedish Governmental Agency for Innovation Systems)

CooperationThe Marine Paint ProgrammeCapeco AB, I-Tech AB, Lotrc AB, Nordox ASAnnika Enejder, Dan Isaksson, Gunnar Skarnemark,Johan Hurtig, Kurt Lfgren, Vratislav Langer

Lars Nordstierna



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