Chalmers University of Technology

Lars Nordstierna Chalmers University of Technology

Formulation research in the Marine Paint Programme

Lars Nordstierna Applied Surface Chemistry Chalmers University of Technology

Lars Nordstierna Chalmers University of Technology

ANTIFOULANTS
Current biocides are not effective

WHY?

Lars Nordstierna Chalmers University of Technology

PROBLEM
Biocide small molecule

Paint polymer network

Lars Nordstierna Chalmers University of Technology

PROBLEM
Rapid leaching of biocides -> excessive use of biocides Reduced life-time

High concentrations influence paint and coating properties

Lars Nordstierna Chalmers University of Technology

PURPOSE

To prevent fouling on ship hulls while minimizing the environmental footprint

Lars Nordstierna Chalmers University of Technology

OBJECTIVE

To deliver a concept for commercially and environmentally optimized marine antifouling paint using a formulation of efficacious biocide mixture that efficiently release the biocides

Lars Nordstierna Chalmers University of Technology

THE MARINE PAINT PROGRAMME

Special Focus Project

Optimisation

Formulation

Performance

Recipes for commercially and environmentally optimised marine paints

Fundamentals

Lars Nordstierna Chalmers University of Technology

THE MARINE PAINT PROGRAMME

Special Focus Project

Optimisation

Formulation

Performance

Recipes for commercially and environmentally optimised marine paints

Fundamentals

Lars Nordstierna Chalmers University of Technology

FORMULATION RESEARCH

Lars Nordstierna Chalmers University of Technology

FORMULATION RESEARCH
Objective

To optimize the release of biocides from the paint

Strategies Binding to paint polymers Binding to nanoparticles Microencapsulation of biocides

Lars Nordstierna Chalmers University of Technology

BINDING TO POLYMERS
Idea

Interactions between medetomidine and binder

Polymer binder, immobile anchor in the coating Medetomidine imidazole functionality Methods
FTIR spectroscopy NMR spectroscopy, relaxometry and diffusometry QCM-D SPR EPR ab initio calculations

Lars Nordstierna Chalmers University of Technology

BINDING TO POLYMERS
Shtykova et al. Prog. Org. Coat. 51 (2004) 125.

Results

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. B 110 (2006) 21808. Andersson et al. J. Phys. Chem. A 114 (2010) 13153. Andersson et al. Colloid Polymer Sci. 289 (2011) 1361. Andersson Trojer et al. Vib. Spec. 61 (2012) 38.

Strong binding between medetomidine and:

- carboxyl groups of long-chain alkyd resin - sulfonate groups of modified polystyrene polymers

- Cu2+ and Zn+ ions coordinated to imidazolemethyl methacrylate copolymers

Lars Nordstierna Chalmers University of Technology

BINDING TO NANOPARTICLES
Idea

Interactions between biocides and metal oxide nanoparticles

Particles, immobile anchor in the coating Prevent premature depletion of the biocide Methods
HPLC FTIR BET NMR spectroscopy Field tests

Lars Nordstierna Chalmers University of Technology

BINDING TO NANOPARTICLES
Results
Shtykova et al. Prog. Org. Coat. 64 (2009) 20.

Biocides:

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

Oxide nanoparticles: Al2O3, CuO, MgO,

SiO2, TiO2, ZnO

Strong adsorption of medetomidine compared to other biocides Efficient release from CuO and ZnO

Lars Nordstierna Chalmers University of Technology

MICROENCAPSULATION OF BIOCIDES
Idea Two-phase compartment

Main release mechanism from micro-reservoir into coating matrix

Lars Nordstierna Chalmers University of Technology

ADVANTAGES

Prevents early depletion

High biocide concentration All possible biocides Protection from paint solvent

Lars Nordstierna Chalmers University of Technology

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

O/W emulsion
Loxley & Vincent J. Colloid Interf. Sci. 208 (1998) 49.

Suspension
Evaporation of volatile solvent Collection by sedimentation, filtration, or centrifugation

Lars Nordstierna Chalmers University of Technology

PAINT AND COMPATIBILITY

Physically/chemically stable

Re-dispersable
In paint system

Compatible
Non-destructive Promising paint additive

Lars Nordstierna Chalmers University of Technology

RELEASE STUDIES
Proof of concept

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

Free vs encapsulated biocide formulated into paints

14C-labelled

biocides leaching from coating into water

water-based paint free biocide water-based paint encapsulated biocide

oil-based paint free biocide oil-based paint encapsulated biocide

Lars Nordstierna Chalmers University of Technology

INDUSTRIAL PRODUCTION
Dichloromethane
Nordstierna et al. J. Dispersion Sci. Technol. 32 (2011) 310. Nydn et al. PCT Int. Appl. WO 2010133548 A2 20101125

Regulations and legislation

Not commercially interesting

Idea Enable industrial production of microparticles for paint Replace dichloromethane with a less toxic solvent

Lars Nordstierna Chalmers University of Technology

APPROACHES
Core-shell particles Microcomposites Replacement of hazardous dichloromethane and much more in the next presentation

Lars Nordstierna Chalmers University of Technology

MODELS AND PREDICTION

Models

HULL

Physical diffusion model

High quality data (release, size) needed Prediction Surface flux of biocide Lifetime of paint protection

Lars Nordstierna Chalmers University of Technology

PERFORMANCE
Field test

ASTM standard D3623 Standard Test Method for Testing Antifouling Panels in Shallow Submergence
Methods
Optimization Laboratory release results Predictions -> Formulation Painted panels -> Field tests

Lars Nordstierna Chalmers University of Technology

PERFORMANCE
Idea Predicted near-surface concentrations, sufficiently high for complete antifouling activity during a certain time of period Results Prediction methodology verified Encapsulated biocides, superior antifouling activity over a longer time than free biocides Effective mixtures of DCOIT, medetomidine (and CuPt, Cu2O)

Lars Nordstierna Chalmers University of Technology

PEOPLE & ACKNOWLEDGMENTS

Controlled release research

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

Funding

Mistra (The Foundation for Strategic Environmental Research) The Swedish Research Council Formas VINNOVA (The Swedish Governmental Agency for Innovation Systems)

Cooperation

The Marine Paint Programme Capeco AB, I-Tech AB, Lotrc AB, Nordox AS Annika Enejder, Dan Isaksson, Gunnar Skarnemark, Johan Hurtig, Kurt Lfgren, Vratislav Langer

Chalmers University of Technology