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7/30/2019 Deniz Boyalar
1/27
Chalmers University of Technology
7/30/2019 Deniz Boyalar
2/27
Chalmers University of Technology
Lars Nordstierna
Lars NordstiernaApplied Surface ChemistryChalmers University of Technology
Formulation research in theMarine Paint Programme
7/30/2019 Deniz Boyalar
3/27
Chalmers University of Technology
ANTIFOULANTS
Current biocides are not effective
WHY?
Lars Nordstierna
7/30/2019 Deniz Boyalar
4/27
Chalmers University of Technology
PROBLEM
Biocide small molecule
Paint polymer network
Lars Nordstierna
7/30/2019 Deniz Boyalar
5/27
Chalmers University of Technology
PROBLEM
Rapid leaching of biocides-> excessive use of biocides
Reduced life-time
High concentrations influencepaint and coating properties
Lars Nordstierna
7/30/2019 Deniz Boyalar
6/27
Chalmers University of Technology
PURPOSE
To prevent fouling on ship
hulls while minimizing theenvironmental footprint
Lars Nordstierna
7/30/2019 Deniz Boyalar
7/27
Chalmers University of Technology
OBJECTIVE
To deliver a concept for commercially
and environmentally optimized marineantifouling paint using a formulationof efficacious biocide mixture thatefficiently release the biocides
Lars Nordstierna
7/30/2019 Deniz Boyalar
8/27
Chalmers University of Technology
THE MARINE PAINT PROGRAMME
Lars Nordstierna
Fundamentals
Optimisa-
tion
Special Focus Project
Formula-
tion
Perfor-
mance
Recipes for commercially
and environmentally
optimised marine paints
7/30/2019 Deniz Boyalar
9/27
Chalmers University of Technology
THE MARINE PAINT PROGRAMME
Lars Nordstierna
Fundamentals
Optimisa-
tion
Special Focus Project
Formula-
tion
Perfor-
mance
Recipes for commercially
and environmentally
optimised marine paints
7/30/2019 Deniz Boyalar
10/27
Chalmers University of TechnologyLars Nordstierna
FORMULATION
RESEARCH
7/30/2019 Deniz Boyalar
11/27
Chalmers University of Technology
Objective
To optimize the release ofbiocides from the paint
Strategies
Binding to paint polymers
Binding to nanoparticles
Microencapsulation of biocides
Lars Nordstierna
FORMULATION RESEARCH
7/30/2019 Deniz Boyalar
12/27
Chalmers University of Technology
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
7/30/2019 Deniz Boyalar
13/27
Chalmers University of Technology
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.
7/30/2019 Deniz Boyalar
14/27
Chalmers University of Technology
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
7/30/2019 Deniz Boyalar
15/27
Chalmers University of Technology
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
Lars Nordstierna
Shtykova et al.Prog. Org. Coat.64 (2009) 20.
BINDING TO NANOPARTICLES
7/30/2019 Deniz Boyalar
16/27
Chalmers University of Technology
Idea
Two-phase compartment
Main release mechanism
from micro-reservoirinto coating matrix
Lars Nordstierna
MICROENCAPSULATION OF BIOCIDES
7/30/2019 Deniz Boyalar
17/27
Chalmers University of Technology
ADVANTAGES
Prevents early depletion
High biocide concentration
All possible biocides
Protection from paint solvent
Lars Nordstierna
7/30/2019 Deniz Boyalar
18/27
Chalmers University of Technology
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.
7/30/2019 Deniz Boyalar
19/27
Chalmers University of Technology
PAINT AND COMPATIBILITY
Physically/chemically stable
Re-dispersable
In paint system
Compatible
Non-destructive
Promising paint additive
Lars Nordstierna
7/30/2019 Deniz Boyalar
20/27
Chalmers University of Technology
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
7/30/2019 Deniz Boyalar
21/27
Chalmers University of Technology
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
L N d ti
7/30/2019 Deniz Boyalar
22/27
Chalmers University of TechnologyLars Nordstierna
APPROACHES
Core-shell particles
Microcomposites
Replacement of hazardousdichloromethane
and much more in thenext presentation
Ch l U i it f T h l
L N d ti
7/30/2019 Deniz Boyalar
23/27
Chalmers University of Technology
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
Ch l U i it f T h l
L N d ti
7/30/2019 Deniz Boyalar
24/27
Chalmers University of Technology
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
Lars Nordstierna
7/30/2019 Deniz Boyalar
25/27
Chalmers University of Technology
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
7/30/2019 Deniz Boyalar
26/27
Chalmers University of Technology
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
Chalmers University of Technology
7/30/2019 Deniz Boyalar
27/27
Chalmers University of Technology