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MARINE BIOCORROSION AND NOVEL

ANTIMICROBIAL POLYMERIC

COMPOSITES

Presented by Maria Boretska Duisburg-Essen University, Germany

Biofilm Centre

MARINE BIO-CORROSION

•SALINITY 2-40% •AERATION •pH AROUND 7 •PRESENCE of H2S

•TEMPERATURE INCREASING ( AREAS CLOSE TO ENGINE) •MICRO- AND MACROFOULING WITH FOLLOWING METAL CRACKING

International Symposium on Corrosion and Fouling, April 3, 2017

HOW IT IS GROWING? • The biofouling community

is composed of FOUR stages and some of these stages can overlap or occur in parallel • Avoiding the FIRST layer of molecular fouling will avoid macrofouling! • Biofouling CAN NOT be observed only from macrofouling point – small bacteria are very important.

HOW TO PROTECT SURFACES FROM MARINE BIOCORROSION?

Seaweed

Mussels

Hydroids

Large cluster of mussels

Types of fouling Types of corrosion

Severe corrosion splash zone

Tidal zone

Accelerated low water corrosion (ALWC)

Local corrosion under cluster of mussels

Local corrosion under soil

CORROSION PREVENTION TECHNIQUES CAN BE

GENERALLY CLASSIFIED INTO 4 GROUPS:

1.Metal Selection and Surface

Conditions

2. Cathodic Protection

3. Corrosion Inhibitors

4. Coating

Variations of possible coating against fouling

planning

ordering

building operation

recycling

HOW IT IS WORKING WITH THE SHIP?

• toxic components into the

atmosphere and the marine

environment

* recoating in dry dock

* paint touch-ups

• toxic components into the

atmosphere and the marine

environment (paint)

• energy consumption

• toxic components into the

atmosphere and the marine

environment

• waste, as not all parts and

products can be recycled

PROBLEMATIC OF MARITIME CORROSION

•Corrosion progression over time in ballast tanks. •Every ship is represented with a black dot. Colors follow the IACS classification (GOOD/FAIR/POOR condition of the tank);

Research team at the Antwerp Maritime Academy (Verstraelen et al. 2009)

WHAT WE CAN DO?

- less ship building & less recycling = less emissions

- Using long-term protective coatings (more then for 25 years)

will save money and environment! - NO RE-COATING in dry

dock for the long-term coating strategy

- Using compounds which DO NOT KILL the living consortium

but JUST CONTROL the amount of sea water organisms on

the surface.

IONIC LIQUIDS – GREEN CHEMISTRY

• A huge variance to use and an exellent properties - thermal stability, non-burning, non-inflammble, hydrophobic and other…

• Two different condition water soluble and insoluble

• Anionic and cationic nature

• Connection with procariotic cell wall cause its destabilisation

• Strong anti-corrosion effect

NNCH

3

V

NNCH

3 NNCH

3

metal surface

+ + + + + + + + + + + + +

+

Cl

+

Cl

+

Cl

Schematic presentation of inhibition properties of imidazolium ionic liquids against metal corrosion in acidic medium or in NaCl solution

TOXICITY AND RELEALISE BEHAVIOUR OF IONIC LIQUIDS

The low overall toxicity of the ionic liquids supports the possible use of these components. Comparison with literature shows that there is no difference in toxicity between freshwater and marine water biota.

Release behavior of polyhexamethylene guanidine molybdate from the antifouling coating. PHMG = polyhexamethylene guanidine.

Protasov, A., Bardeau, J.-F., Morozovskaya, I., Boretska, M., Cherniavska, T., Petrus, L., Tarasyuk, O., Metelytsia, L., Kopernyk, I., Kalashnikova, L., Dzhuzha, O. and Rogalsky, S. (2017), New promising antifouling agent based on polymeric biocide polyhexamethylene guanidine molybdate. Environ Toxicol Chem. doi:10.1002/etc.3782

Antifouling agent Acute toxicity (mg/L) (Daphnia magna)

Acute toxicity (mg/L) (Danio rerio)

Reference

1.EC50 = 50% effective concentration; LC50 = 50% lethal concentration; LD50 = 50% lethal dose; PHMG = polyhexamethylene guanidine.

PHMG molybdate (LD50, 48 h) 0.7 (LD50, 96 h) 17 Present study

Copper (I) oxide (EC50, 48 h) 0.042 (LC50, 96 h) 0.075 [45]

Zinc pyrithione (EC50, 24 h) 0.002 (EC50, 96 h) 0.009 [46, 47]

Irgarol 1051 (EC50, 48 h) 7.3 (LC50, 96 h) 0.4 [48, 49]

Diuron (EC50, 48 h) 8.6 (LC50, 96 h) 3.5 (rainbow trout)

[48, 50]

Sea-Nine 211 (EC50, 48 h) 0.004 (LC50, 96 h) 0.014 (rainbow trout)

[48, 50]

Dichlofluanid (EC50, 48 h) 1.05 (LC50, 96 h) 0.03 (bluegill sunfish)

[48, 49]

Protasov, A., Bardeau, J.-F., Morozovskaya, I., Boretska, M., Cherniavska, T., Petrus, L., Tarasyuk, O., Metelytsia, L., Kopernyk, I., Kalashnikova, L., Dzhuzha, O. and Rogalsky, S. (2017), New promising antifouling agent based on polymeric biocide polyhexamethylene guanidine molybdate. Environ Toxicol Chem. doi:10.1002/etc.3782

TOXICITY DATA

Biofilm formation on the surface of control sample (a) and polyhexamethylene guanidine molybdate–based coating (b) after 28 d of cultivation (confocal laser scanning microscopy).

Painted steel bars after 129 days exposure in Dnipro River: control coating (a) and coating containing 5% (w/w) of PHMG molybdate (b).

FRESH WATER TESTS

PAINTED STEEL BARS AFTER 228 DAYS EXPOSURE IN DNIPRO RIVER: CONTROL COATING (A) AND COATING CONTAINING 5% (W/W) OF PHMG MOLYBDATE (B).

BIOMASS VALUES FOR TAXONOMIC RANKS (g / m2) ON THE SURFACE OF EXPERIMENTAL SUBSTRATES

(selected data, more information could be found in our publication)

Paint ХС-413 control

Paint XC-413/PHMG molybdate

Exposure time (days)

Exposure time (days)

Taxonomic rank

57 94 129 228 57 94 129

228

Dreissenidae 0 0 83 2128 0 1 3 23

Spongia 0 0 4,6 29 0 0 1 0

Bryozoa 0 273 659 0 0 52 15 0

Protasov, A., Bardeau, J.-F., Morozovskaya, I., Boretska, M., Cherniavska, T., Petrus, L., Tarasyuk, O., Metelytsia, L., Kopernyk, I., Kalashnikova, L., Dzhuzha, O. and Rogalsky, S. (2017), New promising antifouling agent based on polymeric biocide polyhexamethylene guanidine molybdate. Environ Toxicol Chem. doi:10.1002/etc.3782

TYPES OF IONIC LIQUIDS APPLIED FOR MARINE CORROSION PREVENTION

Type ionic liquid High concentration (in

1M H2SO4) Low concentration (in

1M H2SO4 )

C16C1-imidazolium bromide

100 mg L-1 10 mg L-1

1,3-dioctyl imidazolium bromide

400 mg L-1 40 mg L-1

C12C1-imidazolium bromide

100 mg L-1 10 mg L-1

imidazolium ionene 100 mg L-1 10 mg L-1

• Grade a steel coupons were attached to small frames, labeled and suspended in sea water in the Ostend harbor.

0,00E+00

5,00E+05

1,00E+06

1,50E+06

control c16c1 ImBr 100ml

c16c1 ImBr 10 mg

1,3-dyocil ImBr 400 mg

1,3-dyocil ImBr 40 mg

c1c1 ImCl 100 mg

C1c1 ImCl 10 mg Im Ionene 100 mg

Im ionene 10 mg

cells

/cm

²

1 MONTH OF INCUBATION

BIOFOULING ON THE STEEL COUPONS (OSTENDE, NORD SEE)

WHAT ELSE WE WANT TO DO?

• Combining the epoxy paint with a range of ionic liquids and painting steel coupons

• Biofouling testing in harbor and simulator of ballast tank condition

• Metagenomics of fouling concortium

• Microscopy and FISH Analysis

• Creating perfect non-fouling , non-toxic and low-cost paint

SHORT RESUME:

1. MARINE CORROSION IS AGGRESSIVE AND EXPENSIVE PROCESS. 2. A LOT OF INDUSTRIAL POWERS THOW ON THE FIGHTING WITH THIS PROBLEM

BUT 3.CORROSION IS A NATURAL PROCESS AND FIGHTING WITH IT IS SENSELESS. WE CAN POSTPONE CORROSION – AND WE CAN DO IT CHEAP AND IN NATURE-FRIENDLY WAY

PEOPLE WHO ARE INVOLVED IN THIS PROJECT:

• DR. G. POTTERS (AMA, Belgium)

• DR. S. ROGALSKY (IBCP, Ukraine)

• DR. M. BORETSKA (IMV, UDE, Ukraine, Germany)

• DR. S. BELLENBERG (UDE, Germany)

• DR. O. MOSHYNETS (IMBG, Ukraine)

• DR. O. SUSLOVA (IMV, Ukraine)

• DR. S. VOICHUK (IMV, Ukraine)

• R. WILLEMEN(AMA, Belgium)

• R. MESKENS(AMA, Belgium)

• CAP. DR. KRIS DE BAERE (AMA, Belgium)

THANK YOU FOR YOUR ATTENTION. ANY QUESTIONS?