J. Mater. Sci. Technol. ›› 2021, Vol. 61: 46-62.DOI: 10.1016/j.jmst.2020.07.002
• Invited Review • Previous Articles Next Articles
Xu Hana, Jianhua Wua,b,*(), Xianhui Zhangb, Junyou Shia,**(), Jiaxin Weia, Yang Yangb, Bo Wub, Yonghui Fenga
Received:
2020-02-25
Revised:
2020-04-12
Accepted:
2020-04-30
Published:
2021-01-20
Online:
2021-01-20
Contact:
Jianhua Wu,Junyou Shi
Xu Han, Jianhua Wu, Xianhui Zhang, Junyou Shi, Jiaxin Wei, Yang Yang, Bo Wu, Yonghui Feng. Special issue on advanced corrosion-resistance materials and emerging applications. The progress on antifouling organic coating: From biocide to biomimetic surface[J]. J. Mater. Sci. Technol., 2021, 61: 46-62.
Condition | ΔRT | ΔSP % | Fuel savings 2020 million tonnes | Money savings $billions |
---|---|---|---|---|
Hydraulically smooth surface | 0 | 0 | 0 | 0 |
Deteriorated coating | 23 | 10 | 44 | 22 |
Heavy slime | 41 | 21 | 92 | 46 |
Small calcareous fouling | 69 | 35 | 160 | 80 |
Medium calcareous fouling | 105 | 54 | 253 | 127 |
Heavy calcareous fouling | 162 | 86 | 408 | 204 |
Table 1 Estimation of annual additional shaft power and fuel savings due to the selection of the fouling control method (Schultz [8] and IMO assuming 2020 data based on the horizontal dynamic smoothing of the ship's outer shell).
Condition | ΔRT | ΔSP % | Fuel savings 2020 million tonnes | Money savings $billions |
---|---|---|---|---|
Hydraulically smooth surface | 0 | 0 | 0 | 0 |
Deteriorated coating | 23 | 10 | 44 | 22 |
Heavy slime | 41 | 21 | 92 | 46 |
Small calcareous fouling | 69 | 35 | 160 | 80 |
Medium calcareous fouling | 105 | 54 | 253 | 127 |
Heavy calcareous fouling | 162 | 86 | 408 | 204 |
Fig. 2. Release kinetics of three biocide-based antifouling coatings: (a) contact leaching coating, (b) controllable depletion coating, (c) self-polishing coating. Copyright ? 2009 Woodhead Publishing Limited.
Fig. 3. (a) Main reaction of the general chemical structure of the hydrolyzable polymethacrylic acid copolymer with seawater, (b) killing mechanism of the biocide AF coating prevents bioadhesion through its toxic effects.
Antifouling system | Since | Binder | Biocide | Mode of action | Key advantages | Key disadvantages | Representative product | Lifetime (month) | Overall cost | Ref. |
---|---|---|---|---|---|---|---|---|---|---|
Contact Leaching Coatings | 1950 | insoluble vinyl,expoxy,acrylc or chlorinated rubber polymers | Copper,Zinc or iron oxides | · Water-soluble biocide penetrates into insoluble matrix · Hydrolysis with biocide release | · Strong mechanical strength | · Biocide return visits are gradually reduced and released into the environment · Short lifetime · Legislative constraints | - | < 24 | - | [ |
Controlled Depletion Coatings | 1955 | Rosin or its dervatives | Copper and Zinc oxide with or without organometallic compounds | Biocides rely on the physical dissolution of soluble matrix (rosin) to release slowly in seawater | · A wide range of invertebrates | · Biocide release is difficult to control · Cu persists in the environment · Short lifetime · Legislative constraints | Interspeed 340 Interspeed 245 | 24-36 | 50 $/m2 15.2$/m2/year | [ |
Self- Polishing Coatings | 1986 | Acrylic or methacrylic acid copolymer | Zinc oxide and Copper oxide or insoluble pigments | Promotes slow and stable release of Cu2O/ZnO by hydrolysis of matrix (methacrylate) | · Effective against invertebrate fouling · Biocide release rate is stable · Anti-fouling activities exist throughout the application period | · The effect of Cu on non-target organisms · Biocide released into the environment · Subject to legislation | Jotun(Sea Quantum) IP(intersmooth Ecoflex SPC) | 60 | 75 $/m2 15 $/m2/year | [ |
Fouling Release Coating | 1993 | Silicone resin or fluoropolymer | Non-biocidal | Low surface energy with silicone and fluoropolymer for low surface adhesion | · Effectively reduce dirt adhesion strength · No biocide release, no legislative restrictions · Saving fuel · Long lifetime | · High initial cost · Self-cleaning efficiency is less than <8 knots · Susceptible to mechanical damage | Intersleek 700 Intersleek 900 | >60 | 116 $/m2 11.6 $/m2/year | [ |
Table 2 Comparative performance of biocide-based antifouling technologies and fouling release coatings.
Antifouling system | Since | Binder | Biocide | Mode of action | Key advantages | Key disadvantages | Representative product | Lifetime (month) | Overall cost | Ref. |
---|---|---|---|---|---|---|---|---|---|---|
Contact Leaching Coatings | 1950 | insoluble vinyl,expoxy,acrylc or chlorinated rubber polymers | Copper,Zinc or iron oxides | · Water-soluble biocide penetrates into insoluble matrix · Hydrolysis with biocide release | · Strong mechanical strength | · Biocide return visits are gradually reduced and released into the environment · Short lifetime · Legislative constraints | - | < 24 | - | [ |
Controlled Depletion Coatings | 1955 | Rosin or its dervatives | Copper and Zinc oxide with or without organometallic compounds | Biocides rely on the physical dissolution of soluble matrix (rosin) to release slowly in seawater | · A wide range of invertebrates | · Biocide release is difficult to control · Cu persists in the environment · Short lifetime · Legislative constraints | Interspeed 340 Interspeed 245 | 24-36 | 50 $/m2 15.2$/m2/year | [ |
Self- Polishing Coatings | 1986 | Acrylic or methacrylic acid copolymer | Zinc oxide and Copper oxide or insoluble pigments | Promotes slow and stable release of Cu2O/ZnO by hydrolysis of matrix (methacrylate) | · Effective against invertebrate fouling · Biocide release rate is stable · Anti-fouling activities exist throughout the application period | · The effect of Cu on non-target organisms · Biocide released into the environment · Subject to legislation | Jotun(Sea Quantum) IP(intersmooth Ecoflex SPC) | 60 | 75 $/m2 15 $/m2/year | [ |
Fouling Release Coating | 1993 | Silicone resin or fluoropolymer | Non-biocidal | Low surface energy with silicone and fluoropolymer for low surface adhesion | · Effectively reduce dirt adhesion strength · No biocide release, no legislative restrictions · Saving fuel · Long lifetime | · High initial cost · Self-cleaning efficiency is less than <8 knots · Susceptible to mechanical damage | Intersleek 700 Intersleek 900 | >60 | 116 $/m2 11.6 $/m2/year | [ |
Coating | Characteristics | Relative fouling resistance and FR performances | Ref. |
---|---|---|---|
PDMS-PUa with 0-10 wt.% DCOIT | E = 0.20-0.81 MPa | Control: PDMS | [ |
Repairing efficiency = 41-100% | ↓Static antifouling performance | ||
↓Barnacle adhesion strength | |||
SBMA-PDMS-SBMA + polyurethane | θw = 100o±2o | Control: IS900 | [ |
↑Removal of Halomonas pacifica and the diatom (microalga) Naviculaincerta | |||
γs = 19 ± 1 mJ m-2 | ↑Settlement of sporelings of Ulva linza | ||
15% PCL-PDMS-PCL + PDMS and PDES | θw,a = 115.8o±0.7o | Controls: PS, PVC | [ |
θw,r = 55.4o±2.7o | ↓Settlement of A. amphitritelarvae | ||
γs = 16.3 ± 2.2 mJ m-2 | ↑The fouling release ability | ||
1-5%silicone oil-modified SiPU | θw = 102o | Controls: IS700, IS900 | [ |
θMethylene = 69o±2o | ↓Barnacle (Amphibalanus amphitrite) and mussels (Geukensia demissa) adhesion strength | ||
γs = 17 ± 0.9 mJ m-2 | ↑Removal of microalgae (Navicula incerta) and macroalgae (Ulva linza) | ||
Silicone oils nanoscale HCs | θw = 106.92o±0.87o | Control: glass | [ |
θhexadecane = 22.89o±0.9o | ↓Attachment of BSA and bacterial | ||
γc = 24.38 ± 0.13 mN m-1 | |||
PEO-PDMS + bis(Si-OH)polydimethylsiloxane | θw,a = 87 ± 1o | Control: PDMS | [ |
θw,r = 78 ± 1o | ↓Adsorption of BSA protein | ||
1 wt.% micro-nano ZnO modified PDMS-PTU | θw = 115.0o±1.2o | Controls: AlMg3, PVC, and pure PTU | [ |
↑Coating mechanical properties | |||
γc = 20.9 ± 0.8 mN m-1 | ↓Barnacle adhesion strength | ||
0.5 wt.% TiO2 NPs modified PDMS | θw = 75.0o±0.8o | ↑Field test in the seawater for AF performance and self-cleaning performance | [ |
PDMS/Ag@SiO2 core-shell nanocomposite (5 wt.%) | θw = 156o±0.2o | Control: RTV11 | [ |
↑Coating mechanical strength | |||
γc = 11.15 mN m-1 | ↑Remove different bacteria and self-cleaning properties | ||
QAS-Tethered PDMS Coatings | γc = 17.0 ± 0.5 mN m-1 | Controls:IS700,IS900 | [ |
↓Biomass retention for all three microorganisms (C. lytica, H. pacifica, N. incerta) | |||
Aminopropylsilyl-containing xerogels | θw = 57o±1o | Control: PDMS | [ |
γc = 25.2 ± 0.7 mN m-1 | ↑Removal of Navicula | ||
↑Settlement of B. amphitrite | |||
Pentablock copolymers Blends with PDMS | θw = 106o± 1o | Controls: PDMS,Glass | [ |
θhexadecane =64o ± 1o | ↓HSA adsorption on test surfaces | ||
γc = 15.8 mN m-1 | ↑Percent removal of sporelings of U. linza | ||
Sylgard 184 PDMS is infused with silicone oil | θoil = 30o | Controls: PDMS,IS700,IS900 | [ |
E = 0.8 ± 0.1 MPa | ↓Mussel adhesion strength |
Table 3 Siloxane-containing FRCs found in the literature.
Coating | Characteristics | Relative fouling resistance and FR performances | Ref. |
---|---|---|---|
PDMS-PUa with 0-10 wt.% DCOIT | E = 0.20-0.81 MPa | Control: PDMS | [ |
Repairing efficiency = 41-100% | ↓Static antifouling performance | ||
↓Barnacle adhesion strength | |||
SBMA-PDMS-SBMA + polyurethane | θw = 100o±2o | Control: IS900 | [ |
↑Removal of Halomonas pacifica and the diatom (microalga) Naviculaincerta | |||
γs = 19 ± 1 mJ m-2 | ↑Settlement of sporelings of Ulva linza | ||
15% PCL-PDMS-PCL + PDMS and PDES | θw,a = 115.8o±0.7o | Controls: PS, PVC | [ |
θw,r = 55.4o±2.7o | ↓Settlement of A. amphitritelarvae | ||
γs = 16.3 ± 2.2 mJ m-2 | ↑The fouling release ability | ||
1-5%silicone oil-modified SiPU | θw = 102o | Controls: IS700, IS900 | [ |
θMethylene = 69o±2o | ↓Barnacle (Amphibalanus amphitrite) and mussels (Geukensia demissa) adhesion strength | ||
γs = 17 ± 0.9 mJ m-2 | ↑Removal of microalgae (Navicula incerta) and macroalgae (Ulva linza) | ||
Silicone oils nanoscale HCs | θw = 106.92o±0.87o | Control: glass | [ |
θhexadecane = 22.89o±0.9o | ↓Attachment of BSA and bacterial | ||
γc = 24.38 ± 0.13 mN m-1 | |||
PEO-PDMS + bis(Si-OH)polydimethylsiloxane | θw,a = 87 ± 1o | Control: PDMS | [ |
θw,r = 78 ± 1o | ↓Adsorption of BSA protein | ||
1 wt.% micro-nano ZnO modified PDMS-PTU | θw = 115.0o±1.2o | Controls: AlMg3, PVC, and pure PTU | [ |
↑Coating mechanical properties | |||
γc = 20.9 ± 0.8 mN m-1 | ↓Barnacle adhesion strength | ||
0.5 wt.% TiO2 NPs modified PDMS | θw = 75.0o±0.8o | ↑Field test in the seawater for AF performance and self-cleaning performance | [ |
PDMS/Ag@SiO2 core-shell nanocomposite (5 wt.%) | θw = 156o±0.2o | Control: RTV11 | [ |
↑Coating mechanical strength | |||
γc = 11.15 mN m-1 | ↑Remove different bacteria and self-cleaning properties | ||
QAS-Tethered PDMS Coatings | γc = 17.0 ± 0.5 mN m-1 | Controls:IS700,IS900 | [ |
↓Biomass retention for all three microorganisms (C. lytica, H. pacifica, N. incerta) | |||
Aminopropylsilyl-containing xerogels | θw = 57o±1o | Control: PDMS | [ |
γc = 25.2 ± 0.7 mN m-1 | ↑Removal of Navicula | ||
↑Settlement of B. amphitrite | |||
Pentablock copolymers Blends with PDMS | θw = 106o± 1o | Controls: PDMS,Glass | [ |
θhexadecane =64o ± 1o | ↓HSA adsorption on test surfaces | ||
γc = 15.8 mN m-1 | ↑Percent removal of sporelings of U. linza | ||
Sylgard 184 PDMS is infused with silicone oil | θoil = 30o | Controls: PDMS,IS700,IS900 | [ |
E = 0.8 ± 0.1 MPa | ↓Mussel adhesion strength |
Coating | Characteristics | Relative fouling resistance and FR performances | Ref. |
---|---|---|---|
MMA-F3MA | θw = 112.4o | [ | |
θDiiodomethane =96.2o | Control: silicon wafer | ||
γs = 10.6 mJ m-2 | ↓Attachment of S. aureus | ||
Si-PHEAA-C3F7 | _ | Control: silicon wafer | [ |
↓Adherent bacteria and protein adsorption | |||
(PtBA-g-PPTFMA)-co-PPEGMEMA | θw = 48.5o | Control: glass | [ |
↓Protein adsorption | |||
PS-P(E/B)-PI + F10H10-PEG550 | θw,a = 125o±3o | Control: PDMS | [ |
θw,r = 25 o±3o | ↓Removal of sporelings of Ulva linza and Navicula | ||
PFPE/PEG1100 | θw = 109.1o± 0.6o | Control: PDMS, | [ |
θhexadecane =67.6o±2.7o | ↓Settlement density of spores of Ulva | ||
γc = 13.1 mN m-1 | ↓Percentage settlement of barnacle cypris larvae | ||
Poly (dimethyl siloxane)-fluoroalkyl | θw,a = 113o±2o | Controls:PDMS,PS | [ |
↑Percentage removal of sporelings of U. linza | |||
θw,r = 21o ±2o | ↓Settlement of B. amphitritecyprids | ||
↓Critical removal stress of adult barnacles | |||
Fluorinate-alkyl bearing silanes (FTSi) | θw,a = 113o | Control: commercial regular paint | [ |
θw,r = 74o | ↓Adherent bacteria and protein adsorption | ||
Poly (dimethylsiloxane) block PEGylated-fluoroalkyl modified polystyrene | θw = 125o±2o | Control: PDMS | [ |
γs = 14.6 mJ m-2 | ↑Percentage removal of sporelings of Ulva | ||
Poly (ethylene glycol)-fluoroalkyl + PDMS | γc = 25 mN m-1 | Control: PDMS | [ |
↓Attachment strength of sporelings of U. linza | |||
↓Percentage settlement of B. amphitritecyprids | |||
MEF-SiMA | θw,a = 106o | Control: PDMS | [ |
θw,r = 75o | ↓Percent removal of sporelings of U. linza | ||
Fluoropolymer-polydimethylsiloxane-poly (ethylene glycol) | θw = 73o±2o | Control:Sylgard 184 PDMS | [ |
E = 7.1 MPa | ↓Protein adsorption |
Table 4 Fluoropolymer-based FRCs in the references.
Coating | Characteristics | Relative fouling resistance and FR performances | Ref. |
---|---|---|---|
MMA-F3MA | θw = 112.4o | [ | |
θDiiodomethane =96.2o | Control: silicon wafer | ||
γs = 10.6 mJ m-2 | ↓Attachment of S. aureus | ||
Si-PHEAA-C3F7 | _ | Control: silicon wafer | [ |
↓Adherent bacteria and protein adsorption | |||
(PtBA-g-PPTFMA)-co-PPEGMEMA | θw = 48.5o | Control: glass | [ |
↓Protein adsorption | |||
PS-P(E/B)-PI + F10H10-PEG550 | θw,a = 125o±3o | Control: PDMS | [ |
θw,r = 25 o±3o | ↓Removal of sporelings of Ulva linza and Navicula | ||
PFPE/PEG1100 | θw = 109.1o± 0.6o | Control: PDMS, | [ |
θhexadecane =67.6o±2.7o | ↓Settlement density of spores of Ulva | ||
γc = 13.1 mN m-1 | ↓Percentage settlement of barnacle cypris larvae | ||
Poly (dimethyl siloxane)-fluoroalkyl | θw,a = 113o±2o | Controls:PDMS,PS | [ |
↑Percentage removal of sporelings of U. linza | |||
θw,r = 21o ±2o | ↓Settlement of B. amphitritecyprids | ||
↓Critical removal stress of adult barnacles | |||
Fluorinate-alkyl bearing silanes (FTSi) | θw,a = 113o | Control: commercial regular paint | [ |
θw,r = 74o | ↓Adherent bacteria and protein adsorption | ||
Poly (dimethylsiloxane) block PEGylated-fluoroalkyl modified polystyrene | θw = 125o±2o | Control: PDMS | [ |
γs = 14.6 mJ m-2 | ↑Percentage removal of sporelings of Ulva | ||
Poly (ethylene glycol)-fluoroalkyl + PDMS | γc = 25 mN m-1 | Control: PDMS | [ |
↓Attachment strength of sporelings of U. linza | |||
↓Percentage settlement of B. amphitritecyprids | |||
MEF-SiMA | θw,a = 106o | Control: PDMS | [ |
θw,r = 75o | ↓Percent removal of sporelings of U. linza | ||
Fluoropolymer-polydimethylsiloxane-poly (ethylene glycol) | θw = 73o±2o | Control:Sylgard 184 PDMS | [ |
E = 7.1 MPa | ↓Protein adsorption |
Fig. 7. Schematic representation of an amphiphilic polymer coating and phase separation surface (a green hydrophilic polyethylene glycol segment and a blue lipophilic fluoropolymer segment).
Coating | Characteristics | Relative fouling resistance and FR performances | Ref. |
---|---|---|---|
HBFP-PEG(14-55%) | θw,a = 80.4o ± 3.3o | [ | |
θw,r = 50.0o ± 4.5o | |||
θDM,a = 61.2o ± 1.1o | Control: glass | ||
θDM,r = 46.8o ± 3.0o | ↓Adsorption of bovine serum albumin (BSA) | ||
γs = 30.07 mJ m-2 | ↑Percentage removal of attached Ulva zoospores | [ | |
γsd = 23.47 mJ m-2 | ↓Settlement of green fouling alga Ulva spores | ||
γsp = 6.6 mJ m-2 | |||
FluoroPEG-co-fluoromethacrylate (FPEG-FA) | θw = 114o ± 0.8o | Control: Teflon | [ |
θhexadecane = 66o | ↓Protein adsorption | ||
Methacrylate-based copolymer containing perfluoroalkylated OEG | θw = 10o ± 3o | Control:bare substrate | [ |
↓Protein adsorption | |||
PDMS-based surface-active block copolymers | θw = 70o ± 0.5o | Control: PDMS | [ |
↑Removal of Navicula incerta and U. linza | |||
Si-PHEAA-PFMA | θw = 46o | Control:silicon wafer | [ |
↓Adsorption of bovine serum albumin (BSA) |
Table 5 Amphiphilic copolymer coatings appearing in the references.
Coating | Characteristics | Relative fouling resistance and FR performances | Ref. |
---|---|---|---|
HBFP-PEG(14-55%) | θw,a = 80.4o ± 3.3o | [ | |
θw,r = 50.0o ± 4.5o | |||
θDM,a = 61.2o ± 1.1o | Control: glass | ||
θDM,r = 46.8o ± 3.0o | ↓Adsorption of bovine serum albumin (BSA) | ||
γs = 30.07 mJ m-2 | ↑Percentage removal of attached Ulva zoospores | [ | |
γsd = 23.47 mJ m-2 | ↓Settlement of green fouling alga Ulva spores | ||
γsp = 6.6 mJ m-2 | |||
FluoroPEG-co-fluoromethacrylate (FPEG-FA) | θw = 114o ± 0.8o | Control: Teflon | [ |
θhexadecane = 66o | ↓Protein adsorption | ||
Methacrylate-based copolymer containing perfluoroalkylated OEG | θw = 10o ± 3o | Control:bare substrate | [ |
↓Protein adsorption | |||
PDMS-based surface-active block copolymers | θw = 70o ± 0.5o | Control: PDMS | [ |
↑Removal of Navicula incerta and U. linza | |||
Si-PHEAA-PFMA | θw = 46o | Control:silicon wafer | [ |
↓Adsorption of bovine serum albumin (BSA) |
Coating | Characteristics | Relative fouling resistance and FR performances | Ref. |
---|---|---|---|
Core-crosslinked PFMA-b-PDMAPM | θw = 70o | Control: glass | [ |
θDiiodomethane = 55o | ↓Adsorption of bovine serum albumin | ||
PMPS-b-(PHEMA-co-PMPC) grafted to the surfaces of HMS | θw = 31.2o | Control: PU | [ |
↓BSA adsorption | |||
SOSA hydrogel | θw = 25o±0.9o | Control: PDMS | [ |
θoil = 159o±3o | ↓Settlement of Navicula and Nitzschia closterium | ||
P(SBMA-co-AA-co-HEMA) + thiol modification of silicon wafers | θw = 13o | Control: silicon wafer | [ |
↑Prevention of bacterial attachment | |||
Protein adsorption | |||
Hydrogel/AgNPs Network &Silicone Network | θw = 103o | Control: blank | [ |
↓Colonies of E. coli incubated on agar plates | |||
↓Settlement of Chlorella, Phaeodactylum tricornutum and Navicula | |||
AA-MMA-TIPSMA | θw = 93o | Control:PS | [[ |
↓Protein adsorption | |||
↓Average density of barnacle Balanus albicostatus |
Table 6 Hydrogel coatings referred to in the references.
Coating | Characteristics | Relative fouling resistance and FR performances | Ref. |
---|---|---|---|
Core-crosslinked PFMA-b-PDMAPM | θw = 70o | Control: glass | [ |
θDiiodomethane = 55o | ↓Adsorption of bovine serum albumin | ||
PMPS-b-(PHEMA-co-PMPC) grafted to the surfaces of HMS | θw = 31.2o | Control: PU | [ |
↓BSA adsorption | |||
SOSA hydrogel | θw = 25o±0.9o | Control: PDMS | [ |
θoil = 159o±3o | ↓Settlement of Navicula and Nitzschia closterium | ||
P(SBMA-co-AA-co-HEMA) + thiol modification of silicon wafers | θw = 13o | Control: silicon wafer | [ |
↑Prevention of bacterial attachment | |||
Protein adsorption | |||
Hydrogel/AgNPs Network &Silicone Network | θw = 103o | Control: blank | [ |
↓Colonies of E. coli incubated on agar plates | |||
↓Settlement of Chlorella, Phaeodactylum tricornutum and Navicula | |||
AA-MMA-TIPSMA | θw = 93o | Control:PS | [[ |
↓Protein adsorption | |||
↓Average density of barnacle Balanus albicostatus |
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