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September 12th 2019
Coatings Trends & Technologies
Teluka Galhenage, Chetan Khatri, Alex Vena, Andrew Labak,
Terry Banks, Grant Tremelling, and Philseok Kim
Novel modular additive approach for designing
biocide-free coatings to control biofouling
World Leaders in Repellent Surfaces
© 2019 Adaptive Surface Technologies
And Sticky Problems Do Matter!
Efficiency
Safety
Economic
Problems
$10B/yr more
fuels burned
More CO2 emission
3.5% of domestic
energy use goes to
waste water treatment
11% of total energy used
for defrost
Poor quality of foods
Wasted time, labor, cost
for cleaning after each batch
More chemicals, more wastes
~2M/yr HAIs, >$30B/yr
spent in the US
40% of HAI = CAUTI
7-18% of consumer
products turns
into waste
© 2019 Adaptive Surface Technologies
Tree 2(12) 364 – 369 (1987), PNAS 101 14138 – 14143 (2004),
Proc. R. Soc. B (2008), Plant Signaling & Behavior (2009), Prog. Nat. Sci. (2009)
A Clever Way to Deal With Preys ‘Sticking’
Lessons learned from Nature:
• Use Liquid Surface
• Keep the liquid by ‘chemistry’
• Keep the liquid by ‘physics'
© 2019 Adaptive Surface Technologies
We turned the lessons from Nature into a new materials design concept that we call SLIPS!
Slippery Liquid-Infused Porous Surfaces
infuse with
a lubricant
liquid/solid
being repelled
surface functionalization/
conditioningsurface
roughening
100% fully slippery liquid interface
lubricating film in and over a solid surface
• Sub-nanometer smoothness
• Excellent repellency to almost everything
• High pressure/temperature tolerance
• Self-healing characteristics
• Highly customizable system
Nature 477 443-447 2011
ACS Nano 6(8) 6569-6577 2012
PNAS 109(33) 13182-13187 2012
PCCP 15 581-585 2013
Nano Lett. 13(4) 1793-1799 2013
Nature Materials 12 529-534 2013
Appl. Phys. Lett. 102 231603 2013
Nature Commun. 4 2013
Nanotechnology 25 2013
Angew. Chem. Int. Ed. 53 2014
First patent filed on 01/19/2011, issued on 09/01/2015
First public disclosure on 06/15/2011 at TechConnect World (Harvard-MIT Tech Innovation Presentation)
“Robust Slippery Surfaces as Optically Transparent, Oleophobic, and Anti-icing Materials”
© 2019 Adaptive Surface Technologies
Yet Another Approach to Create Slippery Surface
Substrate
Surface Treatments
Surface SLIPS(sSLIPS)
✔SLIPS surfaces feature
an immobilized liquid
lubricant overlayer—
completely smooth and
fully slippery
Solid surfaces
are rough and have
many pinning points
Reservoir SLIPS(rSLIPS)
Paints / Curable Mixtures
Substrate
© 2019 Adaptive Surface Technologies
Commercial Uses For Highly Repellent Surfaces
BIOFOULING-FREE SHIPBIOCIDE-FREE, ECO-FRIENDLY
VISCOUS LIQUID MANFUACTURINGEASY-CLEAN, HIGH-EFFICIENCY
Less Fouling
Less Contamination
Less Cleaning
Less Energy Use
Less Environmental Impact
Less Batch Cross-Contamination
Less Waste
Less Energy & Water use
Less Production Downtime
Less Environmental Impact
SUSTAINABLE PACKAGINGEASY-EMPTYING, RECYCLABLE
Less Design Restriction
Less Cleaning
Less Contamination
Less Waste
Less Environmental Impact
© 2019 Adaptive Surface Technologies
Market Segmentation: Biofouling in Marine Environment
~60% of total
marine coating
market
Total annual fuel use: 370 M tonnes ($90B in fuel costs)
Energy use: ~13 Quads (2% of world energy)
CO2 emissions: 1.1 B tonnes
Worldwide Deep sea commercial fleet ~100,000 vessels worldwide
$3.5 Billion
850 Kilo Tons
CAGR – 6.1%
$100M sale of
pleasure craft
underwater coatings
in the US
US Recreational boat marketNo. 1 in pleasure boats ownership in the world
No. 1 in consumption of AF paints
Key suppliers:
Interlux (AkzoNobel)
Pettit Paint (RPM)
Sea Hawk Paints
Private Label paints
No pleasure craft company has been able to create
an effective Biocide Free Foul Release bottom paint
$1.4b aquaculture market in the US
50% direct labor cost for cleaning nets
High demand due to $14b deficit in
seafood annually in the US
15 million aquariums in US
At $10-15 per aquarium
~$200M total market for SLIPS
Niche market
The ultimate solution and “category killer” will be 100% biocide free,
while delivering high anti-fouling performance over long durations
© 2019 Adaptive Surface Technologies
Silicone-based rSLIPS
Substrate
Lubricant Silicone
Controlled
Regeneration
Non-toxic coating chemistry
x
No toxicity
C. reinhardtii (single cell green alga)
‘Baier curve’
J. Mater. Sci: Mater. Med., 18, 1057-1062 (2006)
© 2019 Adaptive Surface Technologies
Silicone-based rSLIPS Shows Some Promise but Not Enough
Long-term Field Performance
2.5 years in Singapore
premium
FR
(pFR)
StaticRegular
Cleaning
(-) Control
(Singapore, July ‘15 – Dec. ‘17)
SLIPS
(Gen. 0)
How can we improve the
performance further?
Gen. 0, 2012-2014Repellency to Soft & Hard Fouling
Releases
soft fouling
Repels
hard fouling
ACS Biomat Sci. Eng.. 1 43-51 2015
Nature Commun. 6 8649 2015
ACS AMI 6 13299-13307 2014
Science 357 668-673 2017
© 2019 Adaptive Surface Technologies
Controlling Biofouling Requires Additional Strategies
Adopted and modified from Frank T Moerman
J. Hygienic Engr. Design, 7, 8-29 (2014)
Physical
Module
Chemical
Module
Amphiphilic chemistry
HLB/solubility
Modular additives
Chemistry of lubricant
Hybrid
Module
Releasing or Bound biocide
Reinforced matrix
Surface texture
Natural antimicrobial compounds
Liquid interface
Slippery surface
Self-lubricating
Self-healing
Surface modulus
AST’s current development focus
Can this be a
non-fouling zone?
© 2019 Adaptive Surface Technologies
Non-Fouling Chemical Moieties
• Natural anti-fouling surfaces generally exhibit both physical and chemical attributes
• Hydrophilic, charge-neutral, hydrogen bonding acceptors are generally known to have very low protein adsorption
• polyethyleneglycol (PEG) – often behaves like hydrogel
• zwitterionic moieties – many of them are found in naturally existing compounds
• water molecules are strongly adhered and form so-called ‘hydration layer’ which requires ‘additional work’ for the fouling organisms to displace in order to attach themselves
• entropic changes associated with conformational changes of these groups with and without water molecules
© 2019 Adaptive Surface Technologies
Physical and Chemical Modules in One System
Additional Layer of Chemical Protection Physical Module + Chemical Module
Lubricant Silicone
Matrix
Bound
Amphiphile
Substrate
Gen. 1 “N1“ (2017)
© 2019 Adaptive Surface Technologies
Laboratory Biological Assay Tests
Navicula incerta
(diatoms)
Ulva linza
(green algae)
Algae
Cellulophaga lytica
Bacteria
Barnacles
Amphibalanus amphitrite
Mussels
Guekensia demissa
Month 1 Month 2 Month 3 Month 4 Month 5 Month 6 Month 7
SLIPS
(Gen. 1)
Copper-
SPC
(Navy
standard)
PVC
(control)
Static panels
Pt. Canaveral, FL
© 2019 Adaptive Surface Technologies
Amphiphilic Lubricant Further Improves Performance
Excellent Dynamic ReleaseImproved Static Performance
Lead pFR Lead AF
8-9 knots, Norway (Jul. ’18 – Nov.’18)
Singapore (Jul. ’18 – Dec.’18)
Gen. 1+ Lead pFR Lead AFGen. 1
Gen. 1+ (aka. ‘N1x’) (Q4 2017)
Gen. 1+Gen. 1
© 2019 Adaptive Surface Technologies
Design & Synthesis of Active Building Blocks/Formulation
silicone backbone
amphiphilic group
spacer
multi-functional brush-like molecular architecture (SAP)
reactive group ***
a b c d e
• initially homogenized system evolves to a
phase separated, structured system
• solubility-driven structuring
• interfacial energy-driven structuring
• evaporative structuring
• curing continues but the speed depends
on humidity
• dynamic contact angle behavior observed
condensation cure
silicone binder system
pigments
/filler
crosslinker
/catalyst
/solvent
lubricantSAP
Active Performance Ingredient (API)
• highly tunable structures (>50 compound library)
• enables modular approach
• structures confirmed by NMR and FT-IR
• up to 1 kg scale (in-house)
• toll manufacturable chemistry
• patent pending on the compounds, compositions,
and articles
(patent pending)
© 2019 Adaptive Surface Technologies
Surface Structure Upon Curing
5:20
10:60
1:40
10:40
15:40
5:40 5:60
50 µm
Optical microscopy
domain size?
% coverage?
their effect on biofouling?
(% loading):(% PEG in SAP)
% amphiphilic component in SAP
% concentration of SAP in the formulation
% loading of lubricant in the formulation
© 2019 Adaptive Surface Technologies
Discontinuous Phase is Concentrated with Hydrophilic Material
PEG (1470 cm-1)
High at circle
center
PEG (1285 cm-1)
High at circle center
Silicone* (1410 cm-1)
High at circle edges
+
+
+ +In
ten
sity
Line Scan of Circular Feature
~7 µm diameter
Confocal Raman
© 2019 Adaptive Surface Technologies
Domain Size and Surface Coverage are Tunable
*due to heterogeneity of the system, exact values may slightly vary but the data here represents the trends
SAP with 40% PEG with varying % loading10% SAP with varying % PEG
© 2019 Adaptive Surface Technologies
The Coated Surface is Not Flat at Microscale
in Air
in Water
(1 month)
Rq : 75 ± 7 nm 148 ± 9 nm
Binder only
No significant roughness change
10% SAP
© 2019 Adaptive Surface Technologies
0 50 100 150
60
70
80
90
100
110
120
Unmodified silicone
100100
100101
Wa
ter
con
tact
an
gle
(d
eg
rees)
Time(s)
Matrix
5:20
5:40
5:60
Matrix + SAP Matrix + SAP + Lubricant
• Synergistic effect of API package, creates more ‘dynamic’ surface
• Absolute values of WCA change – weak correlation to field performance
• The presence of DCA behavior – strong correlation to field performance
© 2019 Adaptive Surface Technologies
XPS Confirms Stratification
C-C/C-H
C-O
High Resolution C1s Scan Depth Profiling
© 2019 Adaptive Surface Technologies
Formulation Prototype Library
with API
Characterization of Wetting
& Surface Properties
SAP-14 SAP-24
Synthesis
Formulation
Analysis
Biological ScreeningField Screening
SAP-14 SAP-24 (-) Control
Short-Term Field Screening
3 months in Port Canaveral FL
Laboratory Scale Rapid
Screening Studies
SAP-14
SAP-24
Stained bacterial biofilm
on coating surface
AST’s Approach: Rapid Throughput Testing (RTT)
Design & Synthesis of
Modular SAPs
SAP-14
SAP-24
Customized
with unique
groups
IP
© 2019 Adaptive Surface Technologies
Field Screening Test (Pt. Canaveral, FL)
“No Harm No Foul” quick screening barge
• Static exposure test
• Can hold up to 450 panels
• High fouling pressure
(best commercial FR fails <3 months)
• Some species show resistance to copper
paints (e.g. Interspeed BRA640)
© 2019 Adaptive Surface Technologies
Towards ‘Non-Fouling’ Coating
32 week
static study
Pt. Canaveral
Florida
© 2019 Adaptive Surface Technologies
Going Beyond Marine Paints
SAP
carrier particles SAP-modified particles
architectural coating interior coating medical device coating
lubricant
compounding
base resin
© 2019 Adaptive Surface Technologies
Conclusions & Outlook
• Successfully demonstrated the pathway to reducing marine fouling with a non-toxic,
environmentally-friendly approach combining the smooth and slippery liquid-based surface
(Physical module) and highly branched amphiphilic SAPs (Chemical module).
• Carefully designed and tested APIs can be introduced as additives to existing marine paint
systems or even other coating systems such as architectural paints, interior coatings, food
or medical coatings, etc. to impart anti-fouling properties.
• Such systems can still utilize conventional antimicrobial or antifungal agents as a new
hybrid approach, where as an added benefit, the concentration of active agents may be
reduced when synergistic effect is achieved.
© 2019 Adaptive Surface Technologies
Acknowledgment
DE-AR0000759
Stefan KolleProf. Joanna Aizenberg
Cathy Zhang, Onye Ahanotu,
Jack Alvarenga, James C. Weaver,
Tom Blough
Shane Stafslien
Prof. Dean Webster
Market Entropy
Illara Consulting
Liz Haslbeck
Eric Holms
Kody Liberman
Prof. Ali Miserez
Snehasish Basu
Address any questions to:
biofouling@adaptivesurface.tech
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