FiroShield
“A different pathway to the conventional fire-retardant coatings”
I3C Symposium on Industrial Infrastructure Research
JTC Summit
23 November 2017
Asst/Prof Aravind Dasari, Prof Tan Kang Hai, Dr IS Zope, Mr Ng Yan Hao
Schools of Materials Science & Engineering AND Civil & Environmental Engineering
E-mail: [email protected] ; Tel: 6790 6402
Mr Ng Kian Wee, Principal Engineer, JTC
Eco Hazards – Flame Retardants Cycle of events
Many halogen (e.g. bromine or chlorine)-based compounds
generate corrosive and toxic combustion products like dioxins
and furans
-potent modulators of cellular growth
-Serious health effects – even Cancer
The Institute for Agriculture & Trade Policy of USA has in fact
suggested that food is a primary way in which people are
exposed to many toxic pollutants, including dioxins as a result of
these chains of events
• Improper dumping / Incomplete combustion of electronic
items is another source of emission of dioxins into the
surrounding environment
Source: IATP, USA
Material-scale: Flame Retardancy
Cross-section of the residue
1200
1000
Neat Polymer
Heat Release Rate, kW/m2
800
600
400
Polymer nanocomposites with
various nanoparticles
200
Carbonaceous matter
0
0 100 200 300 400 500 600 700
Time, s (
Dasari A et al. Nanotechnology 18 (2007) 445602
Dasari, A. et al. Progress in Polymer Science 2013, 38, 1357)
Various approaches with different nanoparticles to achieve
ü V-0 rating (in UL94 test)
ü reduced ignition times and HRR
Applications include
ü Reduced heat of combustion and Cables (outer sheath), coatings,
ü delayed burning facades, computer chassis, etc.
Dasari A, et al. Nanotechnology 2007, 18, 445602
Quicker Ignition! Why exactly?
(Fina A. et al. Polym Adv Technol 2011, 22, 1147)
Metal cations (structural/exchange)
Surface hydroxyl groups
Exchange metal ions : Clay acidity
Ø Bronsted Acidity due to acidic hydrogen site – significant below 3000C
(i.e. decomposition of modifier and localized attack on molten polymer)
Ø BA Strength1
H+ > Al3+, Fe3+ > Mg2+ > Ca2+ > Na+ > K+
Ø Lewis Acidity occurs in absence of water – prominent above 3000C (i.e.
decomposition of molten polymer).
Ø LA arises due to partially coordinated Al3+ atom at clay layer edge,
Hydration Type of Binding
isomorphic substitution of Fe3+ along siloxane surface and crystallographic
Spheres Interaction Energy defect sites.
(kcal/mol)
Inner Sphere Cation-dipole 19
Ø LA sites can accept electrons from donor molecules, can coordinate with
Outer Sphere Hydrogen 10
Bonding
organic radicals and also can abstract electron from vinylic sites2.
Autotransformation: Migration of H+ from exchange position into structural locations to replace Al3+. These free Al3+ ions then
acquire the exchange positions.
1. Clay; Types, Properties and Uses Ed. J. Humphrey and D. Boyd, 2011, Nova Science Publishers, N.Y.
By Aravind Dasari, School of Materials 2. Chem. Mater. 13 (9), 2001, 2979-2990.
Metal ions & PA6 decomposition:
PA6 coordinating with
dehydrated exchange
metal ion
(Sarda, G. et al. Nature 1963, 200, 67)
Decomposition
products coordinating
with metal ions
Zope et al., Polymer 92 (2016) 102-113.
Zope et al., Materials Chemistry and
Metal deactivator Physics 157 (2015) 69-79
Complexes with
Cu2+
Osawa Z. Polym Degrad Stab 1988, 20, 203.
Proposed Chemical Mechanism
Reaction identification
Zope et al. Polymer 92 (2016) 102-113
Classical Intumescent Coatings
Inorganic acid Polyhydric Amides Halogenated
compounds compounds and
spumific agents
Phosphoric Dextrin Urea Chlorinated
paraffins
Sulphuric Sorbitol Urea- Tetrachloropthalic
formaldehyde resins
resin
Ammonium salts Pentaerythritol Polyamides
like phosphates
and sulphates
Haloalkyl Phenol- Dicyandiamide
phosphates formaldehyde
resins
8
Camino G et al. Polym. Degrad. Stab. 23 (1989) 359-376.
Kiliaris, P. et al. Prog. Polym. Sci., 35(2010) 902-958.
Issues with intumescence
A – Resin
B – Resin & APP Intumescent systems rely heavily on
C – Resin & boric the expanded char structure to
acid
create a thermal barrier between
D – Resin & APP &
Boric acid heat source and substrate
A – Bare Steel
B – Resin
C – Resin & APP
D – Resin & boric acid Thickness of coating = 3.5mm
E – Resin & APP &
Boric acid Hydrocarbon curve heating
Jimenez, M., et al Surf. Coat. Technol., 201(2016), 979-987.
Literature – Fire Performance after Environmental Exposure Tests
Performance degradation Blisters on the surface of
Anodic polarization of
after exposure to different coating after exposure to
initially cathodic blister
weathering conditions accelerated weathering
regions leading to blister
conditions
growth laterally
Literature – Fire Performance after Environmental Exposure Tests
Relative % reduction in fire
performance and
intumescent factor (extent
of swelling) in different
systems
Other major issues with traditional coatings
Cementitious Coatings Intumescent Coatings
• Aesthetics, roughness
• Thickness
• Adhesion of the char/residue at high temperatures
to the substrate
• Integrity of the residue (fluffiness and
susceptibility to be blown away due to a draft)
• Requirement of a topcoat (weathering resistance)
• No corrosion protection
Attributes of disruptive technology demonstrated by
FiroShield
Applicability
Ø Substrate can be steel or even concrete or timber
Ø Aesthetically appealing (can be pigmented according to the needs)
Ø Construction productivity (spray applied or rolled-on, minimal thickness)
Performance
Ø Only 5 mm thick – one pot solution
Ø Excellent adhesion to the substrate even at high temperatures and good integrity
of the char
Ø Works by a synergistic combination of mechanisms like endothermic and charring
Finally, the most critical of all - cost-effective (no requirement of sand
blasting [possible to have on-site application] and multi-layered coatings)
Acknowledgements
Project funding: NTU-JTC I3C, RCA 16/277
Thanks to Mr Shiek Anees and Mr Jonathan Siow for
some of the contributions.
This project is a collaboration between JTC and the
Ack. IFM-GEOMAR
Schools of MSE and CEE @ NTU
