Fire Retardant Properties of Intumescent Polypropylene Composites Filled

With Calcium Carbonate

ABSTRACT  Polymer Engineering and Science

This study was aimed to investigate the influence of calcium carbonate (CaCO3), a widely used filler, on
the fire retardancy of intumescent polypropylene composites. Two intumescent systems based on (1)
mixture of ammonium polyphosphate (APP) and pentaerythritol and (2) surface-modified APP (m-APP)
were examined. In terms of steady heat release rate, total heat evolved, and fire growth index determined
by mass loss calorimetry, m-APP performed markedly superior to APP-pentaerythritol. The presence of
CaCO3 in both intumescent formulations caused significant losses in fire retardant performance assessed
by mass loss calorimetry, limiting oxygen index and UL-94 tests. Peak rates of heat release and mass
loss during combustion, and total heat evolved on combustion were increased, whereas time to ignition
was decreased. Characterization of fire residues ascribed the mechanism of deterioration in fire
retardancy to the formation of porous and nonexpanded crystalline calcium phosphate/CaCO3 residues
during combustion rather than the amorphous protective intumescent chars formed in the absence of
CaCO3

ABSTRACT(2) Copyright © 1984 Wiley Heyden Ltd.

Effect of calcium carbonate filler on the fire and smoke properties of moulded polypropylene
‘Oxygen Index’, ‘Rate of Burning and Extent of Burning of Self‐supporting Plastics in a Horizontal
Position’ and ‘Vertical Flammability’ tests were used for examination of polypropylene copolymer HW
607M and the same copolymer filled with 40% w/w calcium carbonate. Room‐scale studies were also
carried out using a range of standard ignition sources. In the latter tests, measurements of the levels of
smoke generated in the test chamber were monitored continuously, and intermittent measurements
were made of the carbon monoxide concentrations. Small‐scale testing showed that addition of the filler
to the polypropylene raised the limiting oxygen index of the polymer from 17.8 to 20.3, which is only
marginally lower than the oxygen concentration in ambient air (20.9); this introduces the possibility of a
filled polypropylene which is not ignitable in air. However, the results of the UL94 and ASTM D635 tests
did not show significant differences in flammability and rates of vertical and horizontal flame spread as
between the two materials, through the unfilled polymer produced extensive burning droplets early in
both tests whilst the filled polymer did not. Such droplets can spread fires to floor coverings, so that the
filled plastic might be preferable in application. In our laboratory tests, the filled samples gave
considerably lower smoke generation than the unfilled ones. At high heat fluxes they generated
considerably less smoke than (smaller) unfilled samples containing the same mass of polymer. This
suggests that the calcium carbonate has specific smoke‐suppressant activity and is not merely acting as
a polymer diluent. In larger‐scale tests, unfilled samples were readily ignited by a domestic match, whilst
the filled samples required an ignition source of 43 kJ (some six times greater than the match source) in
order to light them and sustain ignition. The filled polymer did not melt on ignition and there was no
lateral spread of flame from the sample. Smoke generation was considerably lower, the average optical
density at maximum obscuration being 0.27, compared with 0.84 for the unfilled control. In particular,
smoke suppression achieved by use of calcium carbonate at higher heat‐flux levels is considerably
greater than that expected for an inert diluent.
EGGSHELLS: A NOVEL BIO-FILLER FOR INTUMESCENT FLAME-RETARDANT
COATINGS
ABSTRAC(3) Copyright © 2015 Elsevier B.V. 

The aim of this study was to develop intumescent flame-retardant coatings that incorporate chicken
eggshell (CES) waste as a novel eco-friendly bio-filler. Three flame-retardant additives, namely,
ammonium polyphosphate phase II, pentaerythritol and melamine were mixed with flame-retardant
fillers and acrylic binder to synthesize the intumescent coatings. The fire performance of the coatings
was evaluated in accordance with ‘BS 476: Part 6-Fire Propagation’ and ‘BS 476: Part 7-Surface Spread of
Flame’ test standards. It was found that 4 out of 5 of the coated specimens (B, C, D and E) neither
showed surface spread of flame nor any afterglow combustion upon fire exposure. The addition of
5.0 wt% and 2.5 wt% eggshell bio-filler into formulations B and E, respectively, improved fire protection
due to char formation, with better morphology, height and structure of the protecting shield. The filler
compositions of samples applied at a thickness of 1.5 ± 0.2 mm achieved the lowest fire propagation
index with a value of 4.5 and 5.0, respectively (BS 476 Part 6, Class 0 materials) which indicates excellent
fire-stopping properties. The results showed that the coatings were effective in fire protection, with
good qualities of water resistance, thermal stability, and adhesion strength. Significantly, coating E (with
CES) has proved to be efficient in the protection of plywood against fire.

Keywords
-Acrylic resin

-Chicken eggshell

-Bio-filler

-Eco-friendly

-Intumescent coating

-Flame-retardant

https://www.sciencedirect.com/science/article/pii/S0300944015000120

INTRO
Fire is widely known for its great impact among people and environment. It is consider as one of the most
dangerous disaster. Light materials such as wood which is commonly used to build house and source of cooking are
one of the cause origins of fire burning that will contribute to disaster.
CaCO3, comprises more than 4% of the earth’s crust and is found throughout the world. It is most common
natural forms are chalk, limestone, and marble, produced by the sedimentation of the shells of small fossilized
snails, shellfish, and coral over millions of years.  Although all three forms are identical in chemical terms, they
differ in many other respects, including purity, whiteness, thickness and homogeneity.  Calcium carbonate is one of
the most useful and versatile materials known to man.
As interesting as calcium carbonate may be in nature, its impact and value to our everyday life are truly
extraordinary. Nature returns the favor as calcium carbonate solutions from current deposits provide living
organisms today with the material they need to grow their protective shells and skeletons. Eggshells, for example,
are composed of approximately 95% calcium carbonate.
Calcium carbonate has been widely studied as a non-flammable halogen free FR within a large range of polymers,
copolymers and propellants. Recently, its use in silicone matrix was a central focus: the incorporation of
precipitated CaCO3 in a silicone matrix can increase its thermal stability.

Flame Retardant  Acrylic Eggshell is a water-borne, flame retardant coating designed to maintain or upgrade a
surface to inhibit the spread of flame.  Eggshell, a novel bio-filler for intumescent flame-retardant coatings.
Addition of bio-filler improved the fire protection and adhesion of coating. Combinations of Al(OH)3, Mg(OH)2 and
CES reduced the surface spread of flame. CES has a great potential for use as eco-friendly filler for intumescent
coating.

An eco‐friendly bio‐filler was prepared by reusing of chicken eggshell (CES), and well characterized by Fourier
transform infrared (FTIR) spectroscopy, scanning electron microscope (SEM)‐energy dispersive X‐ray spectroscopy
(EDS), X‐ray fluorescence spectrometry (XRF), and thermo‐gravimetric (TG) analysis. The influence of CES on the
thermal stability, flame‐retardant, and smoke suppression properties of epoxy‐based traditional intumescent
system was investigated by limited oxygen index (LOI), UL 94 test, cone calorimeter test, and TG analysis. The
results shows that the incorporation of CES improves the LOI value of the samples, and IFR‐3 with 37 wt%
intumescent flame retardant (IFR) and 3 wt% CES exhibits the maximum LOI value of 31.5%. The results from cone
calorimeter and smoke density tests reveal that the addition of CES greatly decreases the heat release and smoke
production of the samples concomitant with an increase in the residual weight, which is ascribed to the formation
of a more compact, thermally stable, and intumescent char against heat and mass transfer during burning. The
synergistic effect on fire performance between CES and IFR depends on the content of CES, and an excessive
content of CES diminishes this synergistic effect. The TG analysis shows that the intumescent system containing
CES exhibits high thermal stability and char‐forming ability. Overall, CES can serve as an environmentally friendly
bio‐filler and a promising synergist for intumescent systems