Research Article Fire Propagation Performance of Intumescent Fire Protective Coatings ...downloads.hindawi.com/journals/tswj/2014/805094.pdf · 2019-07-31 · Research Article Fire

Research ArticleFire Propagation Performance of Intumescent Fire ProtectiveCoatings Using Eggshells as a Novel Biofiller

M C Yew1 N H Ramli Sulong1 M K Yew1 M A Amalina2 and M R Johan2

1 Department of Civil Engineering Faculty of Engineering University of Malaya 50603 Lembah Pantai Kuala Lumpur Malaysia2 Centre of Advanced Materials Department of Mechanical Engineering Faculty of Engineering University of Malaya50603 Lembah Pantai Kuala Lumpur Malaysia

Correspondence should be addressed to M C Yew yewmingchiangmailcom

Received 3 April 2014 Accepted 4 July 2014 Published 17 July 2014

Academic Editor Levent Ballice

Copyright copy 2014 M C Yew et al This is an open access article distributed under the Creative Commons Attribution Licensewhich permits unrestricted use distribution and reproduction in any medium provided the original work is properly cited

This paper aims to synthesize and characterize an effective intumescent fire protective coating that incorporates eggshell powder asa novel biofiller The performances of thermal stability char formation fire propagation water resistance and adhesion strength ofcoatings have been evaluated A few intumescent flame-retardant coatings based on these three ecofriendly fire retardant additivesammonium polyphosphate phase II pentaerythritol and melamine mixed together with flame-retardant fillers and acrylic binderhave been prepared and designed for steel The fire performance of the coatings has conducted employing BS 476 Part 6-Firepropagation test The foam structures of the intumescent coatings have been observed using field emission scanning electronmicroscopyOn exposure the coated specimensrsquo B C andDhad been certified to beClass 0 due to the fact that their fire propagationindexes were less than 12 Incorporation of ecofriendly eggshell biofiller into formulation D led to excellent performance in firestopping (index value (119868) = 43) and antioxidation of intumescent coating The coating is also found to be quite effective in waterrepellency uniform foam structure and adhesion strength

1 Introduction

Intumescent fire protective coatings have been widely used aspassive fire protection (PFP) in parts of cars airplanes steelstructures and building components to ensure the fire safetyand building regulations in many countries Intumescentcoating is fire retardant and fire resistant material which hasgained wide acceptance in the world for fire protection Thiscoating is used to achieve PFP for such applications as firestopping and fireproofing to reduce the devastating cost offire in terms of both life hazard and property damage

Structural steel loses its load carrying ability to about 60percent when its temperature exceeds 500∘C in a fire andthis is mainly attributed to high thermal conductivity lowspecific heat and faster degradation of strength and elasticmodulus of steel When heated to about 800∘C the steelssolidity decreases further to about 10 percent of its normalvalue [1 2] Intumescent coatings are designed to performunder severe conditions and to maintain the steel integrity in

the event of a fire [3ndash5] Many researchers have extensivelystudied the properties of intumescent coatings in terms offire protection adhesion strength thermal stability andwaterresistance [6ndash14] The formulation of the coating has to beoptimized in terms of physical and chemical properties inorder to retard the heat transfer and ignition on the steel

Intumescent coatings were composed of three halogen-free flame-retardant additives an acid source (such as phaseII ammonium polyphosphate APP) a carbon source (suchas pentaerythritol PER) and a blowing agent (such asmelamine MEL) mixed together with flame-retardant fillersand polymer binder Intumescent coating expands whenexposed to a sufficiently high temperature (eg in a fire)The heated coating forms a porous char and producesresidues that are swelled by escaping noncombustible gases toestablish a protective barrier against oxygen A combustionresidue can be efficiently puffed up in order to producetough foam over the surfaces to protect the substrate [15]Significantly using flame-retardant fillers such as aluminium

Hindawi Publishing Corporatione Scientific World JournalVolume 2014 Article ID 805094 9 pageshttpdxdoiorg1011552014805094

2 The Scientific World Journal

hydroxide (Al(OH)3) and magnesium hydroxide (Mg(OH)

2)

replacement of conventional flame-retardants is a realisticand promising way to overcome fire propagation and surfacespread of flame because of their low flame retarding efficiency[16ndash19]The performance of the intumescent system dependson the choice of the ingredients and their appropriate combi-nations

These research studies have pointed out a useful biofillerderived from chicken eggshell (CES) waste and its potentialrole in the fire protective coating industry CES waste is anindustrial byproduct and its disposal constitutes a seriousenvironmental hazard It is known that CES waste containsabout 95 calcium carbonate in the form of calcite and5 organic materials such as type X collagen sulfatedpolysaccharides and other proteins [20 21] CES can beutilized in commercial products to create new value in thesewaste materials and it has been highlighted recently becauseof its reclamation potential Although there have been severalattempts to use CES components for various applications[22ndash26] its chemical composition and availabilitymakes CESa potential source of biofiller reinforced biopolymer compos-ites giving additional or improved thermal and mechanicalproperties to the coating [27] The other advantages of usingCES are that it is available in bulk quantity lightweight highthermal stability and being inexpensive and environmentallyfriendly

This paper is concerned with the development and eval-uation of intumescent coatings properties The efficiency ofintumescent coatings on steel is investigated following theBS 476 Part 6-Fire propagation test Moreover the waterresistance thermal stability char formation and adhesionstrength of intumescent coatings were also studied andevaluated

2 Experimental

21 Materials and Method Chicken eggshells (CES) wereused as a biofiller in this study The CES membrane wasremoved and discarded The CES were then cleaned thor-oughly and dried at 90∘C for 12 h in the oven The driedeggshells were mechanically triturated to a powder formand then milled at a milling speed of 280 rpm for 48 hrespectively in a four-roll mill to obtain mean particle sizesof 2299 120583m The acrylic resin composed of acrylic acidmethacrylic acid esters of these acids or acrylonitrile wassupplied by Shinko Paint amp Chemical Sdn Bhd Ammoniumpolyphosphate phase II (119899 gt 1000) melamine and pen-taerythritolwere purchased from InternationalChemical LtdChina Titanium dioxide (R706) aluminium hydroxide andmagnesium hydroxide were purchased from Scientific GroupSdn Bhd Malaysia

Intumescent fire protective coatings were prepared usingacrylic binder pigment and flame-retardant ingredientsThe formulations were prepared using high-speed dispersemixer and the viscosity of the coatings was adjusted to95ndash105KU The compositions of intumescent coatings aregiven in Table 1 The prepared coating was coated on Q235steel plate using a gun sprayer For obtaining effective fire

Table 1 Compositions of intumescent fire protective coatings

Ingredients Parts by weight for formulationsA B C D

APP 1800 1800 1800 1800MEL 900 900 900 900PER 900 900 900 900TiO2 550 550 550 275Al(OH)3 mdash 550 mdash 275Mg(OH)2 550 mdash mdash 275CES mdash mdash 550 275BinderAcrylic resin 5300 5300 5300 5300

retardancy the thickness of the intumescent coatings hasbeen measured and maintained

22 Fire Propagation Test The fire propagation test wasperformed in accordance to the procedure specified in BS476 Part 61989 + A1 Fire propagation [28] The test methodconsists of exposing the product to a row of small flamesfor 20 minutes and an additional impressed irradiance of2 kW from third to the final minute of the test The tem-perature of the evolved combustion products is recordedFurthermore compared to the temperatures generated froma noncombustible specimen the result is expressed as firepropagation index that provides a comparative measure ofthe contribution to the growth of fire made by essentiallyflat material composite or assembly The coated face of thespecimens was exposed to the heating conditions of the testTo be Class 0 certified the fire propagation index (119868)must bele12 The lower the numerical value of the index is the betterthe material it indicates The details of the test procedures onindex of performance of specimens and calculation of resultsare explained as follows

In this test the rate and amount of heat evolved by thespecimen were taken into account while it was heated in anenclosed space under prescribed conditions Specimens ofsteel plate (225times 225times 23mm)were coatedwith intumescentcoatings (thickness of 15 plusmn 02mm) and the index ofperformance was determined from the following equations

1198941=

119905=3

sum119905=05

120579119898minus 120579119888

10119905

1198942=

119905=10

sum119905=4

120579119898minus 120579119888

10119905

1198943=

119905=20

sum119905=12

120579119898minus 120579119888

10119905

119868 = 1198941+ 1198942+ 1198943

(1)

where 119868 is the index of performance 119905 is the time (min) fromthe origin at which readingswere taken 120579

119898is the temperature

The Scientific World Journal 3

Substrate

Substrate

Pull-off force

AdhesiveCoating

Figure 1 The setup for the measurement of adhesion strength

(∘C) of the material at time 119905 and 120579119888is the temperature (∘C)

of the calibration curve at time 119905

23 Thermogravimetric Analysis Thermogravimetric anal-yser (TGA) was carried out at 20∘Cmin under air flow inthe temperature range of 30ndash1000∘C using a TGASDTA851emodel to study the thermal degradation and determine theresidual weight of the coatings

24 Field Emission Scanning Electron Microscopy Micro-scopic analyses were carried out using a field emissionscanning electron microscope (FESEM) GEMINI FESEM toexamine the surface morphology of the intumescent charlayers For FESEM observation low beam energy of 1 kV wasoperated to reduce the possibility of any thermal damage tothe char layers

25 Static Immersion Test Static immersion test is consid-ered as a standard method that evaluates water resistance ofthin films using the gravimetric method Samples of films(dimensions 20 times 10 times 05 plusmn 01mm) were immersed indistilled water at 25∘C At specific time intervals the sampleswere removed and were blotted with a piece of paper towelto absorb excess water on the surfaces Weight change wascalculated by (2) and expressed as a function of time

119864sw =(119882119890minus119882119900)

119882119900

times 100 (2)

where119864sw is the water uptake ratio of the film119882119890denotes the

weight of the film at different times and119882119900is the dry weight

of the sample

26 Adhesion Strength The adhesion strength of the coatedsample was determined by using the Instron Micro Testerequipment A scheme of the adhesion strength measurementsetup is shown in Figure 1

The coatings were each sprayed on one side of 50 times 50 times26mm steel plates with a film thickness of 05 plusmn 005mmThe steel plate with a dry film was attached to a bare steelplate (dimensions 50 times 50 times 26mm) using epoxy glue(thickness of 05 plusmn 005mm) Then the two steel plates werethen continually drawn apart in tensile mode at a constant

rate of 1mmmin using the testing device until the coatingon the steel plate cracked Adhesion strength (119891

119887) inMPa was

calculated based on the following equation

119891119887=119865

119860 (3)

where 119891119887is the adhesion strength MPa 119865 is the crack charge

N 119860 is the sticking area mm2

3 Results and Discussion

31 Fire Propagation In the previous study all the sampleshad satisfied Class 1 prescribed in the BS 476 Part 7 surfacespread of flame test The results of subindex and index ofperformance of fire propagation test are as illustrated inTable 2

The fire propagation results showed that the subindexes(1198941 1198942 1198943) of samples A B C and D were (18 15 57)

(0 84 34) (02 83 29) and (0 38 07) respectivelyHowever the indexes of performance of samples A B C andD were 223 115 112 and 43 respectively In this test onlysample A is not certified to be Class 0 due to the fact that itsfire propagation index was 223 (119868 gt 12)

The tested samples according to BS 476 Part 6 Firepropagation test are as shown in Figure 2 By comparing theresults of fire propagation index of samples A B and C it wasfound that the sample C ((119868) = 112)with the addition of CEShas a much lower fire propagation index than that of samplesA ((119868) = 223) and B ((119868) = 115) Incorporation of CES intothe formulation (sample C) was significantly inhibited by thefire propagation of the coating due to its high thermal stability(decomposition temperature at about 790∘C) [7]

Sample D showed significant improvement in reducingfire propagation ((119868) = 43) compared to samples A B andCThe appropriate combinations of Al(OH)

3CESMg(OH)

2

with flame-retardant ingredients and acrylic binder in formu-lation D led to a highly effective fire stopping behavior

The maximum temperatures of samples A B C andD were 418∘C 391∘C 372∘C and 259∘C respectively Thisresult indicated that the sample D with appropriate com-binations of flame-retardant ingredients and fillers causedthe fire propagation hardly present compared to samplesA B and C This phenomenon is due to the synergist


Table 2 Results of fire propagation test

Time (min) Calibration Specimen A Specimen B Specimen C Specimen DAR + T + M AR + T + A AR + T + CES AR + T + M + A + CES

05 14 18 12 14 121 18 21 15 18 1615 23 26 19 23 192 27 30 22 27 2325 30 34 25 31 263 34 38 30 34 304 72 122 87 55 545 108 212 149 133 1296 129 274 179 169 1817 148 321 223 243 2028 166 364 312 327 2199 182 378 336 372 23410 192 405 372 360 24412 214 417 391 355 24914 230 418 370 349 25316 238 416 326 310 25818 246 403 298 299 26020 257 384 281 290 263

Subindex 1 18 0 02 0Subindex 2 15 84 83 38Subindex 3 57 34 29 07

Index of performance 223 115 112 43

and catalysis effects of these three flame-retardant fillers(Mg(OH)

2Al(OH)

3CES) have chemical reaction with the

fundamental ingredients (in general the acid source APP)on carbonaceous char formation [29ndash31] which improvethe thermal stability and flame retardancy of the coatingBoth Al(OH)

3(decomposition temperature at about 180∘C)

and Mg(OH)2(decomposition temperature at about 330∘C)

hydroxides decompose endothermicallywhenheated accord-ing to the reactions

2Al(OH)3(s) 997888rarr Al

2O3(s) + 3H

2O (g) (4)

Mg(OH)2(s) 997888rarr MgO (s) +H

2O (g) (5)

On exposure Al(OH)3has shown the strong reversibil-

ity of the dehydration reaction with water released insidethe particle recombining with the reactive surface of thefreshly formed alumina resulting in a good flammabilityresistance filler [32] For the endothermic decomposition ofthe Mg(OH)

2filler the gaseous water phase is believed to

envelop the flame thereby excluding oxygen and dilutingflammable gases [33]

However coatings C and D exhibited a uniform expan-sion of the char layer (Figures 2(c) and 2(d)) The formationof a cohesive structure during burning can potentially beinitiated by different phenomena such as the CO

2released

due to the decarbonation of CES at about 790∘C which couldtrap the degradation products into the residue and induce theswelling It can be concluded that incorporation ofCES acts as

an additional blowing agent in reducing sample temperaturefor the coatings [7] CES containing 95 CaCO

3releases

noncombustible gases (carbon dioxide) on heating to formcalcium oxide as follows [34]

CaCO3(s) 997888rarr CaO (s) + CO

2(g) (6)

32 Surface Micrographs of the Foam Structures High mag-nification surface micrographs enable the observation of thesurface morphologies of form structure formation as shownin Figure 3

It was found that the foam structure of samples C andD was significantly improved by filling CES biofiller whichproduced denser and more uniform foam structure com-pared with samples A and B which are porosity nonuniformand tiny form structure The fire protection performanceindicated that the efficiency of the char layer to fire-resistancedepended strongly on its physical structure [27] The charlayer of D had more uniform and dense foam structurewhich could isolate steel substrate from fire and providebetter fire protection Moreover the char layers of A and Bhad porous form structure with high porosity observed Thetiny foam structure could insulate steel substrate from heatand fire However heat might transfer to the steel substratethrough the porous foam structure which could lead to adecline of fire protection The char layer of B showed a broaddistribution of the cell sizeThis foam structure demonstrated


(a) (b)

(c) (d)

Figure 2 Tested samples (a) A (b) B (c) C and (d) D according to BS 476 Part 6-Fire propagation test

that some cells burst which could increase efficiency of heattransfer and decline of fire protection

33Thermal Analysis of the Coating Samples Thermal degra-dation of samples A B C and D was analyzed using theTGA test (Figure 4) The curves of the coatings were similarbetween 100∘C and 285∘C and weight loss of each coating wasless than 34wt at 285∘C whereas the thermal degradationof the samples left a thermally stable char at 900∘C

When the temperature was higher than 300∘C the TGAcurves of the coatings became slightly different from eachother The total weight losses of samples A B C and Dwere about 816 808 739 and 687 respectivelyThe residual weights difference of fillersflame-retardantadditivesbinder composites which could reveal the possiblereaction and reaction temperature between fillers and flame-retardant additives or the binder resin The TGA curveof C showed that the residue weight of the coating wasincreased by adding CES filler compared with coatings Aand B due to its higher decomposition temperature of CEScontains (790∘C) [7] The highest residue weight of coating

D indicated that the combination ofMg(OH)2CESAl(OH)

3

could significantly enhance thermal stability and antioxi-dation of the coating It was found that the presence ofMg(OH)

2CESAl(OH)

3fillers which led to thermal stabi-

lization of coating is remarkably improved in the temperaturerange of 350ndash1000∘C It means the reaction between fillerswith flame-retardant additives showing a synergism behavior[35]

34 Static Immersion Test The weight change rate curves ofthe thin-film coatings are shown in Figure 5 It was observedthat the water could destroy some components of hydrophilicflame-retardant ingredients and break some bonds of binderso the water resistance of intumescent coatings decreasedsignificantly

When samples A B C and Dwere immersed in water for7 days two main processes (permeation and migration) tookplace simultaneously for sample B However the migrationprocess occurred for samples C and D which contain CESfiller Moreover some hydrophilic flame-retardant ingredi-ents might migrate from coating and be solved in water


(a) (b)

(c) (d)

Figure 3 Surface micrographs of the foam structure of samples A B C and D

0

10

20

30

40

50

60

70

80

90

100

100 200 300 400 500 600 700 800 900 1000

Resid

ual w

eigh

t (w

t)

Temperature (∘C)AB

CD

Figure 4 TGA curves of samples A B C and D

during themigration process which resulted in weight loss ofcoating [36] In the permeation process water could infiltrateinto the pore structure of the coating which led to theincrease of weight of the sample

The experimental results show that the weight of coatingsAwas gradually increased and itsweight gain rateswere about408 at 7 days due to the fact that the permeation processof water exceeded the migration process of fire retardantingredients However the weight of coatings C and D was

minus20

minus15

minus10

minus5

0

5

0 1 2 3 4 5 6 7 8

Wei

ght c

hang

e rat

e (

)

Immersion time (day)

AB

CD

Figure 5 Relationship between weight change rate and immersiontime for different coating in water

gradually decreased and reached equilibrium at 6 days due tothe fact that the migration process occurred and their weightloss rates were minus1213 and minus1469 respectively at 7 days

It can be concluded that incorporation of Al(OH)3to

flame-retardant additives and acrylic binder could slow downpermeation of water and migration of fire retardant ingredi-ents due to its poorly solubility in water [37] which led to


Table 3 Adhesion strength of coatings

Coating Crack charge 119865 (N) Sticking area 119860 (m2) Adhesion strength 119891119887

(MPa)A 830 025 times 10minus2 0332B 623 025 times 10minus2 0249C 720 025 times 10minus2 0288D 680 025 times 10minus2 0272

A B C DCoating 0332 0249 0288 0272

020

022

024

026

028

030

032

034

Adh

esio

n str

engt

h (M

Pa)

Figure 6 The adhesion strength of coatings A B C and D

an improvement in resisting water permeation andmigrationability of the coatingWeight loss rate andweight gain weightof all samples were maintained relatively constantly at 6 daysof the test The cracking and blistering phenomena did notoccur in all samples after 7 days of the test

35 Adhesion Strength Table 3 displays the average adhesionstrength values of the coating samplesThe adhesion strengthof coatings A B C and D was 0332MPa 0249MPa0288MPa and 0272MPa respectively (Figure 6)

Coating B had poor adhesion strength of 0249MPacompared with coatings A C and D which had values of0332MPa 0288 and 0272MPa respectively An increasein the adhesion strength of the coating A filled by Mg(OH)

2

filler is due to the strong bonding strength between the metalsurface and acrylic binderMg(OH)

2filler interface adhesion

for effective stress transfer [38] However incorporation ofCES filler in coating C increased the adhesion strengthby 157 compared to coating B The improvement in theadhesion strength is due to the better reinforcement prop-erties between CES filler and acrylic binder [39] This resultindicated that the incorporation of Al(OH)

3filler in coatings

B and D had decreased the adhesion strength comparedwith coatings A and C without addition of Al(OH)

3filler

In conclusion choosing appropriate flame-retardant fillercould strongly influence the bonding strength of intumescentcoating

4 Conclusions

This study has concluded that the intumescent flame pro-tective coatings have been found to be quite effective on

fire resistance performance On exposure the coating pro-vided multicellular insulating foam that acted as an effectivebarrier in the conduction of heat into the steel substrateThe appropriate combinations of Al(OH)

3Mg(OH)

2CES

flame-retardant fillers in flame-retardant ingredients andbinder reduced the fire propagation index while possessinggood water repellency char formation thermal stability andadhesion Addition of CES as a biofiller showed significantimprovement in fire protection which has a great poten-tial for use as ecofriendly filler while at the same time itpreserves the environment Hence this study reveals thatthe appropriate combinations of flame-retardant ingredientsresults proved that using this intumescent coating on steelstructures is a feasible fireproof material to maintain thestructure properties in a fire

Conflict of Interests

The authors declare that there is no conflict of interestsregarding the publication of this paper

Acknowledgments

The authors gratefully acknowledge the financial supportfrom MOHE and University of Malaya for the FRGS-FP047-2013B and IPPP-PG030-2013A Grants allocated to study thisresearch The authors also extend special thanks to Mr YewSeeHing andMrsOoKewTea for their valuable contributionthroughout this project

References

[1] V K R Kodur M Dwaikat and R Fike ldquoHigh-temperatureproperties of steel for fire resistance modeling of structuresrdquoJournal of Materials in Civil Engineering vol 22 no 5 pp 423ndash434 2010

[2] A H Buchanan Structural Design for Fire Safety JohnWiley ampSons Chichester UK 2001

[3] J A Seiner and T A Ward ldquoFire protective coatings forstructural steelrdquo Polymers Paint Colour Journal vol 178 no4207 pp 75ndash78 1988

[4] G K Castle ldquoFire protection of structural steelrdquo Loss Preven-tion vol 8 pp 57ndash64 1974

[5] S C Upadhya ldquoIntumescent coatings in the service of fireprotectionrdquo Paintindia pp 45ndash52 2000

[6] S Duquesne S Magnet C Jama and R Delobel ldquoIntumescentpaints fire protective coatings for metallic substratesrdquo Surfaceand Coatings Technology vol 180-181 pp 302ndash307 2004


[7] M C Yew and N H Ramli Sulong ldquoFire-resistive performanceof intumescent flame-retardant coatings for steelrdquoMaterials andDesign vol 34 pp 719ndash724 2012

[8] M C Yew and N H Ramli Sulong ldquoEffect of epoxy binderon fire protection and bonding strength of intumescent fireprotective coatings for steelrdquo Advanced Materials Research vol168-170 pp 1228ndash1232 2011

[9] B Bodzay K Bocz Z Barkai and G Marosi ldquoInfluence ofrheological additives on char formation and fire resistance ofintumescent coatingsrdquo Polymer Degradation and Stability vol96 no 3 pp 355ndash362 2011

[10] D Enescu A FracheM Lavaselli OMonticelli and FMarinoldquoNovel phosphorous-nitrogen intumescent flame retardant sys-tem Its effects on flame retardancy and thermal properties ofpolypropylenerdquo Polymer Degradation and Stability vol 98 no1 pp 297ndash305 2013

[11] L L Pan G Y Li Y C Su and J S Lian ldquoFire retardantmechanism analysis between ammonium polyphosphate andtriphenyl phosphate in unsaturated polyester resinrdquo PolymerDegradation and Stability vol 97 no 9 pp 1801ndash1806 2012

[12] S A A Ramazani A Rahimi M Frounchi and S RadmanldquoInvestigation of flame retardancy and physical-mechanicalproperties of zinc borate and aluminum hydroxide propylenecompositesrdquoMaterials and Design vol 29 no 5 pp 1051ndash10562008

[13] Y J Chuang Y H Chuang and C Y Lin ldquoFire tests to studyheat insulation scenario of galvanized rolling shutters sprayedwith intumescent coatingsrdquoMaterials and Design vol 30 no 7pp 2576ndash2583 2009

[14] N P G Suardana M S Ku and J K Lim ldquoEffects ofdiammonium phosphate on the flammability and mechanicalproperties of bio-compositesrdquo Materials amp Design vol 32 no4 pp 1990ndash1999 2011

[15] S Bourbigot M le Bras S Duquesne andM Rochery ldquoRecentadvances for intumescent polymersrdquoMacromolecular Materialsand Engineering vol 289 no 6 pp 499ndash511 2004

[16] H Huang M Tian L Liu W Liang and L Zhang ldquoEffectof particle size on flame retardancy of magnesium hydroxidefilled EVA copolymer compositesrdquo Journal of Applied PolymerScience vol 100 no 6 pp 4461ndash4469 2006

[17] J T Yeh H M Yang and S S Huang ldquoCombustion ofpolyethylene filled with metallic hydroxides and crosslinkablepolyethylenerdquo Polymer Degradation and Stability vol 50 no 2pp 229ndash234 1995

[18] M S Cross P A Cusack and P R Hornsby ldquoEffects of tinadditives on the flammability and smoke emission characteris-tics of halogen-free ethylene-vinyl acetate copolymerrdquo PolymerDegradation and Stability vol 79 no 2 pp 309ndash318 2003

[19] C M Tai and R K Y Li ldquoMechanical properties of flameretardant filled polypropylene compositesrdquo Journal of AppliedPolymer Science vol 80 no 14 pp 2718ndash2728 2001

[20] J L Arias D J Fink S Q Xiao A H Heuer and A I CaplanldquoBiomineralization and eggshells cell-mediated acellular com-partments of mineralized extracellular matrixrdquo InternationalReview of Cytology vol 145 pp 217ndash250 1993

[21] J L Arias andM S Fernandez ldquoBiomimetic processes throughthe study of mineralized shellsrdquoMaterials Characterization vol50 no 2-3 pp 189ndash195 2003

[22] S I Ishikawa S Sekine N Miura K Suyama K Ariharaand M Itoh ldquoRemoval of selenium and arsenic by animalbiopolymersrdquo Biological Trace Element Research vol 102 no 1-3 pp 113ndash127 2004

[23] WT Tsai JM Yang CW Lai YHCheng C C Lin andCWYeh ldquoCharacterization and adsorption properties of eggshellsand eggshell membranerdquo Bioresource Technology vol 97 no 3pp 488ndash493 2006

[24] F Yi Z X Guo L X Zhang J Yu and Q Li ldquoSolubleeggshell membrane protein preparation characterization andbiocompatibilityrdquo Biomaterials vol 25 no 19 pp 4591ndash45992004

[25] M C Yew N H Ramli Sulong W T Chong S C Poh BC Ang and K H Tan ldquoIntegration of thermal insulationcoating and moving-air-cavity in a cool roof system for attictemperature reductionrdquo Energy Conversion and Managementvol 75 pp 241ndash248 2013

[26] S Yoo J S Hsieh P Zou and J Kokoszka ldquoUtilization ofcalcium carbonate particles from eggshell waste as coatingpigments for ink-jet printing paperrdquo Bioresource Technologyvol 100 no 24 pp 6416ndash6421 2009

[27] M C Yew N H Ramli Sulong M K Yew M A Amalina andM R Johan ldquoThe formulation and study of the thermal stabilityand mechanical properties of an acrylic coating using chickeneggshell as a novel bio-fillerrdquo Progress in Organic Coatings vol76 no 11 pp 1549ndash1555 2013

[28] Fire tests on building materials and structures BS 476 Part 6method of test for fire propagation for products 1997

[29] S Bourbigot M le Bras R Delobel R Decressain and JAmoureux ldquoSynergistic effect of zeolite in an intumescenceprocess study of the carbonaceous structures using solid-stateNMRrdquo Journal of the Chemical Society Faraday Transactionsvol 92 no 1 pp 149ndash158 1996

[30] S Bourbigot M Le Bras R Delobel and J M TremillonldquoSynergistic effect of zeolite in an intumescence processes Studyof the interactions between the polymer and the additivesrdquoJournal of the Chemical Society vol 92 pp 3435ndash3444 1996

[31] A B Morgan R H Harris Jr T Kashiwagi L J Chyalland J W Gilman ldquoFlammability of polystyrene layered silicate(clay) nanocomposites carbonaceous char formationrdquo Fire andMaterials vol 26 no 6 pp 247ndash253 2002

[32] S P Souza S H Souza and S P Toledo ldquoStandard transitionaluminas Electronmicroscopy studiesrdquoMaterials Research vol3 no 4 pp 104ndash114 2000

[33] P R Hornsby and C L Watson ldquoA study of the mechanism offlame retardance and smoke suppression in polymers filled withmagnesium hydroxiderdquo Polymer Degradation and Stability vol30 no 1 pp 73ndash87 1990

[34] S Bellayer E Tavard S Duquesne A Piechaczyk and S Bour-bigot ldquoMechanism of intumescence of a polyethylenecalciumcarbonatestearic acid systemrdquo Polymer Degradation and Stabil-ity vol 94 no 5 pp 797ndash803 2009

[35] S Duquesne S Magnet C Jama and R Delobel ldquoThermo-plastic resins for thin film intumescent coatingsmdashtowards abetter understanding of their effect on intumescence efficiencyrdquoPolymer Degradation and Stability vol 88 no 1 pp 63ndash692005

[36] J Yeh H Huang C Chen W Su and Y Yu ldquoSiloxane-modified epoxy resin-clay nanocomposite coatings withadvanced anticorrosive properties prepared by a solutiondispersion approachrdquo Surface and Coatings Technology vol200 no 8 pp 2753ndash2763 2006

[37] AluminumHydroxide Determination ofWater Solubility Projectno 29620003 A Study Conducted at the Request of theAluminium REACH Consortium Harlan Laboratories Oxford-shire UK 2010


[38] K Devendra and T Rangaswamy ldquoDetermination of mechan-ical properties of Al

2

O3

Mg(OH)2

and Sic filled E-glassepoxycompositesrdquo International Journal of Engineering Research andApplications vol 2 no 5 pp 2028ndash2033 2012

[39] P Toro R Quijada M Yazdani-Pedram and J L AriasldquoEggshell a new bio-filler for polypropylene compositesrdquoMate-rials Letters vol 61 no 22 pp 4347ndash4350 2007

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Journal of

CrystallographyJournal of


The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014


CoatingsJournal of

Advances in

Materials Science and EngineeringHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Smart Materials Research



MetallurgyJournal of


BioMed Research International

MaterialsJournal of


Nano

materials


Journal ofNanomaterials


hydroxide (Al(OH)3) and magnesium hydroxide (Mg(OH)

2)

replacement of conventional flame-retardants is a realisticand promising way to overcome fire propagation and surfacespread of flame because of their low flame retarding efficiency[16ndash19]The performance of the intumescent system dependson the choice of the ingredients and their appropriate combi-nations

These research studies have pointed out a useful biofillerderived from chicken eggshell (CES) waste and its potentialrole in the fire protective coating industry CES waste is anindustrial byproduct and its disposal constitutes a seriousenvironmental hazard It is known that CES waste containsabout 95 calcium carbonate in the form of calcite and5 organic materials such as type X collagen sulfatedpolysaccharides and other proteins [20 21] CES can beutilized in commercial products to create new value in thesewaste materials and it has been highlighted recently becauseof its reclamation potential Although there have been severalattempts to use CES components for various applications[22ndash26] its chemical composition and availabilitymakes CESa potential source of biofiller reinforced biopolymer compos-ites giving additional or improved thermal and mechanicalproperties to the coating [27] The other advantages of usingCES are that it is available in bulk quantity lightweight highthermal stability and being inexpensive and environmentallyfriendly

This paper is concerned with the development and eval-uation of intumescent coatings properties The efficiency ofintumescent coatings on steel is investigated following theBS 476 Part 6-Fire propagation test Moreover the waterresistance thermal stability char formation and adhesionstrength of intumescent coatings were also studied andevaluated

2 Experimental

21 Materials and Method Chicken eggshells (CES) wereused as a biofiller in this study The CES membrane wasremoved and discarded The CES were then cleaned thor-oughly and dried at 90∘C for 12 h in the oven The driedeggshells were mechanically triturated to a powder formand then milled at a milling speed of 280 rpm for 48 hrespectively in a four-roll mill to obtain mean particle sizesof 2299 120583m The acrylic resin composed of acrylic acidmethacrylic acid esters of these acids or acrylonitrile wassupplied by Shinko Paint amp Chemical Sdn Bhd Ammoniumpolyphosphate phase II (119899 gt 1000) melamine and pen-taerythritolwere purchased from InternationalChemical LtdChina Titanium dioxide (R706) aluminium hydroxide andmagnesium hydroxide were purchased from Scientific GroupSdn Bhd Malaysia

Intumescent fire protective coatings were prepared usingacrylic binder pigment and flame-retardant ingredientsThe formulations were prepared using high-speed dispersemixer and the viscosity of the coatings was adjusted to95ndash105KU The compositions of intumescent coatings aregiven in Table 1 The prepared coating was coated on Q235steel plate using a gun sprayer For obtaining effective fire

Table 1 Compositions of intumescent fire protective coatings

Ingredients Parts by weight for formulationsA B C D

APP 1800 1800 1800 1800MEL 900 900 900 900PER 900 900 900 900TiO2 550 550 550 275Al(OH)3 mdash 550 mdash 275Mg(OH)2 550 mdash mdash 275CES mdash mdash 550 275BinderAcrylic resin 5300 5300 5300 5300

retardancy the thickness of the intumescent coatings hasbeen measured and maintained

22 Fire Propagation Test The fire propagation test wasperformed in accordance to the procedure specified in BS476 Part 61989 + A1 Fire propagation [28] The test methodconsists of exposing the product to a row of small flamesfor 20 minutes and an additional impressed irradiance of2 kW from third to the final minute of the test The tem-perature of the evolved combustion products is recordedFurthermore compared to the temperatures generated froma noncombustible specimen the result is expressed as firepropagation index that provides a comparative measure ofthe contribution to the growth of fire made by essentiallyflat material composite or assembly The coated face of thespecimens was exposed to the heating conditions of the testTo be Class 0 certified the fire propagation index (119868)must bele12 The lower the numerical value of the index is the betterthe material it indicates The details of the test procedures onindex of performance of specimens and calculation of resultsare explained as follows

In this test the rate and amount of heat evolved by thespecimen were taken into account while it was heated in anenclosed space under prescribed conditions Specimens ofsteel plate (225times 225times 23mm)were coatedwith intumescentcoatings (thickness of 15 plusmn 02mm) and the index ofperformance was determined from the following equations

1198941=

119905=3

sum119905=05

120579119898minus 120579119888

10119905

1198942=

119905=10

sum119905=4

120579119898minus 120579119888

10119905

1198943=

119905=20

sum119905=12

120579119898minus 120579119888

10119905

119868 = 1198941+ 1198942+ 1198943

(1)

where 119868 is the index of performance 119905 is the time (min) fromthe origin at which readingswere taken 120579

119898is the temperature


Substrate

Substrate

Pull-off force

AdhesiveCoating







119864sw =(119882119890minus119882119900)

119882119900

times 100 (2)



of the sample




119887) inMPa was


119891119887=119865

119860 (3)









3CESMg(OH)

2






05 14 18 12 14 121 18 21 15 18 1615 23 26 19 23 192 27 30 22 27 2325 30 34 25 31 263 34 38 30 34 304 72 122 87 55 545 108 212 149 133 1296 129 274 179 169 1817 148 321 223 243 2028 166 364 312 327 2199 182 378 336 372 23410 192 405 372 360 24412 214 417 391 355 24914 230 418 370 349 25316 238 416 326 310 25818 246 403 298 299 26020 257 384 281 290 263




2Al(OH)







2O3(s) + 3H

2O (g) (4)


2O (g) (5)






2released



3releases



2(g) (6)




(a) (b)

(c) (d)






3


2CESAl(OH)






(a) (b)

(c) (d)


0

10

20

30

40

50

60

70

80

90

100

100 200 300 400 500 600 700 800 900 1000

Resid

ual w

eigh

t (w

t)


CD




minus20

minus15

minus10

minus5

0

5

0 1 2 3 4 5 6 7 8

Wei

ght c

hang

e rat

e (

)


AB

CD









A B C DCoating 0332 0249 0288 0272

020

022

024

026

028

030

032

034

Adh

esio

n str

engt

h (M

Pa)





2




3filler in coatings


3filler


4 Conclusions



3Mg(OH)

2CES




Acknowledgments


References









































2

O3

Mg(OH)2










CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials




Substrate

Substrate

Pull-off force

AdhesiveCoating







119864sw =(119882119890minus119882119900)

119882119900

times 100 (2)



of the sample




119887) inMPa was


119891119887=119865

119860 (3)









3CESMg(OH)

2






05 14 18 12 14 121 18 21 15 18 1615 23 26 19 23 192 27 30 22 27 2325 30 34 25 31 263 34 38 30 34 304 72 122 87 55 545 108 212 149 133 1296 129 274 179 169 1817 148 321 223 243 2028 166 364 312 327 2199 182 378 336 372 23410 192 405 372 360 24412 214 417 391 355 24914 230 418 370 349 25316 238 416 326 310 25818 246 403 298 299 26020 257 384 281 290 263




2Al(OH)







2O3(s) + 3H

2O (g) (4)


2O (g) (5)






2released



3releases



2(g) (6)




(a) (b)

(c) (d)






3


2CESAl(OH)






(a) (b)

(c) (d)


0

10

20

30

40

50

60

70

80

90

100

100 200 300 400 500 600 700 800 900 1000

Resid

ual w

eigh

t (w

t)


CD




minus20

minus15

minus10

minus5

0

5

0 1 2 3 4 5 6 7 8

Wei

ght c

hang

e rat

e (

)


AB

CD









A B C DCoating 0332 0249 0288 0272

020

022

024

026

028

030

032

034

Adh

esio

n str

engt

h (M

Pa)





2




3filler in coatings


3filler


4 Conclusions



3Mg(OH)

2CES




Acknowledgments


References









































2

O3

Mg(OH)2










CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials






05 14 18 12 14 121 18 21 15 18 1615 23 26 19 23 192 27 30 22 27 2325 30 34 25 31 263 34 38 30 34 304 72 122 87 55 545 108 212 149 133 1296 129 274 179 169 1817 148 321 223 243 2028 166 364 312 327 2199 182 378 336 372 23410 192 405 372 360 24412 214 417 391 355 24914 230 418 370 349 25316 238 416 326 310 25818 246 403 298 299 26020 257 384 281 290 263




2Al(OH)







2O3(s) + 3H

2O (g) (4)


2O (g) (5)






2released



3releases



2(g) (6)




(a) (b)

(c) (d)






3


2CESAl(OH)






(a) (b)

(c) (d)


0

10

20

30

40

50

60

70

80

90

100

100 200 300 400 500 600 700 800 900 1000

Resid

ual w

eigh

t (w

t)


CD




minus20

minus15

minus10

minus5

0

5

0 1 2 3 4 5 6 7 8

Wei

ght c

hang

e rat

e (

)


AB

CD









A B C DCoating 0332 0249 0288 0272

020

022

024

026

028

030

032

034

Adh

esio

n str

engt

h (M

Pa)





2




3filler in coatings


3filler


4 Conclusions



3Mg(OH)

2CES




Acknowledgments


References









































2

O3

Mg(OH)2










CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials




(a) (b)

(c) (d)






3


2CESAl(OH)






(a) (b)

(c) (d)


0

10

20

30

40

50

60

70

80

90

100

100 200 300 400 500 600 700 800 900 1000

Resid

ual w

eigh

t (w

t)


CD




minus20

minus15

minus10

minus5

0

5

0 1 2 3 4 5 6 7 8

Wei

ght c

hang

e rat

e (

)


AB

CD









A B C DCoating 0332 0249 0288 0272

020

022

024

026

028

030

032

034

Adh

esio

n str

engt

h (M

Pa)





2




3filler in coatings


3filler


4 Conclusions



3Mg(OH)

2CES




Acknowledgments


References









































2

O3

Mg(OH)2










CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials




(a) (b)

(c) (d)


0

10

20

30

40

50

60

70

80

90

100

100 200 300 400 500 600 700 800 900 1000

Resid

ual w

eigh

t (w

t)


CD




minus20

minus15

minus10

minus5

0

5

0 1 2 3 4 5 6 7 8

Wei

ght c

hang

e rat

e (

)


AB

CD









A B C DCoating 0332 0249 0288 0272

020

022

024

026

028

030

032

034

Adh

esio

n str

engt

h (M

Pa)





2




3filler in coatings


3filler


4 Conclusions



3Mg(OH)

2CES




Acknowledgments


References









































2

O3

Mg(OH)2










CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials







A B C DCoating 0332 0249 0288 0272

020

022

024

026

028

030

032

034

Adh

esio

n str

engt

h (M

Pa)





2




3filler in coatings


3filler


4 Conclusions



3Mg(OH)

2CES




Acknowledgments


References









































2

O3

Mg(OH)2










CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials





































2

O3

Mg(OH)2










CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials





2

O3

Mg(OH)2










CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials










CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials



Documents

Research Article Fire Propagation Performance of Intumescent Fire Protective Coatings ...downloads.hindawi.com/journals/tswj/2014/805094.pdf · 2019-07-31 · Research Article Fire