combinations of elements: a new paradigm for fire retardancy

MacromolecularChemistry and PhysicsTalents & Trends

Combinations of El Pfor Fire Retardancy

Thi A

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and impair the processing ability of plastic materials. With the reactive approach, only a little amount of the FR may be necessary but it may be very expensive. [ 4 , 5 ]

There are a variety of elements that are considered the backbones of the FRs, these include halogens, phosphorus, nitrogen, silicon, min-erals [typically aluminum trih-droxide (ATH) and magnesium hydroxide (MDH), boron, iron, tin, and antimony]. The last three are typically not used alone but rather

Intr

In increto reweigplastic materials. However, the utiliza-tion of plastics carries a re risk that is not seen with metals and this brings about the need for re retardancy. Plastic materials, when exposed to high temperatures, decompose with the release of heat, smoke, soot, and toxic volatiles with smoke consid-ered as the primary cause of death in most res rather than heat. [ 1 ] There are two ways to render a plastic ame retardant (FR): 1) the plastic can be blended with FRs (additive approach) and 2ducedreactio

peu

eymer from one that produces volatile to one that produces char. The min-erals ATH and MDH decompose endo-thermically with the elimination of water so the heat goes to decompose the mineral and not to decompose the polymer.

There are several laboratory tests that are used to evaluate re retar-dancy; those must often used are the limiting oxygen index (LOI), the UL-94 protocol and the cone calorimeter. LOI measures the minimum concen-tration of oxygen required for a mate-

Trends in Polymer Science

Macrom 2012 Wariappan, C. A. Wilkieartment of Chemistry and Fire rdant Research Facility, Marquette

versity, PO Box 1881, Milwaukee, 53201, USA

are synergists that can make other elements, usually halogens, more effective. It should be noted that the well-used monomeric halogen-based re retardants have been at least partially banned world-wide; it may be expected that only polymeric hal-ogen-based FRs will be used in the

) an FR element can be intro- into the plastic via a chemical n (reactive approach). Both

rial to burn; the higher one can drive up this minimum concentration, the more re safe a material may become. The UL-94 protocol evaluates the ease of extinction of a polymer, the shorter the time for which a material burns the safer it may be. The cone calorimeter measures the rumal Mariappan , Charles

trend article describes some receix common plastic materials, paturated polyester, polyurethanetionally, a single re retardant ele retardancy but in this paper, there

tions of re retardant elements,erial.

classesferent approalowed. necessaimpact

oduction

modern society, there is an asing use of plastic materials place metals due to the lighter ht and high speci c strength of ail: [email protected] future. [

ol. Chem. Phys. 2012, 213, 19871995ILEY-VCH Verlag GmbH & Co. KGaA, Weinheimements: a New

. Wilkie *

t work related to the developmlypropylene, polystyrene, poly

and epoxy resin. Con-ment is used to achieve is a description of com-including a nano-sized

of FRs have advantages in dif-applications. [ 2 , 3 ] The additive h has been most often fol-High loadings are sometimes ry, which can have a negative on the mechanical properties

Firethe vahydrogmake densedthe thwileyonlinelibrary.com

1 ] heat rearadigm

nt of ame retardancy (methyl methacrylate),

retardancy may occur in or phase, by trapping the n and hydroxyl radicals that p the ame, or in the con-phase, changing the course of rmal degradation of the pol-1987 DOI: 10.1002/macp.201200363

lease rate (HRR), that is, how

1988

T. Mariappan and C. A. Wilkie

www.mcp-journal.de

MacromolecularChemistry and Physics

erp

a

big is the re. It is unfortunate that each a diffcannoevalutechn

Thethat mperhaused. typicatain susualretardis thacombmentexamexploFR thawith activethat be redphospprodu

Forgroupodimemontclays,reducby thecontamensno imby otprotoodimeenhanso tha re redue topartiananod

Thicombretardmenscommpylenmethaester/and e

r

p7oae mxtsnnmt rur

ue

es ]

not completely compatible and bleed out; FRs for PP have to mally stable at the processing ature of about 250 C.

escent compositions swell eat is applied and thus form

layer of insulating material, can limit the ow of heat to lymer. The classical intumes-R) composition contains three omponents, acid [ammonium osphate (APP), char-former rythritol), and blowing agent ine)]. A minimum of 30 wt%

loading is necessary for

ei t. w

uv

d

n

e

adiphenyl ether (Deca) plus Sb 2 O 3 in PP-g-MA system. [ 15 ] Hu et al. [ 16 ] studied the ammability of PP/clay and PP/clay/nano-CaCO 3 nanocomposites and showed a synergistic FR effect of nano-composites with IFR additives. Zhang and Wilkie [ 17 ] have studied the re retardancy of PP using metal hydrox-ides (ATH and MDH) and clay combi-nations. The addition of clay imparts good re retardant properties with lower amounts of metal hydroxide. Addition of clay could improve both thermal stability and re retardant properties of PP lled with FRs. [ 18 ]

c

.anosof these evaluations measures erent property of a re and one t correlate the results from one

ation with those of a different ique. situation in the past has been ost often a single FR element,

ps with a synergist, has been This is not to suggest that the l FR package does not con-everal different materials but ly only one of these is the re ant. The premise of this work t, in the future, we will see

inations of re retardant ele-s used together. One obvious ple that has not been often ited is the combination of an t functions in the vapor phase one that is condensed phase . In this case, one might expect the amount of volatiles will uced and that the halogen or horus can then trap what is ced. more than 10 years, many s have been studying nan-nsional materials, typically

morillonite (MMT) and related and it has been found that this es the peak HRR as evaluated cone calorimeter. [ 69 ] Polymers

ining MMT, or other nanodi-ional materials, typically show

provement when evaluated her re retardancy evaluative cols. The utilization of a nan-nsional material also offers ced mechanical performance t if it is combined with another tardant, the loss of properties this material may be at least

lly offset by the presence of the imensional material. [ 6 ]

s trend article addresses the ination of conventional re ants together with nanodi-

ional materials for six different on plastic materials, polypro-

e, polystyrene (PS), poly(methyl crylate), unsaturated poly-

vinyl ester resin, polyurethane, poxy resin.

FlamePolyp

Polypro(LOI = 1and prleaves degrada randocompleproducfragmepropylerequireilar to The reon the which and thare sevadditivtions. [ 11

FRs aretend tobe thertemper

Intumwhen ha thickwhich the pocent (IFbasic cpolyph(pentae(melamof IFRMacromo 2012 WILEY- Charles A. Wilkie retired from Marquettnow professor emeritus. His research gretardancy for more than 30 years and more than 10 years. The group currentlynanocomposites to enhance the re ret

Retardancy of opylene

ylene (PP) burns readily in air %) with melting and dripping duces virtually no soot nor ny residual char. PP starts to thermally above 290 C, via scission mechanism with a

mixture of gaseous pyrolysis of C 4 , C 5 , and C 6 hydrocarbon ts with only small amounts of e monomer present. The FR ents for PP are generally sim-

hose for other polyole ns. [ 10 ] etardancy of PP usually relies se of endothermic additives, equires about 60% additive s the mechanical properties rely impacted, vapor-phase , or intumescent composi-

Many commercially available

effectivrating) for IFRsolubiliythritola lowershow so

Variorials haPP forma V-0 rawith aadditionimprovedue to awhich aheat athe am ame-ran increergistic combin

Thirumal Mariappan obtained his M.Temaster in Chemistry) in Polymer TechnoScience and Technology. Before his Ph.Din some of the research projects from vR&D Institute like CSIR, DRDO, and an Ereceived his Ph.D. in re retardancy of pInstitute of Technology, Kharagpur. He iat Marquette University. l. Chem. Phys. 2012, 213, 19871995VCH Verlag GmbH & Co. KGaA, Weinheim University in 2009 and is oup has been studying re olymer nanocomposites for

is focused on the utilization of rdancy of polymers.

ame retardancy (UL-94 V-0 n PP. [ 12 ] A potential problem compositions is the water

y of both APP and pentaer- Microencapsulated APP has

ater solubility and thus may me improvement. s nanodimensional mate-e been incorporated into IFR

ulations. He et al. [ 13 ] showed ting with 25% of IFR loading dition of organoclays. The of organobentonite can the FR properties of IFRPP n increase of the char residue, cts as an effective barrier for d oxygen, thus improving e retardancy of intumescent tarded PP samples, as well as asing the LOI value. [ 14 ] A syn-effect was observed from the tion of clay and decabromon-

h. degree (after bachelor and logy from Cochin University of work, he worked for 6 years rious Indian Government gineering College. In 2010, he lyurethane foam from Indian currently a postdoctoral fellow www.MaterialsViews.com

DanielaHighlight

DanielaSticky NoteBuscar artculo [18] para saber porque podra haber una mejora con la adicin de arcilla.

ww

Combinations of Elements: a New Paradigm for Fire Retardancy

www.mcp-journal.de


S brcatSi 12by litewitwa1%loapro

Aforandsilisilistaof silicomprelayunHosilichacompolthechaFR IFR

T -zH 2 Oretageof 22.UL-

graphit Table 1. LOI and UL94 data of FR lled PP with different loading of sepiolite. (Reproduced

Sam[wt

PP

PP

PP

PP

PP

PP epiolite is part of a family of ous hydrated magnesium sili-

e with the theoretical formula O 30 Mg 8 (OH) 4 8H 2 O characterized a needle-like morphology. Sepio- showed synergistic FR effect h IFR lled PP and a V-0 rating s observed with 24% of IFR and sepiolite clay (Table 1 ); higher dings of sepiolite decrease the FR perties. [ 19 , 20 ] synergistic FR effect was observed

the combination of fumed silica IFR in PP. The amount of fumed

ca is critical; less than 1% fumed ca loading increases both thermal bility and re retardant properties IFR lled PP, because the fumed ca promotes the formation of a

pact intumescent char layer and vents the cracking of the char er, which effectively protects the derlying polymer from burning. wever, a high loading of fumed ca restricts the formation of rred layers with P-O-P and P-O-C plexes formed from burning of

In thisacid genatioan effAnotheZrO 2 isPP. [ 23 ] Ygistic enano ZhypophWang edifferendioxidenium dand maretardaresults exhibitrating oxides.the ef(CNTs) systemenhancbut sho ame r

Deod

from ref. [ 19 ] with permission).

ple %]

IFR [%]

Sepiolite [wt%]

LOI [%]

- 100 0 0 17.6

- 75 25 0 34.4

- 75 24 1 36.0

- 75 23 2 35.8

- 75 22 3 35.8

- 75 21 4 32.3w.MaterialsViews.com

ymeric materials and destroys swelling behavior of intumescent rred layers, which deteriorates the and thermal properties of the PP/ blends. [ 21 ] he layered phosphate,

irconium phosphate [ -Zr(HPO 4 ) 2 .] is used in intumescent re

ardant PP systems as a synergistic nt. PP with low loading (2.5 wt%) organically modi ed -ZrP with 5 wt% IFR (APP + PER) provides a 94 V-0 rating with an LOI of 37%.

retardananopaPP andrates aof calthe evand ca(2 phr)gives hwith IFof EG,of IFR better

Macrom 2012 WILE case, -ZrP acts as a solid that can catalyze dehydro-n of the polymer, acting as ective crosslinking agent. [ 22 ] r study showed that nano- also synergistic in IFR lled i et al. [ 24 ] also found a syner-ffect of llers, such as ZnO,

nO, zeolite 4A, and aluminum osphite, with IFR lled PP. t al. [ 25 ] studied the effect of t metallic oxides (titanium

, lanthanum trioxide, zirco-ioxide, molybdenum trioxide, nganese dioxide) on the re

ncy of PP lled with IFR. The showed that ZrO 2 and Cr 2 O 3

better ame resistance (V-0 in UL-94) than do the other Du and Fang [ 26 ] investigated fects of carbon nanotubes on the ammability of PPIFR ; the introduction of CNTs es the thermal stability of PP, wed a severe deterioration of etardancy. [ 26 ] har et al. [ 27 ] studied the ame ncy of calcium carbonate

lled w

Flameof Poly

Polystyr ammadency tto high productand bezenes, hfuel is ato largein a veret al. [ 2

could eretardanet al. [ 30 ]

sulfur cof PS Synergyphosphants anriorationobservetional Fameliorperformthe partincludinnickel capresencthe strstabilityto commabilitycontain ammadifferen

UL 94 test Dripping

No rating Yes

V-1 No

V-0 No

V-0 No

V-1 No

V-2 Norticles combined with APP in showed that better burning re caused by the formation cium metaphosphate with olution of ammonia, water, rbon dioxide. A low loading of expandable graphite (EG) igher LOI values for PP lled R and increasing the loading

deteriorates the FR activity lled PP. Moreover, EG shows ame resistance than natural

dependef ciengistic ewas obs

Nyamgistic ecalorimtainingPhysicabetweeresponsergy in

ol. Chem. Phys. 2012, 213, 19871995Y-VCH Verlag GmbH & Co. KGaA, Weinheime at the same loading in PP ith IFR. [ 28 ]

Retardancy styrene

ene (PS) is intrinsically highly ble (LOI = 18%) and has a ten-o depolymerize when exposed temperatures, and the volatile s, styrene monomer, dimer, nzene and lower alkyl ben-ave high fuel value. Since the romatic, it is able to condense

polycyclic structures, resulting y smoky or sooty ame. Yang 9 ] showed that nanosilica ffectively improve the ame cy of brominated PS. Beach

found that a low loading of ould improve the LOI values lled with triphenylphosphate. was observed between

ate and bromine re retard-d clay [ 31 , 32 ] ; signi cant dete- of mechanical properties is

d upon the addition of conven-R but, the addition of clay can ate this. Improvements in re ance of PS/IFR composites by ial substitution of nano llers, g clay, OZrP, CNT, Fe 2 O 3 , and talyst have been reported. The

e of these additives changes ucture, yield, and thermal of the char, which leads

posites with different am- performance. The clay-

ing sample showed the lowest bility. OZrP modi ed with t salts had various effects,

ing on the cations, on the FR cy of IFR system. [ 33 ] A syner-ffect of CNT with Deca/Sb 2 O 3 erved in PS system. [ 34 ] bo et al. [ 35 ] showed syner-

ffects in both TGA and cone etry for PS formulations con- both MgAl-LDH and APP. l and chemical interactions n MgAlLDH and APP are ible for the observed syn- thermal stability and re 1989

1990


www.mcp-journal.de


perstudsucon tdiffATHMWnotparalongistandpea

Tpul aminvesilicvertof Fchatotaredu

Flamme

Polyignas muhighDepscisdurmerthegrosmocompolyditihavratebut reof ois dit isdepacteexcchain m

n

a

C

h

h

d

n

t

t

n

n

usero et al. [ 44 ] found syner-rnieao

. mpd

o

i

nicre

a

u

rlosct

s

e

i

ri

i

formance. Tutunea and Wilkie [ 36 ] ied the effect of nanosized llers

h as layered silicate and MWCNT he re properties of PS lled with erent FR additives (Deca/Sb 2 O 3 , , and RDP). The combination of CNT with either ATH or RDP did

improve FR properties of PS com-ed with the sample containing FR

e. In contrast, there is a syner-ic interaction between MWCNT Deca and a greater reduction of k HRR was observed. he effect of nanosilica and atta-gite clay as nano llers on the

e retardancy of PS has been stigated. Both attapulgite and a nanocomposites improve the ical burning ame retardancy R lled PS by reducing dripping; r formation is promoted and the l heat released during burning is ced. [ 37 ]

e Retardancy of Poly(methyl thacrylate)

(methyl methacrylate) (PMMA) ites readily (LOI = 17%) and softens it burns; the pyrolysate contains ch monomer and little, if any,

-molecular-weight products. olymerization, rather than chain sion, causes PMMA to drip less ing burning than most other poly-s. Depolymerization together with

presence of oxygen in the ester up, probably accounts for the lower ke formation per unit weight in parison with that of hydrocarbon mers under most burning con-

ons. [ 38 ] Halogenated compounds e been used to reduce burning s and ease of ignition of PMMA,

less effort has been devoted to the retardation of PMMA than to that ther polymers. This lack of effort ue partly to the realization that dif cult to inhibit the unzipping olymerization mechanism char-ristic of this polymer. In addition,

ellent transparency and aging racteristics are critical properties

ost applications for PMMA; re

retardinfrom on

Pack of MWCrials canPMMA additiocles aloincludintions, dThe comsigni cmass lowith onMoreovwith thof MWPMMA of nanoobserve

Isitmgated thFR witMWCNTbetter tpropertassesseobservedue to tby strothe amtion buby nano

The modi ecenoatestudiedmine arment inseems PHRR aeffect obehaviodictatedmine iand lowproducePMMA (10%) aperformreductioA synebetweeterms oMacrom 2012 WILEYg additives usually detract e or both of these properties. et al. [ 39 ] showed that a mixture NT and clay nanosized mate- enhance ame retardancy of

to a greater degree than the of either of the nanoparti-

ne. Addition of nanoparticles, g the standard FR formula-

ecrease the time to ignition. bination of MWCNT and clay ntly reduced the HRR and

ss rate relative to compounds ly one type of nanoparticles.

er, they showed a V-0 rating e addition of a small amount NT to the Deca/Sb 2 O 3 lled sample. A synergistic effect -ZrO 2 with TPP in PMMA was d by cone calorimetry. [ 40 ] an and Kaynak [ 41 ] investi-e effect of organophosphinate nano llers (nanoclay and ) in PMMA; nanoclays were an CNT in improving the re

ies of FR lled PMMA samples by cone calorimetry. The

d behavior was explained as he restriction of intumescence

g CNT networks formed on ing surfaces during combus-

enhanced intumescent chars clays. FR properties of PMMA

d with a zinc aluminum unde- LDH and/or melamine were . Higher loadings of mela-e required to obtain enhance- re properties, whereas LDH o give similar reductions in t lower loading (10%). The

f the two additives on the re r of the PMMA samples was by the additive, with mela-creasing the time to PHRR ering the amount of smoke d relative to the LDH-rich composites. Both melamine nd LDH (5%) showed better ance when considering the n in PHRR, FIGRA, and FPI. [ 42 ] rgistic effect was observed EG and silica in PMMA in

f LOI. [ 43 ]

Cinagistic betweeand silthat thsmoke were ncombinand PSmainlysilicon talline ring an

Laacheffect Al 2 O 3 ) o lled and APphosphoxide the theretardaticles areinforlayer pHowev re behicantly

FlameUnsat

Unsatumolecuprecurscondenrated aacid. Sylate ias the polyestreinforcproportposite They aof applface coand buiuses attance toaromatester recan be

ol. Chem. Phys. 2012, 213, 19871995

-VCH Verlag GmbH & Co. KGaA, Weinheime properties in PMMA and PS nano-sized oxides (alumina

ca) and APP. It is noteworthy decrease of peak HRR and s well as an increase of LOI ticed with hydrophobic silica

ed with APP both in PMMA This behavior was ascribed to the formation of a speci c

etaphosphate (SiP 2 O 7 ) crys-hase, which promotes char- an ef cient insulating layer. achi et al. [ 45 , 46 ] studied the f oxide nanoparticles (TiO 2 , n the ammability of PMMA with organophosphinates

P. The combination of either nate or APP with metal

nanoparticles can enhance rmal stability as well as re

cy of PMMA. The nanopar-d the catalytic effect and the ement for the carbonaceous omoted by the FR additives. r, TiO 2 does not improve the avior of the composites signif-

s compared with Al 2 O 3 .

Retardancy of rated Polyester

ated polyester resins are low-ar-weight prepolymers or rs, which are prepared by the ation of a glycol, an unsatu-id, and a saturated aromatic yrene or methyl methacr- most commonly employed cross linking agents for the r resin. Cast and glass ber ed resin constitute a large on of the high volume com-materials currently in use. e employed in a wide range cations such as ooring, sur-atings, boats, transportation, ldings; res may arise in these any time, giving great impor- re hazards. [ 47 ] Because of the c content (styrene) in poly-sins, large amounts of smoke

released. When low smoke www.MaterialsViews.com

www.Ma


www.mcp-journal.de


propertthe usdicyclois adva

The graphitshowedwith et al. [ 49

retardaresin APP, Closants [(ZS), anFlame the resto the presencnates dof APP ment iis a gothe prefurthertion ofsampleformatand utions. [ 4

that thance dsurfactpolyestCloisiteance co25A. Futhat clretardawith APphate,

Atkinence ofnate aon the tainingmore eet al. [ 54

metalliATH, anerties oshows little inpolyestof parti

ability, particularly the com-on of fumed silica and ATH d greater reduction of peak s compared with the mixture mina with ATH and dehy- ATH at the same loading. Hor-et al. [ 55 , 56 ] reviewed the in u-of stannate additives on the ability of different polymers s PVC, PP, PA, ABS, polyester,

poxy resin. The effect of ZHS, and ATH on the ammability yester resin containing deca-diphenyl ether and dibromo-ntyl glycol (DBNPG) was also d; the addition of Sb 2 O 3 to brominated resins provides a

materials made by reacting diiso-cyanates with diols or/diamines. Depending on the ratio of reactants and their types, catalyst, reaction con-ditions, etc., various kinds of PU mate-rials useful for the manufacture of foams ( exible or rigid), elastomers, coatings, and adhesives can be pro-duced. Polyurethanes are readily am-mable (LOI = 16%22%) with release of toxic smoke. The ammability of PU strongly depends on the structure of the polyol, degree of cross-linking, density, and isocyanate index, espe-cially foams. Jayakody et al. [ 59 ] showed the synergistic effect of conventional FR withies are required in a product, e of methyl methacrylate or pentadiene in place of styrene ntageous.

combination of expandable e (EG) and APP mixtures synergistic FR behavior polyester resin. [ 48 ] Nazare ] studied the ame and smoke nt properties of polyester lled with the combination of isite 25A, and smoke suppres-

zinc borate (ZB), zinc stannate d zinc hydrostannate (ZHS)].

retardancy was observed for in lled with APP and ZB due

cross-linking of APP in the e of zinc borate, but zinc stan-o not promote cross-linking and hence show no improve-

n ame retardancy. APP alone od smoke suppressant and in sence of ZB and ZS there is

smoke suppression. Addi- Cloisite 25A to the APP lled shows reductions in smoke ion in both well-ventilated nder-ventilated re condi-

9 , 50 ] Another study showed e improvement of ame resist-epends on the nature of the ant in the clay. For example, er resin lled with APP and 10A show good ame resist-mpared with Cloisite 15A and rthermore, they also showed

ay could improve the ame ncy of polyester resin lled P rather than melamine phos-

IFR mixture, and ATH. [ 51 , 52 ] son et al. [ 53 ] studied the in u-

inorganic tin oxide and stan-dditives such as ZS and ZHS ammability of halogen-con- polyester resin; stannates are

ffective than tin oxide. Tibiletti ] studied the effect of different c oxides such as alumina, d fumed silica on the FR prop-f polyester resin. This study that one particle alone has uence on the re behavior of er resin; however, a mixture cles led to a strong decrease of

ammbinatishoweHRR aof aludratedrocks ence ammsuch aand eSb 2 O 3 ,of polbromoneopestudieboth V-0 racompaaddedwith Zated sZHS githe ll

KanmabiliRDP, cmodi foundwith nFR effand orshowe

Flame

Polyurresent

Figu35 kterialsViews.comMacro

2012 WILEting with higher LOI values red with either ZHS or ATH

alone or in combination HS and Sb 2 O 3 . Both halogen-

amples containing Sb 2 O 3 and ve lower smoke compared with ed sample alone (Figure 1 ). dare et al. [ 57 ] studied the am-ty of poly vinyl ester resin using opper hydroxy dodecyl sulfate ed LHS and Cloisite 15A. They

that the combination of RDP ano llers showed antagonistic

ect. On the other hand, POSS ganoclay with conventional FRs d a synergistic effect. [ 58 ]

Retardancy of Polyurethane

ethanes or/polyureas (PU) rep-a broad group of polymeric

urethanGharenhbility ofand EG. the melaignition tion of bobservedsynergistion of m

Triethphosphotives inpresencheat coovercomerties bacts preand thefor TEP/the sim

re 1 . PHRR, TSR, and smoke values of polyesteW m 2 . (Reproduced from ref. [ 56 ] with permissionmol. Chem. Phys. 2012, 213, 19871995Y-VCH Verlag GmbH & Co. KGaA, Weinheim polydimethylsiloxane in poly-e elastomer. Bashirzadeh and baghi [ 60 ] studied the amma-

exible PUF using melamine Cone calorimetry showed that mine lled sample had higher time, while greater reduc-

oth peak HRR and smoke was from the EG lled sample and

tic behavior with the combina-elamine and EG was observed. ylphosphate (TEP) and red rus (RP) are useful coaddi-

combination with EG; the e of TEP helps to decrease the nductivity of the foam and e the poorer physical prop-

ecause of plasticization. TEP dominantly in the gas phase improved results obtained EG lled foams are due to ultaneous FR action both

r resin containing DBNPG under ). 1991

1992


www.mcp-journal.de


in the solid and in the gas phases, whileactionphasethe abut EGof botFor exAPP uLOI vativelyin rigloadinwas 3

FlypoweAl 2 O 3K 2 O, impro lled investpolyu(PIR) cbromizinc sand laclay iof foa

Mophonithe phospunmo ed chollowsilicon lled et al. [ 6

resistmicrooxideloadinspherdancysiliconthe htion w

Bou ameand Mby MWof PHhigheof TPU

sV

Tn

P

nc

l

o n

oin molding and casting applications because of a unique combination of properties. Epoxy resins are relatively low-molecular-weight prepolymers capable of being processed under a variety of conditions. The diglycidyl ether of bisphenol A (DGEBA) is the most commonly used liquid diepoxide. Although epoxy resins normally are ammable (LOI = 22%), their am-mability can be reduced considerably by the use of a variety of phosphorus and halogen additives or monomers.

e 2 . HRR as a function of time of TPU and TPU/oduced from ref. [ 69 ] with permission).

2. Effect of organoclay on the re rmance index of TPU. (Reproduced ref. [ 70 ] with permission).

als Fire performance

index (FPI)

0.073

% organoclay 0.130

hosphate ester 0.071

hosphate ester ganoclay

0.199 for RP/EG lled foams the FR is effectively only in the solid . [ 61 ] Both APP and EG improve me retardancy of PU materials was better than APP in terms

h re and smoke retardancy. [ 62 ] ample, 15 wt% of both EG and sed alone in rigid PUF gave lues of 32% and 24.5%, respec-

. The optimal ratio of APP to EG id PUF is 1:1 by weight (total g is 15 wt%) and the LOI value

0.5%. [ 63 ] ash, a by-product of coal- red r stations, containing SiO 2 , , Fe 2 O 3 , CaO, SO 3 , MgO, Na 2 O, MnO, TiO 2 , and P 2 O 5 , could ve the ame retardancy of IFR rigid PUF. [ 64 ] Zatorski et al. [ 65 ] igated the ammability of rethane-polyisocyanurate foam ontaining different FRs such as nated triol, phosphorus polyol, tannate, expandable graphite, yered silicates. The addition of

mproves the ame retardancy m containing EG and ZS. desti et al. [ 66 ] showed that phos-um-modi ed clay improves ame retardation of aluminum hinate lled rigid PUF, while di ed and ammonium modi-lays do not. The in uence of microspheres and whisker oxide on the properties of EG PUF was investigated by Bian 7 , 68 ] There is no change in ame

ance of PUF lled with hollow sphere and whisker silicon separately, whereas a high g of EG with hollow micro-

es improves the ame retar- of PUF and moreover, whisker oxide performs better than

ollow microsphere in combina-ith EG. rbigot et al. [ 69 ] studied the

retardancy of TPU using APP WCNT. The substitution of APP CNT is not bene cial in terms

RR (Figure 2 ), even though a r quality char is formed. The LOI /APP (30 vol%) is not improved

by the but a APP exMWCNthe nathe besventioneffects.

The phosphbetter than or lled Tthe timHRR) isretardatant beto ashavailabsituatiosideredof the the FPIretarda

The 3-chlor

Figur(Repr

Tableperfofrom

Materi

TPU

TPU + 5

TPU + p

TPU + p + 5% orMacrom 2012 WILEYubstitution of APP by MWNT -0 rating at 3.2 mm (TPU/

hibits a V-2 rating without ). Hence, they believed that ocomposite approach gives

t results combined with con-al FRs and leads to synergistic

addition of organoclay and ate ester FRs in TPU gave a re performance index (FPI)

ganoclay and phosphate ester U (Table 2 ). The FPI (ratio of e to ignition and the peak

used to characterize the ame cy of materials. It is impor-

ause it correlates to the time over and indicates the time e to escape in a full-scale re n. Therefore, it may be con-as a good individual indicator verall re hazard. The higher value, the better is the ame cy of a material. [ 70 ]

addition of nanoclay with -1, 2-propane diol as chain

extendebility, mechanPU elasmercialdiol as aet al. [ 72

acrylatemabilitymelamidextrin.improveIFR lle

Awadmabilitycontaintion of MWCNTof ame

Flame R

Epoxy rsetting signi cacoatingsol. Chem. Phys. 2012, 213, 19871995-VCH Verlag GmbH & Co. KGaA, Weinheimr improves the thermal sta- ame retardancy, and also ical properties of segmented tomer compared with com- PU containing 1,4-butane chain extender. [ 71 ] Kozlowski

] studied the effect of butyl -modi ed clay on the am- of polyurethane lled with

ne polyphosphate, starch, and Butyl acrylate-modi ed clay s the ame retardancy of the

d PU sample. et al. [73 ] studied the am- of polyurea nanocomposites

ing APP and EG; the addi-nano ller such as clay, POSS, , gives a slight improvement retardancy of FR lled PU.

etardancy of Epoxy Resin

esin is a specialty thermo-plastic that has developed a nt market as adhesives and in reinforced laminates, and

APP-MWCNT (heat ux 35 kW m 2 ). www.MaterialsViews.com

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Many requirfor exPCB anA com re reof tetthe diresin becausand regrowinThe usdisplaergismboric ative cowith t

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Table 3 Fire retardancy of epoxy lled with clay and cref. [

EP

EP + C

EP + 5

EP + C

EP + 10

EP + 10

EP + C

EP + 15applications of epoxy resins e the system to be re resistant, ample, electrical laminates for d certain structural composites. mon method of imparting this sistance is the incorporation

rabromobisphenol-A (TBBA) or glycidyl ether of TBBA into the formulation. However, mainly e of environmental concerns cycling issues, there has been a g interest in halogen-free FRs.

e of ATH and TPP in epoxy resin ys notable ame-retardant syn- [ 74 ] ; the combination of APP and cid leads to the best IFR protec-ating in epoxy resin compared

heir use separately. [ 75 ] artel et al. [ 76 ] studied the FR ties of epoxy lled with phos-

um-modi ed clay with con-nal FR additives (melamine

heat conof claysture. [ 78 ] better lled wwith RDbetter than CNof APP aretardatclay mis no imand CNet al. [ 80

retardan2,2-bis(hydroxy5,5 -bisdihydrospirobiifound syfrom Sp

76 ] with permission).

Sample LOI (%) 1

UL 94 t ig (S) 3 [M

20.5 HB 102

lay 21.2 HB 90

MB 23.3 HB 60

lay + 5 MB 23.5 HB 60

MB 24.1 HB 53

APP 23.8 HB 62

lay + 10 APP 21.9 HB 63

APP 28.9 V0 66aterialsViews.com

and APP) and showed that the retardancy ef ciency does not se linearly with the MB and oncentrations (Table 3 ). The nation of clay with MB or APP antagonism as result of inhi- of the intumescent behavior. er, the combination of phos-

um-modi ed clay with ATH romising approach for ame

ancy. [ 77 ] ther study also showed that corporation of clays did not

he desired FR effect to epoxy probably due to the increased

evaluatetion. WFR behaphosphomelting

Harad ame with pos i l s e s qtita natethe poquioxansystem ence ofNo syn

Macromo 2012 WILEYductivity and lower mobility due to the cross-linked struc-

Katsoulis et al. [ 79 ] showed ame retardation of epoxy ith APP and clay than clay P and TBP. Clay alone gives

ame resistance in epoxy T, whereas the combination nd CNT shows greater ame ion than that of the APPixture. Furthermore, there provement when both clay

T are used with APP. Camino ] studied the combined re t action of phosphonates

3-diethyloxyphosphonyl-4-phenyl)propane (BisP) and

(diethyloxyphosphonyl)-6,6 -xy-3,3,3 ,3 -tetramethyl-1,1 -ndane (SpiroP) and clay and

nergistic and additive effects iroP and BisP with clay when

in epoxtriglyciet al. [ 84

compoof epoadditiopoundsepoxy ably bshow astudied(TiO 2 , LAPP lEP obta20%. AdmationsmallerLiu anof silicsilica, cidylethylsiloxaepoxy the adenhancchar yidid notepoxy and shphoruslane, tpolydimshowedand coprevenchar. Hthat syphorusin term

onventional FRs. (Reproduced from

THE J m 2 ]

10

THE/ML [MJ g m 2 ]

0.2

Residue [%] 2

140 2.4 5.0

130 2.3 9.2

142 2.4 9.8

135 2.4 12.5

129 2.3 12.0

105 1.9 15.6

116 2.2 21.1

84 2.0 35.3d in terms of peak HRR reduc-u et al. [ 81 ] found synergistic vior epoxy resin lled with nium-modi ed clay and low-

phenylsiloxane glass. a et al. [ 82 ] showed that the

retardancy of epoxy lled ly(glycidyloxypropyl) phenyl u iox a n e / o r ga n o - l aye r e d system was superior to ly(glycidyloxypropyl) silses-e/organo-layered titanate probably because the pres-

phenyl promotes charring. ergistic effect was observed

stabilityepoxy rbinationcontainphosphtion andment onduring c

Summ

Nanodimthree menhanci

l. Chem. Phys. 2012, 213, 19871995-VCH Verlag GmbH & Co. KGaA, Weinheimyl isocyanurate. [ 83 ] Wang ] studied the effects of metal nds on the ame retardancy y resin lled with APP; the of APP and metal com-

improves the re safety of resin signi cantly presum-cause the metal compound catalytic effect. Song et al. [ [85 ] the effect of metallic oxides a 2 O 3 ) on the FR properties of ed epoxy resin; APP alone in ins a V-0 rating at a loading of dition of La 2 O 3 causes the for-of a more compact char with carbonaceous microstructure. Chou [ 86 ] studied the effect

on additives such as nano-etraethoxysilane, and digly-er-terminated polydimeth-ne on the ammability of esin lled with phosphorus; ition of silicon compounds

es the thermal stability and lds of epoxy resins. Nanosilica

migrate to the surface of the during thermal degradation wed antagonism with phos-

In the case of tetraethoxysi-e diglycidylether-terminated ethylsiloxane lled sample

signi cant silicon migration ld form a protective layer to

further degradation of the wever, another study showed

nergistic ef ciency of phos-and silicon was not observed s of LOI. [ 87 ] In general, thermal and ame retardancy of

esin are improved by the com- of silicon- and phosphorus-

ing compounds [ 88 , 89 ] because orus provides the char forma- silicon provides the enhance- thermal stability of the char ombustion. [ 90 , 91 ]

ary

ensional materials have ajor areas of application,

ng ame retardancy, barrier 1993

1994


www.mcp-journal.de


[ 17 ] J. Zhang , C. A. Wilkie , in (Eds: another nanomaterial that has not

b

n

ter

properties, and mechanical properties. Basedinvesthesein thmanynumbthe mtrue wherpass.tiallynanoness clays

In that of exmateconveimprobtaionly additrial hall oftheretage.of nais theventi

Ofare creadefar fepoly(the tgenaare inreasonatiocase ameit is Thusare msuita

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It is harticle, consideretardato devadditive

Received2012 ; PuDOI: 10.1

Keywordpoly(mepolystyrpolyeste

upon the very large number of tigations into the properties of materials, since their discovery e mid-1990s, it is surprising to that there are only a small er of products that have reached arket place. This is particularly

in the eld of ame retardancy e many feel that this too shall Some companies that were ini- involved with polymerclay composites have left this busi-and are focusing on other uses of . this trend article, it is shown

there have been a great number amples where nanodimensional rials have been combined with ntional ame retardants and

oved performance has been ned. This is true considering the re performance but the

ion of a nanodimensional mate-as the opportunity to enhance the properties noted above, so use can be a signi cant advan- The authors feel that the future nocomposites in re retardancy ir usage as adjuncts with con-

onal re retardants. the six polymeric materials that overed in the trend article, the r will observe that there are wer cases for polystyrene and

methyl methacrylate). For PS, ypical ame retardant is a halo-ted material and, since these

disfavor, there is not a strong n to attempt to discover combi-ns with nanomaterials. In the of PMMA, there is currently no retardant for this material and

most commonly used with one. efforts on these two polymers

ore directed toward identifying ble ame retardants. ere are a large number of nano-nsional materials. In many , it is quite fortunate that the -type clays were the rst inves-d because they have shown the

properties up to this time. This not mean that there may be

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n evaluated and will excel in eas but it does mean that one e a little suspect when trying

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scientists and engineers will r combinations of ame

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: June 28, 2012; Revised: July 13, blished online: August 23, 2012; 002/macp.201200363

s: epoxy resin; ame retardancy; hyl methacrylate); polypropylene; ne; polyurethane; unsaturated

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combinations of elements: a new paradigm for fire retardancy

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