Composites in Fire 3

Flame-retarded Gelcoats on Composite Laminates

Dr. Susanne Knop Wilfried Krieger

Agenda
z z

Mechanism of phosphorus containing Flame Retardants Fire Testing

Standards Screening Test

z z z

Formulations Results Summary

FR Mechanism - Phosphorus compounds

thermal feedback oxygen heat & smoke heat + combustion products
combustion area

1) formation of polyphosphoric acid

(NH4PO3)n Pred O2

>250C - n NH3 H2O

(HPO3)n (HPO3)n

P4O10

surface char

2) Acid dehydrates polymer and causes a compact surface char that insolates and protects the polymer.

surface pyrolysis

(HPO3)n + CX(H2O)m

charring process
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Char (CX) + (HPO3)n.mH20

FR Mechanism - Intumescent FR
thermal feedback oxygen

production of a voluminous, insolating and protective layer by formation of char and charfoam
heat combustion products smoke charfoam

heat

combustion area Pyrolyse

Basic formulation of an intumescent system: 1) char"-source (e.g. polyalcohols) 2) acid source (e.g. ammoniumpolyphosphate)

pyrolysis charring

3) foaming agent (e.g. melamine)

Intumescent Gelcoat - Mechanism

Flame retardant in the gelcoat gives the freedom for reinforcement in the laminate

layers of charred foam protects laminate gelcoat with Exolit AP laminate with no or less flame retardant
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Intumescent Gelcoat - Screening Test

Laminate

Gelcoat

front bunsen burner

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back thermoelement
directly behind the gelcoat

Intumescent Gelcoat - Screening Test

100 phr chalk

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100 phr ATH

100 phr Exolit

Intumescent Gelcoat - Screening Test

400 350

temperature [C]

300 250 200 150 100 50 0 0 1 2 3 4 5 6 7 8 9 10

time [min]
100 phr chalk 100 phr ATH 100 phr Exolit AP

Formulations
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UP-resins

reinforcement roller resin

gelcoat

Viapal UP 403 BMT Palatal A 400-01

Flame Retardants

in the Gelcoat: Exolit AP 740 in the Laminate: nothing or ATH

mould

Laminate

glass content: about 30 % curing: RT and 80C thickness: 3-4 mm

Screening Test - Viapal

600
100 phr AP 740

500 400 300 200 100 0 0 1 2 3 4 5 6 7

150 phr AP 740 50 phr AP 740

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The more flame retardant the lower the temperature

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Screening Test - Viapal

300 250 200 150 100 50 0 0 1 2 3 4 5 6 7 8 9 10 150 phr AP 740 + 100 phr ATH 100 phr AP 740 + 100 phr ATH 100 phr AP 740 + 50 phr ATH

The more flame retardant the lower the temperature

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German - DIN 5510

railway applications specimen: 5 specimen: 500 x 190 mm test: gas burner with fish tail 3 min flaming, 5 min test classification: destroyed area S4 < 200 mm after burning time S4 < 10 s smoke SR2 < 50 % dripping ST2 = no dripping class: S4 to S1, SR2 to SR1, ST2 to ST1
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Transportation - DIN 5510

250 200
150

Exolit AP 740 in gelcoat Exolit AP 740 in gelcoat

100 50

ATH in laminate ATH in laminate

Viapal Palatal

Flame Retardant [phr]

150 100

50

50

150 100 100 75 75 50 50

50 0

100

100

100 50 50

S4 SR2 ST2

S4 SR2 ST2

S4 SR2 ST2

S3 SR1 ST2

S3 SR1 ST2

S4 SR2 ST2

S4 SR2 ST2

S4 SR2 ST2

S3 SR2 ST2

S3 SR2 ST2

S3 SR1 ST2

S3 SR2 ST2

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German - DIN 4102 B1 - Brandschacht

construction / building applications specimen: 4 specimen: 1000 x 190 mm test: specimen = cage (chimney effect) ring burner 10 min flaming classification: smoke temperature < 200C rest length > 150 mm
UP resin Reichhold 31026 + Exolit AP 740
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class: B1

Construction - DIN 4102 B1

200

Exolit AP 740 in gelcoat Exolit AP 740 in gelcoat

ATH in laminate ATH in laminate

Viapal Palatal

Flame Retardant (phr)

150

100 50

100

150 125
50

100

100

100

100

0 B1
15

B1

B1

6 min

3 min

4 min

French - NF P 92 501 - Epiradiateur

construction / building applications specimen: 5 specimen: 300 x 400 mm test: radiant panel 30 KW/m butane pilot flame 20 min radiation classification: time to ignition flame height burning time class:
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M0 to M4 F (smoke density and toxicity)

NF P 92-501 Epiradiateur
200 180 160 Flame Retardant [phr] 140 120 100 80 60 40 20 0
M2 M1 M3 M3 q=6,67 q=1,84 q=18,4 q=55,1
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Exolit AP 740 in gelcoat Exolit AP 740 in gelcoat

100 50

ATH in laminate ATH in laminate

Viapal Palatal

50 100 100 50

50

150 100 100 75 50 50

50

M2 M2 M2 M4 M4 M3 q=4,63 q=26,5 q=2,50 q=59,9 q=57,4 q=64,1

British - BS 476 part 7

construction / building applications specimen: 6 specimen: 885 x 270 mm test: radiant panel: 35 KW/m pilot flame: 1 cm 10 min radiation classification: burning rate class: class 1 to class 3
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BS 476-7
Exolit AP 740 in gelcoat Exolit AP 740 in gelcoat
Flame Retardant (phr)

150

ATH in laminate ATH in laminate

Viapal Palatal

100

50

50 100 100

50

50

50

0 class 1
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class 1

class 1

class 1

Summary
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Flame retardant mainly on the surface broad application range

UP-Gelcoat Exolit AP 740 Exolit AP 742

z z z z z z

EP-Gelcoat Exolit AP 750

many processes possible

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low density of specimen no or less filler in laminate

non toxic highly effective low water solubility halogen free no corrosive smoke low smoke density

low processing viscosity, easier injection more reinforcement possible, better mechanics

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