• Ashland Composite Polymers


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    • Abstract: Ashland Composite PolymersSolutions for Fire Retardant Composites1/49 Ashland Composite PolymersSolutions for Fire Retardant CompositesIndex• Materials, Composites and Fire• Fire, Smoke & Standards

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Ashland Composite Polymers
Solutions for Fire Retardant Composites
1/49
Ashland Composite Polymers
Solutions for Fire Retardant Composites
Index
• Materials, Composites and Fire
• Fire, Smoke & Standards
• How to Produce Fire Retardant Composites?
• Ashland Portfolio & a few Case Histories
2/49
Ashland Composite Polymers
Solutions for Fire Retardant Composites
Materials
Industry uses many different materials
that can be classified like:
• Wood, Plywood…
• Concrete, Stone, Plaster…
• Paper
• Glass, Ceramics …
• Steel, Aluminium…
• Plastics, Composites…
• Etc.
3/49
Ashland Composite Polymers
Solutions for Fire Retardant Composites
Plastics
Plastics (reinforced or not) have an organic matrix,
split in two kinds of chemistry:
• THERMOPLASTICS
Under heat, they melt
• THERMOSETS
Once cured, they are definitely set
Ashland supplies liquid thermoset resins
for Composites!
4/49
Ashland Composite Polymers
Solutions for Fire Retardant Composites
Composites
Today Composites are being used in
demanding applications with confidence like:
• Structural Parts, Surface Finish,
Corrosion Resistance and…
…FIRE Retardant
There are many test methods allowing
comparison of Composites for Fire (& Smoke)
Resistance and select them eventually.
5/49
Ashland Composite Polymers
Solutions for Fire Retardant Composites
Fire & Combustion
HEAT Burning process
is quite complex
and described by the
Fire Triangle.
The fire can not take place
FUEL OXYGEN if a single angle in the triangle
is missing.
6/49
Ashland Composite Polymers
Solutions for Fire Retardant Composites
Fire & Combustion
Volatiles GAS PHASE
Products Heat
All Organic Materials burn
OXIDATION (FLAME)
and this is an exothermic
reaction.
There is a ‘feedback’
THERMAL DEGRADATION (SOLID)
phenomenon as shown in
CONDENSED PHASE the opposite figure.
7/49
Ashland Composite Polymers
Solutions for Fire Retardant Composites
Fire & Combustion
This process has several phases:
• Heating
• Thermal Degradation
(Free Radicals Generation)
• Ignition of Gases
• Flame Spread
Flame retardation can be effectively achieved by
using physical and chemical actions at every step.
Smoke is also becoming a big concern!
8/49
Ashland Composite Polymers
Solutions for Fire Retardant Composites
Fire Standards
Various equipments are used depending
FLUE
on countries to measure the fire
STRUCTURE behaviour of materials like:
• Reaction to fire:
Epiradiateur, Brandschacht test…
SPECIMEN
• Smoke development:
SUPPORT
NBS chamber
• Reaction to fire, smoke
MEASURING
PILOT FLAME GAUGES development and dripping test:
Euroclass Single Burning Item (SBI)
COMBUSTION CHAMBER
9/49
Ashland Composite Polymers
Solutions for Fire Retardant Composites
NBS Smoke Chamber & NF X 10-702
This method, developed in the The measurement of the toxicity of thermal decomposition products
USA, is used in France for is carried out by the tube furnace method (NF X 70-100).
measuring smoke generated by The smoke performance (opacity of smoke, toxicity of fumes) is
solid materials. divided into 6 classes: F0 = the best, F1, F2, F3, F4 and F5.
PHOTODETECTOR
HOUSING
PHOTODETECTOR
DOOR WITH LIGHT BEAM
GLASS WINDOW
INFRARED RADIATOR
TEST CHAMBER SPECIMEN
BLOW-OUT
WINDOW FOR
PANEL
OPTICAL SYSTEM
TROUGH FOR
PHOTOMETER SPECIMEN MELT
CONTROLS AND SIX TUBE BURNER
MEASURING INSTRUMENTS
LIGHT SOURCE
PHOTOMETER
10/49
Ashland Composite Polymers
Solutions for Fire Retardant Composites
ASTM E662 Smoke Density
11/49
Ashland Composite Polymers
Solutions for Fire Retardant Composites
Epiradiateur Test NF P 92-501
FLUE This French Test is well accepted in
many European countries.
The fire performances are
divided into five classes:
SPECIMEN M0 = no combustion, M1, M2, M3 and M4
IGNITION
GAS
IGNITION
With the Smoke Test
UPTAKE
a classification "M/F" is often
GAS proposed in Transport Applications
UPTAKE
RADIATOR
AIR
SUPPLY
12/49
Ashland Composite Polymers
Solutions for Fire Retardant Composites
ASTM E162 Radiant Panel Test
13/49
Ashland Composite Polymers
Solutions for Fire Retardant Composites
ASTM E-84 Tunnel Test
14/49
Ashland Composite Polymers
Solutions for Fire Retardant Composites
ASTM E-84 Tunnel Test (inside)
This test allows a classification
of all solids using an index,
FSI = Flame Spread Index,
(FSI = 0 is for non-flammable;
FSI = 100 for wood) and
classes. Class I is the best one
with < 25; Class II the next best
with 25/75 and so on.
15/49
Ashland Composite Polymers
Solutions for Fire Retardant Composites
Main Fire Standards Building & Construction
Country Standard Classification
NF P 92-501,
France M0, M1,…, M4
Epiradiateur
DIN 4102,
A1, A2, B1, B2,
Germany Brandschacht
B3
tests
BS 476 Part
UK Class 0, 1,…, 4
6&7
ASTM E-84, Flame Spread
USA
(Tunnel Test) Index
16/49
Ashland Composite Polymers
Solutions for Fire Retardant Composites
Main Fire Standards Transport, Train
Country Standard Classification
Epiradiateur: Mi
NF P 16-101, 102, Glowing Wire: I i
France
103 Smoke Toxicity
(NBS Smoke Chamber ): Fi
Combustibilty: Si
Germany DIN 5510 part 2 Smoke Emissions: SRi
Dripping Test: STi
Ignit ion, Heat Release
Rate, Flame
UK BS 6853
Spread, Smoke opacity
& Toxicity
ASTM E-662 (NBS
USA Smoke Index
Smoke Chamber)
17/49
Ashland Composite Polymers
Solutions for Fire Retardant Composites
Other Fire Standards
Applications Standard Classification
IMO MSC 653 (16) Surface Flammability
International
Maritime IMO MSC 61 (67) Smoke Opacity &
Organization Toxicity
(in a modified NBS
Smoke Chamber)
UL 94 V0, V1, V2,
Electrical
( Flammability) 5VA, 5VB
ASTM E-162
Solid Materials Surface Flammability
(Radiant Panel)
Limit Oxygen Index % LOI (> 21: self-
All
(ISO 4589) extinguishing)
18/49
Ashland Composite Polymers
Solutions for Fire Retardant Composites
A New European Standard for Construction Products
European Standard EN 13501-2.
There are seven "EUROCLASSES" (A1, A2, B, C, D & E) .
Products classified by Five Tests.
• Small Flame (ignitability) pr EN ISO 11925-2.
• Radiant Panel pr EN ISO 9239-1.
• Bomb Calorimeter pr EN ISO 1716.
• Single Burning Item pr EN 13823.
• Little Furnace pr EN ISO 1182.
New EUROCLASSES will replace all
existing national classifications.
19/49
Ashland Composite Polymers
Solutions for Fire Retardant Composites
A New European Standard for Fire Protection in Railways, Vehicles
European Standard pr EN 45545.
Based on small scale tests that will evaluate
fire behaviour to 5 main parameters: FIRST.
• F = Spread of Flame
• I = Ignitability
• R = Rate of Heat Release
• S = Smoke
• T = Toxicity
Presently tests being considered are: IMO = spread of flame (ISO
5658-2) & Toxic Gases Analysis ISO 5659-2 (modified NBS chamber),
Cone Calorimeter / rate of heat release (ISO 5660-1), Glow Wire…
20/49
Ashland Composite Polymers
Solutions for Fire Retardant Composites
Composites and Fire
Composites compete against many
other materials and some of them like
aluminium are non-flammable
(but aluminium melts!).
However efficient solutions exist
dramatically improving the fire
behaviour of GRP!
21/49
Ashland Composite Polymers
Solutions for Fire Retardant Composites
Composites and Fire
Examples of Improvements:
Halogenated Polyesters and
ASTM E84 Flame Spread
synergy with Antimony
ASBESTOS/CEMENT
Common polyesters are in a very low
HALOGENATED
class, with an index of ~ 350. Choosing
HALOGENATED/
ANTIMONY halogenated polyesters gives much
RED OAK better results: 25/75, class II in this
standard. Just by adding antimony, there
PLYWOOD
is an effect of synergy with halogens,
NON-HALOGENATED
bringing the composites up to a Class I
0 25 75 100 200 300 400
(under 25).
22/49
Ashland Composite Polymers
Solutions for Fire Retardant Composites
A Chemical Solution for FR Example
Halogens Chlorine or Bromine based products can be either
mixed in resin as additives or more effectively linked
by reaction in the polymeric backbone.
The halogens mainly affect radical chain mechanism
in the flame.
R–CL R• + CL•
CL• + RH R•+HCL
HCL + H• H2+CL•
HCL + OH• H2O+CL•
23/49
Ashland Composite Polymers
Solutions for Fire Retardant Composites
A Physical Solution for FR Example
Aluminium Trihydrate ATH decomposition reaction starts at ~200 °C
(ATH)
2 Al(OH)3 Al2O3 + 3 H2O ( - HEAT)
This endothermic reaction functions as a heat sink
and a smoke dilution.
This is a halogen-free solution. This is the most efficient
solution to achieve LOW SMOKE + LOW TOXICITY.
24/49
Ashland Composite Polymers
Solutions for Fire Retardant Composites
Summary of Solutions
Polyesters + FR Additives Halogenated Vinyl Esters
• Ortho + TCEP and others • TetraBromobisPhenol-A;
Halogenated Polyesters with or without Sb2O3
• Chlorinated: HET acid or FR Gelcoats
Chlorendic Anhydride Modar® Resins + ATH
• Brominated: TBPA, DBNPG And…
• blends with or without additives
Systems:
Resins / Gelcoats / Intumescent
25/49
Ashland Composite Polymers
Solutions for Fire Retardant Composites
Selection of Solutions
The final FR properties strongly depend on many parameters like:
• Process (HLU, Injection, Pultrusion etc.)
• Dimensions (Thickness, Shape)
• Reinforcement Fibres (Type: glass, carbon, %)
• Curing (Post-Cure or Not)
• Gel-Coat Characteristics (eventually)
• Formulation of the Resin
(inherently FR?, Additives?, Fillers?, and so on)
• and others…
26/49
Ashland Composite Polymers
Solutions for Fire Retardant Composites
Selection of Solutions APPLICATION
YES Stringent specifications? NO
Corrosion Resistance? YES
Polyesters + FR
Additives
NO
FR Epoxy
Vinyl-Esters
Premium Fire Resistance?
Low Smoke/Low Toxicity?
Halogenated
NO Polyesters &
FR Gel-Coats
YES
Modified Acrylics:
Modar Resins
27/49
Ashland Composite Polymers
Solutions for Fire Retardant Composites
Ashland Solutions in Europe
Polyesters + FR Additives
• Aropol™ F 207 TPA & TPB
• Aropol F 195 L
Halogenated Polyesters
• Hetron® Series (clear): F 820; F 830; F 880
• Hetron® Series (filled): F 804; F 805; F 808; F 814; F 240 TF; PR 1804
• Hetron 92 FR, 197
• Hetron 325 FS etc.
Fire Retardant Gel-Coats
• Enguard™ CE, AE
• Maxguard® FR
28/49
Ashland Composite Polymers
Solutions for Fire Retardant Composites
Ashland Solutions in Europe
Halogenated Vinyl Esters
For Corrosion End-uses when Fire Resistance is required too.
• Hetron® FR 992 & FR 992Sb (new! Contains Sb2O3)
• Hetron FR 998/35 Class I Flame Spread without Sb2O3
Modar® Resins + High Loadings of ATH
For the most stringent European Standards:
Fire + Smoke + Toxicity performances
• Modar 835S: Injection & Pultrusion
• Modar 826 HT: Low Shrink System for Pultrusion
• Modar 865: for Structural End-uses
• Modar 814: for Hand-Lay-Up
29/49
Ashland Composite Polymers
Solutions for Fire Retardant Composites
Ashland Case Histories
Norwegian life boat
Aropol F 207 TPA
30/49
Ashland Composite Polymers
Solutions for Fire Retardant Composites
Ashland Case Histories
31/49
Ashland Composite Polymers
Solutions for Fire Retardant Composites
Ashland Case Histories
Air exhaust washer hood
(paper industry)
Hetron FR998/35
32/49
Ashland Composite Polymers
Solutions for Fire Retardant Composites
Ashland Case Histories
Italian high speed train
PENDOLINO
Front head in Hetron 325 FS
33/49
Ashland Composite Polymers
Solutions for Fire Retardant Composites
Ashland Case Histories
French TGV
Hetron
34/49
Ashland Composite Polymers
Solutions for Fire Retardant Composites
Ashland Case Histories
35/49
Ashland Composite Polymers
Solutions for Fire Retardant Composites
Ashland Case Histories
36/49
Ashland Composite Polymers
Solutions for Fire Retardant Composites
Ashland Case Histories
Channel Tunnel
Cable Trays
Modar highly filled
with ATH
37/49
Ashland Composite Polymers
Solutions for Fire Retardant Composites
Ashland Case Histories
Front of Regio Shuttle
Modar + ATH
38/49
Ashland Composite Polymers
Solutions for Fire Retardant Composites
Ashland Case Histories
Mass transit
Modar + ATH
39/49
Ashland Composite Polymers
Solutions for Fire Retardant Composites
Ashland Case Histories
Pultruded profile made from
Modar (filled with ATH)
40/49
Ashland Composite Polymers
Solutions for Fire Retardant Composites
Ashland Case Histories
A HYCOPROD project
– see following slide
41/49
Ashland Composite Polymers
Solutions for Fire Retardant Composites
Ashland Case Histories
Modar for FR part used in this
innovative railway part
42/49
Ashland Composite Polymers
Solutions for Fire Retardant Composites
Ashland Team at Your Service
Plant
Sales Office
43/49
Ashland Composite Polymers
Solutions for Fire Retardant Composites
Product Range 1
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Pr % % (mPa.s.) (b) % (Mpa) (Mpa) (%) (Mpa)
D
HETRON F 240 TF Filled yes 1.45 15 1,2 1,5 1000 30 35 6000 1 55 75
HETRON F 240 TF-5201 Filled yes 1.37 15 1,2 1,5 900 31 35 6000 1 55 75
HETRON F 240 TFE-5201 Filled yes yes 1.37 15 - 1,5 900 31 35 6000 1 55 75
HETRON F 840 TF Filled 1.65 15 1,2 1,5 1000 23 35 4000 1 55 68
HETRON F 840 TF-5201 Filled yes yes 1.6 15 1,2 1,5 800 27 35 4000 1 55 68
HETRON F 805 TF Filled yes 1.68 12 - 20 1,2 1,5 1200 25 35 5000 1 50 70
HETRON F 805 TF U Filled tropicalized yes 1.68 10 1,2 (2) 1,5 1200 25 35 5000 1 50 70
HETRON F 808 TF Filled 1.65 15 1,2 1,5 1000 23 35 4000 1 55 68
HETRON F 814 TF Filled yes 1.65 10 - 20 1,2 1,5 1200 23 35 5000 1 60 60
HETRON F 820 Clear 1.38 25 1 1 400 34 45 3600 1.4 80 60
HETRON F 820 TA Clear yes yes - 20 - 1 700 (1) 200 37 45 3600 1.4 80 60
HETRON F 820 TB Clear yes yes - 35 - 1 700 (1) 200 37 45 3600 1.4 80 60
HETRON F 820 TE Clear yes yes - 20 - 1 700 (1) 200 37 45 3600 1.4 80 60
HETRON F 830 TA Clear yes yes - 15 - 1


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