Fire Retardants
Dr. J. Hao
National Laboratory of Flame Retardant Materials NLFRM
School of Chemical Engineering and Materials Science
Beijing Institute of Technology, Beijing, China
10 Nov 2015
MScFDFR.ppt
Contents
1.
2.
3.
4.
5.
6.
7.
Introduction
Fire Tests
Fire Retardant Chemistry
Halogen Containing FRs
Phosphorus Containing FRs
Intumescent FRs
Inorganic Hydroxides FRs
2
1. Introduction
1.1 Definition of FRs
Fire retardants (FRs) are chemical compounds or
mixtures of chemical compounds that are added
4
Time (min)
The comparison of non-fire retardant textile specimen and fire retarded in flame test
5
Connectors
Construction
1.
2.
3.
Textile/other
Upholstered chairs
A cable array
10
FR Plastics
Non-FR Plastics
(Reference value)
Escape Time
>15 t
Mass Loss
<1/2 m
HRR
<1/4 h
Toxic Gas
1/3 [CO]
[CO]
Smoke
The study shows that the proper selection of FRs can improve fire and life safety.
11
12
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
Polymer Feeder 1
Polymer Feeder 2
Additive Feeder
Filler Feeder 1
Filler Feeder 2
Liquid Feeder
Vacuum Pump
Inlet Screw
Side Feeder
Kneader
Discharge Screw
Wet Cut Pelletizing
Centrifuge
Water Circulation System
Pellet Cooling and Drying Unit
13
Inorganic hydroxides
Melamine, 6%
Cl, 10%
Br, 39%
Inorganics, 22%
P, 23%
14
15
16
Good Choice:
17
Approximate
Processin
Temp. of Decomp. g Temp.
()
()
ATH
Mg(OH) 2
ATH alumina trihydrate,
180
300
Examples,
Recommended for
200
> 200
Time (min)
SPR of 1-PVC, 2-PVC/Cu2O, 3-PVC/MoO3
Heat flux: 25kW.m-2
20
2. Fire Tests
Why carry out fire tests ?
22
23
UL offers
24
Vertical Burning Test: 5VA or 5VB (ASTM D 5048, IEC 6069511-20, IEC 60707 or ISO 9772) is for enclosures for products
that are not easily moved or are attached to a conduit system.
Thin Material Vertical Burning Test: VTM-0, VTM-1, or VTM-2
(ASTM D 4804 or ISO 9773)
Horizontal Burning Foamed Material Test: HBF, HF-1, or HF-2
(ASTM D 4986 or ISO 9772) are used for nonstructural foam
materials.
26
UL 94HB Test
127 mm12.7 mm, thickness < 12.7 mm, > 3.18 mm 0.13 mm
Test Criteria
A burning rate < 38.1 mm/min
(over a 3 inch span for specimens
having a thickness of 3.05 - 12.7 mm)
or
27
127 mm12.7 mm, thickness < 12.7 mm, > 3.18 mm 0.13 mm
94 V-0: t av. BT < 5 s and the drips do not ignite the cotton
94 V-1: t av. BT > 5 s but < 25 s and the cotton is not ignited
94 V-2: self-extinguishing but the cotton is ignited
29
1.
Burning Specimen
2.
3.
Igniter
4.
Wire Screen
5.
Ring Stand
6.
7.
Brass Base
8.
Tee
9.
Cut-Off Value
10.
Orifice in Holder
11.
Pressure Gage
12.
Precision Pressure
13.
Filter
14.
Needle Value
15.
Rotameter
31
32
A mixture of oxygen and nitrogen is metered into the bottom of the tube.
The sample is ignited at its upper end with a flame, which is then
withdrawn, the sample burns like a candle from the top down.
34
All materials could now be assigned an OI value that would relate its relative
flammability to any other material
Limiting Oxygen Indexes of Various Polymer Materials
Polymer Materials
OI (%)
Polyethylene, Polypropylene
17.4
Polystyrene
17.8
Acrylonitrile-butadiene-styrene
18.7
Polyethylene terephthalate
20.6
Polyamide 66
23.0
Polycarbonate
25.0
45.0
Carbon
65.0
Polytetrafluoroethylene
95.0
35
generated by solid
materials within a
closed chamber due to
flaming and/or nonflaming combustion.
NBS Smoke Chamber (ASTM E 662, BS 6401, and NFPA 258)
36
NF: A six-tube burner, fueled with a mixture of propane and air, is used
in combination with the radiant heat.
Ds = G [ log10 (100/T) + F ]
where:
G = V/AL = 132,
V = volume of the closed chamber (m3)
T = percent light transmittance as read from the light sensing instrument, and
F = a correction factor
38
The specific optical density (Ds) vs. time curves of the resulting smoke
39
40
H + O2 HO +
HO + CO CO2 + H
41
X
Halogen FR
halogen radical
X
RH
R
organic radical
HX
hydrogen halide
R
organic radical
42
H2 + X
H2O + X
43
44
45
46
47
Chemical
Structure
Halogen
Content
(%)
TGA 5%,
wt loss ()
M.P.
()
Decabromodiphenyl oxide
(DECA)
---
83
362
300-315
Bis(2,3-dibromopropyl ether) of
TBBA
(BDBPE-TBBA)
---
68
310
106-120
Decabormodiphenyl ethane
(DBDPE)
---
82
450*
335-342
* Decomposition Temperature
49
Chemical
Structure
Halogen
Content
(%)
TGA 5%,
wt loss ()
M.P.
()
Hexaboromcyclododecane
(HBCD)
---
74.7
>250
175-197
Brominated Indan
---
73
325
240-255
Tetrabromobisphenol A
(TBBPA)
---
58.5
305
181
50
Textile 7%
Transportation 6%
Construction 31%
E&E 56%
FR PP applications:
electrical (wire nuts, lamp sockets, coil bobbins, connectors and wire and
cables).
housing of electrical appliances, TV yokes, pipes for water discharge,
fibers for textile applications, film and sheets for roofing.
Influence of the FR: Sb2O3 Ratio (PP)
FR: Sb2O3 ratio
1:1
2:1
3:1
6:1
BDBPE-TBBA (%)
1.5
1.5
1.5
1.5
Sb2O3 (%)
1.5
0.75
0.5
0.25
Fail
V-2
Fail
UL 94 class
3.2 mm
Fail
52
UL 94 V-2: 23%
DIN 4102 B1: 12%
Others: 2 %
DECA
BDBPE-TBBA
Brominated
Indane
PP
100
67.5
84
60
FRs
---
24.4
12
15
ATO
---
8.1
Talc
---
---
---
---
Mg(OH)2
---
---
---
20
Br content (%)
20
11
UL 94, class
NR
35
28
32
21
30
29
19
3.5
Modulus (MPa)
1500
1600
1200
1900
FRs type
Composition (%)
Properties
54
56
15
Polycarbonate
Polyethylene
10
Poly(ethylene
terephthalate)
Polyamide
Filled phenolic
57
Organophosphorus FRs
Triaryl phosphate, Alkyl diaryl phosphate etc. being as nonflammable
plasticizers for poly(vinyl chloride) (PVC), cellulose acetate and engineering
plastics such as modified PPO resin and PC/ABS blends
A flexible PVC + 60 parts of an organic plasticizer, LOI = 22%;
A flexible PVC + 60 parts of an triaryl phosphate, LOI = 30%;
58
6. Intumescent FRs
First development for application in the coatings
60
61
This char
insulates the substrate from flame,
heat and oxygen.
adheres to the surface of molten
materials to prevent it from dripping,
thus eliminating a possible source
of propagation of fire.
64
Virgin PP
IFR-PP
Clorinated FR-PP
Brominated FRPP
100
75
57
67
Exolit IFR 23
25
Alicyclic chlorine FR
34
Aromatic bromine FR
25
Antimony oxide
3.6
Zinc borate
5.4
18
30
27
28
UL-94 rating
NR
V-0
V-0
V-0
Ds (flaming conditions)
Brominated FR-PP
600
Chlorinated FR-PP
400
200
IFR-PP
PP
0
1
time (min)
Fig. Optical smoke density of FR-PP compounds
66
68
LOI > 30% , ABR: 18 mm/min (no FR-FPUF, ABR: 61.8 mm/min)
69
Steel structure
70
71
72
North
America
Europe Japan
Asia
Total volume
Value
(US $ mm)
Halogen
79
73
45
49
246
825
Phosphorus
46
59
11
17
133
426
Antimony
oxides
23
20
16
13
72
342
ATH
232
120
42
402
221
Mg(OH)2
11
24
49
Other
19
30
66
Total
405
289
123
90
907
1929
Thermoplastic
(phr*)
Cross-linking
Type (phr)
EVA**, 19%VA
---
100
EVA, 28%VA
80
---
LLDPE***
20
---
ATH
170
150
Ethylsilane
1.5
Peroxide, Antioxidant
0.07, 0.4
1.0, 0.4
LOI (%)
~ 37
~ 33
> 10
> 18
>180
>180
*phr- per hundred resin, **EVA- Ethylene Vinyl Acetate, ***LLDPE- Linear Low Density Polyethylene
75
Processing
temp. ()
Loading level
(%)
UL-94 rating
Oxygen index
PBT
230
55
60
Fail
V-0
29.8
Nylon 6,6
275
55
60
Fail
V-0
33.3
77