Fire Science &

Flame-Resistant
Fabric Technologies
Drew Child, Ph.D. September 2020
 Outline
Part I: Fire Science Basics
 Combustion chemistry overview
 Chemical Thermodynamics

Part II: Flame Resistant Fabric Strategies

 Thermally stable fibers
 Radical scavengers
 Char-forming polymers

2
 Nomenclature
“FR” can mean both Fire Retardant and Flame
Resistant

A Fire Retardant (n.) is a chemical additive that

suppresses fire by interrupting the fire flow-
diagram. A flame-retardant is a type of fire-
retardant that is incorporated into a material, such
as a fabric.

Flame Resistance (adv.) refers to the property of an

article or material (fabric, plastic part, film, etc.) with
reduced propensity to burn.
3
 01 Fire Science
Basics
What is a Fire in Chemical Terms?

4
 What is fire?
Fire is a chemical reaction that produces heat and
light by the combustion of a fuel in oxygen.

Heat
The fire triangle is a simple way of
looking at fire dynamics. If any of the
three legs; heat, fuel, or oxygen is
removed, the fire will extinguish.
However, it does not tell the complete
story.
Oxygen Fuel
5
 What is fire?
Fire is a chemical reaction that produces heat and
light by the combustion of a fuel in oxygen.

CH4 + 2O2 CO2 + 2H2O + heat

Methane Oxygen Carbon Dioxide Water

6
 What is fire?
Fire is a chemical reaction that produces heat and
light by the combustion of a fuel in oxygen.

CH4 + 2O2 CO2 + 2H2O + heat

Methane Oxygen Carbon Dioxide Water

+ +

7
 What is fire?
Fire is a chemical reaction that produces heat and
light by the combustion of a fuel in oxygen.

CH4 + 2O2 CO2 + 2H2O + heat

Methane Oxygen Carbon Dioxide Water

+ +

Higher Chemical Energy Lower Chemical Energy

8
 Chemical Thermodynamics
The difference between the energy of the starting
materials and the energy of the final products
becomes the energy that is released.

Energy of
Reactants
ENERGY

Energy of
Products
9
 Chemical Thermodynamics
The difference between the energy of the starting
materials and the energy of the final products
becomes the energy that is released.
Energy released
Energy of during the reaction
Reactants
ENERGY

Energy of
Products
10
 Chemical Thermodynamics
The difference between the energy of the starting
materials and the energy of the final products
becomes the energy that is released.
Energy released
Energy of during the reaction
Reactants

The “mechanism”
ENERGY

is the route the

molecules travel
during the
reactions

Energy of
Products
11
 Radical Chain Reaction

Thermal Energy

12
 Chemical Thermodynamics
Energy is required to start the reaction and form the
radical compounds.

Energy of
Reactants
ENERGY

Energy of
Products
13
 Chemical Thermodynamics
Energy is required to start the reaction and form the
radical compounds.

Energy of
Reactants
ENERGY

Energy of
Products
14
 Chemical Thermodynamics
Energy is required to start the reaction and form the
radical compounds.

Energy of
Reactants
ENERGY

Energy of
Products
15
 Chemical Thermodynamics
Energy is required to start the reaction and form the
radical compounds.

Energy of
Reactants
Energy required
to start the
ENERGY

reaction

Energy of
Products
16
 Chemical Thermodynamics
Energy is required to start the reaction and form the
radical compounds.
Energy released
Energy of during the reaction
Reactants
Energy required
to start the
ENERGY

reaction

Energy of
Products
17
 Combustion of Solid
Materials
Because combustion occurs in the gas phase, solid
materials need to decompose into smaller, volatile
molecules.

18
 Combustion of Solid
Materials
Initiation Degradation Radical Formation Combustion

19
 What is Fire? Revisited
Fire is a radical chain reaction that produces heat
and light by the combustion of a fuel in oxygen.

Heat
Fire control strategies, including
Flame Resistant fabric technologies,
rely on disrupting of these four “legs.”

Oxygen Fuel
20
 FR vs. Non-FR Fabrics

21
 02 Flame Resistant
Fabrics
Strategies for Flame Suppression

22
 Flame Retardant Fabric
Terms
Inherent Intrinsic FR Permanent FR Fiber
Durable Topical FR Fabric
There are no universally accepted definitions for these terms. They
may mean something different depending on the source (could be
marketing terms).
This presentation will focus on how they work instead of
how
they’re applied:

 Thermally stable fibers

 Radical scavengers
23
 Char-forming polymers
 High Temperature Fibers
“Aramids”

24
 Thermally Stable Fibers
Thermally Stable Fibers are defined as materials that do not
decompose at temperatures less than 400°C (750°F).

 These fibers produce flame resistant fabrics by reducing

the available amount of volatile compounds available as
fuel.
 Aramids (Aromoatic Amides) are the most widely used.
 Contain no fire-retardant chemicals.

Ploy(meta-phenylene Ploy(para-phenylene terephthalamide)

isophthalamide) “Para-aramid”
25
“Meta-aramid”
 Combustion of Thermally Stable Materials

InitiationX Degradation Radical Formation Combustion

26
 Thermally Stable Fibers
Decomposition
Fiber type Common trade names Primary uses
Temperature (oC)
Nomex® (DuPont)
Protective apparel, fire
Meta-Aramid Conex® (Teijin) 420o C
barrier layers for furniture
Kermel® (Kermel)
Kevlar® (DuPont) Composites, protective
Para-Aramid 550o C
Twaron® (Teijin) apparel

Fireman’s turn-out gear

PBI (polybenzimidizole) PBI (PBI) >700o C
(blends with para-aramid)

PPS (polyphenylensufide Torelina® (Toray) >500o C High temperature filters

PBO (polybenzoxazole) Zylon® (Toyobo) 700-720o C High strength composites

Pod-Z® (Podrun)
POD (polyoxidiazole) Arselon (Svetlogorsk 490o C Protective apparel, filtration
Khimvolokno)

OPAN/PPAN (oxidized Pyron® (Zoltex) Brake pads, apparel, aircraft

>450o C
polyacyrlonitrile) PANOX® (SGL group) fire barrier layers
27
 Example Products Using
Thermally Stable Fibers
Leading Fabric
Leading Fiber Brands
Uniform Shirt
Brands
Nomex IIIA –
4.5oz.

Coverall
Nomex IIIA – 6 oz.

28
 Thermally Stable Fibers
Advantages
 Fabrics are highly durable
and can last many years.
 Does not rely on fire
retardants.
 Can provide protection at
lighter weights.
 No FR agent to consume,
can resist heat for longer
times (i.e. firefighter gear).
29
Disadvantages
 Easily the most expensive
option (initially).
 Fibers are relatively stiff,
resulting in a firmer, harsher
hand; low water absorption.
 Requires special fibers or higher
weight to achieve Cat 2 arc
rating.
 Since no fire retardant is
present, contamination must be
 Radical Scavengers
“Modacrylics”

30
 Radical Scavengers
 Radical scavengers are fire retardant chemicals that release
radicals capable of combining with and scavenging radical
intermediates.

 Mostly based on Bromine or Chlorine.

 Modacrylic is the most common use of radical scavengers in

flame resistant protective apparel.

31
 Radical Scavengers
 Radical scavengers are fire retardant chemicals that release
radicals capable of combining with and scavenging radical
intermediates.

 Mostly based on Bromine or Chlorine.

 Modacrylic is the most common use of radical scavengers in

flame resistant protective apparel.

32
 Radical Scavengers
Small Molecule Radical Scavengers: Used in foams, plastics, and
other molded materials. Used extensively with binders as back
coatings for textile for many years. Most common in plastic parts
(and effective) are the polybrominated compounds.

Polymeric Radical Scavengers: Most common fiber-based radical

scavenger are the modified acrylics (modacrylic). This is a
copolymer of acrylonitrile and vinyl chloride, normally including
an Antimony synergist.

33
Combustion of Radical
Scavengers
Initiation Degradation Radical Formationx Combustion
+
Radical Scavengers
 Example Products Using
Radical Scavengers
Fabric Brands
Uniform Shirt
– 7oz.

Hi-Vis Coverall with

Reflective Trim
– 7oz.

35
 Radical Scavengers
Advantages Disadvantages

 Fabrics can have good  Modacrylic fibers are relatively

flame resistance at low weak and can be brittle (often
loading levels of radical reinforced with para-aramids)
generators
 Modacrylic fabrics have some
 Modacrylic has permanent thermal shrinkage and thermal
FR properties stability issues (limits dye
selection)
 Modacrylic has a nice
hand, at a reasonable cost

36
 Char Formers

37
 Char Formers
 Phosphorous-based char-forming additives are reacted
with cotton or incorporated into Rayon yarns.

 After exposure to heat, the phosphorous creates stable

rings when combined with degraded cotton compounds and
forms a rigid char.

 The char layer protects the fabric from heat and further
degradation.

38
 Combustion of Char Formers

Initiation Degradation x Radical Formation Combustion

Char Formation

39
 Char Formers
Durable char formers chemistry is most commonly
based on THP salts.

OH
OH
OH
P
P
HO HN
HN HN
HO OH HN OH
HN
P O
HN P O
HN
HO
H H OH
HO P N N P OH
+ NH3
P

HO NH

O NH OH
OH HO O
P

OH

Tetrakis hydroxymethylol phosphonium Cross-linked THP polymer

(THP) pre-condensate

40
 Char Formers
The chemical process must be controlled properly to achieve
durable FR properties.
Ammonia Process
Impregnate with
Dry to specific
THP pre-
moisture level
condensate

Fabric is dipped and squeezed with a

solution of the THP pre-condensate
compound

Impregnate with THP pre-condensate

and Nitrogen crosslinker

Thermal Process
41
 Char Formers
The chemical process must be controlled properly to achieve
durable FR properties.
Ammonia Process
Impregnate with React with
Dry to specific
THP pre- gaseous
moisture level
condensate ammonia

Fabric is dipped and squeezed with a Cross-linking

solution of the THP pre-condensate occurs to make
compound the polymer and
react it to the
fiber surface

Impregnate with THP pre-condensate Cure in

and Nitrogen crosslinker thermal oven

Thermal Process
42
 Char Formers
The chemical process must be controlled properly to achieve
durable FR properties.
Ammonia Process
Impregnate with React with
Dry to specific
THP pre- gaseous Oxidize
moisture level
condensate ammonia

Fabric is dipped and squeezed with a Cross-linking Oxidation makes

solution of the THP pre-condensate occurs to make the reaction
compound the polymer and irreversible, so the
react it to the polymer does not
fiber surface “unzip” with
laundering
Impregnate with THP pre-condensate Cure in
Oxidize
and Nitrogen crosslinker thermal oven

Thermal Process
43
 Char Formers
The chemical process must be controlled properly to achieve
durable FR properties.
Ammonia Process
Impregnate with React with
Dry to specific
THP pre- gaseous Oxidize Finishing
moisture level
condensate ammonia

Fabric is dipped and squeezed with a Cross-linking Oxidation makes Includes

solution of the THP pre-condensate occurs to make the reaction formaldehyde
compound. the polymer and irreversible, so the remediation,
react it to the polymer does not softening, and pre-
fiber surface. “unzip” with shrinking.
laundering.
Impregnate with THP pre-condensate Cure in
and Nitrogen crosslinker thermal oven
Oxidize Finishing

Thermal Process
44
 Example Products Using
Char Forming FR Agents
Fabric Brands
Work Shirt – 7oz.

Work Shirt,
ANSI Class 3 Type R

45
 Char Formers
(THP-based Phosphorous Chemistry)

Advantages Disadvantages

 Cost effective, even in Cat 2  Lower service life due to natural

solutions. properties of cotton.

 Comfort properties of cotton  Incomplete crosslinking or

are largely preserved. oxidation can lead to non-
durable coatings.
 Dyeing/finishing attributes of
cotton-based products are  FR properties can be reduced
retained. with repeated chlorine
bleaching.
 Char provides thermal
insulation to protect the wearer
46 from thermal heat transfer.
 Summary & Conclusions
 Fire is a complex chemical reaction. Retarding fire can be accomplished
by interrupting any leg of the fire tetrahedron.

 In flame resistant fabrics, three common techniques are employed: the

use of thermally stable fibers, gas-phase radical scavengers, and solid-
phase char formers.

 Each of the flame-resistant fabric strategies has advantages and

drawbacks. Developers of flame-resistant fabrics often create blends of
fibers and chemistries that attempt to optimize the properties for each
application.

 Whether the FR technology is a property of the fiber structure,

engineered into the fiber, or fabric engineered, flame resistant fabrics
can be produced which are durable for the life of the garment.

47