Fire-safe polymers are
polymers
A polymer (; Greek '' poly-'', "many" + ''-mer'', "part")
is a substance or material consisting of very large molecules called macromolecules, composed of many repeating subunits. Due to their broad spectrum of properties, both synthetic an ...
that are resistant to
degradation
Degradation may refer to:
Science
* Degradation (geology), lowering of a fluvial surface by erosion
* Degradation (telecommunications), of an electronic signal
* Biodegradation of organic substances by living organisms
* Environmental degradatio ...
at high temperatures. There is need for fire-resistant polymers in the construction of small, enclosed spaces such as skyscrapers, boats, and airplane cabins.
[Zhang, H. ''Fire-Safe Polymers and Polymer Composites,'' Federal Aviation Administration technical report; U.S. Department of Transportation: Washington, D.C., 2004.] In these tight spaces, ability to escape in the event of a
fire
Fire is the rapid oxidation of a material (the fuel) in the exothermic chemical process of combustion, releasing heat, light, and various reaction products.
At a certain point in the combustion reaction, called the ignition point, flames a ...
is compromised, increasing
fire
Fire is the rapid oxidation of a material (the fuel) in the exothermic chemical process of combustion, releasing heat, light, and various reaction products.
At a certain point in the combustion reaction, called the ignition point, flames a ...
risk. In fact, some studies report that about 20% of victims of airplane crashes are killed not by the crash itself but by ensuing
fires
Fire is the rapid oxidation of a material (the fuel) in the exothermic chemical process of combustion, releasing heat, light, and various reaction products.
At a certain point in the combustion reaction, called the ignition point, flames are pr ...
.
[Sarkos, C. P. The Effect of Cabin Materials on Aircraft Postcrash Fire Survivability. ''Technical Papers of the Annual Technical Conference'' 1996, ''54'' (3), 3068-3071.] Fire-safe
polymers
A polymer (; Greek '' poly-'', "many" + ''-mer'', "part")
is a substance or material consisting of very large molecules called macromolecules, composed of many repeating subunits. Due to their broad spectrum of properties, both synthetic an ...
also find application as
adhesives
Adhesive, also known as glue, cement, mucilage, or paste, is any non-metallic substance applied to one or both surfaces of two separate items that binds them together and resists their separation.
The use of adhesives offers certain advant ...
in aerospace materials,
[Kumar, D.; Gupta, A. D.; Khullar, M. Heat-resistant thermosetting polymers based on a novel tetrakisaminophenoxycyclotriphosphazene. ''J. Polym. Sci. Part A: Polym. Chem.'' 1993, ''31'' (11), 2739-2745]
insulation
Insulation may refer to:
Thermal
* Thermal insulation, use of materials to reduce rates of heat transfer
** List of insulation materials
** Building insulation, thermal insulation added to buildings for comfort and energy efficiency
*** Insulated ...
for
electronics
The field of electronics is a branch of physics and electrical engineering that deals with the emission, behaviour and effects of electrons using electronic devices. Electronics uses active devices to control electron flow by amplification ...
,
and in military materials such as canvas tenting.
[Hindersinn, R. R. Historical Aspects of Polymer Fire Retardance. In ''Fire and Polymers – Hazards Identification and Prevention;'' Nelson, G. L., Ed.; American Chemical Society: Washington, D.C., 1990; pp 87-96. ]
Some fire-safe
polymers
A polymer (; Greek '' poly-'', "many" + ''-mer'', "part")
is a substance or material consisting of very large molecules called macromolecules, composed of many repeating subunits. Due to their broad spectrum of properties, both synthetic an ...
naturally exhibit an intrinsic resistance to
decomposition
Decomposition or rot is the process by which dead organic substances are broken down into simpler organic or inorganic matter such as carbon dioxide, water, simple sugars and mineral salts. The process is a part of the nutrient cycle and is e ...
, while others are synthesized by incorporating fire-resistant additives and fillers. Current research in developing fire-safe
polymers
A polymer (; Greek '' poly-'', "many" + ''-mer'', "part")
is a substance or material consisting of very large molecules called macromolecules, composed of many repeating subunits. Due to their broad spectrum of properties, both synthetic an ...
is focused on modifying various properties of the
polymers
A polymer (; Greek '' poly-'', "many" + ''-mer'', "part")
is a substance or material consisting of very large molecules called macromolecules, composed of many repeating subunits. Due to their broad spectrum of properties, both synthetic an ...
such as ease of
ignition
Ignition may refer to:
Science and technology
* Firelighting, the human act of creating a fire for warmth, cooking and other uses
* Combustion, an exothermic chemical reaction between a fuel and an oxidant
* Fusion ignition, the point at which a ...
, rate of heat release, and the evolution of smoke and toxic gases.
Standard methods for testing
polymer
A polymer (; Greek '' poly-'', "many" + ''-mer'', "part")
is a substance or material consisting of very large molecules called macromolecules, composed of many repeating subunits. Due to their broad spectrum of properties, both synthetic a ...
flammability
A combustible material is something that can burn (i.e., ''combust'') in air. A combustible material is flammable if it ignites easily at ambient temperatures. In other words, a combustible material ignites with some effort and a flammable mat ...
vary among countries; in the United States common fire tests include the UL 94 small-flame test, the ASTM E 84
Steiner Tunnel, and the ASTM E 622
National Institute of Standards and Technology
The National Institute of Standards and Technology (NIST) is an agency of the United States Department of Commerce whose mission is to promote American innovation and industrial competitiveness. NIST's activities are organized into physical s ...
(NIST) smoke chamber.
Research on developing fire-safe
polymers
A polymer (; Greek '' poly-'', "many" + ''-mer'', "part")
is a substance or material consisting of very large molecules called macromolecules, composed of many repeating subunits. Due to their broad spectrum of properties, both synthetic an ...
with more desirable properties is concentrated at the
University of Massachusetts Amherst
The University of Massachusetts Amherst (UMass Amherst, UMass) is a public research university in Amherst, Massachusetts and the sole public land-grant university in Commonwealth of Massachusetts. Founded in 1863 as an agricultural college, ...
and at the
Federal Aviation Administration
The Federal Aviation Administration (FAA) is the largest transportation agency of the U.S. government and regulates all aspects of civil aviation in the country as well as over surrounding international waters. Its powers include air traffic ...
where a long-term research program on developing fire-safe
polymers
A polymer (; Greek '' poly-'', "many" + ''-mer'', "part")
is a substance or material consisting of very large molecules called macromolecules, composed of many repeating subunits. Due to their broad spectrum of properties, both synthetic an ...
was begun in 1995. The Center for UMass/Industry Research on Polymers (CUMIRP) was established in 1980 in Amherst, MA as a concentrated cluster of scientists from both academia and industry for the purpose of
polymer
A polymer (; Greek '' poly-'', "many" + ''-mer'', "part")
is a substance or material consisting of very large molecules called macromolecules, composed of many repeating subunits. Due to their broad spectrum of properties, both synthetic a ...
science and engineering research.
History
Early history
Controlling the
flammability
A combustible material is something that can burn (i.e., ''combust'') in air. A combustible material is flammable if it ignites easily at ambient temperatures. In other words, a combustible material ignites with some effort and a flammable mat ...
of different materials has been a subject of interest since 450 B.C. when
Egyptians attempted to reduce the
flammability
A combustible material is something that can burn (i.e., ''combust'') in air. A combustible material is flammable if it ignites easily at ambient temperatures. In other words, a combustible material ignites with some effort and a flammable mat ...
of wood by soaking it in
potassium aluminum sulfate (
alum). Between 450 B.C. and the early 20th century, other materials used to reduce the flammability of different materials included mixtures of
alum and
vinegar
Vinegar is an aqueous solution of acetic acid and trace compounds that may include flavorings. Vinegar typically contains 5–8% acetic acid by volume. Usually, the acetic acid is produced by a double fermentation, converting simple sugars to eth ...
;
clay
Clay is a type of fine-grained natural soil material containing clay minerals (hydrous aluminium phyllosilicates, e.g. kaolin, Al2 Si2 O5( OH)4).
Clays develop plasticity when wet, due to a molecular film of water surrounding the clay par ...
and
hair;
clay
Clay is a type of fine-grained natural soil material containing clay minerals (hydrous aluminium phyllosilicates, e.g. kaolin, Al2 Si2 O5( OH)4).
Clays develop plasticity when wet, due to a molecular film of water surrounding the clay par ...
and
gypsum
Gypsum is a soft sulfate mineral composed of calcium sulfate dihydrate, with the chemical formula . It is widely mined and is used as a fertilizer and as the main constituent in many forms of plaster, blackboard or sidewalk chalk, and drywal ...
;
alum,
ferrous sulfate
Iron(II) sulfate (British English: iron(II) sulphate) or ferrous sulfate denotes a range of salts with the formula Fe SO4·''x''H2O. These compounds exist most commonly as the hepta hydrate (''x'' = 7) but several values for x are kn ...
, and
gypsum
Gypsum is a soft sulfate mineral composed of calcium sulfate dihydrate, with the chemical formula . It is widely mined and is used as a fertilizer and as the main constituent in many forms of plaster, blackboard or sidewalk chalk, and drywal ...
; and
ammonium chloride,
ammonium phosphate
Ammonium phosphate is the inorganic compound with the formula (NH4)3PO4. It is the ammonium salt of orthophosphoric acid. A related "double salt", (NH4)3PO4.(NH4)2HPO4 is also recognized but is impractical use. Both triammonium salts evolve ammoni ...
,
borax
Borax is a salt ( ionic compound), a hydrated borate of sodium, with chemical formula often written . It is a colorless crystalline solid, that dissolves in water to make a basic solution. It is commonly available in powder or granular for ...
, and various
acids
In computer science, ACID ( atomicity, consistency, isolation, durability) is a set of properties of database transactions intended to guarantee data validity despite errors, power failures, and other mishaps. In the context of databases, a ...
. These early attempts found application in reducing the flammability of wood for military materials, theater curtains, and other textiles, for example. Important milestones during this early work include the first
patent
A patent is a type of intellectual property that gives its owner the legal right to exclude others from making, using, or selling an invention for a limited period of time in exchange for publishing an enabling disclosure of the invention."A ...
for a mixture for controlling flammability issued to Obadiah Wyld in 1735,
and the first scientific exploration of controlling flammability, which was undertaken by
Joseph Louis Gay-Lussac
Joseph Louis Gay-Lussac (, , ; 6 December 1778 – 9 May 1850) was a French chemist and physicist. He is known mostly for his discovery that water is made of two parts hydrogen and one part oxygen (with Alexander von Humboldt), for two laws ...
in 1821.
Developments since WWII
Research on fire-retardant
polymers
A polymer (; Greek '' poly-'', "many" + ''-mer'', "part")
is a substance or material consisting of very large molecules called macromolecules, composed of many repeating subunits. Due to their broad spectrum of properties, both synthetic an ...
was bolstered by the need for new types of
synthetic polymers in
World War II
World War II or the Second World War, often abbreviated as WWII or WW2, was a world war that lasted from 1939 to 1945. It involved the vast majority of the world's countries—including all of the great powers—forming two opposing ...
. The combination of a
halogenated
In chemistry, halogenation is a chemical reaction that entails the introduction of one or more halogens into a compound. Halide-containing compounds are pervasive, making this type of transformation important, e.g. in the production of polymers, ...
paraffin Paraffin may refer to:
Substances
* Paraffin wax, a white or colorless soft solid that is used as a lubricant and for other applications
* Liquid paraffin (drug), a very highly refined mineral oil used in cosmetics and for medical purposes
* Alkan ...
and
antimony oxide was found to be successful as a
fire retardant
A fire retardant is a substance that is used to slow down or stop the spread of fire or reduce its intensity. This is commonly accomplished by chemical reactions that reduce the flammability of fuels or delay their combustion. Fire retardants m ...
for canvas tenting. Synthesis of
polymers
A polymer (; Greek '' poly-'', "many" + ''-mer'', "part")
is a substance or material consisting of very large molecules called macromolecules, composed of many repeating subunits. Due to their broad spectrum of properties, both synthetic an ...
, such as
polyesters
Polyester is a category of polymers that contain the ester functional group in every repeat unit of their main chain. As a specific material, it most commonly refers to a type called polyethylene terephthalate (PET). Polyesters include natural ...
, with
fire retardant
A fire retardant is a substance that is used to slow down or stop the spread of fire or reduce its intensity. This is commonly accomplished by chemical reactions that reduce the flammability of fuels or delay their combustion. Fire retardants m ...
monomers were also developed around this time.
[Robitschek, P.; Bean, C. T. Flame-Resistant Polyesters from Hexachlorocyclopentadiene. ''Ind. Eng. Chem.'' 1954, ''46'' (8), 1628-1632]
Incorporating flame-resistant additives into
polymers
A polymer (; Greek '' poly-'', "many" + ''-mer'', "part")
is a substance or material consisting of very large molecules called macromolecules, composed of many repeating subunits. Due to their broad spectrum of properties, both synthetic an ...
became a common and relatively cheap way to reduce the flammability of
polymers
A polymer (; Greek '' poly-'', "many" + ''-mer'', "part")
is a substance or material consisting of very large molecules called macromolecules, composed of many repeating subunits. Due to their broad spectrum of properties, both synthetic an ...
,
[Connolly, W. J.; Thornton, A. M. Aluminum Hydrate Filler in Polyester Systems. ''Mod. Plastics'' 1965, ''43'' (2), 154-202.] while synthesizing intrinsically fire-resistant
polymers
A polymer (; Greek '' poly-'', "many" + ''-mer'', "part")
is a substance or material consisting of very large molecules called macromolecules, composed of many repeating subunits. Due to their broad spectrum of properties, both synthetic an ...
has remained a more expensive alternative, although the properties of these
polymers
A polymer (; Greek '' poly-'', "many" + ''-mer'', "part")
is a substance or material consisting of very large molecules called macromolecules, composed of many repeating subunits. Due to their broad spectrum of properties, both synthetic an ...
are usually more efficient at deterring
combustion
Combustion, or burning, is a high-temperature exothermic redox chemical reaction between a fuel (the reductant) and an oxidant, usually atmospheric oxygen, that produces oxidized, often gaseous products, in a mixture termed as smoke. Combus ...
.
Polymer combustion
General mechanistic scheme
Traditional
polymer
A polymer (; Greek '' poly-'', "many" + ''-mer'', "part")
is a substance or material consisting of very large molecules called macromolecules, composed of many repeating subunits. Due to their broad spectrum of properties, both synthetic a ...
s
decompose
Decomposition or rot is the process by which dead organic substances are broken down into simpler organic or inorganic matter such as carbon dioxide, water, simple sugars and mineral salts. The process is a part of the nutrient cycle and is ...
under heat and produce combustible products; thus, they are able to originate and easily propagate
fire
Fire is the rapid oxidation of a material (the fuel) in the exothermic chemical process of combustion, releasing heat, light, and various reaction products.
At a certain point in the combustion reaction, called the ignition point, flames a ...
(as shown in Figure 1).
The
combustion
Combustion, or burning, is a high-temperature exothermic redox chemical reaction between a fuel (the reductant) and an oxidant, usually atmospheric oxygen, that produces oxidized, often gaseous products, in a mixture termed as smoke. Combus ...
process begins when heating a
polymer
A polymer (; Greek '' poly-'', "many" + ''-mer'', "part")
is a substance or material consisting of very large molecules called macromolecules, composed of many repeating subunits. Due to their broad spectrum of properties, both synthetic a ...
yields
volatile products. If these products are sufficiently concentrated, within the
flammability limits
Mixtures of dispersed combustible materials (such as gaseous or vaporised fuels, and some dusts) and oxygen in the air will burn only if the fuel concentration lies within well-defined lower and upper bounds determined experimentally, referred to a ...
, and at a temperature above the ignition temperature, then
combustion
Combustion, or burning, is a high-temperature exothermic redox chemical reaction between a fuel (the reductant) and an oxidant, usually atmospheric oxygen, that produces oxidized, often gaseous products, in a mixture termed as smoke. Combus ...
proceeds. As long as the heat supplied to the
polymer
A polymer (; Greek '' poly-'', "many" + ''-mer'', "part")
is a substance or material consisting of very large molecules called macromolecules, composed of many repeating subunits. Due to their broad spectrum of properties, both synthetic a ...
remains sufficient to sustain its
thermal decomposition
Thermal decomposition, or thermolysis, is a chemical decomposition caused by heat. The decomposition temperature of a substance is the temperature at which the substance chemically decomposes. The reaction is usually endothermic as heat is re ...
at a rate exceeding that required to feed the flame,
combustion
Combustion, or burning, is a high-temperature exothermic redox chemical reaction between a fuel (the reductant) and an oxidant, usually atmospheric oxygen, that produces oxidized, often gaseous products, in a mixture termed as smoke. Combus ...
will continue.
[Camino, G.; Costa, L.; Luda di Cortemiglia, M. P. Overview of Fire Retardant Mechanisms. ''Polym. Degrad. Stabil.'' 1991, ''33'' (2), 131-154]
Purpose and methods of fire-retardant systems
The purpose is to control heat below the critical level. To achieve this, one can create an
endothermic
In thermochemistry, an endothermic process () is any thermodynamic process with an increase in the enthalpy (or internal energy ) of the system.Oxtoby, D. W; Gillis, H.P., Butler, L. J. (2015).''Principle of Modern Chemistry'', Brooks Cole. ...
environment, produce non-combustible products, or add chemicals that would remove fire-propagating
radicals (H and OH), to name a few. These specific chemicals can be added into the
polymer
A polymer (; Greek '' poly-'', "many" + ''-mer'', "part")
is a substance or material consisting of very large molecules called macromolecules, composed of many repeating subunits. Due to their broad spectrum of properties, both synthetic a ...
molecules permanently (see Intrinsically Fire-Resistant Polymers) or as additives and fillers (see Flame-Retardant Additives and Fillers).
Role of oxygen
Oxygen
Oxygen is the chemical element with the symbol O and atomic number 8. It is a member of the chalcogen group in the periodic table, a highly reactive nonmetal, and an oxidizing agent that readily forms oxides with most elements as ...
catalyzes the
pyrolysis
The pyrolysis (or devolatilization) process is the thermal decomposition of materials at elevated temperatures, often in an inert atmosphere. It involves a change of chemical composition. The word is coined from the Greek-derived elements ''py ...
of
polymers
A polymer (; Greek '' poly-'', "many" + ''-mer'', "part")
is a substance or material consisting of very large molecules called macromolecules, composed of many repeating subunits. Due to their broad spectrum of properties, both synthetic an ...
at low concentration and initiates
oxidation
Redox (reduction–oxidation, , ) is a type of chemical reaction in which the oxidation states of substrate change. Oxidation is the loss of electrons or an increase in the oxidation state, while reduction is the gain of electrons or a ...
at high concentration. Transition concentrations are different for different
polymers
A polymer (; Greek '' poly-'', "many" + ''-mer'', "part")
is a substance or material consisting of very large molecules called macromolecules, composed of many repeating subunits. Due to their broad spectrum of properties, both synthetic an ...
. (e.g.,
polypropylene
Polypropylene (PP), also known as polypropene, is a thermoplastic polymer used in a wide variety of applications. It is produced via chain-growth polymerization from the monomer propylene.
Polypropylene
belongs to the group of polyolefins a ...
, between 5% and 15%). Additionally,
polymers
A polymer (; Greek '' poly-'', "many" + ''-mer'', "part")
is a substance or material consisting of very large molecules called macromolecules, composed of many repeating subunits. Due to their broad spectrum of properties, both synthetic an ...
exhibit a structural-dependent relationship with
oxygen
Oxygen is the chemical element with the symbol O and atomic number 8. It is a member of the chalcogen group in the periodic table, a highly reactive nonmetal, and an oxidizing agent that readily forms oxides with most elements as ...
. Some structures are intrinsically more sensitive to
decomposition
Decomposition or rot is the process by which dead organic substances are broken down into simpler organic or inorganic matter such as carbon dioxide, water, simple sugars and mineral salts. The process is a part of the nutrient cycle and is e ...
upon reaction with
oxygen
Oxygen is the chemical element with the symbol O and atomic number 8. It is a member of the chalcogen group in the periodic table, a highly reactive nonmetal, and an oxidizing agent that readily forms oxides with most elements as ...
. The amount of access that
oxygen
Oxygen is the chemical element with the symbol O and atomic number 8. It is a member of the chalcogen group in the periodic table, a highly reactive nonmetal, and an oxidizing agent that readily forms oxides with most elements as ...
has to the surface of the
polymer
A polymer (; Greek '' poly-'', "many" + ''-mer'', "part")
is a substance or material consisting of very large molecules called macromolecules, composed of many repeating subunits. Due to their broad spectrum of properties, both synthetic a ...
also plays a role in
polymer
A polymer (; Greek '' poly-'', "many" + ''-mer'', "part")
is a substance or material consisting of very large molecules called macromolecules, composed of many repeating subunits. Due to their broad spectrum of properties, both synthetic a ...
combustion
Combustion, or burning, is a high-temperature exothermic redox chemical reaction between a fuel (the reductant) and an oxidant, usually atmospheric oxygen, that produces oxidized, often gaseous products, in a mixture termed as smoke. Combus ...
.
Oxygen
Oxygen is the chemical element with the symbol O and atomic number 8. It is a member of the chalcogen group in the periodic table, a highly reactive nonmetal, and an oxidizing agent that readily forms oxides with most elements as ...
is better able to interact with the
polymer
A polymer (; Greek '' poly-'', "many" + ''-mer'', "part")
is a substance or material consisting of very large molecules called macromolecules, composed of many repeating subunits. Due to their broad spectrum of properties, both synthetic a ...
before a flame has actually been ignited.
Role of heating rate
In most cases, results from a typical heating rate (e.g. 10℃/min for mechanical
thermal degradation
Thermal decomposition, or thermolysis, is a chemical decomposition caused by heat. The decomposition temperature of a substance is the temperature at which the substance chemically decomposes. The reaction is usually endothermic as heat is req ...
studies) do not differ significantly from those obtained at higher heating rates. The extent of reaction can, however, be influenced by the heating rate. For example, some reactions may not occur with a low heating rate due to
evaporation of the products.
Role of pressure
Volatile products are removed more efficiently under low pressure, which means the stability of the
polymer
A polymer (; Greek '' poly-'', "many" + ''-mer'', "part")
is a substance or material consisting of very large molecules called macromolecules, composed of many repeating subunits. Due to their broad spectrum of properties, both synthetic a ...
might have been compromised. Decreased pressure also slows down
decomposition
Decomposition or rot is the process by which dead organic substances are broken down into simpler organic or inorganic matter such as carbon dioxide, water, simple sugars and mineral salts. The process is a part of the nutrient cycle and is e ...
of high boiling products.
Intrinsically fire-resistant polymers
The
polymers
A polymer (; Greek '' poly-'', "many" + ''-mer'', "part")
is a substance or material consisting of very large molecules called macromolecules, composed of many repeating subunits. Due to their broad spectrum of properties, both synthetic an ...
that are most efficient at resisting
combustion
Combustion, or burning, is a high-temperature exothermic redox chemical reaction between a fuel (the reductant) and an oxidant, usually atmospheric oxygen, that produces oxidized, often gaseous products, in a mixture termed as smoke. Combus ...
are those that are synthesized as intrinsically fire-resistant. However, these types of
polymers
A polymer (; Greek '' poly-'', "many" + ''-mer'', "part")
is a substance or material consisting of very large molecules called macromolecules, composed of many repeating subunits. Due to their broad spectrum of properties, both synthetic an ...
can be difficult as well as costly to synthesize. Modifying different properties of the
polymers
A polymer (; Greek '' poly-'', "many" + ''-mer'', "part")
is a substance or material consisting of very large molecules called macromolecules, composed of many repeating subunits. Due to their broad spectrum of properties, both synthetic an ...
can increase their intrinsic fire-resistance; increasing
rigidity or
stiffness, the use of
polar
Polar may refer to:
Geography
Polar may refer to:
* Geographical pole, either of two fixed points on the surface of a rotating body or planet, at 90 degrees from the equator, based on the axis around which a body rotates
* Polar climate, the c ...
monomers
In chemistry, a monomer ( ; ''mono-'', "one" + '' -mer'', "part") is a molecule that can react together with other monomer molecules to form a larger polymer chain or three-dimensional network in a process called polymerization.
Classification
Mo ...
, and/or
hydrogen bonding
In chemistry, a hydrogen bond (or H-bond) is a primarily electrostatic force of attraction between a hydrogen (H) atom which is covalently bound to a more electronegative "donor" atom or group (Dn), and another electronegative atom bearing a l ...
between the
polymer
A polymer (; Greek '' poly-'', "many" + ''-mer'', "part")
is a substance or material consisting of very large molecules called macromolecules, composed of many repeating subunits. Due to their broad spectrum of properties, both synthetic a ...
chains can all enhance fire-resistance.
[Frazer, A.H. ''High Temperature Resistant Polymers;'' John Wiley & Sons: New York, 1968]
Linear, single-stranded polymers with cyclic aromatic components
Most intrinsically fire-resistant
polymers
A polymer (; Greek '' poly-'', "many" + ''-mer'', "part")
is a substance or material consisting of very large molecules called macromolecules, composed of many repeating subunits. Due to their broad spectrum of properties, both synthetic an ...
are made by incorporation of aromatic cycles or heterocycles, which lend
rigidity and stability to the
polymers
A polymer (; Greek '' poly-'', "many" + ''-mer'', "part")
is a substance or material consisting of very large molecules called macromolecules, composed of many repeating subunits. Due to their broad spectrum of properties, both synthetic an ...
.
[Mallakpour, S. E.; Hajipour, A.-R.; Mahdavian, A.-R.; Khoee, S. Synthesis and characterization of novel optically active and flame-retardant heterocyclic polyimides. ''J. Appli. Polym. Sci.'' 2000, ''76'' (2), 240-248. ] Polyimides, polybenzoxazoles (PBOs), polybenzimidazoles, and polybenzthiazoles (PBTs) are examples of
polymers
A polymer (; Greek '' poly-'', "many" + ''-mer'', "part")
is a substance or material consisting of very large molecules called macromolecules, composed of many repeating subunits. Due to their broad spectrum of properties, both synthetic an ...
made with aromatic heterocycles (Figure 2).
Polymers
A polymer (; Greek '' poly-'', "many" + ''-mer'', "part")
is a substance or material consisting of very large molecules called macromolecules, composed of many repeating subunits. Due to their broad spectrum of properties, both synthetic an ...
made with aromatic monomers have a tendency to condense into chars upon
combustion
Combustion, or burning, is a high-temperature exothermic redox chemical reaction between a fuel (the reductant) and an oxidant, usually atmospheric oxygen, that produces oxidized, often gaseous products, in a mixture termed as smoke. Combus ...
, decreasing the amount of flammable gas that is released. Syntheses of these types of
polymers
A polymer (; Greek '' poly-'', "many" + ''-mer'', "part")
is a substance or material consisting of very large molecules called macromolecules, composed of many repeating subunits. Due to their broad spectrum of properties, both synthetic an ...
generally employ prepolymers which are further reacted to form the fire-resistant
polymers
A polymer (; Greek '' poly-'', "many" + ''-mer'', "part")
is a substance or material consisting of very large molecules called macromolecules, composed of many repeating subunits. Due to their broad spectrum of properties, both synthetic an ...
.
[Akinseye, T. D.; Harruna, I. I.; Bota, K. B. Processable Precursors .4. Synthesis and Characterization of Processable Precursors to Poly (Phenylene Bixbenzoxazoles). ''Polymer'' 1997, ''38'' (10), 2507-2513]
Ladder polymers
Ladder polymer
In chemistry, a ladder polymer is a type of double stranded polymer with the connectivity of a ladder. In a typical one-dimensional polymer, e.g. polyethylene and polysiloxanes, the monomers form two bonds, giving a chain. In a ladder polymer the ...
s are a subclass of
polymers
A polymer (; Greek '' poly-'', "many" + ''-mer'', "part")
is a substance or material consisting of very large molecules called macromolecules, composed of many repeating subunits. Due to their broad spectrum of properties, both synthetic an ...
made with aromatic cycles or heterocycles. Ladder
polymers
A polymer (; Greek '' poly-'', "many" + ''-mer'', "part")
is a substance or material consisting of very large molecules called macromolecules, composed of many repeating subunits. Due to their broad spectrum of properties, both synthetic an ...
generally have one of two types of general structures, as shown in Figure 3.
One type of ladder
polymer
A polymer (; Greek '' poly-'', "many" + ''-mer'', "part")
is a substance or material consisting of very large molecules called macromolecules, composed of many repeating subunits. Due to their broad spectrum of properties, both synthetic a ...
links two
polymer
A polymer (; Greek '' poly-'', "many" + ''-mer'', "part")
is a substance or material consisting of very large molecules called macromolecules, composed of many repeating subunits. Due to their broad spectrum of properties, both synthetic a ...
chains with periodic
covalent bonds
A covalent bond is a chemical bond that involves the sharing of electrons to form electron pairs between atoms. These electron pairs are known as shared pairs or bonding pairs. The stable balance of attractive and repulsive forces between atoms ...
.
[Sirkecioglu, O.; Tunca, A. A.; Talinli, N.; Akar, A. Ladder type polymers from dihydroxyaromatic compounds and dialdehydes. ''Angew. Makrom. Chem.'' 1999, ''271'' (1), 8-10. ] In another type, the ladder
polymer
A polymer (; Greek '' poly-'', "many" + ''-mer'', "part")
is a substance or material consisting of very large molecules called macromolecules, composed of many repeating subunits. Due to their broad spectrum of properties, both synthetic a ...
consists of a single chain that is double-stranded. Both types of ladder
polymers
A polymer (; Greek '' poly-'', "many" + ''-mer'', "part")
is a substance or material consisting of very large molecules called macromolecules, composed of many repeating subunits. Due to their broad spectrum of properties, both synthetic an ...
exhibit good resistance to
decomposition
Decomposition or rot is the process by which dead organic substances are broken down into simpler organic or inorganic matter such as carbon dioxide, water, simple sugars and mineral salts. The process is a part of the nutrient cycle and is e ...
from heat because the chains do not necessarily fall apart if one
covalent bond is broken. However, this makes the processing of ladder
polymers
A polymer (; Greek '' poly-'', "many" + ''-mer'', "part")
is a substance or material consisting of very large molecules called macromolecules, composed of many repeating subunits. Due to their broad spectrum of properties, both synthetic an ...
difficult because they are not easily melted. These difficulties are compounded because ladder polymers are often highly
insoluble
In chemistry, solubility is the ability of a substance, the solute, to form a solution with another substance, the solvent. Insolubility is the opposite property, the inability of the solute to form such a solution.
The extent of the solubil ...
.
Inorganic and semiorganic polymers
Inorganic and semiorganic
polymers
A polymer (; Greek '' poly-'', "many" + ''-mer'', "part")
is a substance or material consisting of very large molecules called macromolecules, composed of many repeating subunits. Due to their broad spectrum of properties, both synthetic an ...
often employ
silicon
Silicon is a chemical element with the symbol Si and atomic number 14. It is a hard, brittle crystalline solid with a blue-grey metallic luster, and is a tetravalent metalloid and semiconductor. It is a member of group 14 in the periodic ta ...
-
nitrogen
Nitrogen is the chemical element with the symbol N and atomic number 7. Nitrogen is a nonmetal and the lightest member of group 15 of the periodic table, often called the pnictogens. It is a common element in the universe, estimated at se ...
,
boron-
nitrogen
Nitrogen is the chemical element with the symbol N and atomic number 7. Nitrogen is a nonmetal and the lightest member of group 15 of the periodic table, often called the pnictogens. It is a common element in the universe, estimated at se ...
, and
phosphorus
Phosphorus is a chemical element with the symbol P and atomic number 15. Elemental phosphorus exists in two major forms, white phosphorus and red phosphorus, but because it is highly reactive, phosphorus is never found as a free element on Ear ...
-
nitrogen
Nitrogen is the chemical element with the symbol N and atomic number 7. Nitrogen is a nonmetal and the lightest member of group 15 of the periodic table, often called the pnictogens. It is a common element in the universe, estimated at se ...
monomers. The non-burning characteristics of the
inorganic
In chemistry, an inorganic compound is typically a chemical compound that lacks carbon–hydrogen bonds, that is, a compound that is not an organic compound. The study of inorganic compounds is a subfield of chemistry known as ''inorganic chemist ...
components of these
polymers
A polymer (; Greek '' poly-'', "many" + ''-mer'', "part")
is a substance or material consisting of very large molecules called macromolecules, composed of many repeating subunits. Due to their broad spectrum of properties, both synthetic an ...
contribute to their controlled
flammability
A combustible material is something that can burn (i.e., ''combust'') in air. A combustible material is flammable if it ignites easily at ambient temperatures. In other words, a combustible material ignites with some effort and a flammable mat ...
. For example, instead of forming toxic, flammable gasses in abundance,
polymers
A polymer (; Greek '' poly-'', "many" + ''-mer'', "part")
is a substance or material consisting of very large molecules called macromolecules, composed of many repeating subunits. Due to their broad spectrum of properties, both synthetic an ...
prepared with incorporation of
cyclotriphosphazene rings give a high
char yield upon
combustion
Combustion, or burning, is a high-temperature exothermic redox chemical reaction between a fuel (the reductant) and an oxidant, usually atmospheric oxygen, that produces oxidized, often gaseous products, in a mixture termed as smoke. Combus ...
.
Polysialates (
polymers
A polymer (; Greek '' poly-'', "many" + ''-mer'', "part")
is a substance or material consisting of very large molecules called macromolecules, composed of many repeating subunits. Due to their broad spectrum of properties, both synthetic an ...
containing frameworks of
aluminum
Aluminium (aluminum in American and Canadian English) is a chemical element with the symbol Al and atomic number 13. Aluminium has a density lower than those of other common metals, at approximately one third that of steel. It ha ...
,
oxygen
Oxygen is the chemical element with the symbol O and atomic number 8. It is a member of the chalcogen group in the periodic table, a highly reactive nonmetal, and an oxidizing agent that readily forms oxides with most elements as ...
, and
silicon
Silicon is a chemical element with the symbol Si and atomic number 14. It is a hard, brittle crystalline solid with a blue-grey metallic luster, and is a tetravalent metalloid and semiconductor. It is a member of group 14 in the periodic ta ...
) are another type of
inorganic
In chemistry, an inorganic compound is typically a chemical compound that lacks carbon–hydrogen bonds, that is, a compound that is not an organic compound. The study of inorganic compounds is a subfield of chemistry known as ''inorganic chemist ...
polymer
A polymer (; Greek '' poly-'', "many" + ''-mer'', "part")
is a substance or material consisting of very large molecules called macromolecules, composed of many repeating subunits. Due to their broad spectrum of properties, both synthetic a ...
that can be thermally stable up to temperatures of 1300-1400 °C.
[Barbosa, V. F. F.; MacKenzie, K. J. D.; Thaumaturgo, C. Synthesis and characterization of materials based on inorganic polymers of alumina and silica: sodium polysialate polymers. ''Int. J. Inorg. Mater.'' 2000, ''2'' (4), 309-317. ]
Flame-retardant additives and fillers
Additives are divided into two basic types depending on the interaction of the additive and
polymer
A polymer (; Greek '' poly-'', "many" + ''-mer'', "part")
is a substance or material consisting of very large molecules called macromolecules, composed of many repeating subunits. Due to their broad spectrum of properties, both synthetic a ...
.
Reactive
flame retardant
The term flame retardants subsumes a diverse group of chemicals that are added to manufactured materials, such as plastics and textiles, and surface finishes and coatings. Flame retardants are activated by the presence of an ignition source and ...
s are compounds that are chemically built into the
polymer
A polymer (; Greek '' poly-'', "many" + ''-mer'', "part")
is a substance or material consisting of very large molecules called macromolecules, composed of many repeating subunits. Due to their broad spectrum of properties, both synthetic a ...
. They usually contain
heteroatoms. Additive
flame retardant
The term flame retardants subsumes a diverse group of chemicals that are added to manufactured materials, such as plastics and textiles, and surface finishes and coatings. Flame retardants are activated by the presence of an ignition source and ...
s, on the other hand, are compounds that are not
covalently
A covalent bond is a chemical bond that involves the sharing of electrons to form electron pairs between atoms. These electron pairs are known as shared pairs or bonding pairs. The stable balance of attractive and repulsive forces between atom ...
bound to the
polymer
A polymer (; Greek '' poly-'', "many" + ''-mer'', "part")
is a substance or material consisting of very large molecules called macromolecules, composed of many repeating subunits. Due to their broad spectrum of properties, both synthetic a ...
; the flame retardant and the
polymer
A polymer (; Greek '' poly-'', "many" + ''-mer'', "part")
is a substance or material consisting of very large molecules called macromolecules, composed of many repeating subunits. Due to their broad spectrum of properties, both synthetic a ...
are just physically mixed together.
Only a few
elements are being widely used in this field:
aluminum
Aluminium (aluminum in American and Canadian English) is a chemical element with the symbol Al and atomic number 13. Aluminium has a density lower than those of other common metals, at approximately one third that of steel. It ha ...
,
phosphorus
Phosphorus is a chemical element with the symbol P and atomic number 15. Elemental phosphorus exists in two major forms, white phosphorus and red phosphorus, but because it is highly reactive, phosphorus is never found as a free element on Ear ...
,
nitrogen
Nitrogen is the chemical element with the symbol N and atomic number 7. Nitrogen is a nonmetal and the lightest member of group 15 of the periodic table, often called the pnictogens. It is a common element in the universe, estimated at se ...
,
antimony
Antimony is a chemical element with the symbol Sb (from la, stibium) and atomic number 51. A lustrous gray metalloid, it is found in nature mainly as the sulfide mineral stibnite (Sb2S3). Antimony compounds have been known since ancient t ...
,
chlorine
Chlorine is a chemical element with the symbol Cl and atomic number 17. The second-lightest of the halogens, it appears between fluorine and bromine in the periodic table and its properties are mostly intermediate between them. Chlorine i ...
,
bromine
Bromine is a chemical element with the symbol Br and atomic number 35. It is the third-lightest element in group 17 of the periodic table ( halogens) and is a volatile red-brown liquid at room temperature that evaporates readily to form a simi ...
, and in specific applications
magnesium
Magnesium is a chemical element with the symbol Mg and atomic number 12. It is a shiny gray metal having a low density, low melting point and high chemical reactivity. Like the other alkaline earth metals (group 2 of the periodic ta ...
,
zinc
Zinc is a chemical element with the symbol Zn and atomic number 30. Zinc is a slightly brittle metal at room temperature and has a shiny-greyish appearance when oxidation is removed. It is the first element in group 12 (IIB) of the periodi ...
and
carbon
Carbon () is a chemical element with the symbol C and atomic number 6. It is nonmetallic and tetravalent—its atom making four electrons available to form covalent chemical bonds. It belongs to group 14 of the periodic table. Carbon mak ...
. One prominent advantage of the flame retardants (FRs) derived from these elements is that they are relatively easy to manufacture. They are used in important quantities: in 2013, the world consumption of FRs amounted to around 1.8/2.1 Mio t for 2013 with sales of 4.9/5.2 billion USD. Market studies estimate FRs demand to rise between 5/7 % pa to 2.4/2.6 Mio t until 2016/2018 with estimated sales of 6.1/7.1 billion USD.
The most important flame retardants systems used act either in the gas phase where they remove the high energy radicals H and OH from the flame or in the solid phase, where they shield the polymer by forming a charred layer and thus protect the polymer from being attacked by oxygen and heat.
Flame retardants based on bromine or chlorine, as well as a number of phosphorus compounds act chemically in the gas phase and are very efficient. Others only act in the condensed phase such as metal hydroxides (
aluminum trihydrate, or ATH,
magnesium hydroxide, or MDH, and
boehmite), metal oxides and salts (zinc borate and zinc oxide, zinc hydroxystannate), as well as
expandable graphite and some nanocomposites (see below). Phosphorus and nitrogen compounds are also effective in the condensed phase, and as they also may act in the gas phase, they are quite efficient flame retardants. Overviews of the main flame retardants families, their mode of action and applications are given in. Further handbooks on these topics are
A good example for a very efficient phosphorus-based flame retardant system acting in the gas and condensed phases is
aluminium diethyl phosphinate
Aluminium diethyl phosphinate is a chemical compound with formula Al()3. It decomposes above 300 °C.
Applications
In the family of dialkyl phosphinic acid salts, aluminium diethyl phosphinate has been found to be an excellent flame retar ...
in conjunction with synergists such as melamine polyphosphate (MPP) and others. These phosphinates are mainly used to flame retard polyamides (PA) and polybutylene terephthalate (PBT) for flame retardant applications in electrical engineering/electronics (E&E).
[Huang, K.J., Hörold, S., Dietz, M., Schmitt, E. Phosphinates as flame retardants for plastics in electronics. 1st International SKZ Conference on Flame Retardant Plastics, Shanghai, China, 21 September 2009
]
Natural fiber-containing composites
Besides providing satisfactory mechanical properties and renewability,
natural fibers are easier to obtain and much cheaper than man-made materials. Moreover, they are more environmentally friendly.
[Kozlowski, R.; Wladyka-Przybylak, M. Flammability and fire resistance of composites reinforced by natural fibers. ''Polymer Advan. Technol.'' 2008, ''19'' (6), 446-453]
Recent research focuses on application of different types of
fire retardant
A fire retardant is a substance that is used to slow down or stop the spread of fire or reduce its intensity. This is commonly accomplished by chemical reactions that reduce the flammability of fuels or delay their combustion. Fire retardants m ...
s during the manufacturing process as well as applications of
fire retardant
A fire retardant is a substance that is used to slow down or stop the spread of fire or reduce its intensity. This is commonly accomplished by chemical reactions that reduce the flammability of fuels or delay their combustion. Fire retardants m ...
s (especially
intumescent
An intumescent is a substance that swells as a result of heat exposure, leading to an increase in volume and decrease in density. Intumescent materials are typically used in passive fire protection and require listing, approval, and compliance in ...
coatings) at the finishing stage.
Nanocomposites
Nanocomposites have become a hotspot in the research of fire-safe
polymers
A polymer (; Greek '' poly-'', "many" + ''-mer'', "part")
is a substance or material consisting of very large molecules called macromolecules, composed of many repeating subunits. Due to their broad spectrum of properties, both synthetic an ...
because of their relatively low cost and high flexibility for multifunctional properties.
[Bourbigot, S.; Duquesne, S.; Jama C. Polymer Nanocomposites: How to Reach Low Flammability? ''Macromol. Symp.'' 2006, ''233'' (1), 180-190]
Gilman and colleagues did the pioneering work by demonstrating the improvement of fire-retardancy by having nanodispersed
montmorillonite
Montmorillonite is a very soft phyllosilicate group of minerals that form when they precipitate from water solution as microscopic crystals, known as clay. It is named after Montmorillon in France. Montmorillonite, a member of the smectite gro ...
clay in the polymer matrix. Later, organomodified
clays
Clay is a type of fine-grained natural soil material containing clay minerals (hydrous aluminium phyllosilicates, e.g. kaolin, Al2 Si2 O5( OH)4).
Clays develop plasticity when wet, due to a molecular film of water surrounding the clay par ...
, TiO
2 nanoparticles,
silica
Silicon dioxide, also known as silica, is an oxide of silicon with the chemical formula , most commonly found in nature as quartz and in various living organisms. In many parts of the world, silica is the major constituent of sand. Silica is ...
nanoparticles,
layered double hydroxides
Layered double hydroxides (LDH) are a class of ionic solids characterized by a layered structure with the generic layer sequence cB Z AcBsub>''n'', where c represents layers of metal cations, A and B are layers of hydroxide () anions, and Z are l ...
,
carbon nanotubes
A scanning tunneling microscopy image of a single-walled carbon nanotube
Rotating single-walled zigzag carbon nanotube
A carbon nanotube (CNT) is a tube made of carbon with diameters typically measured in nanometers.
''Single-wall carbon na ...
and polyhedral
silsesquioxane
220x220px, thumbnail, A cubic silsesquioxane.
A silsesquioxane is an organosilicon compound with the chemical formula SiO3/2sub>n (R = H, alkyl, aryl, alkenyl or alkoxyl.). Silsesquioxanes are colorless solids that adopt cage-like or polymeric ...
s were proved to work as well.
Recent research has suggested that combining
nanoparticles with traditional
fire retardant
A fire retardant is a substance that is used to slow down or stop the spread of fire or reduce its intensity. This is commonly accomplished by chemical reactions that reduce the flammability of fuels or delay their combustion. Fire retardants m ...
s (e.g.,
intumescent
An intumescent is a substance that swells as a result of heat exposure, leading to an increase in volume and decrease in density. Intumescent materials are typically used in passive fire protection and require listing, approval, and compliance in ...
s) or with surface treatment (e.g., plasma treatment) effectively decreases
flammability
A combustible material is something that can burn (i.e., ''combust'') in air. A combustible material is flammable if it ignites easily at ambient temperatures. In other words, a combustible material ignites with some effort and a flammable mat ...
.
Problems with additives and fillers
Although effective at reducing
flammability
A combustible material is something that can burn (i.e., ''combust'') in air. A combustible material is flammable if it ignites easily at ambient temperatures. In other words, a combustible material ignites with some effort and a flammable mat ...
, flame-retardant additives and fillers have disadvantages as well. Their poor compatibility, high
volatility and other deleterious effects can change properties of
polymers
A polymer (; Greek '' poly-'', "many" + ''-mer'', "part")
is a substance or material consisting of very large molecules called macromolecules, composed of many repeating subunits. Due to their broad spectrum of properties, both synthetic an ...
. Besides, addition of many fire-retardants produces
soot
Soot ( ) is a mass of impure carbon particles resulting from the incomplete combustion of hydrocarbons. It is more properly restricted to the product of the gas-phase combustion process but is commonly extended to include the residual pyrolysed ...
and
carbon monoxide
Carbon monoxide (chemical formula CO) is a colorless, poisonous, odorless, tasteless, flammable gas that is slightly less dense than air. Carbon monoxide consists of one carbon atom and one oxygen atom connected by a triple bond. It is the simple ...
during
combustion
Combustion, or burning, is a high-temperature exothermic redox chemical reaction between a fuel (the reductant) and an oxidant, usually atmospheric oxygen, that produces oxidized, often gaseous products, in a mixture termed as smoke. Combus ...
.
Halogen-containing materials cause even more concerns on environmental
pollution
Pollution is the introduction of contaminants into the natural environment that cause adverse change. Pollution can take the form of any substance (solid, liquid, or gas) or energy (such as radioactivity, heat, sound, or light). Pollutants, the ...
.
[Porter, D.; Metcalfe, E.; Thomas, M. J. K. Nanocomposite Fire Retardants – A Review. ''Fire Mater.'' 2000, ''24'' (1), 45-52. ]
See also
*
Plastics
*
Fireproofing
Fireproofing is rendering something (structures, materials, etc.) resistant to fire, or incombustible; or material for use in making anything fire-proof. It is a passive fire protection measure. "Fireproof" or "fireproofing" can be used as a ...
*
Phenol formaldehyde resin
Phenol formaldehyde resins (PF) or phenolic resins (also infrequently called phenoplasts) are synthetic polymers obtained by the reaction of phenol or substituted phenol with formaldehyde. Used as the basis for Bakelite, PFs were the first commerc ...
*
Pyrolysis
The pyrolysis (or devolatilization) process is the thermal decomposition of materials at elevated temperatures, often in an inert atmosphere. It involves a change of chemical composition. The word is coined from the Greek-derived elements ''py ...
*
Combustion
Combustion, or burning, is a high-temperature exothermic redox chemical reaction between a fuel (the reductant) and an oxidant, usually atmospheric oxygen, that produces oxidized, often gaseous products, in a mixture termed as smoke. Combus ...
*
Fire-retardant gel
Fire-retardant gels are superabsorbent polymer slurries with a "consistency almost like petroleum jelly."
Fire-retardant gels can also be slurries that are composed of a combination of water, starch, and clay.
Used as fire retardants, they can be ...
*
Fire test
References
{{reflist
External links
Fire-Safety Branch of the Federal Aviation Administration
Polymers
Fire protection
Flame retardants