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Analysis of Flame
Retardancy in
Polymer Science
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Analysis of Flame
Retardancy in
Polymer Science
Edited by
Henri Vahabi
lec, LMOPS, Metz, France
University of Lorraine, CentraleSupe
Mohammad Reza Saeb

Department of Polymer Technology, Faculty of Chemistry, Gdansk
sk, Poland
University of Technology, Gdan
Giulio Malucelli
Department of Applied Science and Technology,
Politecnico di Torino, and Local INSTM Unit, Alessandria, Italy
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Contents
CONTRIBUTORS....................................................................................... XIII
PREFACE.................................................................................................. XV
CHAPTER 1 Fundamentals: Flammability, ignition, and fire

spread in polymers.......................................................... 1
Arthur Richard Horrocks
1 Introduction................................................................................ 1
1.1 Polymers and the fire triangle.......................................... 1
1.2 Glossary of terms.............................................................. 3
2 Thermal transitions, thermoplasticity, and geometric
effects......................................................................................... 5
2.1 Thermophysical effects..................................................... 7
2.2 Thermally thin versus thermally thick materials............. 8
2.3 Effect of sample geometry, orientation, and
physical structure.............................................................. 8
3 Fuel-forming reactions: Polymer pyrolysis and ignition......... 10
3.1 Thermal degradation or pyrolysis................................... 10
3.2 Pyrolysis of individual polymer types.............................. 12
4 Oxidative degradation............................................................... 27
5 Combustion and fire spread: Effect of incident heat flux....... 28
5.1 Ignition............................................................................. 30
5.2 Effect of heat flux............................................................. 31
5.3 Smoke.............................................................................. 36
6 Flame retardance: Effect of flame retardants on
ignition, combustion, and smoke generation.......................... 37
6.1 Flame-retardant types and characteristics.................... 39
6.2 Synergism, additivity, and antagonism............................ 41
6.3 Environmental challenges and the potential for
nanotechnology FR developments.................................. 44
v
vi Contents
7 General appraisal of pyrolysis/ignition/burn versus

reaction-to-fire test methodologies........................................ 47
7.1 Simple ignition-based tests............................................. 48
7.2 Reaction-to-fire tests...................................................... 49
7.3 Smoke tests..................................................................... 53
7.4 Exemplar larger-scale, reaction-fire tests..................... 54
8 Conclusions and future perspectives...................................... 56
References..................................................................................... 58
Further reading.............................................................................. 72
CHAPTER 2 Forced combustion: Cone calorimetry........................... 73
Vytenis Babrauskas
1 Introduction.............................................................................. 73
2 The forced-combustion environment...................................... 75
3 Additional instrumentation....................................................... 78
4 Using the data.......................................................................... 81
4.1 Simple methods............................................................... 81
4.2 Data for modeling............................................................ 85
5 Conclusions.............................................................................. 86
Acknowledgment............................................................................ 87
References..................................................................................... 87
CHAPTER 3 Microscale forced combustion:

Pyrolysis-combustion flow calorimetry (PCFC)............ 91
Rodolphe Sonnier
1 Introduction.............................................................................. 91
2 PCFC description...................................................................... 92
3 Study of pyrolysis..................................................................... 95
3.1 Combining PCFC and TGA............................................... 95
3.2 Activation energy for pyrolysis........................................ 95
3.3 Interactions in solid phase.............................................. 97
3.4 Aerobic pyrolysis—Thermo-oxidation............................. 98
4 Combustion............................................................................. 100
4.1 Incomplete combustion in PCFC by controlling
the combustor temperature.......................................... 100
4.2 Monitoring the residence time in combustor................ 102
4.3 Coupling PCFC with gas analyzers................................ 104
4.4 Monitoring the fuel/oxygen ratio................................... 106
5 Prediction of flammability data.............................................. 107
5.1 Predicting the flammability of polymeric
structures....................................................................... 107
Contents vii
5.2 Predicting the temperature of solid surface at

ignition from PCFC......................................................... 108
5.3 Correlations with fire tests............................................ 110
5.4 Milligram-scale flame calorimetry (MFC)..................... 112
6 Concluding remarks and future perspectives....................... 113
Acknowledgments........................................................................ 114
References................................................................................... 114
CHAPTER 4 Evaluation of gas phase: Mechanisms and analyses.... 117
Sabyasachi Gaan
1 Introduction............................................................................ 117
2 Types of gas-phase mechanism............................................ 119
3 Common analytical tools for gas-phase mechanism
evaluation............................................................................... 124
3.1 Thermogravimetry-infrared spectroscopy
(TG-FTIR)/mass spectrometry (MS) coupled
analysis.......................................................................... 124
3.2 Direct insertion probe-mass spectrometry (DIP-MS)... 129
3.3 Pyrolysis-gas chromatography coupled technique....... 131
3.4 Microscale combustion calorimeter (MCC) and its
variations........................................................................ 136
3.5 Cone calorimeter........................................................... 142
3.6 Detection of phosphorus-based gas-phase reactive
species........................................................................... 143
4 Concluding remarks and future perspectives....................... 152
Acknowledgment.......................................................................... 153
References................................................................................... 153
CHAPTER 5 Evaluation of gas phase: Smoke and toxicity analysis...161
Eric Guillaume
1 Introduction............................................................................ 161
2 Smoke contents...................................................................... 161
2.1 Gaseous fire effluents.................................................... 161
2.2 Solid and liquid fire effluents........................................ 165
3 Analysis of smoke.................................................................. 166
3.1 Smoke opacity................................................................ 166
3.2 Smoke gases’ concentrations........................................ 170
4 Impacts of smoke................................................................... 175
4.1 Visibility through smoke................................................ 175
4.2 Smoke inhalation........................................................... 176
4.3 Environmental effects.................................................... 185
viii Contents
5 Conclusions and perspectives................................................ 186

References................................................................................... 186
CHAPTER 6 Evaluation of condensed phase: Char/residue

analysis........................................................................ 191
Serge Bourbigot
1 Introduction............................................................................ 191
2 Fundamentals of char and residue formation....................... 193
2.1 Ceramization.................................................................. 193
2.2 Intumescence................................................................. 193
2.3 Physical barrier (nanocomposite).................................. 194
2.4 Charring......................................................................... 195
3 Chemical characterization: Chemical composition............... 195
3.1 Fourier transform infrared spectroscopy (FTIR)........... 196
3.2 Raman spectroscopy...................................................... 199
3.3 X-ray photoelectron spectroscopy (XPS)....................... 201
3.4 X-ray diffraction (XRD)................................................... 205
3.5 Solid-state nuclear magnetic resonance (ssNMR)....... 207
3.6 Electron spin resonance (ESR)...................................... 213
4 Microscopy: Morphology of the residue................................. 215
4.1 Scanning electron microscopy (SEM)............................ 215
4.2 Electron probe micro-analysis (EPMA)......................... 216
4.3 Transmission electron microscopy (TEM)..................... 217
4.4 X-ray computed tomography (CT).................................. 220
5 Dynamics of char/residue formation..................................... 223
5.1 Viscosity.......................................................................... 223
5.2 Deformation and expansion........................................... 224
6 Conclusions and future trends.............................................. 225
References................................................................................... 226
CHAPTER 7 Analysis of fire resistance of materials....................... 233
Thomas Rogaume, Benjamin Batiot, and Eric Guillaume

1 Introduction............................................................................ 233
2 Definitions and application of fire resistance........................ 237
2.1 Concept of fire resistance............................................. 237
2.2 Fire resistance evaluation—Experimental and modeling
characterization............................................................. 239
2.3 Influence of fire resistance objectives on human
behavior.......................................................................... 241
3 Material applications of fire resistance................................. 242
3.1 Non-combustible materials........................................... 244
Contents ix
3.2 Combustible materials.................................................. 245

4 Conventional approach of fire resistance.............................. 248
4.1 General principles.......................................................... 248
4.2 Building application....................................................... 249
4.3 Transport application..................................................... 261
4.4 Outside Europe............................................................... 265
4.5 Limits of the conventional approach............................. 266
5 Performance approach........................................................... 266
5.1 Fire dynamics for fire resistance.................................. 267
5.2 Fire analysis applied to structural analysis.................. 280
5.3 Thermal analysis............................................................ 283
5.4 Experimental approach using large-scale and
real-scale tests.............................................................. 284
5.5 Structural fire engineering............................................ 286
Acknowledgments........................................................................ 293
References................................................................................... 293
CHAPTER 8 Characterization of high-temperature polymers

for extreme environments........................................... 299
Hao Wu and Joseph H. Koo
1 Introduction............................................................................ 299
2 High-temperature polymers.................................................. 303
2.1 High-temperature thermosets...................................... 303
2.2 High-temperature thermoplastics................................ 308
3 Aerothermal ablation testing for high-temperature
applications............................................................................. 311
3.1 Oxyacetylene test bed (OTB).......................................... 311
3.2 Simulated solid rocket motor (SSRM)........................... 313
3.3 Subscale solid rocket motor (char motor).................... 315
3.4 LHMEL test facilities...................................................... 316
3.5 ICP test facilities............................................................ 318
3.6 Arc jet test facilities....................................................... 321
4 Concluding remarks............................................................... 325
References................................................................................... 326
CHAPTER 9 Correlation between laboratory- and real-scale

fire analyses................................................................. 333
de
Laurent Aprin, Laurent Ferry, Fre ric Heymes,
Rodolphe Sonnier, and Pascal Zavaleta
1 Introduction............................................................................ 333
x Contents
1.1 From microscale to small scale.................................... 336

1.2 Correlations between small-scale tests....................... 339
1.3 From small-scale tests to intermediate- or
large-scale tests............................................................ 340
2 Case study no. 1: Fire behavior of PMMA.............................. 341
2.1 Flammability at microscale........................................... 342
2.2 From small to intermediate scales............................... 342
2.3 Interactions at large scale............................................. 352
2.4 Conclusion...................................................................... 353
3 Case study no. 2: Electric cable tray fires............................. 354
3.1 Assessment of the pHRR of horizontal cable
tray fires......................................................................... 356
3.2 Assessment of the HRR of horizontal cable
tray fires......................................................................... 361
3.3 Conclusion...................................................................... 363
4 Case study no. 3: Wildfires.................................................... 364
4.1 The need for flame retardants research in wildfires
science........................................................................... 365
4.2 Scales in wildfires.......................................................... 366
4.3 Experimental tests in wildfire research........................ 367
4.4 Linking small-scale, large-scale, and real-scale tests...369
4.5 Strategies for upscaling wildfire dynamics................... 369
4.6 Rothermel model........................................................... 370
4.7 Limitations..................................................................... 371
4.8 Conclusions.................................................................... 373
References................................................................................... 374
CHAPTER 10 Fire analysis tests from industrial point of view......... 381
Eric Guillaume
1 Fundamental principles......................................................... 381
2 Scenario-based approach...................................................... 382
2.1 Criteria........................................................................... 382
2.2 Safety objectives............................................................ 382
2.3 Materials, products, and systems problematics........... 384
2.4 Reference scenarios...................................................... 385
3 Building products................................................................... 386
3.1 Europe............................................................................ 386
3.2 North America................................................................ 394
3.3 Other building products................................................. 398
Contents xi
4 Cables..................................................................................... 401
4.1 Europe............................................................................ 401
4.2 Others............................................................................. 405
5 Electrotechnical products...................................................... 406
5.1 Principle......................................................................... 406
5.2 Main test methods......................................................... 406
6 Others..................................................................................... 407
6.1 UL94............................................................................... 407
6.2 Heat release rate measurements................................. 408
6.3 Smoke corrosivity.......................................................... 410
7 Transportation........................................................................ 410
7.1 Road transportation field............................................... 410
7.2 Rail transportation field................................................. 413
7.3 Marine field.................................................................... 425
7.4 Aeronautical field........................................................... 431
References................................................................................... 437
INDEX................................................................................................................... 449
Contributors
Laurent Aprin Laboratory for the Science of Risks (LSR), IMT Mines Ales, Ales, France
Vytenis Babrauskas Fire Science and Technology Inc; John Jay College of Criminal Justice, New York,
NY, United States
Benjamin Batiot Institut Pprime (UPR 3346 CNRS), Universite de Poitiers, Poitiers, France
Serge Bourbigot Univ. Lille, CNRS, INRAE, Centrale Lille, UMR 8207-UMET-Unite Materiaux et
Transformations, Lille; Institut Universitaire de France (IUF), Paris, France
Laurent Ferry IMT Mines Ales, Polymers Composites and Hybrids (PCH), Ales Cedex, France
Sabyasachi Gaan Laboratory of Advanced Fibers, Empa, Swiss Federal Laboratories for Materials
Science and Technology, St. Gallen, Switzerland
Eric Guillaume Efectis France, Saint-Aubin, France
Frederic Heymes Laboratory for the Science of Risks (LSR), IMT Mines Ales, Ales, France
Arthur Richard Horrocks IMRI—University of Bolton, Bolton, United Kingdom
Joseph H. Koo KAI, LLC; Walker Department of Mechanical Engineering, The University of Texas at
Austin, Austin, TX, United States
Thomas Rogaume Institut Pprime (UPR 3346 CNRS), Universite de Poitiers, Poitiers, France
Rodolphe Sonnier IMT Mines Ales, Polymers Composites and Hybrids (PCH), Ales Cedex, France
Hao Wu KAI, LLC, Austin, TX, United States
Pascal Zavaleta Institut de Radioprotection et de Sûrete Nucleaire (IRSN), St Paul-Lez-Durance
Cedex, France
xiii
Preface
Any development in the field of polymer science and technology has always been
accompanied by the quest for design and manufacture of high-performance poly-
meric materials, particularly polymer composites and nanocomposites. In the
meantime, precise analysis of polymers has advanced providing researchers with
useful insights into the processing-microstructure-properties-performance inter-
relationships. Flame-retardant polymeric materials have been at the core of atten-
tion over the past few decades, as evidenced by the commercialization of many
flame-retarded systems. However, there is a continued need for fire analysis mak-
ing it possible to evaluate the fire performance and also to identify the mecha-
nisms underlying the flame retardancy of polymers in both gas and condensed
phases. Typically, fire behavior analysis can be viewed in terms of flammability,
ignitability, heat release during combustion, flame spread, amount and intensity
of smoke, and toxicity. Several standard test methods are available for the analysis
of fire including ASTM, ISO, and EN, a few to mention. Fire tests can be viewed
from the scale perspective as small-scale, bench-scale, and large-scale measure-
ments. Nevertheless, researchers are quite often looking for new ways for the anal-
ysis of fire by correlating the outcomes of standardized tests and/or defining new
measures/indices, aimed at a deeper understanding of the mechanisms control-
ling the flame retardancy of polymers.
Exploring the mechanisms of action of flame retardants in polymers is an essen-
tial requirement. Besides standard methods that mainly focus on the physics of
fire, there will always be the need for supplementary tests to unravel the role of
chemistry, which include the analysis of char (intumescent or compact/dense)
and mineral residue. Since new flame-retardant systems are mainly complex/
hybrid systems, in which two or more flame retardants with similar or different
nature are involved, the analysis of flame retardancy sometimes becomes a seri-
ous challenge for researchers. Such hybrid materials are aimed at covering a
wide variety of applications ranging from cables and protective coatings to
the construction and building materials as well as those in railways and avia-
tion. This book provides useful information about fire analysis in polymer sci-
ence. Starting from general concepts and definitions/terms, several advanced xv
xvi Preface
features of fire analysis are covered by a number of experts from all around the
world with long-standing experience in the field. In Chapter 1, fundamentals of
fire analysis including the flammability, ignition, and fire spread are intro-
duced, followed by Chapter 2 on forced combustion, viewed from the perspec-
tive of cone calorimetry tests. In Chapter 3, forced combustion is discussed in
terms of microscale i.e., pyrolysis-combustion flow calorimetry (PCFC) tests. In
Chapter 4, the gas phase analysis is presented, and mechanisms are described,
followed by further evaluation of smoke analysis overviewed in Chapter 5.
Evaluation of the condensed phase is then surveyed by char/residue analysis
in Chapter 6. Analysis of fire resistance of materials is also discussed in
Chapter 7, followed by characterization of fire in high-performance polymers
used for advanced applications (Chapter 8). The last two chapters are devoted
to the correlation between laboratory-scale and real-scale fire analyses
(Chapter 9) and fire analysis from an industrial perspective (Chapter 10).
The editors of this book hope that the chapters can contribute to deepening the
knowledge of students, technicians, engineers, researchers, and policy makers
of industry working in the field from both academic and industrial sectors. The
evolution in materials, processing, and standard test methods will necessitate
further analyses on the fire retardancy of polymer materials. We brought
together well-known scientists to write this book in the hope that the outcome
could persuade scientists for continued innovation, adaptation and/or estab-
lishment of new test methods in a more robust and reliable manner.
Henri Vahabi
Mohammad Reza Saeb
Giulio Malucelli
CHAPTER 1
Fundamentals: Flammability, ignition,

and fire spread in polymers
Arthur Richard Horrocks
IMRI—University of Bolton, Bolton, United Kingdom
1 Introduction
The fire safety of materials and products is determined by an understanding of
how they may react to an igniting source in the environments in which they are
used, such as domestic dwellings, public buildings, industrial locations, and
transport. The use of polymeric materials for structural items, interior decora-
tion, furnishings, etc., introduces the problem of their potential flammability
and increased fire hazard, which their presence introduces in terms of increas-
ing the risk of fire injury and potential loss of life.
This chapter is intended to provide an overview of the significant aspects that
determine the effect of heat on the polymeric materials, their subsequent igni-
tion and combustion, and the related factors influencing flame spread rates.
The elements of strategies that increase the flame retardancy or resistance of
polymers are particularly stressed. In addition, a general appraisal of these
and how they relate to fire testing methodologies are provided as the basis
for subsequent more in-depth studies later in this book.
The text is provided with a number of significant references to enable the reader
to pursue each topic in far greater depth than is possible here. The references are
followed by an extensive bibliography comprising the most significant texts
published during the last 20 years or so.
1.1 Polymers and the fire triangle

To understand the combustion process, an appreciation of the so-called Fire
Triangle is an essential first requirement. In essence, any combustion requires
the three elements: a fuel, heat, and oxygen acting together in concert. Fig. 1
illustrates this process, and the triangle is “broken” if any one of these factors
is removed. Ideally, the fuel must be either a gas or vapor.
1
Analysis of Flame Retardancy in Polymer Science. https://doi.org/10.1016/B978-0-12-824045-8.00001-0

Copyright © 2022 Elsevier Inc. All rights reserved.
2 C HA PT E R 1 : Fundamentals: Flammability, ignition, and fire spread in polymers
FIG. 1
The fire triangle.
Since polymers are solids, their conversion into flammable fuels, as a result of
the application of heat as a flame, a hot surface, or in radiant form, must first be
understood. This may be represented by the generalized reactions in Scheme 1.
ΔHc heat
Volatiles + flammable gases +
Polymer
non-flammable gases + char

ΔHc
Oxygen
CO + CO2 + H2O
(+ NOx + HCN) + smoke
SCHEME 1
The simple view of the polymer pyrolysis/combustion process.
The heat required to thermally degrade or pyrolyze the polymer is defined as

the heat of pyrolysis, ΔHp, and the reactions involved are usually endothermic.
The evolved volatiles and flammable gases represent the “fuels” in Fig. 1, and at
the temperatures, at which pyrolysis occurs, usually oxidize and ignite in the
presence of oxygen. However, in real fires, perfect oxidation of all volatiles
to carbon dioxide and water does not occur; hence, if there is an inclusion
of carbon monoxide and if nitrogen is present in the polymer (e.g., polyamides,
polyacrylics, wool, silk), there is the probability that nitrogen-containing gases,
NOx, and hydrogen cyanide, HCN, may also be present. Polymers containing
sulfur such as wool, keratin, vulcanized rubber, and polysulfones may include
gases such as hydrogen sulfide and sulfur dioxide in the fire gases. Smoke again
1 Introduction 3
is a product of imperfect combustion. Oxidation is an exothermic reaction and

so heat is evolved, ΔHc, the heat of combustion, which feeds back to pyrolyze
more polymers.
1.2 Glossary of terms

The whole area of polymer, fiber and textile, film/laminate, and composite
material burning properties and their related risk-reducing methodologies
use a number of terms, which in some cases may be quite confusing, especially
to the non-specialist. The following is a list in an alphabetical order of the more
common terms, originally taken from those identified by Lewin [1], and it
includes a number of additions and variations relating to the whole area of
flame-retardant polymers and its literature:
Additive (flame retardant): A (flame retardant) compound added after the

polymer has been synthesized, but before or during its conversion to the
final form (e.g., fiber, plastic), not covalently bound to polymer
substrate.
Afterglow: Glowing combustion in a material after cessation (natural or
induced) of flaming.
Afterglow time: The time the flame continues to burn after the ignition flame
is removed.
Antagonism: The observed effectiveness of combinations of compounds is
less than the sum of the effects of individual components.
Autoignition: Spontaneous ignition of a material when heated in air.
Back-coating: A coating applied to the reverse face of a fabric in a manner that
does not affect the aesthetics or other properties of the face.
Char: The carbonaceous residue or char formed during or remaining after
pyrolysis or combustion.
Char length: The difference between original length and remaining unburned
length of material after testing a specimen by exposure to a flame.
Coating (flame retardant): A layer of secondary material comprising a flame
retardant and a binder or a flame-retardant resin deposited on the polymer
material surface or within the polymer surface.
Combustion: Self-catalyzed exothermic reaction involving fuel and oxidizer.
Condensed-phase flame retardant: A flame retardant that modifies the polymer
pyrolysis process to reduce flammable volatile formation and usually
increase in char.
Damaged length: The extent of damage produced over the specimen by an
ignition source and the subsequent substrate ignition. It may include char,
formation of a hole, discolored region, or zone having reduced tensile
properties or a combination thereof.
Finish (flame retardant): A compound or combination of compounds added

after conversion to the end product (e.g., fiber, yarn, fabric), which may be
chemically bonded or deposited on fiber, yarn, fabric, or thin-film surfaces.
Fire resistance: The capacity of a material or structure to withstand fire
without losing its functional properties.
Flame: Combustion process in the gas phase accompanied by the emission
of visible light.
Flame resistance: The property in a material of exhibiting resistance to
ignition and/or minimal flammability; the term is often synonymous with
flame retardancy, but may be considered to relate to materials, which do not
ignite under a flame but may be damaged by it.
Flame retardance or retardancy: The property in a material of exhibiting
resistance to ignition and reduced flammability; the term is often
synonymous with flame resistance but may be considered to relate to
materials, which will ignite under a flame and which on removal will either
self-extinguish or burn very slowly.
Flame retardant: Chemical compound capable of imparting flame resistance
to (or reducing the flammability of ) a material, to which it is added or
combined with.
Flame propagation: Spread of flame from region to region in a combustible
material (burning velocity ¼ rate of flame propagation). In textile fabrics, the
time to burn a specified length of fabric is more easily defined.
Flame spread: The extent of propagation of flame in space or over a specimen
surface under specified test conditions.
Flaming debris: Materials separating from the specimen during the test
procedure and falling below the initial lower edge of the specimen and
continuing to flame as it falls. These may include molten drips, both flaming
and non-flaming.
Flammability: The tendency of a material to burn with a flame.
Gas- or vapor-phase flame retardant: A flame retardant that interacts with the
flame chemistry, during which volatiles are oxidized by oxygen in air.
Heat flux: The intensity of a heat or igniting source with respect to a defined
area or mass of material.
Ignition: Initiation of combustion. In fire testing, an alternative definition
might be, “The stage, at which the test specimen sustains a flame for a period
of 1 s or more after removal of the igniting flame.”
Ignition time or time to ignite: The time taken for a sample to ignite when
subjected to an ignition source, a direct heat flux or both.
Inherent flame or fire resistance: The property of a polymer, in which the
chemical structure resists pyrolysis and gives off few flammable volatiles,
thereby reducing its ease combustion and increasing its ability to maintain
its functional properties at higher temperatures. Such organic polymers
usually have aromatic structures.
2 Thermal transitions, thermoplasticity, and geometric effects 5
Limiting oxygen index (LOI): Minimum oxygen percent in the environment

that sustains burning under specified test conditions.
Nanocoating, including sol-gel and layer-by-layer: Coatings on polymer surfaces
of >100 nm or even of molecular thickness. Sol-gel coatings generally
comprise a cross-linked surface coating based on silica networks; layer-by-
layer costings comprise multilayer sandwich-type structures, in which each
nanolayer has an equal and opposite electrical charge.
Peak heat release rate: The maximum rate of heat release following the
ignition of a sample.
Pyrolysis: Irreversible chemical decomposition due to non-oxidative heating.
Rate of heat release: The amount of heat released per unit time at a given time
by specimen burning under specified test conditions.
Residual flame time: The time taken for burning fragments (e.g., molten
drips) falling from the sample and which burn on the bottom of the test
cabinet to extinguish.
Self-extinguishing: The incapability to sustain combustion in air under the
specified test conditions after the removal of external heat source.
Smoke: Fine dispersion in air of particles, usually individually invisible, of
carbon and other solids and liquids resulting from incomplete combustion.
Its opacity is due to scattering and/or absorption of visible light.
Smoldering: Combustion without flame and without prior flaming
combustion, but usually with incandescence and smoke.
Surface flash: The rapid spread of flame over the surface of a material without
ignition of its basic structure.
Synergism: The observed effectiveness of combinations of compounds is
greater than the sum of the effects given by individual components.
Thermal transition temperature: The temperature at which a physical or
chemical change occurs when a polymer is heated.
Vertical, horizontal, 30°, 45°, or other defined angle (strip or coupon) test:
Orientation of the test specimen with respect to the horizontal during
flammability testing under specified conditions.
2 Thermal transitions, thermoplasticity,

and geometric effects
The burning behavior of organic polymers is influenced and often determined
by a number of thermal transition temperatures and thermodynamic parame-
ters. Table 1 lists the commonly available polymers with their typical or indic-
ative physical glass or second-order, Tg, and melting, Tm, transitions, if
appropriate, which may be compared with their chemically related transitions
of pyrolysis (under an inert atmosphere), Tp, and ignition and the onset of
flaming combustion, Tc [2,3]. All transition temperatures in Table 1 should
Table 1 Indicative thermal transitions of the more commonly used polymers [2,3].
Tg, °C Tm, °C Tp, °C Tc, °C LOI, ΔHc,
Fiber (softening) (melting) (pyrolysis) (ignition) vol% J/g
Natural polymers
Cellulose – – 350 350 18.4 19
Keratin (e.g., wool) – – 245 600 25 27
Thermoplastic polymers
Nylon 6 50 215 431 450 20–21.5 39
Nylon 6.6 50 265 403 530 20–21.5 32
Poly(ethylene 80–90 255 420–447 480 20–21 24
terephthalate)
Polyacrylic 100 >220a 290 >250 18.2 32
Polyethylene, LDPE 125 105–115 >450 >450 18–19 45
Polyethylene, HDPE 135–140 >450 >450 18–19 45
Polypropylene 20 165 >400 >400 18.6 44
Poly(methyl 110 200b >300 380 18 25
methacrylate), PMMA
Poly(lactic acid), PLA 60–65 150–160 300 – 21–24 –
PVC <80 >180 >180 450 37–39 21
Polystyrene 100 240c >280 19 42
Thermoset polymers
Vinyl ester 110 – >250 – 20–23 –
Unsaturated polyester 90–130 – >250 – 20–22 29–30
Phenol-formaldehyde 270–300 – 440–520 – 25 28–29
Epoxy 120–220 – 360–430 – 22–23 30–31
Inherently flame- and heat-resistant polymers

Meta-aramid 275 375a 410 >500 29–30 26
(e.g., Nomex)
Para-aramid 340 560a >590 >550 29 26
(e.g., Kevlar)
Polyimide (resin) >300 – >450 – 35 26
a
With decomposition.
b
Syndiotactic.
c
Isotactic.
be considered to be indicative only since they have been obtained from various
literature sources, in some cases averaged, and in any case, they are dependent
on polymer history and the method used to record them. In addition, typical
heats of combustion are given as ΔHc. Generally, the lower the respective Tc
(and usually Tp) temperature and the hotter the flame, the more flammable
is the polymer. Table 1 lists also typical limiting oxygen index (LOI) values,
which are measures of the inherent burning character of a material and may
be expressed as a percentage or decimal [4]. The LOI test was developed by Feni-
more and Martin in 1966 [5] and is well established in a number of standards
including ASTM D2863 and ISO EN 4589-2 [6].
Polymers having LOI values of 21 vol% or 0.21 or below ignite easily and burn
rapidly in air (containing 20.8% oxygen). Those with LOI values above 21 vol%
ignite and burn more slowly, and generally when LOI values rise above values
of about 26–28 vol%, polymers usually may be considered to be flame retar-
dant and will pass most small ignition tests when subjected to a small flame
in the horizontal and vertical orientations.
2.1 Thermophysical effects

Thermoplasticity, determined by the magnitude of the second-order tempera-
ture, Tg, which may or may not precede melting, is an important factor that influ-
ences the fire behavior of any polymer. This transition is associated with the
temperature required for polymer segmental motion to occur within the non-
crystalline region of a polymer. In amorphous polymers, such as atactic polysty-
rene and poly(methyl methacrylate), only a second-order transition temperature
may be recorded as is the case in all thermoset polymers (sometimes referred to
as resins), in which covalent cross-links exist between the polymeric chains.
Semi-crystalline polymers, which are often fiber-forming, may also have an
associated melting point, Tm (e.g., polyamides or nylons, polyesters, polyole-
fins), unless the degrees of crystallinity are exceptionally high (e.g., cellulose,
poly(para-aramid)), which result in second-order and/or melting transition
temperatures being so high that thermal decomposition occurs first.
When subjected to heat, a thermoplastic polymer may shrink away from any
igniting flame, thereby giving the illusion of flame retardancy in that the shrink-
age occurs well below the ignition temperature. In fact, in thin materials like
textile fabrics and films, the shrinkage may be sufficient to enable an otherwise
quite flammable polymer not to ignite and so pass a given flammability stan-
dard. Not all thermoplastic polymers melt, especially those with high Tg values,
since thermal decomposition may precede or prevent melting. If a polymer
melts, then molten drips may form which—while removing thermal energy
from the heated zone, and thus preventing or reducing the tendency to
ignite—may also add to the fire hazard if the drips do ignite and so spread
the flame via flaming drips to underlying or adjacent materials. In Table 1, most
of the polymers with well-defined melting points will suffer from this phenom-
enon. Some thermoplastic polymers like polyacrylics will appear to melt, while
decomposing at the same time; this is especially noticeable with some inher-
ently flame- and heat-resistant polymers like poly(meta- and para-)aramids.
2.2 Thermally thin versus thermally thick materials

It is important also while considering these thermophysical effects to consider
the difference between thermally thin and thermally thick materials [7]. Poly-
mers are good thermal insulators, and so when in the bulk form, if exposed to
heat on one surface, will be subjected to only the localized effects that the heat
source generates, with the interior experiencing little increase in temperature for
some time. In other words, a thermal gradient will be created, which could be
close to 1000°C on the surface and ambient temperature within or at the reverse
surface of the material. Such a material is defined as being thermally thick. This
will mean that thermal degradation or pyrolysis reactions generating fuel will
occur at different rates across this gradient. Should the polymer be char-
forming, then it may form a layer of char immediately below the flame zone,
which will act as a further barrier to heat transfer.
On the other hand, if the material is very thin, then the rate of heat transfer
across its thickness may be so fast that no thermal gradient is actually measur-
able. Materials that behave in this manner are typically films, textile fabrics, and
thin laminates and are said to be thermally thin. Experience shows that thermally
thin behavior is observed when material thicknesses are less than 3 or 4 mm,
and so for thicknesses above 5 mm, thermally thick behavior is observed. If heat
fluxes are significantly high (50 kW/m2, a value typically equivalent to an
average room fire above at flashover—see Section 5), then the thermally thin
to thick boundary may be closer to 10 mm, especially in materials like
wood [8].
Thus, thin films, laminates, and textiles are usually considered to be thermally
thin. In the case of textile structures, single layers may be thermally thin but as
layers are added, they may be able to show thermally thick behavior [9]. This
may be usefully exploited when designing heat-protective clothing and espe-
cially firefighters’ garments [10,11].
In conclusion, it is generally the case that thermally thin materials will therefore
ignite sooner and burn much more intensely than thermally thick samples.
2.3 Effect of sample geometry, orientation, and physical

structure
In addition to the effects of thickness, a number of other geometrical factors
may influence the ignition and burning properties of materials, some of which
are summarized below.
Ignition source location and sample orientation: Materials subjected to an
ignition source applied to the top of the sample usually show the longest
ignition time since heat from any generated flame will be dissipated upward,
away from the sample. Conversely, ignition at the bottom of a sample will
produce the shortest time since heat from flames generated will be
transferred to the sample immediately in advance of the flame. Once ignited,
the advancing flame will preheat the material and the flame will accelerate
rapidly as a consequence of this so-called chimney effect. The degree of
acceleration will decrease as the angle of advancing flame reduces from 90°
with respect to the horizontal. Standard test methods usually reflect the
orientation that a given material will be used during its service life and the
fire hazard posed. Thus, for example:
(i) Building wall panels, curtains and blinds, and protective clothing
will be tested in vertical orientations (90°);
(ii) Flooring, including carpets, and car interior fabrics are tested in the
horizontal mode (0°);
(iii) Tenting and internal strappings for aircraft luggage containment
may be tested at other angles such as 30°, 45°, or 60° to the
horizontal.
Face versus edge ignition: Sample edge ignition presents a more severe ignition
condition than face ignition, since in the former the flame will contact not
only the sample face, but also the lower edge surface and, in the case of a thin
laminate, film or textile, the reverse face. Thus, testing methods reflect the
application hazard so that textiles may often be tested at the edge, whereas
wall panels may be exposed to a face ignition source.
Effect of heterogeneity and structure: In multiphase materials containing a
polymer as a binder resin in a composite for example, or dispersed
reinforcing short glass fibers in an extruded or molded item, the action of
heat may cause the structure to delaminate or deconstruct, thereby
exposing inner surfaces to both heat and oxygen. In addition, exposed
reinforcing elements may prevent otherwise molten polymer from
dripping away from the ignition zone. In both cases, the burning
properties of the material will be significantly different from those of the
polymer itself. A good example here is the very common polyester/cotton-
blended textile fabric, which when heated the polyester melts and wets the
surfaces of the adjacent charring cotton fibers, which prevent the former
from dripping away. This so-called scaffolding effect explains why
polyester/cotton-blended fabrics often pose a greater fire hazard than those
comprising cotton alone.
Foams and textiles also contain air or other gases within their structures, which
will significantly affect their burning properties. Thus, low fabric area density
values and open structures aggravate the burning rate and so increase the haz-
ards of burn severity more than heavier and multilayered constructions [12].
Correlations between LOI linearly with respect to area density and logarithmi-
cally with air permeability have been shown for a series of cotton fabrics,
although correlation coefficients were low [13].
3 Fuel-forming reactions: Polymer pyrolysis

and ignition
3.1 Thermal degradation or pyrolysis
The first chemically identifiable thermal transition as stated above is the onset
of pyrolysis, usually associated with the formation of volatiles. It is these, which
if flammable, enable polymeric materials to be consumed by flaming combus-
tion, a gas-phase process. The different structures of the various polymer types
(see Table 1) influence the chemical characteristics of any decomposition, and
this will affect the resistance, if any, to combustion.
Pure polymeric materials degrade via one or more of the following simple
mechanisms:
(i) End chain scission, where individual monomer units successively are
cleaved from the chain end sometimes termed "unzipping";
(ii) Random chain scission, where scissions occur at random locations
along the polymer chain;
(iii) Chain stripping, where atoms or groups not part of the polymer
backbone are cleaved off;
(iv) Cross-linking, where bonds are created between polymer chains; or
(v) A combination of one and more of the above mechanisms.
Table 2 lists various examples of each of these mechanisms and the decompo-
sition polymers, and temperatures, at which they commence to thermally
decompose or pyrolyze, Tp. In practice, plotting the exact temperature, at which
mass loss occurs, is difficult and so values of Tp are often defined as tempera-
tures, at which a given mass loss occurs, e.g., 5%.
However, the intrinsic thermal degradation characteristics of any polymer may
be influenced by impurity species present since polymers are rarely pure in the
true chemical sense. Such impurities may include one or more of the following:
(i) impurities already present in monomeric feeds during commercial

polymerization, although generally monomer purity is recognized as a
critical variable by polymer producers,
(ii) polymerization catalyst residues present in both addition and
condensation polymers,
(iii) products of degradation generated during polymerization and
processing, often of a thermally derived origin. These may include
products of thermal oxidation (see Section 4),
(iv) contaminants introduced during processing, including atmospheric
oxygen and metallic ions released from processing plant equipment.
3 Fuel-forming reactions: Polymer pyrolysis and ignition 11
Table 2 Relative thermal polymers and typical decomposition products for each generalized
mechanisms of polymer decomposition [14].
Mechanism Examples of polymer Typical products
Random chain scission Cellulose Levoglucosan

Polyamide (nylon) 6 and 6.6 Volatile amines, shorter chain fragments
Poly(ethylene terephthalate) Acetaldehyde
Polyethylene Alkanes, alkenes, very little monomer
Polypropylene Alkanes, alkenes, very little monomer
Polystyrene Styrene monomer, dimer, and trimer
General mechanism Shorter monomeric and oligomeric fragments
End chain scission Polymethylmethacrylate 90%–100% monomer
Polytetrafluoroethylene 90%–100% monomer
Polyamide 6 Caprolactam
Poly(lactic acid) Lactide
General mechanism Monomeric evolution
Chain stripping Polyvinyl chloride Hydrogen chloride, aromatic hydrocarbons, and char
Polyvinyl alcohol Water and char
General mechanism Small molecules like water, HCl, and acetic acid and char
Cross-linking Cellulose Char
Polyacrylonitrile Char (and HCN)
Polyaromatics Char
General Much char, few volatile products
These factors tend to be specific to each polymer type and its related polymer-
ization history and will be referred to below when discussing individual poly-
mer degradation behavior, if relevant. Thus, it may be stated that no two
batches of the same polymer actually have identical thermal degradative behav-
iors. In fact, the presence of impurities is usually one which sensitizes the over-
all degradation, as well as giving rise to the slow thermal degradation and
related deterioration in polymer properties. The latter is often experienced
when polymeric products are in use and exposed to service temperatures well
below their normal rapid degradation temperatures as defined by Tp above. In
many cases, the effective lifetime of a polymer in service is determined by the
length of the induction period for these low-temperature degradation reactions
to promote sufficient loss in properties as to render it useless for its intended
purpose. Such induction times may be quantified in terms of times to embrit-
tlement, to lose 50% tensile strength or to change its character (e.g., color) by a
specified magnitude. Prediction of lifetimes at a given service temperature may
be made following the analysis of thermal degradation at higher temperatures,
which then allows apparent activation energies to be determined based on the
assumed Arrhenius Law behavior [15,16]. Thus, stabilizing additives are usu-
ally included during the processing stages of any polymer, and because of
the complexity and often interrelated nature of these secondary reactions, such
stabilizers may be required to minimize thermal degradation and oxidation in a
concerted manner.
3.2 Pyrolysis of individual polymer types

Generally, when heated, the weakest bonds within the polymer will break first,
which then determines the overall characteristics of the subsequent degrada-
tion pathways as described above and illustrated in Table 1. Carbon-carbon
single bonds within polymer chains are stronger than CdN and CdO bonds,
which are more likely to be ruptured when heated in polymers such as polyam-
ides and polyesters. Polymers with side groups such as dOH, dCl, and dCN
will lend themselves to elimination or cross-linking reactions. The outcome of
these reactions is that only the ease of formation of flammable volatile products
will determine the flammability of the polymer, while both elimination (often
giving rise to simple molecules such as H2O, HCl, and HCN) and cross-linking
reactions give rise to eventual char formation. These char-forming reactions
may be enhanced at the expense of volatile formation if the so-called
condensed-phase flame retardants are present (see Section 6). In the discussion
below, the initial stages of thermal degradation are identified for exemplar
polymers, which in most cases give rise to complex degradation mechanisms.
3.2.1 Thermoplastics
As Table 1 shows, not all thermoplastic polymers melt, but those that have well-
defined melting points and which can be melt processed up to temperatures as
high as 300°C or so, have bonds sufficiently resistant to minimize significant
levels of degradation. Thermoplastic polymers that do not melt are generally
those that are non-crystalline, cross-linked, or reactive above their second-order
transition temperature or a combination of some of these factors.
3.2.1.1 Polyolefins
Carbon-carbon single bond strengths in both polyethylene and its many copol-
ymeric variants and polypropylene determine the respective ease with which
initial random chain scissions occur. These reactions are only slightly affected
by the differences in physical structure such as crystallinity, but are influenced
by the presence of impurities present and in the case of polypropylene, the
accessibility to oxygen [17]. However, while it is largely true to say that these
may influence the processability and long-term stability of respective polyole-
fins, they have little or no effect on the flammability.
In the case of polypropylene, pyrolysis is dominated by initial chain scissions,
usually at either carbon-carbon bond adjacent to the labile tertiary hydrogen
atom in the repeat group dCH2dCH.(CH3)d. Heating the polymer, includ-
ing waste polypropylene, generates a mixture of quite clean hydrocarbon fuels
[18,19] and other valuable products such as lubricants [20,21]. This explains
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Fig. 5
SCALE 40
265 REVS. PER MIN.
11¹⁄₄″ × 16″ PORTER-ALLEN.
Fig. 1
Fig. 4
SCALE 40
265 REVS. PER MIN.
4.416 „ „ SEC.
Fig. 2 Fig. 3
Apparatus for Graphically Showing the Acceleration and Retardation of the

Reciprocating Parts of an Engine.
Let the motion be in the direction from the crank. The crank now
begins insensibly, by pulling through the spring e, to arrest the
motion of the weight h. This pull will increase in intensity to the end
of the stroke, when the weight is brought to rest, and the spring will
become correspondingly elongated. Then, by a continuance of the
same pull, the crank puts the cross-head and this free weight in
motion in the reverse direction. This pull gradually relaxes, until at
the mid-stroke it has ceased. The weight h has acquired its full
velocity again; all stress is off the spring, and the spring and weight
are back in the positions in the box d from which they started. This
action is repeated during the opposite half of the revolution, but in
the reverse direction, the pull being changed to a push, and the
spring being compressed instead of elongated. Thus at every point
the position of this free weight shows the amount of the accelerating
or retarding force that is being exerted upon it at that point,
elongating or compressing the spring.
This varying accelerating or retarding force is recorded as follows:
A paper b, Fig. 2, is stretched on the surface ff. This surface is the
arc of a circle described about the center j, and is secured on the
lath B, so that as this lath vibrates by the motion of the cross-head
the different points in the length of the paper pass successively
under the pencil. This is set in the end of the long arm a of the right-
angled lever-arms 4 to 1 seen in Fig. 2, which is actuated by the rod
e passing centrally through the spring and secured in the head c.
This pencil has thus imparted to it a transverse motion four times as
great as the longitudinal motion of the weight h in the box d. The
pencil is kept lifted from the paper (as permitted by the elasticity of
the arm a) by the cord m. By letting the pencil down and turning the
engine by hand, the neutral line x, Fig. 2, is drawn. Then when the
engine is running, on letting the pencil come in contact with the
paper, the diagonal lines are drawn as shown on Fig. 2.
Edwin F. Williams
If the rotation of the shaft were uniform and there were no lost
motion in the shaft or connecting-rod, this diagonal line would repeat
itself precisely, and would be a straight line modified by the angular
vibration of the connecting-rod. On the other hand, these lost
motions and the variations in the rotative speed must be exactly
recorded, the latter being exhibited with a degree of accuracy not
attainable by computation and plotting, and their correctness would
be self-demonstrated. For this purpose this instrument must be
found highly valuable, if it is really desired to have these variations
revealed rather than concealed. Fig. 5 represents the inertia diagram
drawn by this instrument applied to a Porter-Allen engine running in
the Boston Post Office at the speed of 265 revolutions per minute.
Fig. 4 shows the same diagram with the transverse motion of the
pencil enlarged to correspond with the scale of the indicator, so
exhibiting the force actually exerted on the crank-pin at every point,
which is represented by the shaded area, and from which the
rotative effect on the crank can be computed. The steam pressure
absorbed at the commencement of the stroke by the inertia of these
parts is represented by the blank area above the atmospheric line
xx. This is not all imparted to the crank at the end on account of the
compression.
I have myself had no experience in the use of this instrument, but I
do not see why it might not be so made that the diagonal line or lines
in Fig. 4 would be drawn at once. The variations of motion would
thus be shown much more accurately than they can be by the
enlargement of these small indications. This would require the spring
e to bear the same relation to the inertia of the weight h that the
spring of the indicator bears to the steam pressure on its piston area.
The steam diagram and the inertia diagram would then be drawn to
the same scale. A separate instrument would be required for each
scale. It would seem desirable that this instrument, which is not
expensive, should be brought before the public in this practical
shape.
The 16″×30″ engine exhibited at this fair of the American Institute
was sold from the exhibition to the Arlington Mills, at Lawrence,
Mass. For a reason that will appear later, I have always regarded this
sale as the most important one that I ever made.
CHAPTER XIX
Boiler Tests in Exhibition of 1871. We Lose Mr. Allen. Importance of Having a

Business Man as President. Devotion of Mr. Hope.
he next year we were not exhibitors at the Institute

fair, but our boiler remained in its place and was run by
the Institute. This boiler and its setting are shown
correctly in the accompanying reproduction of a
drawing made about that time, except that it consisted
of nine sections instead of six. At the close of the
exhibition a boiler test was made by the Institute, through a
committee of which Professor Thurston, at that time Professor of
Mechanical Engineering in the Stevens Institute, afterwards until his
death Director of the Sibley College of Mechanic Arts, in Cornell
University, was the chairman. Five boilers, including the Allen boiler,
were tested, one on each day, in a continuous run of twelve hours.
The four besides our own were all different from the boilers exhibited
the year before.
A week was spent in preparation for this test. A large wooden tank
was constructed, in which was built a surface condenser, consisting
of a pile of sections of the Root boiler, laid horizontally, having a total
of 1100 square feet of cooling surface. The steam was exhausted
into the pipes which were surrounded by the cooling water, thus
reversing the construction of surface condensers.
Professor Robert H. Thurston
ALLEN BOILER.
OF
80 HORSE POWERS.
Area of Effective Heating Surface 810-Square Feet.
Area of Grate 24-Square Feet.
scale-1 inch-1 foot. Allen Engine Works.
July-1872.
Each boiler was tested by setting its damper and its steam-valve
wide open, so burning all the coal that could be burned by it under its
draft, and delivering freely all the steam that it made. This latter
entered the condenser at the top, and the water formed by
condensation was drawn off at the bottom, while the condensing
water entered the tank at the bottom and was drawn off at the top,
the currents of steam and water being thus opposite to each other,
which was an ideal construction. The condensing water at a
temperature of 45.5 degrees flowed in under the pressure in the city
main and was measured in a Worthington meter, and the
temperature of the overflow taken. The condensed steam was drawn
off into a barrel and weighed, 300 pounds at a time, and its
temperature taken. This method was an excellent one.
Not having high chimneys, no boiler had a strong draft, as shown
by the coal burned per square foot of grate. Our draft was the
strongest of all. Only the Allen boiler and the Root boiler gave
superheated steam, and the competition between them was very
close. The valve being wide open, giving a free current into the
condenser, the superheat of our steam fell to 13.23 degrees
Fahrenheit. Root’s superheat was 16.08 degrees.
Root’s boiler, the trial of which occupied the first day, blew steam
from the open try-cock, from water at 46 degrees Fahrenheit, in
sixteen minutes from lighting the fire. Next morning our boiler blew
steam from water at the same temperature, in twelve minutes, and
Mr. Root holding his watch could not resist the ejaculation,
“Wonderful boiler!” The Allen boiler, burning 13.88 pounds of coal
per square foot of grate per hour, evaporated one cubic foot of water
per hour from each 17.41 square feet of heating surface. Root’s
boiler, burning 11.73 pounds of coal per square foot of grate per
hour, required 23.59 square feet of heating surface to evaporate one
cubic foot of water per hour.
Our stronger draft, 13.88 against 11.73, accounted for 3.2 pounds
of the above superior evaporative efficiency, leaving 3 pounds to be
accounted for by the more rapid circulation in the Allen boiler. The
great value of the inclination of the tubes was thus established. The
report contains this sentence: “The Committee desire to express
their appreciation of the excellent general arrangement and
proportions which gave to the Allen boiler its remarkably high
steaming capacity.”
The reader will observe in the plan of this boiler the pains taken to
maintain as far as possible parallel currents of the heated gases
through the boiler, and taking the flues off at the bottom, thus
bringing all the heating surfaces at the same distance from the
furnace into approximately equal efficiency.
RESULTS OF THE COMPETITIVE TRIAL OF STEAM BOILERS AT
THE FAIR OF THE AMERICAN INSTITUTE, NOVEMBER, 1871.
Name. Ratio of Ra
Square Feet. heating Total Weights. wa
surface pri
Grate Heating to grate Coal. Com- Feed. Steam. Primed to w
surface. surface. surface. bustible. water. eva
ra
A. B. C. D. E. F. G. H.
Root 27 876¹⁄₂ 32.5 3800 3185.5 27896 27896 0. 0.
Allen 32¹⁄₄ 920 28.5 5375 4527 39670 39670 0. 0.
Phleger 23 600 26.1 2800 2274 20428 19782.94 645.06 3.2
Lowe 37³⁄₄ 913 24.2 4400 3705 34000 31663.35 2336.65 6.9
Blanchard 8¹⁄₂ 440 51.8 1232 1047.5 10152.5 9855.6 296.9 3.
The boiler had one defect, seen in the front view, cross-section. A
straight passage 2 inches wide was given to the gases between
each pair of tubes.
The boilers having all had a preliminary trial during the first week, I
observed the vapor arising from the exposed surface of the water in
the tank, and that this unmeasured loss of heat differed considerably
in the different boilers, and was enormously greatest on the trial of
the Allen boiler. I said nothing, but went down early on next Monday
morning and on my way bought a common tin cup about 3 inches
deep and 4 inches in diameter, and secured it in one corner of the
tank, immersed to a quarter of an inch below its rim, and filled even
full of water. This was completed before the arrival of the Committee,
and was at once approved by them. I made it my business every day
to note the fall of the water level by evaporation from this cup. On the
trial of the Allen boiler only the water in the cup was all evaporated,
and I had to fill it again. The temperature of the water in the cup was
always 8 degrees below that of the surrounding water. It was thus
obvious that the evaporation from the tank was greater than the fall
of the level in the cup would indicate. The Committee considered
that this should be increased as the tension of the vapors. The result
was that the report contained the following item: Units of heat carried
away by evaporation at the surface of the tank:
Root boiler 721,390.8 units
Allen boiler 1,178,404.5 „
Phleger boiler 378,371 „
Lowe boiler 692,055 „
Blanchard boiler 268,707 „
The same Bulkley pyrometer was used in all the furnaces to
indicate the temperature of the escaping gases. On Tuesday
morning, when my boiler was to be tried, I saw that before my arrival
the pyrometer had been set in the brick chimney, where the readings
could be conveniently taken by a person standing on the brick
surface of the boiler chamber. Its readings averaged 260 degrees
Fahrenheit. I did not believe this to be true. At about half-past two
o’clock, when seven readings had been taken, one each half hour,
having got ready some bricks and mortar and tools, I pulled the
pyrometer out and filled up the hole. I then knocked a hole in the
side of the brickwork at the bottom, in front of the flue, and set the
pyrometer there. The reading rose to 405 degrees, which was the
temperature at which the gases then entered the flue, and averaged
about 385 degrees during the remainder of the sixteen readings.
Root’s average was 416 degrees, and Phleger’s (also tubular)
averaged 503. Obviously the readings taken before the pyrometer
was moved should have been rejected; but the boys who did this
kind of work added them all together, and our average temperature
is printed 345.87 degrees, giving the boiler more credit than it was
entitled to by about 40 degrees. I lost a little by this operation. While I
was bricking up the hole the fireman came around and told me I was
spoiling his fire. When I got the figures of water evaporated and coal
burned, I found that in that half hour I had only 900 pounds (three
barrels) credited to the boiler, instead of 1800 pounds (six barrels)
during every other half hour, being a loss of about .023 in water
weighed in the barrel, 38,400 pounds, instead of 39,300 pounds,
while, curiously enough, the coal burned was rather increased.
The point of interest in this incident was the fact that the gases
had lost 125 degrees of heat in traversing a distance in flues and
chimney of less than 20 feet. This seems difficult to believe, but they
did. There was no leakage as the excellent draft clearly proved, nor
any other way of accounting for the discrepancy. The length of the
pyrometer tube exposed to the heated gases was the same in both
positions. The heat had been lost by radiation through the brickwork.
I have been waiting ever since for a chance to turn this knowledge to
useful account, but it has not come yet. I will content myself with
suggesting to somebody else the idea of facing the boiler setting,
flues and chimney, not only outside but inside also after leaving the
furnace, with white encaustic tiles, which will neither absorb nor
radiate heat appreciably. This will pay in maintaining the temperature
in a large degree to the top of the chimney, so increasing, perhaps
doubling, the strength of the draft. An enormous amount of heat
must be lost through the extended surface of the brick boiler setting.
It is always observed that the hotter a boiler-room is kept the greater
the efficiency of the boiler becomes. This is a slight indication of the
great gain which might be effected by the plan I propose.
Before this boiler trial we had lost Mr. Allen. He had conceived the
idea of the pneumatic riveter and the high-speed air-compressor to
furnish this riveter with power. In the latter he utilized the inertia of
the reciprocating parts, including two pistons, the steam and the air
piston. This he did with my cordial consent, and indeed there was
nothing patentable about that feature anyway. Mr. Allen thus became
the originator of the important system of pneumatic riveting, in its two
methods, by percussion and by pressure. Mr. Allen sold out his stock
in the engine company to Mr. Hope and Mr. Smith, and built a shop
in Mott Haven for the manufacture of the riveters and compressors.
He took the boiler in the fair in part payment, and sold it directly to a
party who had erected a wood-working shop at some point on the
Harlem River.
The Croton water which had been fed to the boiler contained no
lime, but some sediment. Mr. Allen had the boiler taken down and
brought to our shop for inspection and cleaning. I determined to
improve the opportunity to observe the effect of the circulation on the
deposit of sediment, and the result of the examination proved most
interesting. Each inclined tube had been provided at the end with a
brass plug, by removing which it could be cleaned by the running out
of the water which it contained. This had not yet been done.
I took out the tubes on one side of one section, ten in all, five over
the furnace and five behind the bridge wall, and planed them in two
longitudinally, and had the following revelation: The tubes over the
furnace were entirely empty. In those back of the bridge wall a
deposit of sediment appeared, only about an inch deep in the first
one, and increasing regularly to a depth of 18 inches in the last one,
which was not the tube receiving the feed-water. So the water fed
into the last tube of each section deposited its sediment most largely
in the first tube it reached, in which the circulation was least active,
and had deposited it all before reaching the tubes over the furnace.
The remaining long tubes were then cleaned, the tubes cut in two
were replaced by new ones, and the boiler delivered to Mr. Allen.
The next stage in its history was very funny. The purchaser, to save
the cost of Croton water, fed his boiler from the Harlem River, and
within a month it was found to be filled solid with salt. What was
done about it I never heard.
I thought I could sell the boilers where, as in New York City, they
could be fed with water free from lime, and I made a few such sales,
but the inspiration which led me to employ the second drum for
superheating the steam had deserted me.
I came to the conclusion that by making the first drum a large one,
and not extending the nipples into the drum to trap a puddle of water,
as I had done, I could superheat the steam in one drum. That was a
blunder. I had underestimated the furious circulation, which carried a
large amount of spray into the drum. I was misled by the quiet
position of the water-level, as always shown in the glass gauge.
Instead of superheated steam, I found the boiler to give very wet
steam. That fault, of course, I could have remedied by returning to
my first design. But I was discouraged by other things. The first, of
course, was the impossibility of removing scale by any mechanical
means. The most serious discouragement was a cracked header.
The inclined tubes, on any plan for their use that I could then design,
made cast-iron headers necessary. I had taken great pains to obtain
perfect castings, making them of the best iron in baked molds in iron
flasks, of uniform thickness, ⁵⁄₈ in., and ³⁄₄ in. where threaded, with
cores held perfectly central and remarkably well vented, and felt that
I could rely on their soundness; but this defect showed that I could
not. So reluctantly I abandoned the manufacture of the boiler.
I believe, however, that there is yet a future for the inclined boiler
tube, with independent circulation in each tube, the whole made
entirely from forged steel; and that better results will be obtained
from it than any other form of boiler has as yet given. I have been
told by Chief Engineer Melville that all water admitted to the boilers
in the United States Navy is made pure enough for pharmaceutical
purposes. If this can be done in the navy, where sea water and the
mud of harbors have to be used, it can be done anywhere. Cooling
towers make it practicable to return all water to the boiler even from
non-condensing engines. Then only the waste needs to be made
good, and any water can be purified for this purpose. Oil or grease
with the feed-water is readily avoided. Only electrolysis remains to
be provided against, which can be done by avoiding the use of any
alloy of copper in contact with the water. We may then have boilers
of the most durable character and safe to carry any desired
pressure.
The following incident near the close of my experience in Harlem
would be too ridiculous to print except for its consequence. One day
Mr. Smith sent me word that he would like to see me in his office.
When I entered he asked me, “What do you pay for the castings of
your governor arms and balls?” Of course he knew perfectly well, as
he had the bills and the books, but that was his way of introducing
the subject. I replied, “Forty cents a pound.” He held up both hands
in affected amazement, and exclaimed, “Forty cents a pound! Well,
sir, I can assure you of one thing, no more of this company’s money
is going to be squandered in that way.” I overlooked his insulting
language and manner, and said quietly, “Are you sure, Mr. Smith,
that you have all the information you need to form a correct judgment
in this matter?” “I am sure,” he replied, “what the market price is of
copper and tin, and that I can get castings made from our own metal
at a price that will bring the cost to not more than 25 cents a pound.”
“This, then, I presume, is all you know about the subject,” I said,
“and you ought to know a great deal more, which I will tell you. It is
necessary that I can rely upon getting a pure copper and tin alloy, in
the proportion known as gun-metal, on account of its strength, its
rigidity, and its wearing qualities. The latter is of especial importance,
because the governor joints are in continual motion under the weight
of the heavy counterpoise. Experience shows that this purity cannot
be relied upon where it is possible that any inferior metal can
become mixed with this alloy in even the smallest proportion. This for
us, not making our own castings, must be wholly a matter of
confidence.
“Another risk must be avoided, that is, of getting bad castings. The
castings must not have the least imperfection. The time lost, through
finding defects that make it necessary to reject arms after more or
less work has been put on them, would soon wipe out all the little
gain you look for; as these castings, at 40 cents a pound, only cost
about five dollars a set, as an average of all the sizes.
“I made a careful study of this subject when I commenced the
governor manufacture about fifteen years ago, and found David
Francis, who had a small gun-metal foundry on Vestry Street, to be
just the man I wanted. No inferior metal ever goes into his place. He
enjoyed the entire confidence of manufacturers. He has made my
governor arms and balls ever since. I have never had a bad casting
from him, and always got the pure metal, and have paid him the
same price that everybody pays him for small castings. I consider
the security that I have had respecting this metal to have been
fundamental to the great success of my governors, and that I would
be crazy to make any such change as you propose.”
He made no reply, and I left him, supposing my statement to have
been perfectly satisfactory. What was my amazement when, a few
days after, he informed me that he had made a contract with a brass
molder on Rose Street for casting our governor arms, “subject to
your approval, sir,” and he asked me to visit the place and see what
its facilities were.
I told him I would go, but that my position on the subject was
already well known to him. I found the place on a little lane, and that
the business done in it was making brass castings for plumbers. The
proprietor told me he had never made gun-metal castings, but he
could make any kind of composition, and I could rely on getting them
of just the metal I furnished him.
I reported to Mr. Smith that such an arrangement would be
ruinous, that his plan of furnishing the metal was most
unbusinesslike. “What do you know about business?” he shouted
with a sneer. “I know,” said I, “that if you should propose this plan to
any well-informed, practical man, he would laugh in your face, and
tell you if you wanted to ruin your business this would be as good a
way as any to do it.” He replied, “That is not the question, sir; the
only question is, will you, or will you not, approve the contract I have
made?” “I will not,” I replied, and walked out of his office.
A few days after I received a note from Mr. Hope, asking me to call
on him. I called next day, and he told me that Mr. Smith had been to
see him, with a bitter complaint of my insubordination and defiance
of his authority, which he would not endure, and he asked me to tell
him what the trouble was about. I told him substantially as above
related. “Is that all?” said he. I assured him that it was all the trouble
that I knew of. Mr. Hope replied, “I cannot express my amazement at
his interference with your management. That must be absolutely
entrusted to you, and he ought to see it. He is a rational man and I
can easily show him his error, and that you must take the stand you
have done. I don’t think you will have any more trouble.”
I did not hear again from Mr. Hope for a fortnight, during which
time I had no occasion to meet Mr. Smith. Finally a letter came from
him, telling me that I must prepare for the worst; he had exhausted
all his efforts on Mr. Smith, and found him absolutely immovable,
declaring that I must go, I was of no use there, anyway. Mr. Hope
said he told him his conduct was outrageous and suicidal. If I went,
that I would be the end of the business. He snapped his fingers at
that, saying, “Mr. Goodfellow can make the engines, and I can sell
them; what more do you want?” He declared that no business could
succeed unless the will of the president was law. They had several
very disagreeable conferences, which Mr. Smith always closed by
saying, “Repay me my investment in this company,” which he figured
at $24,000, “and I’ll give you my stock.” He had announced to Mr.
Hope his determination to call a meeting of the directors to discharge
me, and as he had a majority of votes, having some time before
given to each of his two sons qualifying shares and had them elected
members of the board of directors, he held the power in his hands to
do it.
Directly after, I received a copy of a notice of a regular meeting of
the board, convened strictly according to law. I could see no ray of
light. The night before the meeting I walked the Third Avenue bridge
half the night. The meeting was called to order by Mr. Smith at the
appointed hour. Mr. Hope was absent. Mr. Smith said Mr. Hope had
sent word to him the day before that he might be detained, but if so
would come up on the next boat, which ran hourly, and asked Mr.
Smith to wait that time for him.
So the meeting was adjourned for an hour, when Mr. Hope arrived.
Mr. Smith prefaced the resolutions discharging me from my
position as superintendent and electing Mr. Goodfellow in my place,
by quite an oration, setting forth the solemn sense of his Christian
duty which left him no alternative, and the necessity of proper
subordination in any business, if it was to be successful, and the
especially aggravated character of my offense, and the demoralizing
nature of my example.
He was about to put the question on the adoption of the
resolutions, when Mr. Hope said, “Before you put this question to
vote, Mr. Smith, I would like to say a word. I have concluded to
accept your offer. Here is my certified check for $24,000 to your
order, and I demand from you the transfer to me of the stock in this
company standing in your name and the names of your sons.”
When the Smiths were gone (they left by the next boat) Mr. Hope
and I sat down to confer on the business of the company. When
these matters were concluded, I said to him, “Mr. Hope, if you had
determined to make this grand proof of your confidence in the engine
and in myself, why did you not tell me sooner, and save my wife and
myself a great deal of distress?”
“My dear fellow,” he replied, “I did not know till this morning that I
should be able to do it. That is why I was late.”
CHAPTER XX
Close of the Engine Manufacture in Harlem. My Occupation During a Three Years’

Suspension.
n the autumn of ’72, following the above incident, we

had a proof of the sagacity of Mr. Smith in rejecting my
plan for the establishment of works for the
manufacture of the engines, and taking a five years’
lease of an abandoned shanty. The property had
changed hands, and we received a note from the new
owner, saying that he had purchased the property with a view to its
improvement. He should therefore be unable to renew our lease, and
he gave us six months’ notice, that we might have time in which to
make other arrangements before its expiration.
Here was a situation. To move and establish the business in a new
locality would require a large expenditure, and we had no money.
The natural thing to do would be to enlarge our capital. On
consultation with several parties, Mr. Hope found the financial
situation at that time would not warrant this attempt. The Civil War
had ended between seven and eight years before. Hard times had
been generally anticipated after its close, but to the surprise of
capitalists these did not come. The country continued to be
apparently prosperous. The best observers were, however,
convinced that a financial reaction was inevitable, and the longer it
was delayed the more serious it was likely to be; an anticipation that
was more than realized in Black Friday in September, 1873, and the
collapse of values and years of absolute stagnation that followed.
For some time before that eventful day capitalists had felt anxious
and there had been a growing timidity and indisposition to invest in
any enterprise, however substantial it might be, so there was nothing
for us to do but to wind up our business and wait for more propitious
times, when we might attempt its revival.
In the winter of ’72-3 I had a call from my friend, J. C. Hoadley,
accompanied by Mr. Charles H. Waters, manager of the Clinton Wire
Cloth Company. Mr. Waters wished to obtain one of our engines. I
told him I was very sorry, but we should not be able to make one for
him. I then explained our situation. Our lease would expire in a
month or two, and could not be renewed, and we had made
arrangements then to close our business, had sold all our tools
deliverable before that date, were rushing two engines to completion,
but absolutely could not undertake another order.
“Never mind,” said he, “one of your engines I must have.” He then
told me that he was about to introduce a new feature in weaving wire
cloth. This was then woven in various narrow widths, according to
customers’ orders, having a selvage on each side. He had satisfied
himself that this latter was unnecessary. The wire, being bent in
weaving, had no tendency to ravel, and he had planned a loom to
weave the cloth seven feet in width, and slit it up into narrow widths
as required. In this loom the shuttle alone would weigh a hundred
and fifty pounds, besides the great weight of wire it would carry; it
had to be thrown nearly twelve feet, and he wanted to make as many
picks per minute as any narrow loom could do. In order to make
these throws uniformly, he required absolutely uniform motion. From
a careful study of slow-moving variable cut-off engines, he had
satisfied himself that none of them could give him the uniformity of
motion he needed. They were driven by a succession of violent
punches, these excessive amounts of force at the commencement of
each stroke were absorbed by the fly-wheel, the velocity of which
had to be increased to do it, and at the end of the stroke its velocity
had to be reduced in the same degree, to supply the total failure of
the force of the steam. This involved a variation of speed which in
ordinary business would not be regarded, but which would ruin the
action of this new loom. In the high speed of my engine, and the
action of the reciprocating fly-wheel, which compensated the
inequalities of the steam pressure without affecting the uniformity of
the speed, he found just what he needed, and that engine he must
have. I was astonished at the man’s penetration.

Analysis of Flame Retardancy in Polymer Science Henri Vahabi Full Chapter

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Analysis of Flame Retardancy In

Polymer Science Henri Vahabi

Mohammad Reza Saeb

For information on all Elsevier publications

Publisher: Susan Dennis

Typeset by STRAIVE, India

CHAPTER 1 Fundamentals: Flammability, ignition, and fire

7 General appraisal of pyrolysis/ignition/burn versus

CHAPTER 2 Forced combustion: Cone calorimetry........................... 73

CHAPTER 3 Microscale forced combustion:

5.2 Predicting the temperature of solid surface at

CHAPTER 4 Evaluation of gas phase: Mechanisms and analyses.... 117

CHAPTER 5 Evaluation of gas phase: Smoke and toxicity analysis...161

5 Conclusions and perspectives................................................ 186

CHAPTER 6 Evaluation of condensed phase: Char/residue

CHAPTER 7 Analysis of fire resistance of materials....................... 233

Thomas Rogaume, Benjamin Batiot, and Eric Guillaume

3.2 Combustible materials.................................................. 245

CHAPTER 8 Characterization of high-temperature polymers

CHAPTER 9 Correlation between laboratory- and real-scale

1.1 From microscale to small scale.................................... 336

CHAPTER 10 Fire analysis tests from industrial point of view......... 381

Fundamentals: Flammability, ignition,

1.1 Polymers and the fire triangle

Analysis of Flame Retardancy in Polymer Science. https://doi.org/10.1016/B978-0-12-824045-8.00001-0

non-flammable gases + char

The heat required to thermally degrade or pyrolyze the polymer is defined as

is a product of imperfect combustion. Oxidation is an exothermic reaction and

1.2 Glossary of terms

Additive (flame retardant): A (flame retardant) compound added after the

Finish (flame retardant): A compound or combination of compounds added

Limiting oxygen index (LOI): Minimum oxygen percent in the environment

2 Thermal transitions, thermoplasticity,

Inherently flame- and heat-resistant polymers

2.1 Thermophysical effects

2.2 Thermally thin versus thermally thick materials

2.3 Effect of sample geometry, orientation, and physical

3 Fuel-forming reactions: Polymer pyrolysis

(i) impurities already present in monomeric feeds during commercial

Random chain scission Cellulose Levoglucosan

3.2 Pyrolysis of individual polymer types

Apparatus for Graphically Showing the Acceleration and Retardation of the

Boiler Tests in Exhibition of 1871. We Lose Mr. Allen. Importance of Having a

he next year we were not exhibitors at the Institute

Close of the Engine Manufacture in Harlem. My Occupation During a Three Years’

n the autumn of ’72, following the above incident, we

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