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EXPANDED PTFE APPLICATIONS
HANDBOOK
PLASTICS DESIGN LIBRARY (PDL)
PDL HANDBOOK SERIES
Series Editor: Sina Ebnesajjad, PhD (sina@FluoroConsultants.com)
President, FluoroConsultants Group, LLC
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EXPANDED PTFE APPLICATIONS
HANDBOOK
TECHNOLOGY, MANUFACTURING AND
APPLICATIONS

Sina Ebnesajjad
President, FluoroConsultants Group, LLC

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 Contents

Preface ................................................................................................................................................................... xi
Acknowledgment ................................................................................................................................................. xiii

1 History of Polytetrafluoroethylene and Expanded PTFE Membrane ..................................................... 1

Part I: Discovery of Polytetrafluoroethylene ..................................................................................................1
1.1 Discovery of Polytetrafluoroethylene .......................................................................................................1
1.2 Roy Plunkett’s Story .................................................................................................................................1
1.3 Commercialization of Polytetrafluoroethylene.........................................................................................3
Part II: Invention of Expanded Polytetrafluoroethylene ..................................................................................4
1.4 A New Type of Polytetrafluoroethylene...................................................................................................4
1.5 Early History of W.L. Gore and Associates.............................................................................................4
1.6 Discovery of Expanded Polytetrafluoroethylene......................................................................................5
References.........................................................................................................................................................7

2 Polytetrafluoroethylene: Properties and Structure .................................................................................... 9

2.1 Introduction...............................................................................................................................................9
2.2 Impact of F and CeF Bonds on the Properties of Polytetrafluoroethylene ............................................9
2.3 Crystalline Structure of Polytetrafluoroethylene....................................................................................12
2.4 Branched Tetrafluoroethylene Chains: Perfluorinated EthyleneePropylene Copolymer .....................12
2.4.1 Perfluorinated EthyleneePropylene Copolymer ......................................................................... 13
2.5 Reaction Mechanisms .............................................................................................................................14
2.6 Impact of Solvents on Fluoropolymers ..................................................................................................15
2.7 Molecular Interaction of Polytetrafluoroethylene: Low Friction and Low Surface Energy .................16
2.8 Conformations and Transitions of Polytetrafluoroethylene ...................................................................18
2.8.1 Images of the Polytetrafluoroethylene Molecule ........................................................................ 19
2.9 Microstructure and Fracture of Polytetrafluoroethylene ........................................................................20
References.......................................................................................................................................................22

3 Manufacturing Polytetrafluoroethylene by Emulsion Polymerization .................................................. 25

3.1 Introduction...........................................................................................................................................25
3.2 Tetrafluoroethylene Preparation............................................................................................................26
3.3 Polymerization of Tetrafluoroethylene .................................................................................................29
3.4 Tetrafluoroethylene Polymers ...............................................................................................................31
3.4.1 Ammonium Perfluorooctanoate (Also C8)................................................................................ 32
3.4.2 Alternatives to Ammonium Perfluorooctanoate........................................................................ 33
3.5 Preparation of Polytetrafluoroethylene by Emulsion Polymerization .................................................35
3.6 Emulsion Polymerization of Tetrafluoroethylene With Ammonium Perfluorooctanoate
Replacements ........................................................................................................................................42

v
vi C ONTENTS

3.7 Mechanism of Emulsion Polymerization of Tetrafluoroethylene ........................................................44

3.8 Development of Polytetrafluoroethylene for Expanded Polytetrafluoroethylene Applications ..........45
Stretch Ratio and Ultimate Stretch Ratio Test ....................................................................... 47
Preparation of Test Specimen ................................................................................................. 47
Stretch Procedure.....................................................................................................................48
Tensile Break Strength Test .................................................................................................... 48
Stretching Rate ........................................................................................................................48
Stress Relaxation Time............................................................................................................ 48
Stretch Test ..............................................................................................................................51
Measurement of Stress Relaxation Time ................................................................................ 52
Stretch Procedure.....................................................................................................................55
Stress Relaxation Time............................................................................................................ 56
Break Strength ......................................................................................................................... 56
Creep Rate ...............................................................................................................................56
Evaluation of Extrusion Pressure and Stretchability ..............................................................57
Measurement of Tensile Break Strength................................................................................. 57
Measurement of the Endothermic Ratio ................................................................................. 57
Measurement of the Stress Relaxation Time .......................................................................... 58
3.9 Fine Powder (Coagulated Dispersion) Products ..................................................................................59
3.10 Characterization of Polytetrafluoroethylene.........................................................................................60
Fine Powder Polytetrafluoroethylene Resins .......................................................................... 60
Dispersions of Polytetrafluoroethylene ...................................................................................62
References.......................................................................................................................................................62

4 Fabrication and Processing of Fine Powder Polytetrafluoroethylene.................................................... 65

4.1 Introduction...........................................................................................................................................65
4.2 Background ...........................................................................................................................................65
4.3 Paste Extrusion Fundamentals..............................................................................................................66
4.4 Resin Handling and Storage .................................................................................................................68
4.5 Extrusion Aid or Lubricant...................................................................................................................71
4.6 Blending the Resin With Lubricant......................................................................................................74
4.6.1 Pigment Addition....................................................................................................................... 77
4.7 Preforming ............................................................................................................................................77
4.8 Extrusion Equipment and Process ........................................................................................................79
4.8.1 Extruder...................................................................................................................................... 80
4.8.2 Die .............................................................................................................................................. 81
4.8.3 Drying ........................................................................................................................................83
4.8.4 Sintering and Cooling ................................................................................................................ 83
4.8.5 Reduction Ratio ......................................................................................................................... 84
4.9 Extrusion of Tubing ..............................................................................................................................85
4.9.1 Blending Lubricant and Pigment and Preforming ....................................................................87
4.9.2 Extrusion of Spaghetti Tubing...................................................................................................87
4.10 Unsintered Tape ....................................................................................................................................90
4.10.1 Blending Lubricant and Pigment and Preforming .................................................................. 90
C ONTENTS vii

4.10.2 Extrusion of Round and Rectangular Bead............................................................................. 91

4.10.3 Calendaring ..............................................................................................................................92
4.10.4 Stretching the Polytetrafluoroethylene Tape ........................................................................... 94
4.10.5 Final Tape Product................................................................................................................... 95
References.......................................................................................................................................................96

5 Expansion of Polytetrafluoroethylene Resins............................................................................................ 99

5.1 Introduction.............................................................................................................................................99
5.2 Manufacturing Expanded Polytetrafluoroethylene Articles...................................................................99
5.2.1 Basic Polytetrafluoroethylene Expansion Processes ................................................................. 100
5.2.2 Uniaxial Expansion.................................................................................................................... 101
5.2.3 Biaxial Expansion ......................................................................................................................107
5.3 Microstructure of Polytetrafluoroethylene............................................................................................111
5.4 Microstructure of Expanded Polytetrafluoroethylene ..........................................................................116
5.5 Formation of Expanded Polytetrafluoroethylene .................................................................................118
5.6 Amorphous Locking .............................................................................................................................122
5.7 Characterization of Membrane Pores ...................................................................................................122
5.7.1 Bubble Point .............................................................................................................................. 123
5.7.2 Derivation YoungeLaplace Equation........................................................................................124
5.7.3 Mercury Porosimetry ................................................................................................................. 124
5.8 Summary ...............................................................................................................................................125
References.....................................................................................................................................................125

6 Manufacturing of Various Shapes of Expanded Polytetrafluoroethylene (ePTFE) ........................... 129

6.1 Planar Expanded Polytetrafluoroethylene Membranes ........................................................................129
6.1.1 Uniaxial Orientation ..................................................................................................................130
6.1.2 Biaxial Expansion (Orientation)................................................................................................ 131
6.2 Tubular Expanded Polytetrafluoroethylene Shapes..............................................................................134
6.2.1 Complex Shape Tubular Expanded Polytetrafluoroethylene ....................................................140
6.3 Expanded Polytetrafluoroethylene Fiber ..............................................................................................142
6.3.1 High Tensile Strength Polytetrafluoroethylene Fiber................................................................ 142
6.3.2 Production of Expanded Polytetrafluoroethylene Fiber............................................................143
6.4 Densified Porous Polytetrafluoroethylene Membranes ........................................................................149
6.5 Expanded Polytetrafluoroethylene Sheets ............................................................................................153
6.6 Expanded Polytetrafluoroethylene Tapes and Rods .............................................................................159
References.....................................................................................................................................................159

7 Properties, Characteristics, and Applications of Expanded PTFE (ePTFE) Products...................... 163

7.1 Introduction...........................................................................................................................................163
7.2 Properties and Characteristics ..............................................................................................................163
7.3 Applications ..........................................................................................................................................166
7.3.1 Industrial and Process Filtration................................................................................................ 167
7.3.2 Microfiltration Applications ...................................................................................................... 168
7.3.3 Vent Filters and Breathers ......................................................................................................... 168
7.3.4 Medical and Biological Uses..................................................................................................... 168
viii C ONTENTS

7.3.5 Cables and Cable Assemblies....................................................................................................168

7.3.6 Electronic and Electrochemical Materials ................................................................................168
7.3.7 Sealants ......................................................................................................................................169
7.3.8 Fibers and Fabrics......................................................................................................................169
References.....................................................................................................................................................169

8 Expanded PTFE Use in Fabrics and Apparel ........................................................................................ 171

8.1 Introduction...........................................................................................................................................171
8.2 Breathable Expanded Polytetrafluoroethylene Fabric Structure..........................................................172
8.3 Development History ............................................................................................................................178
8.4 Outdoor Apparel ...................................................................................................................................182
8.4.1 Testing Apparel..........................................................................................................................184
8.4.2 Outdoor Footwear ......................................................................................................................186
8.4.3 Testing Footwear........................................................................................................................186
8.4.4 Outdoor Gloves ..........................................................................................................................188
8.5 Protective Apparel ................................................................................................................................188
8.6 Summary ...............................................................................................................................................190
References.....................................................................................................................................................190

9 Medical and Surgical Applications of Expanded PTFE........................................................................ 193

9.1 Introduction...........................................................................................................................................193
9.2 Definition of Medical Devices..............................................................................................................193
9.3 Classification of Devices ......................................................................................................................195
9.4 Designing Medical Devices..................................................................................................................196
9.5 Biomaterials ..........................................................................................................................................196
9.6 Expanded Polytetrafluoroethylene........................................................................................................196
9.7 Examples of Applications.....................................................................................................................198
9.7.1 Vascular Grafts...........................................................................................................................198
9.7.2 Patches........................................................................................................................................202
9.7.3 Expanded Polytetrafluoroethylene Lipoatrophy Implants.........................................................202
9.7.4 Expanded Polytetrafluoroethylene Sutures................................................................................204
9.7.5 Lead Assembly of Implanted Devices ......................................................................................205
9.7.6 Stents .......................................................................................................................................... 207
References.....................................................................................................................................................209

10 Filtration ..................................................................................................................................................... 213

10.1 Introduction.........................................................................................................................................213
10.2 Classification of Filtration Processes .................................................................................................213
10.3 Surface Filtration Processes................................................................................................................214
10.4 Types of Filtration...............................................................................................................................215
10.4.1 GaseSolid Filtration .............................................................................................................. 215
10.4.2 SolideLiquid Filtration ......................................................................................................... 223
10.5 Examples of Filtration Applications...................................................................................................224
References.....................................................................................................................................................230
C ONTENTS ix

11 Industrial and Other Applications of Expanded PTFE ........................................................................ 233

11.1 Expanded Polytetrafluoroethylene Fiber ............................................................................................233
11.1.1 Oral Care................................................................................................................................233
11.1.2 Sutures.................................................................................................................................... 235
11.1.3 Sewing Threads......................................................................................................................236
11.1.4 Fishing Line ...........................................................................................................................238
11.1.5 Weaving and Knitting Fiber .................................................................................................. 240
11.1.6 Ropes......................................................................................................................................242
11.2 Gaskets and Seals ...............................................................................................................................244
11.2.1 Testing Gaskets ......................................................................................................................247
11.3 Expanded Polytetrafluoroethylene Vents............................................................................................248
References.....................................................................................................................................................250

12 Electrical and Electronic Applications of Expanded PTFE.................................................................. 253

12.1 Coaxial Cables ....................................................................................................................................254
12.2 Hook-Up Wire.....................................................................................................................................255
12.3 Electromagnetic Interference Shielding Gasket.................................................................................256
12.4 Disk Drive Filters................................................................................................................................257
References.....................................................................................................................................................258

13 Surface Modification of Expanded Polytetrafluoroethylene ................................................................. 259

13.1 Introduction.........................................................................................................................................259
13.2 Surface Treatment of Polytetrafluoroethylene ...................................................................................260
13.3 Surface Treatment of Expanded Polytetrafluoroethylene Membrane................................................263
13.3.1 Surface Modification for Hydrophilicity and Adhesion .......................................................263
13.3.2 Surface Modification to Reduce Thrombogenicity ...............................................................265
13.3.3 Mechanical Alteration of Expanded Polytetrafluoroethylene Surface ................................. 268
References.....................................................................................................................................................271

14 The Competitive Scene .............................................................................................................................. 275

14.1 Introduction.........................................................................................................................................275
14.2 Other Expanded Polytetrafluoroethylene Players...............................................................................275
14.2.1 General Electric .....................................................................................................................275
14.2.2 Donaldson Corporation.......................................................................................................... 276
14.2.3 DeWal Industries.................................................................................................................... 276
14.2.4 Zeus Industrial Products ........................................................................................................ 276
14.2.5 C. R. Bard Corporation.......................................................................................................... 276
14.2.6 Maquet Cardiovascular .......................................................................................................... 276
14.2.7 Porex Corporation..................................................................................................................276
14.2.8 Phillips Scientific ...................................................................................................................276
14.2.9 Asian Manufacturers.............................................................................................................. 277

Index ................................................................................................................................................................... 279

This page intentionally left blank

I have marveled at the elegant and intricate
structure of expanded microporous membranes of
polytetrafluorethylene (PTFE) for decades. Thanks to
scanning electron microscopy, one can see the
minutia of the membrane scaffolding. The beauty of
the chaotic yet ordered microporous structure comes
in tandem with its remarkable utility. The words
“elegant” and “beauty” may raise eyebrows as they
do in mathematics. David H. Bailey (retired Senior
Scientist, Lawrence Berkeley National Laboratory,
University of California, Davis) and Jonathan M.
Borwein (Professor of Mathematics, University of
Newcastle, Australia) wrote in a 2014 blog post
(Why Mathematics Is Beautiful and Why It Matters,
February 14, 2018, Huffington Post): all (mathe-
matical) esthetic responses seem in part to come from
identifying simplicity in complexity, pattern in chaos,
structure in stasis. I have found this description true
of microporous membranes of PTFE.
Naturally, I set out to learn all I could about this
beautiful membrane. These days there are few
commercial products about which one does not find
scores of books and in-depth articles. Consequently, I
expected to find books, at least one, and papers. To
my surprise, there was little published about the
fundamentals of expanded PTFE membranes and
films, how they are formed and made, how they work,
and a host of other questions. Certainly, there are
innumerable articles about the membrane’s varied
applications, plenty of commercial literature and
a plethora of patents.
So I set out on a decade and a half long journey to
explore and learn, on my own, about this micropo-
rous membrane (ePTFE). This book presents the
results of my ePTFE educational journey. I hope and
pray it offers a convenient starting point for those
who wish to learn about the ePTFE membranes.
The book begins with two short chapters
describing a short history of ePTFE and the proper-
ties of PTFE. Chapter 3 discusses polymerization and
finishing of PTFE by emulsion method (fine powder
PTFE) placing emphasis on grades specially
Preface
developed for membrane manufacturing. Chapter 4
describes processing of fine powder PTFE into
precursor films and other shapes for the production of
microporous membranes. Chapter 5 focuses on how
expanded PTFE membranes and other shapes are
formed followed by discussion of techniques to make
different shapes of ePTFE in Chapter 6.
Chapter 7 describes the properties and character-
istics of ePTFE membranes along with a brief
discussion of its important applications. Chapters 8
through 12 discuss key applications of ePTFE.
Chapter 13 discusses a number of methods for
treatment and modification of surfaces of micropo-
rous membranes. Those superficial alterations allow
impartation of hydrophilicity or special functions to
the membrane surface. Chapter 14 discusses the
manufacturers of expanded microporous PTFE
membrane.
This has been a difficult book to write and has
taken almost 6 years to complete. Any publisher
other than Elsevier would have long canceled my
contract. Now that the book is published I have two
hopes. First, the book, flawed as it may be, would be
beneficial to those who seek information about
expanded PTFE membranes. Second, I hope what is
correct and what is incorrect motivates brighter
minds to write their own books about this subject.
The colossal impact of these membranes on human
life certainly warrants such efforts. I hope to receive
as many critiques of this book as possible, with
a promise to make corrections in the next edition.
The readers who wish to dispense with discussions
of polymer and precursor film preparation can begin
reading the book with Chapter 5. A modest knowl-
edge of PTFE and its properties is required for
a deeper understanding of the discussions. The
applications chapters can be approached without
reading the other chapters.
Sina Ebnesajjad
Chadds Ford, Pennsylvania
August 2016
xi
This page intentionally left blank
 Acknowledgment
Many people have contributed to this book Parkinson Freudenberg Sealing
including everyone whose work has been mentioned Technologies Technologies
in this book in some shape and form. I have tried to STM, Inc. Donaldson Corp.
acknowledge all who have helped me with this book.
To my profound regret I may have missed some International Polymer Poly Fluoro Ltd.
names. Please accept my sincere apologies for the Engineering, Co.
oversight. A short note to the publisher or to me Adtech Polymer Diener Electronic
directly will allow correction in the electronic online Engineering
copy and future editions. I am most grateful to many Outdoor Sports Center Henniker Plasma
companies and individuals who have contributed
data, photographs, and illustrations to this book. www.eventfabrics.com PVA TePla Co.
Authors and companies have been cited in the book Madison Chemical Acton Technologies
or in the reference section of each chapter. Industries
I have listed the names and website of companies
REI Co-Op Enercon Ind.
wherever their material has been used. I offer you my
heartfelt thanks for your enriching contributions to this Atrium Medical Corp. Tri-Star Technologies
book. I hope the following list (in the order of GE Life Sciences Ingenta
appearance in the book) is not missing any companies.
If there is an error, a short note to the publisher or me Mayo Foundation for DeWal Industries
Education and Res
will be appreciated so that the error could be corrected:
Clarcor Industrial Air, Zeus Industrial Products
BHA Industrial Filtration
W. L. Gore & Pall Corporation
Associates Eaton Corp. Maquet Cardiovascular
C. R. Bard Davol Inc. Coreflon Corp. PORTEF ePTFE Filters Porex Corporation
Willy A. Bachofen Amann & Soehne G Advantec MFS, Inc. Phillips Scientific
DuPont/Chemours Sunteca Corp.
Buflovak, LLC WLT Dichtungstechnik,
I have used numerous illustrations and much
e.K. data from W. L. Gore & Associates in this book.
That is simply because of the paramount role
Jennings International Virginia Sealing the company has played in the development
Products of expanded polytetrafluoroethylene (ePTFE)
QPD Inc. Teadit North America membranes and products based on those
membranes. Rarely, if ever, a single company has
Bruckner USA All State Gasket
played such a substantial role in the development of
Summit Filter Leader GT Corporation a product that has cascaded into billions of dollars
Corporation throughout the market value chains. To be sure
Marshall and Williams, RAM Gasket Solutions a number of manufacturers of ePTFE have also
Div. Parkinson made technological and applications contributions.
Technology My deepest thanks go to W. L. Gore & Associates

xiii
xiv
and other ePTFE manufacturers for the generosity
they have extended to me.
I would like to thank the individuals who played
a key role in attainment of permission for the use of
W. L. Gore illustrations and data in this book. Ms.
Amy E. Calhoun, the leader of Enterprise Commu-
nications at W. L. Gore & Associates devoted
significant time to this matter. She consulted
a number of people at W. L. Gore & Associates and
provided me with guidance and the needed permis-
sion to use the illustrations and artwork in this book.
Thank you Amy. Ms. Jenny E. Maher was instru-
mental in facilitating the process of obtaining
permission. Thank you Jenny.
I would like to express my appreciation to
Matthew Deans the senior publisher of William
Andrew imprint for his support. David Jackson,
acquisitions editor of Plastics Design Library (PDL)
has supported me throughout this project and others
in every possible way. He has been my energetic
partner in the efforts to grow the number of titles and
ACKNOWLEDGMENT
the breadth of subject matters of PDL. Ms. Nicky
Carter was the production manager of this book.
Nicky’s good nature and patience, in addition to her
support, were vital during the production of this book.
I would like to thank my friend and soul mate
Ghazale Dastghaib for her infinite support and
patience over the decades while I have been writing
and editing books. Without her love and comradery I
could have never had the wonderful career I have had.
None of the views or information presented in this
book reflects the opinion of any of the companies
(especially W. L. Gore & Associates) or individuals
that have contributed to the book. If there are errors, I
own them. A note indicating the specific error to the
publisher, for the purpose of correction, would be
much appreciated. Contact information can be found
in the front matter of this book.
Sina Ebnesajjad
Chadds Ford, Pennsylvania
August 2016
 1 History of Polytetrafluoroethylene and Expanded
PTFE Membrane
O U T L I N E
Part I: Discovery of
Polytetrafluoroethylene
1.1 Discovery of Polytetrafluoroethylene
1.2 Roy Plunkett’s Story
1.3 Commercialization of
Polytetrafluoroethylene
Part I: Discovery of
Polytetrafluoroethylene [1a]
Many people around the world, regardless of
whether or not they have been directly involved in the
creation and production of polymer, are familiar with
the origins of fluoropolymers. Teflon®, DuPont’s
trademark name for polytetrafluoroethylene (PTFE),
is world renowned. The classic story of the discovery
of fluoropolymers is replete with the magical com-
bination of curiosity, perseverance, and serendipity. It
is helpful to note the environment and context in
which polymer science began. This section places the
invaluable discovery made by Roy Plunkett [1b] in
the context of the times and of the events and per-
sonalities that shaped science, industry, and the world
in the 1930s and 1940s. Plunkett’s finding is even
more impressive when viewed through the prism of
this context.
1.1 Discovery of
Polytetrafluoroethylene
For those who do not already know the story, let
us begin with the ending. By 1938, Dr. Roy Plunkett
had been working at DuPont for 2 years, developing
Expanded PTFE Applications Handbook. http://dx.doi.org/10.1016/B978-1-4377-7855-7.00001-8
Copyright © 2017 Elsevier Inc. All rights reserved.
Part II: Invention of Expanded
1 Polytetrafluoroethylene 4
1 1.4 A New Type of Polytetrafluoroethylene 4
1 1.5 Early History of W.L. Gore and Associates 4
1.6 Discovery of Expanded Polytetrafluoroethylene 5
3
References 7
new fluorinated refrigerants that were safer than old
gases because of being nonflammable, nontoxic,
colorless, and odorless. He reacted tetrafluoro-
ethylene (TFE) with hydrochloric acid (HCl) for
synthesis of a refrigerant, CClF2eCHF2 [2]. As he
had done on many other occasions, on the morning
of April 6, 1938, Plunkett checked the pressure on a
full cylinder of TFE. He was surprised to find no
pressure, and yet the weight of the cylinder was the
same as it had been the previous day. Plunkett and
his technician removed the valve and shook the
cylinder upside down. When they cut open the gas
cylinder, they recovered a small amount of a slip-
pery white substance (Fig. 1.1). They analyzed the
waxy powder and named this new substance poly-
tetrafluoroethylene, later trademarked as Teflon® by
the DuPont Company. The rest, as they say, is his-
tory (Fig. 1.2).
1.2 Roy Plunkett’s Story
Roy was born into a poor farm family in New
Carlisle, Ohio. When the Great Depression began he
was a student at Manchester College in North Man-
chester, Indiana, where he shared a room with an
older student named Paul Flory. Roy graduated with a
bachelor of arts in chemistry in 1932 and followed
1
2 E XPANDED PTFE A PPLICATIONS H ANDBOOK

Paul to graduate school at Ohio State University.

Figure 1.1 Depiction of the discovery of polytetra-
fluoroethylene by Roy Plunkett and his assistant,
Jack Rebok [3].
Courtesy: The DuPont Co.
Within 2 years of one another, Roy and Paul both
earned Masters and PhD degrees from Ohio State
University. In 1936, Roy joined DuPont Central
Research, where Paul had been working since 1934.
Roy quickly advanced to Kinetic Chemical Co., a
joint venture that DuPont and General Motors (GM)
had set up to produce safe refrigerants to replace
ammonia and sulfur dioxide. Roy was given a
laboratory in DuPont’s Jackson Laboratory on the
shore of the Delaware River in Deep Water, New
Jersey. Roy’s laboratory was across the hall from a
laboratory run by a colleague named Charlie, whose
research focused on synthesizing new organic
compounds. Roy was trying to expand the line of
fluorocarbons, known as Freon, to meet the needs
brought on by the explosive growth of automobile
production at GM.
Excitement erupted in Roy’s lab on April 6, 1938,
when he found no pressure in the TFE cylinder and
discovered the strange new substance inside. What
was this slippery white powder? Because he had
time, knowledge, and curiosity, he paused to ask

Figure 1.2 Photograph of the notebook page in which Plunkett recorded the discovery of
polytetrafluoroethylene [3].
Courtesy: The DuPont Co.
1: H ISTORY OF P OLYTETRAFLUOROETHYLENE AND E XPANDED PTFE M EMBRANE
questions. He was not working under relentless
pressure to meet next month’s deadline because
companies like DuPont, that funded research like
Roy’s, understood that success in research required a
reasonably low-stress work environment. One won-
ders how history might have been different had Roy
had been given an inflexible objective. What would
have happened if Roy had, upon determining that the
foreign substance had no properties that would
further his fluorocarbon research, wiped up the
powder and carried on with his daily tasks? But Roy
was a well-trained scientist with the freedom and
curiosity to investigate this unexpected finding.
When Charlie heard the racket across the hall, he
walked over to Roy’s lab to investigate. He later said,
“I noticed commotion in the laboratory of Roy
Plunkett, which was across the hall from my own. I
investigated and witnessed the sawing open of a
cylinder from which was obtained the first sample of
Teflon® fluoropolymer.” This is the description of
that day at Jackson Laboratory that Charlie Pedersen
shared in his 1987 Nobel Lecture. Pedersen (Fig. 1.3)
went on to invent new crown ether compounds, for
which he was awarded the Nobel Prize in Chemistry.
After logging the results of his discovery that day,
Roy Plunkett continued with his research. Several
years later, wartime needs rescued his discovery from
oblivion. The Manhattan Project was a covert pro-
gram whose aim was to develop an atom bomb before
Figure 1.3 Dr. Charles J. Pedersen, 1987 Nobel
Laureate in Chemistry (retired from DuPont).
3
Nazi Germany. Lieutenant General Leslie Richard
Groves, who led the project, made critical decisions
to prioritize the various methods of isotope separa-
tion; and he acquired the raw materials needed by the
scientists and engineers working on the project.
In the course of his search for new materials to
meet the novel needs of the Manhattan Project,
General Groves came across PTFE. After hearing
about the properties of PTFE and its resistance to
different chemicals, General Grove is purported to
have said that the cost, even at $100 a pound, was a
bargain! Scientists working on the project badly
needed corrosion-resistant materials for the uranium
enrichment process. U-235 had to be separated from
U-238 using differential diffusion of UF6. UF6 is
highly corrosive to most metals, but PTFE stands up
to it. Once the scientists involved in the Manhattan
Project verified its properties, the US Patent Office
placed PTFE under a national “secrecy order” and
from then on it was referred to as “K-416.” Only one
patent, with minimal content, was issued to DuPont
in 1941 to recognize its rights to the invention [4b].
The next time anyone outside of DuPont heard of
PTFE was after World War II, in 1946, under the
now-famous trademark of Teflon®. DuPont learned a
great deal about PTFE during its intense efforts to
produce it for the Manhattan Project. When resources
formerly reserved for the war effort became available
again to scientists and manufacturers in the US and
around the world, it was time to move the production
of PTFE from pilot plant to a commercial
manufacturing operationdand DuPont was ready.
Dr. Plunkett’s own words describe the impact of
his discovery: “The discovery of polytetrafluoro-
ethylene (PTFE) has been variously described as (1)
an example of serendipity, (2) a lucky accident and
(3) a flash of genius. Perhaps all three were involved.
There is complete agreement, however, on the results
of that discovery. It revolutionized the plastics in-
dustry and led to vigorous applications not otherwise
possible” [4a].
1.3 Commercialization of
Polytetrafluoroethylene
Efficient monomer synthesis methods, polymeri-
zation technologies, and various forms of PTFE had
to be developed. The fact that large-scale monomer
synthesis and controlled polymerization had not been
fully developed was a technical impediment to
4 E XPANDED PTFE A PPLICATIONS H ANDBOOK
commercialization of the new polymer. Intensive
studies resolved these problems, and small-scale
production of Teflon® began in Arlington, New Jer-
sey, in 1947. In 1950, DuPont scaled up the com-
mercial production of Teflon® in the US with the
construction of a new plant in Parkersburg, West
Virginia. In 1947, Imperial Chemical Industries built
the first PTFE plant outside the US, in the United
Kingdom.
PTFE cannot be dissolved in any solvent, acid, or
base, and when melted it forms a stiff clear gel with
no flow. Special processing techniques normally used
for molding metal powders were modified to fabri-
cate parts from PTFE. Another process, called paste
extrusion, was borrowed from ceramic processing.
Roy Plunkett’s discovery of PTFE was just the
beginning. Throughout this embryonic stage of
polymer science there was much excitement and
curiosity and debate in scientific circles, and many
scientists around the world built upon this discovery.
Scientists devoted a great deal of effort, from the
1940s through the 1960s, to developing technologies
to fabricate useful objects from the three forms of
PTFE: granular, fine powder, and dispersion. Over
time, through the 1980s, a variety of TFE copolymers
were developed that could be processed by melt
extrusion techniques and solution processing [5].
Part II: Invention of Expanded
Polytetrafluoroethylene
In 2008, W.L. Gore and Associates celebrated the
50th anniversary of the founding of their company.
Ironically, 2008 also marked the 70th anniversary of
Roy Plunkett’s discovery of PTFE at DuPont. W.L.
Gore is where expanded polytetrafluoroethylene
(ePTFE) was discovered and perfected over the
years. The discovery stories of PTFE and ePTFE are
separate yet intertwined, similar though unique.
Both discoveries were the result of the technical
brilliance, creativity, curiosity, perseverance, and
business savvy of their respective masterminds.
Foremost among the common qualities is curiosity,
because these scientists were curious enough to
recognize an anomaly and pursue with vigor what
many might have considered a setback or an odd
effect. Both PTFE and ePTFE are still used in the
development of innumerable new products that have
made vital contributions to humankind for more than
half a century. PTFE and ePTFE have also generated
tens of billions of dollars’ worth of business.
1.4 A New Type of
Polytetrafluoroethylene
W.L. Gore was a successful small company, barely
a decade old, when Bob Gore discovered ePTFE,
which the company named Gore-Tex. ePTFE trans-
formed W.L. Gore into a multibillion-dollar giant of
creativity that has continued to try to find new
product development opportunities in which ePTFE
plays a key role. Without the discovery of PTFE and
fluoropolymers, DuPont would have still been a large
corporation, albeit somewhat diminished. In the
absence of ePTFE, W.L. Gore and Associates,
whatever its fate, would not have been the company
that it became, thanks to Gore-Tex.
The discovery and evolution of ePTFE is inextri-
cably linked to the history of W.L. Gore as a com-
pany, and so this chapter tells that story. W.L. Gore’s
unique management style and structure have been
credited for its sustained growth through innovation
and creativity. Over the past five decades, the com-
pany has brought the technology of Gore-Tex into a
myriad of applications. The end-use products utiliz-
ing ePTFE have enhanced people’s lives beyond
imagination. There is some controversy over which
company or individual first invented the concept of
PTFE expansion. Regardless of the answer to this
question, however, it is W.L. Gore that continues to
propel ePTFE to new frontiers.
Over time, competitors began to produce ePTFE
membranes and products containing them. This book
presents the contributions of many of these com-
panies and explores the valuable role that W.L. Gore
and its competitors played in the evolution of ePTFE
technology.
1.5 Early History of W.L. Gore and
Associates
Wilbert (“Bill”) L. Gore was born in 1912 in
Meridian, Idaho. He spent most of his formative
years in Salt Lake City, Utah. Bill studied chemistry
and engineering and received both a bachelor of
science degree in chemical engineering, in 1933, and
a Master of Science in chemistry, in 1935, from the
University of Utah in Salt Lake City. Bill was a quiet
1: H ISTORY OF P OLYTETRAFLUOROETHYLENE AND E XPANDED PTFE M EMBRANE
and modest man with a passion for innovation and
tinkering. In 1935, he married Genevieve Walton,
who also became Bill’s lifelong business partner.
Both Bill and Vieve developed a great love for the
outdoors that they bequeathed to their five children.
That so many of the Gore-Tex apparel fabrics
enhance the outdoor experience for sportsmen,
hunters, and others is not surprising.
In 1941, Bill Gore was employed by DuPont,
where he was assigned to working on advancing the
company’s research into polymers, resins, and plas-
tics. During World War II, when PTFE was placed
under a secrecy order, DuPont was prevented from
developing commercial PTFE products. When the
secrecy order was lifted in 1946, opening the way for
commercialization of PTFE, Bill Gore worked for the
next 12 years on the development of new applications
for PTFE. A new plant was built in Parkersburg,
Virginia, to produce the new polymer, and a flurry of
research and development work got underway at
DuPont to find applications for Teflon® PTFE. The
focus of this work ranged from solving fundamental
problems with polymerization and finishing of tet-
rafluoroethylene polymers to finding end uses and
markets for the product.
Bill Gore’s interests were focused primarily on
finding new uses for Teflon®. The fundamental
properties of PTFE rendered the material useful for
many applications. No other material possesses all
the properties of PTFE, which include a low dielec-
tric constant (it is a good electrical insulator); high
thermal resistance; a low coefficient of friction; low
flammability; resistance to UV light, hydrophobicity,
and oleophobicity; and chemical inertness. Only
imagination could expand the breadth of new appli-
cations for this special plastic. Bill Gore was a man
who possessed such imagination.
DuPont in the 1950s was a basic materials sup-
plier and did not produce many fabricated products;
it did not go down the value chain, as they say. The
company, which was over 150 years old at this point,
had a well-entrenched culture. Corporate environ-
ments were (are) hardly fertile ground for non-
conformers, mavericks, or those who, like Bill Gore,
were possessed of an entrepreneurial spirit and
driven to innovate. Bill Gore felt the need to leave
the large corporate environment to pursue his in-
terests, and so in 1958 he leave DuPont to establish
his own business. The suggestion that he leave
DuPont has been attributed to his wife Vieve. In
addition to being the mother of their five children,
5
Figure 1.4 First W.L. Gore product [7].
Courtesy: Motion Design System. Bill and Bob Gore, article
on the 50th anniversary of W.L. Gore, Penton Media, Inc.,
2008.
she supported the fledgling company in many ways.
Vieve maintained her active role in the company
until the end of her life. When she died in 2005, the
annual sales of W.L. Gore and Associates
approached 2 billion dollars.
W.L. Gore’s first commercially viable were wire
and cable insulated with PTFE. Bill Gore’s eldest
son, Bob, played an important role in these in-
novations. Bob, who was at the time a chemical
engineering student at the University of Delaware, is
credited with coming up with the concept that
resulted in Gore’s first patent [6a] for PTFE-insulated
wire and cable [6b].
W.L. Gore’s first order was from the city of Den-
ver, Colorado, for 7.5 miles of insulated ribbon cable
(Fig. 1.4). For the company’s first 10 years, these
products comprised the core of the W.L. Gore’s sales.
Multi-Tet cables, as they were called, were recog-
nized for high performance in the defense industry
and in the nascent field of computers. The cables
were even used in the Apollo space program for the
first moon landing.
1.6 Discovery of Expanded
Polytetrafluoroethylene
By the late 1960s, W.L. Gore was a successful
wire and cable supplier. Bob Gore, who had earned a
bachelor’s degree from the University of Delaware in
1959 and a master’s and a PhD from the University of
Minnesota (all in chemical engineering), joined the
company’s board of directors in 1961 and began
6 E XPANDED PTFE A PPLICATIONS H ANDBOOK
working at the company full time in 1963. As
competition grew and other companies began to
produce similar cables, Bill Gore looked for ways to
reduce costs and to develop new products.
Bill thought they might cut costs, and perhaps
create a new form of PTFE, if they could find a way
to stretch the PTFE insulation [8]. His idea was to
introduce air into the polymer structure and basically
create a foam form of PTFE. The cost of the cables
would be reduced because they would use less
polymer for insulation. Because PTFE is a thermo-
plastic but not melt processible, stretching it is
difficult. Bob placed rods of PTFE in an oven and
attempted to stretch the heated rods by hand. But the
rods broke regardless of the temperature Bob used or
the rate at which he stretched them. While they knew
that PTFE stretches when it is elongated at very slow
rates (<5 cm/min), these rates are not commercially
practical; so Bob needed to find a method for
stretching it more quickly.
The story goes that, late one night in 1969, Bob
became frustrated because of his inability to stretch
the PTFE rods. As he later explained, “We were
having really bad luck with that so I started to
experiment with it at high temperatures. The more
carefully I tried to stretch the material, the more
easily it broke. That seemed counterintuitive to me.
One evening, I took a piece that had been treated at
high temperature and gave it a fast yank (Fig. 1.5),
and was surprised to find that it stretched 1000
percent, rather than the 10 to 20 percent we had been
seeing” [9].
Figure 1.5 Bob Gore’s depiction of Gore-Tex discov-
ery [7].
Courtesy Motion System Design.
Gore ascertained that the ePTFE (trademarked
Gore-Tex) was both “very porous and very strong.”
This discovery, of the conditions under which it
would stretch to this degree this quickly, set the stage
for the creation of hundreds of products and funda-
mentally altered the trajectory of the manufacturing
efforts of W.L. Gore and Associates. “I guess that
would be my biggest discovery, the basic Gore-Tex®
material,” Bob Gore once noted.
The expanded form possesses the basic properties
of PTFEdincluding chemical inertness, low friction
constant, wide-use temperature range, hydrophobicity,
outdoor durability, and biocompatibilitydin addition
to porosity, air permeability, and extreme strength.
Given this range of properties, the potential applica-
tions of the expanded form were limitless. ePTFE is
found in thousands of medical, industrial, and fabric
products, as well as in electronic products [9].
Bob Gore and his family originally lived in the
Rockies, where they used to “hike and go back-
packing for several weeks, carrying everything on
[their] backs.” Given his family’s love for the
outdoors, Bob Gore finds the use of ePTFE in out-
doors garments and adventure gear personally
rewarding.
Moreover, ePTFE has facilitated new technologies
and treatments in the field of medicine because of its
biocompatibility. Millions of people have received
ePTFE medical implants, which are configured to
exclude or accept tissue in-growth depending on the
needs of the specific application. Biocompatible
ePTFE is used in vascular grafts, cardiovascular and
soft tissue patches, facial implants, surgical sutures,
and endovascular prostheses.
ePTFE was first used as a joint sealant, and since
then the number of its applications in the industrial
arena has grown rapidly. W.L. Gore still produces
sealants and the world’s tightest, most chemically
resistant gaskets. The ePTFE membrane is the key to
filtration products for a range of particle sizes, from
pollutants found in the energy, mineral, metal, and
chemical industries to clean room and computer disk
drive micro contaminants [9].
The original W.L. Gore product line, which
constituted insulated wires and cables, benefited
from the discovery of ePTFE. ePTFE combines the
chemical, thermal, and flammability characteristics
of PTFE with the electrical properties of air. It has
greater thermal stability, lower loss tangent, higher
velocity of propagation, more flexibility, and a lower
dielectric constant than solid PTFE.
1: H ISTORY OF P OLYTETRAFLUOROETHYLENE AND E XPANDED PTFE M EMBRANE
ePTFE has been also used in printed circuit
boards, electromagnetic interference shielding ma-
terial, and fiber optic assemblies. It has diverse ap-
plications in the defense industry, industrial
automation, computers, telecommunications, and
medical technologies.
Today, with more than 2 billion dollars in sales,
the company operates over 45 facilities throughout
the world and employs thousands of associates.
Bob Gore has stated that two fundamental core
principles have underpinned the company’s growth.
The first principle is the pursuit of product develop-
ment through leadership in fluoropolymers, and
particularly ePTFE. The second principle is a
commitment to creating a unique, fulfilling work
environment. Bob’s parents initiated and articulated
this commitment in the early days of the company.
Numerous organizations have recognized Bob
Gore’s accomplishments. He was awarded the 2005
Perkin Medal by the Society of Chemical Industry,
was elected to the National Academy of Engineers,
and received the Society of Plastics Engineers award
for benefits to society through the use of plastics as
well as an award for lifetime achievement in fluo-
ropolymers from DuPont and the WinthropeSears
Award from the Chemical Heritage Foundation. In
2006, he was inducted into the National Inventors
Hall of Fame.
W.L. Gore’s serious commitment to research and
development has resulted in a continually broadening
range of products. The company’s unique corporate
culture, which they refer to as a “flat lattice” struc-
ture, stresses freedom, fairness, commitment, and
good judgment in an open and creative work envi-
ronment. Associates have no titles, communicate
directly with one another, and work closely together
in teams and task forces. Gore associates believe this
unique culture enables the company to respond
quickly to changing market developments and that it
has been a key element in the company’s success and
growth [11e13].
References
[1] (a) S. Ebnesejjad, Introduction to Fluoropol-
ymers: Materials, Technology, and Applications,
Elsevier, New York, 2013 ch. 3.
7
(b) R.J. Plunkett, US Patent 2,230,654, Assigned
to DuPont Co, Februaury 4, 1941.
[2] R.J. Plunkett, The history of polytetrafluoro-
ethylene: discovery and development, in:
R.B. Seymour, G.S. Kirshenbaum (Eds.), High
Performance Polymers: Their Origin and
Development, Proceedings of the Symposium on
the History of High Performance Polymers at the
ACS Meeting Held in New York, April 1986,
Elsevier, New York, 1987.
[3] A. Kinnane (Ed.), DuPont: From the Banks of the
Brandywine to Miracles of Science, Johns
Hopkins, Baltimore, MD, 2002.
[4] (a) R.J. Plunkett, in: Speech at the American
Chemical Society Meeting, New York, April
15e18, 1986.
(b) S. Ebnesajjad, Fluoroplastics, Volume 1:
Non-melt Processible Fluoropolymers, second
ed., Elsevier, New York, 2014.
[5] S. Ebnesajjad, Fluoroplastics, Volume 2: Melt
Processible Fluoropolymers, second ed.,
Elsevier, New York, 2016.
[6] (a) US Patent 3,082,292, Assigned to Robert W.
Gore, September 22, 1964.
(b) www.fundinguniverse.com/company-
histories/WL-Gore-amp;-Associates-Inc-
Company-History.html.
[7] Bill, Bob Gore, Motion System Design
Magazine, Penton Media, Inc, 2008.
[8] C.C. Manz, H.P. Sims, Business Without Bosses:
How Self-managing Teams Are Building High,
John Wiley & Sons, New York, 1993.
[9] University of Delaware, Alumni News,
2008e2009, May 2, 2015. www.che.udel.edu/
downloads/2009ChEgNewsletter.pdf.
[10] http://dedo.delaware.gov/information/
databook/technology.pdf.
[11] The Culture of W.L. Gore & Associates. www.
gore.com/en_xx/aboutus/culture/index.html.
[12] J.P. Riederer, M. Baier, G. Graefe, Innovation
managementdan overview and some best
practices, C-LAB Rep. 4 (3) (2005) 9.
[13] G. Hamel, B. Breen, The Future of Management,
Harvard Business School Press, Boston, MA,
2007.
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 2 Polytetrafluoroethylene: Properties
and Structure

O U T L I N E

2.1 Introduction 9 2.7 Molecular Interaction of

Polytetrafluoroethylene:
2.2 Impact of F and CeF Bonds on the
Low Friction and Low Surface Energy 16
Properties of Polytetrafluoroethylene 9
2.8 Conformations and Transitions of
2.3 Crystalline Structure of Polytetrafluoroethylene 12
Polytetrafluoroethylene 18
2.4 Branched Tetrafluoroethylene Chains: 2.8.1 Images of the Polytetrafluoroethylene
Perfluorinated EthyleneePropylene Molecule 19
Copolymer 12
2.9 Microstructure and Fracture
2.4.1 Perfluorinated EthyleneePropylene
of Polytetrafluoroethylene 20
Copolymer 13
References 22
2.5 Reaction Mechanisms 14
2.6 Impact of Solvents on Fluoropolymers 15

2.1 Introduction Understanding the role fluorine plays in altering the

The main ingredient of an overwhelming majority
of expanded polytetrafluoroethylene (ePTFE) pro-
duced in the world, as the name indicates, is poly-
tetrafluoroethylene (PTFE) resin. This chapter
examines the important properties of PTFE,
including the extreme properties exhibited by PTFE,
and focuses on the significant impact of replacing
hydrogen with fluorine in hydrocarbon macromole-
cules. This substitution enhances a number of PTFE’s
properties, including thermal stability, chemical
resistance, electrical characteristics, and the coeffi-
cient of friction.
Another critical area this chapter considers is
the mechanical behavior of PTFE under various
stress/strain conditions. This is important because
the unique mechanical response of PTFE at high
strain rates is foundational for ePTFE products.
properties of a polymer will result in a more in-
depth appreciation of, and deeper insight into, the
characteristics of fluorinated polymers.
2.2 Impact of F and CeF Bonds
on the Properties of
Polytetrafluoroethylene
Fluorine is a highly reactive element with the
highest electronegativity of all the elements (4
Pauling on a relative scale of 0.7e4) [1]. The change
in the properties of compounds where fluorine has
replaced hydrogen can be attributed to the differ-
ences between CeF and CeH bonds.
A simple way to frame the issue is to explore the
differences between linear polyethylene (PE) and
PTFE. The two chemical structures appear to be

Expanded PTFE Applications Handbook. http://dx.doi.org/10.1016/B978-1-4377-7855-7.00002-X

Copyright © 2017 Elsevier Inc. All rights reserved. 9
10 E XPANDED PTFE A PPLICATIONS H ANDBOOK

similar on paper, yet in PTFE replacing H with F
results in the distortion of the geometry of PE:
Polyethylene
H H H H
C C C C
H H H H
Polytetrafluoroethylene
F F F F
C C C C
F F F F
Let us compare the CeF and CeH bonds. Table 2.1
[1,5] summarizes the key differences in the electronic
properties and sizes of F and H. In comparing fluorine
and hydrogen, several relevant differences are noted:
1. Fluorine is the most electronegative of all
elements
2. Fluorine has unshared electron pairs
3. F is more easily converted to its ionic F

4. The CeF bond is stronger than the CeH bond
5. Fluorine is larger than hydrogen
The electronegativity of carbon (2.5 Paulings) is
somewhat higher than that of hydrogen (2.1 Paul-
ings) and significantly lower than that of fluorine (4
Paulings). These electronegativity values imply that
the polarity of the CeF bond is opposite to that of
the CeH bond, and the CeF bond is more highly
polarized (see Fig. 2.1). In other words, fluorine has
a higher electron density it pulls the shared pair of
electrons closer to itself relative to the center point
of the CeF bond. Conversely, in the CeH bond the
electron pair is closer to carbon, which has a higher
electron density.
The difference in polarity of CeH and CeF bonds
affects the relative stability of the its conformations
of the two polymer (PTFE and PE) chains. Crystal-
lization of PE takes place in a planar and trans
conformation.
The crystal structure of PTFE, e(CF2)ne, is un-
usual because it has a number of crystal forms
(Fig. 2.2) and because there is substantial molecular
motion within the crystal well below its melting
point. PTFE can only be forced into a planar
conformation (form or phase III) at extremely high
pressures [6]. In contrast, at below 19 C, PTFE
crystallizes as an incommensurate helix with
approximately 0.169 nm per repeat distance [30],
thus requiring 13 carbon atoms for a 180-degree turn
to be completed. At above 19 C, the repeat distance
increases to 0.195 nm, which means that 15 carbon
atoms will be required for a 180-degree turn to be
completed [7]. At temperatures above 19 C the
chains are capable of angular displacement, and this
angular displacement increases at temperatures
above 30 C until the melting point is reached
(342 C).
Substitution of F for H in the CeH bond increases
the bond strength from 99.5 kcal/mol for the CeH
bond to 116 kcal/mol for the CeF bond, which is
substantial. Consequently, PTFE’s thermal stability
and chemical resistance are much higher than those

Table 2.1 Electronic Properties of Hydrogen and Halogens [1,5]

Element Ionization Electron CeX Bond

(Preferred Energy Affinity Energy in CeX Bond
Ionic Electronic Electronegativity (kcal/g atom) (kcal/g atom) CX4 Length in
Form) Configuration (Pauling) XD D ee > X X D ee > Xe (kcal/mol) CX4 (Å)
H 1s1 2.1 315.0 17.8 99.5 1.091
(Hþ)
F 1s1 4.0 403.3 83.5 116 1.317
(F) 2s22p5
Cl 1s1 3.0 300.3 87.3 78 1.766
(Cl) 2s22p5
3s23p53d0
X ¼ H, F or Cl.
2: P OLYTETRAFLUOROETHYLENE : P ROPERTIES AND S TRUCTURE 11

Center Point of the C—H Bond Most of the properties of PE and PTFE differ
significantly. The following four properties in
↓ particular are vastly altered in PTFE:
H+α C-2α H+α
Shared Pair Shared Pair
of Electrons of Electrons 1. PTFE has one of the lowest surface energies
Center Point of the C—F Bond among the organic polymers
↓ 2. PTFE is the most chemically resistant organic
F-δ C+2δ F-δ polymer
Shared Pair Shared Pair
of Electrons of Electrons 3. PTFE is one of the most thermally stable
δ α
among the organic polymers
4. PTFE’s melting point and specific gravity are
Figure 2.1 The comparative polarization of CeH and more than double those of PE
CeF bonds.
Table 2.2 lists the properties of PTFE and PE.
Commercial PE melts at 100e140 C, depending
on the extent of branching, as compared to PTFE,
III which melts at 327 C (first melting point 342 C).
0.6
One could expect that weak intermolecular forces
in PTFE should result in a lower melting point, or
II at most in a somewhat higher melting point because
Pressure (GPa)

0.4
0.2
IV
280 300 320
Temperature (K)
Figure 2.2 Phase diagram of polytetrafluoroethylene
[31].
of PE because more energy is required to break the
CeF bond. Additionally, the size of the F atom and
the length of the CeF bond (Table 2.1) are such that
the carbon backbone of PTFE is blanketed with
fluorine atoms, thus rendering the CeF bond
impervious to solvent attack. The polarity and
strength of the CeF bond rule out an F atom
abstraction mechanism for formation of chain
branches in PTFE. Instead, fully and partially fluo-
rinated comonomers with pendent groups are poly-
merized with tetrafluoroethylene (TFE) to produce
copolymers.
In contrast, highly branched PE (>8 branches per
100 carbon atoms) can be synthesized with relative
ease [8]. The branching mechanism is a tool used to
reduce the crystallinity of PE to produce polymers
with differing properties.
of the extremely high molecular weight of PTFE.
On the contrary, however, PTFE’s melting point
I is significantly higher than that of PE. Why?
The nature of the intermolecular forces in PTFE,
which are responsible for its high melting point, is not
fully understood. The answer may lie in the differ-
340 360 380 ences between the molecular structure conformation
and the crystalline structure of PE and PTFE. Because
fluorine atoms are much larger than hydrogen atoms,
there is less chain mobility in PTFE than in PE. Steric
repulsion, due to the size of the fluorine atoms, pre-
vents the PTFE from forming a PE-like planar zigzag
conformation. Instead, its conformation is helical
and steric repulsion is minimized.
PTFE is insoluble in common solvents. The
replacement of H with the highly electronegative F
renders PTFE immiscible with protonated material.
Conversely, PE can be plasticized and dissolved
above its melting point much more easily than
PTFE. PTFE absorbs only small amounts of per-
halogenated solvents such as perchloroethylene and
carbon tetrachloride. The insolubility of PTFE in
solvents is one of its most important characteristics
in many applications, such as in lined pipe and
other lined equipment for processing corrosive
chemicals.
In summary, the characteristics of F and CeF
bonds give rise to the high melting point, low solu-
bility, high thermal stability, low friction, and low
surface energy of PTFE.
12 E XPANDED PTFE A PPLICATIONS H ANDBOOK

Table 2.2 A Comparison of Polytetrafluoroethylene transition at 19 C between phases II and IV is

(PTFE) and Polyethylene Properties [2e4] unraveling in the helical conformation from a
well-ordered triclinic structure with 13 atoms/180
Property PTFE Polyethylene
degrees turn to a partially ordered hexagonal phase
Density 2.2e2.3 0.92e1 with 15 atoms/180 degrees turn [1,8,12,30,34e36].
Melting 342 (first) 327 105e140 Further rotational disordering and untwisting
temperature ( C) (second) of the helices occur above 30 C, giving way to
Dielectric 2.0 2.3 phase I to form a pseudohexagonal structure with
constant (1 kHz) dynamic conformational disorder and long-range
positional and orientational order [1,2]. There also
Dynamic 0.04 0.33
coefficient of exists a fourth phase (III) at high pressure, as seen
friction in Fig. 2.2 [37].
Fig. 2.3 shows PTFE crystallites, which appear as
Surface energy 18 33
striations throughout the micrograph. The extent of
(dynes/g)
crystallization, the size of the crystallites, and the
Resistance to Excellent, no Susceptible to packing order increase with the decrease in the
solvents and known solvent hot cooling rate from the molten state. PTFE molecules
chemicals hydrocarbons
crystallize in an accordion style in which the chain
Thermal Stabilitya folds back and forth on itself. The uniformity of the
T1/2 ( C) 505 404 width of the crystals indicates the regularity of the
structure of PTFE molecules.
K350 (%/min) 0.000002 0.008
The crystal model, in which the chain folding is
Eact (kJ/mol) 339 264 regular and sharp with a uniform fold period is
Melt creep 10 e10
10 12
e called adjacent reentry model (Fig. 2.4). The chains
viscosityb (Poise) reenter through the adjacent neighbor, with only a
Refractive index 1.35 1.51 few exceptions due to multiple nucleation and
chain-end defects. This is a very idealized visuali-
Chain branching No Yes
propensity
zation of the chain-folding process and not appli-
a
cable to the majority of polymers. There are sharp
T1/2 is the temperature at which 50% of the polymer is lost after
heating in a vacuum for 30 min; K350 is the rate of volatilization, ie,
boundaries between the crystal and the amorphous
weight loss, at 350 C; Eact is the activation energy of thermal phases.
degradation.
b
Melt creep viscosity for PTFE at 380 C. Please see S. Ebnesajjad,
Fluoroplastics, Vol. 1: Non-Melt Processible Fluoroplastics, second
ed., Plastics Design Library, Elsevier, Oxford, UK, 2014, for the
definition and procedure to measure melt creep viscosity, which is 2.4 Branched Tetrafluoroethylene
specific to PTFE.
Chains: Perfluorinated
EthyleneePropylene Copolymer
TFE polymerization allows an overwhelming
2.3 Crystalline Structure of majority of the chains to crystallize, despite their
Polytetrafluoroethylene very large molecular weight. This high degree of
crystallization is important to the development
Bunn and Howells first reported the crystalline of properties such as high modulus, low coeffi-
structure of PTFE in 1954 [32]. As Fig. 2.2 illus- cient of friction, and high heat-deflection tem-
trates, PTFE has two atmospheric pressure crystal- perature. Crystallinity of virgin PTFE (never
line transitions, at 19 C [32] and at 30 C [33]. melted) is in the range of 92e98% [9], which
Substantial molecular motion within the crystal is is consistent with an unbranched chain structure.
observed well below the melting point of 327 C in Properties of PTFE are altered by the inducement
once-melted PTFE and of 342 C in the as- of branching or substitution of a different atom
polymerized PTFE. PTFE has a and g glass-like for fluorine. An example is described in this
transitions at
80 C and 126 C [34]. The first-order section.
2: P OLYTETRAFLUOROETHYLENE : P ROPERTIES AND S TRUCTURE 13

Figure 2.3 Crystalline structure of polytetrafluoroethylene cooled down from 355 C to 200 C at 4.6 C per hour
(image formed by scanning electron microscopy) [38].

Figure 2.4 Schematic diagram of three chain-folding model in polymer crystals: (A) adjacent reentry with sharp
folds; (B) adjacent reentry with loose folds; and (C) random reentry or switchboard model [39].

2.4.1 Perfluorinated contains a tertiary carbon at the branch point bonded

EthyleneePropylene Copolymer
Perfluorinated ethyleneepropylene copolymer
(FEP), a copolymer of TEF and hexafluoropropylene,
to a pendent CF3. This carbon should have less
thermal stability than primary carbons and, to a lesser
extent, than secondary carbons that constitute the rest
of the backbone of the polymer chain. This decreased
14 E XPANDED PTFE A PPLICATIONS H ANDBOOK

Table 2.3 A Comparison of the Properties of FEP

and PTFE [10]

Property FEP PTFE

Melting point ( C) 265 327

Processing temperature 360 400

Figure 2.5 Comparison of thermal degradation of
perfluorinated ethyleneepropylene copolymer (FEP)
and polytetrafluoroethylene (PTFE) by thermogravi-
metric analysis [10].
stability is due to a steric effect in which the chain
departs from a helix at the branch point. Fig. 2.5
shows the results of thermogravimetric analysis of
PTFE and FEP after 1 h of heating in the air. The
lines in Fig. 2.5 start at a degradation rate of 0.02%
weight loss/hour at 300 C for FEP and 0.03% weight
loss/hour at 425 C for PTFE.
F F F F F F
FEP C C C C C C
F F F F F approaches the carbon side of the double bond (I)
F C F searching for a positive charge, which leads to the
F formation of a carbon ion (II). For example, if the
Table 2.3 provides a comparison of the properties
of FEP and PTFE. Melting point, processing tem-
perature, degradation temperature, and upper
continuous use temperature are all significantly lower
for FEP. The most important of these properties is the
use temperature. The reason for lower thermal sta-
bility in FEP lies in the greater susceptibility of the
tertiary carbon bonded to the pendent per-
fluoromethyl group to oxidation. FEP has about half
the crystallinity of PTFE, even though its molecular
weight is an order of magnitude lower. CF3 side
chains disrupt the crystallization sufficiently to
reduce the crystalline content. The melt viscosity of
FEP is almost 100 million times lower than that of
PTFE, which places it among the melt-processible
thermoplastic polymers.
( C)
Thermogravimetric 380 465
analysis loss
temperature of 1%/h
( C)
Upper continuous use 200 260
temperature ( C)
MV (380 C) (Poise) 104e105 1011e1012
Crystallinity of virgin 40e50 92e98
polymer (% wt)
FEP, perfluorinated ethyleneepropylene copolymer; PTFE,
polytetrafluoroethylene.
2.5 Reaction Mechanisms
Perfluoroolefins such as PTFE are generally, in
spite of broad chemical resistance, more vulnerable
to attack by nucleophiles than electrophiles, which is
the opposite of the case of hydrocarbon olefins.
Nucleophilic attacks occur on the fluoroolefins by the
scheme proposed in Fig. 2.6. The nucleophile (Nuc)
nucleophilic compound was methoxy sodium, the
CH3eOe side of the molecule would be approaching
TFE. The carbon ion (II) is unstable and will give off
a F
ion and generate reaction products. The nature
of the reaction medium determines which product is
generated. In the example of methoxy sodium, in the
absence of a proton donor such as water, F
would
combine with Naþ to produce NaF and per-
fluorovinyl methyl ether (III).
Reactions of TFE oligomers and nucleophiles
have been reported, such as the pentamer (1) of TFE
with alkoxide nucleophiles (see Fig. 2.7), sulfur-
containing nucleophiles and amines. The presence
of a mobile double bond in the pentamer molecule
renders it susceptible to attack by nucleophiles. It
can either replace a fluorine atom at a vinyl position
or attack the double bond, causing rearrangement
towards a terminal position. When the pentamer
was reacted with alkoxide nucleophiles such as
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however, the more he washed in the hot tears, the redder grew his
clothes, until he was just the colour of the scarlet bean blossom.
“You told me a story,” said Gillydrop to the giant when he saw how
red he was getting.
“I know I did,” said Dunderhead, drying his eyes, for he had now
wept enough, and was growing hungry; “but if I hadn’t told you a
story, I wouldn’t have got any supper. You’ll never be green again, so
don’t trouble your head. I’m going to get some wood to cook these
nice fat children.”
On hearing this, Teddy and Tilly roared like bulls, and Gillydrop
roared too, for he was afraid he would never be able to go back to
Faeryland in his red clothes; but the giant only laughed at them, and
went out to light a fire under his big kettle.
Gillydrop was naturally very cross with the giant for having deceived
him, and determined to punish him for having done so. Bringing the
two children to Dunderhead for his supper could not be the kindly
deed he had to do, or else he would have turned green again; so
Gillydrop made up his mind to take Teddy and Tilly back to earth,
and thus leave Dunderhead without his supper. While he was thus
making up his mind, seated at one end of the table, the two children,
seated at the other end, were crying bitterly at the plight in which
they now found themselves, for it certainly is not a nice thing to be
boiled for an ogre’s supper.
“Poor mother!” wailed Tilly, weeping; “she’ll miss us so much.”
“I don’t know if she will,” replied Teddy dolefully; “we’ve always been
so naughty, I daresay she’ll be glad we’ve gone.”
“Oh no, she won’t,” said Tilly, nodding her head; “she loves us too
much for that; but if we could get back I’d be so good.”
“And so would I,” cried Teddy; and then they both wept again, while
Gillydrop, seeing their tears, wept also out of sheer sympathy.
“Perhaps the giant will only eat one of us,” said Tilly after a pause;
“so while one of us is boiling, the other must run away and go back
to comfort mother.”
“Who will be boiled?” asked Teddy sadly. “Will you, Tilly?”
“I don’t like being boiled,” answered Tilly, with a shudder. “I’m sure it
isn’t nice.”
“Well, I don’t like being boiled either,” observed Teddy. “Suppose we
draw lots who is to run away.”
“Yes, that would be fair,” said Tilly, drying her eyes; “and the one who
wins must go back to cheer mother.”
Gillydrop was quite sorry now that he had brought them for
Dunderhead’s supper, when he heard how they regretted their
mother; so he made up his mind to save them.
“You shall neither of you be boiled,” he said, walking up to them
across the table, which was like a large plain. “I will take you back to
your mother.”
“But how?” asked Teddy and Tilly, both together. “We cannot go back
across the sea alone.”
“Oh yes, you can,” replied the Red Elf. “I brought you here, and can
send you back; that is, if I only had a leaf.”
“Here is one,” cried Tilly eagerly, pulling a faded leaf out of her
pocket. “I picked it up in the wood to-day, it had such pretty red and
yellow colours.”
“Oh, that will do for a boat,” said Gillydrop joyfully.
“But it’s so small,” objected Teddy.
“I’ll make it large enough,” said the elf. “You’ll see.”
“But how can we go on without sails or oars?” said Tilly timidly.
“You don’t need any,” rejoined Gillydrop, laughing; “you know every
tree has power to draw back its own leaves. The boat we came in
was a leaf, and, as soon as it was launched on the air, it went
straight back to the tree in the Country of the Giants upon which it
had grown; and as this leaf comes from a tree on earth, it will go
straight back to its tree.”
“Then we can get home,” cried Tilly, clapping her hands, “for the tree
isn’t far from mother’s cottage.”
“Mind, you are never to be naughty again,” said Gillydrop solemnly.
“Oh, no, no!” cried both children.
“And be very, very good to your mother.”
“Yes, yes! We’ll be very good.”
“Then go down to the beach by the path,” said Gillydrop, spreading
his wings. “I’ll fly down and get the boat ready; be quick, or the giant
will return.”
Then he flew away through the open window, and Teddy scrambled
down the steep path, followed by Tilly, both of them in a great fright
lest the giant should catch sight of them and pop them into his big
kettle. When they reached the beach, they found Gillydrop had
launched the leaf, which had now been transformed into a beautiful
red and yellow coloured boat.
“Good-bye,” said Gillydrop, as soon as they were comfortably seated
in the boat. “I’m sorry I brought you here, but it will do you no harm,
as it will teach you to be good. Mind you don’t quarrel in the boat—if
you do, the leaf will vanish, and you’ll sink for ever in the black
waves.”
“Oh, we’ll be very, very good,” promised both the children eagerly,
and then Gillydrop gave the boat a push, so that it moved rapidly
away from the land, leaving him seated on the beach, a lonely little
red figure.
Teddy and Tilly were rather afraid at finding themselves alone in the
darkness, but they kissed one another, and fell asleep, while the
leaf-boat sailed rapidly over the Sea of Darkness towards its parent
tree. When the children awoke, they found themselves lying on the
ground under the tree, and there above them was their red and
yellow boat, hanging, a red and yellow leaf, on a high bough.
“Now we’ll go home,” cried Tilly, jumping up; “now we’ll go home to
mother.”
“And be very good,” said Teddy, also rising.
“Yes; very, very good,” replied Tilly. And then, taking one another’s
hands, they ran home to their cottage through the dark forest.
Dame Alice, who thought they had lost themselves in the wood, was
very glad to see them, and, after she had kissed them, gave them a
good supper of bread and milk, which they enjoyed very much, for
you see they were very hungry with the long journey.
They told Dame Alice all their adventures, and she was very glad
they had gone to the Giants’ Country, for she guessed, like the wise
mother she was, that this was the lesson the faeries had foretold.
Ever afterwards, Teddy and Tilly were good children; there never
were two such good children, because they thought, if they were not
good, they would be taken back to the Giants’ Country and boiled for
an ogre’s supper. But after a time they liked to do good actions
because they found it pleasant, and Dame Alice was so pleased with
their behaviour that she made a rhyme about them, which soon
passed into a proverb:
“The magic power of a faery
Cures a child when quite contrary.”
 III.

HOW THE RED ELF RETURNED TO FAERYLAND.

When Gillydrop saw the magic boat disappear into the darkness of
the sea, he thought that, now he had done one kindly deed, his
clothes would change from red to green, and he would be able to
return to his dear Faeryland. But nothing of the sort occurred, and
the poor elf began to cry again, thinking he was lost for ever, but this
time his tears were not red, which was a good sign, although he did
not know it.
Very soon he heard Dunderhead roaring for the loss of his supper,
so, drying his eyes, he flew back again to the hall of the castle, to
see what the giant was doing. He found a great fire was lighted, over
which was suspended a great kettle filled with water, which was now
boiling hot. Dunderhead was searching everywhere for the children,
and when he saw Gillydrop he shook his great fist at him.
“Where’s my supper, you red rag?” he roared fiercely.
“Your supper has gone back to earth,” replied Gillydrop angrily, for no
one likes to be called a red rag. “You told me a story, so I thought I’d
punish you.”
“Oh, did you?” bellowed Dunderhead, in a rage. “Then I’ll punish you
also for spoiling my supper.” And before Gillydrop could fly away, he
caught him in his great hand and popped him into the boiling water.
Oh, it was terribly hot, and Gillydrop thought it was all over with him;
but, being a Faery, he could not be killed, as the foolish giant might
have known. He sank down, down, right to the bottom of the great
kettle, and then arose once more to the top. As soon as he found his
head above water, he sprang out of the kettle and flew away high
above the head of Dunderhead, who could only shake his fist at him.
To his delight and surprise, Gillydrop found his clothes had all
changed from red to green, and instead of being dressed in crimson,
his suit was now of a beautiful emerald colour. He was so delighted
that he flew down on to the floor of the hall, and began to dance and
sing, while the giant joined in as he tried to catch him; so that they
had quite a duet.
Gillydrop. Now I’m gay instead of sad,
For I’m good instead of bad:
Dreadful lessons I have had.
Giant. I will catch and beat you!

Gillydrop. Tho’ a naughty elf I’ve been,

Now my clothes are nice and clean:
I dance once more a faery green.
Giant. I will catch and eat you!

But you see he could not do that, because Gillydrop was too quick
for him, and flew round the hall, laughing at Dunderhead, who roared
with anger. Then the elf flew out on to the terrace which overlooked
the Sea of Darkness, followed by the giant. Gillydrop flew down on to
the beach to escape the ogre, and Dunderhead tried to follow; but,
as he could not fly, he fell right into the Sea of Darkness. Dear me!
what a terrible splash he made! The waves arose as high as the
castle walls, but then they settled down again over Dunderhead, who
was suffocated in the black billows. He was the very last of the
giants, and now his bones lie white and gleaming in the depths of the
Sea of Darkness, where nobody will ever find them—nor do I think
any one would trouble to look for them.
As for Gillydrop, now that Dunderhead was dead, he flew away
across the dreary plain towards Faeryland, and soon arrived at the
borders of the sullen grey sea which still rolled under the pale light of
the moon. Gillydrop was not a bit afraid now, because his clothes
were green once more, and he had performed one kindly deed; so
he sat down on the seashore and sang this song:
“When from Faeryland I fled,
All my nice clothes turned to red;
Now in emerald suit I stand—
Take me back to Faeryland.”
And as he sang the grey ocean faded away, and in its place he saw
the green trees of the faery forest, waving their branches in the silver
moonlight. Only a bright sparkling stream now flowed between
Gillydrop and Faeryland; so, spreading his silver and blue wings, he
flew across the water, singing gaily:
“Thanks, dear Oberon. At last
All my naughtiness is past;
Home I come without a stain,
And will never roam again.”

So at last Gillydrop got back to Faeryland after all his trials, and ever
afterwards was one of the most contented elves ever known. You
may be sure he never wanted to see the Country of the Giants
again, and whatever King Oberon said he did willingly, because he
knew it must be right.
He was quite a hero among the faeries, and had the honour of telling
all his adventures to King Oberon himself, which he did so nicely that
the King gave him a title, and ever afterwards he was called “Sir
Gillydrop the Fearless.”
 SHADOWLAND

IT was Christmas Eve, and the snow, falling heavily over a great city,
was trying to hide with its beautiful white robe all the black, ugly
houses and the narrow, muddy streets. The gas lamps stood up
proudly, each on its tall post, and cast their yellow light on the
crowds of people hurrying along with their arms filled with many
lovely presents for good children.
“They are poor things,” said the gas lamps scornfully. “If we did not
shed our light upon them, they would be lost in the streets.”
“Ah, but the people you despise made you,” cried the church bells,
which were calling the people to prayer. “They made you—they
made you, and gave you your beautiful yellow crowns.”
But the street lamps said nothing, because they could not deny what
the church bells said, and instead of acknowledging that they owed
all their beauty to the people they despised, remained obstinately
silent.
Near one of these lamp-posts, at the end of a street, stood a
ragged boy, who shivered dreadfully in his old clothes, and stamped
about to keep himself warm. The boy’s name was Tom, and he was
a crossing-sweeper, as could be seen by his well-worn broom. He
was very cold and very hungry, for he had not earned a copper all
day, and the gaily-dressed army of people swept selfishly past him,
thinking only of their Christmas dinners and warm homes.
The snowflakes fell from the leaden-coloured sky like great white
angels, to tell the earth that Christ would be born again on that night,
but Tom did not have any such ideas, as he was quite ignorant of
angels, and even of the birth of the child-Christ. He only looked upon
the snow as a cold and cruel thing, which made him shiver with pain,
and was a great trouble to brush away from his crossing.
 And overhead the mellow bells clashed out
their glad tidings in the bitterly chill air, while
below, in the warm, well-lighted churches, the
organ rolled out its hymns of praise, and the
worshippers said to one another, “Christ is
born again.”
But poor Tom!
Ah, how cold and hungry he was, standing in
the bright glare of the lamp, with his rags drawn closely round him for
protection against the falling snow. The throng of people grew
thinner and thinner, the gaily-decorated shops put up their shutters,
the lights died out in the painted windows of the churches, the bells
were silent, and only poor Tom remained in the deserted, lonely
streets, with the falling snowflakes changing him to a white statue.
He was thinking about going to his garret, when a gentleman,
wrapped in furs, passed along quickly, and just as he came near
Tom, dropped his purse, but, not perceiving his loss, walked on
rapidly through the driving snow. Tom’s first idea was to pick the
purse up and restore it to its owner, whom Tom knew very well by
sight, for he was a poet, who daily passed by Tom’s crossing. Then
Tom paused for a moment as he thought of all the beautiful things
the money in that purse would buy; while he hesitated, the poet
disappeared in the darkness of the night, so Tom was left alone with
the purse at his feet.
There it lay, a black object on the pure white
snow, and as Tom picked it up, he felt that it
was filled with money. Oh, how many things of
use to him could that money buy—bread and
meat and a cup of warm coffee—which would
do him good. Tom slipped it into his pocket, and thought he would
buy something to eat; but just at that moment he seemed to hear a
whisper in the air,—
 AS TOM PICKED IT UP HE FELT THAT IT WAS
FILLED WITH MONEY

“Thou shalt not steal.”

With a start of terror Tom looked around, thinking a policeman had
spoken, and would take him off to prison for stealing the purse, but
no policeman was in sight. He saw nothing but the whirling flakes
and his ragged shadow cast blackly on the white snow by the light of
the lamp. It could not have been the shadow speaking, as Tom
thought, for he knew that shadows never speak; but, ah! he did not
know the many wonderful things there are in this wonderful world of
ours.
Whoever had made the remark touched Tom’s heart, for he
remembered how his poor mother had blessed him when she died,
and told him to be an honest boy. It certainly would not be honest to
steal money out of the purse, but Tom was so cold and hungry that
he half thought he would do so. He took out the purse again and
looked at its contents—four shining sovereigns and some silver.
Then he put it back in his pocket, and trudged home with his broom
under his arm.
Home!—ah, what a dreary, cheerless home it was!—nothing but a
garret on the top of an old house—a bare garret, with no table or
chairs, but only the sacks upon which Tom slept at night.
He closed the door, and then lighted a little bit of candle he had
picked up in the streets with one of the matches from a box given
him by a ragged match-seller.
Tom placed the candle on the floor, and, kneeling down, opened the
purse to look at the money once more. Oh, how tempted he was to
take one of those shillings and buy some food and wood—it would
be a merry Christmas for him then! Other people were enjoying their
Christmas, and why should he not do the same? The great poet who
had dropped the purse had plenty of money, and would never miss
this small sum; so Tom, desperate with hunger, took a shilling, and,
hiding the purse under his bed, was about to blow out the candle
before creeping down-stairs to buy some food, when he heard a soft
voice whisper,—
“Don’t go, Tom.”
He turned round, and there was the shadow
cast by the reflection of the candle-light on the
wall. It was a very black shadow, much
blacker than Tom had ever seen before, and
as he looked it grew blacker and blacker on
the wall, then seemed to grow out of it until it
left the wall altogether, and stood by itself in
the centre of the floor, a waving, black shadow
of a ragged boy. Curiously enough, however,
Tom could not see its face, but only the outline
of its whole figure, yet it stood there shaking with every flicker of the
candle, and Tom could feel that its eyes were looking right into him.
“Don’t go, Tom,” said the shadow, in a voice so like his own that he
started. “If you go, you will be lost for ever.”
“Lost?” said Tom, with a laugh; “why, I couldn’t lose myself. I know
every street in the city.”
“I don’t mean really lost,” replied the shadow; “but it will be your first
step on the downward path.”
“Who are you?” asked Tom, rather afraid of the shadow, but keeping
a bold front.
“I am your shadow,” it replied, sighing. “I follow you wherever you go,
but only appear when there is light about you. If you had not lighted
that candle I would not have appeared, nor could I have spoken.”
“Was it you who spoke at the lamp-post?” said Tom doubtfully.
“Yes, it was I,” answered the shadow. “I wanted to save you then, as
I do now, from committing a crime. Sit down, Tom, and let us talk.”
Tom sat down, and the shadow sat down also. Then for the first time
he caught a passing glimpse of its face, just like his own, only the
eyes were sad—oh, so sad and mournful!
“Thou shalt not steal,” said the shadow solemnly.
“I don’t want to steal,” replied Tom sulkily; “but I’m cold and hungry.
This shilling would buy me fire and food. I don’t call that stealing.”
“Yes, but it is stealing,” answered the shadow, wringing its hands;
“and you know it is. If you steal you will be put in prison, and then I
shall have to go also. Think of that, Tom, think of that.”
Tom did not say a word, but sat on the floor looking at the bright
shilling in his hand which could procure him so many comforts. The
shadow saw how eager he was to take the shilling, and, with a sigh,
began to talk again.
“Think of your mother, Tom,” it said softly. “She was the wife of a
gentleman—your father; but he lost all his money, and when he died
she could get no one to help her. Do you remember how she died
herself in this very place, and how she implored you with her last
breath to be an honest boy?”
“Yes, I remember,” said Tom huskily; “but she did not know how cold
and hungry I would be.”
“Yes she did—she did,” urged the shadow. “She also had felt cold
and hunger, but she never complained. She never stole, and now
she has her reward, because she is a bright angel.”
“I don’t know what an angel is,” said Tom crossly; “but if she’s all
right, why doesn’t she help me?”
“She does help you, Tom,” said the shadow; “and it was because she
saw you were tempted to steal to-night that she asked me to help
you. She cannot speak as I do, because she is not a shadow.”
“Well, help me if you’re able,” said Tom defiantly; “but I don’t believe
you can.”
The candle on the floor had burnt very low, and as Tom said the last
words his shadow bent nearer and nearer, until he again saw those
mournful eyes, which sent a shiver through his whole body. It
stretched out its arms, and Tom felt them close round him like soft,
clinging mist; the candle flared up for a moment, and then went out,
leaving Tom in darkness altogether. But he did not feel a bit afraid,
for the soft arms of the shadow were round him, and he felt that it
was carrying him through the air.
They journeyed for miles and miles, but Tom knew not which
direction they were taking until a soft light seemed to spread all
around, and Tom felt that he was in the midst of a large crowd,
although he saw no one near him. Then he felt his bare feet touch
some soft, cloudy ground, that felt like a sponge; the shadowy arms
unclasped themselves, and he heard a voice, soft as the whispering
of winds in summer, sigh,—
“This is the Kingdom of Shadows.”
Then Tom’s eyes became accustomed to the subdued twilight, and
he saw on every side a number of shadows hurrying hither and
thither. He seemed to be in the centre of a wide plain, over which
hung a pale white mist, through which glimmered the soft light. The
shadows were all gliding about this plain; some thin, some fat, some
tall, others short; they all appeared to have business to do, and each
appeared to be intent only on his own concerns. Tom’s own shadow
kept close to him, and whispered constantly in his ear of strange
doings.
“These are the shadows of the past and of the future,” it sighed; “all
the shadows of human beings and their doings are here; see, there
is a funeral.”
And a funeral it was which came gliding over the smooth, white plain;
the great black hearse, the dark horses with nodding plumes, and
then a long train of mourners; all this came out of the mist at one
end, glided slowly over the plain, and vanished in the veil of mist at
the other. Then a bridal procession appeared; afterwards a great
army, clashing cymbals and blowing trumpets from whence no sound
of music proceeded; then the coronation triumph of a king, and later
on a confused multitude of men, women, and children, all hurrying
onward with eager rapidity. But they all came out of the mist and
went into the mist, only appearing on the white plain for a few
minutes, like the shadows of a magic lantern.
“The stage of the world,” whispered Tom’s shadow. “Birth, death, and
marriage, triumphs and festivities, joys and sorrows, all pass from
mist to mist, and none know whence they come or whither they go.”
“But what has this got to do with me?” asked Tom, who was feeling
rather bewildered.
“You are a man,” said his shadow reproachfully, “and must take an
interest in all that men do; but come, and I will show you what will
happen if you steal the purse.”
They glided over the plain towards the distant curtain of mist, but
how they travelled over the immense distance so rapidly Tom did not
know, for in a moment it seemed to him that he had come many
miles, and found himself suddenly before a grey, misty veil, with his
own shadow beside him, and many other shadows around.
As he stood there, a whisper like the murmur of the sea on a pebbly
beach sounded in his ears, and he seemed to guess, rather than
hear, what the shadows said.
“Now he will see—now he will see—he must choose the good or the
bad. Which will he choose?—which will he choose?”
Then the grey veil stirred, as if shaken by a gentle wind, and,
blowing aside, disclosed what seemed to Tom to be a great sheet of
ice of dazzling whiteness set up on end. As he looked, however,
shadows began to appear on the milky surface which acted a kind of
play and then vanished, and in the play he was always the central
figure.
First he saw himself pick up the purse in the snowy street; then hide
it in his bed. He saw his ragged shadow glide down-stairs from the
garret to buy food; the shopman looking at him, then at the shilling;
then a policeman arresting him and finding the purse hidden in the
bed. Afterwards he saw himself in prison; then released, and
prowling about the streets. Years seemed to pass as he looked, and
his shadow became taller and stouter, but always wearing a ragged
dress. After many years he seemed to see his shadow breaking into
a house—meet the owner of the house, and kill him. Afterwards the
shadow of himself stood in the dock; then crouched in prison; and,
last of all, he appeared standing under a black gallows with a rope
round his neck. At length all the shadows vanished, and the surface
of the ice mirror again became stainless, whilst a voice whispered in
his ear, “All this will happen if you steal the purse.”
Then the shadows again came on to the mirror and acted another
play; but this time it was much more pleasant.
Tom saw his shadow representative take the purse back to the poet
who had lost it. Then he saw himself in a school, learning all kinds of
wonderful things; and the years rolled by, as they had done in the
other play, unfolding the shadows of a beautiful life. He saw himself
become a great and famous poet, who wrote beautiful books to
make people wise and good. Then he saw himself in church, with a
woman’s shadow by his
side, and he knew, in some mysterious way, that it was the daughter
of the poet who had lost the purse. And as the happy years rolled on
he saw himself rich and honourable, and the end of all was a
magnificent funeral, taking his body to be buried in the great church
wherein many famous men were laid. Then the shadows vanished,
and the mirror became pure again, while over it the grey mists fell
like a soft veil, and once more the voice of his shadow said,—
“All this will happen if you remain honest.”
Then the crowd of shadows around Tom looked at him with their
mournful eyes, and a whispering question ran through the fantastic
throng,—
“Which will he choose?—which will he choose?”
“I will choose the honest life,” cried Tom loudly. “Yes, I will give back
the purse to the poet.”
At this the shadows around seemed to rejoice, and he could see
beautiful faces smiling at him from amid the crowd. The shadow
multitude broke in a wild dance of joy, keeping time to some aerial
music which Tom could not hear; and his own shadow, with
happiness shining out of its mournful eyes, threw its arms round him
once more. A dark veil seemed to fall over him, and the great white
plain, the glimmering mists, and the restless shadows, vanished
together.
When Tom opened his eyes again, he found himself lying on the
floor of his garret, cold and hungry still, but with his heart filled with a
great joy, for the shilling was still clutched in his hand, and he knew
he had not stolen the money. He took the purse from under the
sacks, replaced the shilling, and then went out, in the bright sunshine
of the Christmas morning, to give back the lost purse to its owner.
Overhead the bells rang out merrily, as if they were rejoicing at Tom’s
victory over himself, and a beautiful lady, who was on her way to
church, gave Tom some money to get food. He went and bought a
loaf and a cup of coffee, then, thankful for his good fortune, he
trudged off to the poet’s house.
The great poet received him very kindly, and,
after thanking Tom for returning his purse,
asked him why he had done so instead of
keeping it? Whereupon Tom told the poet all
about the shadow, which interested the poet
very much. He also had been to Shadowland
and seen strange things, which he told to the world in wonderful
verse.
“This boy is a genius,” he said to his wife, “and I must help him.”
Then it all happened as the magic mirror had foretold, for Tom was
put to school by the kind poet, and became a very clever man. He
also wrote poems, which the world received with joy; and when he
became a famous man, the kind poet gave him his own daughter in
marriage, and the bells which had rang the birth of the child-Christ
when Tom was a poor ragged boy, now rang out joyously in honour
of his marriage.
“He has conquered,” they clashed out in the warm, balmy air; “he is
the victor, and now he will be happy.”
And he was happy, very very happy, and felt deeply thankful to the
shadow who had shown him the way to be happy. His own shadow
never left him, but it never spoke to him again, though when Tom felt
tempted to do wrong, he heard a whisper advising him to do right.
Some people said that this was the voice of conscience, but Tom
knew it was the voice of his dear shadow, who still watched over
him.
And one day he took his wife to the garret where he had lived when
a poor boy, and told her how he had been to Shadowland, and
learned that to be honest and noble was the only true way to
happiness. His wife laughed, and said Tom had been dreaming; but
Tom shook his head, and said that it was no dream, but a great truth.
Now, who do you think was right—Tom or his wife?
THE WATER-WITCH
 I.

FIRE AND WATER.

ONCE upon a time, long long years ago, there was a shepherd
called Duldy, who dwelt in the forests which clothed the base of the
great mountain of Kel. This mountain was in the centre of an
immense plain, watered by many rivers, and dotted over with many
cities, for the kingdom of Metella was a very rich place indeed, so
rich that the inhabitants looked upon gold in the same way as we
look upon tin or iron, as quite a common thing. The plain was very
fertile by reason of the great rivers which flowed through it like silver
threads, and all these rivers took their rise in the mountain of Kel, a
mighty snow-clad peak which shot up, white and shining, to the blue
sky from amidst the bright green of its encircling forests.
There were old stories handed down from father to son, which said
that the mountain was once a volcano, which, breathing nothing but
fire, sent great streams of red-hot lava down to the fertile plain, to
wither and blight all the beautiful gardens and rich corn-fields. But
the fires in the breast of the mountain had long since died out, and
for many centuries the black, rugged summit had been covered with
snow, while countless streams, caused by the melting of the glaciers,
fell down its rocky sides, and, flowing through the cool, green pine
forests, spread themselves over the thirsty plain, so that it bloomed
like a beautiful garden.
Duldy lived in these scented pine forests, and
was supposed to be the son of an old couple
called Dull and Day, from whence by joining
both names he got his own Duldy; but he was
really a lost child whom old Father Dull had
found, seventeen years before, on the banks
of the Foam, one of the bright sparkling
streams which flowed from the snowy heights
above. Dull took the child home to his wife
Day, who was overcome with joy, for she