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 FLUORINATED COATINGS
AND FINISHES HANDBOOK
The Definitive User’s Guide
Second Edition

Laurence W. McKeen

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Dedicated to my mother (Helene) and father (Veikko)

Paints and coatings are much more complex than
most expect. My first introduction to paint chemistry
came, as I was job hunting in my final year of grad-
uate school at the University of Wisconsin. I was
trained there as a theoretical and experimental analyt-
ical chemist at the time. My graduate work focused on
complex computer interpretation of high-resolution
mass spectroscopy. DuPont called and offered an
interview at their technical center of paint technology
at the time, the Marshall Laboratory in Philadelphia,
PA. They told me it was their premier paint and
coating development laboratory. I remember thinking,
“paint.how boring,” and I almost did not accept the
offer to interview. Fortunately, I gave it a chance and
learned how truly complex paint formulations were.
Interactions among all the components complicate
the systems beyond theoretical modeling and analysis
in most cases. I also learned that there were uses or
functions of paints and coatings beyond appearance
and rust protection and there were dozens of ways
to apply the coatings.
While interviewing for the job in the Marshall
Lab’s analytical chemistry section, I learned how
complex the analytical chemistry of paints was due
to the complex mixtures formed in them. Part of
my initial assignment was focused on developing
ways of analyzing unknown liquid and solid paint
samples, including competitive product analysis.
This work was challenging, enjoyable, and inter-
esting. One would be surprised with what can be
learned from a small paint chip. Within a couple
years, I expressed an interest in the formulation of
paints. DuPont reassigned me to the TeflonÒ finishes
group, where I spent the next 33 years learning what I
am communicating in this work. I retired on
December 31, 2013.
This book will be not only a reference book but
also more tutorial in nature. It teaches the practice
and theory of fluorinated coatings at every step.
There are literally thousands of people using thou-
sands of different fluoropolymer coatings globally.
Much of my time with the DuPont customers was
Foreword
been devoted to teaching the basics of paint formula-
tion, how it impacts their coatings processes, and
why things did not always work as expected. The
problems and solutions were often more physics
and engineering than chemistry. The content of this
book should help readers understand some of prob-
lems encountered, interpret their own observations
and arrive into possible solutions. A better under-
standing will also lead to better communication
between the coaters and coatings suppliers, which
could shorten product and process development time.
Most of the chapters have few references because
what I have included is what I have learned during
years developing, formulating, and studying fluoro-
polymer coatings around the world. There are lots
of potential references in the public literature, but I
did not use them. In sections where I discuss some
specific products or product lines, the information
reflects what was considered up to date at the time
of publication. Product lines are continually modi-
fied, added, and eliminated. There are no proprietary
disclosures in this book.
Color is used in this book in both electronic and
print which significantly adds to its readability. The
first chapter introduces the fluoropolymers that have
been used or could be used in coatings. The discovery
of fluoropolymers opens the chapter. The structures
of the fluoropolymers are given and the basic proper-
ties are summarized. Chapter 2 provides background
on how fluoropolymers are made and finished in
which I have attempted to keep present the chemistry
as simply and clearly as possible. It has been signif-
icantly changed from the first edition with the addi-
tion of the section on polymerization surfactants
and polymerization aids that has been news for the
past 10 years. This section is based upon a chapter
from the work of Sina Ebnesajjad. The section on
micropowder production has been expanded.
Chapter 3 is an introduction to the components of
paint and introduces the next four chapters of this
book, which discuss the components or ingredients
of paints and coatings in detail. Chapter 4 discusses
xvii
xviii
binders, the nonfluoropolymers that are often used in
fluorocoatings. The structures and properties of these
materials are disclosed. New sections on electroless
plating and solegel chemistry enhance this chapter.
The question, “How do you get a nonstick coating
to stick to the substrate?” is also answered. Chapter 5
deals with pigments, fillers, and extenders. The
dispersion processes used to prepare them for use
in coatings are summarized. Types of pigments are
reviewed. Pigments are not only used for color; the
other functions of pigments, barrier properties, rein-
forcement and abrasion resistance, conductivity and
corrosion resistance are discussed. Chapter 6 is
an in-depth discussion about solvents. Chapter 7
is a summary of additives, those minor paint compo-
nents sometimes called “snake oils” that often make
or break the commercial success of a fluorocoating.
Chapter 8 delves into preparing the substrate for
coating. This is a critical chapter as substrate prepa-
ration impacts adhesion and eventually the perfor-
mance of the coated item. It has been significantly
enhanced over the first edition.
Chapter 9 focuses on liquid fluorocoating formula-
tions. Included in this chapter are some guidelines on
making coatings, both aqueous and nonaqueous, and
preparing them for use. There are also tables of
commercial products with technology and property
information when it is publicly available. Chapter 10
summarizes the different ways liquid coatings are
applied and what formulation factors are important
in each application method.
Chapter 11 focuses on powder coatings and films.
The section of fluoropolymer film is new and is an
alternate way to put a fluoropolymer onto a substrate.
Chapter 12 is called coating processing, but it essen-
tially is about baking or curing the fluorocoatings.
Included in this chapter are details about what
happens during the bake, along with the different
technologies used for baking and monitoring that
process.
Chapter 13 moves onto coating property character-
ization and coating performance. Many of the perfor-
mance tests for coating manufacturers and end user’s
F OREWORD
use are discussed. Some of these are specification
tests. Others are important in helping a potential
customer to select a coating. Included are references
to standard test protocols. A section on environ-
mental exposure has been heavily rewritten and
expanded. Weathering is now covered in detail.
Chapter 14 is a new chapter on the permeation of
fluoropolymer coatings. It covered theoretical models
which make it easier to understand the process.
Chapter 15 is also new and is an introduction to the
tribology of fluorocoatings. Tribology is the study of
friction and wear. Discussions include classifications
of the many types of wear and erosion, how to charac-
terize wear, and many ways it is measured. There is
also a section containing tribological data for many
fluoropolymers that can be applied to coatings work.
Chapter 16 is related to performance, but it deals
specifically with coating defects. Many photographic
examples are included along with an explanation of
what causes the defects and possible ways to fix
them.
Chapter 17 is a summary of some of what has been
done with fluorocoatings, where they are used. A
history of coating development starts the chapter.
Housewares are covered in detail and contains lists
of products by the major housewares coatings
producers. There are many applications of fluoro-
coatings that are less commonly known. Chapter 18
closes this work with a discussion about many of
the health and safety aspects of using and applying
fluorocoatings.
Three Appendices are included. Appendix I
includes samples of tabular and graphical properties
of fluoropolymers, mechanical, thermal, and electri-
cal. Appendix II contains permeability data of
various fluoropolymers to water vapor, oxygen, and
other gasses and vapors. Appendix III is an extensive
compilation of chemical resistance tables.
I am a teacher at heart. I hope you will find this
work instructive and useful.
Larry McKeen
2015

I spent over 35 years with DuPont, 33 of which
was in TeflonÒ Finishes Research and Development.
It was known by many other names over those years.
This book is a summary of some of what I have
learned during that time. It does not contain anything
proprietary. I enjoyed working with many colleagues
and coworkers at DuPont and all of them furthered
my understanding of the fluorinated coating tech-
nologies. Some of them include, in no particular
order, Mr Michael Witsch, Mr William McHale,
Mr Craig Hennessey, and Dr Peter Huesmann.
Dr Charles DeBoer persuaded me to come to DuPont
and was a mentor to me for years.
A number of teachers have greatly impacted on my
education and deserve special thanks. Ms Anna Kruse
was my high school chemistry teacher (Lyman Hall
High School, Wallingford, CT) who not only was
a great educator but also motivated this particular
young student to study chemistry beyond the class-
room. That included writing articles for an educa-
tional chemistry magazine while in high school. There
were after school projects, one that eventually led
to the 1969 International Science Fair. The many
Acknowledgments
outstanding chemistry teachers at Rensselaer Poly-
technic Institute provided the best and most thorough
undergraduate chemistry education in the country.
Finally, my major professor at the University of
Wisconsin, Professor James W. Taylor was a great
educator and ultimately developed my teaching
abilities.
I have taught much to our customers, but they
probably do not realize how much more I have
learned from them. Many of the sections in this book
have resulted from lectures and discussions on those
subjects with customers. Their questions have helped
focus and crystallize this work and my understanding
of the technology.
The author is especially appreciative of the confi-
dence, support, and patience of my friend and editor
Sina Ebnesajjad. Without his support and encourage-
ment my work on the original edition of this book may
have been abandoned before completion.
My family has been particularly supportive
through the long hours of writing and research from
my home office. My wife, Linda, has been behind
this work 100%.
xix

Fluoropolymer coatings are widely used in many
industries, though consumers and many engineers
and scientists are only aware of their use as nonstick
coatings for cookware. There are thousands of ap-
plications, some of which are discussed later in this
book. This work will be useful to students, engineers,
paint applicators, and the end users that buy and
specify fluoropolymer-coated parts.
This book aims to:
1. Provide information on coating formulation
including what is in a fluoropolymer paint
and why
2. Provide guidelines on the performance of the
various types of coatings to aid in selection
or provide an understanding on why some coat-
ings work or do not work in an application
3. Provide collections of data on raw materials for
potential formulators
4. Provide application and curing information.
This book is part of the PDL Series or the Plastics
Design Library, a William Andrew imprint of
Elsevier. Several PDL volumes cover in detail the
technology of polymers, plastics, and elastomers that
are used as raw materials in fluorinated coatings. It is
important to understand what these raw materials are
and what their properties are because those properties
are imparted to the coatings in which they are used.
It is essential to understand the shortcomings or
limits of the finishes. Many of these volumes cover
fluoropolymers of fluorinated materials directly. Two
volumes of this series cover in great detail the
chemistry and use of the raw fluoropolymers.1,2
Those texts provide extensive property comparisons.
This book on coatings could not possibly contain
performance properties of all fluorinated coatings
because they number in the thousands.
While there are literally thousands of fluorine-
containing polymers described in the technical and
academic literature and those known only in the
Fluorinated Coatings and Finishes Handbook. http://dx.doi.org/10.1016/B978-0-323-37126-1.00001-1
Copyright © 2016 Elsevier Inc. All rights reserved.
1 Fluoropolymers
laboratory, this work will focus only on the
commercially available materials.
1.1 The Discovery of
Fluoropolymers
The story of the discovery of fluoropolymers by
DuPont has been related by many. It began not by a
well-designed purposeful experiment based on poly-
merization or organic chemistry. The first fluoropol-
ymer was discovered by accident. Dr Roy Plunkett
(earned his PhD at Ohio State University in 1936) of
the DuPont company was the image of a classical
chemist: ingenious, but more important, observant.3
In 1938, he had been at DuPont for only 2 years and
was doing research on the development of fluorinated
refrigerants in a joint venture of DuPont and General
Motors called Kinetic Chemicals.
This work took place in what is now known as
DuPont’s Jackson Laboratory on the site of the
Chambers Works in New Jersey across the Delaware
River from Wilmington. It is now in the shadow of
the Delaware Memorial Bridge. He was exper-
imenting with tetrafluoroethylene (TFE) looking for
a synthetic route to a useful refrigerant (CClF2e
CHF2).4 The effort was spurred by the desire to create
safe, nonflammable, nontoxic, colorless, and odorless
refrigerants.
On the morning of April 6, 1938, when Plunkett
checked the pressure on a cylinder of TFE that he
was certain was full, he found no pressure. Many
chemists might have thought the cylinder had
leaked its contents, but the observant Plunkett
noted that the cylinder had not lost weight. Charles
Pederson reflected on this day in his Nobel Lau-
reate lecture of December 8, 1987, “.I noticed
commotion in the laboratory of Roy Plunkett,
which was across the hall from my own. I investi-
gated and witnessed the sawing open of a cylinder
from which was obtained the first sample of
TeflonÒ fluoropolymer.” After opening, shaking the
1
2 F LUORINATED C OATINGS
Figure 1.1 Photographic reenactment of the discov-
ery of polytetrafluoroethylene in Roy Plunkett’s Labo-
ratory in Jackson Laboratory April 6, 1938.
Courtesy of DuPont.
cylinder upside down yielded a few grams of a
waxy looking white powderdthe first polymer of
TFE (see Figure 1.1).
Plunkett analyzed the white powder and it was
conclusively proven to be polytetrafluoroethylene
(PTFE). The slippery PTFE could not be dissolved
in any solvent, acid, or base, and upon melting,
formed a stiff clear gel without flow. Later, research
led to the discovery of processing techniques similar
to those used with metal powders (sintering). At the
time, the Manhattan Project was seeking new
corrosion-resistant materials for gaskets, packings,
and liners for uranium hexafluoride (UF6) handling.
PTFE provided the answer and was used in pro-
duction. The US government maintained a veil of
secrecy over the PTFE project until well after the
end of World War II. For security reasons, it was
called by a code name, K 416. The US government
took all of the output from the small, heavily
guarded, production plant located in Arlington, New
Jersey. Commercial production was therefore
delayed until 1947. Plunkett patented it in US Patent
2,230,654 on February 4, 1941. Because of the
secrecy, no other patents issued until Brubaker’s
patent 2,393,967 in 1947.
Large-scale monomer synthesis and controlled
polymerization were technical problems to be
AND F INISHES H ANDBOOK
resolved. Intensive studies solved these problems and
small-scale production of TeflonÒ (trademarked in
1944, but not publicly revealed until 1946) began in
1947. In 1950, DuPont scaled up the commercial
production of TeflonÒ in the United States with the
construction of a new plant in Parkersburg, West
Virginia. In 1947, Imperial Chemical Industries built
the first PTFE plant outside the United States, in
Western Europe. Since then, many more plants have
been built around the globe. Over the last six decades,
many forms of PTFE and copolymers of other
monomers and TFE have been developed and
commercialized.
The words of Plunkett himself best summarize the
discovery of PTFE. He recounted the story of TeflonÒ
in a talk to the American Chemical Society at its
April 1986 meeting in New York. “The discovery of
polytetrafluoroethylene (PTFE) has been variously
described as:
1. An example of serendipity
2. A lucky accident
3. A flash of genius.
Perhaps all three were involved. There is com-
plete agreement, however, on the results of that
discovery. It revolutionized the plastics industry and
led to vigorous applications not otherwise possible.”
The discovery created a new industry, with annual
sales of fluoropolymers of billions of dollars and
value added to tens of billions dollars.
Fluoropolymers have entered every aspect of
human life, often unseen yet functional, and the
extension of fluorine chemistry has revolutionized
many industries from pharmaceutical to prosthetics to
crop protection to space craft.
A timeline of the discovery of other fluoropol-
ymers is found later in this chapter in Section 1.2.3.
1.2 What Are Fluoropolymers?
Traditionally, a fluoropolymer or fluoroplastic is
defined as a polymer consisting of carbon (C) and
fluorine (F). The monomers used to make the various
fluoropolymers are shown in Figure 1.2.
The following sections briefly describe the struc-
tures and properties of the various fluoropolymers. It
is important to keep in mind that there are variations
in most of these polymers. The most common
1: F LUOROPOLYMERS 3

Tetrafluoroethylene (TFE) Ethylene

Hexafluoropropylene (HFP) Perfluoromethyl Vinyl ether (PMVE)

Perfluoroethyl Vinyl ether (EVE) Perfluoropropyl Vinyl ether (PPVE)

Chlorotrifluoroethylene (CTFE) Vinyl Fluoride (VF)

Vinylidene Fluoride (VF2)

Figure 1.2 Structures of many monomers used to make fluoropolymers.

variation is the molecular weight, which will affect 1.2.1.1 Polytetrafluoroethylene

the melting point somewhat, and the viscosity of the
An example of a linear fluoropolymer is the TFE
polymer above its melt point, properties that are
polymer (PTFE) discovered by Plunkett. Its structure
very important in determining processing conditions
in simplistic form is shown in Figure 1.3.
and use.
Formed by the polymerization of TFE, the
(eCF2eCF2e) groups repeat many thousands of
times. To understand some of the properties of PTFE,
the structure is better viewed in a ball and stick model
1.2.1 Perfluorinated Polymers
or a space filling three-dimensional model, which are
As mentioned in the previous section, a fluoropol- shown in Figure 1.4. It is important to understand the
ymer or fluoroplastic is defined as a polymer con- basic properties of fluoropolymers when learning
sisting of primarily carbon (C) and fluorine (F).
Sometimes these are referred to as perfluoropolymers
to distinguish them from partially fluorinated poly-
mers, fluoroelastomers, and other polymers that
contain lesser amounts fluorine (by weight percent) in
their chemical structure. For example, fluorosilicone
and fluoroacrylate polymers are not referred to as
fluoropolymers. Figure 1.3 Structure of polytetrafluoroethylene.
4 F LUORINATED C OATINGS
Figure 1.4 Three-dimensional representations of
polytetrafluoroethylene (gray is carbon, green is
fluorine).
about coating properties. The polymer properties are
retained to varying degrees in the formulated finishes.
The fundamental properties of fluoropolymers evolve
from the atomic structure of fluorine and carbon and
their covalent bonding in specific chemical structures.
Because PTFE has a linear structure, it is a good
subject for discussion of extreme properties. The
backbone is formed of carbonecarbon bonds and
carbonefluorine bonds. Both are extremely strong
bonds (CeC ¼ 607 kJ/mol and CeF ¼ 552 kJ/mol).
The basic properties of PTFE stem from these two
very strong chemical bonds. PTFE as pictured in
Figure 1.4 shows a rodlike shape even though it
shows only a small section of the molecule. The size
of the fluorine atom allows the formation of a uni-
form and continuous covering around the carbone
carbon bonds and protects them from attack, thus
imparting chemical resistance and stability to the
molecule. PTFE is rated for use up to 500 F. PTFE
does not dissolve in any common solvent. The fluo-
rine sheath is also responsible for the low surface
energy (18 dyn/cm) and low coefficient of friction
(0.05e0.8, static) of PTFE. Another attribute of the
uniform fluorine sheath is the electrical inertness (or
nonpolarity) of the PTFE molecule. Electrical fields
impart only slight polarization in this molecule, so
volume and surface resistivity are high.
The PTFE molecule is simple and is quite ordered,
so it can align itself with other molecules or other
portions of the same molecule. These three-
dimensional representations are particularly useful
in showing this. Disordered regions are called amor-
phous regions. This is important because polymers
with high crystallinity require more energy to melt. In
other words, they have higher melting points.
AND F INISHES H ANDBOOK
When this happens, it forms what is called a
crystalline region. Crystalline polymers have a sub-
stantial fraction of their mass in the form of parallel,
closely packed molecules. High-molecular weight
PTFE resins have high crystallinity and therefore very
high melting points, typically as high as 320e342 C
(608e648 F). The crystallinity in PTFE is typically
92e98%.5 Further, the viscosity in the molten state
(called melt viscosity) is so high that high-molecular
weight PTFE particles do not melt and flow out. They
sinter much like powdered metals; they stick to each
other at the contact points. Reducing the molecular
weight can significantly change this and these mate-
rials are discussed in Chapter 2.3.4.
The polymerization process must have a start and
an end (initiation and termination). Therefore, there
are endgroups that may not be much like the rest of
the polymer. Endgroups are present in small con-
centrations when the molecular weight of the poly-
mer is high; however, their presence and type can
affect the degradation behavior.
PTFE is called a homopolymer, a polymer made
from a single monomer. Recently, many PTFE
manufacturers have been adding very small amounts
of other monomers to their PTFE polymerizations to
produce alternate grades of PTFE designed for
specific applications. Generally, polymers made
from two monomers are called copolymers, but
fluoropolymer manufacturers still call these grades
homopolymer. Chemours grades of this type are
called TeflonÒ NXT Resins. These modified gran-
ular PTFE materials retain the exceptional chemical,
thermal, antistick, and low-friction properties of
conventional PTFE resin, but offer some improve-
ments such as:
1. Improved permeation resistance
2. Less creep
3. Smoother, less porous surfaces
4. Better high-voltage insulation.
The copolymers described in the next sections
contain significantly more of the non-TFE monomers.
1.2.1.2 Fluorinated Ethylene Propylene
Copolymer
If one of the fluorine atoms on TFE is replaced
with a trifluoromethyl group (eCF3), then the new
monomer is called hexafluoropropylene (HFP).
1: F LUOROPOLYMERS
Figure 1.5 Chemical structure of fluorinated ethylene
propylene copolymer.
Polymerization of monomers (HFP) and TFE yield a
different fluoropolymer called fluorinated ethylene
propylene (FEP). The number of HFP groups is
typically 5% or less. This basic structure is shown in
Figure 1.5.
To understand some of the properties of FEP, the
structure is better viewed in a ball and stick model or
a space filling three-dimensional model as shown in
Figure 1.6.
The effect of this small change is to put a “bump”
along the polymer chain. This disrupts the crystalli-
zation of the FEP, which has a typical as-polymerized
crystallinity of 70% versus 98% for PTFE. It also
lowers its melting point. The reduction of the melting
point depends on the amount of trifluoromethyl groups
added and secondarily on the molecular weight, but
most FEP resins melt around 274 C (525 F), though
lower melting points are possible. Even high-
molecular weight FEP will melt and flow. The high
chemical resistance, low surface energy, and good
electrical insulation properties of PTFE are retained.
1.2.1.3 Perfluoroalkoxy Polymers
Making a more dramatic change in the side group,
chemists put a perfluoroalkoxy (PFA) group on the
Figure 1.6 Three-dimensional representations of
fluorinated ethylene propylene (gray is carbon, green
is fluorine).
5
Figure 1.7 Chemical structure of perfluoroalkoxy
polymer.
polymer chain. This group is signified as eOeRf,
where Rf can be any number of totally fluorinated
carbons. A typical group is perfluoropropylether
(eOeCF2eCF2eCF3). These polymers are called
PFA and the perfluoroalkylvinylether group is typi-
cally added at only a couple mole percent. Another
common PFA group is perfluoromethylether
(eOeCF3) making a polymer called MFA. A
structure of PFA is shown in Figure 1.7.
The large side group reduces the crystallinity
drastically. This is apparent in the three-dimensional
structures shown in Figure 1.8. The melting point is
generally between 305 C and 310 C (581e590 F)
depending on the molecular weight. The melt vis-
cosity is also dramatically dependent on the molecular
weight. Since PFA is still perfluorinated as with FEP,
the high chemical resistance, low surface energy,
and good electrical insulation properties are retained.
1.2.1.4 Teflon AF®
A perfluorinated polymer made by Chemours
called Teflon AFÒ breaks down the crystallinity
completely, hence its designation amorphous fluo-
ropolymer (AF). It is a copolymer (Figure 1.9) made
from 2,2-bistrifluoromethyl-4,5-difluoro-1,3-dioxole
and TFE.
To understand some of the properties of PFA, the
structure is better viewed in a ball and stick model or
a space filling three-dimensional model as shown in
Figure 1.10. The large side group reduces the crys-
tallinity drastically. The melting point is generally
between 305 C and 310 C (581e590 F) depending
on the molecular weight. The melt viscosity is also
dramatically dependent on the molecular weight.
Since PFA is still perfluorinated as with FEP, the high
chemical resistance, low surface energy, and good
electrical insulation properties are retained.
6 F LUORINATED C OATINGS
Figure 1.8 Three-dimensional representations of
perfluoroalkoxy (gray is carbon, green is fluorine,
red is oxygen, and the small pink balls are the
electron pairs on the oxygen atom).
The Teflon AFÒ family of amorphous fluoropol-
ymers is similar to TeflonÒ PTFE and PFA in many of
the usual properties, but is unique in the following
ways:
1. It is a true amorphous fluoropolymer
2. It has somewhat higher coefficient of friction
than TeflonÒ PTFE and PFA
Figure 1.9 The chemical structure of TeflonÒ AF
polymer.
AND F INISHES H ANDBOOK
Figure 1.10 Three-dimensional representations of
TeflonÒ AF (gray is carbon, green is fluorine, and
red is oxygen).
3. It has excellent mechanical and physical prop-
erties at end-use temperature up to 300 C
(572 F)
4. It has excellent light transmission from ultravi-
olet (UV) through a good portion of infrared
5. It has very low refractive index
6. It has lowest dielectric constant of any plastic
even at gigahertz frequencies
7. It has solubility to a limited extent in selected
perfluorinated solvents.
TeflonÒ AF can be designed to have some solu-
bility in selected perfluorinated solvents but remains
chemically resistant to all other solvents and process
chemicals. The solubility is typically only 3e15% by
weight, but this allows you to solution-cast extremely
thin coatings in the submicron thickness range.
1: F LUOROPOLYMERS 7

1.2.1.5 Other Fully Fluorinated Polymers

Inevitably, polymerization of more than two
monomers would be made by the polymer chemists.
Terpolymer is the term generally applied to these
kinds of polymers. There are a few commercial
examples. One such terpolymer is a polymer of TFE,
HFP, and vinylidene fluoride. It provides a combi-
nation of performance advantages different than
any other melt processible fluorothermoplastic. It
is called DyneonÒ THVÒ fluorothermoplastic.
Another terpolymer is made from HFP, TFE, and
ethylene and is called DyneonÒ HTEÒ. Another
example is ethylene tetrafluoroethylene (ETFE),
which usually contains a small amount of
Figure 1.12 Three-dimensional representations of
Perfluorobutyl ethylene (PFBE) to enhance stress
ethylene tetrafluoroethylene (gray is carbon, green
crack resistance and mechanical properties.
is fluorine, and white is hydrogen).

1.2.2 Partially Fluorinated

Polymers
If monomers have other atoms such as hydrogen or
chlorine in place of any fluorine atoms, then homo-
polymers made from that monomer are considered
partially fluorinated polymers. Similarly, if a copol-
ymer has a monomer that contains other atoms, then
that copolymer is also considered to be partially
fluorinated.
1.2.2.1 ETFE Copolymers
ETFE is a copolymer of ethylene and TFE
(Figure 1.11). The basic molecular structure of ETFE
is shown in Figure 1.11.
This simplistic structure shows alternating units of
TFE and ethylene. While this can be readily made,
many grades of ETFE vary the ratio of the two
monomers to optimize properties for specific end
uses. The space filling models of ETFE structure are
shown in Figure 1.12.
ETFE is a fluoroplastic with excellent electrical
and chemical properties. It also has excellent me-
chanical properties. ETFE is especially suited for
Figure 1.11 The chemical structure of ethylene tet-
rafluoroethylene copolymers.
uses requiring high mechanical strength, chemical,
thermal, and/or electrical properties. The mechanical
properties of ETFE are superior to those of PTFE and
FEP. ETFE has:
1. Excellent resistance to extremes of tempera-
ture; ETFE has a working temperature range
of 200 C to 150 C
2. Excellent chemical resistance
3. Good mechanical strength with excellent
tensile strength and elongation and has supe-
rior physical properties compared to most
fluoropolymers
4. With low smoke and flame characteristics,
ETFE is rated 94V-0 by the Underwriters Lab-
oratories Inc. It is odorless and nontoxic
5. Outstanding resistance to weather and aging
6. Excellent dielectric properties
7. Nonstick characteristics.
1.2.2.2 Ethylene Fluorinated Ethylene
Propylene Terpolymers
Ethylene fluorinated ethylene propylene (EFEP)
is a terpolymer of ethylene, TFE, and HFP
(Figure 1.13). At the present time, it is made only
by Daikin. The basic molecular structure of EFEP
is shown in Figure 1.13.
This simplistic structure shows three monomers,
HFP, TFE, and ethylene. The ratio of the
8 F LUORINATED C OATINGS AND F INISHES H ANDBOOK

Figure 1.13 The chemical structure of ethylene Figure 1.14 The chemical structure of polyvinylidene
fluorinated ethylene propylene terpolymers. fluoride.

ingredients is not 1:1:1 as indicated by the struc-

ture. The polymer retains ETFE-like toughness but
processes at a lower temperature. Its properties in
summary are:

1. Very low processing temperature

2. Excellent thermal stability
3. Low coefficient of friction
4. Good nonstick
5. High transparency
6. Excellent chemical resistance Figure 1.15 Three-dimensional representations of
7. Good electrical properties polyvinylidene fluoride (gray is carbon, green is
8. High purity fluorine, and white is hydrogen).
9. Excellent weathering.

1.2.2.3 Polyvinylidene Fluoride equipment and long-life architectural finishes on

The polymers made from 1,1-di-fluoro-ethene (or
vinylidene fluoride) are known as polyvinylidene
fluoride (PVDF). They are resistant to oils and fats,
water and steam, and gas and odors, making them of
particular value for the food industry. PVDF is known
for its exceptional chemical stability and excellent
resistance to UV radiation. It is used chiefly in the
production and coating of equipment used in
aggressive environments, and where high levels of
mechanical and thermal resistance are required. It
has also been used in architectural applications as a
coating on metal siding, where it provides excep-
tional resistance to environmental exposure. The
chemical structure of PVDF is shown in Figure 1.14.
One of the trade names of PVDF is KYNARÒ. The
alternating CH2 and CF2 groups along the polymer
chain (see Figures 1.14 and 1.15) provide a unique
polarity that influences its solubility and electric
properties. At elevated temperatures, PVDF can be
dissolved in polar solvents such as organic esters and
amines.
This selective solubility offers a way to prepare
corrosion-resistant coatings for chemical process
building panels.
Key attributes of PVDF include:
1. Mechanical strength and toughness
2. High abrasion resistance
3. High thermal stability
4. High dielectric strength
5. High purity
6. Readily melt processible
7. Resistant to most chemicals and solvents
8. Resistant to UV and nuclear radiation
9. Resistant to weathering
10. Resistant to fungi
11. Low permeability to most gases and liquids
12. Low flame and smoke characteristics.
Architectural coatings contain a minimum of 70%
by weight of PVDF resin. The coating is usually
applied in a factory by coil coating, where it can be
accurately baked. The coated flat panels are formed
1: F LUOROPOLYMERS
by bending or stamping before use. The coating
provides the following properties in this application:
1. Color retention
2. Chalk resistance
3. Corrosion resistance
4. Flexibility
5. Stain resistance
6. Overall exterior durability.
1.2.2.4 Polyvinyl Fluoride
Polyvinyl fluoride (PVF) is a homopolymer vinyl
fluoride. The following is the molecular structure of
PVF (Figure 1.16) and the three-dimensional repre-
sentation is shown in Figure 1.17.
Chemours is the only known manufacturer of this
polymer and they call it as TedlarÒ. The structure
above shows a head-to-tail configuration of the CF
monomer; there are no fluorine atoms on adjacent
carbons. But in reality, vinyl fluoride polymerizes in
Figure 1.16 The chemical structure of polyvinyl
fluoride.
Figure 1.17 Three-dimensional representations of
polyvinyl fluoride (gray is carbon, green is fluorine,
and blue is hydrogen in this Figure).
9
both head-to-head and head-to-tail configurations.
Chemours’ commercial PVF contains 10e12% of
head-to-head and tail-to-tail units, also called
inversions.6
PVF has excellent resistance to weathering, stain-
ing, and chemical attack (except ketones and esters).
It exhibits very slow burning and low permeability to
vapor. Its most visible use is on the interiors of the
passenger compartments of commercial aircraft.
PVF is generally available only in film form.
ChemoursÔ TedlarÒ films are available as clear,
translucent, or opaque white film and in several
surface finishes. There is one commercial coating
application. It is used to coat automotive brakes
lines, where it offers an improvement in corrosion
protection.
1.2.2.5 Ethylene Chlorotrifluoroethylene
Copolymer
Ethylene chlorotrifluoroethylene (ECTFE) is a
copolymer of ethylene and chlorotrifluoroethylene.
The molecular structure of ECTFE is shown in
Figures 1.18 and 1.19.
This simplified structure shows the ratio of the
monomers being one-to-one and strictly alternating,
but this is not required. Commonly known by the
trade name, HalarÒ, ECTFE is an expensive, melt-
processible, semicrystalline, whitish semiopaque
thermoplastic with good chemical resistance and
barrier properties. It also has good tensile and creep
properties and good high-frequency electrical char-
acteristics. Applications include chemically resistant
linings, valve and pump components, barrier films,
and release/vacuum bagging films.
1.2.2.6 Polychlorotrifluoroethylene
Polymers
Polychlorotrifluoroethylene (CTFE) is a homo-
polymer of chlorotrifluoroethylene, characterized
Figure 1.18 The chemical structure of ethylene
chlorotrifluoroethylene copolymer.
10
Figure 1.19 Three-dimensional representations of ethylene chlorotrifluoroethylene (gray is carbon, yellow-green
is fluorine, large green is chlorine, and white is hydrogen).
Figure 1.20 The chemical structure of polychlorotri-
fluoroethylene copolymer.
by the chemical structural formula shown in
Figures 1.20 and 1.21.
The addition of the one chlorine bond contributes
to lower the melt viscosity to permit extrusion and
injection molding. It also contributes to the trans-
parency, the exceptional flow, and the rigidity char-
acteristics of the polymer. Fluorine is responsible for
its chemical inertness and zero moisture absorption.
Therefore, CTFE has unique properties. Its resistance
to cold flow, dimensional stability, rigidity, low gas
permeability, and low moisture absorption is superior
to any other fluoropolymer. It can be used at very low
temperatures.
1.2.2.7 Fluoroalkyl-Modified Polymers
There are many polymers reported in the academic
literature and by industry that take standard polymers
like polyesters, acrylics, and polyimides and include
monomers containing perfluorinated side groups.7
Figure 1.21 Three-dimensional representations of polychlorotrifluoroethylene (gray is carbon, yellow-green is
fluorine, and large green is chlorine).
F LUORINATED C OATINGS AND F INISHES H ANDBOOK
These perfluorinated side groups frequently impart
property improvements even when the amount of
fluorine added is small. The groups tend to concen-
trate themselves on coating surfaces. Partially fluo-
rinated fluoropolymers are significantly different
from the perfluoropolymers with respect to properties
and processing characteristics. For example, per-
fluoropolymers are more thermally stable but physi-
cally less hard than partially fluorinated polymers.
The former has much higher “hardness” than the
latter.
While there are literally thousands of fluorine-
containing polymers described in technical litera-
ture, and those known only in the laboratory, this
section focuses only on commercially available ma-
terials. There are a series of fluoropolymer coatings
aimed at architectural applications. Some of these are
coatings based on mixtures of nonfluoropolymers
with a fluoropolymer such as KynarÒ, but a couple
are tailored special fluoropolymers.
1. PPG: CoraflonÒ
2. Asahi Glass: LumiflonÒ
3. DOW Corning: Fluorosilicone hybrid
technology.
One polymer deserves special mention, Lumi-
flonÒ. LumiflonÒ is the trade name applied to a
series of optimized molecules generally called
1: F LUOROPOLYMERS
Figure 1.22 The chemical structure of LumiflonÒ.
fluoroethylene vinyl ether (FEVE).8 The general
structure is shown in Figure 1.22. This structure is
similar to the material DOW Corning calls TFEC
(Tetrafluoroethylene Copolymer).
Its weatherability, solubility, gloss, hardness, and
flexibility can be optimized for individual applica-
tions by varying the R-groups and X-groups in this
structure. The fact that it is soluble and cross-linkable
is significant and it also can be formulated into air-
dry or low-bake coatings.
When properly designed, the molecule has the
following characteristics:
1. Excellent weatherability. It retains a lot of the
fluoropolymer properties such as good chemi-
cal stability and has excellent weatherability
as expected from many common hydrocarbon-
based coating resins
2. The polymer can be dissolved in several
organic solvents
3. It can be designed to give you a choice of
curing conditions from ambient temperatures
to high temperatures
4. It has good appearance, it is a transparent fluo-
roresin, and so both clear film and light solid
color are possible including high gloss.
Figure 1.23 Discovery timeline of the major fluoropolymer types.
11
1.2.3 Fluoropolymer Discovery
Timeline
A timeline of the discovery of the major fluo-
ropolymer types is shown in Figure 1.23. It is apparent
that there have not been any new types discovered in
over 30 years. However, while this is true, there have
been many minor modifications through the intro-
duction of small amounts of comonomers, changes in
the polymerization processes, control or modification
of endgroups and molecular weights, and post-
polymerization processing.
1.3 Comparison of Fluoropolymer
Properties
The properties of neat or pure fluoropolymers can
have a direct impact on fluorocoatings containing
them. These are thoroughly documented in other
books of the PDL Hand Book Series. Mechanical
properties such as tensile strength, modulus, and
elongation affect coating durability and postform-
ability (bending and stretching).9 Thermal properties
affect the continuous use temperature of coating
systems.10 Tribology (friction and wear),11 perme-
ability,12 weathering,13 and irradiation properties14
can also be important. These references may also
include data on the binder polymers discussed
in Chapter 4. The following sections are some
mechanical, thermal, chemical resistance, and elec-
trical properties. Tribology and permeability are
covered in Chapters 15 and 14, respectively. Weath-
ering and irradiation properties are not included and
12
the references should be consulted if these are
needed.
Some properties for the fluoropolymers are
contained in Appendix 1.
References
1. Ebnesajjad S. Fluoroplastics. Non-melt process-
ible fluoroplastics, the definitive user’s guide and
databook. 2nd ed., vol. 1. Norwich, NY: William
Andrew, Inc.; 2014.
2. Ebnesajjad S. Fluoroplastics. Melt processible
fluoroplastics, the definitive user’s guide and
databook. 2nd ed., vol. 2. Norwich, NY: William
Andrew, Inc.; 2015.
3. Plunkett RJ. US patent 2,230,654, assigned to
Chemours Co. Febrauary 4, 1941.
4. Plunkett RJ. The history of polytetrafluoro-
ethylene: discovery and development.
In: Seymour RB, Kirshenbaum GS, editors. High
performance polymers: their origin and devel-
opment, proc. symp. hist. high perf. polymers, at
the ACS meeting in New York, April 1986.
New York: Elsevier; 1987.
5. Gangal SV. Polytetrafluoroethylene, homopoly-
mers of tetrafluoroethylene. In: Encyclopedia of
polymer science and engineering. 3rd ed., vol. 11.
New York: John Wiley & Sons; 1980. p. 25e35.
F LUORINATED C OATINGS AND F INISHES H ANDBOOK
6. Lin FMC. Chain microstructure studies of
poly(vinyl fluoride) by high resolution NMR
spectroscopy [Ph.D. dissertation]. University of
Akron; 1981.
7. Anton D. Surface-fluorinated coatings. Adv Mater
1998;10(15):1197e205.
8. Asakawa A. Performance of durable fluoropol-
ymer coatings. Paint Coat Ind September
2003;19(9).
9. McKeen L. The effect of creep and other time
related factors on plastics and elastomers. 3rd ed.
Waltham, MA: William Andrew; 2014.
10. McKeen L. The effect of long term thermal
exposure on plastics and elastomers. Waltham,
MA: William Andrew; 2013.
11. McKeen L. Fatigue and tribological properties of
plastics and elastomers. 2nd ed. Waltham, MA:
William Andrew; 2009.
12. McKeen L. Permeability properties of plastics
and elastomers. Waltham, MA: William Andrew;
2011.
13. McKeen L. The effect of UV light and weather on
plastics and elastomers. Waltham, MA: William
Andrew; 2013.
14. McKeen L. The effect of sterilization on plastics
and elastomers. Waltham, MA: William Andrew;
2012.
 2 Producing Fluoromonomers, Fluoropolymers,
and Fluoropolymer Finishing
This chapter will summarize some of the processes
used to make fluoropolymers and the monomers used
to make them. The processing steps used to take the
fluoropolymer from the reactor to a form that cus-
tomers can buy and use will also be covered. This
includes dispersions and powders. A summary of the
polymerization surfactants and aids that have seen
worldwide news coverage will also be summarized.
Further detail is available in another volume of this
series.1 Tables of commercial dispersions and pow-
ders are also included.
2.1 Monomers
In this section, synthesis of polytetrafluoroethylene
(PTFE) and properties of major monomers for poly-
merization of melt-processible fluoropolymers used in
the majority of coatings are discussed. Tetrafluoro-
ethylene (TFE) is the primary monomer. As described
earlier in Chapter 1, small amounts of other monomers
are incorporated in the TFE polymer structure to
modify its properties and processing characteristics.
These monomers include hexafluoropropylene (HFP)
and perfluoroalkylvinylethers (PAVEs). A number of
specialty monomers, though less common, are also
used to modify the PTFE structure but are discussed in
previous volumes of this series.1e5
2.1.1 Synthesis of TFE
TFE (CF2]CF2, also known as R1114) is the main
building block of all perfluorinated polymers.
Commercially important techniques for TFE prepara-
tion use a mined mineral fluorspar (CaF2) and sulfuric
acid to make hydrofluoric acid (HF), and chloroform as
the starting ingredients.6e13 The reaction scheme is
shown in Eqns (2.1)e(2.4). HF preparation:
CaF2 þ H2SO4 / 2HF þ CaSO4
Chloroform preparation:
CH4 þ 3Cl2 / CHCl3 þ 3HCl
Fluorinated Coatings and Finishes Handbook. http://dx.doi.org/10.1016/B978-0-323-37126-1.00002-3
Copyright © 2016 Elsevier Inc. All rights reserved.
Chlorodifluoromethane preparation:
CHCl3 þ 2HF / CHClF2
þ 2HCl (SbF3 catalyst) (2.3)
TFE synthesis:
2CHClF2 4 CF2]CF2 þ 2HCl (pyrolysis) (2.4)
More detail is available in the literature.1
2.1.2 Synthesis of HFP
HFP (CF3CF]CF2, also known as R1216) is used
as a comonomer in a number of fluoropolymers such
as fluorinated ethylene propylene (FEP) copolymer.
It is also used to “modify” the properties of
homofluoropolymers. HFP has been prepared in a
number of ways. Excellent HFP yields from the
thermal degradation of sodium heptafluorobutyrate
(CF3CF2CF2COONa) have been reported.14 Cracking
TFE in a stainless steel tube at 700 C to 800 C
under vacuum also produces HFP. Thermal decom-
position of PTFE under 20 torr vacuum at 860 C
yields 58% HFP.15
A more recently developed technique is the py-
rolysis of a mixture of TFE and carbon dioxide at
atmospheric pressure at 700 Ce900 C. Conversions
of 20e80% and HFP yields of better than 80% were
obtained.16
2.1.3 Synthesis of PAVEs
PAVEs are synthesized according to the steps
shown in Eqns (2.5)e(2.7).
1. HFP is converted to hexafluoropropylene
epoxy (HFPO) by reaction Eqn (2.5) with
hydrogen peroxide or another oxidizer in a
basic pH solution.17
(2.1)
ð2:5Þ
(2.2)
13
14
2. The HFPO is reacted with a perfluorinated
acyl fluoride to produce perfluoro-2-alkoxy-
propionyl fluoride according to Eqn (2.6):
ð2:6Þ
3. Perfluoro-2-alkoxy-propionyl fluoride is reacted
with sodium carbonate at high temperature18:
ð2:7Þ
2.1.4 Properties of Monomers
TFE is a colorless, odorless, tasteless, nontoxic
gas, which boils at 76.3 C and freezes
at 142.5 C. Critical temperature and pressure of
TFE are 33.3 C and 39.2 MPa. TFE is stored as a
liquid; vapor pressure at 20 C is 1 MPa. Its heat of
formation is reported to be 151.9 kcal/mol. Poly-
merization of TFE is highly exothermic and gener-
ates 41.12 kcal/mol heat. The extent of exothermic
reaction of TFE polymerization can be seen when
it is compared with the polymerization of vinyl
chloride and styrene, which have heats of polymeri-
zation of 23e26 kcal/mol and 16.7 kcal/mol,
respectively.19
Polymerization of TFE to high-molecular weight
requires extremely high purity of the monomer. The
removal of all traces of telogenic hydrogen or
chlorine-bearing impurities is critically important.
The products of the pyrolysis reaction are cooled,
scrubbed with a dilute basic solution to remove HCl,
and dried. The remaining gas is compressed and
distilled to recover the unreacted CHClF2 and to
recover high-purity TFE.20 TFE can autopolymerize
if it is not inhibited (which is how Plunkett discov-
ered PTFE as discussed in Chapter 1). Common TFE
autopolymerization inhibitors include a variety of
terpenes, such as a-pinene, terpene B, and D-limo-
nene,21 which appear to act as scavengers of oxygen,
a polymerization initiator.
TFE is highly flammable and can undergo violent
deflagration in the absence of air and shown in
Eqn (2.8).
C2F4 / C þ CF4 (2.8)
Heat of reaction values between 57 and 62 kcal/
mol (at 25 C and 1 atm) has been reported for TFE
F LUORINATED C OATINGS AND F INISHES H ANDBOOK
deflagration.19 This is similar to the amount of heat
released by the explosion of black gunpowder. Ex-
plosion is always a concern to manufacturers. To
eliminate transportation accident concerns, TFE
preparation and polymerization are usually carried
out at the same site. Mixtures of TFE with carbon
dioxide are known to be fairly safe.
HFP (CF3CF]CF2) is used as a comonomer in a
number of fluoropolymers including FEP copolymer.
It is also used to “modify” the properties of
homofluoropolymers.
HFP is a colorless, odorless, tasteless, and rela-
tively low-toxicity gas, which boils at 29.4 C and
freezes at 156.2 C. Critical temperature and pres-
sure of HFP are 85 C and 3254 MPa. Unlike TFE,
HFP is extremely stable with respect to autopoly-
merization and may be stored in liquid state without
the addition of telogen.22
Perfluoropropylvinylether (PPVE) is a commer-
cially significant example of PAVEs. PPVE is an
odorless, colorless liquid at room temperature. It is
extremely flammable and burns with a colorless
flame. It is less toxic than HFP and copolymerizes
with TFE.
2.2 Polymerization
A general understanding of the polymerization
process is useful and can be applied to coatings
technology. Impurities and endgroups are affected by
the polymerization chemistry and they can impact the
performance of coatings. Some of this technology is
included at this time. Other volumes of this series24
describe the polymerization processes and history in
great detail for most of the commercial fluoropol-
ymers. This text will discuss the polymerization
process in general, and the details of a couple poly-
merizations that demonstrate the general concepts,
leaving the details to the polymer chemists and
engineers.
All the monomers used to make homopolymers
and copolymers are unsaturated (they have a
carbonecarbon double bond). The polymerization is
generally free radical as described by the following
scheme as shown in Eqns (2.9)e(2.15).
ð2:9Þ
2: P RODUCING F LUOROMONOMERS , F LUOROPOLYMERS ,
This reaction is called a polyaddition reaction and
generally proceeds by a free radical addition mech-
anism or ionic polymerization mechanism.23
This is a chain reaction, with each monomer being
added to the chain end, which lengthens the chain, but
keeps the end reactive. Most fluoropolymer-producing
reactions proceed by the free radical mechanism.
A general description of free radical polymeriza-
tion makes the understanding of the fluoropolymer
variants of it easier to understand. Basically, there are
four types of chemical reactions occurring.
First, there is a process that starts the polymeri-
zation, called chain initiation. It is like the spark of
the process and it generates a highly reactive mole-
cule called a radical. These are generated usually by
heating up a reactive molecule called an initiator.
The following equation describes initiation:
ReR0 / R þ R0  (2.10)
The initiator (ReR0 ) breaks into two radicals
 0 
(R and R ). The radicals are highly reactive and
generally cannot be isolated; they are transient. The
double bonds in the monomer molecules (M) are
attacked by the radical and opened up transferring the
radical to the end of the chain. The process that
continues is called chain propagation.
R þ M / RM (2.11)
The monomer continues to add, building a long
linear polymer:
RM þ M / RMM (2.12)
RMMn þ M / RMMnþ1 (2.13)
This goes on while there is plenty of monomer
present. Eventually, it does stop. The radical can be
transferred to a molecule (YZ) in a step called chain
transfer. The molecule YZ is usually called a chain
transfer agent.
RMMn þ YZ / RMMnY þ Z (2.14)
The polymer molecule stops growing, but a new
radical is formed that could start a new polymer
molecule. Eventually, two radicals meet and react to
cancel out the two reactive radicals, halting the chain
reaction.
RMMn þ  MmR / RMnMmR (2.15)
A simple understanding of this scheme should
make the following discussion of PTFE polymeri-
zation easier to understand.
AND F LUOROPOLYMER F INISHING 15
2.2.1 Polymerization of
Homofluoropolymer PTFE
Polymerization of TFE to make PTFE is the only
polymerization that discussed in detail in this book. It
indicates some of the complexity and engineering
difficulties found in fluoropolymer manufacturing.
Further discussions can be found in earlier volumes
of this series.24
TFE is the monomer used for making PTFE. TFE
is polymerized in water in the presence of an initiator,
a surfactant, and other additives (The subject of
surfactant is covered in Chapter 3). Two different
methods of free radical polymerization are common
for production of different types of PTFE. Suspension
polymerization is used to produce granular PTFE
resins. Granular PTFE is extremely high-molecular
weight and is used in molding applications. TFE is
polymerized in water in the presence of a very small
amount of dispersant, or no surfactant accompanied
by vigorous agitation. The dispersant, which acts like
a soap that surrounds the particles in the water and is
rapidly consumed during the initial phase of poly-
merization reaction, forms small particles that seed
the aqueous medium. Further polymerization occurs
in gas phase because of the absence of a surfactant,
thus leading to the precipitation of the polymer.
Emulsion or dispersion polymerization is the
method used to manufacture dispersion and fine pow-
der PTFE products. These are the PTFE materials
generally used in coatings. Fine powder resins are also
called coagulated dispersion, which is descriptive of
their production method, described later in this chapter
(Section 2.3.3). Mild agitation, plentiful dispersant,
and a wax additive set the dispersion polymerization
apart from the suspension method. Dispersion and fine
powder products are polymerized by the same method.
The finishing steps convert the polymerization product,
which is dispersion, to the two different product forms.
Familiarity with the important types of PTFE and
the commercially significant technologies of pro-
ducing them helps with better understanding coat-
ings. Although the exact polymerization technologies
being practiced by resin manufacturers are closely
guarded secrets, the descriptions and discussions of
the important public disclosures in patents and other
publications should provide an adequate under-
standing of the subject.
Polymerization of TFE proceeds by a free radical
mechanism. An initiator (sometimes called a catalyst)
starts the reaction. The choice of the initiator is based
16
on the desired reaction temperature. If polymerization
is carried out at low temperatures (<30 C), a redox
catalyst, such as potassium permanganate, is used
(These compounds ionize into charged fragments
such as KMNO4 þ Water / Kþ þ MNO 4 ). A
bisulfite or persulfate is the typical initiator for higher
temperature TFE polymerization. The initiator affects
the endgroups of the PTFE at a different stage of the
polymerization. The key point is that there is no sulfur
when persulfate is the initiator. Bisulfite initiators
form sulfonic acid endgroups, which can influence
thermal stability and color.
The free radical mechanism discussed here is
exactly analogous to the general discussion of free
radical polymerization discussed earlier in this
chapter (Section 2.2). The reaction is initiated by a
catalyst or by an initiator. A persulfate is the typical
initiator for higher temperature TFE polymerization.
The reaction scheme for persulfate initiation is
shown in Eqns (2.16)e(2.21).
Initiator fragments, or free radicals, are formed by
degradation of persulfate under heat as shown in
Eqn (2.16).
K2 S2 O8 þ Heat/2SO4  þ 2Kþ (2.16)
Initiation takes place by formation of new free
radicals by reaction of persulfate fragments with TFE
dissolved in the aqueous phase:
SO4  þ CF2 ]CF2 / SO4 CF2 eCF2  (2.17)
Propagation is the growth of the free radicals of
the initiation step by further addition of TFE:
 ymers of PTFE due to the difficulty and slow rate of
SO4(CF2eCF2) þ nCF2]CF2 /
 void closure in this polymer. Voids affect permeation
SO4(CF2eCF2)ne(CF2eCF2) (2.18)
Free radicals undergo hydrolysis where a hydroxyl
endgroup replaces the sulfate eventually forming an
acid endgroup:
 A reduction in the viscosity of PTFE without exten-
SO4(CF2eCF2)ne(CF2eCF2) þ H2O /
HO(CF2eCF2)ne(CF2eCF2) þ H2SO4 (2.19)
HO(CF2eCF2)ne(CF2eCF2) þH2O /
COOHCF2e(CF2eCF2)n þ 2HF (2.20)
Termination is the last step before the growth in
molecular weight of the free radicals halts:
COOHeCF2e(CF2eCF2)n þ COOHe
CF2e(CF2eCF2)m / COOHe
(CF2eCF2)mþnþ1eCOOH (2.21)
F LUORINATED C OATINGS AND F INISHES H ANDBOOK
Alternative courses of hydrolysis can affect the
endgroups at a different stage of the polymerization.
TFE polymerizes completely linearly without
branching. This gives rise to a virtually perfect linear
chain structure even at high-molecular weights. The
chains have minimal interactions and crystallize to
form a nearly 100% crystalline structure. Controlling
the crystallinity of the polymer is important in the
development of good mechanical properties. The
only means of controlling the extent of recrystalli-
zation after melting in homopolymers of TFE (no
other comonomer) is by driving up the molecular
weight of the polymer. The extremely long chains of
PTFE have a much better probability of chain
entanglement in the molten phase and little chance to
crystallize to the premelt extent (>90e95%). This is
precisely the reason that it is essential to polymerize
TFE to 106e107 for commercial applications. It is
speculated that molecular weight may be as high as
50 million.25 Molecular weight of PTFE can be
controlled by means of certain polymerization pa-
rameters such as initiator content, telogens, and chain
transfer agents.
Because of the very high-molecular weight of
PTFE, its melt viscosity is extremely high. The melt
creep viscosity of PTFE is 10 GPa (1011 P) at
380 C.26 This is more than a million times too
viscous for melt processing in extrusion or injection
molding. PTFE may be a thermoplastic, but it de-
velops no flow upon melting. The closure of voids in
articles made from this polymer does not take place
with the ease and completeness of the other ther-
moplastics such as polyolefins. A small fraction of
void volume remains in parts made from homopol-
and mechanical properties such as flex life and stress
crack resistance.
The residual voids must be eliminated to improve
mechanical properties and resistance to permeation.
sive recrystallization is required. Many manufac-
turers have polymerized a small amount of a
comonomer with TFE to disrupt the crystalline
structure of PTFE.
All forms of PTFE are produced by batch poly-
merization under elevated pressure in specially
designed reactors. Polymerization media is high-
purity water, which is virtually devoid of inorganic
and organic impurities that impact the reaction by
inhibition and retardation of the free radical
2: P RODUCING F LUOROMONOMERS , F LUOROPOLYMERS ,
polymerization. The surfactant of choice in these
reactions is anionic, and often a perfluorinated car-
boxylic ammonium salt. In general, the important
characteristics of the polymerization processes
include little or no dispersing agent, and vigorous
agitation at elevated temperature and pressure.
Polymerization of TFE is done under constant
pressure conditions to control the molecular weight
and its distribution. It also affects the kinetics of
polymerization. Pressure ranges from 0.03 to
3.5 MPa20 and is held constant by feeding monomer
into the reactor. The initiator and temperature are
interrelated. Ionic, inorganic initiators such as
ammonium persulfate or alkali metal persulfates
such as potassium and lithium persulfates would be
effective in the range of 40e90 C. Organic peroxides
such as bis (o-carboxypropionyl) peroxide also
called disuccinic acid peroxide can also initiate the
polymerization.27 As the temperature is lowered, at
some point the effectiveness of the persulfates is
diminished due to insufficient decomposition rate.
Redox initiators such as potassium permanganate
must replace them.
Water is primarily the heat transfer medium and
does not interfere with the reaction but, even in low
concentrations, most organic chemicals do. Metal
ions such as iron may impart unwanted color.
A small quantity of an anionic dispersing agent
that is predominantly nontelogenic is added to seed
the polymerization. The most common dispersants
were the ammonium salts of perfluorocarboxylic
acids, containing 7e20 carbon atoms. Typical con-
centration of dispersants is 5e500 ppm, which is
insufficient to cause formation of colloidal polymer
particles. In the early stages of polymerization, a
dispersion forms which becomes unstable as soon as
the dispersing agent is consumed. The instability
occurs at fairly low solids content, about 0.2% by
weight. From there on, most of the polymerization
occurs directly onto the larger granular particles,
which are, porous water repellent, therefore, float on
the water. The reaction tends to continue for some
time, even after agitation is stopped, supporting the
direct polymerization hypothesis.
TFE easily polymerizes at moderate pressures and
temperatures. It is necessary to control the rate and to
transfer the significant heat generated by the
exothermic polymerization reaction. This is accom-
plished by circulating a cold fluid through the poly-
merization reactor jacket and cooling the aqueous
phase, which is the heat transfer media. An important
AND F LUOROPOLYMER F INISHING 17
concern in the suspension process is the buildup of
PTFE on the inner wall of the reactor, which reduces
heat transfer. Development of hot spots on the reactor
wall can result in deflagration (exothermic and
explosive), if it goes unchecked.
A typical batch begins with the charging of highly
purified water (resistivity of 18 MU-cm, the purifi-
cation processes involve successive steps of filtration
and deionization) to a reactor which is equipped with
a stirrer, followed by evacuation, and pressurization
with TFE. The feed rate of TFE is controlled to
maintain a constant pressure in the reactor
throughout the polymerization. The content of the
reactor is vigorously agitated at 0.0004e0.002 kg m/
sec/ml. Temperature is controlled by adjusting the
temperature of the coolant medium in the jacket.
Stopping the monomer after a certain feed weight has
been reached ends the polymerization. The reaction
is allowed to continue in order to consume the ma-
jority of the remaining TFE.
A number of different techniques are used for the
polymerization of various monomers. Distinctions
from conventional methods include variables such as
aqueous or nonaqueous medium, batch or continuous
production, and suspension or emulsion regimes.
Ammonium perfluorooctanoate (known APFO,
also C8) was an essential processing aid in the
manufacture of fluoropolymers until recently. It is a
polymerization aid that played a critical role in the
polymerization of TFE and fluorinated comonomers
used to produce PTFE, perfluoroalkoxy (PFAdMFA),
and FEP. It acted as an intermediate for the majority of
fluoropolymers and was eliminated during the finish-
ing steps. This subject is discussed in the next section.
2.2.2 Polymerization
of Surfactants
The following section is an edited version of
Chapter 7 of Sina Ebnesajjad’s book Fluoroplastics,
Volume 1.1 Refer to that work for a more detailed
discussion.
Two types of polymerization technologies are used
to make fluoropolymers: (1) Emulsion and (2) Sus-
pension. Emulsion polymerization of TFE requires
the use of a fluorinated surfactant often referred to as
a polymerization aid. This process is used to make
homopolymers and copolymers as well as fluorinated
elastomers. Suspension polymerization is also
commonly used to make TFE homopolymers and
some types of copolymers. This method, however,
18
does not require a surfactant. A small amount of
surfactant, however, allows a more predictable
commencement and progress of the suspension
polymerization reaction early in the cycle. The
polymerization aid of choice, starting in the 1950s
until the early 2000s, had been ammonium per-
fluorooctanoate, also known as APFO or C8 (CAS
3825-26-1), which is an ammonium salt of per-
fluorooctanoic acid (PFOA). APFO was also used
as a surfactant in a variety of coatings and finishes in
the past.
The abbreviation PFOA has been used rather
loosely in the literature to refer to both acid and salt
forms. There are differences in the properties of the
acid and salt forms. The acid form is substantially
insoluble and is not usually used as a surfactant in the
polymerization of fluoropolymers.
APFO was designated as bioaccumulative and
persistent in the environment by the US Environ-
mental Protection Agency (EPA) in the early 2000s.
Consequently, during the decades of 2000s and
2010s, fluoropolymer manufacturers took steps to
abate environmental emissions by first reducing and
then eliminating the use of APFO from dispersion
products. The industry committed to reduce the
emission of APFO by at least 95% by the year 2010
over the baseline year of 2000. Fluoropolymer
manufacturers further committed voluntarily to work
toward the elimination of the use of APFO entirely by
2015.
Because of the significance of the story, this
chapter includes a brief discussion of the events
leading to the banning of APFO. APFO is an example
of perfluorinated compounds that have drawn the
attention and action of environmental protection
authorities worldwide. The basic chemistry and
technical information covered are applicable to
the development of alternative polymerization
surfactants.
A word of caution to the readers: The subject of
PFOA and APFO contamination has been highly
controversial. In addition to credible scientific in-
formation, a great deal of other information can be
found from a variety of sources. Most of this infor-
mation has not been reviewed through a formal sci-
entific process. Indeed, opinion is a more apt
description of the information. The author has
limited the sources used to describe the issue of
contamination in this chapter to the peer-reviewed
scientific publications and those published by
governmental authorities.
F LUORINATED C OATINGS AND F INISHES H ANDBOOK
The descriptions of perfluorinated organic com-
pounds and contamination in this chapter are far too
brief to do justice to the subject. Readers interested in
a complete understanding of the topic are advised to
study the references listed in this chapter and other
sources. The bias in this chapter is to narrow down
the topic to the status of PFOA and APFO which until
the early 2000s were the surfactants of choice for
PTFE production. One point is certain and that is that
progress in APFO replacement took place rapidly
because of the cooperation among the fluoropolymer
industry, governments, and advocacy groups.
Even though perfluorooctane sulfonate (PFOS) is
not used in polymerization of fluoropolymers, it is
covered in this chapter to tell a more complete story.
The major application of PFOS includes uses in
firefighting and in chromium plating bath. A deriva-
tive of PFOS called perfluorooctanesulfonamide was
used for imparting stain resistance to material sur-
faces, such as carpet.
2.2.2.1 Perfluorooctane Sulfonate
PFOS (Figure 2.1), PFOA (Figure 2.2), and other
similar compounds are part of a chemical family
called fluorinated surfactants.28 In fluorinated sur-
factants, the hydrophobic part of the molecule in-
cludes some fluorine. When all hydrogen atoms in
the hydrophobic segment of the molecule are
replaced with fluorine, the compound is called per-
fluorinated (or Perfluoro-). Perfluorinated surfactants
are members of the group to which PFOS and PFOA
belong. Both are fully fluorinated compounds.29
Perfluorinated surfactants have the unique ability
to lower aqueous surface tension drastically, improve
Figure 2.1 Chemical structure of perfluorooctane
sulfonate (C8F17SO3).
Figure 2.2 Chemical structure of perfluorooctanoic
acid (C8HF15O2).
2: P RODUCING F LUOROMONOMERS , F LUOROPOLYMERS , AND F LUOROPOLYMER F INISHING 19

wetting and leveling, and remain chemically stable
under severe end-use conditions. Fluorinated sur-
factants are significantly more surface active than
analogous hydrogenated compounds. Perfluorinated
surfactants are both hydrophobic and oleophobic on
one end, the latter characteristic renders them surface
active in organic moieties. Perfluorinated surfactants
are resistant to heat and fire, acids, bases, and redox/
oxidizing agents. The ensemble of these unique
properties is not found in other compounds, which
makes their replacement virtually impossible in
many applications. Physical and chemical properties
of PFOS and PFOA have been captured in Table 2.1.
PFOS and its derivatives have the largest con-
sumption volume of all fluorinated surfactants
because of this group’s various applications. They are
used to constitute the active ingredient of well-known
brands for consumer products based on poly-
fluorinated chemistry such as ZonylÒ, ScotchgardÒ,
and StainmasterÒ according to the US Environmental
Agency.30,31
In the year 2000, the total emissions of PFOS and
PFOA reached a peak. After 2001, emissions of both
compounds declined because of the measures taken
to reduce manufacture and consumption and to pre-
vent release to the environment.33
2.2.2.2 Perfluorooctanoic Acid
The structural formula of PFOA (CAS 335-67-1)
and its properties are illustrated in Figure 2.2 and
Table 2.1. Salts of PFOA have been used as a pro-
cessing aid in the manufacture of fluoropolymers. In
contrast to PFOA, which is insoluble in water, its
salts (Table 2.2)30 readily dissolve in water. PFOA
salts are used as a polymerization aid to obtain flu-
oropolymer in emulsion form, improve the physical
properties of the polymer, and increase the rate of
polymerization.
PFOA can also be produced by the breakdown of
some fluorinated telomers, substances that are used in
surface treatment products to impart soil, stain,
grease, and water resistance. Some telomers are also
used as high-performance surfactants in products that
must flow evenly, such as paints, coatings, and
cleaning products, firefighting foams for use on

Table 2.1 Physical and Chemical Properties of PFOS and PFOA32

Property PFOS (Potassium Salt) PFOA

CAS number 2795-39-3 335-67-1
Physical description (physical state White powder White powder/waxy white solid
at room temperature and
atmospheric pressure)
Molecular weight (g/mol) 538 (Potassium salt) 414
Water solubility (mg/l at 25 C) 570 (Purified), 370 (freshwater), 9.5  103 (purified)
25 (filtered seawater)
Melting point ( C) >400 45e50
Boiling point ( C) Not measurable 188
 6
Vapor pressure at 20 C (mmHg) 2.48  10 0.017
6
Airewater partition coefficient <2  10 Not available
(Pa m3/mol)
Octanolewater partition coefficient Not measurable Not measurable
(log Kow)
Organic carbon partition coefficient 2.57 2.06
(log Koc)
Henry’s law constant (atm m3/mol) 3.05  109 Not measurable
Half-life Atmospheric: 114 days Atmospheric: 90 days
Water: >41 years (at 25 C) Water: >92 years (at 25 C)
PFOS, perfluorooctane sulfonate; PFOA, perfluorooctanoic acid.
20 F LUORINATED C OATINGS AND F INISHES H ANDBOOK

Table 2.2 Commercially Used PFOA-Based Salts

and Compounds30

PFOA Compound CAS Number

PFOA 335-67-1
Ammonium salt of 3825-26-1
PFOA
Sodium salt of PFOA 335-95-5
Potassium salt of PFOA 2395-00-8
Silver salt of PFOA 335-93-3
Fluoride acid of PFOA 335-66-0
Methyl ester of PFOA 376-27-2
Ethyl ester of PFOA 3108-24-5
PFOA, perfluorooctanoic acid.

liquid fuel fires, or the engineering coatings used in

semiconductor manufacture.34
Fluorotelomers are fluorocarbon-based oligomers.
They are often used as intermediates to produce
fluorinated compounds. For example, a fluorotelomer
iodide can be used as an intermediate to prepare
fluorinated compounds including fluorinated surfac-
tants. DuPont (Chemours) Daikin, Clariant, Asahi
Glass, and some other companies use the telomeri-
zation process to manufacture fluorotelomers. It
produces a linear perfluorocarbon with a relatively
short-chain length.29 Commercial products that are
made by telomerization are usually mixtures of per-
fluorinated straight chain compounds with even car-
bon numbers. The products are fractionated by
distillation to obtain pure compounds.35 Equations
(2.2)e(2.4) show the general reaction sequence for
surfactant preparation.
5C2F4 þ IF5 þ 2I2 / 5C2F5I(catalyst) (2.22)
C2F5I þ 3C2F4 / CF3(CF2)7I (2.23)
CF3(CF2)7I þ SO3 / F3(CF2)6COOH (2.24)
A major advantage of the telomerization process is
that it yields only straight chain compounds.
2.2.2.3 Issues with PFOS
In a pioneering study in 2001, Giesy and Kannan
reported36 about the global distribution of PFOS
measured in the tissues of wildlife such as fish, birds,
and marine mammals. Among the species studied
were bald eagles, polar bears, albatrosses, and
Figure 2.3 Structures of target fluorinated organic
compounds in wildlife tissues.
various species of seals. Samples were collected from
the urban areas of the Great Lakes region and coastal
marine areas and rivers of the United States and
Europe. Samples were also collected from a number
of more remote locations such as the Arctic and the
North Pacific oceans. Samples were analyzed for
PFOS, perfluorooctane sulfonylamide, per-
fluorohexane sulfonate, and PFOA. The most preva-
lent data were for PFOS, as this was found in every
sample (Figure 2.3).
The results indicated that PFOS was widespread in
the environment. Concentrations of PFOS in the
wildlife from populated and industrial areas were
greater than those in animals from remote marine
locations. Fish-eating animals such as mink and bald
eagles contained concentrations of PFOS signifi-
cantly in excess of the PFOS concentrations in their
diets. Liver tissues of mink that were fed carp
(120 ng PFOS/g wet) from Lake Michigan, under
laboratory conditions, demonstrated a bio-
accumulation factor of 22. This observation suggests
that PFOS can bioaccumulate to higher levels than
that found in the food chain. The available data
indicated that the concentrations of PFOS in wildlife
were less than those required to cause adverse effects
in laboratory animals.36
A 2001 article by Hansen et al. confirmed the
spread of perfluorinated compounds in the environ-
ment and bioaccumulation in animals and in
2: P RODUCING F LUOROMONOMERS , F LUOROPOLYMERS ,
humans.37 The 2001 Giesy and Kannan discovery has
been followed up by a number of studies, every one
of which has further corroborated the persistence and
presence of PFOS, PFOA, and other perfluorinated
compounds in the ecosystems, wildlife, and
humans.38e45
In May 2000, the 3M Company announced
voluntary ceasing of manufacturing materials based
on perfluorooctanesulfonyl fluoride (C8F17SO2F)
after a metabolite of this compound, PFOS (C8F17SO3)
was found to be widespread in human populations
and wildlife. By the end of 2002, 3M had stopped
production of all PFOS and PFOA. In June 2003,
the 3M Company began replacement of PFOS in
the ScotchgardÒ brand with a C4 chemicald
perfluorobutane sulfonate (PFBS). PFBS is the
atmospheric degradation product of C4 chemicals
that have been produced as substitutes to the C8
analogs since they were phased out in 2002.40
Studies have found less bioaccumulation of fluo-
rinated C4 compounds in the wildlife. For example, a
study of harbor seals from the Dutch Wadden Sea
found low levels of PFBS in the spleen of the seals.
No perfluorobutanoic acid was detected above the
detection limit.46 In another study, the potential
hazard that PFBS may pose to avian species was
studied using acute dietary studies with juvenile
mallards and northern bobwhite quail. In addition, a
quail dietary chronic study of reproduction was
conducted. Body weight gains of quail and mallard
exposed to 10,000 mg PFBS/kg feed were statisti-
cally less than those of unexposed controls. Con-
centrations of PFBS in blood serum, liver, and eggs
were, however, dose dependent but were less than the
administered dose, indicating biodiminution.
2.2.2.4 Problems with PFOA
The findings on PFOS led the EPA to review
similar chemicals to determine whether they might
present similar concerns. The agency began investi-
gating PFOA in the 1990s and found that it, too, is
very persistent in the environment, is found at very
low levels both in the environment and in the blood of
the general US population, and causes developmental
and other adverse effects in laboratory animals.47
Emissions to the environmentdincluding air, soil,
and waterdof perfluorinated substances may happen
directly from the production and processing plants.
There are releases, however, which occur during use
AND F LUOROPOLYMER F INISHING 21
(indoor or outdoor) and disposal of products con-
taining these substances.
One of the puzzling features of the perfluorinated
compounds’ contamination in the environment has
been identification of substances like PFOS and
PFOA in remote Arctic areas such as in polar bears.40
The PFOS and PFOA concentrations were relatively
high in comparison to the concentrations of other
contaminants. The long-range transportation of
PFOA in particular has been perplexing. PFOA is
highly soluble in water and typically present as an
anion (conjugate base) in solution. It has low vapor
pressure; therefore, the aquatic environment is
expected to be its primary sink, with some additional
partitioning to sediment.48
Investigators, however, have found that long-range
air transport of PFOA can be reasoned by the fact that
fluorotelomer alcohols and some other nonpolar
perfluorinated alkyl compounds are more volatile and
less water soluble and therefore have a greater ten-
dency to escape the water phase.40 Short-chained
fluorotelomer alcohols have an atmospheric lifetime
of 20 days, which renders them capable of traveling
nearly 7000 km. They may consequently be trans-
ported to the remote Arctic areas. Besides air trans-
port, seawater, wildlife, and humans could also carry
these compounds to the Arctic zone.
Perfluorinated octane sulfonate compounds can
degrade to the most stable form, PFOA. Studies have
demonstrated that PFOA is the final degradation
product of perfluorinated chemicals such as fluori-
nated telomers in a variety of reactions.28,49e52
PFOA was measured in the blood and organs of
wildlife and humans in every geographic region of
the world. Significantly, blood samples did not
belong to those who were occupationally exposed to
perfluorinated compounds such as PFOA or PFOS.
Table 2.3 provides a summary of the measured con-
centrations of perfluorinated compounds in human
blood (ng/ml). The data originate from numerous
studies and were collated by Jahnke.40 The locations
of the samples cover virtually every region of the
world. The presence of PFOA in the worldwide
specimens was ubiquitous.
A revealing study analyzed blood samples of 645
individuals (332 men and 313 women) in the age
range of 20e69 years. Samples were acquired from
six American Red Cross blood banks located in Los
Angeles, California; Portland, Oregon; Minneapolis-
St. Paul, Minnesota; Charlotte, North Carolina;
Hagerstown, Maryland; and Boston, Massachusetts.
Table 2.3 Measured Concentrations of Perfluorinated Compounds in Human Blood (ng/ml)40

Origin n Date PFHxS PFOS PFDS PFOSA PFHxA PFOA

22
United States 65 <1.5e21.4 6.7e81.5 <1.5 <5e35.2
2.2
United States 126 5e1880 91e10,600 0.5e612 21e6160
60 1e210 15e946 <LOQ 6e298
United States <1.2e5.9 <6.1e58.3 <1.3e22.1 <3.0e7.0
United States 175 0.2e32 <1.3e164 <1.3e26 <3e88
Colombia 56 <0.4e0.9 4.6e14 <0.4e5.6 3.7e12.2
Brazil 29 <0.6e15.3 4.3e35 <0.4e2.3 <20
Italy 50 <1e2.1 <1e10.3 <1.3e2.3 <3
Poland 25 2000e2004 <0.4e2.6 16e116 <0.4e7.7 9.7e40
Belgium 20 <1e1.4 4.5e27 <3 <1e13
India 45 <1e2.9 <1e3.1 <3 <3e3.5
Malaysia 23 1.2e6.8 6.2e18.8 1.3e11 <10
Korea 50 0.9e2. 3.0e92 <0.1e7.2 <15e256
Canada 56 2002 3.7e65.1 <4.8 <1.2e7.2
Sweden 66 1997e2000 0.4e28.4 1.7e37.0 <0.1e4.5 0.4e22.9 <0.1e1.6 0.5e12.4
Australia 20 2002e2003 2.7e19 12.7e29.5 0.36e2.4 5.0e9.9

F LUORINATED C OATINGS
Sweden 12 2004 1.8e11.8 8.2e48.0 <0.1e0.33 <0.10e0.49 2.4e5.3
Germany 356 2005 2.1e55 0.5e19.1
China 85 2004 Mean 3.72e79.2
United States 16 2004e2005 0.9e8.6
Japan 15 2003 4.9e17.6 <1.0 <0.5e2.3
1.6e5.3 <1.0 <0.5

AND
Japan 39 1977 GM 1.1 GM 0.2
23 2003 GM 3.5 GM 2.8

F INISHES H ANDBOOK
225 2003 GM 3.5e28.1 GM 2.8e12.4
Germany 10 1985 14.9e103.7 5.6e32.8
16 2004 8.3e33.1 3.0e36.0
United States 178 1974 <1.4e2.5 21.1e40.2 <1.0e3.0
178 1989 1.3e1.6 25.0e44.0 4.4e6.7
PFHxS, perfluorohexane sulfonate; PFOS, perfluorooctane sulfonate; PFOSA, perfluorooctane sulfonylamide; PFOA, perfluorooctanoic acid; LOQ, limit of quantification; GM, geometric
mean; PFDS, perfluorodecane sulfonate; PFHxA, perfluorohexanoate.
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legationem suscepissemus. Nos vero invicem intueri, et tam ineptam
percunctationem admirari. Illi nihilominus perseverare, et nobis, ut
responderemus, instabant. At quum soli Attilae, non aliis
Imperatorem mandata exponere iussisse respondissemus, Scotta
offensus, hoc sibi a suo duce praeceptum esse dixit, neque sua
sponte se ad nos venisse. Nos vero obtestari, nusquam hanc legem
legatis impositam, ut per alios mandata edant et palam faciant,
antequam eos, ad quos missi sint, adierint, et in conspectum eorum
venerint. Neque hoc Scythas nescire, qui saepenumero legatos ad
Imperatorem miserint. Idem et nobis contingere par esse, neque
aliter nos mandata esse dicturos. Quibus auditis ad Attilam
perrexerunt, unde non multo post sine Edecone reversi, omnia, quae
cum illis agere in mandatis habebamus, dixerunt, confestimque, nisi
quid aliud nobis cum illis rei esset, discedere iusserunt. Quae ubi
audivimus, animis dubii suspensique haesimus. Nec enim satis
intelligere poteramus, qua ratione occulta Imperatoris consilia
patefacta essent. Quamobrem potius esse duximus, nihil quicquam
de mandatis nostris efferre, priusquam nobis Attilam adeundi
potestas fieret: itaque respondimus: “Sive ea, quae Scythae modo
protulerunt, sive alia nuntiaturi venerimus, neminem nisi ducem
vestrum quaerere decet, neque de his cum aliis ullo pacto disserere
constituimus.” Ille vero nos quam primum abire iusserunt. Dum
reditum parabamus, Bigilas nos propter responsionem Scythis
factam increpavit. Longe enim potius fuisse in mendacio deprehendi,
quam re infecta domum reverti. “Si enim, inquit, cum Attila collocutus
fuissem, facile illi a contentione cum Romanis discedere
persuasissem, quippe qui antea familiaritatem cum illo in legatione
cum Anatolio suscepta contraxi.” Atque inde Edeconem quoque
bene sibi velle dixit, ideoque specie legationis et eorum, quae vere
aut falso dicturi essent, ope viam se inventuros esse speravit, qua
compositas in Attilam insidias exsequerentur, et aurum, quo Edecon
sibi ad eam rem opus esse eunucho dixerat, adferretur, quod certis
hominibus divideretur. Sed Bigilam latebat, se proditum: Edecon
enim, sive simulate cum Eunucho pactus, sive ut ab Oreste sibi
caveret, ne ob eam causam, quam in Serdica inter coenandum nobis
indicaverat, iratus ad Attilam deferret, quod sine se secretos
sermones cum Imperatore et eunucho habuisset, Attilae
comparatam in ipsum coniurationem aperuit, et auri summam, quam
in eam rem mitti convenerat, simul et ea, quae per nos in ista
legatione tractanda erant, enuntiavit. Iumentis iam adornatis et
necessitate ad iter tempore noctis carpendum adacti, occurrere ex
barbaris, qui dicerent, Attilam iubere nos propter tempus noctis
intempestivum remanere. In eundem igitur locum, unde
proficiscebamur, praesto fuere, qui bovem agebant et pisces
fluviatiles nobis ab Attila missos adferebant. Coenati nos dormitum
contulimus. Luce orta in spem adducebamur, Attilam se ad lenitatem
daturum, et aliquod mite responsum ad nos ab ipso emanaturum. Ille
vero denuo eosdem misit, iussitque abire, si nihil aliud negotii, nisi
quod iam omnibus cognitum erat, nobis cum illo intercederet. Nullo
dato responso ad iter nos accinximus, etsi Bigilas omni ope
contenderet, ut responderemus nos alia dicenda habere. Ego vero
cum Maximinum moerore confici viderem, assumto Rusticio, qui
barbarorum linguae peritus erat, et nobiscum in Scythiam venerat
non legationis, sed privatae rei causa, ad Constantium ex Italia
oriundum, quem ad Attilam Aëtius, Occidentalium Romanorum dux,
ut illi ab epistolis esset, miserat, Scottam adii, (nec enim aderat
Onegesius,) et cum illo per Rusticium interpretem collocutus, eum
plurima dona a Maximino laturum dixi, si illi aditus ad Attilam copiam
faceret. Legatum enim venire de rebus, quae non solum Romanis et
Hunnis maximam essent utilitatem allaturae, sed etiam ipsi
Onegesio. Imperatorem enim poscere, illum ad se legatum ab Attila
mitti, qui diiudicaret controversias inter utramque gentem, unde
nonnisi ingentibus donis cumulatus esset rediturus. Oportere igitur
illum, cum Onegesius non adsit, in tam praeclara actione nos aut
potius fratrem ipsum adiuvare. Et ipsi quoque Attilam plurimum
fidere dixi me accepisse. Sed non satis firma esse audita, nisi re ipsa
notum faceret quantum illi Attila tribueret. Atque ille: “Ne amplius,
inquit, dubii sitis. Aeque ac frater apud Attilam valeo auctoritate, seu
verbis, seu facto opus est.” Et ascenso equo, ad Attilae tentorium
contendit. Ego vero ad Maximinum rediens, qui una cum Bigila
angebatur animo, et incertus erat quid constituendum esset, narravi
sermones, quos habueram cum Scotta, et quae ab ipso audieram.
Atque adeo illum excitavi ad praeparanda munera, quibus Scottam
remuneraretur, et praemeditandum, quibus verbis Attilam affaretur.
Surrexerunt igitur (offenderam enim illos in solo herbido iacentes), et
operam a me egregie navatam laudarunt, et eos, qui se iam cum
iumentis itineri accinxerant, revocarunt. Tum etiam qua oratione
Attilam aggrederentur, et quo modo dona Imperatoris, et quae
Maximinus ipse adferebat, traderent, inter se agitarunt. Dum in
harum rerum cura versabamur, Attilas nos per Scottam arcessivit:
itaque ad eius tentorium iter direximus, quod barbarorum multitudine,
qui in orbem excubias agebant, erat circumdatum. Introducti Attilam
sedentem in sella lignea invenimus. Stetimus paulo remotius ab eius
solio: mox processit Maximinus et salutavit barbarum. Et Imperatoris
litteras tradens dixit, salvum et incolumem illum suosque precari
Imperatorem. Et barbarus, “Sit et Romanis quemadmodum et mihi
cupiunt,” inquit. Statimque ad Bigilam convertit orationem, feram
impudentem vocans, quaerebat, qua re impulsus ad ipsum venisset,
cum sibi eorum, quae et ipse et Anatolius de pace sensissent,
conscius esset: non enim prius ad se legatos accedere debuisse,
quam omnes profugi, qui apud Romanos exstarent, redditi essent.
Bigila vero respondente, nullum amplius apud Romanos reperiri
transfugam Scythici generis; omnes enim redditos esse; magis
exasperatus Attilas, in eum multa probra et convitia ingessit. Et cum
clamore dixit, se illum in crucem acturum et praedam vulturibus
praebiturum fuisse, nisi leges legationis hac impudentis eius
orationis et temeritatis poena offendere vereretur. Etenim restare
adhuc apud Romanos plures transfugas, quorum nomina, ut erant in
charta descripta, iussit scribas recitare. Hi ubi omnia legerant, Attilas
Bigilam una cum Esla sine mora proficisci iussit Romanis
denuntiatum, ut omnes transfugas Scythicae nationis, quotquot in
eorum potestate essent, redderent, a tempore Carpilionis, filii Aëtii,
Romanorum Occidentalium ducis, qui obses apud eum fuerat. Non
enim se servos suos secum manus conserere passurum esse,
quamquam ne iis quidem, qui suae ditionis custodiam illis
promiserint, prodesse possint. Quae enim urbs, quod castellum ab
illis possit defendi, quod evertere aut diruere apud se constitutum
habuerit? Postquam exposuerint a se de transfugis decreta, redire
eos quamprimum iussit renuntiatum, utrum transfugas reddere, an
bellum eo nomine malint suscipere. Non multo ante Maximinum
paulum exspectare iusserat, dum ad ea, quae Imperator scripserat,
per se responsum daret, munera petiit. Quae postquam dedimus, in
tentorium nostrum nos recepimus, et de singulis, quae dicta fuerant,
inter nos disseruimus. Cum autem Bigilas admiraretur, qui fieret, ut
Attilas, qui sibi iampridem, cum legatus ad illum veniret, comis et
perhumanus visus esset, tunc se acerbis contumeliis affecisset, dixi,
vereri me, ne qui ex barbaris, qui in Serdica nobiscum epulati erant,
Attilam infensum nobis reddidissent, et Bigilam Romanorum
Imperatorem deum, Attilam vero hominem appellasse, retulissent.
Quam orationem Maximinus ut verisimilem est amplexus, quia
coniurationis in Attilam ab eunucho initae particeps non fuerat. Sed
Bigilas ambiguus animi erat, neque causam suspicari posse
videbatur, quare Attilas eum tam acerbis convitiis insectatus esset.
Nec enim in animum suum inducere poterat, ut nobis postea retulit,
enuntiata fuisse, quae in convivio in Serdica dicta fuerant, nec
coniurationem in Attilam detectam, cum nemo ex omni multitudine,
quae Attilam circumstabat, excepto Edecone, prae metu, qui
omnium mentes pervaserat, cum Attila sermonem instituere auderet,
Edeconem autem studiose operam daturum censeret, omnia silentio
transigere, tum propter iusiurandum, tum propter negotii gravitatem:
ne, quia clandestinis in Attilam consiliis interfuerat, reus iudicatus,
poena mortis afficeretur. Haec cum ambigua mente volveremus,
Edecon supervenit, et abducto a nostro coetu Bigila (fingebat enim
velle vere et serio de praemeditatis inter eos insidiis agere), ubi
aurum adferri praecepit, quod his daretur, qui exsequendo facinori
operam navaturi essent, discessit. Ego vero cum Bigilam curiosius
inquirerem, quos sermones secum Edecon habuisset, decipere
conatus est, deceptus et ipse, et veram causam occultans
commentus est sibi Edeconem dixisse, Attilam illi quoque propter
transfugas succensuisse. Oportuisse enim aut omnes restitui, aut
legatos summa auctoritate praeditos ad illum venire. Haec dum
loquebamur, advenere ab Attila, qui Bigilam et nos prohiberent,
captivum Romanum, aut barbarum mancipium, aut equos, aut
quicquam aliud emere, praeterquam quae ad victum necessaria
erant, donec inter Romanos et Hunnos de rebus controversis
convenisset. Haec callide et praemeditato consilio barbarus faciebat,
quo facilius Bigilam in consilio contra se exsequendo deprehenderat,
cum nullam satis idoneam causam comminisci posset, cur aurum
adferret. Nos quoque praetenta causa responsi, quod ad legationem
editurus erat, Onegesium opperire coëgit, ut munera, quae ad eum
Imperator miserat, et tradere volebamus, acciperet. Etenim tum forte
Onegesius una cum seniore ex Attilae liberis ad Acatziros missus
fuerat. Ea gens est Scythica, quae in potestatem Attilae hac de
causa venit. In eam gentem plures secundum populos et gentes
imperium exercebant, quos Imperator Theodosius, firmata inter eos
concordia, ab Attilae societate ad colendam cum Romanis pacem et
societatem muneribus traducere conatus est. Qui ea munera
attulerat non pro cuiusque gentis regis merito et gradu ea
distribuerat. Caridachus enim secundo loco acceperat, qui regum
antiquior, primus accipere debuerat. Ille, tanquam contemptus et sibi
debitis praemiis frustratus, Attilam contra ceteros reges auxilio
vocaverat. Is nihil cunctatus, magno exercitu emisso eorum alios
sustulit, alios ad deditionem compulit. Deinde Caridachum ad se
vocat, tanquam illi victoriam, et quae ex victoria consecutus fuerat,
impertiturus. Sed iste dolum et insidiis suspicatus, difficile et grave
esse homini respondit, in dei conspectum venire. Si enim immotis
oculis solis orbem intueri nemo potest, quomodo quis sine sensu
doloris cum deorum maximo congrediatur? Atque ita Caridachus
regnum suaque omnia salva sibi et integra conservavit, et reliqua
omnis Acatzirorum regio in ius ditionemque Attilae concessit. Ei genti
cum seniorem ex filiis regem Attilas constituere decrevisset, ad hanc
rem conficiendam Onegesium miserat. Itaque nos exspectare, ut
dictum est, iubens, Bigilam cum Esla ad Romanos amandavit,
specie quidem transfugarum repetendorum, sed revera, ut aurum
Edeconi promissum adferret.
Post Bigilae discessum unum tantum diem in his locis commorati,
postridie una cum Attila ad loca magis ad septentrionem vergentia
profecti sumus. Haud longum viae spatium cum barbaris progressi,
alio iter vertimus, Scythis, qui viam ducebant, nos id facere
iubentibus. Attilas interea in quodam vico substitit, in quo filiam
Escam uxorem, etsi plures alias haberet. Scytharum legibus id
permittentibus, ducere voluit. Illinc facili et aequali via, per planitiem
iter fecimus, et in multos fluvios navigabiles incidimus. Quorum post
Istrum maximi sunt Drecon dictus, et Tigas, et Tiphisas. Et hos
quidem naviculis unico ligno confectis, quas in quotidiano usu
habent qui ad flumina habitant, relinquos lembis ex propinquo
desumptis, quos barbari curribus imponunt, et per loca restagnantia
important, traiecimus. Congerebantur vero nobis ex vicis
commeatus, pro frumento milium, pro vino medus; sic enim locorum
incolae vocant. Servi quoque, qui nos comitabantur, milium secum
portabant, potionem ex hordeo praebentes, quam camum barbari
appellant. Longavia confecta, die ad noctem inclinante, ad paludem
quandam, ad quam aquatum (erat enim eius aqua potui apta)
proximi vici incolae ibant, tentoria fiximus. Ingens ventus et procella
derepente exorta cum tonitru et crebris fulguribus et multo imbre
tentorium nostrum disiecit, et omnia nostra utensilia in proximam
paludem volvit. Turbinibus in aëre excitatis, et casu, qui contigerat,
perterrefacti, locum illum deseruimus, et dissociati, huc illuc
palantes, viam unusquisque nostrum, quam sibi commodam duxit,
sub tenebris et imbribus est persecutus. Tandem tuguria vici
subeuntes, (illuc enim divisis itineribus omnes diverteramus,)
convenimus, et ea, quae nobis deerant, cum clamore perquisivimus.
Ad quem strepitum Scythae exilientes calamos, quibus ad ignem
utuntur, usserunt: et accenso lumine, interrogarunt, quid nobis
vellemus, qui tantos clamores ederemus. Barbari, qui nos
comitabantur, responderunt, nos tempestate perculsos turbari.
Itaque nos liberaliter invitatos hospitio exceperunt, et calamis siccis
ignem accenderunt. Vici domina una ex Bledae uxoribus erat. Haec
nobis cibaria et mulieres formosas, cum quibus amori indulgeremus
(hoc enim apud Scythas honori ducitur,) suppeditavit. Mulieribus pro
cibis praebitis gratias egimus, et sub tectis nostris somnum
capientes, ab earum consuetudine abstinuimus. Simul atque illuxit,
ad ea, quae ex nostra supellectile desiderabantur, perquirenda
curam convertimus. Haec partim in eo loco, ubi pridie
consederamus, partim in ripa paludis, partim in ipsa palude reperta
recepimus. In his desiccandis totum diem in illo vico (tempestas
enim desierat, et clarus sol apparebat,) contrivimus. Deinde curatis
equis et reliquis iumentis, reginam salutatum ivimus. Hanc vicissim
donis remunerati sumus tribus pateris argenteis, velleribus rubris,
pipere Indico, palmulis et variis cupediis, quae omnia a barbaris, ut
ignota, magni aestimantur. Nec multo post omnia fausta feliciaque
illis hospitalitatis ergo precati, discessimus. Septem dierum itinere
emenso, Scythae, qui nos ducebant, in quodam vico nos consistere
iusserunt, quia post Attilam, qui hac via proficisceretur, iter nobis
faciendum esset. Hic obvios habuimus legatos a Romanis
occidentalibus, etiam ad Attilam missos. Erant autem praecipui
Romulus Comitis dignitate decoratus et Primutus, Noricae regionis
praefectus, et Romanus, militaris ordinis ductor. His aderat
Constantius, quem Aëtius ad Attilam, ut illi in conscribendis epistolis
deserviret, miserat, et Tatullus, Orestis eius, qui cum Edecone erat,
pater, non legationis causa, sed privati officii et familiaritatis ergo.
Constantio enim in Italiis agenti magnus cum illis usus intercesserat:
Tatullum affinitas movebat. Orestes enim, eius filius, Romuli filiam e
Patavione, Norici civitate, uxorem duxerat. Legati autem veniebant,
ut Attilam lenirent, qui sibi Sylvanum, Armii mensae Romae
praefectum, tradi postulabat, propterea quod pateras aureas a
Constantio quodam acceperat. Hic Constantius, ex Galliis
Occidentalibus ortus, ad Attilam et Bledam, ut illis in conscribendis
epistolis operam daret, quemadmodum et post illum alter
Constantius, missus fuerat. Ille vero, quo tempore Sirmium oppidum,
in Paeonia situm, Scythae obsidebant, aurea vasa a civitatis
episcopo acceperat, ut ex eorum pretio, si se superstite urbem capi
contigisset, quoad satis esset, pro sua libertate solveretur: sin
periisset, cives in servitutem abducti redimerentur. Sed Constantius
post urbis excidium de pacto illo parum sollicitus. Romam cuiusdam
negotii causa profectus, vasa ad Sylvanum detulit, et aurum ab eo
accepit, conventique, ut, si intra tempus praefinitum aurum mutuo
sumtum redderet, vasa reciperet: ni fecisset, Sylvanus vasa sibi
haberet et his pro arbitrio uteretur. Hunc Constantium Attilas et
Bleda, cum illis proditionis nomine suspectus esset, in crucem
egerunt. Ex quo, ut de poculis aureis iudicium ad Attilam est
delatum, sibi tradi Sylvanum, tanquam furem eorum, quae sua
essent, flagitavit. Legati igitur ab Aëtio et Romanorum occidentalium
Imperatore venerant, qui decerent, Sylvanum Constantii creditorem
vasa aurea pro credito oppignerata, non furto ablata, penes se
habuisse, quae sacerdotibus, qui primi se obtulissent, nummis
argenteis permutasset. Nec enim fas esse hominibus pocula Deo
consecrata propriis usibus applicare. Itaque nisi tam iusta causa aut
divini numinis reverentia a petendis poculis dimoveatur, retento
Sylvano, aurum se pro pateris praebiturum. Hominem enim, qui nihil
deliquerit, minime se dediturum esse. Haec erat igitur horum virorum
legationis causa, qui barbarum sequebantur, ut responsum ferrent,
et dimitterentur. Cum vero nobis eadem via eundem esset, qua
Attilas incedebat, parumper morati, dum praecederet, non multo post
secuti, cum reliqua multitudine, traiectis quibusdam amnibus, ad
quendam magnum vicum pervenimus. Hic erant Attilae aedes, quae
reliquis omnibus ubicumque locorum praestantiores esse ferebantur.
Erant hae ex lignis et tabulis eximie politis exstructae et ambitu
ligneo circumdatae, non ad munimentum, sed ad ornatum
comparato. Proxima regiae erat Onegesii domus, et ipsa quoque
ambitu ligneo constans, non tamen aeque, ac Attilae, turribus
insignis. Haud longo intervallo a circuitu domus distabat balneum,
quod Onegesius, qui secundum Attilam plurimum apud Scythas
opibus valebat, lapidibus ex Paeonia advectis aedificaverat. Nec
enim apud eos, qui in ea parte Scythae habitant, ullus est aut lapis,
aut arbos, sed materia aliunde advecta utuntur. Huius autem balnei
architectus, e Sirmio captivus abductus, mercedem operis sui
libertatem se consecuturum sperans, falsus sua spe, cum nihil minus
cogitaret, in longe duriorem apud Scythas incidit servitutem.
Balneatorem enim cum Onegesius instituit, ut sibi totique suae
familiae, cum lavarentur, operas praestaret. In hunc vicum
adventanti Attilae puellae obviam prodierunt, quae per series
incedebant, sub linteis tenuibus et candidis, quam maxime in
longitudinem extensis, ita ut sub unoquoque linteo, manibus
mulierum ab utraque parte in altum sublato, septem puellae aut
etiam plures progredientes, (erant autem multi huiusmodi mulierum
sub illis linteis ordines,) Scythica carmina canerent. Iam proxime
Onegesii domum accesserat, (per ipsam enim via ducebat ad
regiam,) cum foras prosiliret Onegesii uxor, magna ancillarum
comitata multitudine, quae opsonia et vinum ferebant, qui maximus
est apud Scythas honos. Haec Attilam salutavit rogavitque, ut ex
cibis desumeret, quos cum summa testificatione suae erga illum
voluntatis attulerat. Itaque uxori hominis sibi necessarii gratificaturus,
comedit, equo insidens, barbaris, qui in eius comitatu erant,
suspensam tabulam (erat autem argentea) attollentibus. Deinde
degustato calice, qui illi fuerat oblatus, in regiam se recepit. Erat
autem illa reliquis conspectior et in altiori loco sita. Nos vero in
aedibus Onegesii (sic ille praeceperat; redierat enim cum Attilae
filio;) remansimus. Illic coenam sumpsimus, excipiente nos eius
uxore comitata illustrioribus, qui eum genere contingebant. Illi enim
animum nobiscum convivio exhilarare per otium minime licuit; quia
quae gesserat in negotio, ad quod missus fuerat, et adversum, qui
filio Attilae contigerat, casum (dextram enim delapsus fregerat)
renuntiaturus, tum primum a reditu in Attilae conspectum venerat.
Post coenam, aedibus Onegesii relictis, propius Attilae aedes
tentoria posuimus, ut Maximinus, quem Attilam convenire, et cum
his, qui ei a consiliis erant, colloquia facere oportebat, minime longo
ab Attila distaret intervallo. Illic igitur, quo primum devertimus,
noctem transegimus. Luce orta misit me Maximinus ad Onegesium,
ut illi tum quae ipse dabat, tum ab Imperatore missa munera
traderem et ut ipse cognosceret, an illi secum et quo tempore
colloquium inire luberet. Perrexi igitur ad Onegesium cum famulis,
qui dona portabant: quum ianuae clausae essent, exspectavi, donec
aperirentur, et aliquis exiret, qui eum mei adventus certiorem faceret.
Itaque tempus mihi terenti et circa murorum ambitum domus
Onegesii ambulanti, progressus nescio quis, quem barbarum ex
Scythico vestitu esse rebar, Graeca voce me salutavit dicens “χαιρε.”
Mirari ego, qui fieret, ut Graece loqueretur vir Scytha: etenim ex
variis gentibus commixti, barbaricam linguam colunt, sive Hunnorum,
sive Gothorum, aut etiam Romanam, hi scilicet, quibus cum
Romanis frequentius est commercium. Neque quisquam eorum
facile loquitur Graece, nisi si qui sint captivi e Thracia aut Illyrico
maritimo. Sed illi ab obvio quoque dignosci possunt et a vestibus
laceris et capitis squalore, tanquam qui in miseram inciderint
fortunam. Hic vero opulenti Scythae speciem prae se ferebat: erat
enim bene et eleganter vestitus, capite in rotundum raso. Hunc
resalutans interrogavi, quis esset, et unde in terram barbaram
veniens, vitae Scythicae institutum sequi delegisset. Ille quam ob
causam hoc ex ipso quaererem, rogavit “Mihi vero, inquam, haec a
te ut sciscitarer, causa fuit, quod Graece locutus es.” Tum ridens ait,
se Graecum esse genere, ad mercaturam faciendam Viminacium,
Mysorum ad Istrum urbem, accessisse, in ea domicilium longo
tempore habuisse, uxorem quoque divitem duxisse; parta illic
felicitate capta urbe exutum fuisse, et propterea quod dives erat, se
suaque omnia in praedae divisione Onegesio cessisse. Etenim esse
apud eos in more positum, ut praecipui ab Attila Scythiae principes
captivos ditiores sibi seponant, quoniam plurimum auctoritate valent.
Postea ubi adversus Romanos et Acatzirorum gentem fortissime
dimicasset, libertatem se ex more Scytharum, omnibus, quae bello
acquisierat, barbaro domino traditis, recuperasse. Uxorem quoque
barbaram duxisse, et ex ea liberos sustulisse, et Onegesii mensae
participem, hoc vitae genus longe potius priore ducere. “Qui enim
apud Scythas degunt, inquit, tolerato bellorum labore, sine ulla
sollicitudine vitam peragunt. Tum unusquisque bonis, quae sibi
fortuna indulsit, fruitur, neque quisquam illi ulla in re molestus est.
Qui vero sub Romanis aetatem agunt, facile in bello pereunt. Hos
enim in aliis sui conservandi spem collocare necesse est,
quandoquidem per tyrannos minime licet arma, quibus unusquisque
se tueatur, gestare. Atque adeo his, quibus id iure licet, valde est
perniciosa ducum ignavia, qui bellum minime gnaviter gerunt. At in
pace longe acerbiora sunt, quae accidunt, quam calamitates, quae
ex bello proveniunt et propter duram exactionem tributorum, et
propter improborum vexationes, quum leges non in omnes valeant.
Si quis dives aut potens eas sit transgressus, ille quidem iniquitatis
suae poenas non luet: sin aliquis inops, qui negotia gerere nesciat,
hunc poena a legibus statuta manet. Nisi forte eum priusquam
sententia feratur, longo in litibus continuato tempore, multis
praeterea exhaustis opibus, vita defecerit. At mercede et pretio,
quod legum et iuris est obtinere, omnium iniquissimum est. Nec enim
iniuria affecto quisquam fori iudicialis potestatem faciet, priusquam
pecuniam iudicis et eius ministrorum commodo cessuram deponat.”
Haec atque huiusmodi multa cum in medium proferret, ego precatus,
ut quod sentirem, patienter et benigne audiret, respondi, reipublicae
Romanae auctores, sapientes et optimos viros, ne quidquam temere
ageretur, alios legum custodes fecisse, aliis armorum curam
commisisse, ut, ad nullam aliam rem intenti, quam ut se ad pugnam
praepararent, militaria opera exercerent, et propulsata per assiduam
belli meditationem omni formidine, consueta militiae exercitatione,
animis firmati, in aciem descenderent. “Alios, inquam, qui agris
colendis et culturae terrae operam darent, annona militari ab his
exacta, eos alere voluerunt, quo pro sua salute dimicarent.
Constituerunt quoque, qui iniuria affectis prospicerent, et iura eorum,
qui propter naturae infirmitatem sibi ipsi consulere non valerent,
tuerentur, quique iure dicendo, quae leges iuberent, servarent.
Neque vero sua providentia destitutos reliquerunt eos, qui iudicibus
adsunt, sed horum esse partes prospicere, qua ratione ius
assequatur, qui sententia iudicum obtinuit, et iniurius iudicatus, id
solum, quod iudicii calculus fert, et nihil praeterea, facere cogatur. Si
enim non essent huic rei praepositi, aut victore insolentius
insurgente, aut eo, qui adversam sententiam reportavit, in preversa
mente perstante, ex una lite alterius litis nasceretur exordium. Est
autem his constitutum argentum ab illis, qui litibus certant, ut
militibus ab agricolis. Quid enim aequius, quam eum, qui opituletur et
auxilium ferat, alere et officium mutuo officio rependere?
quemadmodum equiti emolumento est equi, pastori boum et venatori
canum cura, et reliquorum animantium, quae homines custodiae et
utilitatis causa alunt. Cum enim sumptus in litem factos qui causa
cadunt solvant, damnum nulli alii rei, quam suae iniquitati, imputent
oportet. Quod ad longum tempus attinet, quod in litibus consumitur,
si quando id evenit, id iuris providentius dicendi gratia fit, ne iudices
properantes ab accurata iudicandi ratione aberrent. Sic enim iudicant
melius esse, tardius finem litibus imponere, quam festinantes non
solum iniquum ius in hominem statuere, verum etiam in deum,
iustitiae inventorem, peccare. Leges autem in omnes positae sunt, ut
illis etiam ipse Imperator pareat. Neque, id quod tua accusatione
continetur, potentiores si tenuioribus vim inferant, id illis est impune,
nisi quis forte latens poenam effugerit; quod non solum divitibus, sed
etiam inopibus plerumque usu venit: nam hi quoque, si argumenta
deficiunt, peccatorum poenas non solvunt. Quod non solum apud
Romanos, sed etiam ubique gentium accidit. Gratiam vero plurimam
ipsum pro recepta libertate fortunae debere, neque eam domino
acceptam referre. Cum enim eum in bellum eduxerit, potuisse ab
hostibus propter rei militaris imperitiam occidi, aut si fugisset, ab eo,
in cuius dominio erat, puniri. Longe autem Romani benignius servis
consuluerunt. Patrum enim, aut praeceptorum affectum erga eos
exhibent, et ut a malis abstineant, curant, et eorum, quae honesta
ducunt, participes efficiunt. Denique corrigunt eos in his, quae
delinquunt, sicut et suos liberos. Nec enim servos morte officere,
sicut apud Scythas, fas est. Libertatis vero adipiscendae plures sunt
modi. Non enim solum qui vita fruuntur, sed etiam qui e vivis
excedunt, libertatem tribuere possunt, quum de bonis suis, ut cuique
placeat, statuere liceat, et quodcunque quis moriens de rebus
domesticis iusserit, lex sit.” Tum ille plorans inquit, leges apud
Romanos bonas et rem publicam praeclare constitutam esse, sed
magistratus, qui non aeque ac prisci probi et prudentes sunt, eam
labefactant et pervertunt.
Haec inter nos disserentibus aliquis ex domesticis Onegesii
septorum domus fores aperuit. Ego statim accurrere et quaerere;
quas res ageret Onegesius; me enim habere a Maximino, qui
legatus a Romanis venisset, quod illi dicerem. Ille vero Onegesium
mihi sui facturum copiam respondit, si paullum opperirer; exiturum
enim esse. Nec multo temporis spatio interiecto, ut ipsum exeuntem
vidi, progressus dixi: “Te Romanorum legatus salutat, et dona tibi ab
ipso una cum auro ab Imperatore misso adfero.” Et quum maxime
ille eum convenire cuperet, ubi et quando vellet colloqui, quaesivi.
Ille suos, qui aderant, iussit aurum et munera recipere, et me
Maximino renuntiare, se protinus ad eum accedere. Reverti igitur ad
Maximinum, et renuntiavi, Onegesium ad eum venturum esse: nec
mora, in tentorium nostrum advenit, et Maximinum affatus dixit, se
Imperatori et illi pro muneribus gratias agere, et percunctatus est,
quandoquidem se arcessisset, quid esset, quod illum vellet: tum
Maximinus, instare tempus, ait, quo posset maiorem gloriam apud
homines adipisci, si ad Imperatorem accedens, quae sunt inter
Romanos et Hunnos controversa, sua prudentia componeret, et inter
utramque gentem concordiam stabiliret: quae res non solum utilitati
utriusque gentis esset cessura, sed etiam eius domui tanta bona
praebitura, ut ipse una cum suis liberis in posterum Imperatori
totique imperatorio generi in perpetuum devinctus foret. Tum
Onegesius dixit, qua in re gratificaretur Imperatori, et per se
contentiones dirimeret. Maximinus respondit, si in rem praesentem
descendens, Imperatori gratiam referret, et dissidiorum causas
sedulo perscrutans, de rebus controversis secundum conditiones
foederibus adscriptas iudicium suum interponeret. Tum Onegesius
dixit, se Imperatori et iis, qui ei a consiliis essent, ea dicturum esse,
quae Attilas sibi praeciperet. “An Romani existimant, inquit, se ullis
precibus exorari posse, ut prodat dominum suum, et nihili faciat
educationem apud Scythas, uxores et liberos suos, neque potiorem
ducat apud Attilam servitutem, quam apud Romanos ingentes
opes?” Ceterum se domi remanentem maiori eorum rebus
adiumento futurum, quippe qui domini iram placaret, si quibus in
rebus irasceretur, quam si ad eos accedens criminationi se obiiceret,
si forte quid contra quam Attilae rationibus commodum videretur
faceret. Quae cum dixisset et mihi veniam dedisset eum de his, quae
ex ipso intelligere cuperemus, adeundi, (Maximino enim in dignitate
constituto parum decorus erat continuus congressus,) abiit. Postridie
ad domus Attilae interiora septa me contuli dona ferens eius uxori,
quae Cerca vocabatur. Ex ea tres illi liberi, quorum maximus natu
iam tum Acatzirorum et reliquarum gentium, qua Scythia ad Pontum
patet, regnum tenebat. Intra illa septa erant multa aedificia, partim ex
tabulis sculptis et eleganter compactis, partim ex trabibus opere puro
et in rectitudinem affabre dolatis, in quibus ligna in circulos curvata
imposita erant. Circuli autem a solo incipientes paullatim in altum
assurgebant. Hic habitabat Attilae uxor, ad quam a barbaris, qui circa
ianuas erant, nactus aditum, ipsam deprehendi in molli stragula
iacentem. Erat autem pavimentum laneis tapetibus stratum, in
quibus constitimus. Eam famulorum multitudo in orbem
circumstabat, et ancillae ex adverso humi sedentes telas coloribus
variegabant, quae vestibus barbarorum ad ornatum superiniiciuntur.
Cerca salutata, et muneribus traditis, egressus, exspectans dum
Onegesius regia exiret, (iam enim e domo sua illuc venerat,) ad
reliqua aedificia, ubi Attilas commorabatur, processi. Hic dum ego
starem cum reliqua multitudine, (nec enim accessu ullius loci
prohibebar, quippe qui Attilae custodibus et barbaris, qui eum
assectabantur, eram notus,) vidi magnam turbam, qua prodibat,
currentem, tumultum et strepitum excitantem. Attilas domo egressus,
gravi vultu, omnium oculis quaqua versus in eum conversis,
incedens cum Onegesio, pro aedibus substitit. Hic eum multi, quibus
erant lites, adierunt, et eius iudicium exceperunt. Deinde domum
repetiit, et barbararum gentium legatos, qui ad se venerant, admisit.
Me vero, dum Onegesium exspectabam, Romulus, Promutus et
Romanus, legati de vasis aureis ex Italia ad Attilam missi, una cum
Rusticio, qui in comitatu Constantii erat, et Constantiolo ex Paeonum
regione, quae Attilae parebat, me sunt sermone adorti, et
interrogaverunt, utrum dimissi, an manere coacti essemus. “Id
ipsum, inquam, ut sciam ex Onegesio, intra ista septa opperior.” Tum
ego illos vicissim percunctari, an aliquod mite responsum ad ea, de
quibus legati venerant, ab Attila tulissent. Nequaquam aiunt illum
deduci a sententia, sed bellum minari et denuntiare, ni Sylvanus aut
pocula dedantur. Nos vero cum barbari miraremur animi
impotentiam, Romulus, vir multis honorificentissimis legationibus
functus et multo rerum usu praeditus, ait, secunda fortuna et potentia
inde collecta adeo illum efferri, ut iustis sermonibus nullum apud si
locum relinqueret, nisi eos ex re sua esse censeret. Nemo unquam
eorum, qui in Scythia, vel alibi regnarunt, tantas res tam brevi
tempore gessit. Totius Scythiae dominatum sibi comparavit, et ad
Oceani insulas usque imperium suum extendit, ut etiam a Romanis
tributa exigat. Nec his contentus, ad longe maiora animum adiecit, et
latius imperii sui fines protendere et Persas bello aggredi cogitat.
Uno ex nobis quaerente, qua via e Scythia in Persas tendere posset,
Romulus dixit, non longo locorum intervallo Medos dissitos esse a
Scythis, neque Hunnos hanc viam nescire, sed olim, fame per eorum
regionem grassante, cum Romani propter bellum, quod tunc
temporis gerebant, minime cum illis proelio decertarent, hac
irrupisse, et ad Medos usque Bazicum et Cursicum, duces ipsorum,
e regiis Scythis oriundos, penetrasse, qui postea cum magna
hominum multitudine Romam ad contrahendam armorum societatem
venissent. Hos narrasse, per quandam desertam regionem illis iter
fuisse, et paludem trajecisse, quam Romulus existimabat esse
Maeotidem: deinde, quindecim diebus elapsis, per montes quosdam,
quos superassent, in Mediam descendisse. Ibi praedas agentibus et
excursionibus agros vastantibus Persicum agmen superveniens telis
aëra replevisse. Itaque imminentis periculi metu retro abscessisse,
et per montes regressos, pauxillum praedae abegisse. Magnam
enim partem Medos extorsisse: ipsos autem, ut persequentium
hostium impetum evitarent, ad aliam viam deflexisse. Et per loca, ubi
ex petra maritima flamma ardet, illinc profectos, ... dierum itinere in
sedes suas revertisse. Atque ex eo satis vidisse, non magno
intervallo Scythiam a Medis distare. Quamobrem si Attilam cupido
ceperit Medos invadendi, non multum operae et laboris in eam
invasionem consumpturum, neque magnis itineribus defatigatum iri,
ut Medos, Parthos et Persas adoriatur, et cogat tributi illationi se
submittere. Adesse enim illi magnas copias, quas nulla gens
sustinere possit. Nobis vero optantibus, ut Persis arma inferret, et a
nobis in illos belli molem averteret: “Verendum est, inquit
Constantiolus, ne, Persis facile devictis, non iam amplius amicus,
sed dominus in nos revertatur.” Nunc enim auro accepto pro
dignitate eum contentum esse. Quodsi Medos, Parthos et Persas
domuerit, minime eum Romanorum a suo seiunctum regnum sed
eos manifesto servos suos reputantem, gravia illis et intolerabilia
imperaturum esse. Dignitas autem, cuius mentionem Constantiolus
fecit, erat Romanorum exercituum ducis, quam Attilas ab Imperatore
acceperat, et stipendia eius, qui exercitus regebat, missa sibi non
recusabat. Innuebat igitur, Attilam, Medis, Parthis et Persis subactis,
hoc nomen, quo Romanis illum vocare lubet, et dignitatem, quam illi
ornamenti loco esse existimant, repudiaturum, et pro duce
coacturum eos se regem appellare. Iam tum enim indignatus
dicebat, illi servos esse exercituum duces, sibi vero viros
Imperatoribus Romanis dignitate pares. Et brevi quidem sibi
potentiae accessionem fore, quod et deus, Martis ense in lucem
protracto, portenderit. Hic tanquam sacer et deo bellorum praesidi
dedicatus, a Scytharum regibus olim colebatur, et mulsit saeculis
non visus, bovis ministerio fuerat tunc temporis erutus.
Dum ita de praesenti rerum statu confabulamur, Onegesius foras
prodiit, ad quem, ut ex eo disceremus, quae nostrae curae
commissa fuerant, accessimus. Ille vero prius cum nescio quibus
barbaris collucutus, quarere me ex Maximino iussit, quem Romani
ex consularibus legatum ad Attilam essent missuri. Ut in tentorium
veni, et Maximino, quae mihi Onegesius dixerat, retuli, habita de eo,
quod barbaris respondendum esset, deliberatione, redii, dixique
Onegesio, Romanos magnopere desiderare, illum suarum cum Attila
controversiarum disceptatorem ad se accedere. Qua spe si
exciderint, Imperatorem, quem sibi libuerit, legatum missurum.
Extemplo me Maximinum arcessere iussit, quem, ut venit, ad Attilam
deduxit. Unde non multo post Maximinus reversus, narravit,
barbarum velle, Imperatorem ad se mittere legatos aut Nomum, aut
Anatolium, aut Senatorem, neque ullos alios praeter hos
admissurum. Et cum Maximinus obiiceret, minime convenire,
legatos, qui ad se mittantur, designando, suspectos Imperatori
reddere, Attilam respondisse, si haec abnuerint, armis se
controversias disceptaturum. Reversis nobis in tentorium, ecce ad
nos Orestis pater, “Vos ambos, inquit, ad convivium invitat Attilas, fiet
vero illud ad nonam diei horam.” Tempore condicto observato, ut
venimus, et una quoque Romanorum Occidentalium legati, stetimus
in limine coenaculi coram Attila. Hic pincernae, ut mos est in illis
regionibus, calicem tradiderunt, ut ante accubitum vota faceremus.
Quo facto, et calice degustato, ipsa solia, in quibus nos sedentes
coenare oportebat, ascendimus. Omnia sedilia circa parietes cubiculi
ab utraque parte disposita erant: medius in lecto sedebat Attilas,
altero lecto a tergo strato, pone quem erant quidam gradus, qui ad
eius cubile ferebant, linteis candidis et variis tapetibus ornatus gratia
contectum, simile cubilibus, quae Romani et Graeci nubentibus
adornare pro more habent. Et primum quidem convivarum locum
eius habebant, qui ad Attilae dextram sedebat, secundum eius, qui
ad laevam: in quo nos et Berichus, vir apud Scythas nobilis, sed
Berichus superiore loco. Nam Onegesius in sella ad dextram regii
thori, et e regione Onegesii duo ex Attilae filiis sedebant. Senior
enim in eodem, quo pater, throno, non prope, sed multum infra
accumbebat, oculis prae pudore propter patris praesentiam semper
in terram coniectis. Omnibus ordine sedentibus, qui Attilae erat a
poculis ingrediens pateram vini tradit. Hanc ubi suscepit, proximum
ordine salutavit, qui salutatione honoratus surrexit, neque prius eum
sedere fas erat, quam merum degustans, aut etiam ebibens,
poculum pocillatori redderet. Sedenti autem Attilae eodem modo, qui
convivio intererant, pocula suscipientes et post salutationem
degustantes, honorem exhibebant. Unicuique vero unus pocillator
aderat, quem, quum pincerna Attilae exiret, introire suo ordine
oportuit. Secundo et reliquis deinceps ad hunc modum honore
affectis, Attilas nos quoque eodem modo salutavit secundum
ordinem sellarum. Tum omnibus salutationis honore delato,
pincernae recesserunt. Mensae vero iuxta Attilae mensam erant
erectae, excipiendis tribus et quatuor, aut etiam pluribus convivis
idoneae, quorum unusquisque poterat minime transgressus sedium
ordines ex ferculis, quod sibi libitum erat, desumere. Deinde primus
in medium accessit Attilae minister, patinam carnibus plenam ferens.
Post ipsum qui panem ministrabant et opsonia mensis apposuerunt.
Sed ceteris quidem barbaris et nobis lautissima coena praeparata
erat et in discis argenteis reposita, Attilae in quadra lignea, et nihil
praeter carnes. Moderatum pariter in reliquis omnibus sese
praebebat. Convivis aurea et argentea pocula suppeditabantur,
Attilae poculum erat ligneum. Simplex admodum illius vestis nulla re,
nisi munditie, ornata erat. Neque eius ensis, neque calceorum
barbarorum ligamina, neque eius equi frena, ut reliquorum
Scytharum, auro aut lapidibus aut alia quacunque re pretiosa erant
ornata. Ut opsonia primorum ferculorum fuere consumpta,
surreximus, neque prius quisquam nostrum ad sedem suam est
reversus, quam sibi traditam pateram vini plenam, servato priore
ordine, Attilam salvum et incolumem precatus, ebibisset. Eo ad hunc
modum honore culto, sedimus. Tum nova fercula cuique mensae
sunt illata, quae alia continebant esculenta, ex quibus ubi omnes,
quoad satis esset, comedissent, eodem modo surreximus, et epoto
calice rursus consedimus. Adveniente vespere, facibusque accensis,
duo Scythae coram Attila prodierunt, et versus a se factos, quibus
eius victorias et bellicas virtutes canebant, recitarunt. In quos
convivae oculos defixerunt; et alii quidem versibus delectabantur,
aliis bellorum recordatio animos excitabat, aliis manabant lacrymae,
quorum corpus aetate debilitatum erat, et vigor animi quiescere
cogebatur. Post cantus et carmina Scytha nescio quis mente captus
absurda et inepta nec sani quicquam habentia effundens risum
omnibus commovit. Postremo Zercon Maurusius introivit. Edecon
enim illi persuaserat, ut ad Attilam veniret, omnem operam et
studium pollicitus, quo uxorem recuperaret. Hanc enim, cum illi
Bleda faveret, in barbarorum regione acceperat, eamque in Scythia,
ab Attila ad Actium dono missus, reliquerat. Sed hac spe frustratus
est, quia Attilas illi succensuit, quod ad sua remigrasset. Itaque tunc
arrepta festivitatis occasione progressus, et forma et habitu et
pronuntiatione et verbis confuse ab eo prolatis, Romanae Hunnorum
et Gothorum linguam intermiscens, omnes laetitia implevit et effecit,
ut in vehementem risum prorumperent. Sed Attilas semper eodem
vultu, omnis mutationis expers, et immotus permansit, neque
quicquam facere, aut dicere, quod iocum, aut hilaritatem prae se
ferret, conspectus est: praeter quam quod iuniorem ex filiis
introeuntem et adventatem, nomine Irnach, placidis et laetis oculis
est intuitus, et eum gena traxit. Ego vero cum admirarer, Attilam
reliquos suos liberos parvi facere, ad hunc solum animum adiicere,
unus ex barbaris, qui prope me sedebat et Latinae linguae usum
habebat fide prius accepta, me nihil eorum, quae dicerentur,
evulgaturum, dixit, vates Attilae vaticinatos esse, eius genus, quod
alioquin interiturum erat, ab hoc puero restauratum iri. Ut vero
convivium ad multam noctem protraxerunt, non diutius nobis
compotationi indulgendum esse rati exivimus.
Die exorto, Onegesium adivimus dicentes, nos dimitti oportere,
neque nobis diutius tempus terendum esse. Ille, Attilam quoque in
ea esse voluntate, et nos dimittere constituisse, respondit. Itaque
non multo post consilium procerum de his, quae Attilas statuerat,
habuit, et litteras, quae Imperatori redderentur, digessit. Aderant
quoque, quorum curae epistolas scribere incumbebat, inter quos erat
Rusticius, vir e superiore Mysia ortus, qui ab hostibus captus, cum
dicendi facultate valeret, barbaro operam in conscribendis epistolis
navabat. Dimisso consilio, ab Onegesio precibus contendimus, ut
Syllae uxori et eius liberis, qui in expugatione urbis Ratiariae una
cum matre in servitutem redacti erant, libertatem restitueret. Et vero
ab his liberandis minime abhorrebat, sed eorum libertatem magna
pecuniae summa a nobis emptam volebat. Itaque nos eum supplices
orare et obtestari, ut, habita eorum pristinae fortunae ratione,
praesentis calamitatis commiseratione moveretur. Ille, ut Attilam
adiit, mulierem pro quingentis aureis liberam dimisit et eius filios
dono ad Imperatorem misit. Interea Recan, Attilae uxor, in aedes
Adamis, qui eius res domesticas curabat, nos ad coenam invitavit.
Ab eo una cum pluribus Scythiae principibus comiter excepti sumus
et iucundis sermonibus et magnifico epularum apparatu. Tum
unusquisque eorum, qui aderant, surgens, Scythica comitate
poculum plenum nobis porrexit, et eum, qui ante se biberat,
amplexus et exosculatus, illud excepit. A coena nos in tentorium
nostrum recipientes, somnum cepimus. Postridie iterum nos Attilas
ad coenam invitavit, et eodem, quo prius, ritu ad eum accessimus et
ad hilaritatem nos convertimus. Tum autem non senior ex filiis Attilae
in eius thoro una cum ipso accumbebat, sed Oebarsius, eius
patruus. Per totum convivii tempus nos blandis sermonibus
appellans Imperatori dicere iussit, ut Constantio, quem ad eum
Aetius, ut ab epistolis esset, miserat, uxorem daret eam, quam illi
promisisset. Etenim Constantius una cum Attilae legatis ad
Theodosium venerat, et se operam daturum, ut pax longo tempore
inter Romanos et Hunnos servaretur, dixerat, modo sibi uxorem
locupletem matrimonio copularet. Huic petitioni Imperator annuerat,
et Saturnini filiam, viri et opibus, et genere clari et ornati, se illi nuptui
daturum promiserat. Saturninum autem interemerat Athenais seu
Eudocia, (utroque enim nomine vocabatur,) neque Imperatori ad
exitum perducere, quod promiserat, per Zenonem, virum
consularem, licuit. Is enim olim magna Isaurorum multitudine
stipatus, urbi Constantinopoli, quae bello premebatur, praesidio
fuerat. Qui quum orientalium exercituum dux esset, puellam custodia
eduxit, et Rufo cuidam, uni ex suis necessariis, despondit. Hac
puella sibi subtracta, Constantius barbarum orabat, ne sibi factam
contumeliam negligeret, sed perficeret, ut sibi uxor daretur aut ea,
quae erepta fuerat, aut etiam alia, quae dotem adferret. Quamobrem
per coenae tempus barbarus Maximinum Imperatori dicere iussit,
non oportere Constantium spe ab ipso excitata falli, et ab Imperatoris
dignitate alienum videri, mendacem esse. Haec Attilas Maximino
mandavit, propterea quod Constantius illi ingentem pecuniae
summam pollicitus erat, si uxorem e Romanis puellis locupletem
duceret. Sub nocte a coena discessimus.
Tribus deinde diebus elapsis, muneribus donati dimissi sumus.
Attilas quoque Berichum, virum e Scythiae primoribus, multorum
vicorum in Scythia dominum, et qui in convivio superiore loco
sederat, nobiscum legatum ad Imperatorem misit. Hunc enim et alias
Romani pro legato admiserant. Nobis autem iter conficientibus et in
vico quodam commorantibus, captus est vir Scytha, qui a Romanis
explorandi gratia in barbaram regionem descenderat, quem crucis
supplicio affici Attilas praecepit. Postridie etiam dum per alios vicos
progrederemur, duo, qui apud Scythas serviebant, manibus vincti
post terga trahebantur, quod his, quos belli casus dominos fecisset,
vitam eripuissent. Hos, immissis inter duo ligna uncis praedita
capitibus, in cruce necarunt. Berichus vero, quamdiu Scythiam
peragravimus, eadem via nobiscum iverat, et placidus et amicus
visus erat. Ut Istrum traiecimus, propter quasdam vanas causas, a
servis ortas, nos inimicorum loco habuit. Et primum quidem equum,
quem Maximino dono dederat, ad se revocavit. Etenim Attilas omnes
Scythiae principes, qui in ipsius comitatu erant, donis Maximinum
ornare iusserat, et unusquisque certatim illi equum miserat, inter
quos et Berichus. At ille cum moderationis gloriam sibi comparare
studeret, ex equis oblatis paucos acceperat, reliquos reiecerat.
Berichus igitur equum, quem Maximino dederat, ademit, neque
deinceps eadem via ire aut coenari nobiscum voluit. Itaque
hospitalitatis tessera, in barbara regione contracta, eo usque
progressa est. Hinc per Philippopolim ad Adrianopolim nobis iter fuit.
In hac civitate quiescentes, Berichum rursus allocuti cum eo, quod
tamdiu erga nos silentium tenuisset, expostulavimus. Nec enim
ullam fuisse causam cur nobis irasceretur, quandoquidem in nulla re
cum offenderamus. Itaque eo placato et ad coenam invitato, ab
Adrianopoli movimus. In itinere Bigilam, qui in Scythiam revertebatur,
obvium habuimus: quo edocto, quae Attilas ad legationem nostram
responderat, coeptum iter continuavimus. Ut Constantinopolim
venimus, Berichum existimabamus iram abiecisse, sed agrestis et
ferae suae naturae minime est oblitus. Nam Maximinum insimulavit
dixisse, quum in Scythiam transiisset, Areobindi et Asparis,
exercituum ducum, auctoritatem apud Imperatorem nullius esse
ponderis, et cum barbarorum levitatem et inconstantiam notasset,
eorum gesta in nullo pretio habuisse.
Reversum Bigilam, quum in iis locis advenisset, ubi tum Attilas
commorabatur, circumstantes barbari ad id praeparati
comprehenderunt, et manus in pecunias, quas Edeconi adferebat,
iniecerunt. Quam ipsum ad Attilam adduxissent, is ex eo quaesivit,
cuius rei gratia tantum auri asportasset. Illi respondit, ut suis et
comitum suorum necessitatibus provideret, ne rerum necessariarum
inopia, aut equorum, aut aliorum animalium vecturae aptorum
penuria, quae per longa itinera deperierant, a studio obeundarum
legationum avocaretur. Praeterea ad redemptionem captivorum
pecuniam paratam esse. Multos enim ex Romanis a se magnopere
petiisse, ut propinquos suos redimeret. Cui Attilas: “Sed neque iam,
o turpis bestia, Bigilam appellans, ullum tibi tuis cavillationibus iudicii