Professional Documents
Culture Documents
Second Edition
Sina Ebnesajjad
Pradip R. Khaladkar
William Andrew is an imprint of Elsevier
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vii
viii C ONTENTS
The aim of the present book is to address the use of and 6 describe processes used to convert fluoropoly-
fluoropolymers in the chemical processing industry mers into shapes and parts. Chapter 7 covers the
(CPI) and other allied industries including food, fabrication techniques used to finish or alter the fluo-
beverage, pharmaceutical, semiconductor, and pulp ropolymer shapes/parts. Chapter 8 reviews the design
and paper industries. This book is both a reference and construction of the basic equipment components
and a source for learning the basics for those involved of a chemical processing plant.
in the entire product value chain related to the chem- Chapter 9 discusses the operation and mainte-
ical industries, from fluoropolymer producers all the nance of vessels and tanks. Chapter 10 provides
way to the end users. The reader will be able to learn methodology and analytical techniques for the failure
about how the unique characteristics of fluoroplastics analysis of fluoropolymer parts. Chapters 11e13 are
are utilized in the design and construction of equip- devoted to the cost analysis, safety considerations,
ment exposed to harsh chemical environments. The and future trends of fluoropolymers. The Glossary
book offers information helpful to engineers, mainte- offers a short description of technical words and
nance personnel, students, material managers, and all terms of art.
others involved in the CPIs. We have tried to present the data in SI units
In this book practical matters have been empha- throughout the book as much as possible. A large
sized over the theoretical subjects. There are number of parts are, however, still specified in
numerous sources for in-depth study of topics, English units. In such cases, conversion factors
including polymerization and the polymer science have been listed in footnotes to allow the reader to
of fluoropolymers. Those references have been listed convert to metric units.
at the end of the chapters, as both bibliography and None of the views or information presented in this
additional reading sources. Review papers are partic- book reflects the opinions of any of the companies or
ularly helpful as a starting point for finding additional individuals that have contributed to the book. If there
sources for concentrated reading in selected areas. are errors, they are oversights on the part of the
The chapters of this book have been written authors. A note to the publisher indicating the
to allow sequential or singular reading of them. specific error, to correct the future editions, would
Chapters 1 and 2 introduce the reader to fluoropoly- be much appreciated.
mers, fluoroelastomers, and the other materials of
construction used to manufacture parts that come in Sina Ebnesajjad
contact with chemicals in factories. Chapters 3 and Pradip R. Khaladkar
4 concentrate on the properties and selection of fluo- April 2017
ropolymers for the construction of parts. Chapters 5
xiii
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Acknowledgments
We owe the majority of our learning and experi- references section at the end of each chapter. We
ence in the field of fluoropolymers to our employ- sincerely thank the contributions that the data
ment at the DuPont Fluoroproducts (now Chemours supplied by each company have made to this book.
Corp) and FluoroConsultants Group (Sina) and Special thanks go to our friend Dr. Lawrence
DuPont Engineering Technology (Pradip). Special McKeen for contributing the powder coating tech-
thanks go to DuPont Fluoroproducts (now Chemours nology section included in Chapter 8.
Corp) for the contribution of information, figures, Our sincere thanks go to Nicky Carter for
photographs, illustrations, and tables. Attribution has managing the production of our book with care
been made to the companies wherever the contrib- and patience. Support by David Jackson facilitated
uted material appears. the completion of the second edition of our book.
We thank all the companies that have supplied We sincerely appreciate the support offered for this
the authors with information, figures, photographs, book and others by Matthew Deans.
and tables. They have been acknowledged in the
xv
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1 Introduction to Fluoropolymers
PVF
PFA Cl Cl
ECTFE
Table 1.3 Commercialization Timeline of Major Fluoropolymers Versus Key Processing/Application Trade-Offs [10]
Year
Fluoropolymer Commercialized Monomers Trade-off D Trade-off L
PTFE 1947 TFE Continuous use Nonemelt-
temperature 260 C processible
PCTFE 1953 CTFE Melt-processible/nonemelt- Maximum
processible continuous use
temperature 180 C
FEP 1960 TFE, HFPc Melt-processible Maximum
continuous use
temperature 200 C
PVF 1961 VFa Thin film/weatherable Maximum
continuous use
temperature 107 C
PVDF 1961 VDFb Melt-processible Maximum
continuous use
temperature 150 C
ECTFE 1970 CTFE, Ed Hardness/toughness Maximum
continuous use
temperature 150 C
PFA 1972 TFE, PAVEe Melt-processible, Low molecular
continuous use temperature weight
260 C
ETFE 1973 TFE, E Hardness/toughness Maximum
continuous use
temperature 150 C
Teflon AF 1985 TFE, PDDf Soluble in special High cost
halogenated solvents
CTFE, chlorotrifluoroethylene; E, ethylene; ECTFE, ethylene chlorotrifluoroethylene; ETFE, ethylene tetrafluoroethylene; FEP, fluorinated
ethylene propylene; HFP, hexafluoropropylene; PAVE, perfluoroalkylvinylether; PCTFE, polychlorotrifluoroethylene; PDD, 2,2-
bistrifluoromethyl-4,5 difluoro-1,3-dioxole; PFA, perfluoroalkoxy; PTFE, polytetrafluoroethylene; PVDF, polyvinylidene fluoride; PVF, poly-
vinylfluoride; TFE, tetrafluoroethylene; VDF, vinylidene fluoride; VF, vinyl fluoride.
a
Vinyl fluoride (CH2 ] CHF).
b
Vinylidene fluoride (CH2 ] CF2).
c
Hexafluoropropylene (CF2 ] CF e CF3).
d
Ethylene (CH2 ] CH2).
e
Perfluoroalkylvinylether (CF2 ] CF e O e Rf).
f
Perfluoro-2,2-dimethyl-1,3-dioxole.
(200 C) (Table 1.3). PFA, which was introduced in ETFE has a lower continuous use temperature
1973, offers both melt-processing and the same upper (150 C) than PTFE (260 C), less chemical resistance,
continuous use temperature as PTFE (260 C). and a higher coefficient of friction. Mechanical
ETFE addresses the need for a mechanically properties including tensile strength, elongation at
stronger polymer, albeit at some loss of properties break, and tensile modulus are enhanced. Examples of
compared to perfluoropolymers because of the pres- beneficial performance include increased cut-through
ence of hydrogen in its molecule: resistance as wire insulation when compared to PTFE.
Teflon AF is an amorphous fluoropolymer that is
soluble in select halogenated solvents. It is applied by
solution coating processes followed by removal of
the solvent. The amorphous fluoropolymer coating is
as resistant to nearly as many chemicals as PTFE.
1: I NTRODUCTION TO F LUOROPOLYMERS 5
The coating can be very thin ranging from less than a the properties of these plastics. Fluoropolymers use
micrometer and upwards. Other amorphous fluo- spans across all facets of human life from household
ropolymer brands include Lumiflon and Cytop by appliances and cookware to aerospace and electronic
Asahi Glass Corp. industries. Useful properties (Table 1.2) of fluo-
There are a number of other polymers in this family ropolymers in various applications include chemical
including PCTFE, PVF, PVDF, ECTFE, TFE/hexa- resistance, thermal stability, cryogenic properties,
fluoropropylene/vinylidene fluoride terpolymers, and low coefficient of friction, low surface energy, low
chlorotrifluoroethylene/vinyl ether copolymers. dielectric constant, high volume and surface re-
sistivity, and flame resistance. Applications of fluo-
ropolymers, typically, exploit one or a combination
1.5 Applications of of fluoropolymer properties (Table 1.4) that differ-
Fluoropolymers entiate them from other plastics.
In the chemical processing industry fluoropol-
Consumption of fluoropolymers has increased ymers are selected mainly for their resistance to
over time, as technological advances have required chemical attack usually at above or below room
Table 1.4 Major Applications and Some Uses of Fluoropolymers [10]
temperature. These plastics are used to fabricate For airports, stadiums, and other structures,
linings for carbon steel vessels and for piping and fiberglass fabrics coated with fluoropolymers are
other fluid handling components. They provide du- fabricated into roofing and enclosures. Cables or air
rable, low maintenance, and economical alternatives pressure are applied to from a range of innovative
to exotic metal alloys. In these applications, fluo- structures from these architectural fabrics. Fluo-
ropolymers also offer thermal stability for use at high ropolymers provide excellent resistance to weath-
temperatures. As they do not react with process ering, including exposure to the ultraviolet rays in
streams, fluoropolymers help prevent contamination sunlight, flame resistance for safety, and low surface
of products of chemical processes. energy for soil resistance and easy cleaning.
Electrical properties of fluoropolymers are highly
valuable in electronic and electrical applications. In
data communications, for example, FEP is used to References
insulate cables installed in air-handling spaces (ple- [1] R.J. Plunkett, US Patent 2,230,654, assigned to
nums) in office buildings. FEP supplies the excellent DuPont Co. (Feb. 4, 1941).
dielectric properties these cables required to perform [2] R.J. Plunkett, The history of polytetrafluoro-
well at high data transmission rates as well as long- ethylene: discovery and development, in:
term stability. The performance of FEP insulated R.B. Seymour, G.S. Kirshenbaum (Eds.), High
cables remains unchanged over the life of the cabling Performance Polymers: Their Origin and
system. Most importantly, FEP aids these cables meet Development, Proc. Symp. Hist. High Perf.
the strict building code requirements for low flame Polymers: At the ACS Meeting in New York,
spread and low smoke generation. April 1986, Elsevier, New York, 1987.
Fluoropolymers are used to insulate wire in critical [3] S.V. Gangal, Polytetrafluoroethylene, homopol-
aerospace and industrial applications where chemical ymers of tetrafluoroethylene, in: second ed.En-
and thermal resistance in addition to cut-through cyclopedia of Polymer Science and Engineering,
resistance and flex fatigue durability are essential. 16, John Wiley & Sons, New York, 1989, pp.
Fluoropolymers are also materials of construction for 577e600.
high-frequency cable connectors and for thermo- [4] V. Gangal, P.D. Brothers, Perfluorinated poly-
couple wiring required to resist high temperatures. mers, polytetrafluoroethylene, Pub. Online Ency.
In the automotive, office equipment, and other Polym. Sci. Eng. (June 2010).
industries, the mechanical properties of fluoropol- [5] Big Chemical Encyclopedia, http://chempedia.
ymers are beneficial in low-friction bearings and info/info/99237/, April 18, 2016.
seals that resist attack by hydrocarbons and other [6] University of Waterloo, Canada, www.science.
fluids. In food processing, the Food and Drug uwaterloo.ca, April 18, 2016.
Administration (FDA) has approved fluoropolymer [7] S.V. Gangal, Polytetrafluoroethylene, in: fourth
grades as fabrication material for equipment due to ed.Kirk-Othmer Encyclopedia of Chemical
their resistance to oil and cleaning materials, and Technology, 11, John Wiley & Sons, New York,
their antistick and low friction properties. 2000, pp. 621e644.
Fluoropolymers are applied as nonstick coatings [8] W.A. Zisman, Surface properties of plastics,
for cookware and appliance surfaces. These appli- Record of Chemical Progress 26 (1965) 1.
cations depend on thermal and chemical resistance as [9] Properties Handbook No. H-37051-3, Teflon
well as antistick performance. PTFE and ETFE are PTFE Fluoropolymers Resin, DuPont, July 1996.
selected to insulate appliance wiring because both [10] S. Ebnesajjad, Fluoroplastics, in: Non-Melt
materials withstand high temperatures. Processible Fluoroplastics, second ed., vol. 1,
Medical articles such as surgical patches and Plastics Design Library, Elsevier, Oxford, UK,
cardiovascular grafts rely on the long-term stability 2014.
of fluoropolymers as well as their biocompatibility,
purity, inert surface, and flex fatigue resistance.
2 Materials of Construction
manufacturers. The creation of a multitude of mate- 1. A fiberglass tank is made of vinyl ester resin,
rials in a relatively short time led to high expectations which is a thermoset and is semirigid in its
and less-than-careful application of some of these composite form.
materials. Failures, some catastrophic, inevitably 2. A rubber (elastomeric) gasket can be made of
occurred. Notable among these were ruptures of FRP polychloroprene, which is a thermoset and is
storage tanks and vessels resulting in total discharge nonrigid.
of corrosive and hazardous contents. Less notable but
equally damaging failures also occurred in linings of 3. A fluoropolymer lining for a vessel is thermo-
various types. The underlying causes were improper plastic and nonrigid.
material selection, design, quality of fabrication,
exceeding operating parameters, inability to inspect
adequately, or some combination of these. 2.4 Comparison Between Polymer-
Based Materials and Metals
2.3 Definition of Polymer-Based There are some obvious and subtle differences
between polymer-based materials and metals. The
Materials
obvious differences are in strength (high for metals),
Polymers are long chain molecules made from elongation (high for polymers), and maximum-use
organic chemicals. These materials are defined by temperature (much higher for metals). Not so
three distinct characteristics. obvious are anisotropy (polymers), homogeneity
(metals), changing properties in service (plastics),
Organic chemistry basis responsiveness to nondestructive testing (high for
metals), ability to predict remaining life (low for
Mechanical strength basis
polymers), ability to carry out accelerated testing
Thermal processing basis for corrosion rates (high for metals), and sensitivity
to workmanship (high for polymers). All these fac-
Polymers can be distinguished from each other by tors make using plastics as effective as metals and
their generic organic chemistry description such as with the same degree of confidence and a challenge
polyolefins, fluorocarbons, styrenics, epoxies, etc. for the end user.
They can also be classified by their mechanical Phenomenology of corrosion for metals and
strength: rigid (elastic modulus >690 MPa), semi- polymer materials is not the same. For example, the
rigid (modulus between 69 and 690 MPa), and terms such as corrosion rate, pitting, end grain
nonrigid (modulus <69 MPa). Additionally, poly- attack, and intergranular attack used to describe
meric materials are classified by the way they are metals’ behaviors are not applicable to plastics. Not
thermally processed: thermoplastics and thermosets. only are the terms for plastics different (blistering,
Thermoplastics are those which can be remelted and discoloration, cracking, etc.) but they are based on a
reprocessed repeatedly. Thermosets cannot be naked-eye observation and not at a microscopic level
remelted for reprocessing since they are cross-linked as for metals.
(also known as vulcanized in the world of elasto-
mers). Any attempt to remelt thermosets will result in
degradation and, ultimately, charring. 2.4.1 Position of Fluoropolymers
Fluoropolymers are thermoplastic and nonrigid in the Materials Spectrum
materials while fluoroelastomers have elastomeric
properties. See Tables 2.1 and 2.2 for a comparison of Fluoropolymers are fluorine-containing polymers.
physical and mechanical properties of select plastics They are thermoplastic in nature and are semirigid
and elastomers including fluorinated materials. and are classified in two ways:
Elastomers are a special class of nonrigid materials
distinguished by high elongation and high recovery. Homopolymers or copolymers (preferred by
A complete description of a polymer system must chemists)
necessarily include references to all three categories. Fully fluorinated or partially fluorinated
Some following examples illustrate the point. (preferred by engineers)
2: M ATERIALS
Table 2.1 Physical and Mechanical Properties of Plastics [1,2]
OF
Mold Tensile Break Tensile Flexural Flexural Impact
C ONSTRUCTION
Specific Shrinkage, Strength, Elongation, Modulus, Strength, Modulus, Notched Izod Compressive
Gravity % MPa % MPa MPa MPa 238C J/m (238C) Strength, MPa
Test method D792 D955 D638 D638 D638 D790 D790 D256 D695
ASTM
Polystyrene 1.06 0.5 46 2.2 3172 96 3103 10.8 96.6
ABS 1.05 0.6 48 8.0 2069 72 2621 242 69
SAN 1.08 0.4 72 3.0 3862 103 3793 27 103
Polypropylene 0.90 1.5 32 15.0 1310 41 2069 27 34.5
Polyethylene 0.96 2.0 30 9.0 1034 38 1517 70 27.6
Polyacetal 1.41 1.8 61 60.0 2827 90 2552 70 36
Polyester 1.30 2.0 55 200.0 2758 88 2345 10.8 90
Polyamide, 1.13 1.3 81 200.0 2758 103 2759 53.8 90
nylon 6
Polyamide, 1.14 1.8 79 300.0 1310 103 1310 53.8 34
nylon 6,6
Polycarbonate 1.20 0.6 62 110.0 2379 93 2345 161 86
Polysulfone 1.24 0.7 70 75.0 2482 106 2690 32 96.6
Test method D792 Measured on D4894-5 D4894-5 D638 D790 D790 D256
ASTM parts D1708 D638 D1708 D638
PTFE 2.14e2.22 2e0 20e35 300e550 550 No break 340e620 188 34.5
PFA 2.15 3.5e6.0 20e26 300 276 551 No break
FEP 2.15 3.5e6.0 20e28 300 345 No break 655 No break 15.2
ETFE 1.71 1e7 45 150e300 827 38 1034e1171 No break 17.2
PVDF 1.78 0.2e3 31e52 50e250 1040e2070 45e74 1140e2240 107e427 55e110
ETFE, ethylene tetrafluoroethylene; FEP, fluorinated ethylene propylene; PFA, perfluoroalkoxy; PTFE, polytetrafluoroethylene; PVDF, polyvinylidene fluoride.
9
10
Table 2.2 Physical and Mechanical Properties of Elastomers [3]
Trade Name
F LUOROPOLYMER A PPLICATIONS
Viton Aflas Fluorosilicone Kalrez Adiprene Neoprene Hypalon Nordel
Chemical Name
Continuous-use Min 29 to 7 29 80 to 68 38 54 62 54 59
temperature, C Max 227 204 to 230 232 290 to 315 121 149 135 163
Tensile strength, MPa a 3.4e20.7 13.8e22.1 3.4e9.6 3.4e10.3 2.1e24.1 3.4e27.6 e 2.1e24.1
Tensile modulus at 1.4e14 6.2e17.2 6.2 6.2e13.1 0.7e20.7 0.7e20.7 3.1e3.4 0.7e20.7
100% elongation, MPaa
IN THE
Hardness (durometer) 50e95 A 60e100 A 35e80 A 65e95 A 30e90 A 15e95 A 40e100 A 30e90 A
Compression set 9e16, 70 h at 25, 70 h at 93 17e25, 22 h at 149 20e40, 20e60, 70 h at 20e60 h at 100 38e80, 22 h at 100 20e60, 70 h at
at temperature, C 24 70 h at 21 100 100
24-h Water
Weak Bases and Salts Strong Bases Strong Acids Strong Oxidants Absorption
Weight
Material 258C 938C 258C 938C 258C 938C 258C 938C Change, %
Polyacetal 1e3 2e5 1e5 2e5 5 5 5 5 0.23
ABS 1 2e4 1 2e4 1e4 5 1e5 5 0.1e0.4
Nylons 1 2 2 3 5 5 5 5 0.2e1.9
Polyester 1 3e4 2 5 3 4e5 2 3e5 0.06e0.09
Polyethylene 1 1 1 1 1 1 1 1 <0.01
Polystyrene 1 5 1 5 4 5 4 5 0.03e0.60
Polysulfone 1 1 1 1 1 1 1 1 0.2e0.3
Polyvinyl chloride 1 5 1 5 1 5 2 5 0.04e1.0
PTFE 1 1 1 1 1 1 1 1 0
PFA 1 1 1 1 1 1 1 1 <0.03
FEP 1 1 1 1 1 1 1 1 <0.01
ETFE 1 1 1 1 1 1 1 1 <0.03
PVDF 1 1 1 2 1 2 1 2 0.04
Polychlorotrifluoroethylene 1 1 1 1 1 1 1 1 0.01e0.10
ETFE, ethylene tetrafluoroethylene; FEP, fluorinated ethylene propylene; PFA, perfluoroalkoxy polymer; PTFE, polytetrafluoroethylene; PVDF, polyvinylidene fluoride.
a
Effect is defined by ASTM D543 and D2299: 1, no effect or inert; 2, slight effect; 3, mild effect; 4, softening or swelling; 5, severe degradation.
11
12
Table 2.4 Effecta of Organic Chemicals on Polymers [1,2]
F LUOROPOLYMER A PPLICATIONS
ABS 4 5 2 3e5 3e5 5 3e5 5
Nylons 1 1 1 1 1 2 1 1
Polyester 2 5 1 3e5 3 5 2 3e4
Polyethylene 3 4 3 4 3 4 3 4
Polystyrene 4 5 4 5 5 5 4 5
Polysulfone 4 4 1 1 5 5 3 4
PVC 4 5 1 5 5 5 4 5
PTFE 1 1 1 1 1 1 1 1
PFA 1 1 1 1 1 1 1 1
IN THE
FEP 1 1 1 1 1 1 1 1
ETFE 1 1 1 1 1 1 1 1
Polymer Monomer Unit Melt Pointa Melt Viscosity, Pa$sb Melt Flow Rate, dg/min Fabrication Technique
OF
10 12c
Granular PTFE eCF2eCF2e 327 10 e10 Compression molding
C ONSTRUCTION
Fine powder PTFE eCF2eCF2e 327 1010e1012c Paste extrusion
10 12c
Dispersion PTFE eCF2eCF2e 317e337 10 e10 Coating methods
4 5d
FEP eCF2eCF2eC(CF3)F 260e282 10 e10 0.8e18e Melt processing
eCF2e
PFA eCF2eCF2$C(OeRf) 302e310 4 103e3 104d 1e18f Melt processing
FeCF2e
ETFE eCF2eCF2eCH2eCH2 254e279 0.7e10 103g 3.7e16h Melt processing
i
PCTFE eCClFeCF2e 210e215 1e10 Compression molding/
melt processing
ECTFE eCClFeCF2eCH2eCH2e 240 e 1e50 Melt processing
3 j
PVDF eCF2eCH2e 155e192 0.2e17 10 5e180 Melt processing
Polyvinyl fluoride eCHFeCH2e 190 e e Melt extrusion of
dispersion in latent
solvent
Soluble fluoropolymers e[CF2eCF2]n-me[Cf]mk 305 e e Latex application
methods
ECTFE, ethylene chlorotrifluoroethylene; ETFE, ethylene tetrafluoroethylene; FEP, fluorinated ethylene propylene; PCTFE, polychlorotrifluoroethylene; PFA, perfluoroalkoxy polymer; PTFE,
polytetrafluoroethylene; PVDF, polyvinylidene fluoride.
a
Second melt point for PTFE.
b
From Ref. [5].
c
Melt creep viscosity by according to procedure MVS Patent.
d
By capillary rheometer ASTM D 2116.
e
Melt flow rate by ASTM D 2116.
f
By capillary rheometer ASTM D 3307.
g
By capillary rheometer ASTM D 3159.
h
Melt flow rate by ASTM D 3159.
i
By capillary rheometer at 230 C.
j
Melt flow rate at 265 C.
k
Cf is the comonomer m > 0.2 weight fraction.
13
14 F LUOROPOLYMER A PPLICATIONS IN THE C HEMICAL P ROCESSING I NDUSTRIES
resistance of polymers to chemicals of all types in- resistant among all thermoplastics (Tables 3.3e3.7).
creases with an increase in their fluorine content. Few substances chemically interact with these plas-
Therefore, the chemical resistance of ethylene tics. Exceptions among commercially encountered
tetrafluoroethylene (ETFE), ethylene chlorotri- materials include alkali metals, especially in a molten
fluoroethylene (ECTFE), and polyvinylidene fluoride state, and gaseous fluorine at high temperatures and
(PVDF) is generally inferior to that of perfluorinated pressures. Perfluoropolymers are attacked by certain
polymers such as perfluoroalkoxy (PFA) and fluori- halogenated compounds containing fluorine such as
nated ethylene propylene (FEP). chlorine trifluoride (ClF3), bromine trifluoride
(BrF3), iodine pentafluoride (IF5), and oxygen
difluoride (OF2). The inertness of these polymers
3.2 Influence of Processing arises from their molecular structure [7]. Extensive
on Fluoroplastics information about chemical resistance of fluoropol-
ymers has been published in References [2,3,8].
Crystallinity affects a number of important prop- A few chemicals have been reported to attack
erties of semicrystalline thermoplastics including perfluoropolymers at or near their upper service
fluoropolymers. The degree of crystallinity in a temperature (260 C) [5]. Those compounds include
fabricated part depends on the processing conditions 80% sodium, potassium hydroxide, and strong Lewis
such as the length of exposure to temperatures above bases such as metal hydrides like boranes (B2H6),
the melting point and the cooling rate. Elimination of aluminum chloride, ammonia, and some amines
bubbles, trapped air, and voids during processing (ReNH2) and imines (R ¼ NH). Slow oxidative
have a major impact on a number of properties of a attacks may occur in the presence of 70% nitric acid
part including mechanical, electrical, and resistance at 250 C under pressure. It is important to test the
to permeation of chemicals. A group of per- effect of these reagents on perfluoropolymers under
fluoropolymer properties that remain relatively in- the specific application temperature to determine the
dependent of the fabrication conditions are listed in material limitations.
Table 3.2. Partially fluorinated fluoroplastics contain Perfluoropolymers derive their chemical resis-
hydrogen or chlorine and can undergo significant tance from a strong carbonefluorine bond and an
thermal degradation if they are overexposed ther- impermeable sheath of fluorine atoms surrounding
mally during processing. Thermal degradation alters the carbonecarbon chain. Relatively high crystal-
many of the properties listed in Table 3.2 for partially line content renders these polymers insoluble in
fluorinated fluoroplastics. solvents.
A commercially significant perfluoropolymer is the
copolymer of tetrafluoroethylene-perfluoromethyl
3.3 Chemical Compatibility of vinyl ether (MFA). It has chemical resistance char-
Fluoropolymers acteristics similar to the other perfluoropolymers such
3.3.1 Chemical Compatibility of as PTFE, PFA, and FEP.
Some halogenated solvents are absorbed by per-
Perfluoropolymers fluoropolymers without any chemical interaction or
Perfluoropolymers such as polytetrafluoroethylene degradation. The action is strictly physical and the
(PTFE), PFA, and FEP are by far the most chemically removal of the absorbed species restores the
Table 3.4 Chemical Resistance of Polytetrafluoroethylene to Common Acids and Bases [5]
Table 3.4 Chemical Resistance of Polytetrafluoroethylene to Common Acids and Bases [5] (Continued )
Table 3.5 Chemical Compatibility of Polytetrafluoroethylene (PTFE) With Halogenated Chemicals [5]
Table 3.6 Effect of Immersion in Inorganic Chemicals for 168 h on Perfluoroalkoxy [6]
Table 3.7 Effect of Immersion in Organic Chemicals for 168 h on Perfluoroalkoxy [6]
Table 3.7 Effect of Immersion in Organic Chemicals for 168 h on Perfluoroalkoxy [6] (Continued )
fluoropolymer back to its original state. Too much atom and a molecule of oxygen. The atomic oxygen
absorption by a perfluoropolymer sample is likely to is highly reactive allowing it to attack and etch most
be an indication of excessive porosity. A highly polymers. PTFE has been reported to be very resis-
porous sample may appear blistered because of the tant to etching by ozone in low earth orbit environ-
expansion of vapors in the surface pores. A properly ment testing, where atomic oxygen is the most
fabricated part does not exhibit blistering. abundant species [9,10].
O3 / O2 þ O
3.3.1.1 Effect of Ozone on Resistance of polymers to ozone attack was stud-
Fluoropolymers ied in space environments in “actual” applications. In
Ozone is considered a corrosive substance against the laboratory, glow discharge or plasma etching is
plastics due to its ability to readily degrade into an the common method for laboratory study of ozone
3: P ROPERTIES OF N EAT (U NFILLED ) AND F ILLED F LUOROPOLYMERS 23
effect. Plasma and low earth orbit environments are bonded to them. The ultimate stability was reached in
not equivalent. For instance, oxygen plasma contains the linear PTFE chain, which consists of all CF2
a variety of other particles including electrons and groups with the exception of the few end groups.
free radicals in addition to atomic oxygen. In
contrast, atomic oxygen is the dominant constituent
of low earth orbit. 3.3.1.2 Oxygen Compatibility of
The results indicated oxygen uptake was least for Polytetrafluoroethylene
PTFE and most for polyethylene in experiments in Oxygen is singled out due to its propensity to
which a series of fluorinated polyolefins were facilitate autoignition of organic material including
exposed to ozone “out of glow.” This means that plastics. Fluoropolymers are extensively used for
plasma or glow discharge was used to produce atomic oxygen services because of their low flammability.
oxygen that etched the sample placed outside the Oxygen does not interact with PTFE under most
discharge zone. The results of “out of glow” plasma circumstances.
etching and low earth orbit, by and large, were in Limiting oxygen index (LOI) of PTFE is greater
agreement [11]. than 95% under ambient conditions. This means that
Maximum oxygen uptake decreased with an in- PTFE does not burn without an ignition source in an
crease in the fluorine content of the polymers. For atmosphere containing less than 95% oxygen. LOI is
example, PVDF took up less oxygen as a result of O3 not a complete predictor of all practical conditions in
exposure than polyethylene, although more than which oxygen and PTFE may interact. A number of
PTFE, in the same experiment [11]. The exception to considerations apply.
this trend was polyvinyl fluoride (PVF); it had a higher Increased pressure and temperature can accelerate
etch rate than polyethylene (Table 3.8). Why was PVF autoignition of PTFE, that is, ignition can occur
more susceptible to ozone attack than polyethylene? without initiation by an external source. Combina-
Golub [12] has proposed an explanation attrib- tions of high temperatures and high flow rates
uting the high etch rate of PVF to the ease of fluorine through small orifices can initiate reaction with
formation from the decomposition of this polymer. PTFE. Organic impurities such as grease, oil, and dirt
Fluorine promotes degradation of molecular oxygen react violently with oxygen and generate heat, which
to its active atomic form (O2 / 2O), further reacting can be sufficient for igniting PTFE. Surfaces are the
with PVF, thus enhancing the etch rate. PVDF and most common locations of contamination. Before
FEP molecules have lower etch rates due to the use, all surfaces that come in contact with oxygen
higher stability of the CF2 group to oxygen attack must be meticulously cleaned to assure that they are
than CFH in PVF or CH2 in polyethylene. Both free of any organic contaminants.
PVDF and ETFE have low etch rates due to the Surface condition can affect the safety of liquid
protection provided to the CH2 groups by CF2 groups oxygen (LOX) contact with PTFE. Despite its
Table 3.8 Relative Mass Loss Rates for Polymer Films Exposed to Low Earth Orbit [11]
extremely low temperature, LOX can react with elongation were found to change little after 3000-h
organic contaminants and ignite PTFE. Thorough exposure of unfilled ETFE to boiling water.
cleaning of the surfaces of all parts that come in ECTFE is resistant to strong mineral and oxidizing
contact with oxygen is required. ASTM D2512 pre- acids, alkalis, metal etchants, LOX, and virtually all
scribes procedures to determine the compatibility of organic solvents with the exception of hot amines
materials with LOX. This standard determines the such as aniline and dimethyl amine. ECTFE is sus-
relative sensitivity of materials under impact condi- ceptible to attack by metallic sodium and potassium;
tions by using an impact tester developed at the Army the rate of attack is dependent on the time and tem-
Ballistic Missile Agency. Materials that are sensitive perature of exposure. Some halogenated solvents can
to impact energy are usually likely to react with ox- plasticize ECTFE without impairing its usefulness.
ygen when subjected to other forms of energy such as After discontinuing contact between the part and the
heat. PTFE is commonly used in oxygen systems solvent, it dries up and mechanical properties recover
because of its resistance to ignition by mechanical to the original values. Clearly, the interaction be-
impact, high autoignition temperature, high LOI, and tween ECTFE and the solvents in these cases is
low heat of combustion [13]. strictly physical and not chemical. ECTFE is
compatible with LOX as determined by National
3.3.2 Chemical Compatibility of Aeronautics and Space Administration (NASA) test
Partially Fluorinated method MSFC-SPEC-106B [14]. It is also resistant
to nitrogen tetroxide and monomethylhydrazine.
Fluoropolymers
Partially fluorinated fluoropolymers with com- 3.3.3 Chemical Compatibility of
mercial significance include PVDF, ETFE, ECTFE, Polychlorotrifluoroethylene
and polyvinyl fluoride (PVF). The presence of
Polychlorotrifluoroethylene (PCTFE) resists attack
hydrogen in these plastics lowers the fluorine content
by most industrial chemicals. The exceptions include
compared to perfluoropolymers and renders them
alkali metal complexes and organic amines. Chlorine
susceptible to some chemicals. This means that care
gas, nitrogen tetraoxide, and a number of halogenated
must be taken in the selection of these polymers to
solvents are absorbed by PCTFE. Most silicones
ensure compatibility of process fluids.
induce stress cracking. Tables 3.9 and 3.10 summa-
PVDF, in general, resists inorganic acids, bases,
rize weight gain of low-and high-molecular weight
salt solutions, oxidizing agents, and halogens. It is,
grades after exposure to each chemical for a period of
however, attacked by concentrated sulfuric acid and
2 weeks at room temperature. Low-molecular weight
medium concentration alkaline solutions. PVDF is
PCTFE absorbs slightly more of some compounds
unaffected by alcohols, chlorinated solvents,
than the high-molecular weight polymer.
aliphatic and aromatic hydrocarbons, and crude oil. It
swells in some polar solvents such as ketones and
esters. PVDF dissolves in some polar solvents 3.4 Permeation Fundamentals
such as dimethylformamide, dimethylacetamide, and
N-methylpyrrolidone. Hot amines attack PVDF. Permeation can be defined as the passage of gases
ETFE has excellent resistance to a great many and liquids through a second material such as a solid.
chemicals. It is somewhat affected by oxidizers, It is a significant consideration in the selection of
chlorinated solvents, ketones, and esters but resists plastic material for the construction of chemical
acids, alkalis, and organic solvents. Tests should be processing equipment because process fluids may
conducted in each specific application to verify the travel across the thickness of the polymer by
validity of the values (data) provided. This is usually permeation. Permeated species in sufficient quanti-
done either by testing in laboratory or by placing ties could cause one or more of corrosion, contami-
coupons of materials in the process stream for nation, and unacceptable environmental emission.
exposure. The coupons are taken out periodically for In its simplest form, permeation can be expressed,
inspection and measurement of properties. For using Fick’s first law, as a product of the solubility
example, hydrolytic stability of ETFE is measured by and diffusion coefficient of the permeant in the
the retention of its physical properties after extensive polymer. Permeation of a gas can be calculated from
exposure to boiling water. Tensile strength and Eq. (3.1). This equation is derived from Fick’s first
3: P ROPERTIES OF N EAT (U NFILLED ) AND F ILLED F LUOROPOLYMERS 25
Table 3.9 Weight Gain of PCTFE After 2 Weeks’ Exposure to Inorganic Reagents at Ambient Temperature [15]
Table 3.10 Weight Gain of PCTFE After 2 Weeks’ Exposure to Organic Chemicals at Ambient
Temperature [15]
Table 3.10 Weight Gain of PCTFE After 2 Weeks’ Exposure to Organic Chemicals at Ambient
Temperature [15] (Continued )
law of mass transfer. Permeation concerns the P (cm3/s$cm$atm) is the permeability of the gas, D
movement of a species through the molecules of is the diffusion coefficient (cm3/s) and S (cm3/cm3-
another species, e.g., a gas through a polymer. It does atm) is the solubility coefficient.
not take into account transport of material through Several factors affect the permeation rate of the
cracks, voids, and in general physical flaws in the polymer (Table 3.11). Temperature increase raises
structure of the second species such as the polymer. the permeation rate for two reasons. First, the sol-
Both phenomena result in the migration of chemicals ubility of the permeating agent in the polymer in-
through the structure of the solid. This means that creases at higher temperatures. Second, the
after an appropriate plastic material has been selected polymer chain movements increase, which allow
to meet the permeation requirements of a process, the easier diffusion of the permeating agent. Perme-
equipment must be fabricated carefully to avoid flaws ation rate of gases increases at higher partial
in the polymer structure. pressures. For liquids, permeation rates rise with an
increase in the concentration of the permeating
P ¼ D$S (3.1) agent. Unless the permeating agent species are
3: P ROPERTIES OF N EAT (U NFILLED ) AND F ILLED F LUOROPOLYMERS 27
highly soluble in the polymer, permeation rate in- reaches a plateau. At lower thicknesses, the effect of
creases linearly with pressure, concentration, and surface structure begins to play a significant role in
the area of permeation. the permeation. A more oriented (ordered) surface
Permeation rate decreases at higher thickness, as will serve to inhibit permeation.
illustrated in Table 3.12 and Fig. 3.1, for two types of Chemical and physical characteristics of the
PTFE and a perfluorinated ethylene propylene polymer have powerful effects of the rate of perme-
copolymer (FEP). The effect of thickness is usually ation, as much as four orders of magnitude [18].
nonlinear. Permeation rate is very high at a low Chemical affinity for the permeating agent, inter-
thickness and rapidly decreases with an increase in molecular forces such as van der Waals and hydrogen
the thickness. After a critical thickness is reached, the bonding forces, degree of crystallinity, and degree of
effect of thickness is diminished and permeation rate cross-linking are the influential variables.
Table 3.12 Comparative Permeation Rates for Modified (Teflon NXT) and Standard Polytetrafluoroethylene
(PTFE) [17]
Thickness,
Permeant mm PTFE Teflon NXT PTFE Teflon NXT PTFE Teflon NXT
Perchloroethylene 1 5.5 2 13 4 e e
2 1.4 0.1 0.019 0.005 e e
4 0.08 0.05 0.006 0 e e
5 0.055 0.05 e e e e
Hexane 2 3.4 0.2 23.4 0 e e
5 0.045 0.015 e e e e
Methyl ethyl ketone 2 36.3 23.3 49.4 34.2 e e
5 22.6 20.8 35.5 25.2 e e
HCl, 20% 1 0.4 0.1 e e e e
Helium 2 e e e e 93 1
5 e e e e 0.18 0.12
28 F LUOROPOLYMER A PPLICATIONS IN THE C HEMICAL P ROCESSING I NDUSTRIES
(grams/sq.in./24 hrs)
Transmission Rate 0.30 Cross-linking is size dependent and smaller species
0.25
may permeate.
The molecular size of the permeant, its chemical
0.20
structure, and condensation characteristics affect
0.15 permeation. Diffusion of the permeant increases as its
0.10 molecular size decreases, thus contributing to an in-
0.05 crease in permeation. Molecular structure is impor-
0.00 tant. A polar chemical will normally have a lower
0 50 100 150 200 250 300 permeation rate in a nonpolar polymer than a nonpolar
Thickness (µm) species and vice versa. This is due to the ability of
Figure 3.1 Water vapor transmission rate of Teflon chemicals with similar structures to the polymer to
fluorinated ethylene propylene resins at 40 C. Note: swell the polymer, that is, to create space between the
values are averages only and not for specification chains for permeation. A more easily condensed
purposes. chemical will also be more effective in swelling of the
Courtesy: Chemours Co., www.Teflon.com. polymer, resulting in higher rates of permeation.
»Hän on kadonnut.»
»Tarkoitatte —»
»Ei, ei; me olemme juuri saaneet sen selville. Hän on ollut poissa
kymmenen päivää.»
Poliisi oli etsinyt turhaan läpi koko seudun, sen tiesin; se oli pannut
liikkeelle kaiken kykynsä löytääkseen sen salaperäisen naisen, joka
oli käynyt herra Holladayn konttorissa, eikä ollut saanut selville
jälkeäkään hänestä. Mutta tämä ei lannistanut rohkeuttani; sillä
toivoin voivani alkaa etsintäni tietämällä asioita, joista poliisilla ei ollut
selkoa. Brooks, ajuri, voisi sanoa minulle…
»Mille puolelle?»
»Niin, sen hän tekikin. Panin sen erityisesti merkille, sillä minusta
tuntui kummalliselta, ettei hän antanut minun kyyditä sitä katua niin
pitkälle kuin hänen tarvitsi mennä. Se on niin siivoton seutu se.»
»Niin», tiedän sen. »No, kun kyyditsitte häntä 28 päivänä, sinä
päivänä, kun hänellä palatessaan oli kamarineiti mukanaan, minne
hän ajoi silloin?»
»Niin.»
»Niin, hän meni yli oikealle puolelle katua aivan samoin kuin
edelliselläkin kerralla.»
»En, hänellä oli tiheä harso silmillään. Tuo toinen nainen oli hänen
mukanaan, ja hän sanoi vain 'Kotiin!' omituisella epäselvällä äänellä,
kun autoin heitä vaunuihin.»
Mutta mitä osaa hän oli jutussa näytellyt? Hetkisen harhailin kuin
sokea pimeydessä, mutta ainoastaan hetkisen. Olipa hänellä ollut
siinä mikä tehtävä hyvänsä, niin oli hänet selvästi jätetty vartioimaan
meitä, vakuuttautuakseen siitä, että me emme seuranneet
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pelättävissä. Nyt ymmärsin hänen huolensa neiti Holladaysta, 'minä
otan niin lämpimästi osaa hänen kohtaloonsa!' Hänelle oli tärkeätä
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epäillyt? Ja eräs vanha sananparsi, jota hän oli käyttänyt eräänä
iltana, muistui mieleeni:
Mutta raivoni meni ohi. Ei, hän ei saanut millään ehdolla tietää,
että epäilin häntä; siitä edusta en saanut luopua. Olihan mahdollista,
että minä vielä voisin hämmästyttää häntä, eksyttää hänet
harhateille, panna satimen hänen tielleen. Älykkyystaistelu tulisi
myöhemmin — ehkäpä jo tänä iltana — mutta tällä hetkellä en voinut
muuta tehdä kuin toteuttaa ensimmäisen suunnitelmani. Kuitenkaan
hän ei saanut epäillä, mihin suuntaan tutkimukseni menivät — minun
täytyi pettää hänet.
»Luulen, että olette oikeilla jäljillä, Lester», sanoi hän. »Mutta ette
voi toivoa voivanne tehdä itse paljoa. Se on sitäpaitsi laaja työ. Eikö
olisi parasta palkata viisi, kuusi yksityissalapoliisia ja alistaa heidät
valvontanne alle? Silloin voisitte säästyä tuosta hermostuttavasta
työstä ja samalla kertaa ennättäisi nopeammin etsiskellä talot.
Sitäpaitsi voisivat kenties kokeneemmat henkilöt saada ajatuksia,
jotka ehkä menevät teidän ohitsenne.»
»Sallikaa minun pysyä yksinäni vielä pari päivää!» sanoin, »en ole
vielä menettänyt toivoa onnistumisesta. Jos en onnistu, niin onhan
aikaa ottaa vierasta apua. Luulen joka tapauksessa panneeni asian
alulle, ja tahdon nähdä kuinka se kehittyy.»
»Tänä aamuna heti jälkeen kymmenen tuli eräs mies juosten ylös
portaita Cortlandkadun asemalle Seitsemännen puistokadun
ilmaradalla ennättääkseen junaan, joka juuri oli lähtemässä, mutta
kaatui äkisti asemasillalle sydäntaudin kohtaamana. Sairasvaunut
kutsuttiin puhelimella Hudson Streetin sairaalasta ja mies vietiin
sinne. Kello kahdentoista aikaan sanottiin, että hän todennäköisesti
tulisi paranemaan. Hän oli vielä liian heikko puhumaan, m.m. muiden
esineiden ohella löydettiin hänen lompakostaan kortti Cafe
Jourdainista Läntisen Houston kadun 54:stä. Sieltä kysyttyä saatiin
tietää, että hänen nimensä on Pierre Bethune, että hän on äskettäin
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maassa.»
Cafe Jourdainissa