ORGANIC FIBERS 10

Linda L. Clements

10.1 INTRODUCTION A different type of h g h performance organic

Before the first aramid fibers were introduced fiber, extended chain polyethylene fibers, was
added in the 1970s. While inferior to inorganic
in the 1960s and 1970s, organic fibers were rel-
fibers in some properties, organic fibers provide
atively low performance materials, primarily
combinations of properties not available with
used in textile applications. Now several dif-
ferent types of high performance organic inorganic fibers and so have made possible new
fibers exist, all competitive with inorganic designs and applications.
In this chapter, only high performance
fibers in some or even most of their properties.
The market demand for these fibers exceeds organic fibers which are commercially avail-
one billion dollars (Adams and Farrow, 1993a). able will be discussed in detail, although fibers
The main applications for high perfor- which are nearing commercialization will be
mance organic fibers today are in asbestos discussed briefly. For a more complete review
replacement, ballistics, rubber reinforcement, of both commercially available and experi-
ropes and cables and composites. Most of the mental high performance organic fibers, see
Yang (1989, 1992).
usage is of aramid fibers, with over 18000
metric tons used each year. Both usage and
existing capacity for other organic fibers are 10.2 ARAMID FIBERS
only a fraction of this value (Adams and
Farrow, 1993a). 10.2.1 OVERVIEW
Tlus broad market for organic fibers is a
direct outgrowth of applying the basic princi- Aramid fiber is the generic term for a specific
ples of polymer science to produce a new and type of ’aromatic polyamide fiber.’ The US
exceptional engineering material. In the 1950sit Federal Trade Commission defines an aramid
was recognized that if a means could be found fiber as ‘a manufactured fiber in which the
to form certain intractable polymers into fiber-forming substance is a long-chain syn-
extended chain fibers, very high stiffnesses, thetic polyamide in which at least 85% of the
strengths and use temperatures could be amide linkages are attached directly to two
achieved. The difficulty of producing such aromatic rings.’
fibers was solved in the 1960sby spinning from Thus, in an aramid, most of the amide
liquid crystalline solutions. The first fibers pro- groups are directly connected to two aromatic
duced by t h s process were the aramids, which rings, with nothing else intervening. It should
have since been followed by other such fibers. not be surprising that aramids have quite dif-
ferent properties from nylons and other
conventional polyamides since the latter poly-
Handbook of Composites. Edited by S.T. Peters. Published
mers contain few if any aromatic groups in the
in 1998 by Chapman & Hall, London. ISBN 0 412 54020 7 main chain of the polymer.
 Aramid fibers 203

Aramid fibers can be separated into two include DuPont’s KevlarO, Akzo’s TwarorP,
types: the para- aramids and the meta-aramids. Teijin’s TechnoraO and Kaiser VIAM‘s Amosa
In para-aramids, the chain-extending bonds are and S W @fibers, while meta-aramids include
in the para-position on the aromatic ring, as in DuPont’s Nomexs and Teijin’s TeijinconexO
poly-p-phenylene terephthalamide (PPTA) (Fig. fibers. Hoechst AG also markets a para-aramid
10.1(a)),co-poly-p-phenylene/3,4’-oxydipheny- fiber in Europe. The para-aramids are the fibers
lene terephthalamide (Fig. lO.l(b)) and used in high performance applicationsand thus
poly-p-phenylene-benzimidazole-terephthala- will be emphasized in this chapter.
mide (Fig. lO.l(c)). In meta-aramids, on the
other hand, the chain-extending bonds are in
10.2.2 MANUFACTURE
the meta-position on the aromatic ring, as in
poly-m-phenyleneisophthalamide (MPIA) (Fig. Historically, meta-aramid fibers were the first
10.1(d)). Commercially available para-aramids to be produced, with DuPont’s Nomex fiber

0
II
-0 .C
\
H

k-(=&IA \
H

H 1 -0;-
-0
0
I1
C
0
H
I
N
\
1

HI
0-
-0
0 H H
I1 I I
C

0
I1
C
\
I
N-
H d+-
0
Fig. 10.1 Structural formulae of (a) the para-aramid poly-p-phenylene terephthalamide (PPTA), (b) the
para-aramid co-poly-p-phenylene/3,4’-oxydiphenyleneterephthalamide, (c) the para-aramid poly-p-
phenylene-benzimidazole-terephthalamide(PBIA), and (d) the meta-aramid poly-m-phenylene isophthal-
amide (MPIA).
204 Organicfibers

being introduced in the 1960s. The first para- 10.2.3 STRUCTURE

aramids were synthesized in 1965 by S.L.
The excellent properties of para-aramids result
Kwolek of DuPont (Kwolek, 1971; Kwolek,
from both chemistry and physical microstruc-
1972; Kwolek, 1974).Forming these into usable
tures. In both meta- and para-aramids, the
fibers is very difficult because para-aramids
aromatic rings in the backbone chain produce
show no melting point and are soluble in a
high thermal resistance. In addition, in para-
limited number of solvents.
aramids the orientation of the chain-extending
The problem of spinning the polymer into
bonds produces a polymer which is an
fibers was solved for PPTA following the dis-
extended-chain rigid rod. Spinning produces a
covery that the polymer would dissolve in
fiber made up of extended-chain crystallites
strong acids to form a liquid crystalline solu-
which are almost completely aligned parallel
tion. Undiluted sulfuric acid is the solvent
to the draw direction and to each other. The
usually used. Blades (1973, 1974) devised a
crystallites have a very high length-to-diame-
special manufacturing process - known as
ter ratio and extensive interconnection of
continuous dry jet wet spinning - for forming
molecules between crystallites. Thus, an
the liquid crystalline solution into filaments.
unbroken ’infinite’ filament can be formed.
The polymer solution is extruded through
Within the crystallite the chains are bonded
spinnerets at elevated temperature through an
to one another by hydrogen bonds, as shown
air layer into a coagulating water bath. The
in Fig. 10.2. Although these bonds are not
cold water bath also contains a base to neu-
nearly as strong as the covalent bonds which
tralize and remove the retained acid.
occur within the molecules, hundreds or even
Continuous dry jet wet spinning is the man-
thousands of such bonds form between adja-
ufacturing technique used for most
cent para-aramid molecules. Since the
para-aramid fibers. Teijin’s Technora fiber,
molecules are rigid, the only way to separate
however, is produced by wet spinning fol-
them in tension is to break all of the hydrogen
lowed by drawing (Hongu and Phillips, 1990).
bonds at once. This requires a large force and

0
I
H
H
H

-N
I
0
II
0
A&=(-*
H
I \

-C H
\ llc - e \
0

0
-0
H

Fig. 10.2 Schematic showing hydrogen bonding between PPTA molecules in the crystallite.
 Aramid fibers 205

is the reason para-aramid fibers are exception- mechanical, thermal, physical and other proper-
ally strong in axial tension. However, since the ties. This anisotropy may produce design
bonds can be broken easily one at a time, the limitations, but can also be used to advantage.
fibers are quite susceptible to damage by
bending, buckling or transverse loading.
Physical and thermal properties
In meta-aramids, on the other hand, a
crooked chain results. Since even in pure ten- Table 10.1 compares the physical and thermal
sion the chain-extending bonds can flex and properties of some representative aramid
rotate, meta-aramids are much less rigid than fibers.
para-aramids and not as strong. However, Due to their highly aromatic and ordered
because the chains are more flexible, meta- structure, aramids have very high thermal
aramids are easier to manufacture than resistance for organic materials. They do not
para-aramids and are less expensive. melt prior to decomposition,in spite of the fact
that they are technically classified as thermo-
plastics. This is because melting of the
10.2.4 PROPERTIES
crystalline phase, like rupturing the fiber in
Aramid fibers offer some significant advan- tension, would require that all of the hydrogen
tages over other fibers, but also have their bonds between two molecules be severed at
drawbacks and limitations. Both advantages once. Nonetheless, because of decomposition,
and limitations will be described more fully in their temperature resistance is not equal to
the sections on properties and in the sections that of inorganic fibers. Thermogravimetric
on design considerations and applications. analysis of Kevlar fibers shows that weight
Both DuPont’s Kevlar family of fibers and loss begins at above 350°C (660°F)in air (Penn
Akzo‘s Twaron fibers are based upon PPTA and Larsen, 1979; Yang, 1992), with complete
(Fig. lO.l(a)). Teijin’s Technora fiber and the decomposition occurring at between 427 and
para-aramid marketed by Hoechst AG in 482°C (800 and 900°F) (DuPont, 1992a).
Europe, on the other hand, are a para-aramid Exposure to elevated temperature will
copolymer, co-poly-p-phenylene/3,4’-oxy- degrade the properties of aramid fibers. Figure
diphenylene terephthalamide (Fig. lO.l(b)).It is 10.3 shows the strength retention of Kevlar 29
likely that Kaiser VIAM’s SVM fibers are poly- and Technora fibers as a function of time and
p-phenylene-benzimidazole-terephthalamide temperature. This change in properties occurs
(PBIA), (Fig. lO.l(c)) rather than PPTA as a result of slow oxidation. For this reason,
(Gerzeski, 1989). Kaiser VIAM’s Armos fiber the long-term use temperature of para-aramid
may be PBIA or PPTA. Both DuPont’s Nomex fibers is typically limited to about 150-175°C
and Teijin’s Teijinconex fibers are based upon (300-350°F).
MPIA (Fig. lO.l(d)).These chemical and struc- In the transverse direction para-aramids are
tural differences produce different properties like most other materials in that they expand
for the fibers. In addition, differences in spin- with increasing temperature. However, in the
ning conditions and, most importantly, longitudinal direction the fibers actually con-
post-spinning heat treatments are used to alter tract somewhat as temperature increases. The
properties further. For example, by changing negative thermal expansion coefficient of
processing conditions, Kevlar fibers can be para-aramids can be used to advantage to
produced with elastic moduli ranging from 63 design composites with tailored or zero ther-
to 143 GPa (9 to 21 Msi) and elongations at mal expansion coefficient.
break from 1.5 to 4.4%. Aramids are flame resistant but can be
Because of the anisotropy of their microstruc- ignited. While pulp or dust of Kevlar may con-
ture, para-aramid fibers have very anisotropic tinue to smolder once ignited, fabrics do not
206 Organicfibers

Table 10.1 Physical and thermal properties of representative aramid fibers

Fiber Kevlar 49 Twaron HM Technora Nomex Teijinconex

Type para-aramid para-aramid para-aramid meta-aramid meta-aramid
copolymer
Reference for data DuPont Akzo Teijin DuPont Teijin
1992a 1990,1991 1989,1993 1981,1993g 1991
Density 1.44 1.45 1.39 1.38 1.38
g cm-3 (lb in-?) (0.0520) (0.0524) (0.0502) (0.0499) (0.0499)
Melting temperature -538°C" >5OO0C - >371"C
(1000°F) (>932"F) (>700"F)
Decomposition 427482°C 500°C 500°C 371°C 400430°C
temperature in air (800-900°F) (930°F) (930°F) (700°F) (750-805°F)
Long-term use 149-177°C -
temperature in air (300-350°F)
Longitudinal linear -4.9 -3.5 -6.2 +15 +20
thermal expansion (-2.7) (-1.95) (-3.4) (+8.3) (+11)
coefficientb
10-6/ "C
OF)

Transverse linear +66"

thermal expansion (+37)
coefficientb:
/"C ( / O F )
Specific heatb 1.42 1.42 1.09 1.21 1.05
kJ/kg K (BTU/lb OF) (0.34) (0.339) (0.26) (0.29) (0.25)
Longitudinal thermal
conductivityb 4.11' 4.0 0.13 0.13
W/m K (2.38) (2.3) (22) (22)
BTU/h ft OF)
Transverse thermal
conductivityb 4.82' 5.0
W/m K (2.79) (2.9)
BTU/h ft OF)
Equilibrium 3.5% 3.5% 2.0% 4.5% 5.0-5.5%
moisture contentb
Typical filament 12 or 15 12 12 max: 15-17 -10 to 15 X 45
diameter (0.48 or 0.59) (0.48) (0.48) (0.6-0.7) (-0.4 to 0.6 X 1.1)
pm in)
Typical filament round round round oval to oval to
shape dogbone dogbone

* Data from Yang, 1992.

Varies with temperature; room temperature values are given.
Data from Chiao and Chiao, 1982.
 Arumidfibers 207

rL I I I I

100

.
be 80

-
C
0
+
C
2w 60
L11

fm
-
e
I= 40
iz
- Technorag
20 -

0' I I I I L

0.1 1 10 100 1000

Time, h

Fig. 10.3 Strength retention of Kevlar 29 and Technora fibers following elevated temperature exposure
(DuPont, 1992a; Teijin, 1989).

continue to burn when the flame source is
removed (DuPont, 1992a). The lower thermal
conductivity of aramids compared to inor-
ganic fibers can improve the fire resistance of
their composites, since aramids do not readily
conduct heat into the more volatile matrix.
Mechanical properties
Composite materials are most commonly used
because of their superior strength and/or stiff-
ness at a given weight as compared to
conventional structural materials. Figure 10.4
compares the specific strengths and specific
stiffnesses of various reinforcing fibers. (The
strengths and stiffness in Fig. 10.4 are expressed
in units of grams per denier (gpd). This is a tex-
tile term often used for organic fibers which
measures specific strength and/or stiffness. This
term is further explained in the appendix to this
chapter.) As can be seen, aramid fibers perfonn
very well. In fact, until the emergence of high
strength intermediate modulus carbon fibers
and the commercialization of polyethylene
fibers in the mid-l980s, aramid fiber composites
had the highest specific strengths of all compos-
ite materials. Although composites from newer
fibers have taken over that position, aramids
still offer outstanding combinations of proper-
ties, such as high specific strength, toughness,
creep resistance and moderate cost, for specific
applications.
Table 10.2 compares the mechanical proper-
ties in axial tension of several commercially
available aramid fibers.
Aramid fibers have some definite limita-
tions. They are weak in bending and show
obvious damage if subjected to kinking or
buckling. As a result, they are also weak in com-
pression (where microbuckling is inevitable)
and in transverse tension (wherebond-by-bond
breakage of hydrogen bonds is likely). In addi-
tion, even though the para-aramid chain is
quite polar in nature, almost all of the polar
groups are fully involved in hydrogen bonding
to other aramid molecules. As a result, para-
aramid fibers do not form strong bonds with
other materials such as composite matrices,
208 Organicfibers

Table 10.2 Axial tensile mechanical properties of representative aramid fibers

Fiber Reference Spec$c Initial tensile Tensile strength, Elongation at

gravity modulus, GPa (Msi) MPa ( h i ) break, %
Bare" Epoxy- Bare" Epoxy- Bare"
impregnatedb impregnatedb
Kevlar DuPont, 1993h 1.44 71.8 2920 - 3.6
Type 956, (10.4) (424)
1500 denier
Kevlar 29 DuPont, 1992a, 1.44 70.5 83.0 2920 3600 3.6
Type 964, DuPont, 19938 (10.2) (12.0) (424) (525)
1500 denier
Kevlar 49 DuPont, 1992a, 1.44 112.4 124.0 3000
Type 965, DuPont, 1993g (16.3) (18.0) (435)
1140 denier
Kevlar 68 DuPont, 1993g 1.44 99.13 3050 - 2.9
Type 9898, (14.4) (442)
1420 denier
Kevlar 119 DuPont, 1990 - 54.6 3050 - 4.4
1500 denier (7.9) (442)
Kevlar 129 DuPont, 1993i 1.44 96.0 3380 - 3.3
denier (13.9) (490)
unspecified
Kevlar 149 DuPont, 19938 1.47 142.7 2340 - 1.5
Type 965A, (20.7) (339)
1140 denier
Kevlar HT DuPont, 19938 1.44 99.1 3370 - 3.3
Type 964C, (14.4) (489)
1000 denier
Kevlar KM2 DuPont, 1992d - 63.4 3280 - 4.0
850 denier (9.2) (476)
Twaron Akzo, 1991 1.44 70 2800 3500 3.6
(10.2) (406) (508)
Twaron Perkins, 1993 1.44 88 3230 - 3.3
Type 2000, (12.8) (468)
930 denier
'microfilament'
Twaron HM Akzo, 1991 1.45 103 3500 2.5
(14.9) (508)
Armos Kaiser VIAM, - 147 - 3.2
58.8 tex 1993a' (21.4)
SVM Kaiser VIAM, 1.43 123
58.8(300) 1993g' (17.8)
X17-1000 Gerzeski, 1989
Continued on next page
 Aramid fibers 209

Table 10.2 Continued

Fiber Reference Specific Initial tensile Tensile strength, Elongation at

gravity modulus, GPa (Msij MPa (ksij break, %
Bare" Epoxy- Bare" Epoxy- Bare"
impregnatedb impregnatedb
~~ ~

Technora Teijin, 1989 1.39 73 - 3440 - 4.6

(10.6) (498)
Nomex DuPont, 1993g 1.38 11.6 - 596 - 28.0
Type 430, (1.68) (86.6)
1200 denier
Teijinconex Teijin, 1991 1.38 7.9-9.7 - 610-670 - 3545
(1.1-1.4) - (88-97)
Teijinconex Teijin, 1991 1.38 11.6-12.2 - 730-850 - 20-30
HT (1.7-1.8) (110-120)

a Data for DuPont fibers taken from conditioned yarns tested according to ASTM Standard D885.
Modulus data for Akzo fibers from testing according to ASTM Standard D885M. Test technique
unspecified for Akzo fiber strengths and elongations and for all data from Kaiser VIAM and Teijin fibers.
Data for DuPont fibers taken from epoxy-impregnated strands tested according to ASTM Standard
D2343. Data for Akzo fibers from testing according to impregnated strand test method DIN 65356, part
2. Test technique unspecified for Kaiser VIAM fibers.
Preliminary data.
50 . . . . I .. I . I . . . I l l l l l l . . . . l l . . I I I I . . I . I . .

40 - PED HM -
Armos
0
Carbon TlOOOG 0
'pectra 'Oo0
Dyneema SKBO Carbon
30 - Technora Tekmilon
0
'spectra 900
. Vectran HS
0 Kevlar 49
. Twaron O O S ~0 Carbon T-300
. .waron HM
2o - S-Glass
0 Kevlar 149 0 Carbon T-50

. PE (H.C.) Boron
E-Glass

. Steel
Carbon P-100
1
2 10 Organicfibers

further aggravating the poor transverse, bending
and compressive properties of the fiber itself.
The basic chemical structure differences
between the aramid fibers produce many of
the mechanical property differences seen in
Table 10.2. The ether (-0-) linkages in the
backbone of the Technora copolymer fiber pro-
duce a lower modulus than that of Kevlar and
Twaron PPTA-based fibers. On the other hand,
the additional cyclic ring in the SVM PBIA-
based fibers produces a higher basic modulus.
However, heat treatment and other fabrication
steps can also alter mechanical properties sig-
nificantly, as is seen in the property differences
between the various Kevlar fibers.
The mechanical properties of aramid com-
posites are illustrated in the data of Table 10.3.
For this filament-wound composite the longi-
tudinal compressive strength was about
one-eighth that in longitudinal tension, the in-
plane shear strength was one-seventy-fifth and
the transverse tensile strength over two hun-
dred times smaller. While the relative values of
properties may change for composites made
from other aramid fibers and/or other matrices
and/or prepared using other fabrication
processes, the general trend is valid: aramid
fiber composites have poor off-axis properties.
In axial tension, both aramid fibers and
their composites are linear to failure. In spite
of this fact, the same microstructural charac-
teristics which lead to the weakness of aramid
fibers in buckling also make them very tough.
During failure, the widespread bending, buck-
ling and other internal damage to the fibers
absorbs a great deal of energy. Similarly, the
strength of aramid fibers is not very strain rate
sensitive: an increase in strain rate of more
than four orders of magnitude only decreases
the tensile strength by about 15%. (Abbott et
al., 1975) This property alone provides design
advantages over all inorganic and many other
organic fibers.
The mechanical properties of aramid fibers
decrease with increasing temperature. Figure
10.5 shows the fiber elastic modulus as a func-
tion of temperature for several organic fibers.
At 177°C (350°F) the modulus of para-aramid
fibers is about 80% of that at room tempera-
ture. Figure 10.6 compares the fiber tensile

Table 10.3 Mechanical properties of a filament-wound composite of 60 vol YO aramid fiber in a room-tem-
perature curable epoxy matrix (Clements and Moore, 1977)
Fiber: DuPonf’s Kevlar 49, Type 968, 1420 denier
Matrix: 100 parts Dow Chemical DER 332 (diglycidyl ether of bisphenol-A epoxy) and 45 parts Jefferson
Chemical reffamine T-403 polyether triamine
Cure: 1 day at room tnnperuture, postcure 16 h ut 85°C (185°F)
Elastic constants:
Longitudinal Young’s modulus E,,, GPa (Msi) 81.8 f 1.5” (11.9 k 0.22)
Transverse Young’s modulus E,,, GPa (Msi) 5.10 k 0.10 (0.74 & 0.014)
Shear modulus G,,, GPa (Msi) 1.82 k 0.09 (0.26 f 0.013)
Major Poisson’s ratio vl, 0.310 k 0.035
Minor Poisson‘s ration u,, 0.0193 f 0.0014
Ultimates: Tension Compression In-plane shear
Longitudinal strength, MPa (ksi) 1850 f 50 (268 f 7.3) 235 f 3 (34.1 k 0.4) -
Longitudinal ultimate strain, Yo 2.23 f 0.06 0.48 5 0.3 -
Transverse strength, MPa (ksi) 7.9 k 1.1(1.15 f 0.15) 53 f 3 (7.7 f 0.4) -
Transverse ultimate strain, Yo 0.161 f 0.023 1.41 f 0.12 -
Shear stress at 0.2%, offset, MPa (ksi) - - 24.2 f 2.4 (3.51 k 0.35)
Shear strain at 0.2% offset, Yo - - 1.55 k 0.16
-
a Limits are 95% confidence limits. Each value is the result of five or more tests.
 Aramidfibers 211

si s
- 5
25 -

1992a; Teijin, 1989).

3500 -1 a - 1 8 - m q
500

:
Techno ra

- 400
2500 1 Kevlar

.-
n=
;:0003
8
g 2000
300 Y"
f
0, m
1500 - c
t? - 200 ?!
3i Polyester
looo;,
Nylon - 100
500

0 , ,: 0

Fig. 10.6 Tensile strength as a function of temperature for two para-aramid fibers and for two polymer
fibers and steel (DuPont, 1993h; Teijin, 1989).
212 Organicfibers

strength as a function of temperature for sev- wet transverse tensile and in-plane shear
eral organic fibers. For Kevlar fiber the strengths were only about half of the 52% r.h.
strength at 177°C (350°F) is about 80% of that values. The data in boiling water illustrate that
at room temperature, while for Technora the the drops in strength due to the presence of
strength is about 70% of the room temperature moisture alone were almost as severe as those
value. On the other hand, at cryogenic tem- due to the combined presence of moisture and
peratures modulus increases slightly and elevated temperature. This relative loss in
strength is not degraded. properties is less for the Technora para-aramid
The presence of moisture also reduces the co-polymer fiber. Care must be exercised when
mechanical properties of aramid fibers and using aramid composites in high moisture
their composites. The effect upon longitudinal applications.
tensile properties is relatively small, but the Both para-aramid co-polymers and homo-
loss is pronounced for off-axis properties. polymers exhibit very little creep. In general,
Table 10.4 illustrates this loss for Kevlar 49 creep strain increases with increasing tempera-
fiber in a room-temperature curable epoxy. ture, increasing stress and decreasing fiber
The longitudinal tensile strength in water at modulus. Like all high performance fibers,
room temperature was 88% of that for com- under long term loading, para- aramids are
posites equilibrated at room temperature and subject to stress rupture, i.e. failure of the fiber
52% relative humidity (r.h.). The wet longitu- under sustained loading with little or no
dinal compressive strength, on the other hand, accompanying creep. Figure 10.7 compares the
was only 75% of the 52% r.h. value, while the stress rupture performance of Kevlar 49 to that

Table 10.4 The effect of environments on the mechanical properties of a filament-wound composite of 50
vol Yo of an aramid fiber in a room-temperature curable epoxy matrix (Wu, 1980)
Fiber: DuPont's Kevlar 49, 4560 denier
Matrix: 100 parts Dow Chemical DER 332 (diglycidyl ether of bisphenol-A epoxy) and 45 parts Jefierson
Chemical Jeffamine T-403 polyether triamine
Cure: Infrared heating, postcure 2 h at 100°C (212°F)
Strength, MPa (ksi)
23"C, dry 23°C' 52% r.k. 23"C, water 1OO"C, water
________
Longitudinal 1370 f 6 2 " 1340 f 112 1190 f 62 1150 f 1 2 4
tension (199 f 9) (194 f 16) (173 f 9) (167 f 18)
Longitudinal 188 f 1 2 169 f 20 126 f 22 107 f 2 1
compression (27.3 f 1.7) (24.5 f 2.9) (18.3 f 3.2) (15.5 f 3.0)
Transverse 7.6 f 1.6 74 f 1.2 3.9 f 0.7 3.6 f 0.2
tension (1.10 f 0.23) (1.07 k 0.17) (0.57 f 0.10) (0.52 f 0.03)
Transverse 31.3 f 3 . 2 29 f 4.0 22.5 f 3 . 2 22.1 f 23.6
compression (4.54 kO.46) (4.21 f 0.58) (3.26 f 0.46) (3.20 f 3.42)
In-plane shear 27 f 3 . 0 26.5 f 1.6 13.8 f 2.2 13.6 f 2.5
(3.92 f 0.44) (3.84 f 0.23) (2.00 f 0.32) (1.97 f 0.36)
Hygrothermal Properties
Equilibrium moisture - 4.1 7.8 8.9
concentration, Yo
~

Limits are 95% confidence limits. Each strength is the average of five tests.
 Aramid fibers 213

0
+, 100
!
.I4
2 90 Kevlafl 49
1
W
o 80
d

a
. 70
a
u
," 60
a
a
0 50
.rl
rl

2a 40

10-2 10-1 1 io io2 103 104 105

Lifetime, h

Fig. 10.7 Stress-rupture behavior of epoxy-impregnated Kevlar 49 fibers compared to that of epoxy-
impregnated S-glass fibers (Chiao,Chiao and Sherry, 1976).

of Sglass. Para-aramids perform well under
these conditions, but the phenomenon of stress
rupture must be considered in any design
where long term loading is anticipated.
Strength retention cannot be used to estimate
the remaining life of aramid fibers or compos-
ites under long term load (Chiao, Sherry and
Chiao, 1976),so estimates of long term behavior
must be derived from actual data, or acceler-
ated testing methods (Chiao and Chiao, 1982).
Para-aramid fibers and their composites per-
form very well in fatigue. For aramids,
tension-tension fatigue generally is not of sig-
nificant concern in applications where an
adequate static safety factor has been used
(Yang, 1992). Aramid composites have been
found to be superior to glass fiber composites in
both tensile-tensile and flexural fatigue load-
ing. For the same lifetime (cycles to failure),
Kevlar 49/epoxy composites can operate at a
significantly larger percentage of their static
strength than can glass-reinforced composites
(DuPont, 1986). Para-aramids also can be
expected to perform better than carbon fibers in
fatigue (Teijin, 1989; Yang, 1992). Technora
para-aramid co-polymer is found to have even
better fatigue resistance than the para-aramid
homopolymer fibers (Teijin, 1989).
Chemical and environmental properties
PPTA fibers are quite stable chemically; their
resistance to neutral chemicals is usually very
high. They are, however, subject to attack by
acids and bases, especially by strong acids.
Because the spin process used for Teijin's
Technora para-aramid co-polymer produces a
very pure polymer, the chemical and environ-
mental resistance of Technora is superior to
that of the PPTA fibers. Table 10.5 reports the
resistance of Kevlar and Technora fibers to
various chemicals. Technora has better acid
and alkali resistance than PPTA and its steam
resistance is also superior.
214 Organicfibers

Table 10.5 Stability of para-aramid fibers in various chemicals

Concentration, Temperature, Time, Effect on breaking strength"

Chemical Yo "C ( O F ) hr None Slight Moderate Appreciable Degraded
Acids
Acetic 40 21 (70) 1000 Kb
40 95-99 (203-210) 100 Tb K
Formic 90 21 (70) 100 K
90 95-99 (203-210) 100 T K
Hydrochloric 20 20 (68) 100 T
10 71 (160) 10 K
Nitric 10 20-21 (68-70) 100 T K
Phosphoric 10 20-21 (68-70) 100 K,T
10 21 (70) 1000 K
10 99 (210) 100 K
Sulfuric 10 99 (210) 10 K
20 95 (203) 100 T
40 95 (203) 100 T
Alkalis
Ammonium hydroxide 28 21 (70) 1000 K
Sodium hydroxide 10 21 (70) 1000 K
10 95-99 (203-210) 100 T K
Portland cement saturated 95 (203) 100 T
saturated 180 (356) 15 T
Organic solvents
Acetone 100 boil 100 K
Benzene 100 20 (68) 784 T
100 21 (70) 1000 K
Carbon tetrachloride 100 boil 100 K
Ethylene chloride 100 20 (68) 1000 T
Ethylene glycol/water 50/50 99 (210) 1000 K
Ethylene glycol 100 95 (203) 300 T
Gasoline 100 20 (68) 784 T
Gasoline-leaded 100 21 (70) 1000 K
Methyl alcohol 100 21 (70) 1000 K,T
N-Methyl pyrrolidone 100 95 (203) 100 T
Other
Sodium chloride 3 21 (70) 1000 K
10 99 (210) 100 K
10 121 (250) 100 K
Sea water 100 95 (203) 1000 T
Sea water (New Jersey) 100 - 1 yr K
Steam 100 120 (248) 400 T
100 150 (302) 48 K
100 150 (302) 100 T
100 200 (392) 100 T
Water, tap 100 99 (210) 100 K
a None, 0-10% strength loss; slight, 11-20% strength loss; moderate, 2140% strength loss; appreciable,
41430% strength loss; degraded, 81-100% strength loss.
K is for Kevlar aramid fiber (DuPont 1989,1993h);T is for Technora aramid fiber (Teijin, 1989).

Para-aramids are strong ultraviolet (W)
absorbers. Upon exposure, the yellow or gold
fibers turn first orange and then brown, due to
degradation. The degradation occurs only in
the presence of oxygen and is not enhanced by
either moisture or atmospheric contaminants
(DuPont, 1992a). Extended exposure may
cause a loss of mechanical properties. Bare
1667 dtex (1500 denier) Kevlar 29 was found to
have 71% strength retention after 1 month of
outdoor exposure in Wilmington, DE and 43%
after 4 months (Yang, 1992).In both processing
and applications, para-aramids must be pro-
tected from W exposure, such as by painting
or coating. However, since para-aramids are
self-screening, UV protection may also be
effected simply by dense packing of the fiber
itself, with or without a matrix. Thus, bare
12.7mm (0.5 in) 3-strand Kevlar 49 rope was
found to have 90% strength retention after 6
months outdoors in Florida and 69% strength
retention after 24 months (DuPont, 1986).
Unlike inorganic fibers, aramid fibers absorb
water. For some aramid fibers the equilibrium
moisture content (see appendix on page 241 for
defirution) is quite high (5% for SVM, 7% for
Kevlar, Kevlar 29 and Twaron), moderate for
others (3.5% for Kevlar 49 and Twaron HM)
and reasonably low for some (2% for Armos
and Technora and about 1% for Kevlar 149)
(Akzo, 1991; Kaiser VIAM, 1993a; Teijin, 1989;
Yang, 1992). The equilibrium moisture content
is directly proportional to the relative humidity,
rising for Kevlar 49 to 6.2% at 96% r.h. (DuPont,
1992a). Absorbed moisture has only a small
effect upon the tensile properties of the fibers,
but a significant effect upon the transverse ten-
sile, compressive, shear and flexural properties
of the composite. The gain of moisture is com-
pletely reversible and once removed produces
no permanent property changes.
Electrical and optical properties
Aramid fibers are electrical insulators. The
process used to make the Technora fiber, how-
ever, leaves it with fewer ionic impurities than
Aramid fibers 215
in the para-aramid homopolymers and thus
improved electrical properties. Technora fiber
has a resistivity of 5 x lo’* Q/cm (Teijin, 1989).
The dielectric constant of PPTA is 3.85 (Allied,
1989).
The refractive index of Kevlar 49 fiber is 2.0
parallel to the fiber axis and 1.6 perpendicular
(DuPont, 1986).Aramid fibers are opaque and
are yellow to gold in color.
10.2.5 TREATMENTS
Unlike inorganic fibers, few surface treatments
are used on aramid fibers to promote matrix
adhesion. One reason is the futility of increas-
ing the matrix bonding to the surface of a fiber
which readily fails by defibrillation. Most dra-
matic improvements in fiber/matrix bonding
give only modest improvements in off-axis
strengths since they simply move the locus of
failure from the surface to the interior of the fil-
ament. In other cases, longitudinal tensile
strengths are adversely affected by otherwise
successful surface treatments. Not all attempts
at designing surface treatments have been
unsuccessful, but for the most part the surface
treatment used on commercial fibers is mini-
mal compared to that used for inorganic fibers.
Finishes - lubricants which aid in subse-
quent processing steps - are applied to aramid
fibers for some applications. Available finishes
are designed for such purposes as lubrication
during weaving operations, improving abra-
sion resistance for cable applications or better
performance in rubber goods. If the fiber is to
be used in a high performance composite,
however, the user will usually wish to avoid or
remove any finish before impregnating the
fiber with a matrix.
Commercial aramid fibers may also be
twisted. Twist may be quite useful in some
applications and a small amount of twist will
increase the strength of bare yarn or cord.
[This optimum twist for Kevlar fibers occurs at
a twist multiplier of 1.1.At about this value,
the strength of bare yarn is the highest and the
modulus is only slightly decreased from the
2 16 Organic fibers
untwisted level (DuPont, 1992b).] Twist will
make the fiber easier to handle, make subse-
quent weaving or braiding operations easier
and will improve the abrasion resistance of the
fiber. It is also required for rope and cable
applications. However, once the fiber is used
in composite matrix fiber, twist is not desir-
able. This is because twist interferes with full
impregnation of the fiber with resin and with
stress transfer between adjacent fiber bundles.
It also increases stress concentrations, particu-
larly at higher twist levels. For this reason,
most of the aramid fiber manufacturers supply
most or all of their fibers untwisted or with
minimal twist.
10.2.6 FORMS AND AVAILABILITY
Table 10.6 lists most of the commercial types of
para-aramid fibers. Some of these fibers are
readily available in a variety of fiber deniers,
package sizes, finishes and so forth, while oth-
ers are available only in limited quantities for
specific applications. Due to constant changes
in market conditions and other factors, the
user is advised to check with the fiber manu-
facturer concerning current availabilities. The
mechanical properties of fibers with different
deniers and/or finishes and other treatments
will vary somewhat from each other and from
the nominal values given in Table 10.2.
In addition to the yarns, tows and rovings
listed in Table 10.6, DuPont’s Kevlar fibers are
also available as staple (short fibers), floc (pre-
cision cut fibers of very short lengths) pulp
(very short and high fibrillated fibers) and in
specialty compounded forms (DuPont, 1992a,
1993h).A variety of fabrics are also produced.
In addition, DuPont produces a colored fiber,
Kevlar 100, in sage green, yellow, black and
royal blue (Yang, 1992).Both Teijin’s Technora
and Akzo’s Twaron fibers are available as sta-
ple and chopped fiber (very short lengths) and
in a variety of fabrics (Teijin, 1989;Akzo, 1991).
Technora is also marketed in black as well as
natural color. Kaiser VIAM‘s Armos and SVM
fibers are also expected to be offered as tape,
staple, pulp and in various fabrics.
While the meta-aramid fibers are not usu-
ally used as fiber reinforcements in
composites, they are used extensively as rein-
forcements for honeycomb sandwich core
materials. The use of such materials along
with composite face sheet panels has greatly
extended the overall usage of composite mate-
rials, particularly in the aerospace industry.
Information about the availability and
package sizes of the fibers shown in Table 10.6,
about other products and about special formu-
lations can be obtained from Table 10.7. At the
time of this publication, Kaiser VIAM’s Armos
and SVM fibers are just being imported from
Russia. For this reason, information on the
fibers and their availability is limited in this
chapter, but should be readily available later
from the contact given in Table 10.7.
Pricing
Para-aramid fibers are currently priced from
about $20 per pound for the larger denier fibers
to about $60 per pound for most of the small
denier, higher modulus fibers. (However, some
of the very fine denier specialty fibers from
some manufacturers cost hundreds of dollars
per pound.) Prices can vary significantly for
similar fibers of different deniers or from dif-
ferent manufacturers and thus price quotes
should always be obtained before any decision
is made upon use of a specific fiber.
10.2.7 DESIGN CONSIDERATIONS
In the 1970s and early 1980s aramids began to
replace carbon and glass fibers in many appli-
cations. However, the development of high
strength intermediate modulus carbon fibers in
the mid-1980s and the commercialization of
tough, high strength polyethylene fibers
reversed this trend. Today aramid fibers are
used mainly in applications where they offer a
unique combination of properties, such as high
specific strength combined with toughness and
creep resistance.
 Aramidfibers 217

Table 10.6 Availability of commercial para-aramid fibers"

Product Count Filament Comments/typical applications

~ _ _ _ _ _ _ _ _
(reference)
number/ diameter
dtex (den) yarn pm ( 1 C 3 i n )
Kevlarb (DuPont, 1993g; Yang, 1992)
Type 950 1110 (1000) 666 12 (0.48) Finish: tire reinforcement
1670 (1500) 1000 12 (0.48)
2500 (2250) 1000 15 (0.59)
3330 (3000) 1333 15 (0.59)
Type956 800 (720) 490 12 (0.48) Mechanical rubber goods: hoses, belts, etc.
1110 (1000) 666 12 (0.48)
1670 (1500) 1000 12 (0.48)
2500 (2250) 1000 15 (0.59)
3330 (3000) 1333 15 (0.59)
Kevlar 29 (DuPont, 1992b,1993a, 1993b, 1993f, 19938)
Type 960 1670 (1500) 1000 12 (0.48) Cordage finish: high lubricity for improved
3330 (3000) 1333 15 (0.59) abrasion resistance; ropes and cables
17 OOO(15 000) 100OOR' 12 (0.48)
Type 961 1110 (1000) 666 12 (0.48) Textile finish; ropes and cables
1670 (1500) 1000 12 (0.48)
3330 (3000) 1333 15 (0.59)
5000 (4500) 3000 12 (0.48)
17 OOO(15 000) lOOOOR 12 (0.48)
Type 962 1670 (1500) 1000 12 (0.48) No finish; ropes and cables
3330 (3000) 1333 15 (0.59)
Type 963 3330 (3000) 1333 15 (0.59) Textile finish; non-apparel ballistic armor
Type964 215 (200) 134 12 (0.48) Textile finish; ballistics and apparel,
430 (400) 267 12 (0.48) ignition cables
1110 (1000) 666 12 (0.48)
1670 (1500) 1000 12 (0.48)
Kevlar 49 (DuPont, 1992b, 1993c-g)
Type 965 61 (55) 25 15 (0.59) Textile finish; woven reinforcement in
215 (195) 134 12 (0.48) aerospace composites, ballistic armor, and
420 (380) 267 12 (0.48) printed circuit boards
1270 (1140) 768 12 (0.48)
1580 (1420) 1000 12 (0.48)
2400 (2160) 1000 15 (0.59)
Type968 215 (195) 134 12 (0.48) No finish; marine composites, fiber optic
420 (380) 267 12 (0.48) cable reinforcement, ropes, filament-wound
1270 (1140) 768 12 (0.48) composites
1580 (1420) 1000 12 (0.48)
2400 (2160) 1000 15 (0.59)
3160 (2840) 1333 15 (0.59)
4800 (4320) 2000R 15 (0.59)
5070 (4560) 3200R 12 (0.48)
7900 (7100) 5000R 12 (0.48)
Continued on next page
218 Organicfibers

Table 10.6 Continued

Product Count Filament Commenfs/fypicalapplications

(reference)
number/ diameter
dtex (den) yarn pm ( 1 P i n )
~ _ _
Type 978 1580 (1420) 1000 12 (0.48) Cordage finish: high lubricity for improved
2400 (2160) 1000 15 (0.59) abrasion resistance; ropes and cables
5070 (4560) 3200R 12 (0.48)
Type 989 1580 (1420) 1000 12 (0.48) Textile finish; fiber optic cable
2400 (2160) 1000 15 (0.59) reinforcement
3160 (2840) 1333 15 (0.59)
4800 (4320) 2000R 15 (0.59)
6300 (5680) 2666R 15 (0.59)
7900 (7100) 5000R 12 (0.48)
9500 (8520) 4000R 15 (0.59)
Kevlar 68 (DuPont, 1992b, 1992c, 19938)
Type9568 215 (195) 90 12 (0.48) High performance mechanical rubber goods
1580 (1420) 1000 12 (0.48)
Type9898 420 (380) 267 12 (0.48) Textile finish; fiber optic cable
1580 (1420) 1000 12 (0.48) reinforcement
2400 (2160) 1000 15 (0.59)
3160 (2840) 1333 15 (0.59)
4800 (4320) 2000 15 (0.59)
7900 (7100) 5000R 12 (0.48)
Kevlar 129 (DuPont, 1990, 1993h)
Type 956E 1670 (1500) 1000 12 (0.48) Power transmission belts, high-performance
tires, high fatigue applications
Kevlar 129 (DuPont, 1992c, 1993h, 1993i)
Type 956C 1110 (1000) 666 12 (0.48) Mechanical rubber goods
Type964C 830 (750) 500 12 (0.48) Personal body armor
930 (840) 6OOL 12 (0.48)
1110 (1000) 666 12 (0.48)
1580 (1420) 1000 12 (0.48)
Kevlar 249 (DuPont, 1992c, 19938)
Type965A 420 (380) 267 12 (0.48) Woven reinforcement in aerospace composites,
1270 (1140) 768 12 (0.48) hard ballistic armor, printed circuit
1580 (1420) 1000 12 (0.48) boards
Type 968A 1270 (1140) 768 12 (0.48) No finish; marine composites, fiber optic
1580 (1420) 1000 12 (0.48) cable reinforcements, ropes, filament-wound
4730 (4260) 3000R 12 (0.48) composites
7890 (7100) 5000R 12 (0.48)
Kevlar HT (DuPont, 19938)
Type 964C 1110 (1000) 666 12 (0.48) Advanced ballistic protection
Kevlar K M 2 (DuPont, 1992d)
945 (850) 560 12 (0.48) Ballistic protection: helmets, composite armor

Continued on next page

 Ararnidfibers 219

Table 10.6 Continued

Product Count Filameizf Comments/typical applications

(reference)
number/ diameter
dtex (den) yarn Fnz ( l C 3 i n )
Twarond (Akzo, 1990,1991; DeCos, 1993)
Type 1000 420 (380) 250 12 (0.48) Standard finish; multipurpose
840 (760) 500 12 (0.48)
1100 (990) 750 10.5 (0.41)
1260 (1130) 750 12 (0.48)
1680 (1510) 1000 12 (0.48)
2520 (2270) 1500R 12 (0.48)
3360 (3020) 2000R 12 (0.48)
Type1001 420' (380) 250 12 (0.48) Adhesive-activated finish; tires,
840 (760) 500 12 (0.48) mechanical rubber goods, composites
1100' (990) 750 10.5 (0.41)
1260 (1130) 750 12 (0.48)
1680 (1510) 1000 12 (0.48)
3360 (3020) 2000R 12 (0.48)
Type 1010 1680 (1510) 1000 12 (0.48) Very low finish level; composites
3360 (3020) 2000R 12 (0.48)
Type 1020 1680 (1510) 1000 12 (0.48) Special finish for increased abrasion
resistance; cables, ropes, nets
Type 1030 17 OOO(15 300) 5000R 12 (0.48) PTFE + silicone oil impregnated; braided packings
Type 1031 14 OOO'(12 600) 5000R 12 (0.48) PTFE + silicone oil impregnated; braided packings
Type1040 420 (380) 250 12 (0.48) Tangled yarn; multipurpose
840 (760) 500 12 (0.48)
1100' (990) 750 10.5 (0.41)
1260 (1130) 750 12 (0.48)
1680 (1510) 1000 12 (0.48)
Type 1041 1260' (1130) 750 12 (0.48) Adhesive-activated finish; fabrics
1680' (1510) 1000 12 (0.48)
Type2000 930 (840) 1000 6.6 (0.26) Standard finish; high tenacity for
1110 (1000) 1000 8 (0.31) ballistic applications. 930 dtex
1680 (1510) 1000 12 (0.48) fiber is 'microfilament'.
Twaron HM (Akzo, 1991)
Type 1055 1210 (1090) 750 11.5 (0.45) Standard finish; multipurpose
1610 (1450) 1000 11.5 (0.45)
2420 (2180) 1500R 11.5 (0.45)
3220 (2900) 2000R 11.5 (0.45)
4830 (4350) 3000R 11.5 (0.45)
6440 (5800) 4000R 11.5 (0.45)
8050 (7245) 5000R 11.5 (0.45)
Type 1056 1210 (1090) 750 11.5 (0.45) Very low finish level; composites
1610 (1450) 1000 11.5 (0.45)
2420 (2180) 1500R 11.5 (0.45)
6440 (5800) 4000R 11.5 (0.45)
8050 (7245) 5000R 11.5 (0.45) Continued on next page
220 Organicfibers

Table 10.6 Continued

Product Count Filament Comments/typical applications

-
(reference)
number/ diameter
dtex (den) yarn pm (1Win)
Twaron IM (Akzo, 1991)
Type 1111 420' (380) 250 12 (0.48) Easily removed finish; fiber optic cable
1260 (1130) 750 12 (0.48) reinforcements, ballistics, composites
1680 (1510) 1000 12 (0.48)
2520 (2270) 1500R 12 (0.48)
Armos (Kaiser VIAM, 1993a)
588 (530) - - - Twisted 48 t/m; multipurpose
SVM(Kaiser VIAM, 1993b-j)
63 (57) - - - Type A1 lubricating finish
143 (130) - - - Lubricating finish on 'acidic' fiber
294 (265) - - - Lubricating finish on 'neutral' fiber
294 (265) - - - Lubricating finish on 'acidic' fiber
294 (265) - - - Type A1 lubricating finish on 'acidic' fiber
588 (530) - - - Two different heat treatments available
588 (530) - - - Type A1 lubricating finish on 'acidic' fiber
Technoru' (Teijin, 1989; Mahn 1993)
T-200 1110 (1000) 666 12 (0.48) Rubber reinforcement
1670 (1500) 1000 12 (0.48)
T-202 440 (400) 1667 12 (0.48) Rubber reinforcement, pre-activated type
1670 (1500) 1000 12 (0.48)
T-220 1110 (1000) 666 12 (0.48) Rope, cable, and cord
1670 (1500) 1000 12 (0.48)
T-221 1110 (1000) 666 12 (0.48) Rope, cable, and cord
1670 (1500) 1000 12 (0.48)
T-230 1670 (1500) 1000 12 (0.48) Fiber-reinforced plastics, rope
T-240 60 (55) 36 12 (0.48) Woven and knitted fabrics, fiber-reinforced
110 (100) 67 12 (0.48) plastics
220 (200) 133 12 (0.48)
440 (400) 267 12 (0.48)
1110 (1000) 666 12 (0.48)
T-241 1670 (1500) 1000 12 (0.48) Woven and knitted fabrics, fiber-reinforced
8330 (7500) 5000R 12 (0.48) plastics
T-360 608 (55) 36 12 (0.48) 'Spunnized' yarn (made up of long but not
220 (200) 67 12 (0.48) continuous filaments) for protective
440 (400) 133 12 (0.48) clothing and other fabric applications
1110 (1000) 267 12 (0.48)
1670 (1500) 1000 12 (0.48)
T-370 220 (200) 133 12 (0.48) High tenacity 'spunnized' yarn for
440 (400) 267 12 (0.48) reinforcement of rubber, etc.
For footnotes see next page
 Aramid fibers 221

Table 10.7 Sources of information o n commercial aramid fibers

Product Information source

Armos and SVM Kaiser VIAM; 880 Doolittle Drive, San Leandro, CA 94577, USA
fibers

Kevlar fibers DuPont Fibers; P.O. Box 80705, Wilmington, DE 19880-0705, USA, (800)
4-KEVLAR
Technora fibers Teijin Limited, 11, 1-chome, Minamihonmachi, Chuo-ku, Osaka 541, Japan
Teijin America Inc; 10 East 50th Street, New York, NY 10022, USA
Twaron fibers Akzo, Aramide Maatschappij v.o.f., P.O. Box 9300,6800 SB A r h e m ,
Westervoortsedijk 73, The Netherlands
Akzo Fibers Inc., 801-F Blacklawn Rd., Conyers, GA 30207, USA

The outstanding toughness of aramids is
often the reason they are used over cheaper,
stiffer or even stronger fibers. Unlike glass and
carbon composites, aramid composites loaded in
compression, flexure or shear fail in a non-brittle
manner, with significant work being required to
fail the composite. Their fatigue resistance is also
excellent. If other concerns such as cost or stiff-
ness preclude the use of aramid composites,
aramids are often used as a hybrid with another
fiber to improve the toughness of the composite.
The poor off-axis and compressive proper-
ties of aramid fibers must be considered in any
design. However, because of their high strength
in axial tension and their toughness, aramid
fibers are often outstanding in applications
such as pressure vessels where the loading is
almost totally in longitudinal tension.
Aramid fibers absorb moisture. Where
either the physical swelling of the fiber or the
amount of moisture absorbed is of significant
concern, one of the lower absorption aramids,
such as Kevlar 149, Armos, or Technora should
be considered.
Aramids are strong UV absorbers and dete-
riorate when exposed to ultraviolet light.
Protective coatings or the self-screening ability
of the fiber should be used to avoid deterio-
ration.
Aramid fibers are opaque and thus the pen-
etration of resin into the fiber bundles cannot
be determined visually for a aramid compos-
ite as it can for those made with glass fibers.
In fabric applications the weave used is
important to the resulting properties. The
same is true for sandwich construction. In
these cases, the fiber, fabric, or honeycomb
supplier can provide design assistance.
The choice of resin system for use with
aramid fibers is an important one. Epoxy resins
give better translation of fiber properties than
do polyesters, producing better shear strength
and flexural properties, but lower impact resis-
tance. Vinyl ester resins give both good shear
strength and impact resistance. Thermoplastic
matrices are also used, particularly in chopped
fiber composites, because of their improved
impact resistance over thermosets. However,

Footnotes for Table 10.6

a All availabilities are subject to market conditions and should be verified with the manufacturer.
All Kevlar fibers are supplied untwisted.
E The ' R indicates that this fiber is a 'roving,' meaning in this case that it is composed of more than one 'end' of yam.

Twaron fibers are normally supplied untwisted. In some circumstances twist may be supplied on special request.
e Under development.
' Technora fibers are supplied with twist as requested. Finishes are supplied as requested or as is appropriate to the
application. For special applications,Technora fibers can be supplied in larger than 12 pm filament diameters.
These fibers, and others 'spun' yarns (composed of discontinuous filaments) are normally measured by '(English)
cotton count' (ECC) rather than dtex or denier, where ECC = 5315/denier.
222 Organicfibers

for thermoplastics the penetration of the resinMany of these are not as structural composites.
into the fiber bundle and the quality of the For example, aramids are used in many rope
fiber-matrix bond is almost always of concern. and cable applications. In mooring ropes to
Because aramids are very tough fibers, they secure oil tankers and to anchor off-shore oil
are somewhat difficult to cut and their com- platforms, the lighter weight compared to
posites can be difficult to machine. Special steel makes the aramid ropes much easier to
handle. In addition, they do not corrode, are
shears and other tools are available for cutting
aramids and many successful machining tech- easier to maintain and have an extension
niques have been developed. The fiber under load which is far superior to both steel
manufacturers are an excellent source of infor-and other organic fibers.
mation in this area. Aramids are widely used to reinforce
As with all high performance fibers, aramidsmechanical rubber goods. The largest volume
should be handled with care before and during of such usage is in pneumatic tires, where
processing. Rough handling will damage any aramids are lighter than steel and offer higher
high performance fiber. In addition, because ofstrength and modulus than other organic
their sensitivity to ultraviolet light, aramidsfibers. Significant usage is also seen in belts
should be protected from such exposure. The and hoses. The excellent fatigue and creep
fibers also should not be exposed to excessive resistance of aramids are important factors in
their usage in these applications. Corrosion
moisture prior to processing. If the fiber is to be
twisted, braided, or woven, it is preferable toresistance and electrical resistivity may also be
condition the fiber for one to two days at roomimportant. Aramids are also used in athletic
temperature and intermediate moisture content shoes and in rubberized sheet materials as
prior to processing (DuPont, 1993h). However, used in aircraft evacuation slides and life rafts.
if the fiber is to be resin-impregnated and In some cases, non-composite applications
processed directly into a composite, so long ashave led to composite uses. For example,
fiber handling is careful, superior properties aramids have long been used in soft body
may be attained by drying the fiber prior to armor, where the fibers absorb and disperse
processing. Tlus is because of improved bond- bullet impact energy to other fibers in the fab-
ing of resin to the filament surfaces. ric weave. This application has now seen a
Aramid fibers present minimal safety or derivative usage in rigid composite ballistic
environmental concerns. In lifelong animal armor, composite helmets and composite spa11
inhalation studies with Kevlar fibers, no liners. In these applications the toughness, RF
health effects were observed at any workplace transparency and fire and corrosion resistance
levels. Nonetheless, as with any textile fiber,of aramid fibers were significant factors in
inhalation of fibrous particles should be their selection.
avoided. Extensive animal and human skin In spite of significantly higher fiber costs
patch tests with Kevlar fibers have shown no than glass, aramids are used in canoes, kayaks,
racing shells and small boats where maximiz-
sensitivity and little irritation, and rat feeding
studies have shown oral toxicity to be very ing strength and minimizing weight are
low. Combustion by-products are similar to important. Aramids offer weight savings for
wool. Aramid yarns are also essentially inert superior speed and better handling and/or
in the environment (DuPont, 1993h). improved range and fuel economy. Toughness
and overall durability and vibrational damp-
ing are also superior with aramids. The
10.2.8 APPLICATIONS
superior properties of aramids allow boats to
Aramid fibers are used in numerous applica- be built at an overall cost only 10-15% higher
tions, some of which are listed in Table 10.6. than with glass fibers and with superior perfor-
 Extended h i i i polyefhylcviefibers 223

mance (DuPont, 1983). These same properties properties but they also have limitations that
have led to the use of aramids in skis. must be considered in design.
Their high strength-to-weight ratio com- Commercially available high strength, h g h
bined with outstanding toughness has led to modulus polyethylene fibers include Spectrakh'
numerous applications of aramids in aero- fibers from Allied-Signal Corporation,
space. In both civilian and military aircraft, the DyneemaO SK60 from Dyneema Vof, Tekmilon"
toughness of aramids - and resulting resis- from Mitsui Petrochemicals and a new, as yet
tance to damage from impacts ranging from unnamed, fiber from Hoechst Celanese.
bird strikes to shrapnel - insures their contin-
ued usage. Engine nacelles and the tail cone on
10.3.2 MANUFACTURE
the McDonnell Douglas DC-9-80 are made
from Kevlar composites and approximately The traditional method of producing fibers
10% of the empty airframe weight of De from polyethylene is to spin them from a poly-
Havilland Aircraft's DASH-8 turboprop com- mer melt. This technique yields fibers
muter aircraft is Kevlar composite. Aramid composed of folded-chain crystalline regions
composites are also widely used in rotorcraft with non-crystalline regions interspersed. With
and other vertical lift aircraft. extraordinary means, the modulus of the
absolute best of such fibers can be brought to
about 80 GPa (11.5Msi). It was long recognized,
10.2.9 CONCLUSIONS
however, that if polyethylene could somehow
Although composites of other fibers have now be produced with extended chain crystallinity,
supplanted aramid composites as having the a very high modulus fiber would result. [The
highest specific strengths, aramids still offer theoretical modulus for polyethylene is
combinations of properties not available with 320 GPa (46 Msi) (Adams and Eby, 1987).]
any other fiber. For example, aramids offer Following earlier work by Pennings, in the
high specific strength, toughness and creep late 1970s Smith and Lemstra of DSM (The
resistance, combined with moderate cost. Netherlands) developed a process with com-
However, the applications of aramid compos- mercial potential which yielded a highly
ites continue to be limited by their poor oriented extended-chain polyethylene fiber
compressive and off-axis properties and in (Hongu and Phillips, 1990).At the same time,
some applications, their tendency to absorb both Toyobo Inc. of Japan and Allied Chemical
water. Nonetheless, aramids will continue to Company in the USA were working on a sim-
be the fiber of choice where properties such as ilar approach. DSM, however, was the first to
outstanding impact resistance combined with patent the process and both Toyobo and Allied
creep resistance are critical. judged it impossible to circumvent the basic
patent filed by DSM. Thus, both companies
entered into technical association with DSM to
10.3 EXTENDED CHAIN POLYETHYLENE
produce polyethylene fibers. Toyobo Inc.
FIBERS
linked with DSM to form the joint venture -
Dyneema Vof - to produce and market the
10.3.1 OVERVIEW
new fiber. In the USA, Allied-Signal is licensed
High performance polyethylene fibers, with from DSM/Stamicarbon to produce and mar-
outstanding strength-to-weight and stiffness- ket a similar fiber.
to-weight performance, show promise in The process which is used to produce most
various specialized applications. While such commercial high strength, high modulus poly-
fibers are not as widely known as aramid and ethylene fibers is called gel spinning, the name
carbon fibers, they possess many superior derived from the gel-like appearance of the
224 Organicfibers

as-spun and quenched fibers. Ultra-high mol-

ecular weight linear polyethylene is dissolved
in a volatile solvent to form a dilute isotropic
solution that is then spun through a spinneret
and quenched in cold water to form a gel pre-
cursor fiber. Following solvent extraction, this
fiber is then hot-drawn to a very high draw
ratio (= 30), yielding a very highly oriented,
highly crystalline, lightweight fiber
(Dyneema, 1987; Jaffe, 1989; Ward and
McIntyre, 1986; Yang, 1992).
Another approach to producing a high
strength polyethylene fiber is melt extrusion
followed by multiple stage drawing of a much
lower molecular weight polyethylene. The
modulus of an experimental fiber of this type,
220 GPa (32 Msi), is the highest ever achieved
for polyethylene (Adams and Eby, 1987). The
new polyethylene fiber from Hoechst Celanese
is the only commercial version of such a fiber.
This fiber has only about 50% of the strength
and 75% of the modulus of gel spun fibers. In
this case, the expense of dealing with a volatile
and potentially toxic solvent is avoided, low-
ering the overall price of the fiber significantly.
Fig. 10.8 Schematic illustrating the difference
between (a) conventional polyethylene fibers and
10.3.3 STRUCTURE (b) gel-spun extended chain fibers.
Figure 10.8 illustrates the difference between
conventional polyethylene fibers and gel-spun hydrogen bonds nor strong covalent bonds
or melt-extruded and drawn extended-chain between them. They are, in fact, held together
fibers. Figure 10.8(a)is a schematic of a con- by weak dispersion-type van der Waals bonds
ventional melt-drawn polyethylene fiber. The which have a distinct effect upon properties.
fiber consists of folded chain crystallites,
mostly oriented in the draw direction, which
10.3.4 PROPERTIES
are joined to one another by tie molecules and
have between them interspersed non-crys- Polyethylene fibers offer a unique combina-
talline material. Figure 10.8(b)is a schematic of tion of properties: low specific gravity, high
a gel-spun and hot-drawn extended-chain specific modulus, high specific strength, high
polyethylene fiber. Such fibers show minimal energy to break, high abrasion resistance,
chain folding, high crystallinity and a very excellent chemical resistance, good ultraviolet
high degree of axial orientation (>95%). resistance and low moisture absorption. They
Since these fibers are based on polyethyl- have outstanding anti-ballistic and vibrational
ene, they have a density of only two-thirds damping characteristics, as well as a low
that of aramid fibers and about one-half that of dielectric constant. However there are trade-
carbon fibers. However, the polyethylene crys- offs involved in the use of polyethylene fibers.
tallites have neither relatively strong They are limited to fairly low use temperatures,
 Extended chain polyethylene fibers 225

they produce composites with poor off-axis treated Spectra 900 fiber in an epoxy matrix
and compressive properties and have poor was found to be -9 x lO"/OC (-5 x 104/OF) in
creep resistance. the axial direction and 100 x lO"/"C (56 x
As with aramid fibers, the anisotropy of 104/"F) in the transverse direction. The axial
their microstructure gives polyethylene fibers thermal expansion coefficient of a similar com-
anisotropic mechanical, thermal and physical posite of Spectra 1000 fiber was -10 x lO"/"C
properties which can be used to advantage in (-5.6 x 10"/OF) and the transverse coefficient
some applications. was 105 x lO"/OC (58 x 10"/"F) (Allied, 1989).
Polyethylene fibers are the only high perfor-
mance fibers with a specific gravity of less than
Physical and thermal properties
1 and thus are the only fibers that float. Their
Polyethylene fibers have a relatively low melt- density is about two-thirds that of aramid
ing point [147"C (297"F)I and thus a low use fibers and about half that of carbon fibers.
temperature. In general, polyethylene fibers Polyethylene fibers will burn slowly if ignited,
are limited to use below 100°C (212°F). They decomposing into carbon dioxide and water.
will, however, tolerate brief exposure (30 min The filament diameters of commercial poly-
or less) at temperatures near the melting point ethylene fibers are relatively large, typically
without major property loss (Dyneema, 1987; 23-38 pm (0.91-1.50 x in), although the
Weedon and Tam, 1986). diameter of Mitsui's Tekmilon monofilament
As would be expected from the lower melt- fibers can be as large as 121 pm (4.76 x in).
ing temperature, the properties of polyethylene The filament cross-section is typically irregu-
fibers are much more sensitive to temperature lar and somewhat elliptical.
than are aramids. Like aramid fibers,
polyethylene fibers contract with temperature
Mechanical properties
in the axial direction, while expanding in the
transverse direction. The thermal expansion Gel-spun polyethylene fibers offer some
coefficient of a composite of 60 vol% plasma- tremendous advantages over other fibers. As

Table 10.8 Axial tensile mechanical properties of representative high performance polyethylene fibers

Fiber Reference Fiber type Spec@ Tensile Tensile Elongation

gravity modulus, strength, at break, %
GPa (Msi) MPa (ksi)
-
Dyneema Dyneema, 1987 gel-spun 0.97 87 2620 -

SK60 (12.7) (380)

Hoechst Hoechst melt- 0.96 55 1300 4
Celanese fiber Celanese, 1993 extruded (8.0) (189)
Spectra 900 Allied, 1993 gel-spun 0.97 86-103 2080-2400 3.6-3.7
(12.5-14.9) (300-350)
Spectra 1000 Allied, 1993 gel-spun 0.97 128-171 2740-3000 2.8-3.1
(18.6-24.8) (397435)
Tekmilon Mitsui, 1989 gel-spun 0.96 59-98 1470-3430 4-6
monofilament (8.6-14.2) (213498)
Tekmilon Mitsui, 1989 gel-spun 0.96 88.3 2450 3
multifilament (12.8) (356)
226 Organicfibers

can be seen in Fig. 10.4, these fibers offer very
high specific stiffnesses and specific strengths,
equivalent or superior to all of the aramid
fibers and to most of the carbon fibers. This
superior performance is offered at a lower
price than that of competitive fibers.
Table 10.8 compares the mechanical proper-
ties of representative commercially available
polyethylene fibers.
Like aramid fibers and for similar reasons,
polyethylene fibers have poor compressive
and off-axis properties. Since the fiber is held
together internally by only very weak van der
Waals bonds, the transverse strength of the
fiber is even worse than that for the aramids.
In addition, the inertness of the polyethylene
fiber means that the untreated fiber bonds
very poorly to a matrix. Although gas plasma
surface treatment can improve the interfacial
bond strength significantly, polyethylene fiber
composites will still have poor off-axis proper-
ties.
Table 10.9 gives mechanical properties for
Spectra fiber composites, including those
made from plasma-treated fibers.
In spite their weak transverse strength, but
because of the non-stick nature of polyethylene
and thus its low coefficient of friction, polyeth-
ylene fibers perform much better than aramids
in abrasion resistance and polyethylene fabrics
are much less easily damaged than are those of
aramid fibers. The abrasion resistance of poly-
ethylene fibers can be up to ten times that of
aramids (Dyneema, 1987)and can be improved

Table 10.9 Mechanical properties of Spectra polyethylene fiber composites” (Allied, 1989)

Matrix: Bisphenol A based epoxy

__ - ~

Spectra 900 Spectra 900 P T ~ Spectra 1000 Spectra 100 PT

-
Axial Tensile Properties:
Volume percent fiber 58 50 53 54
Modulus, GPa (Msi) 27 f 1 24 f 1 50 50 f 3
(4.0 f 0.1) (3.5 f 0.1) (7.3) (7.2 f 0.5)
Strength, MPa (ksi) 552 zk 90 676 f 103 1034 c 228 889 f 55
(80 f 13) *
(98 15) (150 f 33) (129 f 8)
Elongation, % - 3.6 f 0.2 - 2.1 i-0.4
Axial Compressive Properties:
Volume percent fiber 70 70 55 65
Modulus, GPa (Msi) 32 f 5 40 k 5 19c6 54 f 3
(4.7 k 0.7) (5.8 + 0.7) (2.7 f 0.9) (7.8 f 0.4)
Strength, MPa (ksi) 52 k 2 59 + 1 72 f 3 69 f 1
(7.5 f 0.3) (8.6 c 0.2) (10.5 f 0.4) (10.0 f 0.2)
Elongation, YO - - 3.8 k 0.5 3.8 f 0.2
Flexural Properties:
Volume percent fiber 58 54 54 53
Modulus, GPa (Msi) 22 k 1 30f1 23 zk 1 38 f 3
(3.2 f 0.2) (4.3 f 0.2) (3.3 k 0.2) (5.5 f 0.5)
Strength, MPa (ksi) 145 f 7 200 f 7 159 +. 7 214 f 7
(21 k 1) (29 f 1) (23 f 1) (31 k 1)
Short Beam Shear Properties:
Volume percent fiber 58 54 54 53
Strength, MPa (ksi) 8.3 f 0.7 28.3 f 0.7 9.0 c 0.7 21 e 3
(1.2 f 0.1) (4.1 f 0.1) (1.3 f 0.1) (3.1 f 0.4)
a Numbers of specimens tested and criteria for limits not specified.
PT indicates a fiber with gas plasma surface treatment.
 Extended chain polyethylene fibers 227

even further by the use of lubricants.
Because of their high strength, polyethylene
fibers exhibit very high energy to break. On a
per-weight basis, the impact energy absorp-
tion of polyethylene composites is superior to
that of all other fiber composites.
Polyethylene fibers are more affected by
temperature than are higher melting point
fibers. The loss in modulus as function of tem-
perature is shown in Fig. 10.9 for Tekmilon
multifilament fiber and Spectra fibers. Fig. 10.10
shows the loss in strength as a function of tem-
perature for Tekmilon multifilament, Spectra
900 and Spectra 1000 fibers. Because of their
very high specific strength at room tempera-
ture, however, polyethylene fibers still
outperform most other fibers to about 100°C
(212°F).
Room temperature strength retention of
polyethylene fibers following annealing at
temperatures of up to 125°C (260°F) is excel-
lent, while modulus loss following such
exposure is 20-30%. The loss in both modulus
and strength are reduced if annealing is per-
formed under tensile loading.
Unlike aramid fibers and their composites,
polyethylene fibers and composites show very
little or no loss of properties, axial or off-axis,
when exposed to moisture.
Creep resistance of extended-chain polyeth-
ylene is of concern. Because of its low melting
temperature, the resistance of the fiber to creep,
even at room temperature, is less than ideal.
This is significant, since the creep of carbon,
glass and aramid fibers is minimal. Spectra
1000 is a 'stabilized' version of the fiber, which
shows better creep resistance than the Spectra
900 fiber. Figure 10.11 shows the creep
response of the two Spectra fibers at room, ele-
vated and low temperatures. At low load levels
at room temperature and/or at low tempera-
tures the creep encountered is not severe,
especially for the Spectra 1000 fiber, but at
higher loads or temperatures the creep is much

r L 1 . 8 8 I , I I I I , , I S *

- - 15
100

0 75 - .-ul
a
c) - 10 =
ul i
-33 -3
50 - U
0
z I

- 5
25 -

0 ~ ~ . l l ~ l . ~ ' ~ ~ ~ 0 ~ l ~ ~ ~ ~ I * l l l l

Fig. 10.9 Modulus as a function of temperature for Spectra 900, Spectra 1000, and Tekmilon multifilament
polyethylene fibers (Prevorsek, 1989; Mitsui, 1989).
228 Organicfibers

Temperature, OF

50 100 150 200 250 300

500

3000 -
- 400
2500 -
0 .-
- 300 -$
% 2000 1
f f0,
VI C
5 1500 1 - 200 3;
e
i7l
1000 -
- 100
500 -

0
0 25 50 75 100 125 150
Temperature, OC

Fig. 10.10 Strength as a function of temperature for Spectra 900, Spectra 1000, and Tekmilon multifilament
polyethylene fibers (Allied, 1991e; Mitsui, 1989).

- Spectra 900

.___-- ------RT, 10% Load

0 ~ ~
0 10 20 30 40 50 60 70 80 90 100

time, h
<a)

Fig. 10.11 Creep of Spectra extended chain polyethylene fibers (a) at room temperature and 10% of static
ultimate and at room temperature and 30% of static ultimate.
 Extended chain polyethylene fibers 229

6:
.-C
e
G 1
t - Spectra 900
Spectra 1000
.___

0 25 50 75 100 125 150 175

time, h
(a)

time, h
<C)

Fig. 10.11 (Continued) Creep of Spectra extended chain polyethylene fibers (b) at 5°C (41°F)and 20% of
static ultimate, and (c) at 70°C (160°F)and 275 MPa (40 ksi), which is 18% of static ultimate for Spectra 900
and 11%of static ultimate for Spectra 1000 (Allied, 1991a, 1991b, 1991c, 1991d).
230 Organic fibers

more significant. The creep of polyethylene
fibers does not preclude their use in applica-
tions such as sailcloth or structural
reinforcement, but does require that the creep
demands of an application be carefully evalu-
ated. Because of their relatively poor creep
resistance, polyethylene fibers are often
hybridized with other, more creep resistant
fibers in applications where prolonged loading
is anticipated.
The fatigue resistance of polyethylene fibers
is excellent. In one test of loading and unload-
ing of ropes, polyethylene fiber ropes
withstood approximately eight times the cycles
before break as aramid fiber ropes (Weedon and
Tam, 2986). T ~ indicates
E a superiority in ten-
sile fatigue even to aramid fibers, which are
known for their excellent fatigue resistance.
Chemical and environmental properties
Polyethylene is inert. It is stable in almost all
organic solvents and in a variety of other chem-
icals. It is also biologically inert. It is the best of
all high modulus fibers in an alkaline environ-
ment (Jaffe, 1989). It shows superior chemical
resistance to PPTA in hydrochloric, nitric and
sulfuric acid (Dyneema, 1987).Table 10.10 com-
pares the chemical resistance of Spectra
polyethylene fiber to that of aramid fiber.
Polyethylene fibers also show good resis-
tance to UV exposure. After 100 hours UV
exposure in a fadeometer, Dyneema SK60
retained 70% of its original strength and after
1500 hours, retained 25% strength. This latter
exposure is equivalent to about 2 years of out-
door exposure (Dyneema, 1987).
Polyethylene fibers are hydrophobic and
thus absorb very little moisture. The moisture
regain of polyethylene fibers is less than 1%.
Their weatherability is excellent: after 600
hours exposure in a Weatherometer, Tekmilon
fiber retained 80% of its strength and 90% of its
modulus. Following similar exposure, an
aramid fiber had only 40% strength retention
(Mitsui, 1989).Because of their excellent chem-
ical and moisture resistance, articles made
with polyethylene fibers can be cleaned in
soap and water.

Table 10.10 Comparison of strength retention after chemical immersion for polyethylene and aramid
fibers (Allied, 1989)

Strength retention, YO
Spectra Aramid
6 months 2 years 6 months 2 years
Chemical (4380 h) (17 500 h) (4380 h) (17 500 h)
Sea water 100 100 100 98
Hydraulic fluid 100 100 100 87
Kerosene 100 100 100 97
GasoIine 100 100 93 a

Toluene 100 100 72

Glacial acetic acid 100 100 82
1M hydrochloric acid 100 100 40
5M sodium hydroxide 100 100 42
Ammonium hydroxide (29%) 100 100 70
Perchloroethylene 100 100 75
10"/0detergent solution 100 100 91
Chlorine bleach 91 73 0
Too weak to test
 Extended chain polyethylene fibers 231

Electrical and optical properties bonding of the fiber to matrices. Through

1992, Allied-Signal marketed plasma-treated
Polyethylene fibers are electrically non-con-
Spectra fibers. However, polyethylene surface
ductive. The dielectric constant of Spectra
treatments are available after fiber purchase
fiber is 2.2, with a loss tangent of 2 x lo4
from specialty companies. The fiber manufac-
(Allied, 1993).This compares to dielectric con-
turers can suggest sources of these services.
stants for aramid fibers of 3.85, quartz fibers of
The inertness and high abrasion resistance
3.78 and E-glass fiber of 6.31 (Allied, 1989).
of polyethylene fibers means that little or no
They are white in color and are transparent to
finish is required. This is fortuitous since adhe-
X-rays, radar and sonar.
sion to polyethylene is so difficult that finishes
generally will not stay on the fibers. All Spectra
fibers are supplied with ’low percent process
10.3.5 TREATMENTS
finishes’ whose purpose is simply to aid in
Because of their chemical inertness, polyethyl- holding the filaments together in the bundle.
ene fibers bond poorly to matrices, with Like aramid fibers, polyethylene fibers may
consequent negative effects upon the mechan- be twisted, particularly for applications such as
ical properties of their composites. Surface marine cables. For bare fiber, twist initially
treatment by acid etch, plasma etch or corona increases the strength, although it decreases
discharge can significantly improve the the modulus of the fiber. For Spectra fiber, the

Table 10.11 Availability of commercial polyethylene fibers

Product Count Fihmen t Cornmen t s

(reference)
number/ diameter
dtex (den) yarn pm (IO”in)
Dyneema SK60 444 (400)
(Dyneema, 1987) 888 (800)
1780 (1600)
Hoechst Celanese fiber 100 (90)b
(Adams, 1993) 200 (180)
Spectra 900 722 (650) 60 38 (1.50) All Spectra fibers are supplied
(Allied, 1990, 1993) 1333 (1200) 120 38 (1.50) untwisted and with only sufficient
5333 (4800) 480 38 (1.50) finish to hold the fiber bundle
together
Spectra 1000 239 (215) 60 23 (0.91)
(Allied, 1990, 1993) 417 (375) 60 30 (1.18)
722 (650) 120 28 (1.10)
1444 (1300) 240 28 (1.10)
Tekmilon (Mitsui, 1989)
Monofilament 5.6 (5) 1 27 (1.06)
22.2 (20) 1 54 (2.13)
111 (100) 1 121 (4.76)
Multifilament 555 (500) 50 =38 ( ~ 1 . 5 )
1110 (1000) 100 =38 (~1.5)
a All availabilities are subject to market conditions and should be verified with the manufacturer.
This fiber is newly commercially available. It will be supplied in multiples of 100 dtex.
232 Organicfibers

strength of the bare fiber is optimized at a twist Pricing

multiplier of 3, but at this value there is also
Spectra fibers are currently priced from about
about a 20% loss in modulus. As with aramids,
$15/lb for larger denier fibers to about $45/lb
however, twist is not desirable in fibers used in
for the small denier fibers. Dyneema fibers are
composites. Polyethylene fiber manufacturers
not marketed in the USA. Because of the strong
provide most of their fibers untwisted.
yen, at the time of writing Tekmilon fibers are
significantly more expensive than Spectra
10.3.6 FORMS AND AVAILABILITY fibers in the USA. The new melt-extruded
polyethylene fiber from Hoechst Celanese is
Table 10.11 lists the availability of most of the
designed to offer good properties at a lower
commercial high performance polyethylene
cost than the gel spun fibers. It costs 15-50%
fibers. In most cases, each denier of fiber is
less than the comparable Spectra fibers.
available in only one package size and weight.
The mechanical properties of different deniers
may vary somewhat from the nominal values 10.3.7 DESIGN CONSIDERATIONS
given in Table 10.9.
Like aramid fibers, polyethylene fibers are
In addition to the fiber forms listed in Table
mainly used in applications where they offer
10.11, Dyneema SK60 is available in various
a unique combination of properties. This
fabrics. Spectra fibers are also available as
property combination includes outstanding
chopped fiber in lengths from 6 to 20 rnm (0.25
specific strengths and stiffnesses, high
to 0.8 in) and in fabrics of various weaves.
toughness, outstanding abrasion resistance
Tekmilon is available as monofilament, multi-
and very low density.
filament and tape.
In any design, the relatively low melting
Information about the availability of the
point and low use temperature of polyethylene
fibers shown in Table 10.11; information about
fibers as well as the relatively poor creep
other products and about special formulations
resistance must be considered. The creep resis-
can be obtained from the sources given in
tance is improved in a fiber such as
Table 10.12.

Table 10.12 Sources of information on commercial polyethylene fibers

Product Information source

Dyneema fibers Dyneema Vof, Dr. Nolenslaan 119A, PO Box 599,6130 AN Sittard, The
Netherlands
Dyneema Japan Ltd., 2-8, Dojima Hama 2-chome, Kita-ku, Osaka 530,
Japan
Hoechst Celanese’s Hoechst Celanese Corporation, PO Box 32414, Charlotte, NC 28232-2414, USA
high performance
polyethylene fiber
Spectra fibers Allied Fibers, Allied-Signal Inc., High Performance Fibers Technical
Center, PO Box 31, Petersburg, VA 23804, USA
Tekmilon fibers Mitsui Petrochemical Industries Ltd., Advanced Materials and Products
Department, Kasumigaseki Bldg., 2-5, Kasumigaseki 3-chome, Chiyoda-
ku, Tokyo 100, Japan
Mitsui Petrochemicals (America), Ltd., 1000 Louisiana, Suite 5690,
Houston,
TX 77002, USA

Allied-Signal’s Spectra 1000, which has signifi-
cantly improved creep resistance compared to
Spectra 900. Polyethylene fibers are often
hybridized with other more creep-resistant
fibers in applications where prolonged loading
is anticipated. Without hybridization polyeth-
ylene fibers must be limited to applications
where long term, high load level, or elevated
temperature loading is not anticipated, or
where creep is otherwise not of concern.
As with aramids, the poor off-axis and com-
pressive properties of polyethylene fiber
composites may also be concern. This is not a
problem, of course, in applications where the
loading is mainly in axial tension.
The X-ray and radar transparency of the
fiber can present significant design advan-
tages. The UV resistance of the fiber is very
good and thus does not present a design prob-
lem in most applications.
Because of its chemical inertness, polyethyl-
ene fibers are almost impossible to dye,
although color can be added during the fiber
spinning process. As with aramids, polyethyl-
ene fibers are optically opaque, so resin
penetration within a composite cannot be
determined visually.
Polyethylene fibers can be used with a vari-
ety of resins, including polyurethanes,
epoxies, vinyl esters, polyesters and thermo-
plastics, so long as the composite can be
processed below 120°C (250°F).Polyesters are
economical, vinylester resin systems provide
outstanding impact properties and epoxies
give better translation of structural properties.
The preferred thermosetting matrix cure tem-
perature is 93-104°C (200-220°F) (Allied,
1990). The fiber manufacturers can be very
helpful in choosing an appropriate resin sys-
tem for an application.
As with aramids, polyethylene fiber com-
posites are relatively hard to machine and
producing a smooth final machined surface
requires special techniques. Machining tech-
niques developed for aramid composites can
be used successfully, as can hot knife or hot
wire cutting (Allied, 1989).
Extended chain polyethylene fibers 233
Polyethylene fibers can be damaged by
rough handling and should be handled with
care before and during processing. They pre-
sent minimal safety or environmental concerns
and most are biocompatible, offering another
potential design advantage.
10.3.8 APPLICATIONS
Most of the current applications of polyethyl-
ene fibers are not in structural composites.
One of the main uses is in ropes and cables,
particularly in marine and off-shore applica-
tions. The fibers are used because of their high
strength, outstanding abrasion resistance (up
to ten times that of aramids), low density
(since they float), good UV stability, resistance
to seawater and high durability. The fibers are
also used as marine sewing threads.
In another major application, UV- and
water-resistance are again important. Both
Spectra and Dyneema fabrics are used, typi-
cally with a film coating, in sails. Unlike
aramids, polyethylene sail can be folded and
repacked numerous times without damage.
This latter quality also led to the selection of
Spectra fabric for the anchor balloon of the
Hilton Earthwinds round-the-world balloon
flight project and to their usage in lightweight,
durable backpacks.
Polyethylene fabrics are used as filter
cloths, where the excellent chemical resistance
is a tremendous advantage. Spectra fabric has
been used in oil containment and recovery
systems following the Persian Gulf war. The
fabric is treated so that water passes through it
but oils and other floating pollution do not.
Because of their excellent biocompatibility,
polyethylene fibers are used as sutures and as
artificial ligaments. They are also used in sur-
gical gloves, because of their excellent cut
resistance, biocompatibility and low absorp-
tion of fluids. While the poor temperature
resistance rules out the use of polyethylene
fibers in thermal protection, they are used in
industrial protective clothing and in ballistic
protection and impact shields, with or without
234 Organic fibers
a matrix. Allied makes a special non-woven
polyethylene fabric called Spectra Shield@,
which has alternating unidirectional layers
held together by a polymer matrix and gives
outstanding performance in such applications.
As composites, polyethylene fibers and fab-
rics are used in boat hulls, water skis,
sailboards, canoes and kayaks. They have
been explored for sporting goods ranging
from archery bows to ski poles. In all these
examples the excellent impact resistance they
impart to their composites is another signifi-
cant advantage. In applications such as skis
and tennis rackets, as well as speaker cones,
the excellent vibrational damping capability is
also an advantage. However, in spite of this
superior performance, the much higher cost of
polyethylene compared to glass has limited
the usage in boat hulls and sporting goods to
high end applications such as racing competi-
tions where performance and/or safety are
more important than cost. In some cases, how-
ever, the addition of polyethylene fiber
actually lowers the overall cost of the product.
One such application is in wrapping ice
hockey sticks with Spectra fiber to improve
their durability. In this case, the additional cost
to wrap the stick is more than offset by the
longer life achieved.
Polyethylene fibers are also used to rein-
force rubbers and elastomers. In many of
these applications, their excellent vibrational
damping characteristics are important.
However, the temperature sensitivity limits
the usage in tires to off-road vehicles
(Dyneema, 1987). Because of their X-ray,
radar and sonar transparency and low dielec-
tric constant, they have significant potential
in applications such as radomes, sonar domes
and X-ray tables.
As mentioned before, polyethylene can be
hybridized with other fibers to provide signif-
icant improvements in impact resistance.
Current hybrid applications range from bike
frames to impact shields.
CONCLUSIONS
For many applications extended-chain poly-
ethylene fibers are superior to all other fibers,
particularly when properties such as tough-
ness, dielectric constant, and/or hydrolytic
stability are of concern. However, because of
their relatively low melting temperature, poly-
ethylene fibers must be limited to moderate
temperatures and to applications where the
creep response is acceptable.
For sail-cloth, marine rope, pressure vessels
and other applications where the service tem-
perature is not a governing factor,
polyethylene fibers can be expected to make
serious inroads into or even dominate their
respective industries. However, they cannot
supplant aramid, carbon, or glass fibers in
applications where elevated service tempera-
ture or creep resistance are critical.
10.4 OTHER ORGANIC FIBERS
10.4.1 AROMATIC POLYESTER FIBERS
Aromatic polyester fibers are prepared by
spinning from a liquid crystalline melt fol-
lowed by heat treatment to form high strength,
high modulus fibers. While many such fibers
have been synthesized since the late 1970s, the
only fiber commercially available in the USA
today is Vectran@fiber from Hoechst Celanese
Inc. The general structural formula of this fiber
is shown in Fig. 10.12.
Vectran was developed in the 1970s in
response to tire customers who wanted equiva-
lent performance to aramid fibers but at a lower
p:
Y
Fig. 10.12 General structural formula of Vectran.
aromatic polyester fiber.
 Other organic fibers 235

cost. Hoechst Celanese was successful in pro-
viding a fiber with the desired performance,
but unfortunately the resulting cost was even
hgher than the aramids. Shortly thereafter,
Hoechst Celanese stopped marketing Vectran
fiber and marketed Vectran resin instead.
Vectran resin quickly became the material of
choice in the electronics and computer indus-
tries for small, very close tolerance connectors,
plugs and other components. Based upon this
success, in 1989 Hoechst Celanese reintroduced
Vectran as a fiber product. Since the fiber is
more expensive, by 1.5to 3 times, than aramids,
the marketing focus is on areas where aramids
do not meet the performance requirements
(Adams and Farrow, 1993a).
Vectran is a polyester-polyarylate fiber.
Unlike the aramids, Vectran melts at high tem-
perature. It is melt spun on conventional
polyester spinning equipment and the as-spun
fibers are then heat treated in a sequence of
steps (Adams and Farrow, 1993b).It is the only
commercially available melt-spun liquid crys-
talline polymer fiber (Hoechst Celanese, 1990).
Properties
Vectran HS offers a unique combination of
properties: high strength, no creep, low mois-
ture absorption, negative coefficient of
thermal expansion, good property retention
over a broad temperature range and excellent
chemical resistance.
The density of Vectran HS is 1.41 g ~ m - ~
(0.0509 lbs in") (Hoechst Celanese, 1990). It
melts at 330°C (636°F). Like aramid fibers,
Vectran HS has a negative axial coefficient of
thermal expansion. From 20°C (68°F) to 145°C
(293°F) its longitudinal linear thermal expan-
sion coefficient is 4 . 8 x lo4 /"C ( - 2 . 7 ~
/OF). The coefficient increases to -14.6 x 10"
/"C (-8.1 x lo4 / O F ) from 145°C (293°F) to
200°C (392°F) and to -26.7 x lo4 /"C (-14.8 x
/ O F ) from 200°C (392°F) to 290°C (554°F)
(Beers and Ramirez, 1990).It has good temper-
ature resistance, although not as good as
aramid fibers since it melts at high tempera-
ture. Its shrinkage in hot air at 177°C (350°F)or
in boiling water is less than 0.5%.
Vectran HS fiber is outstanding in its
mechanical properties. Its axial mechanical
properties are summarized in Table 10.13.
Vectran displays no creep when tested for 2760
h at 50% of its ultimate tensile strength. This
behavior is significantly better than both
aramid and polyethylene fibers. Vectran also
has excellent vibrational damping characteris-
tics, better than aramids. Vectran HS has
superior abrasion resistance to Kevlar 29,
although not as good as polyethylene fibers. In
flexural fatigue, Vectran HS braid exhibited a
10% reduction in strength after one million

Table 10.13 Axial tensile mechanical properties of representative non-aramid, non-polyethylene organic
fibers

Fiber Reference Specific Tensile Tensile Elongation

gravity modulus strength, at break, %
GPa (Msi) MPa (ksi)
Vectran HS Hoechst Celanese, 1.41 64.8 2840 3.3
1990 (9.4) (412)
Adams and Farrow, 1.41 62-86 2500-3100 2.2-2.5
1993a (9.0-1 2.5) (363450)
PBO (Dow) Burk, 1993 1.56 152 5650 3.5
(22) (820)
PBO, high Burk, 1993 1.56 276 5520 1.5
modulus (Dow) (40) (800)
236 Organicfibers

cycles (and maintained this strength level to
five million cycles), while a Kevlar 29 braid
showed a 30% strength reduction under the
same conditions (Beers and Ramirez, 1990).
Vectran absorbs very little water, having a
moisture regain of less than 0.1%. It is
hydrolytically stable. It has excellent chemical
resistance being resistant to organic solvents,
to acids at less than 90% concentration and to
bases at less than 30% concentration (Hoechst
Celanese, 1990).
Vectran's dielectric constant is 3.3at 1 kHz
(Hoechst Celanese, 1990).
Like aramid and polyethylene fibers,
Vectran is difficult to cut and its composites are
difficult to machine. Typical aramid composite
machining techniques can be used successfully.
Forms, availability and treatments
Vectran is produced in the USA by Hoechst
Celanese Corporation and in Japan by the
Kuraray Corporation under license from
Hoechst Celanese. It is available as Vectran
HS, a high strength reinforcement fiber,
Vectran M, a high performance matrix fiber,
and as engineered, commingled combinations
of Vectran HS with Vectran M and S-2 Glass
fiber with Vectran M.
Vectran HS fiber is available in dtex (deniers)
of 222 (200),833 (750), 1000 (900)and 1667
(1500).These fibers are composed of 40,150,180
and 300 filaments respectively, with the fila-
ments being 23 pm (0.91x 10" in) in diameter.
Vectran HS fibers are offered with or without a
standard textile finish to assist in processing
and/or to provide (dramatically improved)
abrasion resistance. Commingled Vectran HS or
M fibers have no finish. (In the commingled S-2
glasslvectran M products, the glass fibers are
producer-sized.) (Hoechst Celanese, 1990).
More information on Vectran can be
obtained from the source listed in Table 10.14.
Applications
As with aramid and polyethylene fibers, ropes
and cables are an important usage. Marine
cables, fish nets, towing ropes, cargo tie
downs, slings, sails, bicycle brake cables and
optical fiber reinforcement all have been made
from Vectran HS. Olympic target archers use
bow strings from Vectran HS having a propri-
etary abrasion resistant finish. The result is
increased arrow speed with no creep of the
string. At the last America's Cup yacht races,
Vectran HS was used in at least six yachts,
either in sails or in marine cables. Vectran sails
stretch far less than either aramid or polyeth-
ylene and they have four to six times the life of
aramid sails (Adams and Farrow, 1993a).
Safety materials and protective garments
have also been made of Vectran in industries
ranging from meat packing to metal working.
In these applications, Vectran is superior to
aramids, which have poor resistance to bleach,
and to polyethylene fibers, which are sensitive
to the high temperatures used in drying laun-
dered garments.
Vectran composites have been used in aero-
space applications and in recreation and
leisure applications such as canoes, golf clubs,
baseball bats, hockey sticks, tennis rackets,
bicycles, skis, ping pong paddles, paragliders
and stereo speaker cones. Vectran properties of
importance in these applications include the
low moisture absorption, the excellent damp-
ing characteristics, high stiffness, lack of creep

Table 10.14 Sources of information on non-aramid, non-polyethylene organic fibers

Product Itzj?ormation source

Vectran fibers Hoechst Celanese Corporation, P.O. Box 32414, Charlotte, NC 28232-2414, USA
PBI fibers Hoechst Celanese Corporation, P.O. Box 32414, Charlotte, NC 28232-2414, USA
PBO fibers The Dow Chemical Company, Midland, MI 48674, USA

and good flexural fatigue properties. Vectran
is used where the cost of the fiber is secondary
to its performance (Adams and Farrow,
1993a).
Hybrid tennis rackets have been made by
Prince Manufacturing Company and Dunlop.
Vectran HS is combined with carbon fiber to
give greater speed and power with vibration
characteristics as good as wood. Jennifer
Capriatti played with a Vectran racquet at
Wimbledon in 1992.
Other actual or potential uses include
antenna guy wires, chemical resistant pack-
ings and gaskets, heat and creep resistant
belting, medical and surgical equipment, pres-
sure vessels, printed circuit board substrates
and aerial tow ropes.
10.4.2 AROMATIC HETEROCYCLIC POLYMER
FIBERS
Two aromatic heterocyclic polymer fibers are
currently available or in development in the
United States. These are PBI fiber from
Hoechst Celanese and PBO fiber from Dow
Chemical Company.
PBI fiber
PBI fiber is produced from a high performance
polybenzimidazole. Chemically it is poly-2,2'-
rn-phenylene-5,5'-benzimidazole,with the
structural formula shown in Fig. 10.13. The
fiber was commercialized by Hoechst Celanese
Fig. 10.13 Structural formula of poly-2,2'-rn-pheny- stretched to improve its orientation and prop-
lene-5,5'- benzimidazole (PBI) (Yang, 1992).
Other organic fibers 237
Fig. 10.14 Structural formula of poly-p-phenylene
benzobisoxazole (PBO) (Yang, 1992).
in 1983. It has excellent chemical and solvent
resistance and does not burn. It is, however,
more expensive than the aramids and has an
intrinsically high moisture absorption. It is
used mainly in woven form in fireblocking lay-
ers, including aircraft seat cushions and
fire-fighting overgear. It was also used in
chemical warfare suits in Operation Desert
Storm. In order to reduce cost, PBI is also used
in blends with aramids for thermal protective
apparel. PBI has potential applications as a
fiber reinforcement in composites, but cur-
rently its only composites application is as a
matrix resin or as a matrix-precursor for car-
bon-carbon composites (Yang, 1992; Conrad,
1993). More information on PBI can be
obtained from the source given in Table 10.14.
PBO fiber
PBO fiber is a polybenzoxazole, specifically
poly-p-phenylene benzobisoxazole, with the
structural formula shown in Fig. 10.14. PBO
fiber resulted from a US Air Force program
aimed at developing high strength fibers for
advanced composites. In the late 1980s, Dow
Chemical purchased worldwide rights to the
polymer. Dow has now constructed pilot plant
facilities for monomer, polymer and fiber and
the fiber is available for evaluation in pre-pro-
duction quantities (Burk, 1993).
As with aramids, PBO fibers are spun from
a liquid crystalline solution using dry-jet wet
spinning. This is, however, a more difficult
process than for aramids. The fiber is then heat
erties (Wolfe, 1990).
238 Organic fibers
PBO is one of the most thermally and
thermo-oxidatively stable organic polymers
known. No weight loss was observed for PBO
held at 316°C (600°F) (Wolfe, 1990)and weight
loss of only O.O6%/h was observed at 370°C
(700°F) (Burk, 1993). Its decomposition tem-
perature is 600°C (1110°F) (Burk, 1993).
Exposed to flame, PBO chars, but does not
support combustion. (Wolfe, 1990) Dow's PBO
fiber has a longitudinal coefficient of thermal
expansion of -6 x 104/OC (-3.3 x lO"/"F)
(Burk, 1993).
PBO fiber has a significantly higher tensile
strength and modulus than any other known
organic fiber. PBO fibers have been produced
with tensile moduli of as high as 470 GPa
(68 Msi). Dow's current pre-production fibers
do not achieve these high levels, but do
nonetheless have excellent axial mechanical
properties, as shown in Table 10.13. However,
like all other high performance organic fibers,
PBO fibers are quite weak in compression,
with a fiber compressive strength comparable
to that of aramids (Burk, 1993).They also bond
poorly to epoxy matrices, so their off-axis
properties are also poor (Wolfe, 1990). For
these reasons, as with other organic fiber com-
posites, PBO composites are limited to
applications where structural loading is
mainly in axial tension.
Moisture regain for Dow's PBO is 2.0% for
the standard fiber and less than 0.570 for the
high modulus version. The moisture resis-
tance is significantly better than aramids
(Burk, 1993).PBO is highly resistant to hydrol-
ysis, acid chemical attack, bases, solvents,
electron bombardment and laser radiation. Its
UV stability is outstanding (Wolfe, 1990).
Dow's PBO fiber has a lower and more stable
dielectric constant than that of aramids, 3.0 at
100 kHz (Burk, 1993).
The price for commercial PBO will be vol-
ume dependent, but will be higher than that
for aramids. PBO fiber will be used where
aramids and other fibers do not meet the per-
formance needs, particularly for strength,
modulus and flammability. Potential applica-
tions include composites loaded in tension,
such as pressure vessels, missile cases and ten-
sile beams. PBO fiber composites may also be
used in non-load-bearing applications where
high temperature exposure or harsh chemical
environments are anticipated, such as rocket
insulation systems and brake and transmis-
sion systems. The high strength could also
lower the weight of composites used in space-
craft and in recreation and sporting goods.
PBO also has significant potential application
to ballistics, where, as a fabric or composite, it
performs equally well at half the weight of an
aramid. PBO composites could provide out-
standing containment systems for high speed
rotors and turbines where high temperature
exposure is of concern. The fibers also have
potential for bomb containment systems, for
fire resistant and cut resistant apparel and fire
blocks, as well as ropes and cables (Burk,
1993).
More information on PBO can be obtained
from the source given in Table 10.14.
10.5 CONCLUSIONS
While high performance organic fibers are not
competitive with inorganic fibers in all of their
properties, they offer certain properties and
combinations of properties that are unavail-
able with inorganic fibers. All suffer from
certain limitations, such as poor off-axis and
compression properties and/or temperature
limitations. However, if these limitations are
properly considered, high performance
organic fibers can make possible designs that
can be achieved in no other way.
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as the weight in grams of 1000 meters of the
material. A related term is decitex (dtex),0.1
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parable to the US quantity 'denier.'
Equilibrium moisture content: moisture
absorbed by a fiber after it has been dried at
50°C (122°F)for 2 h and then equilibrated at
20°C (68°F)and 55% relative humidity
Strength retention: percent of room tempera-
ture strength retained following exposure
to the conditions indicated
Tenacity: the ultimate failure strength of a fiber
per unit original area per unit weight. The
most commonly used units are 'grams per
denier' (gpd) and 'newtons per tex'
(N/ tex).

10.6 APPENDIX Conversion factors

DEFINITIONS AND CONVERSION FACTORS Fiber size:

1 tex = 9 denier = 10" kg/m
Definitions Twist:
1 tpi (turns per inch) = 39.37 t/m (turns per
Denier: Term in common usage in the fiber meter)
industry in the USA to describe the fineness Twist multiplier = [t/m (dtex)'/*]/3000= [tpi
of a fiber or fiber bundle. The denier is (denier)'/'/ 731
defined as the weight in grams of 9000 Modulus, stress, strength, and tenacity:
meters of the material. This is also known as 1kgf / mm2 = 9.806550 MPa
the 'count'. Its inverse measure is the 1 ksi = 6.894757 MPa
'yield', expressed in yards per pound or 1cN/tex = 0.01 N/tex = 10 pf MPa = 1.45 pf ksi
meters per kilogram. where pf is the specific gravity of the fiber
Tex: Term in common usage in the fiber indus- 1 gpd = 8.826 cN/tex = 88.26 pf MPa = 12.8 pf
try outside the USA to describe the fineness ksi
of a fiber or fiber bundle. The tex is defined