Indian Jo urnal o f Fibre & Tex til e Researc h

Vo l. 27, Septe mber 2002, pp. 290- 306

Review Articles

Aramid fibres - An overview

M Jass:tI" & S Ghosh
De partme nt o f Tex til e T ec hno logy, Indi an Inst itute o f Tcc hn o logy, New De lhi 11 00 16, In dia

Received 16 lilly 200 1; accepted 24 Septelllber 200 1

The hi sto ry, prepa rati o n a nd stru cture of a ra mid s in ge ne ral a nd of No mex a nd Kev lar a ramid fi bres in part ic ul ar a rc
disc ussed. T he structure-pro pe rty co rre lat ion a nd th e applica ti o n a reas o f these fibres a rc re viewed . Aram id fibres a rc
characte ri zed by their superior therma l propert ies, resista nce to c he mi cals a nd o ut sta ndin g mec hani ca l pro pe rt ies.
Key words : Aramid fib re, Arom ati c po lya mi dcs, Kev lar, Liq uid c rystallin e spinning, No mex, T ec hno ra

1 Introduction
The first organic fibre with hi gh enough tensile
modulus and strength to be used as reinforcement in
adva nced composites was an aromati c polyamide
fibre or aramid fibre. As aramids have 5-10% hi gher
mechani cal properti es th an oth er sy ntheti c fibres,
these are di splac ing metal wires and inorganic fibres
fro m the market of hi gh performance uses like various
struc tural compos ites fo r appli cati on in aircraft,
marine and automobile, ropes for offs hore oil rigs,
and bullet proof ves ts. The fibres not onl y have much
better mechanical properti es th an steel and glass
fibres on an eq ual we ight basis, but also maintain
th ese properti es at hi gh temperatures as aram id
polymers are excellent heat and flame resistant. So,
they also have wide appli cati ons in areas like
protecti ve clothing in hostil e environment where heat,
chemical and radi ati on are prese nt, furni shin g in
public places as fl ame resistant, industri al filters and
hollow fibres for desalinati on by reverse os mosis. The
word ' Aramid ' is a ge neri c term for a manu factured
fibre in whi ch the fibre formin g substance is a long chain sy ntheti c polyamide, in which at \east 85% of
amide linkages are attached directl y to two aromati c
n ngs, as defin ed by the U.S. Federal Trade
Commission. Therefore, by definiti on, the aramid
famil y will cover Kev lar, Nomex, Techn ora,
Teijinconex, Twaron, etc. fibres. In thi s review, an
attempt has been made to present a brief overview of

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aramid fibres, giving emphas is on th eir structureproperty correlations and th eir di fferent outstanding
applications.
The hi story of development of aramid fibres is
given in Table I. It took a long time to fi gure out how
to make an ything useful out of aramid fibres because
it would not di ssolve in anythin g. Therefo re,
processing it as a soluti on was not poss ible. It
wouldn ' t melt below - 500C, so melting it dow n was
out too. The development of aro mati c polyamides
changed dramati cally in direction wi th the di scovery
of lyotropic liquid crystalline aramids. Kwo lek 5 , a
DuPont Research Scienti st, prepared the first high
molecul ar weight lyotropi c aramid . He synthes ized
the ri gid chain poly (p-benza mide) in high mo lecu lar
we ight and with limited crys tallinity to promote the
di sso lution of this seemingly intrac table polymer in
amide salt solve nts. Thi s di scovery all owed the
deve lopment of a novel fibre spin ning process fo r
ani sotropic solution by Bl ades 6 , res ulting In
commerci ali zation of Kevl ar. The synthes is of
numerous aromati c polyamide compos itions and the
development of a number of com mercial aramid
fibres foll owed this. In additi on to aro mati c
pol yamides, aromatic heterocyclic polymers like poly
(p-phenylene benzobi sthi azo le) (PBZT) and poly (pphenylene benzobi soxazole) (PBZO) also have hi ghl y
ordered structures in solid 7. 8 . DuPont is world 's
leading producer of aramid fibres, co ntro lling abo ut
two-thirds of the market. Teijin Ltd , Japan, is the
second largest producer.Others include Rh onePoul ene, France; Toray Industri es Inc. , Japa n;
Aco rdi s9 ; Akzo Nobel NY, Netherl ands.

JASSAL& GHOSH: ARAMlD FIBRES

291

Tablc I- Hi story of devclopmcnt of aramid fibre

Produccr

Basc polymer

DuPont Co., USA

MPD-I

Introduct ion or ribrc-B

DuPont Co. , USA

(i)PBA
(ii )PPD-T

1972

Introduction of Tcijincorcx
Commcrciali sation of Kev lar
Introduction of Twaron
Introduction of Kcrmcl 2
Introduction of Fenilon'

Tcijin Ltd, Japan & DuPont Co., USA

Akzo Chcmicals BF, Ncthcrlands
Rhonc-Poulenc, Francc
USSR

MPD-I
PPD-T
PPD-T
MPD-I
MPD-I

1976

Int rod uction of SYM fibrc (formc rl y Yniivlon)3

USS R

Polyhctero arylcne

1978

Dcvelopment of arcnka aramid fibrc

Ycar

Evc nt

1938

Commcrciali za tion of Nylon

1962

Introduction of Nomcx fibrc

1965

Discovcry of ani sotropic polymcr by P.F. Flor/

1970

Di scovcry of air-gap spinning

197 1

1987

Int roduc ti on of HMO-50 (Tcch nora ) aramid fibrc

Tcijin Ltd, Japan

1988

Commcrcia li sation of Twaron (formcrly Arneka)

Introducti on of PBO-HM

Toyobo, Japan
Toyobo. Japan

1996

Introduction of Trevar (discontinucd latcr)

Hocchst. Gc rman y

1997

Kcv lar 49 HS by ncw fib rc tcchnology (NFT)

DuPont Co., USA

1998

Introduction or Armos4

Russia

p-aromatic hydrocyc lic

copolya midc

MPD-I-Poly(m-phenylcne iso phthalam idc); PBA-Pol y(p-bc nza midc);and

PPD-T - Poly(p -phenylcne tcrcphthalamidc)

2 Preparation of Aramid Fibres

2.1 Synthesis

Ri gid molecul es in solution behave differently

from fl exible mol ec ules. Flexible molecules, in going
from dilute to higher concentrations, pack together by
bending and entangling, forming random coils. But
rigid molecules, in going from dilute to high er
concentrations, cannot form random coils because
their movement is restricted . Therefore, at a critical
concentration , th ey have transition to a liquid
crystalline state. In this state, th e molecules are
aligned parallel to each oth er in randomly oriented
domains or aggregates of the rod -like polymer
mo!ecules . Therefore, th e usual methods for the
preparation of aliphatic polyamides are unsuited to the
preparation of hi gh mol ec ul ar weight aromatic
polyamides. Howevcr, two methods are ava ilable for
the preparation of medium to hi gh mol ec ular weight
polymer:
(i) Low-temperature polycondensation (preferably
below SO DC to avoid degradation, side reaction and
crosslinking), and
(ii ) Direct polycondensation in so lution using
phosphites (in presence of metal sa lts).
Among th e two low-temperature polycondensation
method s availabl e,
namely
interfacial poI-

condensation and solution polycondensation , the

second process is preferred, because in interfacial
polymerization the molecular weight distributi on is
broad , which is not suitable for preparation of fibres.
In solution polycondensation , the polymeri zation
medium is an inert solvent for at least one of th e
reactant and solvent or swelling agent for th e pol ymer
(preferably a solvent). The preferred solvents are
dimethyl acetamide (DMAc), N-methyl-2-pyrrolido ne
(NMP), hexamethyl phosphoric triamide (HMPA ) and
tetramethyl urea (TMU). But no orga ni c solvent i..
sufficiently powerful fo r aral11ids to keep the pol ymer
in so lution as its mol ec ular weight builds up.
However, by addition of lithium or calcium chloride
the solvating power of many organic solven ts is
greatly increased. Typical polymeri zation co ndi tion s
for some co mmerciall y attractive aramids are given in
Table 2 .The chain confor:nation of different arami ds
is shown in Fig. I whi Ie the chemical reactions
occurring during the sy nthesis are show n in Fig. 2.
The Nomex (meta aramid ) polymer was
produced usin g l1l-phenylenediamine and dichlori de
of III-i sophth alic acid . Amorphous heat-resistant
polyamides (copolymers of meta and para aram ids)
have been prepared by solution polymeri zation in ,meth yl pyrrolidone (NMP) fro m eq uimol ar amoun ts

292

INDIAN J. FIBRE TEXT. RES ., SEPTEMBER 2002

Table 2- Polyme ri zalion condili o ns for ccrlain aramids

SI.No.

Monomer

Solvc nl

Polymcr

ll inh

p-Phcnylencd iamine
Terephlhaloyl chloridc
Isophlhaloy l chl ori de

HMPA/NMP

95/5 Copoly (p-pheny le ne le re phlhalamicIc/i sophlhalam ide)

4.48

Isop hlhal oy l chloridc

p-Phcnylcncdiaminc
Tcrcplllhaloyl chloridc

HMPA/NMP

5/95 Copoly(p-phc ny Icnc isophlhalam idcllc rcp hlh alamicIe)

3.9

p -Phcny le nediamine
p-Phcnylcnc dii socyanalc
Tcrcphlhaloyl c hloridc

HMPA/NMP
LiCI

90/1 0 Copo ly (p-phcnylcnc-p-phcnylcnc diisocyano Ic rcphlh alam id c)

1. 83

HMPA/NMP
LiCI
HMPA/N MP
LiCI

95/5 Copolymcr

2.87

80/20 Copoly mc r

2. 82

p-Phcnylenediamine
2, 5-Bis(p-aminophenyl)1,3,4-oxad iazo lc
Tcrcphlhaloyl chloridc

HMPA/NMP
LiCI

Copoly (p-phc ny lenc)/2, 5-bis - (p -am in ophcny l)- I, 3, 4Ic rcphthal a midc

o x~ d iazo

4.48

fl - Phcny Ic ncdiami nc
2-C hl oro-pphe ny lc ncd ia minc
Tcrcphlh aloy l ch loride

DMAC/LizCO,

50/50 Copoly (p-phcnylcnc/2-chloro-p -phcnylcnc Icrcphthalamicle)

3.85

HMPA - Hexa mclhy l phosphoric lri a midc.

DMAC- Dimelhyl acelam idc.
NMP- N- mClh yl-2-pyrrolicIonc.

Fig. I-Chain co nform at io n of difTerent aramid s (a) poly(pphenylcne

Icrephlhal amide), (b) po ly(3 , 4' - diphenyl ether
tcrcp hlh alam idc), and (c) poly(4, 4 '-cliphc ny l cth e r le rcphth alamidc)

o f 4 , 4 ' -methylene diamine, p-phenylenediamine,

isophth a loy l ch loride and te rephth aloyl chloride.
Despi te the a morphou s character of polyamide, it
offe rs exce ll e nt resistance to common o rga lll c
solven ts and inorganic soluti o ns.

Th e preparation of AB polyamides rpo ly (p benzamide)] using ac id c hloride and am ine

condensation requires protectio n of amine gro up with
a labile group, which is removed as th e polymeri zation
proceeds. Both
monomer sui fi n y I
lO
derivative and hydroc hl o ride salt
have been
polymerized to hig h mo lecular weigh ts usin g lowte mpe rature solution techniqu e. The polymeri zatio n
of these derivatives requires the sto ic hi ometri c
a mount of hydroxide o r water as base. The in orga ni c
sa lts generated , in situ, in crease th e so lubili ty and
stabilize the resulting so luti o ns. In DM AC , lithium
carbonate or hydride is preferred II I. Polyme r
mol ec ular wei g ht is strong ly affected by the reacti on
te mperature. Maximum values are obtai ned whe n th e
initial temperature is 0-5 C and th e fi nal temperature
is 30C or less . Pre fe rred mo nomer co nce ntrati o ns
depe nd on the so lve nt used and vary from 1.1 m/litre
in HMPA to about 0.5 m/litre in DMA C.
T he problems assoc iated with the limited so lu bility
of poly( I, 4-benzam ide) have bee n avo ided by
utili zin g so lid state polymerization of hydrochloride
salt derivative of monomer in the abse nce of solve nt
o r in hexane slurry with pyridine as acid acceptor I I .

293

JASSAL& GHOSH: ARAMID FIBR ES

Diamine

Dia cid chlorioe

Tel

PPD

5-10% (6.07%) solo

8=-120"C (90"C)

O.l - I s(0 .08s)

<9S"C
(85C)

Polymerizer A.

4-1 55

mixing and cooling

(4.7 s)

40-9S"C
(57"C)

NH z

-rQ:r-

NHz + CI

o
II

POlyme ril~r

B,
60-3005
high shear
(75s)
mlxlIlg and cooli ng

(a)

II

-c -rQJ- c- ~~H~NH-C0=t

rn-ph" n ylellell i ~rllillt:

lsophthaJoyl

(MPD)

chloride

CI

MPD-I

2HCI

(b)
N~--15'-NHz
~

n CI-C

O--C -

II~ II
o
0

CI

poly(p~ phenylene

Hel

terephthalamide)

PPD-T

(c)
Fig. 2-Polyconcle nsa ti o n reaetion s fo r po ly meri zati o n (a) Pre parati o n o f PPT-D fibre, (b) Po ly meri zati o n o f
ve nt polyco nde ns:1 ti oll of T wa ron/ Kev la r

o JllexlCo nex, a nd (e) So l-

294

INDIAN J. F!BRE TEXT. RES., SEPTEMBER 2002

The polymer conta ining rough ly needle-like

structu re of monomers is reported with inhere nt
viscosity of 4. 1 dl Ig. High mol ec ular weig ht poly ( I,
4-benzamide) with l1 inh = 1.7 dl/g in H2SO.1 have also
been produced by reactin g 4-aminobenzo ic ac id with
triphenyl phosphite in N-methylpyrrolidone/pyridine
(NMP/Py) soluti on containing lithium chl oride.
Mo lec ular weight is dependent on concentrat ion,
temperature,
solvent
cO mpOSiti On,
monomer
co ncen trati on and the base used 12.
Poly ( 1,4- phenylene terephthalamide) (PPD-T) of
high molecular weigh t ca n be prepared by lowtemperature solution technique l 3 . PPD-T is less
solu ble in amide type of so lvents than is PBA and,
th erefore, th e most suitabl e conditions require HMPA
alone or mixed with NMp l " 15, alt hough oth er
mix tures 16 also produce fi bre-formi ng polymers. The
high est molec ular weight of PPD-T was obtained in
1:2 ratio of HMPA: NMP or I: 1.4 ratio of DMAC:
HMPA and thi s suggests sa lt formation wh ich
promotes PPD-T so lvation. Preparati on in DMAC and
NMP or in mixtures of th ese solvents at all rat ios
resu lt in low molecular weight pol ymer show ing no
synergisti c solvent effec t, possibly beca use no sa lt is
formed . Addition of salt to th e mixture of DMACHMPA or NMP-HMPA res ults in low mol ec ular
we ight PPD-T. NMP containing di sso lved CaCI 2 is
the preferred solvent for commercial producti on.
During the polymerisation, th e molecular weight
increases very rapid ly with in th e first few seco nds of
reaction. Although th e reaction mix ture gelation
occurs quickly , polymeri zati on continues at a greatly
reduced rate. Critical factors influencing polymer
molecular weight include stoichiometry , solvent
composit ion, temperature, reacta nt co ncentration and
mixing.
By choosing a suitabl e so lvent, gelation ca n be
delayed until high molecular weight is reach ed. PPDT molecular weight reac hes a maximum l5 at about
0.25 m/litre in HMPA/NMP (2: I , vol./vo l. ) but in
100% HMPA the maximum occurred at 0.7 m/litre.
At low co ncentrations, the un desirab le side reacti ons
with solvent become important to limi t th e mo lec ular
weight and th e high co ncentration may induce gel
fo rmation at lower molecular weigh t.
In the laboratory , th e reaction between 1, 4phe nylened iami ne and terephthaloyl chl oride is
carried out by dissolvi ng th e diamine in a solvent and
cooling (0 to -15C) . The low initial temperature
minimizes the side reactions and prevents the reac tio n
exotherm from overheating th e mass. The acid

ch loride is added as a finely divided solid with very

efficien t mixing. The reaction can continue in the ge l
sta te at a much slower rate for several hours. Intrinsic
viscosity val ues of 5-6 dl/g are typi ca l of polymers
prepared by thi s method.
In large-sca le continuous polymeri zation of PPD-T,
th e problems of cont rol of stoichiometry, rapid
mixing and gelati on are overcome by the use of
spec iall y designed mi xing apparatus. Use of such
mixing dev ice allows continuous mlxlllg by
impingi ng a stream of I, 4- phenylenediamine
so luti on and a stream of molten terephthaloyl
ch loride. Residence time in th e mixture is less th an
one second. T hen the reactants enter a hi gh shear
contin uous sc rew mix er, where th e mo lecular weight
increases substantiall y to produce a polymer with
intrinsic viscosity of 4-4.5 dl/g .
The third stage of polymeri zation rakes place in a
high shear twin screw meter with blades arranged to
all ow for substantial recyc le zones with in the mixer.
These recycle zones reduce th e ex ternal cooling
requirement and increase the res idence time in the
mixer, resulting ifI higher molecul ar we ight and lower
reaction temperatures. The process system ass igned to
DuPont describes a system using HMPA as so lvent.
N M P co ntai ni ng large amounts of ca lci um ch loride
can be an alternate so lvent system with better
chemical and thermal stability than HMPA, makin g
the solve nt recovery easier. Calcium ch loride is a
more effective so lvent additive as conce ntration
increases. Since the so lu bi lity of CaCl 2 in NMP is
onl y 6% at 20C, th e favoured polymeri zati on
cond iti ons use a slurry or sa lt in th e orga nic phase. As
the polymeri za tion proceeds, the sa lt continues to
dissolve, probab ly du e to the formati on of
CaCl 2/am ide comp lexes. Presence of N, N'
dimethy lan iline, an acid acceptor, furth er enhances
the molecular weight. Thi s solvent system produces
polymer of comparable mol ec ular weight to that
formed in HMPA solu ti on.
The effect of th e conditions of sy nth esis on th e
mol ec ular weigh
characteristi cs of aromatic
po lyamides is exami ned and discu ssed in relation to
the properti es of wet-spun aramid fibres by Manin a
el 01. 17.
Segmented copolymers cons lstlll g of
crys talli zable p-phenylene terephthal am ide ester units
and poly (tetramethyl ene oxide) segments were
sy nth esized by Niesten el al. 18 . The length of the poly
(tetramet hylene oxide) segments ill th e polymers was
varied from 650 g/mol to 2900 g/mol and th e effect of
low Tg segments was investigated using the thermal

JASSAL& GHOSH: ARAM ID FIBRES

295

methods. One-step polycondensati on of 3,3'-,4,4'biphenyltetracarboxy lic di anhydride with aro matic

di amines in phenol as solvent and with phydroxybenzoic aci d as acce lerato r has been used
successfully to produ ce polyamides for stron g
fi bres l9 .
2.2 Fibre Formation

Aramids deco mpose before or during melting, and

hence are spun from solution. Although both dry and
wet spinning techniqu es are suitabl e, the ultimate
properties vary depending on the polymer structure
and the meth od empl oyed.
2.2.1 Dope Structure

The linear aramid molec ul ar stru ctures, such as

PB A and PPD-T, are lyotropic liquid crystals. Under
the certain favourable conditions of solvent, conce ntration and molecul ar we ight, the molecul es form
nematic liquid crystal s, i.e. they are organized in essenti ally parall el arrays . In th e absence of ex ternal
ori enting fi eld, the mUltiple arrays or domains, eac h
with hi gh molec ul ar ori entati on but randoml y ori ented
with respect to eac h other, are formed. In the prese nce
of ori enting field, th ese domains orient easil y in the
field as detail ed by Wissbrun 20 and BelTY and Strong 21 .
The viscosity of PPD-T in 100% sulphuri c acid as
a function of concentration (for two different
molec ul ar weights) is show n in Fig. 3. It is observed
th at as the concentration increases, th ere is a rapid
increase in viscosity of polymer soluti on until a
criti cal concentration is reached, after which the
viscosity rapidl y drops. The increase is th e ex pected
rise in viscosi ty with concentrati on for an isotropic
polymer, the criti cal concentrati on marks th e start of
nematic (isotropic) phase form ati on and th e viscosity
drop shows low-viscos ity be haviour of nemati c liquid
crystals l5. The critical polymer co ncentrati on needed
for meso ph ase fo rmati on is dependent on the
molec ul ar weight of th e polymer.
For soluti on spinning process, the hi gh molec ul ar
weight polymer, hi gh polymer concentration in the
dope and the low dope viscos ity are req uired for obtaining good mechani cal properties, easy processibility and low cost. Fig. 4 shows a phase di agra m for
PPT-D in 100% sulphuri c ac id . In the hi gh co ncentration (18-23 % PPT-D), low viscos ity region of interest
the dope is so li d up to abo ut 80e. These dopes are
requ ired to be melted before sp inning and fo r low
tempera ture coag ul at ion, these are req uired to be dryjet wet spun . The process is best described as melt

Fig. 3-Vi scosity-concentrat ion-tempcraturc pro ril e or PPDTH2SO.j soluti on

Isotroo ic
solution

160

~
oU

/.

120

e
15.

/)/--

80

~
40

Anisotropic
solution

I~I J~:~;;;,
'T

~~
/m

===-s;::./

I ==---/n'::.

==-: Region for

1::7

AnJ so tr 0 pic
solid

wet spinning

__L-~_ _- L_ _~~~~_ _~

OL-~~.~

10

12

14

16

1'6

20

22

Wt %

Fi g. 4--Phasc diagram of ani sotrop ic soluli on of PPD-T in 10%

H 2SO.1

spinning of PPT-D in nemati c phase, wi th fibre precipitatin g in th e air gap and th e ac id stripped off in the
coag ulati on bath. It is also ev ident from the phase
diagram th at up to conce ntrati ons of 10%, the dope
viscosity remai ns low and such dopes can be wet spun .
2.2.2 Aramid Spinning

The anisotropic polymer dope (i n concentrated

sulphuri c ac id) is ex truded through spinnerets at about
loooe through about I cm air gap into cold water (04C). The fibre precipitates in the air gap and the ac id
is removed in th e coag ul ati on bath . The spinneret
capillary and air gap causes rotation and ali gnment of
do mains, resulting in hi ghl y crystalline and ori ented

296

INDIAN J. F! BRE T EXT. RES., SEPTEM BER 2002

as-spun fibres (Fig. 5). When the anisotropic solution

passes throu gh the capillary hole, the capillary shear
causes some of the liquid crystal domains to ori ent
along the direction of shear; however, at th e capill ary
exit, so me deorientation of liquid crystal domain
occurs because of soluti on visco-elasti city. The
deori entati on is qui ckly overcome by fil ament
attenu ati on under spinning tension. The attenu ated
fil ament, after was hing, neutra li zation and drying
results in hi ghl y crystalline, hi gh- strength and hi ghmodulus fibre. The isotropic so lution, spun by wet
spinning, is ex posed to th e coagul ant as soon as it ex it
the spinneret nozzle, preve nting the so luti on from
complete attenu ati on and hence res ults in low
tenac ity, intermedi ate modulus and hi gh elongati on.
The process claimed by DuPont22 prov ides fo r th e
wet spinning of meta-aramid polymer so lutions
hav ing a salt content of atleast 3% by weight to
produce a one-step, full y wet drawab le fibre whi ch
has des irable phys ical properti es without hot draw ing
of the fi bre. Another patent 23 prov ides a hi ghl y
ori ented aramid fibre with hi gh tensile strength , hi gh
tensile modulus and low breakage elonga ti on by
spinning th e liquid crystal polymers, such as aramids,
and drafting the polymer into or adjacent to a first
coagul ati on bath . A polymer soluti on with a
co ncentrati on of 4-24 weight% is ex truded as a stream
into non-coagul ati on fluid and the stream is stretched
in the non-coagul ating flui d and passed th ro ugh
coag ul ating bath where it is drafted by using a
draftin g roller. As a res ult, a hi ghl y ori ented aramid
fibre with tensile strength of 1500-5000Mpa, tensile
modulus of 200-500 Gpa and the elongati on of 0.81.4 is obtained. For th e wet spinning of aramid fibres
with enh anced mechani cal properti es, incorporati on
of 2, 6-naphhthylene units co ntai ning copolymer in
the weight rati o of 95 :5 - 85:1 5 is claimed24 .
In an effo rt to reduce th e nepping tendency of hi ghmodulus Kevlar fibres, sci enti sts from DuPont
prepared th e Kev lar fibres by wet spinning the PPD-T
fo llowed by washing to water content > 50%. The
fibres were then coated with poly (orga nosiloxane),
ethylene ox ide and propylene ox ide block copolymer
or its deri vati ve and stretched under a tension of 1-10
gpd and dri ed. Nepsll 0000 m were found to be 4.8
with fibre tenacity of 24.8 gpd hav ing a modulus of
876 gpd 17.
Research workers of Asahi Chemi cal Indu stries 25
have used the copper compoun ds with sulphi dising
agents to prepare electrically co nductive p-ar'amid
fib res. PPD-T fibres we re spun by ani sotropic dopes

Spinning sol ution

T= 85'C

Air gap

T: R.T.

Liqllid L~s ta lli n~ dOJ11Jins

Elongation stretch
al ign m ent of
doma in di rection s

Coagulation bath

T: 5 C

Solidit ica ti on by
cooling
Romo val of sol vent

Fig. 5--Schcmatic diag ram of the ext ru sion of the liqui d crystal line soluti on through the spinn ing hole and subseq uent el ongation
stre tch in the air gap

havin g p-ori ented aro mati c polya mide in 98.5 %

H2 S0 4 at 30C. Fibres were th en treated with
coagul atin g solution, followed by was hin g. Was hed
fibres were impreg nated with copper compoun ds and
sulphidi sing agents.
2.2.3 Fibre Hea t Treatment

The ph ys ical and tensil e properties of as-sp un

aramid fibres can be furth er imp roved by heat
treatment under tension. The effect of heat treatment
on the fibres spun by different techniques is show n in
Fig. 6 . In wet-sp un ya rns, both te naci ty and modu lu s
increase expo nenti ally with increasi ng telll peralure
(a nd draw rat io) . The effecti ve increase beg ins at
about 360C (Tg of polymer) and the properti es atta in
a max imum at about 550C (Trn of polymer). During
the heat treatment, wet-spun yarn s show majo r
increase in crystal Iini ty, structure perfec ti on and
ori entati on. In dry jet-s pun ya rns, a j um p in mod ulus
is observed, essentiall y indepe ndent of temperature, at
temperatures greater th an about 200C. The fi nal
modulus level is a fun cti on of prec ursor mod ulus (or
ori entati on), with tenac ity remaini ng co nstant. A
moderate increase in the structural perfec ti ons is also
indicated by th e density increase.

297

JASSAL& G HOSH: ARA MID FIBRES

3 Structure and Property

The fun ctional properties of ara mid fibres,
particularly the tensi le properties, are related to the
fibre structure at molecular level. The polymer chain

confo rmati on and ri gidity, crysta lline ori entation and

crys tallinity are the key properti es go verning th e fina l
fibre properti es. The ph ys ical properties 26 of some
co mmercial aram ids are shown in Table 3.
3.1 Fibre Structure

Wet spun

Wet spun

.c
u
Cl

cu

I-

200

400

600

200

.c

Vl
"...

"

"-

Cl

cu

:;:

..- / '

I
I

"0
0

600

Dry Jet-wet spun

Dr y Jet - wet spun

~

400

l-

/
/

o
TempQruture, C
Fig. 6--Sc hcmatic diagra m or thc rcsponsc or dry j ct-wct spun
PPT-D rib rc to hcat trca tmcn t

When PPD-T so lution are ex truded throu gh a

spi nn eret and draw n through an air gap durin g fibre
manufacture, th e liquid crys talline domains can orient
and align in flow direction.Thus, Kev lar can acquire a
hi gh degree of alignment of long strai ght polymer
chai ns parallel to fibre axis. The ex truded material
also possesses a fibrillar st ru cture. Kev lar fibre
co ntains several levels of superimposed mi croscopic
and macroscopic stru ctures including the crysta l
latti ce, pleated structure, fibrillar structure and sk incore structure. Studies by electron diffraction and the
dark fi eld transmi ss ion electron mi croscopy of PPD-T
point to an unusual radi al orientat ion of hydrogen
bonded sheets and pleated structure27 . The pl eated
stru cture has been observed both for Kev lar 29 and
Kev lar 49, but absent in the product of hi ghest
modulus, Kev lar 149 (refs 28 & 29). The pleats are

Tablc 3- Propcrti cs of somc aram id librcs

Fibrc

Charactcri sti c

Crystallinc Loop strcngth

Loop
M odulus"
modulus
g/dcn
clongat ion Gpa (gpd)
Gpa
%

Tcnsilc
strcn gth
GPa (gpd)

Ex tcns ion Rclativc

to brcak dcnsity
%

Nomcx

17(140)

0.6 (5)

22

1.38

Fibrc 8

128 ( 1000)

(22)

l AS

Kcv lar 29

Rcgular

153

11.2

2. 1

70 (550)

2.9 (23)

I A4

Kcvlar 49

Hi gh modulus

156

10.5

1.3

135 (950)

2.9 (23)

2.8

lAS

Kcvlar 100

Colourcd

156

10.9

2.3

60(475)

(23)

3.9

IA4

Kcv lar 11 9

Hi gh durability

156

12. 1

2.7

55 (430)

3. 1 (24)

4A

I A4

Kcvla r 129

High strcngth

156

99 (780)

3A (26.5)

3.3

l AS

Kevlar 149

Ultra hi gh modu lus

156

143( 1100)

2.3 (IS)

1.5

I A7

120

3.5

2.8
3.3

6.2

Kcvlar 98 1

0.6

Twaron

Regular

156

79 (622 )

Twaron HM

High mod ulus

156

123(960)

(22 .1 )

Tcchnora

Rcgular

91

70 (570)

3.3 (27)

4.3

1.39

3.7

1.32

Trcvar V 106
X-SOD

10.2

77(657)
( 18.5)

2A

1.47

Ekonol

136 (1100)

3.S (3 1)

2.6

IA

Vcctran

91 (700)

3.2 (25)

Armos

140-145

4.5

Modu las (G pa)=gpd x dcnsity I 11 .33

28 .5-29

IA4

106(820)

98

LOI
%

25

IA7
3

IA3

37 -43

INDI AN J. FIBRE TEXT. RES ., SEPTEMBeR 2002

298

around 500 nm long with adjacent co mponents of

pleat being at appro ximately equal but oppos ite angles
of 170 o .
Thc fibrillar col umns, which arc aggrcgatcs of
clongated, ori cnted Iiqu id crystalIin c domai ns, li e
along th c axial plea ts (Fig. 7). The surface
.
' -f
microst
ru cture 0 bserve db y atomiC
rce '
microscopy'30
rcvcals th at many plea ts are parallel to fibre axis
dircction . The polymcr cha in oricntat ion ang le
obtaincd from azimuthal x- ray diffracti on is about 1220 0 for Kev lar 29 and < 12 for Kev lar 49.Thc
experimcntal limits of proced ure do not pcr mit
diffcrent iat ion of Kevlar J 49 evcn th ough very high
modul us indicates further improvement in oricntat ion .
Ke vlar also exhibits skin -co rc di ITcrcntiati on JI -3J .
Morgan el a/.J! statcd , in th cir chain cnd modcl of a
stru ctural defect, th at thc skin cxhibits a marc
co ntinuous stru ctural integ rity in fibrc dircction than
th e corc, and th e thi ck ncss of th c skin is less than
Ifll1l . Li el a/.J-1 also reportcd th c cxplicit skin-corc
structure from SEM (scan nin g clectron mi croscopy)
and TEM (t ransm issio n clcctron mi croscopy)
obsc rvation s.
At th e surface, the po lymcr ehains tcnd to be
arranged less pcrfect ly and th c surface crystall ine
structures can bc influenccd by seve ral parametcrs
such as fibre manufac turin g cond iti ons, posttreatmcnt and absorbed water. PPD-T is hi ghl y
crys tallin c; crystallinity varies from 6H % to 85 % for

b = 515

Kcv lar 29 and from 76% to 95 % for Kev lar 49 . The

cx tendcd polymcr chain s in th e fibre-ax is direction
leads to stitT, ri g id mol ecu les th at con tribut e high
longitudinal modulus of elastic it y. The arom atic ring
as well as th e co njugation of elec tron s give th e
material hi gh thermal stabi li ty, chemica l sta bility and
mce hani ca l st iffness. The hydroge n bonds in the
transverse direc ti on and rhe covale nt bonds in th e
fibre axis direct ion lead to a grea t mechanical
prope rt y anisotropy.
The Technora (HM-50) fibre also sho\\s a high
deg ree of ori cntation and some th ree-dimcnsional
order, whi ch is not as extcnsive as that obscrved in
PPD-T.
3.2 Fihre Properti es

Aramid fibres arc characterized by medium to ultrahi gh strength, medium to low elongation and
moderately hi gh to ultra -high modulus with the
dcnsi ti es for crystalline fibres rangi ng from 1. 35 g/cnr'
to 1.45 g/c m.1 . Fibres of low ori~nt;tion MPD-t (e.g.
Nomex ) ~havc a dcnsi ty of 1.35 g/cm '. Fibres for~l
PPD-T (c.g. Kcvlar) have a dcnsity of - I AS g/cnr'.
Ileat-resistant and fl ame-resistant aramid fibres
co ntain a hi gh proporti on or mcta-oriented phen ylene
rin gs, whereas ultra-h igh strength hi gh- Illodulus
fibres con tain main ly para-oriented phenylcne rings.
The meta-o ri ent ed pol yme rs are cons idcred to be
chain-foldin g polymcrs. But small ang lc x-ray
Fi bri(

Ordered
l amella

=~
~':::::

c=128A
(Fib re axis)

:::::::/... -

-,

-'

41----

o-f}-N

a =785

/
./

zone

--,

Ode ct

II>

Tie
point

d
1\.1
t...

.D

LL

---~,-

-;
, -- -

-3
--~

(a)

R600nm

(b )
rc

I-ig. 7-{a) Radiall y arranged plca led

PPD-T ribre

~hec l ~ lrul'lLire

in KC I' Iar -19 ribres (b) Til t: L1nil cell or PPTA

cry~lal

)
(c) Fihrilla r Illorphology or

JA SSAL& GHOSH: ARAM ID FIBRES

diffraction studi es of the rod-l ike para-oriented

polymers show no ev idence of chain folding.
3.2.1 Chemical Properties

The hyd rophili city of amide linkage leads to moisture abso rpt ion by all aram ids. In add ition to the
chemi cal composition , the fibre stru cture also plays a
criti cal ro le in determini ng the moisture abso rption .
Different Kevlar products absorb moisture to different
extent. The diffusion coefficient of skin follows : Kevlar 149> reou
lar Kev lar > Kev lar 49 and th e diffusion
b
coefficient of core follo ws: reg ular Kev lar > Kev lar 49
> Kevlar 149 trend') for penetra nt conce ntration of less
than 0.02 g/cm 3 . Moisture uptake of regular Kev lar is
sim ilar to th at of Kev lar 49 but Kev lar 149 uptak es
moisture very less co nlpared to other two. At 20C and
55 % RH , Kev lar 29 absorbs - 7% whereas Kev lar 149
absorbs - I %. Water mo lec ul es are considered to be
abso rbed by the amide gro ups at th e chain ends, intrafibrillar latti ce deficits, and inner surfaces of th e microvoids to fo rm small wa ter clusters at low va por
press ure 35 .
PPD-T fibres show very good chem ical resistance
to th e attack of organ ic solve nts and aqueous salt
soluti ons. Howeve r, strong ac ids and bases do attack
th e fibre at elevated temperatures, causing hydrol ysis
of am ide lin kage and loss of strength. These fibre s are
more res istant to acids than Nylo n 6, 6 fibres, but not
as resi stant as polyes ter fibres, except at eleva ted
te mperature. Res istance to stron g bases is co mparabl e
to that of Nylon 6, 6 fibres.
Aramid fibres are exceedin gly difficult to dye by
the co nve nti onal meth ods du e to th eir ve ry hi gh 7~.
. ic
. d yes'16" 17 and
But using th e reco mmencIe(I cation
pyridi ne ,'or so lve nt dy eing, deep shades and exce ll ent
light fastn ess have been reported for Nomex and
pol yisophthal amid es of both 4, 4' -di am innod iphenylmethan e and 2, 2-bi s(4-a mino phen yl) propane.
The aromatic nat ure of p-aramid is responsibl e for
a substanti al absorpti on of UV li ght, whi ch, in turn ,
leads to a ch ange of colour du e to ox idative reac ti ons
as wel l as drop in fibre properti es.

!OOC, a seco nd order tranSItion at 360C, foll owcd

by melting and chemical decompos iti on at 500575C. Glass tran sition temperature (7~ ) ranges from
250C to > 400C. Some aramid fibres such as
Nomex shrink away from a hi gh heat so urce or from a
flam e. Aramid fibres characteristically burn onl y with
diffi culty beca use of hi gh LOI va lues. Burning
produces a thi ck char th at acts as a th ermal barri er.
The bond di ssoc iati on energ ies of C-C and C-N
bonds in the main chain arc signifi ca ntl y hi gher in
aroma ti c com pound s than those in aliphatic oncs,
whi ch ooive hi 0oher th erm al stability to aromati c materi als (Fig.8 & Fig.9). So, p-phenylene terep hth alamide
is stab le up to 550C. Excellent thennosta bili ty of
poly (p -p henyl ene benzobi sthiazo le) is du e to its
full y aromati c charac ter and hi ghl y ri gid molecu le.
Introd uction of flex ible groups such as -0- into main
chain (as in Techn ora) leads to more nex ible chains
and lower therma l stability.
24
_ 20
"D
0..

-'" 16

Dl?nsities
Ny lon
Polyester
Kevla r
Glass
Wire

100

200

300

400

Mod ulus

500

600

700

( gp d )

Fi g. !i- Te ns ile: stre ng lh - m ()dlll ~: :, relations i"o r hi gh pe ri"ormance

ri bres

2 .5
-0

0.
U>

2.0

..c

'"

Aramid fibres do not melt in th e co nventi onal se nse

beca use deco mpos iti on occ urs simultaneo usly.
Pyrolys is of poly (p-p hcnyl ene terephthalamide) fibre
leads to products such as p-phenylened iamine, aniline
and be nzo nitril e, indi catin g a homolyt ic cleavage of
amide bond. The differential sca nnin g ca lorimetry
st udi es of PPD-T revea ls moisture evo luti on of about

1.1_
1.38
1.45
2.5 5
7. 9

4 L-__~__~~~~__~~~~~~__~

3.2.2 Thermal Properties

299

1.5

"-

"-

V;
~

1.0

'iii
c

'"

>-

"-

Nylon 6
~

0.5

"-,

"-

"-

0
0

100

200

300

"-

"" "-

,
400

Temperature

Fig. 9 -Te ns il e stre ng th

1'.1"

"-

""

500

"",

600

70 0

( C)

te mpe rature of" po ly amid e and a ralllid

300

INDI AN J. FIBRE TEXT. RES . SEPTEMBER 2002

The C-N bond of Ihe amide gro up in poly (pphenylene terephthalamide) has a doubl e bond charac ter. The conjugation between th e amide gro ups and
the aromatic ring in p -a ramids is res ponsibl e for th e
ye ll ow colour and increased chain ri g idity, wh ich help
into excell ent retenti on of physi ca l properties at elevated temperature. At 300C, Kev lar retains about
50% of its strength of room temperature, whi le the
modulus remains at 70% of thi s levelJH . Excellent orientation of chain extended mol ecules in th ese hi gh
performance fibres resu lts in an an isotropy of thermal
expa nsion coefficient. Aramids have a slight negati ve
longitudinal coefficient of thermal expansion of about
(-2 to -4) x 1O-6/ K and a positive transverse expans ion
of 60 x 1O-6/ K. Its high crystallin ity resu lts in neg ligible sh rinkage both at hi gh temperature in air 0. 1%
at 17rC) and in hot water 0.1 % at I OOC). They
also have a low th ermal conductivity that varies by
about an order of magnitude in the longitudina l versus
transverse direction.

Co r bon
( HT)

25

.c

-::;, 15
c

QJ

.!::

VI

10

Polyester

c
~

1r
Etongo' lOn ('Yo)
Fig. IO- Mcchani cal propcrtics or Kc vlar cOlllpared to other in du strial fibn:s

30
'~ 20

3.2.3 Mechanical Properties

Typical stress-strain curve of Kevlar yarn as compared to other industrial filament yarns is shown in
Fig. 10. These curves show that Kev lar yarn has a
break tenaci ty of 22 gpd, whi ch is more than 5 times
that of steel wire and twi ce that of nylon, polyester or
glass fibre . Kevlar shows an unusuall y high initial
modulus of 475 gpd, which is twi ce that of steel wire
and fibreglass. As a spun fibre, Kevlar 29 has a
modulus of 62 GPa. Heat treatment under ten:; ion increases crystalline orientation. The resulting Kevlar 29
fibre has a modulus of 131 GPa. The outstanding high
strength of Kevl ar can be summarized as follows:
- Due to its aromatic and amid e group.
When the Kevlar is spun into fibres, the
polymers have a crystalline arrangement, with the
polymer chains oriented parallel to th e fibre axis. This
high crystallinity contributes significantly to its
unique strength and rigidity.
- Indiv idual polymer strands of Kev lar are held
together by H-bonds that form between the polar
amide groups on adjacent chain .
- The aromatic components of Kevlar polymers
have a radial (spoke-like) orientation, which gives a
high degree of symmetry and regularity to the internal
structure of the fibres. This is confirmed by the bright
synchro ton radiation
(Xi\NES
image).
This
crysta lline- like regularity is the largest contributing
JX
factor in the strength of Kevlar. Al len and Roche
have introduced the concept of asymptotic modulus as

Ny !o n

' Vi

Corbon
p- . \,."",id

-3

-2

-1

( 'Yo )
p - I\ra",id

-10
Cor bon

-20
Fig. II - Tcils ik

cOll1prcs~; ivc

properti es 0 1' ;1I'<Illlids

a measure of ori entatio n and related it to th e pleatcd

morphology of the fibre.
Kevlar fibres retain useful strenglh and modulu s at
elevated tempera tures as hi gh as 300C. These fibres
extrapolate to zero strength at about 6-Hl )C compared
to 250C for nylon. It does not undergo an y
embrittlement/degraclation at tempera! urc as low a!-.
196C. Kevlar behaves elast ically in tens ion. When
subjected to ax ial compression or severe bcndin g. it
shows non-li near plastic deformation. f ig . I I shows
that the fib re exhib its a yie ld point at a compressive
strain of 0.3-0.5 %. This corresponds to formation 01"
1l
st ructural defects known as Kink bands (a t -J.5-60 to
the fibre ax is). These bands are related to comp ress ive
huckling of th e aramid molecules b) molecular
rotation of the an,ide carbon - nitrogc n bo nd. whi ch,

JASSA L & GHOS H: A RAM ID FIBRES

in turn, refl ec ts weak latera l properties of these hi gh ly

anisotroic materials39 . Th is occ urs by a transiti on from
the norm al extended trans co nfigura ti on to a kinked
cis-co nfiguration. This resu lts in a bend in the chain,
whic h propagates across the unit cell and th e
microfibri ls and finall y results a ki nk band ac ross the
fibre. Therefore, the systems for structura l app lication
should be carefully designed to avoid compressive
failure. On the other hand , ductile response rath er
than britt le response can be an advantage in end uses
where non-brittle ductile respon se for damage
tolerance is importan t, as in advanccd co mposites. In
spite of the significant morpho log ical changes, th e
fibre loses 40 only 10% of its tensil e strength cven after
experiencing a co mpression st rain of 3%.
Fatigue bchaviour of aramid is also dcpendcnt on
the mode of fibrc deformation (tension I'S.
compression). With tensionllcns ion fatigue, no failure
is observed even at loads as high as 60% of brcaking
7
strength and 10 cyc les. Tcnsilc failure initiatcs at thc
fibril ends and propagates via shea r failure betwcen
the fibrils. Skin-core gradient in the fibre causes nonuniform load sharin g and hcncc redu ces st rengt h.
Howeve r, the compressive fatigue of organic hi ghperformancc fibres is significan tl y worsc. The
retention of ten si le strcngth dccrcases with increascd
comprcssive strain. At 0.5 % strain, no st rcn gth loss is
observcd even after 106 cyclcs, whilc at 1% strain ,
loss is observed withi n 10" cyclcs.
Poly (p-p hen ylenc tcrephthalamide) fibrc exhibits
very low crcep even at clcvatcd tempcrature. At 50%
of brcaking load aftcr 107 s, thc crcep strain for
Kevlar is only 0.3 %. Thc longcr lifetime
characteri stics of high melting polymer arc mainl y
attributed to hi gh activation energy of primary bond
breaking. Ke vlar creeps undcr high st resses. Crcep
rate is almost uniform and the a:ll0unt of cree p strain
increases lincarly with log (tilllc) to break.
Tcnacity of p-aramid fibrcs dcpcnds on the
moisturc contcnt a!ld is influenccd by the following
two factors:
- Inter-molccula r intcractions which incrcasc by
hydrogcn bonds creatcd by watcr moleculcs, and
- ! \ plast ifi cation cffcct.
These incrcase tcnacity to some extcn t whcn th c
moisturc contcnt is incrcascd, but with furthcr
Incrcase In moi sture content th e tenacity will
dccrcasc.
... Applications
The initial moti\'ation for developmcnt of high-

30 1

pcrformance fibres ca me from the aerospace industry

seeki ng fibrcs fo r use in high- mol ccu lar weight,
strong compos ite structural pa rts. But at prescnt, the
broad spectrum of ara mid fibre applicatio ns ca n be
div idcd into fo ll ow ing two categori es:
T he use of aram id fab rics in appa rcl- related
ap pli cation , such as fire protective clothin g and
bull ct proof vests .
Rei nforcem ent applicat ion such as tyrc cord or
automotivc components such as gaskets and
clu tch linings and advanced plasti c composites
used in aircraft and aerospace equipment s,
mi litary vchic les, sports goods and man y others.
Aramid fibrcs have renewed intercst in reccnt years
partly bccausc of their use in thc co nstru ction of
advanced compositc material s.
Thc meta-aramid (Nomex ) has excellent th ermal
rcs istance, good tc xtilc propcrties but rath cr poor
mechanical propcrtics for high- performance fibre. Its
applications include protcctive clothing, hot gas
filtcrs, indu strial coated fabrics, felt sc rims and
rcinforccmcnt of rubberi zcd bclts and hoscs . Its
inhcrcnt di clec tric strength, mechanical toughn ess and
thermal stability provide high usabi lity and reliability.
The para-aramid (KevlarHI ) providcs uniqu c
combinations of tou ghness , cxtra high tenacit y and
modulus and excep tional thermal stabi lit y. Thcrforc.
the end uscs of para-aramid covcr a broad ran gc of
industrial ,
aerospace,
military
and
civili an
applicat ions, which incl ud c cut-, heat- and
bullctlfragment- resi stant (ballistic) appare l, hard
armors, brake and transmission friction parts.
reinforced tyres and rubber goods, ropes and cables.
various forms of composites, filamen t wound pressure
vesse ls,
industrial
glovcs,
circ uit
board
rcinforcements, ctc. Kevlar 49 HS (Hi gh Strength ),
prcparcd by DuPont 's New Fibrc Technology in
1997, is specifically intended for filament winding
applications and has a tcnsile st rength 25 % hi ghcr
than that of thc standard Kev lar 49, giving it a
combination of hi gh st rcngt h, lo w weight and good
impact resistancc. This will allow filament wound
com pos it c cylinders to be used for hi gher press ure
duties , such as oxygen and industrial gas bottles , fu el
tank , rocket motor cas ings, clectri cal swi tch gear
dcvices and o lT-s hore flcxible pipcs. Othcr
copolymcrs co nt ain in g combination of mcta- and
para- substitutcd monomcrs ha ve been devclopcd for
optimum propcrties. Whil e each application has it -;
spccil"ic
rcquircments,
allllost
ail
or thcm
characteristica ll y utili zc high strcngt h, hi gh modulu -; .

302

INDI AN J. fOl BRE TEXT. RES. , SE PTEMB ER 2002

high tou ghness, th erm al and dimensional stability,

low cree p, and li ght we ight of th ese fibres.
tt Co mposi tes with Soft Materials

This was one of th e earl iest app li ca ti ons of para mids. The first use o r th ese materials was in tyres
due to their hi gh modulus, hi gh fat igue resistance and
good ad hesio n to rubber. Thc compos ites were
des igned to provide good adhes ion betw een the
rein fo rcing fibre and mat rix co upl ed with axial
compressive strai n below - 0.8 % for durability and
life of tyres. Kev lar has been used in tyres for more
than 20 years; an ea rl y application was in
circ umferential belts for th e first radial tyres used in
fo rmul a one racing. It has also been used in the
carcass of motor cyc les and as a li ght we ight bead
co re material replacing steel41 . Automo ti ve prod ucts
(belt and hose) and co nveyor belts also require rubber
reinforce men t. In th ese appli cat ions, fJ-aramids not
onl y ofTel' better fatigue res istan ce but also lead to
better wear properties and belt life.
The forces on fibrcs in a radial tyre ha ve bee n
mathematically modell ed by both DuPont and tyre
Illanufacturers. These stud ies show that th e fibres near
the edge of th e normal cut belt can undergo severe
co mpress ive cycling durin g cornering. Experiments
ha ve confirmed that th e major mech ani sm of strength
loss for aram id fibre in th e belt of a tyre wi ll be
co mpressive fatigue unl ess spec ial care is taken in th e
design. Fi g. II sho ws th e effec t of repeated
compress ional loading on tensile strength of Kevlar.
Hcre, the single fil aments were subj ected to repeated
compress ive strains of 1%, 0.8 % and 0.5 % and the
residual stren gth was meas ured after different
numbers of cyc les. No strength loss was see n after
several hundred thou sand cycl es at 0.5 % st rain , but at
hi gher strain levels, th e strength losses began to
appear at some thres hold poi nt and increased
th ereafter with continu ed cycling .Therfore, it was
necessary to design a reinforcement system to keep
compressive strains under 0.5 % in order to obtain th e
fatigue perrormance required in tyre and to compete
with steel wire cords42 .
Two approaches to acceptabl e fatigue performan ce
were taken. The first was to optimize th e cord
structure design used in the belt. Tyre cords are
normally made by twistin g individual yarns and
combining these yarns by furth er twi stin g into a cord.
Compressive fatigue res istance is proportional to twi st
level. Cord tensil e strength and modulus decrease
with increased twi st. Therefore, the cord was designed

with a twist level se lec ted to achieve th e best balancc

of tens il e properti es and fatigue resistan ce. Another
approac h was to redcsig n th e belt to place more cord
at th e criti ca l be lt edge region, th ereby reduc ing
compress ive stresses on the indi vidua l filaments. Th is
was done by fo lding th e bottom belt around the edge
of top belt, whi ch provides 50% more fibre in the
criti ca l region than in th e norm al cut bel t.
The benefits from these des ign cha nges are such
that, at a given twist level, th e fo lded belt is superi or
to th e normal cut belt and is propo rti onal to twi st
leve l. These tes ts also show th at satisfactory
pe rform ance ca n be ob tained at a one-to-five
replacemen t ratio ve rsus steel corel.
4.2 Advanced Composites

Along with th e hi gh spec ific strength and stiffness,

th e weight reduc ti on and impact damage tolerance are
important factors in produci ng co nven ti onal ai rcraft
stru ctural co mpone nt. Aramid- reinforced composites
ca n abso rb 2-4 times as mu ch energy as carbon fibre
materi.a 141 . 41. . In tIle app I"Icatl on 0 I' wouncI press ure
vessel , fJ- arumids are mai n Iy used. The performance
meas urement in thi s application involves burst
press ure times vo lume of th e vesse l normali zed for its
weig ht (PY/W) and the fibre is exposed to stresses
both parallel and normal to fibre axes, Aralllid based
products show 25-30% better perf rill ance than glass
or carbon fibre,12.44. The fibre stru ct ure of jJ-aralllids
respon sible for low co mpress ive stren gth provides an
inheren t ad va ntage over carbon fibre in damage
tol eran ce and crash worthiness . Thi s is related to its
ductile compress ive failure mode. Th e du ctility of jJaramid is show n by th e fl ex ural stress-s train
behaviour ror unidirec ti onal epoxy mat ri x co mposites
and aluminium (Fig . 12). The response to strain for
Kevla r resembles that of alumini ull1 beca use in
bendin g, one side of th e compos ite is in com pressio n
and yi elding co ntributes to th e meta l -like behaviour.
But th e rigid copl ana r rin g stru cture of carbon fibre
does not permit yielding and leads to brittl e response.
By combining Kevlar and carbon into a hybrid , better
properties like, hi gh energy absorp ti on and good
stru ctural integri ty after crushin g can be obtain ed.
Thus, the fibre st ructure responsible for low
cOlllpressi ve stren gth of Kev lar can be used to ge t
advantage in hybrid composite sys tems. Hyb rid
composites of Kevlar and ca rbon are bein g used in
commercial aircraft (e.g. Boeing 767) and helicopters
(S ikorsky ). ]n small bu siness aircraft, an earl y
advance into ex tensive use of co mposites in primary

JASSAL & GHOS H: ARAM ID FIBRES

Temperalur. 25 'C
15 wi

r.

Kovlar pulp

Equal cos l basis

1.5 Kevlar pulp d. g"l. furrt>d silica

303

co mpression of horizontal or inclined planar structure.

This t ec hnique~:1 enables homogeneo us or contrasting
materials such as bricks, concrete and co mposite
panels to be held together tightly in modul es reta incd
by prestressing cab les, It may have ideal tse tn
earthquake prone areas.
-tA Protective Apparel

E poxy
10'1---:-"'-------,---....:::::,,~---=

10-2

100

10'1

10'

Shear rote/s,1
Gravitational
sag

10 2

103

I I

Agitaled tank

105

SPr~yin9

Brushing

Cenlrifugal pump

Fig. 12- Visc osi t)'

I'S

, hcar rate

ror epoxy

Illatrix cOIllPositc

structure is also occurring. The new aircral'ts are being

designed to take full advantage of composite
properties and the ability to fabricate complex shapes
with minimal need for riv ets and fasteners to reduce
w:::ight and manufacturing costs. Foamed concrete
reinforced with aramid fibre can be made as an
effective soil sca lant. Aramid is used in top laye r of
concrete to preve nt .It t' rom crac k'Illg between beams ~~ .
,t3 Ropes and Cables

High speci fic strength and spec i fic modul us, lack
of creep and ou tstanding dimensional stability allow
aramid fibres for rope and cordage stronger and
li ghter than steel or other materials. Non-rusting
mooring lines can be prepared from Kevlar 29, which
is used in oil rigs to probe large depths because in air
the specific strength of Kevlar is 7 times of steel , but
in sca water it is more than 20 times of steel. Risertensioner line:- . are used on floating offshore oil
drilling platforms, The purpose of the ri se r-tensioner
line is to keep the riser pipe or outer drill casing at a
constant elevation and under uniform tension while
the vessel surges with the waves. Experimental
studies had show n that th e small diametei' ropes of
Kevlar made in low- twist stranded wire rope
stn 'cture ean far surpass steel ropes in cycl ing
performance ovcr pulleys as the platform moves with
wave~;.

Electro-mechanical cables and fibre optics

reinforced with Kevlar have been introduced
successfully into tel eco mmunication systems. In civil
engineering constructicns, namely bridges and roofs,
Kevlar is used in cab les to maintain permanent

Fab ri cs made up of Nomex , are used in protect i\,c

clothi ngs of firemen, for gas and electric utilit y
operati ves, for worker of petroleum fuel , etc. They
can also be used in transports, in seats and mattresses
in public and private sectors and heat-exposed
workp laces to protect people and products against fire
risks . Fi reproof doors in hotels and theatres can be
made from them. Near Scotland, three offshore
platforms in th e North Sea were equipped with
Twaron- reinforced expansion panels for protecti on
against explosion damage~~. The blends of Nomex
and Kevlar ensure insulating protection of the
material due to the very low shrinkage of Kev lar in
flames.
The extraordinary mechanical properties of Kevl ar
result in excellent cut and puncture resistance. These
properties combined with thermal characteristics ale
responsible for universal applicability of this material
in protective gloves (from surgical to industrial uses in
metal industry, glass industry and meat processing
plantsrl~. -15, A recent development of DuPont is Kedar
indust rial glove having olephobic moisture- repell ent
fini :,h that keeps hand dry and clean throughout the
working lire of glove. Gloves made of 100% Ke ylar
are twice as cut resistant as nylon gloves an(; rour times
safer than leather~5. In air bag preparation methods,
airframe protector is made, which is a unique
segmented air bag with a Kevlar shell to disperse
impact loads to the sensitive spinal areas.
-t.S Ballistics

Ballistic protection is a class of protective clothing

which protects an individual from bullets, steel
fragments from hand held weapons and exploding
munitions~(l. ~7 . It shou ld stop th" bullet from
penetrating and abso rb its kinetic energy by the work
of deformation. Kevlar has Ion. been used for thi s
purpose due to its good dynamic energy absorption
characteristics, high specific strength and modulus,
and excellent thermal properties , High 7~ and thermal
stabi lit y ensure integrity of the ballistic structure at
relatively hi gh tempe rature in the event of impact.
When a fibre is struck tran sverse ly by the hi gh-speed

304

INDIAN J. FIBR E TEXT. RES .. SE PTEMBER 2002

projectil e, a longitudinal stress wavefront propagates

ou tward at th e speed of so und in th e fibre. Thi s speed
is equal to the sq uare root of th e spec ifi c modulu s.
Kcv lar's hi gh crystalline and ori ent ed stru ct ure gives
ri se to high dynamic modulus wh ich enhan ces the rat e
of wave propagation to 7700 mis, whic h is 3-4 tim es
' wave spee d
Illg IleI' tIlan tIlat I'lor ny 1on .17 . ~x . Jt .IS tIliS
that determines th e amount of material that ca n
beco me involved in th e impact eve nt. T hu s paraaramid can invo lve 3-4 times th e vo lume of material
in interaction th an nylon , res ultin g in a higher total
energy absorbing capacity and energy of impact
dissipating capac ity"0. Today , thi s protection is widely
used by both civilian and military organi zation s
aro und th e world. Helmets and body armour used by
policeman or law enforcement office rs should tak e
care for bullet impact, assault \'l ith blunt instrument,
fall from motorcycle and hi gh speed crash during a
chase, whereas that used by the military personals or
persons of bomb squad should be co ncern ed of th e
protection from fra gmenting muniti ons .
Soft armour is co nstructed from multipl e layers of
woven fabric without a res in binder, sewn togeth er
with meander or cross-wi se sea m. The layers are sew n
together with hi gh tenacity aramid sew ing threads,
whereas th e hard armor or composite laminate armor
co nsists of multilayered fabrics combined togeth er
with a resin binder. Some of th e ap pli ca ti ons in the
form of hard composites include military helmets,
spall liners and other fra gment protection uses on
vehicles and ships. A light weight armor was made
50
out of Dyneema SK 60 or Spectra with Aramid
which has multilayers of aramid positioned in front of
. I t can a Iso be use d as so f't boy
d armour')0 . 5 I
matrIx.
Anti- ballistic panel can be prepared which consists
of a laminated structure made of a core layer of
foa med plastic material and the shield layer of aramid
to protect a projecti Ie passing through by absorbing
the impact of projectile5~ .
4.6 Short Fibre Application

By replacin g asbestos, the aramid short fibres

and pulp are finding g rowing applications with a
large ran ge of poss ibiliti es. Major applications
include friction products (brakes & clutches),
gaskets and thixotropes, and additives that improve
wear resi stance of thermoplastic composites. Kevlar
pulp is a fibre product in the form of highly
fibrillated particles with the average length of 0.8-5
mm. Different types of pulp differ in fibre len gt h,
particle size distribution and extent of fibrillation .

The end use app li cation determin es which of th e

short fibre fo rm s is to be used. In brak e pads and
linin g it is used by mouldin g a dry or wet mixture
of pulp, filler and res in'))'')') .As gas ket paper, it is
used by drainin g an aqu eo us suspension of pul p,
fillers and latex on a paper mach ine, and in
comp ressed gas kets by ca lend erill g a mi xture of
pulp , fill ers and so luti on of rubber in tolu ene. 56 Due
to its fibrillar stru cture, th e aramid pulp creates a
good mechani ca l bo nd with th e surroundin g matri x,
hence transferri ng its hi gh streng th and hi g h
modulu s of e lasti city to the matri x.
Introduct ion of Kevlar pulp into fr icti on products
in place of asbestos requires :'eforrnati on of mixes. In
co ntrast to 50-60% of asbestos, less than J 0% of
Kevlar is added to th e mix (Tabl e 4). In general ,
friction products co ntaining p -a ramid pulp show
stable frictional characteri stic, hi gh hea t stabi Iity,
reduced wear and 3-5 times longe r life.Th erefore, in
avionics sys tem it is used in wing leading and trailing
edges, radomes, con trol surface edges, etc.
In gaskets, Kevlar pulp is also a sub stitute for
asbestos. The use of poly (4- meth yl-l, 3-phenylene
terephthalamide)
for
manufacture
of
selfex tin gui shin g sheets for gaskets, elec trica l or th erm al
insulator had been studi ed by scienti sts from Mitsui
Toatso Chemical s Inc. 57 . They prepared a pulp
co ntainin g poly (4-methyl-l, 3-phenylene terephthalamide) and th en processed the pulp at 250C under
pressure of 100 kg/cm 2 to give a thermal shrinkageres istant sheet with self-extinguishing properties. The
sheet had tensil e strength of 10 kg/cm 2 . They
compared that pulp with poly (II/-phenylene
Table 4--Exa mpl es or mi xes with Ke\'lnr pulp
Material

Compos ition
%

Fri cti on produci mi x

Dol omite riller 200 mesh)
BaSO.j
Cashew rriction particles"
NC 126 resin"
Kevlar pulp

50
15
15
15

Gaskct material
Elastomcr binder

10- 18

Curing arcn t, ant iox idant . etc.

Kevl ar pulp

10

Structured silica

10

Talc
" 3M trademark cardo lilc

61 -69

JA SSAL& GHOSH : ARA MID FIBRES

isophth alamide); th e latter showed a hi gh shrinkage

co mpared
to
poly
(4- methyl-l , 3-phenylenc
terep hthal am ide). For friction products, less than 10%
Kev lar is used in stead of 85% asbcstos in typical
mixes. As shown in Tabl e 4. both new mixing
conditi ons and new fi ll er had bccn idcnt ifi cd for this
development. Such compositcs yie ld gaskets with
hi gh tensi le st rength , creep rcsistance, co mp ressib ility
and recovery equ al to or better than th ose of asbestos.
1n many applications. th e lower chl oride co ntent
co mparcd with th at of asbestos is an important
advantage. DuPont and Frenzelit54 prepa red a matcrial
for automotivc gasket. whi ch olTers sign ificant cost
an d ratio performancc be ncfits over co nve nti onal
multil ayer steel gaskets. The compa ni es ha ve
combined th e strength and durability of graphitc and
Kevlar fibre fo r developmcnt of soft, crecp- and
temperature- res istant 'fibre- rcinforced gaskcts'.
The primary rcquircment in scalants and adhesion
industry is for pseudo- plastic material. Kev lar pulp (at
only 1.5% concentration) in cpoxy resin leads to a viscosity of 4 x 106 cP (at 1O,2/ s ), whil e fumcd sili ca (the
traditi onal material used in this application) requires
4.9% addition to increase th e viscosit y to 0.3 x 1(/'
cP(at 1O'2/s). At hi gh shear rate ( 103/s), th e viscosity of
both th e formulation s decreases to 1.4 x 104 cP and 2.5
x 104 cP respectively. A co mpl ete match of performance between the two materials can bc attai ned by decrcasing the pulp content to 0.3 % with cost advan tage.
Anoth er ncw appl ica ti on is th e use of Ke vlar pulp
to mak e a wet laid nonwove n fabri c in elcc troni c
circuit boards55 . Thi s ceramic hyb rid circuit boa rd ca n
be used in co mputer, and avionics beca use Kev lar
makes the boa rd lighter and thinn er. It also prov ides
for higher density circui try for more co mpon ents on
board in less space because of its short run eco nomi cs
and reliabilit y.
~ .7

Pcrmsclcctivc Usc

Aramids are applied 111 ho ll ow-fi bre pcrmcation

sepa rati on membranes to puri fy sea water and
brackish water. DuPont 's II l-a ramid fib re ' Nomex
Delta Mi cro 43' can be applied in hot gas filtration
app licati on in th e 1'01'111 of nonwoven .
4.8 Electdcal Application

Aramids have hi gh volume res lst lvIlI CS and hi gh

dielectri c strength s, which are retained at elevated
temperature.Therfore, they ha ve pote nt ial to be used
as hi gh temperature dielect ri cs, particularly in motors
and transformers. Nome x paper, whi ch is made of

305

Nomcx fibres interlocked with No mex fibrids i.e .

shear-precipitated polymer, has twice th e diel ectric
st rength of hi gh qual ity rag paper5X. 59. omex papers
are used as \I/ ire wrap, slot and phasc insulation on
motor gencrators and transform ers. They are stable
over wide moisture range, self-ex tin gui shing, and
co mp atible wi th varnishes and resin s.
Nomex is used in insulation in instrument panel
transfo rms duc to its good heat resistance and
excellent diclectric property. DuPont has a prod uct,
named ARACON TM , a metai clad aramid fibre .
which is a conductive fibrc for EM I shi elding and
sig nal wire; here, Kev lar's microwave res istance.
li ghtweight and high strength propcrties are utili zed.
4.9 Communication

Fibrc optics market and telecommunication are the

fast grow ing rece nt markets of aramids. Kevlar and
Twaron are used for reinforccment of delicate glass
fi brc system. Optical fi bre cables are designcd to
maintain the integrity of data tran sm is. ion through the
opti cal fibre in th e cab le. Mcchanical reinforcemcnt.
given to cablc to protect it aga inst environmental and
mcchani cal attacks, is made by a pultruded rod or
Twaron with epoxy res in as a co ntrol element and a
. hera irem
' f'orccment .JI1 thconn
I'
S6 60. 6 ' .
penp
0 f' fiI Iaments"
It competes mainl y with E-glass in this ap pli cation.
~.IO

Other Uses

Aramid fibrcs are also bcing used recent ly as

reinforcin g fibrcs in composites for leisure industry as
sa il ing boat hull s and tenni s rackets, for transport
indust ry as airfreight co ntainers to save weight, as
radom (radar-transparent part ), ai rdu cti ng and fai ri ne.
in aircraft industry , anel as moisture wicking fibre 6c .

5 Conclusions
Thc preparati on and utili zation of aramid fibres are
the iJl1porta nt steps in the field of fibres for highperformance tcch ni cal tex ti les and composites for
aircra ft, aerospace, marine, automob ile and othe r
industri es. Kevlar fi bres lack in fatig ue strength and
have poor compressio n strength , but its hi gh tensJ!
stren gth , high [ensil e modulu s, low brea 'age
elon gati on and resis tance to chemi cals mak e it
suitab le for strong compos ite stru ctura l parts 1'01' man y
high-performan ce appli cations. Meta-aramid fibre.'
have excellent th ermal resistance properties. Aram lJ
fibre s can also be tailor-made to use for asbesto, replacemcnt In gaskets (Kevlar pu p), permselecti \t:
appli catio n (holiow fibre), reinforce men t of glas
fibres for fibre opti cs and telecommun icati on, etc.

INI)I \ '\

306

I '

'i \

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J 5 Bcvillgton. ( 1\::r)a Il1l110n Prcss. New 1'01'''). 11) ~{l) . :', ,'7,<,
l3air T /. M orgall I' W & Killain I: L, MII('/'IJIIIO /(,[, lIit'l.
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