Indian Journal of" Fibre & Tex til e Rese arch

Vo l. 27 , September 2002 . pp. 266-273

Modification of cotton fabr ics via radiation graft copolymerization with

acryli c acid, acrylonitril e and their mixtures
,
Eglnl H K EI -Gend y"
National Ce ntre fo r Radiation Research :lIld Technolo gv , A tomic Energy A uthority . P. O. Bo x 29. Nasre Cit y. Cairo, [gYPl

Necei l'et/ 2<) U eCC'lII/;cr lOGO; fn'ised f('ceil'l'd alld (/cc('fl1ed 6 ./11111' 200 I

Radia ti on-i nduced grartin g or acry lic acid (A ,\,·j . dcry lonitri le (AN) and th eir mixtures ont o cotton rab ri cs has bee ll
~ tlldied at 2.56 Gy/<; gamma dose rate and lAO rab ri c- in-liqu or r'Hio. Th e grartin g process w as pe rrorill ed in th e pl'csc ncc or
aqucous AAc co ntaining 0.75 % (owm) M ohr's sal t, :llId 65: 15 Illctha nol -wat er m i x t~lrc ror AN. Thc elTcct or monomer
co nccntra ti on and irrad iation time (dosc) on thc dcgree of" grarti ng has also been in vcs ti g.Hcd. T he t'ejJendcncc or th e initial
gra ftin g rat e on monomer co ncentrati on rollows a sccond ord er kincti cs ror AN and a negat i ve rirst order onc f"o r AAc.
Grafts fro m monomcr mi xtures show difre rent kinctic behavi ou r. depend ing on AN/AAc rati os in so lutions with co nstant
monomers mi xtu re co nce nt rati on o r 20%. The degree or graftin g incrcases wit h the increase in AN/AAc ra tio rrom ~OIRO to
R012 0 ror all th e doses appli ed. Th e reac ti on order changes rrolll a pos iti ve order or 0.55 to a neg ative order or OA I as the
ra ti o o f AN / AAc decreases. T he swe lling properties or co tton rab ri cs improve w ith th e increase in degrec or graftin g or AAc
and deteri orat e with the incrcase in graft y ield or A N , Fabri cs graft ed w ith monomcr Plixtures show swe lling bch.l viou r
bctwee n those or AAc and A N . The elect ri cal co nduc tivity or grart s prepared fmm th e monomers or th cir Illix tures , hows a
fas t initial dec rease rollowed by a te ndency to leve l-o rl' as the graft y ield incrcases up to 35%, irrespect i ve or the ty pe or
monomer or thc mixture ratio. Th e dyea bi lity or ClJ tt on rabrics towa rd s Sandocryl Blue B-3G, a basic dye. i mpro ves
co nsiderabl y as the graft y iel d wit h AAc increases up to 20% w ith no rurth er apprec iab le chan ges ror hi gher degrees or
graft ing. Grans \V i th AN and AAc/AN Illi xt ures show lowe r dyei ng alTinit y than th at ror AAe grafts. Th e pi I or the dye bath
arfec ts co nsiderabl y the dyeab ility o f the grafted ra hri cs, giv ing an opt im um co ndition at pi I 3.0, Proposed sche mes for
graftin g and dye ing or co tton fabrics w ith Sandony l Blue B-3G are gi vc n,

Kcywords: Ac ry lic acid, Acrylo ni tril e, Cotton, Dyeing, Rad iation -induccd graJ'tin g

! Introduction repell cncy and rot rcs istance of co tt on are im proved

Co tt on is the most wide ly used text ile fibrc due to
' [S abundance, low cos t and wel l-know n phys ical and
:ncchan ica l pro p ert i e~;, It has inhercnt drawbacks such
~L ' poor so lu bilit y ill co mmon so l vcnts, poor creasc
'_slstancc, lack of thcrmal plas ti ci ty and poor
Ji mcnsional stabi I ity. Thesc drawbacks dirccted
attention towards improvin g the properti cs of
.;etl ulose th rough changing its physical and chcmi cal
,-,tructure. Radiatio n grafting is onc of th c pro mi si ng
"nethou in thi s field. Thc graft copolymcr formcd
l'l)(ltfies thc cel lul ose molecu les through crt.:ati on of
: ranc nes of sY:lIhetic poly mers that co nfer certain
,~ S lra Ie properti cs w ithout destroying its intrinsic
" rope rtics.
~ f'v e ral _'esearchers have found that graft
',oooi merizati on of cotto n with different vinyl
'l onomers tmproves thc strength, to u!!hness, lcx-
~ I ':'. 1--1
"~L raston reS tstance and t I1crmoo asttctty , ':-'hc
i'hllnc: 634232X; Fax: 002-02-27-102 0X:
t:- Illad: Eglal_Elgcnd) ((1, hotillai I.COIll
by graftin g the fabrics wit h acrylate monomers and
5x
po ly acry lonitril e - . It has been shown ea rli e r~ that th e
dyeabi I i ty of cotton fabric s towards D ri malan Reel, a
reac ti ve dye, increases with the increase in th e degree
o f grafting w ith dieth y laminoeth y l me thacrylate. It
has also becn found that swellin g o f the fabrics in a
proper so lvent before irrad iati on impro ved th e graft
lO
co polymeri zation process , Chapiro and Stann ett and
Hu ng and Rapson " havc reported that pre-swelling of
ce llul osc w ith dipo lar swelling agents, such as WaLer,
(ormami de and fo rmi c ac id, before radiation grafting
in monomer soluti ons con tainin g methanol, ethanol or
acctic acid tmprov cs thc grafting process
considerabl y . Non-wettin g solvents sho wed poor
grafting leve ls w hen grafting styrene, mcthyl
methacrylate, v in y l acetate and vin yl py rid ine onto
cel lul ose l~ .
his investigation was ca rried out to modify thc
p ysica l and dyeing propenies of co tton fabrics via
, ircct radiation graft ing of acrylollitrile (A N ), acrylic
d 'id (AAc) and thcir mixturcs on to colton fabrtcs. T hc
 EL-GENDY: MOD IFICAT IO OF COTTO
effects of monomer co ncentration , fabric- to- liquor
rati o and irradiation time (dose) on th e degree of
graft ing have been st udi ed to reach the optimu m
co nditi on that produces uni fo rm and homogeneo us
grafts all over the fabric.
2 Materials and Methods
2.1 Materials
Mi ll -scoured and bleac hed co tton fabric s, obtained
frolll EL- Beida Dyers Co., Karl' EL- Dawar, Egypt,
were treated with sodium carbo nate (Sg/L) and non-
ionic detergent (Sandozi n NIT liquid) at boil for 4h ,
thoro ughl y was hed with co ld water, dried at ambient
temperature and th en used for grafti ng.
Reagent-g rade acrylic acid and acrylon itrile
monomers, obtained from Aldrich (German y) and
BDH (England) respec ti ve ly, were used.
Ferrous ammoniu m su lphate (Mohr' salt),
methanol, aceti c ac id and Sand oz in NIT liqu id were
used.
Sandocryl Blue B-3G, a bas ic dye, suppli ed by
Sandoz, Switzerland , was used.
2.2 Methods
2.2.1 Radiati on Graftin g
Graft ing of th e fab ri cs was ca rri ed out by th e di rect
irradiati on method ina [,(ICo ga mm a so urce at a dose
rate of 2. S6 Gy/s . Samp les were immersed in th e
respective mo nomer-solvent so luti on, de-aera ted with
bubbling nitrogen for S min and left overni ght before
being placed in the gamma cell.
The grafted fab ri cs we re removed from the reac ti on
tube after irradiation to th e des ired dose. The
homopolymer was extracted from the grafted fabri c
with boil ing water in th e case of AAc and by using
dimethyl formamide in case of AN. The samples were
then dried to co nsta nt we ight. The deg ree of grafting
was determin ed as the percentage increase in we igh!
using the fol lowing relati ons hip :
Degree of grafting = 100 r(Wg - Wo)/Wo1
where Wo and Wg are th e weights of initia l and fin al
grafted samples respecti vely .
2.2.2 Uetcrm inalion of Water Uptakc
Grafted and ungrafted fabri cs with known weights
were immersed in distilled water at ambien t
temperat ure until equil ibriu lll was reached. Tht:
samples were the n removed and the excess wat 'r
deposited on the surface was quickl y removed wi "-
blotting paper and th en weighed The per cen waie;'
uptake was cal ulated ali folio"" s:
FABR ICS VI A RADIATIO GRAFT COPOLYMERI ZATIO 267
Water uptake (%)= I00 [( W\\ - Wd )/Wd!
where W\\' and Wd are the we ights of wet and dry
sa mpl es respectively.
2.2.3 E lcctrical Conductivity Measuremcnt
Conductivi ty measurements were carri ed out usin g
Mega ohm meter from WTW Instruments, German y.
The average value of th e electri ca l resistance of th e
sa mpl e was meas ured by app lying diffe rent voltages
and recordin g the correspo ndi ng cu rren ts. The
e lec tric al conducti vity (cr) was ca lculated as foll ows:
cr =.rII?/\ n- cm-
I I
where N, II and .r arc th e ohm ic resis tance, area and
thickness of the sampl e respectively.
2.2.4 Uycing
Aqu eous dye bath co ntainin g 2% (owl-) dye was
prepared from Sa ndocryl Blue B-3G at a fabric-to-
liquor rat io of I :SO. The requ ired we ight of dye W,L
pasted in acetic acid befo re the addition of the
dis till ed water. T he dyeing process was ca rri ed out in
th e prese nce of 10% sod iu m sulphate and O.lg/L
Sa nd ozin NIT liqu id as a welling age nt. The pH of th e
dyebath was adjus ted to 3.9 and the temperature wa ~
th en ra ised to th e boil in 20 min . The sol ution was
kept at th e boil for I h. The dyed fab ri cs were rinsed
with water, soaped with Sandozin NIT (0. 1%) at th e
bo il for 30 min and fin all y dried at room temperatur
2.2.5 Colour SII"cngth Meas urement
The colo ur strength of th e cI 'ed samples was
meas ured using ICS- Texicom UV/vi .. pectro-
photometer at a ma ximu m wavelength of 660 nm . The
colo ur stre ngth. ex pressed as K/S, was calculated
from the Ku belka- Mun k equation ":
KIS= !CI-R )"/2R!-!(I-I ")"12R,,l
where Rand Ro are the deCimal fraction of the
reflectan ce of the coloured and uncolou red samples ;
K. th e absorption coefficient; an d S, th e scatteri ng
coe fficie nt.
3 Results a nd DisclIssion
it is of prime importance III radiation-i ndu ced gmf
copolyme rization to choos(' rhe proper solvent that
gives th e highest degree of grartll1g toge th r wit h "
homogenous dis tribu tion O F th grafts allo\' >r the
surface ot" th e fabnc. E>..pcnmen " were carried 0"
O!l AAc and AN monomer. usi g differe nt salve n
, . II ~ B
aWl '110'1 n f' ·-to-llquOl' ,., tlOS e.-t resu lb we"c
268 INDI A N J. FI13IU: rl:x r. RES .. SEPTEMBER 2002

obtained when the di still ed water was lIsed ill grai"ti ng 12.0 ,------::;;""""l.--- - - -- - -- -- --,
AAc onto collon fabrics , while meth anol-lo-water
(65: 15 ) gave hi gh and homogeneoll s graft y ield of A N 11.0
onto the fabrics. Fabric-to-l iquor rati o of 1:.+0 wa s
"0
used for both the systems during this work. Q)
.>' 10.0
<=
ro
3.1 Grafti ng wit h Acrylic Acid ~
Preliminary experiments to gr:1ft co llon fabri cs in 9.0
aqu eo us AAc solu tions gav e low graft yie lds. T o 8.5~-O-~-~!7_-L--~I~-L-~,~--~--~
0.2 0 .6 1.0 1. 4 1. 8
enhance the grafting proces s, Mohr's salt was added Mohr's salt concentra tion, wt %
to inhibit th e hOlllopoly merizati on process. Fi ~. I Fig. I- EITccl of M oh r's sail cOllcelllrati oll O il the &rai"1 y ield of
shows th e depen dence of th e graft y ield 0 11 the COltOIl fabri cs !Irrali iat ioll dosc. I() kGy: .llld aqucous AAc L·Olle ..
co ncentration o f M ohr' s sa lt for fab ri cs irrad iated at a 10\V t ~ I

dose of 10 kG y and 10% aqueou s ;\ ;\c so lutioJl . Th e

res ults indicate that a ma x imum graft y ield is oht .l i llcd 18r-------------------------------~

at inhibitor concentrati on o f 0.75% (o wm ). Thi s

co ncentration was used in all AAc ex perim ents.
'if. 16
The effect of fabric-to-liquor ratio on th e graft y ield u
Qi
of fabrics irradiated at a dose of 10 kGy dose and 10% ':;'
~
AAc solution containing 0.75 % M ohr's sa lt is shown
in Fi g.2. The results indicate a linear increase in the a~ 14
degree of grafting from 13<.0 to 17% as the fabric-to -
liquor ratio is increased from I: 10 to I :40. No further 12~----------~~----------~L-----~
increase in gran y ield is noticed at higher rati os. Thi s 1:4 1:26 1:48
Fabric - to - liquor ra tio
rati o was kept con. tant throughout thi s slUdy.
Fig. 2- Ellcct of fabric- to- liquor rati o on the graft y ield of colt on
Collon graft copoly mers with AA c ha v ing different fabrics IGrafting co nditions: t o% AA c, O . 7 5 ~ (owm) M oh r' s
y ields were prepared by performin g th e experiments salt . and 10 kG y radiati on dose I
under eli fferent monomer concentrations and
irradi ation times. T able I shows th e effec t o f irradia- T ablc I- Ellec t of irradi ati on tim e and AAc co nce ntrati on
tion time and monomer co nce ntration ( 10 - 40% owl) on tb e gran y ield of colton fa bri cs irradi ated al 2.56 Gy/s
on th e graft y ield at 32"C. It is seen that th e grart yi eld dose rate and 32"C
increases linearl y wi th the increase o f irradiati on time Irradi ati on Graft yie ld at
in the initial peri od and th en tends to level-o f r at timc. min 1{)'If AAc 2Wk AAc 30S, AAe -IO'"k AAc
higher times . For th e same irradi ati on time, the initial (J 0 () () ()

graft y ield decreases with the increase i n monomer 13 10.86 7 -1.5 2.-IX
concentrati on. As the i rradiation time exceeds th e 32.5 11.59 10.9 9.3 5.5
ini ti al stages, the graft y ield-time relati onship chan ges 45.5 12 1-I .X6 II 7.9
and indi ca tes an oppos ite ef fec t. Th e end gra ft y ield at 65 Jj.07 IS 17.X I I. I
130 min irradiati on tim e ( 10 kG y) is hi ghest for 40% lJ7 13 .59 16.3-1 20.6 IX. I
AAc conce ntrati on <.lnd lowest for 10% A Ac JjO 1-1.55 18.38 20 22.8
~o n ce ntratio n .
The order o f th e react ion kineti cs ror graftin g A A c
lmto collon fab rics is obta i ned by pl olli ng th e initial irradiation peri od, graftin g ini tially occurs at
:ogari thll1 of the initi al ra te of graftin g versus the th e swol len surfaces by aqu eou s AAc solu ti on.
!ogarithm of AAc co nce ntrat ion (Fig. 3) . Th e fo llowed by conti nu ous monomer di Ilu:-, ion [Itrough
·.::lationship is iinear wi th a sl ope o r - I. indicatin g a grafted layers to reach the ac ti ve fabr ic :,ites to give
.1egative fi r~ t order kineti cs. A t higher irradiati on homogeneous distributi on o f th e graft ed chains in the
' imes, the above dependence changes to a positive fabric. T he homopolymerizati on of A;\c plays an
qruer one. i mportant role at longer irradiati on times or higher
The abnormal behaviour of g.raft ing AAc onto doses. Poly(acry lic acid) is i nso lubl e i n its monomer
~l) 1I0n fabncs can be explai ned as follows. For the and has poor so lu bility i n the aqueous solu ti on at test
 EL-GENDY: MOD IFICATION OF COTTON FAB RI CS V IA RADI AT ION GR A FT COPOLYMER IZAT ION 269

1.B 160,

-
.<:

o~
Qj
1.6
-o- 10wt %
... 20wt %
--~

120
l§ o ;ft. -I:r 30 wt %
OJ
c
<2 1.4
di
.C:::
*' 40wt %
co
0,
'0 o ""r.l
Ol
80
E 0
§ 1.2 dl
QJ
Co 0,

~-­
OJ dl
0
....J 0 40
1.0

~~~~='~--
~I_~ I
A 1.0 1.1 1.2 1.3 1.4 1.5 1.6
Logarithm 01 acryl ic aCid concen tration, wt % 0
0 l, O 80 120 16 C
Fig. 3-Loga rithill ic pl ot oj" initial !!raftin!! rat e ve rsus AAc Irradiation time . min
conce ntration
Fig. -I--Dcgrce of gra ftin g as a fun ction of Irrad iati on tilllc ;11
dilTcn:nt acrylo nitrile concc nt ratio ns Ilrradiation dose rate. 2.:'>6
condi ti ons and forms a gelatin ous layer ove r the Gy/s and fabri c-to- liquor ratio. I AOI
fabric surfaces . T he homopo ly mer, depending on th e
initia l AAc concentrati on, rctards th e monomer £ 2 .5.---------------------------------~

diffusion to free radical s and hence slows th e gra fti ng o~

process. M oreover, the co nsiderab ly hi gh rate of (l)

'§ 2.0
homopolymerization of AAc (its G R va lue of II is OJ
c
cl ose to that o f colton) decreases the effec ti ve :to
~ 1.5
mono mer concentration to co ntinu e the grafti ng OJ
'0
process speciall y at high doses w here the degree of E
E 1.0
grafting tends to level off. Th e increase in the degree .~

of grafting with the increase in monomer OJ

concentrati on at longer irradiati on times and at the
end degree of grafti ng ( 130 mi n) su pport s thc idca
th at the degree in graftin g is dependent not onl y on
the amount of free radicals but also on the diffu siv it y
of the monomer through the grafted laye rs whic h
leads to the increase in the final degrce of graft in g as
well as the rate of ~ raftin g. Similar results werc
reported by l-I eg'.lLi e T (~/.t5. ~
3.2 Gra rtin g with Ac ry lonitrile
Th e dependence of the degree of grafting 0 11
" irradi ation time for 10-40 % AN concentration is
shown in Fig. 4. The figure shows an inducti on peri od
after whi ch there is an initial linear increase in
irradiation time followed by a tendency to level-o ff at
longer times. Th e observat ion o f induct ion peri ods
during th e init ial irradi ati on gra ftin g processes is
frequently noticed and depends on the di ffercnt
fac tors such as dose ra te, monomer concentrati on,
presence of oxygen in the graft ing so lu tions and the
presence of i nh ibi tors tn the as-recei ved
monomers16. 17.
T he dependence of the i nitial grafting rate on
monomer eonce lllration is show n in Fig.5. The figure
< ,,)vv s the logarithmic plot of graftin g ra te ve rsus
o
--.J O. 5 L -_ _ _L -_ _L -_ _L-_--.JL-_ ----'_ ___~
1.0 1.1 1.2 1. 3 1.4 1.5 1. 6
Loga rithm of aC'f'ylnlll tnk concentration, wt %
Fi~. 5---Logari thJ11i c plot o r grart ing ra tc \'c r s u ~. acrylo nitri le
co nccntral ion
monomer concentration. It is observed that thc
relat ionsh ip increases linea rl y w ith a slope o f 2,
i ndicating a second order kinetic s. This high order
dependence of AN grafting on colton is attributed [()
the larger free radical yie ld of the polymcr (cott on )
ove r that of th t' monomcr (A N ). This enhances
grafting over homopo lym eri za ti on as supported by th t'
respect i ve radiation che mical y ield (G R val ue) of
A (5) and cotto n( I I ) (ref. 16).
3.3 G rafting wi th Ac r y li c Acid-Acry lonitrile Mixture
The effect of relati ve co ncentration s of AAc and
AN monomers on the graftin g y ield and rate of graft-
ing of colton fabrics is show n in Figs 6 and 7 respec-
tively. T he fabric s were irradiated in mi xture so lu-
tio ns having different AAc/AN ra ti os such that th e
total monomer conce ntrati on i n al l tests was constant
at 20% owf. The dosc rate and fab ri c-to- liquor ratI o
we re as gi ve n before. ig. 6 shows the c. ependence of
270 INDI AN J. FIBR ETEXT. RES., SEPTEMBER 2002

70 r-----------------------------------~
A Ac / AN propo rtion Th e slope of the relationshi p is 0.55 for AN and -0.4 1
-<>- 20 / 80 for AAc. The dependence of the graftin g rate on
60 ...... 40 /60
--6:- 60/ 40 monomer concent rati on in th e mix tures of th e con-
oF. 50 * 80/20 stan t co nce ntration (20%) is as follows:
c»
~ 40 RI=KdAN 1°55
ro
0,
'0 30 R2= K 2 IAAcr() ·11
OJ
OJ
0, where HI and R2 are the graftin g rat es; and Kland K2.
~ 20
th e rate constants for AN and AAc in the mi xt ure.
10
The grafting of cotton fabrics w ith AN and AA c
O~ __- J_ _ _ _- L_ _ _ _ ~_ _~L__ __ L_ _ _ __ L_ _~
can be explained by th e addition of fabric macro-
o 20 60 80 100 120 140
Irradiat ion time, min rad ical to the monomer double bond to form a
co valent bond between monomer and fabri c with th e
Fig. 6--Dcgrcc of graftin g as a function of irradiati on time at
diffcre nt AAc/AN ratios for comonoillcr conccntration of 20 wt % creation of free radi ca l on the monomer. Subseq uent
[Irradiatio n dosc rate, 2.56 Gy/s and fabric-to-liq uor rat io. I :40[ addition of monomer to the initiated chain propaga tes
grafting. Termination of the grafting process occurs
L 1. 7r------ -- - - -- -- - - -- - - - - - - - - -- - - - - -- -- , by th e formation of a covalent bond between two free
~ o
oF. radicals. Th e proposed schemes for th e graftin g
~ 1.5
• process are given be low:
c
i:
'0," 1.3
Crajiil/g lI 'illi!lN
Q)

~ 1.1
o ANlnAAclAN
'0 • A~~A~I~ Initiati on
~ H
~
.~
~

.3
0.9

O. 7 0~-----O:;'-.-;;-3- - - ------,0:'-::.6,.------.;;
.
0." "9--------:':-';.,;------71.'5 Add ili on or monomer
F ' + CH1
eN
- C ~ F- (~ Hl - C'
eN

Logarithm of monomer concentration in comonomer, wt %

H H H
F eHl - C- CH. - C' <E-- CH,. - C,
Fig. 7- Logar ithmic plots of graftin g rat c vc rsus AN and AAc C:N • eN C"N
conccntrati on in AAc/AN comonomcr cOllcclltrati oll of 20 wt% Propagati on +
[Irradiatioll dosc ratc. 2.56 Gy/s and fabri c- to- liqu or rati o. 1:401 H H
(11-2) f ('H) = ~' 1 ~ F'-f- CH1 - \"---1.---
the degree of grafting on irradiation time at AAc/A N C~ eN
ratio rangi ng from 20180 to 80/20. The results indicate
l enni nation
that as th e rati o increases th e degree of grafti ng de-
Combinati on
creases. Th e results are in co nsistence with th e effect F~'I ' n + F J\<I '",~ P n..,.,
of each monomer on the graft yie ld si nce increase in
I)i sproporli onati on
AAc concentration resu lts in th e decrease of gra ft
yield up to irradiation time of 25 min while co nsider-
able increase in the degree of graftin g is obtain ed wi th
the increase in A concentration (Table I and Fig. 4) . wh ere F' , M and P are th e fabric free radi ca l. th e
It is worth mentioning that th e magnilude of gra ft monomer and the copol y mer respecti vely.
y ield for A is about 6 times higher th an that for Ac
at all doses used and the end gra ft y ields at irradiati on C ra /iil/g lI'illi !I!Ic
time of 135 min are 23 % an d 140% for AAc and AN Graft ing with Ac is exactl 'imilar to that of AN
respecti vely, The rol e o f each monomer in rh e mixtu r except that the CN groups are replaced by th e COOH
on the reaction kinetics is sh own in ig.7 where th e gro ups.
logarithm ic plots of the rate of graft ing an d monomer
3.4 Properties of Grafted Cotton Fa lrics
conce ntrat ion in th e comonom er are )resented . Al-
3.4. 1 ate ' Uptake
though the resul ts are scattereJ, li near straight lines
are drawn to fit reasonabl the results. A posit ive rela- The water uptake values for cotton fabrics grafted
ionship IS IOLmd for AN and a negative one for AAl. with AAc, AN and their mixtures ,\I'e shown in Fig. R.
 EL-GENDY: MODIFICATION OF COTTON FABR ICS VIA RADIATIO N GRAFT COPOLYM ERI ZAT ION 271

200 ------- - - -- - - - - - - - - -- - - -- - - - - -- - - ---, E

:;; 6 ~- ---------------- --------
o
'#. 16 0 --0- A.Ac
...... AN
15 o
O AAc
• AN

-I:r- A Ac I AN (40/60)
" 6 AAc+AN
~ A Ac I AN (80/20) w 4

6
I'}
0
•
40L-__-L____~__~~--~--~~--~~~_
o 10 20 30 40 50 60 70 • • I I I

Degree of grafting, % 10 20 30 40 50 60 70
Degree of grafting, %

Fig. 8-Wat cr uptakc versus dcgl'cc or gra rtin g for c0 11 on-g-

Fig. 9--E ITect or dcgrec or g r~lflill g Oil thc elcctrical cOllciucti vll y
PAAc. cOllon-g- PAN and cOllon-g-colllollolllcr
of co tt on fabri cs

It is observed that th e water uptake of graft 3.4.2 Electrica l Properti es

copolymers of AAc increases linearly from 106% for
ungrafted cotton to 180% with th e increase in the
de~ree
b
of bGraftin bG up to 10% fo llowed by a tendency
to level-off with further increase in graft yield.
Acrylo nitrile graft copolymers show an opposite
behaviour. The water uptake decreases from 106% to
80% as the degree of graftin g is increased to 40%.
AAc/AN graft co polymers (40/60 and 80120) show
water uptake values between th e two ex tremes of
those for AAc and AN graft co polymers, depending
on the relative percentage of th e monomers in the
'"Graft in '"G so lutio n. The res ults indicate that th e wat.er
uptake decreases as the percentage of AN in the
mixture increases. The water uptak e of th e grafted
cotton fabric s increases in the fo ll owi ng ord er:
AAc > AAc/AN (8 0/20 ) > AAc/A N (40/60 ) > AN
The increase in the wa ter uptake with the increase
in the degree of graftin g of AAc-g-co poly mers can be
attributed to the increase of the carboxylic groups in
th e grafted fabrics du e to their hydrophilic properti es.
AN-g-copolymers, however, give an opposite effect
of the water uptake due to the hydrophobic propc rti es
of -CN gro ups of A . Consequently , th e increase in
the degree of graft ing with AN results in a decrease in
water uptake. Fabrics grafted with differe nt mixtures
of the homopol ymers are expected to show wa ter
uptake de pendi ng on the co mpet ing effects of AAc
:lI1d AN in the grafts. This mea ns that th e wa ter
uptake dec reases as the percentage of AN in the
grafted fabrics increases. The co ntri buti on of AN in a
50/50 mixt ure towards water uptake is expec ted to be
hig her than that of AAc si nce the degree of graftin g
with N is about 6 times higher than that of AAc
(Table I and Fig. 4) and co nseq uent ly its participation
i n the property cha nge IS sig nificant.
The dependence of the electrical conducti vlty on
the degree of grafting of fab rics grafted with AAc ,
AN and their 50/50 mixture is shown in Fig. 9. The
fi bGure shows a bcre neral trend of the decrease of the
electrical co nducti vity with th e increase in graft yield.
irrespective of the type of th e graft copolymer. The
rate of change of th e elect rical co ndu ctiv ity wi th the
chan bcre in the de b
cr ree of graftin bG is fast at lo we r graft
.......,
yields fo ll owed by a gradu al dec rease up to a mini -
mum va lue at 35 % graft yield . The electrical co nducti -
vit y dec reases from 6.5 x lO' l~ to 2x lO,I,I ohm'l m'l as
the graft yield increases to 35 %. The decrease in th e
electrical conductivity of cotton fa bri cs wit h th e
increase in graft yie ld is different from the res ul ts
obtai ned for nylon-6 fab ri cs grafted with NVp lx and
fluo rinated polymers grafted . .
with AAc I~ ,a lt IlOUg h In
.
both .::ases the ca rbox yli c gro ups are in troduced in the
fab rics . This apparent difference is due to the fact
that the stru cture of ungrafted nylo n-6 fabric does not
co ntai n functional gro ups th at can easil y co ndu ct
electric curren t. Cotton fabric , howeve r, co ntains
seve ral O H groups that ca n conduct electricity. The
in trodu cti on of COO H andlo r CN groups via graftin g
with AAc, AN or their mixtures seems to decrease the
overall co ndu cti ng efficie ncy of cotton fab ric as the
decrree of graft in (T increases. Co nseq uentl y, the
'" ~ '"
electrica l co nducti vity of cotton fab ri cs is expected to
decrease with the increase in graft yield till saturation
at 35 %.
3.4.3 Dyei ng Properties
3.-U.1 Effect of pH on Dyeability of Fabric
T he el'fect of pH on the colour stre ngth (KIS) of
" rafted and un arafted fab rics is show n in Fib(T . IO . It is
b '"
observed that the un grafted fabrics have no affi nity
towards Sandocryl Blue in acidic or alkaline aqueous
272 I D IAN J. FI BRE TEXT. RES. , SE PTEMBER 2002

20 The co lodr strength of th e grafted f abri cs prepared

o Ungr<-iftcd cotton from AAc/AN (40:60) mixture w ith 13. 1% graft y ield
-
-;;:; 16

2'::
•
6
1\ 5% A Ac grafts
96% AN grafts
X 13. 1% (..fO%AAc +GO%AN) gr:lfl ~
decreases from IS 100.5 as the pH increases from 3. 9
to 11.5. Th e res ul ts are sim i lar to those obtained for
£; 12
OJ
c:
~
AAc-graft copo ly mers w ith graft yiel d of 4.5 % ex cept
en 8 that the KIS va l ues are higher than th ose of th e laller
'3
0 6
(5
u
at the intermediate pH values. Th is similarity in th e
4
ini tial and fina l co lour streng th va lues is due to th e
0 fact that th e effec ti ve co nce ntrati on o f AAc in 13. 1%
3 12 graft y ield is about 5.2 %. T hi s emphas izes that th e
pH values
dyeing affinity of fabrics grafted in the com onomer
Fig. 1000EfTect o f pH on th e colour strength or grart ed and un- mi xture is onl y due to the addi tion of the carbox ylic
grafted COLLon fab ri cs I Dyein g condit ions: dye, 2% (owl) ; fabric - groups to th e fab ri c struct ure via AA c. The role of AN
to- liquor rati o, I :50; and bath temperature, g5"CI in th e grafted fabric is giv ing a ye ll ow ish oran ge
co lour of i ntensity that depends on th e degree o f
30 r-----------------------------------~ grafting. Upon dyeing, th e expec ted blue co lour of
_ 25
-0- A Ac gratis
dye turn s to greeni sh.
(f)
-..- AN grafts
;C 2 0 -lr- EIfHc:ive AAc Itl AAc ~ AN mi:d.ure
3.4.3.2 Effect of G raft Yield on Dyca bility of Fabrics

The effec t of the degree of grafting on the co lour

°0~--~5~--·~1~0-----1~5----~20~---J25~--~30
Graft yield. %
Fig. II --Depcndcnce or co lour strength on the graft y ield or
COLLon fabrics
solutions (pH 3.9- 11 ,5). [t is also observed fro m
Fig, 10 th at th e grafted and dyed fabri cs show hi gher
K/S va lues th an the ungra fted ones at all pH va lues.
T he results also indica te th at th e co lour strength
decreases w ith th e increase in pH and the magni tude
of th e decrease depends on th e type of monomer
grafted onto th e fabri cs. The fab ri cs grafted w ith AAc
gi ve hi gh co lour strength val ue ( I S.5) at pH 3.9.
Increase in pH to 5.6 res ul ts in a rap id decrease in K/S
to 7. Further increase in pH to 11 .5 results in a
gradual decrease in co lour strength till reac hing the
val ue of 0.5 fo r ungrafted fab rics . Fabri cs grafted w ith
AN show an initi al KIS of 6.5 at pH 3.9 followed by a
linear decrease up to th e va lue of ungrafted ones in
th e alk<l line medi um. [t is clear from th e res ults th at
the affin ity of th e fab rics towards thi s bas ic dye in
acidic solutions is about three times hi gher for fabrics
grafted w ith AAc th an th at for AN grafts although th e
degree of grafti ng of the latter is tw ice as hi gh as th at
for AAc gra fts. Thi s i ndi cates th at the introdu ction of
the carboxy li c groups of AAc on to cotton fabri cs via
grafting is res ponsible for the increased affinit y of the
fabrics towa rds basic dyes.
strength of grafted and ungra fted cotto n fa bri cs dyed
in 2% ow l' aqueous so luti ons, adj usted to pH 3.9, is
show n in Fig. II . [t is observed tha t the colour
strength of dyed fabri cs increases as th e degree of
graftin g increases to reach its maxi mu m valu e and
th ereafter it leve ls off or s h ow ~' a tendency to
decrease. Ac ry lonitril e graft copo lyme rs do not show
significa nt affinity towards basic dye st udied since the
co lour strength increases from 2 (th e va lue o f
ungrafted fabri cs) to 7.5 as th e graft y ield increases to
2S %. Fabri cs grafted w ith AAc or AAc/AN mi xtu re
show co nsiderably hi gh increase (from 2 to 25 ) in
co lour strength as th e degree of graftin g increases to
20%. Th e fa bri cs grafted w ith AAcl AN mixture
co ntain almos t th e same effec ti ve graft yield as th at
obtain ed in AAc alone. [t is clear from th e results that
AAc rath er th an A N is responsi ble for th e increase in
co lour strength of grafted fabri cs.
T he increase in th e co lour streng th o f cotton fabric s
w ith th e increase in graft y ield can th us be attributed
to th e increase in the COO H f uncti on al groups in th e
fibre stru cture. T his enhances th e dye up take up to a
graft yield of 20%. Th e leve ling oil in the colour
strength at hi gher degrees of gra fting may be
ex plain ed by th e depl eti on of th e aq ueous solution
fro m th e dye th ro ugh th e increas ing number of active
functi onal groups associated w ith the grafted f,1brics
w hil e th e dye co ncentrat ion is kept constan t, thu s
decreas ing th e dri ving force for the di ffus ion of the
dye into graft ed regIOns. T he react ion between the
 EL-GENDY: MODIFICATION OF COTTON FABRICS VIA RADIATION GRAFT COPOLYMERIZATION
basic dye and AAc-grafted fabrics can be presented as
follows:
HI
F-[-CH2 -y:---.. Jn-- F-[-CH2 -
COOH
H KlS value of grafted and ungrafted fabric s is observed
I
nHCI + F.[. CH2- ~ -'-l n '-
COO-Dye
4 Conclusions
4.1 Modification of the properties of cotton fabrics is
achieved via direct radiation grafting with AAc , AN
and their mixtures. The optimum grafting of the fab-
rics occurs at 2.56 Gy/s dose rate and 1:40 fabric-to-
liquor ratio when the graftin g is performed in the
presence of aqueous AAc containing 0.75 % owm
Mohr's salt as inhibitor and in 65 : 15 methanol-water
mixture for AN .
4.2 The grafting process follows a second order kinet-
ics for AN and a negative first order one for AAc. The
reaction order for mon o mer mixtures shows different
kinetic behaviour dependin g on AN/AAc ratio in so-
lution and th e total monomers content.
4.3 The swelling properties of cotton fabrics improve
with the increase in deg ree of graft in g o f AAc and
detoriorate with the in crease in gra ft y ield of AN.
Fabrics grafted with mo nomers mixture show swell-
ing behavi our between those of AAc and AN.
4.4 The electrical conductivity of grafts prepared
fro m the monomers or their mixture shows a fast in i-
ti al decrease followed by a te nde ncy to level off as the
graft yie ld in creases up to 35%, irrespective of the
type of monomer or the mi xture rati o.
4.5 The dyeability of cotton fabrics towards Sandocryl
Blue B-3G , a basic dye, improves considerably as the
graft yield of AAc increases. Slight but steady increase
in colour stren gth of AN -grafted fa bri cs is obtained as
the graft yield increases. The increase in colour
273
strength of fabrics grafted with monomers mixture is
due to the effective AAc-grafted content of the fabric.
4.6 The pH of the dye bath affects considerably the
H colour strength of grafted fabric s. Generall y, the
~' ---ln -. + n H maximum colour strength values are . obtained in
coo'
+ acidic medium at pH 3.9 while no difference in the
~ {nDy~+ }CI' when dyed in alkaline medium at pH II.
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