TROUBLESHOOTING IN PREPARATION

A Systematic Approach
J. W. Rucker and C. B. Smith
Textile Chemistry Department
North Carol i na State Uni versi ty
Raleigh, North Carolina 27695-8302
Introducti on
An ol d sayi ng i n t he t ext i l e wet processi ng i ndust ry i s "wel l pre-
pared-hal f dyed. " Thi s st at ement i s not quot ed t o i mpl y t hat t he maj ori t y
of probl ems whi ch occur i n dyei ng i s due to i nadequate preparati on, but
that i n many cases probl ems whi ch are not detected i n preparati on do l ead
t o f aul t y dyei ngs . Gruni g [l ] breaks down the percentage of defects i n
t ext i l e wet processi ng accordi ng t o ori gi n as f ol l ows:
Table 1: Def ect s i n Text i l e Wet Processi ng Accordi ng t o Ori gi n [ l ]
Ori gi n of Def ect Percent age of Def ect s
Fi ni shi ng
Dyeing and Printing
Di verse
- s ubs t rat e qual i t y
-using wrong products
- negl i gence
- uncont rol l ed t race i mpuri t i es
Bi ol ogi cal , chemi cal , t echni cal , and
mechani cal i ncl udi ng storage and
machinery problems
Preparati on
- proces s def i ci enci es
- deposi t s and resi dues
-bleach damage
-mercerizing damage
11
23
21
24
21
Al t hough 21 percent of def ect s i n wet processi ng i s di rect l y at t ri but abl e
t o preparat i on, many of t he def ect s l i st ed under t he "di verse" and "bi o-
l ogi cal , chemi cal , et c. " cat egori es ( part i cul arl y subst rat e qual i t y and
uncont rol l ed t race i mpuri t i es) can l ead t o i nadequat e preparat i on. I t i s
pos s i bl e, t heref ore, t hat up t o 66 percent of t he def ect s i n f i ni s hed
f abri cs are due t o t reat ment s or l ack of t reat ment s pri or t o dyei ng.
2
Si nce many preparati on probl ems that occur are due to the qual i ty of
t he subst rat e and may not show up unt i l l at er processi ng, i t i s of t en
di f f i cul t t o percei ve probl ems duri ng t he preparat i on processes. Thus t he
obj ect i ve of t hi s di s cus s i on i s t hus t o out l i ne a s ys t emat i c i n- proces s
approach for detecti ng and el i mi nati ng potenti al probl ems duri ng prepara-
t i on. The procedures suggested wi l l requi re substanti al testi ng and good,
accurate recordkeepi ng, but they shoul d ai d i n detecti ng probl ems before
they show up duri ng l ater processes; thereby reduci ng the amount of
i nferi or qual i ty goods produced i n preparati on. The speci fi c areas whi ch
must be eval uated on a regul ar basi s to control producti on qual i ty i ncl ude:
( 1) commodi t y and speci al t y chemi cal s, ( 2) wat er; ( 3) grei ge f abri c, and
( 4) processes, i ncl udi ng process vari abl es and t reat ed f abri c anal ysi s.
Commodity and Specialty Chemical Analysis
Many users of chemi cal products take for granted that the qual i ty of a
purchased product is always the same. This assumption may be correct most
of t he t i me, but t he one t i me t hat i t i s not can cause qual i t y probl ems.
Chemi cal suppl i ers, as i s t he case wi t h al l manuf act urers, do have qual i t y
problems from time to time. When a producti on l ot does not meet speci fi ca-
t i ons , t he y ( l i ke ot he r manuf ac t ur e r s i nc l udi ng t e xt i l e ) , wi l l i ni t i al l y
at t empt some repai r procedure t o get i t wi t hi n speci f i cat i ons. Al t hough
t he repai red product t hen meet s t he suppl i er' s speci f i cat i ons, i t may not
f unct i on cons i s t ent l y i n t he us er' s proces s . I f t he product cannot be
bought t o wi t hi n speci f i cat i ons, t he suppl i er wi l l probabl y shi p i t t o a
cust omer t hat he knows i s not l i kel y t o anal yze i t . I n ei t her, cas e t he
lot may be completely used up before the customer becomes aware that he has
a qual i ty probl em. Thi s i s especi al l y t rue i n preparat i on, where def ect s
may not show up unti l l ater processi ng. I t i s t heref ore i mperat i ve t hat
each l ot purchased be anal yzed before use.
Every chemi cal shoul d be anal yzed as i t i s recei ved to determi ne the
concent rat i on of t he act i ve i ngredi ent . Improper dilution of the compound
by the manufacturer or decomposition of compounds such as enzymes or
hydrogen peroxi de may l ead to l ower acti vi ty and resul t i n i nadequate
preparati on treatments. In addi ti on to checki ng for acti vi ty, compounds
shoul d be checked to determi ne whether or not they functi on properl y under
process condi t i ons. They shoul d be anal yzed i n the l aboratory i n the
treatment i n whi ch they wi l l by used wi th the appropri ate temperature, pH,
and other compounds, and the resul ts compared to those obtai ned i n a
simultaneous treatment using a sample of the compound from a manufacturer's
standard. It may be hel pf ul t o use a l ower concent rat i on i n t hi s anal ysi s
t han act ual l y requi red i n t he process because di f f erences i n t he ef f ect i ve-
ness of the compound may be more apparent at the lower concentration than
at t hat used i n t he act ual process. In usi ng a l ower concentrati on,
however, i nteracti ons between the compound and others i n the sol uti on that
l ead t o reduced sol ubi l i t y, preci pi t at i on, et c. may not be as appar-
ent . Compati bi l i ty shoul d therefore al so be checked at concentrati ons
equal t o or hi gher t han process condi t i ons.
3
A qui ck way to check for the acti vi ty and composi ti on of a compound i s
t o compare i t s ul t ravi ol et or vi si bl e spect rum t o t he st andard spect rum of
the compound. Many dyehouses are equipped with spectrophotometers for
det ermi ni ng t he st rengt h of dye sol ut i ons. Although only colored compounds
absorb i n the vi si bl e porti on of the spectrum, many col orl ess compounds
used i n preparat i on absorb ul t ravi ol et l i ght . Many wet t i ng agent s,
penetrants, chel ati ng agents, and even hydrogen peroxi de absorb i n the UV
regi on. Beer-Lambert' s Law i s al so obeyed i n the UV, that i s, absorbance
i s di rect l y proport i onal t o concent rat i on. I t i s t heref ore wi s e t o have
absorpti on spectra at standard concentrati ons for al l compounds that absorb
vi s i bl e or UV l i ght . The compound must be sol ubl e i n the sol vent to obtai n
t he correct spect ra, and organi c sol vent s shoul d be used i f t he compound i s
not sol ubl e i n wat er. When a new l ot of a compound i s recei ved i ts
spectrum (at the same concentrati on as the standard) can be easi l y obtai ned
and compared to the standard. Any change in absorbance at the wavelength
of maxi mum absorbance i ndi cat es t hat t he act i vi t y of t he new l ot i s
di f f erent f rom t he st andard ( l ower absorbance, l ower act i vi t y) . Any
change i n t he shape of t he absorpt i on spect ra of t he new l ot i ndi cat es t hat
i t has a di f f erent composi t i on f rom t he st andard.
There are standard tests for anal yzi ng many of the compounds used i n
t he preparat i on processes. These t est s al ong wi t h a ref erence f or t he
det ai l ed procedure are l i st ed i n Tabl e 2.
Table 2: Standard Procedures for Analyzing Compounds Used in Preparation
Processes
Compound
Wetting Agents
Type of Anal ysi s
Ef f ect i venes s
Rewet t i ng
For Mer cer i zat i on
Enzymes A c t i v i t y
Noni oni c Sur f act ant s Cl oud Poi nt
Ani oni c Sur f act ant s Ac t i v i t y
Chel at i ng Agent s Ac t i v i t y
Hydrogen Peroxide Concent r at i on
Sodium Hypochlorite Avai l abl e Chl or i ne
Sodi um Chl or i t e Concent r at i on
Reference
2 , p. 49
2 , p. 88
2 , p. 98
2, p. 163
6 p. 695
3, p. 50
2, p. 264
4, p. 162
5, p. 29
5, p. 35
5 , p . 3 4
4
Water Analysis
The i mport ance of wat er qual i t y i n t ext i l e wet processi ng i s di s-
cus s ed i n anot her art i cl e of t hi s s eri es . Impuri t i es t hat are of part i cu-
l ar i nt erest i n t he preparat i on processes are t race quant i t i es of met al
i ons . Calcium and magnesium ions, f or i ns t ance, wi l l preci pi t at e s oaps
used or produced i n scouri ng l eadi ng t o deposi t i on of st i cky i nsol ubl e
soaps on the substrate. Transi t i on met al i ons l i ke i ron, copper, mangan-
ese, zi nc, ni ckel , cobal t , and chromi um cat al yze t he decomposi t i on of
hydrogen peroxi de and degradati on of cotton i n both peroxi de and hypochl o-
- ri t e bl eachi ng. In some processes speci fi c metal i ons may have benefi ci al
e f f e c t s . Cal ci um and parti cul arl y magnesi um stabi l i ze hydrogen peroxi de
and i nhi bi t degradat i on of cot t on i n peroxi de bl eachi ng. Cal ci um al so
st abi l i zes al pha amyl ase enzymes used i n desi zi ng st arch. Al t hough t he
presence of some met al i ons may be desi reabl e i n speci f i c process sol u-
t i ons, seasonal or ot her vari at i ons i n t he l evel of t hese i ons i n wat er can
l ead t o vari at i ons i n t reat ment s. It i s t heref ore i mport ant t o peri odi -
cal l y anal yze process water for the concentrati on of metal i on contami n-
ants. Qui ck tests for commonl y occurri ng metal l i c contami nants i n water
are des cri bed i n t he ot her art i cl e.
Grei qe Fabri c Anal ysi s
The grei ge substrate shoul d al so be anal yzed to determi ne the type
and percent of si ze; l evel of oi l s, f at s and waxes; and t race met al i ons
i n t he f i bers . Thi s i nf ormat i on wi l l det ermi ne t he t ypes as wel l as t he
severi t y of t he preparat i on t reat ment s requi red and i ndi cat e precaut i ons
whi ch must be taken i n prepari ng the substrate. '
Si nce the techni que for removi ng warp si zes depends on the type of
s i ze, i t i s i mperat i ve t hat t he s i ze on f abri cs be i dent i f i ed bef ore
des i zi ng. Most vert i cal processors usual l y know t he t ype and l evel of si ze
on woven fabri cs al ong wi th other components i n the si ze formul ati on. Most
commission dyers, however, do not have t hi s t ype of i nf ormat i on and shoul d
caref ul l y anal yze t he subst rat e bef ore preparat i on. Even if the informa-
t i on i s known, i t i s wi s e t o conf i rm i t . Wi t h a s eri es of s t andard
sol ut i ons, qui ck spot t est s can be conduct ed t o det ermi ne t ype of warp si ze
on f abri cs. Li vengood [ 7] publ i shed a seri es of qui ck spot t est s f or
det ect i ng t he pres ence of s t arch, pol yvi nyl al cohol ( part i al l y and f ul l y
hydrol yzed) , carboxymet hyl cel l ul ose, st arch/ pol yvi nyl al cohol bl ends,
acryl i c and pol yes t er s i zes on f abri cs . Af t er det ermi ni ng t he t ype of
si ze, several sampl es of t he f abri c shoul d be t horoughl y desi zed i n t he
l aborat ory t o det ermi ne t he percent si ze.
A sol vent extracti on shoul d al so be conducted on several sampl es of
t he f abri c t o det ermi ne t he oi l , f at , and wax cont ent of t he f abri c. Thi s
anal ysi s wi l l i ndi cate the amount of these i mpuri ti es that must be removed
i n the scouri ng process and thus the ti me, temperature and chemi cal
amounts required. It i s most i mport ant f or kni t s because t hese are
t he maj or i mpuri t i es present .
5
A good general practi ce to fol l ow i s to determi ne the water, enzymes
and solvent extractable content using AATCC Test Method 97-1982 [2, p.
1521, f or each s t yl e, cons t ruct i on, et c. I t i s equal l y i mport ant t o
mai ntai n good records for each test; If probl ems i n preparati on are
rel at ed t o s peci f i c t ypes and/ or l evel s of i mpuri t i es , t hen t rends wi l l
begi n to show up over ti me. The f abri c shoul d al so be anal yzed f or
presence of i ron and copper i n t he f i bers [ 5, p. 64] . Al t hough t race
quant i t i es of t hese met al s do not adversel y af f ect bl eachi ng, hi gher l evel s
can l ead t o severe f i ber degradat i on, requi ri ng t he f abri c t o be soured
bef ore bl eachi ng. The f abri c shoul d al so be vi sual l y assessed f or t he
presence of rust spot s or met al f i l i ngs whi ch can l ead t o l ocal i zed
degradati on duri ng bl eachi ng. If present proper treatments (souri ng or
t reat ment wi t h oxal i c aci d) shoul d agai n be gi ven bef ore bl eachi ng.
The Preparati on Processes
In t hi s sect i on, each speci f i c preparat i on processes ( desi zi ng, scour-
i ng, bl eachi ng, and merceri zat i on) i s di s cus s ed. The bas i c pri nci pl es of
each process are present ed al ong wi t h t he ef f ect t hat process vari abl es
( pH, t emperat ure, et c. ) and chemi cal s have on t he process. A syst emat i c
procedure f or anal yzi ng t he t reat ed subst rat e af t er each process f or
determi ni ng the thoroughness of the treatment al ong wi th possi bl e causes of
i nadequat e t reat ment s i s al s o pres ent ed. Al t ernat i ve procedures , i f
avai l abl e , wi l l al s o be di s c us s e d.
Des i zi ng
Warp si ze i s appl i ed to warp yarns to i mprove thei r strength duri ng
the weavi ng process. The materi al coats the yarns and can act as a dye
and chemi cal resi st i n t ext i l e wet processi ng. It must therefore be
removed before any subsequent wet processi ng of the fabri c. The desi ze
procedure depends on t he t ype of si ze. It i s t heref ore necessary t o
know what t ype of s i ze i s on t he f abri c bef ore des i zi ng. Thi s can eas i l y
be determi ned by spot tests as di scussed above.
St a r c h i s t he mo s t di f f i c ul t s i z e t o r e mo v e . I t do e s no t r e a di l y
di ssol ve i n water and must be broken down chemi cal l y i nto water sol ubl e
compounds by ei ther enzymes, oxi di zi ng agents, or aci ds. Enzymes break
down st arch i nt o wat er sol ubl e sugars and dext ri nes, oxi di zi ng agent s
oxi di ze st arch i nt o compounds t hat are sol ubl e i n al kal i ne sol ut i on, whi l e
aci ds hydrol yze starch i nto water sol ubl e compounds. Enzymes are speci fi c
i n t hei r act i on i n t hat t hey do not at t ack cot t on, whi l e oxi di zi ng agent s
and aci ds can degrade cot t on i n addi t i on t o st arch. St arch i s t heref ore
usual l y desi zed wi th enzymes.
Starch i s actual l y composed on two components, a strai ght chai n
pol ysacchari de of gl ucose and a branched chai n pol ysacchari de of gl ucose.
Amyl ose, t he st rai ght chai n component , i s rel at i vel y l ow i n mol ecul ar
wei ght, water sol ubl e, and makes up 20-30% of starch. Amyl opecti n, the
branched chai n component, i s rel ati vel y hi gh i n mol ecul ar wei ght, water
6
i nsol ubl e, and makes up 70- 80% of st ar ch. I t i s t he r e f or e t he a myl ope c t i n
component t hat i s di f f i cul t t o r emove i n des i zi ng.
The enzyme t hat i s s peci f i c t o s t ar ch i s amyl as e. Ther e ar e al s o t wo
t ypes of amyl as e, al pha and bet a. Al pha amyl as e at t acks t he s t ar ch chai ns
at r andom l eadi ng t o a r api d r educt i on i n mol ecul ar wei ght and t hus r api d
s o l u b i l i z a t i o n o f s t a r c h . Bet a amyl as e, on t he ot her hand, s ucces s i vel y
r emoves t er mi nal gl ucos e uni t s f r om s t ar ch chai ns . I t s a c t i o n i s a l s o
t er mi nat ed at br anch poi nt s i n amyl opect i n, l eavi ng r el at i vel y l ar ge
mol e c ul a r we i ght f r a c t i ons t ha t a r e di f f i c ul t t o s ol ubi l i z e . The r e f or e ,
al pha amyl ase shoul d be used t o obt ai n r api d and t hor ough di gest i on of
s t a r c h . Mor e s peci f i cal l y, bact er i al al pha amyl as e pr epar ed i n cul t ur es
i s p r e f e r a b l e b e c a u s e i t i s t h e p u r e s t a n d mo s t s t a b l e s o u r c e . Ot h e r t y p e s
of t he enzyme i ncl ude mal t amyl as e and pancr eat i c amyl as e. Many f act or s
af f ect t he s t abi l i t y of amyl as e enzymes s o i t s houl d be checked f or
act i vi t y usi ng AATCC Test Met hod 103-1984, "Bact eri al Al pha-Amyl ase
Enzymes Us ed i n Des i zi ng, As s ay of " [ 2, p. 163] bef or e us i ng. I t s houl d be
poi nt ed out al s o t hat amyl as e enzymes ar e no l onger cons i der ed a s peci al t y
chemi cal but have now t aken on a commodi t y st at us [ 8] .
Pr oces s par amet er s t hat af f ect enzymat i c des i zi ng ar e i n gener al t hos e
a f f e c t t he a c t i vi t y of t he e nz yme . They i ncl ude pH, t emper at ur e, and
compounds whi ch enhance or decr eas e act i vi t y. For bact er i al amyl as e,
act i vi t y of t he enzyme i ncr eases r api dl y wi t h pH up t o maxi mum i n t he
neut r al pH r ange and t hen decr eas es s i gni f i cant l y. The pH r ange of 6. 5 t o
7. 5 i s gener al l y r ecommended, but t he opt i mum pH may var y wi t h suppl i er ,
t e mpe r a t ur e , a nd ot he r c ondi t i ons . Act i vi t y i ncr eas es wi t h t emper at ur e up
to a maximum and then decreases. The maximum depends on several factors
i ncl udi ng s our ce of amyl as e, pr es ence of s t abi l i zer s i n t he bat h, and
a mo u n t o f s t a r c h i t s e l f . Bact er i al al pha amyl as e i s mor e s t abl e at hi gh
t emper at ur es t han ot her s our ces . Cal ci um i ons and sodi um chl or i de i n-
c r e a s e s t he he a t s t a bi l i t y of a l pha a myl a s e . The hi ghe r t he l e ve l of
s t a r c h, t he hi ghe r t he he a t s t a bi l i t y of a l pha a myl a s e . I n ge ne r a l ,
maxi mum enzyme act i vi t y i s obt ai ned i n t he t emper at ur e r ange of 160- 212F
dependi ng on t he above f act or s. Compounds whi ch reduce enzyme act i vi t y and
s houl d not be al l owed t o cont ami nat e t he des i ze bat h i ncl ude copper and
zi nc i ons , s ome ani oni c wet t i ng agent s , chel at i ng agent s , oxi di zi ng and
reduci ng agents.
Typi cal des i ze pr oces s es i nvol ve t he f ol l owi ng s t eps :
1 . Sa t u r a t i n g t h e f a b r i c wi t h t h e f o l l o wi n g s o l u t i o n a t 1 6 0 F
0. l -1. 0% Bact er i al amyl ase enzyme
10. 0% Sodi um chl or i de
0. 5% Cal ci um chl or i de
O. l - 0. 2% Wet t i ng agent ( noni oni c)
2 . Di ge s t i on of t he s t a r c h, e i t he r
a .
Bat ch f or 2- 12 hour s
b: J-box f or l 0- 30 mi nut es at 170- 180F
C. Steam for 30-120 seconds at 210-212F
7
3 . Thorough washing at 180F or above
The washi ng step i s very i mportant i n removi ng the dextri ni zed starch from
t he f abri c.
Af t er desi zi ng, t he f abri c shoul d be syst emat i cal l y anal yzed t o
det ermi ne t he uni f ormi t y and t horoughness of t he t reat ment . It shoul d
f i rst be wei ghed t o det ermi ne t he percent si ze removed. The resul t s shoul d
be compared t o t hose obt ai ned i n t he l ab. If t hey are l ower t hen ei t her
t he t reat ment or washi ng have not been t horough. Iodi ne spot t est s shoul d
then be conducted on the fabri c. The fabri c shoul d not be spotted randoml y
but f rom si de- cent er- si de at di f f erent poi nt s al ong t he l engt h of t he
f a br i c . The resul t s of t hi s eval uat i on wi l l gi ve some i dea of t he cause
of any i nadequate treatment as fol l ows:
a. If none of t he spot s produce bl ue col orat i on, t hen t he f abri c has
been evenl y and thoroughl y desi zed.
b. If t he spot s produce a l i ght bl ue col orat i on of uni f orm i nt ensi t y,
a sampl e of t he f abri c shoul d be gi ven a hot al kal i ne wash.
Af t er ri nsi ng and dryi ng t he sampl e, spot i t agai n wi t h i odi ne
s ol ut i on. If no bl ue col orat i on resul t s, t hen t he resi dual amount
of si ze remai ni ng i n t he f abri c wi l l be removed i n t he al kal i ne
s cour t hat f ol l ows .
C. If t he spot s produce deep bl ue t o vi ol et col orat i on of uni f orm
i nt ens i t y, t he f abri c s houl d be checked as i n s t ep "b. " I f t he
i odi ne s pot s s t i l l t urn bl ue af t er t he hot al kal i ne was h, t here
of t he st arch, and t he source of t he
Th e f o l l o wi n g i s a l i s t o f f a c t o r s
starch removal , and each shoul d be
has been' i nadequat e di gest i on
problem must be determined.
t hat coul d l ead t o i ncompl et e
checked:
- - Process vari abl es
pH of bat h ( 6. 5- 7. 5)
Temperature of bath (150-16OF)
Wet pick-up (100%)
Ti me and temperature of di gesti on
--Proper bath and mix preparation
f or exampl e, heat i ng wi t h l i ve st eam can i nact i vat e t he
enzyme or i ntroduce rust i nto the mi x or treatment bath
- - Act i vi t y of enzyme
AATCC Test Method 103-1984
- - Ef f ect i venes s of wet t i ng agent
Drop a pi ece of grei ge f abri c i n t he bat h. I t s houl d s i nk
i n 2- 3 seconds.
AATCC Test Method 17-1985 12, p. 491
8
- - Compat i bi l i t y of wet t i ng agent
Some ani oni cs i nacti vate enzymes, noni oni cs preferred.
Compati bi l i ty of noni oni c at bath temperature (cl oud poi nt)
Compat i bi l i t y of noni oni c wi t h el ect rol yt es i n bat h
--Metal s i n water (copper and zi nc i nacti vate enzymes)
--Contami nants i n bath (hydrogen peroxi de, chel ati ng agents, etc)
--Wash water temperature (above 18OF)
d. If the spots produce uni form col orati on al ong a si de or the
cent er of t he f abri c, t hen t he pad pressure i s not uni f orm al ong
t he wi dt h of t he f abri c.
e . If t he spot s produce nonuni f orm col orat i on, t hat i s, no col orat i on
i n some areas and vari at i on i n t he i nt ensi t y of bl ue col or
el sewhere, t hen t he- f abri c has not been evenl y t reat ed. There are
several possi bl e causes of nonuni form treatment whi ch shoul d be
i nvest i gat ed. A poor wetti ng agent may l ead to di fferent degrees
of wet t i ng and penet rat i on of t he f abri c by t he bat h. If the bath
temperature i s above the cl oud poi nt of a noni oni c wetti ng agent,
t he i nsol ubi l i zed compound may set t l e ont o t he f abri c l eadi ng t o
r e s i s t s po t s . If the bath l evel i s l ow then there may be uneven
pi ck- up of t he s ol ut i on l eadi ng t o an unl evel t reat ment . Si nce
the desi ze bath i s usual l y covered wi th foam, i t may be necessary
to add a defoamer to accuratel y determi ne the actual bath l evel .
If a defoamer i s used, i t shoul d be checked beforehand to make
sure that i t does not i nacti vate the enzyme and extreme care
t aken i n i t s us e. Improper use of defoamers can lead to the
f ormat i on of yel l ow spot s on t he f abri c i n l at er processi ng
or dye r e s i s t s pot s . Other possi bl e causes of an uneven treatment
i ncl ude water or condensati on spots on the fabri c, temperature
vari ati ons duri ng di gesti on and nonuni form washi ng.
Syntheti c pol ymer si zes such as pol yvi nyl al cohol (PVA) and carboxy-
methyl cel l ul ose (CMC) are very popul ar because i n most cases they are
very easy to remove compared to starch. Care must be taken in desizing
these si zes, however, because they are avai l abl e i n many grades wi th
va r yi ng s ol ubi l i t y pr ope r t i e s . PVA, f or i nst ance, i s avai l abl e i n grades
rangi ng from ful l y hydrol yzed (FH Grade) to parti al l y acetyl ated (PA
Grade). The FA Grade i s more di f f i cul t t o sol ubi l i ze and t hus requi res
more time and higher temperature for complete removal. The grade of PVA on
si zed f abri cs can be det ermi ned by spot t i ng wi t h an i odi ne/ bori c aci d
s o l ut i o n [ 7 ] . Fabri c si zed wi t h t he part i al l y acet yl at ed grade wi l l t urn
deep bl ue-purpl e when spotted wi th the sol uti on whi l e no col orati on wi l l
resul t when f abri c si zed wi t h t he f ul l y hydrol yzed grade i s spot t ed. In
general , PVA i s desi zed wi th a hot water wash at 180-190F at a neutral pH.
Condi ti ons that can make PVA ve' ry di ffi cul t to remove i n desi zi ng i ncl ude
overdryi ng of t he f abri c and al kal i ne pH duri ng hot wat er desi zi ng. The
f abri c shoul d t heref ore not be heat set pri or t o desi zi ng. PVA gel s under
9
al kal i ne condi t i ons so t he wash wat er shoul d be neut ral . Al l grades of
CMC are readi l y sol ubi l i zed i n water and can be easi l y desi zed wi th a warm
water wash at 150-160F.
The desi red fabri c shoul d be anal yzed as di scussed above to determi ne
t he source of any probl ems i n desi zi ng. The percent si ze removed shoul d be
det ermi ned and compared wi t h l aborat ory resul t s. The syst emat i c spot t est
anal ysi s shoul d al so be conduct ed. Fabri c si zed wi th PVA i s spotted wi th
an i odi ne/ bori c aci d sol ut i on whi l e f abri c si zed wi t h CMC i s spot t ed wi t h a
f erri c chl ori de/ pot assi um t hi ocyanat e sol ut i on f ol l owed by a pot assi um
f errocyani de s ol ut i on [ 7] .
An al t ernat i ve desi ze procedure i s oxi dat i ve desi zi ng wi t h peroxi des.
The oxi di zi ng agent i s hydrogen peroxi de or i n some cases a combi nati on of
hydrogen peroxi de and potassi um di persul fate, and the process i s done
under hi ghl y al kal i ne condi t i ons. Advant ages of oxi dat i ve desi zi ng
i ncl ude: (1) i t degrades and removes starch, PVA, and CMC so the type of
si ze on t he f abri c or si ze bl ends do not af f ect t he procedure, ( 2) some
scouri ng and bl eachi ng act i on are al so obt ai ned, and ( 3) i n some cases t he
scouri ng process can actual l y be combi ned wi th desi zi ng. Disadvantages
i ncl ude t he hi gh ri s k of degradat i on of cot t on res ul t i ng i n s t rengt h l os s ,
oxycel l ul ose f ormat i on, and pos s i bl e s t rengt h l os s of pol yes t er i n
pol yest er/ cot t on bl ends. The t ypi cal desi ze procedure i nvol ves t he
f ol l owi ng st eps:
1. Sat urat e t he f abri c wi t h t he f ol l owi ng desi ze sol ut i on at 140F:
0. 06 g/ l Magnesi um sul f at e
3. 0 g/ l Di et hyl enet ri ami nepent aacet i c aci d ( 40%) , DTPA
40. 0 g/ l Sodi um Hydroxi de
5 . 0 g / l We t t i ng a g e nt ( no ni o ni c )
4. 0 g/ l Hydr oge n pe r oxi de
2. St eam f or l 0- 15 mi nut es at 212F
3. Thorough washi ng at 180F or above
Thi s procedure i s reported to produce more uni forml y desi zed fabri cs due
t o t he hi gh s ol ubi l i t y of t he s i zes i n al kal i ne peroxi de s ol ut i on [ 9] .
Scourinq
Thi s process removes wat er i nsol ubl e mat eri al s such as oi l s, f at s,
and waxes f rom t ext i l e f i bers. These i mpuri t i es coat f i bers and i nhi bi t
rapi d wet t i ng, absorbancy and absorpt i on of dye and chemi cal sol ut i ons. In
addi t i on t he scouri ng process sof t ens and swel l s mot es whi ch f aci l i t at es
t hei r dest ruct i on duri ng bl eachi ng. Oi l s and fats are removed by saponi -.
f i cat i on wi t h hot sodi um hydroxi de sol ut i on. Thi s process breaks t he
compounds down into water soluble glycerol and soaps and is the same
process tradi ti onal l y used i n the home to make soaps from ani mal fat.
Unsaponi fi abl e materi al s such as waxes and di rt are removed by emul si fi ca-
t i on. Thi s process requi res t he use of surf act ant s t o di sperse t he wat er
10
i nsol ubl e mat eri al i nt o f i ne dropl et s or part i cl es i n t he aqueous medi um.
Bot h of t hese processes ( saponi f i cat i on and emul si f i cat i on) t ake pl ace i n
t he t ypi cal scouri ng process.
The t ypi cal scouri ng process i nvol ves t he f ol l owi ng st eps:
1. Sat urat e t he f abri c wi t h t he f ol l owi ng sol ut i on at 180F:
0 . l - 0 . 2 % Sur f a c t a nt
0. 3- 0. 5% Se que s t e r i ng age nt
4. 0% Sodi um hydroxi de
2. Steaming
it:
60-90 minutes at 212F in J-box
20-30 minutes at 212F in open-width steamer
3 . Thorough washing at 180F
In scouri ng pol yester/ cotton bl ends, the sodi um hydroxi de concentrati on
shoul d be reduced to 2. 0% to prevent al kal i ne hydrol ysi s of the pol yester.
The choi ce of auxi l i ari es ( surf act ant and chel at i ng agent ) i s cruci al
t o obt ai n a compl et e and t horough scour. The surf act ant emul si f i es
unsaponi f i abl e mat eri al s and i s especi al l y i mport ant i n scouri ng pol yest er-
/ cot t on bl ends si nce t he sodi um hydroxi de concent rat i on i s l ower. Noni oni c
surf act ant s are general l y pref erred over ani oni cs because t hey are excel -
l ent emul s i f i ers . Care shoul d be t aken i n sel ect i ng a noni oni c surf act ant ,
however, because of t he i nverse ef f ect of t emperat ure on t he sol ubi l i t y
of noni oni c surf act ant s. If the process temperature i s above the cl oud
poi nt of t he surf act ant , t he surf act ant wi l l be i nef f ect i ve and may
act ual l y be deposi t ed on t he subst rat e. Best emul si f i cat i on of i mpuri t i es
by noni oni cs occurs at a temperature just bel ow the cl oud poi nt, so the the
surfactant used shoul d have a cl oud poi nt temperature just above the
operat i ng t emperat ure t o be most ef f ect i ve. The presence of al kal i or
el ect rol yt es i n t he bat h wi l l - l ower t he cl oud poi nt of noni oni c surf act -
ant s, and t he degree t o whi ch i t i s l owered i ncreases wi t h concent rat i on.
The cl oud poi nt shoul d therefore be checked under use condi ti ons to ensure
t hat t he s urf act ant i s ef f ect i ve under t hos e condi t i ons .
There are techni ques for reduci ng or compl etel y el i mi nati ng the
adverse ef f ect of t emperat ure on noni oni c surf act ant s. Noni oni c/ ani oni c
bl ends whi ch are commerci al l y sol d do not exhi bi t a cl oud poi nt. The same
effect can be obtai ned by si mpl y addi ng an ani onIc surfactant to the scour
bat h i n addi t i on t o t he noni oni c surf act ant . Crypt o- noni oni c surf act ant s
do not exhi bi t a cl oud poi nt . These are noni oni c surf act ant s t hat are
capped wi t h an i oni c group, and t hey exhi bi t t he excel l ent emul si f yi ng
propert i es of noni oni cs al ong wi t h t he good sol ubi l t y propert i es of
ani oni cs . If ani oni c surf act ant s are pref erred f or scouri ng, t he phosphat e
ester types are general l y recommended.
11
Sequest eri ng agent s t i e up pol yval ent cat i ons such as cal ci um and
magnesi um i n water and i n fi bers whi ch prevents the preci pi tati on of soaps.
Al though soaps are no l onger used i n scouri ng, they are formed by the
s aponi f i cat i on react i on. I f pol yval ent cat i ons are pres ent , i ns ol ubl e
soaps wi l l f orm, set t l e on t he f abri c, and produce resi st spot s. There
are four major types of sequesteri ng agents to choose from, i norgani c
pol yphosphates, ami nocarboxyl i c aci ds, organophosphoni c aci ds, and hydroxy-
carboxyl i c aci ds. The i norgani c pol yphosphates such as sodi um tri pol yphos-
phate and sodi um hexametaphosphate are probabl y the best overal l i n that i n
addi t i on t o sequest eri ng most met al s t hey al so ai d i n cl eansi ng t he f i bers.
They may, however, hydrol yze at hi gh temperature and l oose thei r effecti ve-
nes s . The ami nocarboxyl i c aci d types such as ethyl enedi ami netetraaceti c
aci d (EDTA) are very good i n that they sequester most metal i ons and are
very st abl e under al kal i ne condi t i ons. They are t he most used t ypes. The
organophosphoni c aci d types such as ethyl enedi ami netetra(methyl ene phos-
phoni c aci d) are al so very ef f ect i ve but comparat i vel y expensi ve. The
hydroxycarboxyl i c aci ds ( oxal at es , ci t rat es , et c. ) are excel l ent f or
sequesteri ng i ron but not effecti ve for cal ci um and magnesi um.
Af t er scouri ng, t he f abri c shoul d be checked f or t horoughness of
scouri ng. Usi ng a cl ean eyedropper pl ace a drop of water on the fabri c
and measure t he t i me requi red f or t he specul ar ref l ect ance of t he drop t o
di sappear. The fabri c shoul d wet i n l ess than 5 seconds and preferabl y
i n l ess t han 3 seconds. AATCC Test Method 79-1986, "Absorbency of Bleached
Text i l es" [ 2] p. 1143 i s a more preci se met hod of conduct i ng t hi s t est .
Agai n t est i ng shoul d be done syst emat i cal l y, checki ng t he f abri c f rom
s i de- - cent er- - s i de at di f f erent poi nt s al ong t he l engt h of t he f abri c and
eval uat ed as f ol l ows:
a . If al l t he wat er drops wet t he f abri c i n l ess t han f i ve seconds,
the fabri c has been adequatel y and uni forml y scoured.
b. I f t he wet t i ng t i me f or al l t he drops i s great er t han f i ve
seconds, t he f abri c has not been adequat el y scoured. The f ol l ow-
i ng factors can l ead to i ncompl ete scouri ng and shoul d be care-
f u l l y c h e c k e d :
- - Process vari abl es
Temperature of saturation (18OF)
Wet pick-up (100%)
Time and temperature in steamer
Wash water temperature (above 180F)
--Proper bath preparati on and chemi cal concentrati ons
- - Compat i bi l i t y and ef f ect i veness of surf act ant under act ual use
condi t i ons
C. If t he wet t i ng t i me i s not uni f orm f rom si de- - cent er- - si de but
uni f orm al ong t he l engt h of t he f abri c, t hen t he pad pressure i s
n o t u n i f o r m a c r o s s t h e wi d t h o f t h e p a d .
I
12
d. If t he wet t i ng t i me i s not uni f orm al ong t he l engt h of t he
f abri c, t he bat h s houl d be t i t rat ed peri odi cal l y f or al kal i
cont ent . Vari ati ons i n chemi cal feed rates or uneven moi sture
content in goods coming from the desize washer may also produce
t hi s t ype of nonuni f ormi t y.
e . If t here i s no uni f orm pat t ern i n t he wet t i ng t i mes, t he f ol l owi ng
factors shoul d be checked:
- - St abi l i t y of surf act ant ( cl oud poi nt above bat h t emperat ure)
- - Wat er hardness ( ef f ect i veness of sequest eri ng agent )
- - Feed of chemi cal s i nt o sat urat or ( evenl y di st ri but ed and no
gel l i ng of s urf act ant )
--Condensati on or water spots on fabri c
- - Uni f ormi t y and ef f ect i veness of washi ng
--Improper defoamer use or i ncompl ete desi zi ng
Thi s systemati c checki ng of the scoured fabri c narrows the source of
probl ems and shoul d si mpl i f y t hei r det ect i on.
An al t ernat i ve t o aqueous scouri ng i s sol vent scouri ng. Thi s process
uses organi c sol vent s such as perchl oroet hyl ene and t ri chl oroet hyl ene as a
scouring medium instead of water. The oi l s, f at s, and waxes on f i bers are
eas i l y s ol ubi l i zed i n t he s ol vent . This process does not produce any
fiber damage, has l ow energy requi rements, and i s excel l ent for removi ng
oi l y i mpuri t i es f rom wool and synt het i cs. It , however, does requi re
speci al equi pment, expensi ve sol vents, and frequentl y produces hazardous
wast e mat eri al s. Al so, i t does not swel l and sof t en mot es i n cot t on f i bers
and t hus does not f aci l i t at e t hei r removal i n bl eachi ng. Emul si f i ed
sol vents may al so be added to-aqueous baths to ai d i n removal of oi l y
i mpuri t i es f rom f i bers.
Bl eachi ng
The bl eachi ng process dest roys col or i mpuri t i es i n f i bers produci ng a
whi t e subst rat e whi ch i s ( i n t he case of cot t on) al so f ree f rom mot es.
Thi s i s usual l y accompl i shed by t reat i ng t he f i bers wi t h oxi di zi ng agent s
whi ch oxi di ze t he col or i mpuri t i es t o col orl ess compounds. Oxi di zi ng
agent s, however, can al so oxi di ze f i bers ( part i cul arl y cot t on) l eadi ng t o a
reduct i on i n f i ber st rengt h. Condi ti ons duri ng bl eachi ng must therefore
be caref ul l y cont rol l ed t o maxi mi ze dest ruct i on of t he col or i mpuri t i es
but minimize fiber degradation. Hydrogen peroxide, sodium hypochlorite,
and sodium chlorite are the most common bleaching agents. Hydrogen
peroxi de i s by far the major one today as i t i s used to bl each at l east 90%
of al l cot t on and cot t on bl ends . Thi s di scussi on wi l l t heref ore be
l i mi ted to bl eachi ng wi th hydrogen peroxi de.
13
Neut ral hydrogen peroxi de i s not an ef f ect i ve bl eachi ng agent . I t
must be acti vated by addi ng al kal i to i ncrease pH and generate the perhy-
droxyl i on whi ch i s t he act i ve s peci es i n bl eachi ng. Al kal i ne condi t i ons ,
however, can produce undesi reabl e resul ts such as peroxi de decomposi ti on
and fi ber degradati on. Tabl e 3 shows t he ef f ect of pH i n t he al kal i ne
range on bl eachi ng ef f ect i veness, f i ber degradat i on and peroxi de st abi l i t y
i n bl eachi ng cot t on f i bers. With increasing pH Whiteness Index (WI) as
determined by AATCC Test Method 110-1979 [2, p. 172} increases to a maximum
at a pH of 11. 0 and t hen decreases. Fi ber degradati on as determi ned by
CUEN fluidity (AATCC Test Method 82-1984) [2, p. 116] is at a minimum at a
pH of 9. 0 but t hat obt ai ned at a pH of 10. 1 i s wel l wi t hi n accept abl e
val ues . Above a pH of 11. 0 f i ber degradat i on i s severe. Peroxi de st abi l -
i t y decreases wi t h pH as hydrogen peroxi de i t sel f i s very st abl e, but t he
perhydroxyl i on i s not. The pH range of 10. 2 - 10. 7 i s consi dered opti mum
for bl eachi ng cotton wi th hydrogen peroxi de. Lower pH val ues can l ead to
s i l i c a t e de po s i t i o n due t o de c r e a s i ng s ol ubi l i t y of s odi um s i l i c a t e a s we l l
as l ower whi t eness due t o l ess act i vat i on of t he peroxi de.
Table 3: Effect of pH on Bl eachi ng Effecti veness, Fi ber Degradati on, and
Peroxi de St abi l i t y i n Bl eachi ng Cot t on Fi bers
I n i t i a l
p H
Fi nal
p H
Whiteness
Index
CUEN
Fl ui di t y
% Peroxide
Remaininq
8 . 0 4 . 4 66. 8 5. 48
9 . 0 8 . 7 67. 3 1. 44
10. 1 9 . 9 71. 3 2. 44
11. 0 11. 7 72. 2 7. 29
12. 0 12. 4 69. 5 17. 8
Unbleached 34. 2 0. 96
Formulation:
2. 0 g/ l Hydrogen peroxi de (50%)
5. 0 g/ l Sodi um s i l i cat e ( 42O Be)
0 . 5 g / l Ma g n e s i u m s u l f a t e
Sodium hydroxide (pH)
72. 5
71. 6
63. 3
7 . 0
2 . 0
Time = 60 minutes
Temp = 9oc
14
Sodi um si l i cate and magnesi um sul fate are usual l y added to hydrogen
peroxi de bl each sol ut i ons. The rol e of each i s not compl etel y understood,
but i t i s general l y t hought t hat t he combi nat i on f orms magnesi um si l i cat e
whi ch i n t urn st abi l i zes t he decomposi t i on of peroxi de caused by t race
t rans i t i on met al i ons i n t he f i bers and s ol ut i on. The res ul t s s hown i n
Tabl e 4 i ndi cat e t hat t he maj or rol e of sodi um si l i cat e- i s t hat of ai di ng
i n, perhaps cat al yzi ng, bl eachi ng. The major role of magnesium ions is
t hat of st abi l i zat i on of pH duri ng bl eachi ng. In doi ng so f i ber degrada-
ti on and peroxi de decomposi ti on are reduced. The ability of magnesium ions
to hel p mai ntai n the pH bel ow 11. 0 reduces the formati on of oxycel l ul ose
whi ch occurs under hi ghl y al kal i ne condi ti ons. I t al s o s ubs t ant i al l y
i ncreases the stabi l i ty of hydrogen peroxi de as peroxi de decomposi ti on
i ncreases wi th pH. These resul ts show that magnesi um i ons are as i mportant
i n peroxi de bl each sol ut i ons as sodi um si l i cat e. It may not, however, be
necessary to add magnesi um sul fate to the bl each sol uti on as the quanti ty
present i n f ai rl y hard wat er may be suf f i ci ent . If t he wat er used i s not
hard or has been softened, then magnesi um sul fate shoul d be added.
The ti me, temperature, and concentrati on of compounds i n the bl each
s ol ut i on are al l i nt errel at ed. Hydrogen peroxi de can effecti vel y bl each
cotton at l ow temperatures, but l onger ti mes and hi gher chemi cal concentra-
t i ons are requi red. As the temperature of bl eachi ng i ncreases shorter
ti mes and l ower chemi cal concentrati ons can be empl oyed. Tabl e 5 shows
the rel ati onshi p between ti me, temperature, and chemi cal concentrati on.
Table 4: Effect of Sodium Silicate and Magnesium Sulfate in Bleaching
Cotton with 2.0 g/l Hydrogen Peroxide (50%) for 60 Minutes at
90C.
Compound Added Concent rat i on ( q/ l )
Sodi um si l i cat e 5 . 0 5 . 0
Ma g n e s i u m s u l f a t e 0 . 5 0 . 5
Ini t i al pH 10. 7 10. 7 10. 7
Fi nal pH 11. 2 10. 6 10. 5
Whiteness Index 71. 6 73. 1 67. 6
CUEN Fluidity 3. 10 1. 82 1. 02
% Peroxide Remaining 16. 5 67. 4 68. 8
15
Tabl e 5: Rel ati onshi p between Ti me, Temperature, and Concentrati on of
Chemi cal s i n Peroxi de Bl eachi ng [10]
Time (min. ) 50-60 8- 10
2
12-16(hr)
Temperature (C) 100 100 l OO 15-25
Hydrogen peroxide, 100% (%) 0 . 2 5 - 0 . 5 0 . 5 - 1 . 5 1 . 5 - 2 . 0 2 . 0 - 4 . 0
Sodi um si l i cate (%) 1. 0- 1. 2 1 . 2 - 1 . 5 0 . 8 - 1 . 0 1. 5- 2. 0
Sodium hydroxide (%) 0 . 1 - 0 . 1 5 0 . 2 - 0 . 4 0 . 5 - 0 . 8 1. 0- 1. 5
Al l chemi cal concentrati ons are expressed as percentages based on the
wei ght of dry f abri c.
Af t er bl eachi ng, f abri c shoul d be vi sual l y observed f or mot es and
pi n- hol es . I t shoul d be pract i cal l y f ree of mot es. Inadequat e mot e
removal usual l y resul ts when the pH i s too l ow duri ng bl eachi ng, peroxi de
decomposi ti on duri ng bl eachi ng i s hi gh, or the motes are not adequatel y
sof t ened i n scouri ng. Pi n- hol es are t he res ul t of l ocal i zed f i ber degrada-
ti on by hydrogen peroxi de and i s usual l y catal yzed by metal i ons such as
iron and copper. There are many sources of these metal i ons that shoul d be
checked. They may be present in the water supply. A common source or iron
i s rust from water and steam suppl y l i nes. Rust may al so be present on the
f abri c as a resul t of cont act bet ween wet f abri c and met al . Met al shavi ngs
f rom previ ous processi ng may al so be a source of met al s i n t he f abri c. In
addi t i on, met al i ons are i nherent l y compl exed wi t h t he f i bers, and t he
amount wi l l vary wi th source of fi bers and/ or growi ng condi ti ons.
The whi teness i ndex (WI) of the fabri c shoul d be measured systemati -
cal l y f rom s i de t o cent er t o s i de al ong t he l engt h of t he f abri c. The
WI val ue may vary wi th the i nstrument used for i ts determi nati on, but i n
general should be. between 72 and 80. AATCC Test Method 110-1979, "Reflect-
ance, Bl ue, and Whi t eness of Bl eached Fabri c" [ 2, p. 172] out l i nes t he
procedure for measurement, and acceptabl e standards shoul d be set up by the
bl eacher wi t h hi s i nst rument at i on. Syst emat i c t est i ng agai n wi l l hel p
pi npoi nt causes of i nadequat e bl eachi ng. A uniformly low WI indicates that
one or more of t he process paramet ers i s not correct . Such f act ors as t he
concent rat i on of chemi cal i s t he bl each sol ut i on, pH or al kal i of bl each
sol uti on, percent wet pi ckup, and ti me and temperature of steami ng shoul d
be checked. In addi t i on t he resi dual peroxi de on t he f abri c af t er st eami ng
shoul d al so be checked. It shoul d be at l east 15%. If peroxi de decomposes
too much duri ng steami ng, the fabri c tends to yel l ow under the hi ghl y
al kal i ne condi t i ons . I f res i dual peroxi de i s l ow, s t abi l i zat i on of t he
bl each sol ut i on i n not adequat e. , If t he WI i s not uni f orm, vari at i on i s
pad pressure al ong f abri c, vari at i on i n chemi cal concent rat i on i n t he
sat urat or, or vari at i on i n t emperat ure duri ng st eami ng are usual l y t he
1 6
causes. The peroxi de and al kal i cont ent s of t he bl each sol ut i on shoul d be
checked periodically, AATCC Test Method 102-1985, "Hydrogen Peroxide:
Potassium Permanganate Method," [2, p. 162] and AATCC Test Method 98-1982,
"Al kal i i n Bl each Baths Contai ni ng Hydrogen Peroxi de" [2, p. 153].
Several sampl es of the bl eached fabri c shoul d be dyed wi th a di rect
dye al ong wi th a sampl e known to be properl y bl eached. The sampl es shoul d
be i nspected for resi st marks and compared to the properl y bl eached sampl e
for depth of shade. Li ght dyei ngs or l i ght pat ches or spot s i ndi cat e
ei t her si l i cat e deposi t s or oxycel l ul ose f ormat i on duri ng bl eachi ng.
Si l i cat e deposi t i on can be det ect ed by t he f ormat i on of an i nt ense yel l ow
col or i n a mol ybdi c aci d t est conduct ed on t he ashed f abri c [ 5, p. 62] .
Deposi t i on of si l i cat es on t he f abri c can be caused by several f act ors:
( 1) Improper rat i o of Na20 t o Si 02 i n t he bl each sol ut i on. The rat i o
should be approximately 1 : 1 . ( 2) Low pH duri ng bl eachi ng, si nce sol ubi l -
i t y of sodi um si l i cat e i ncreases wi t h pH i n t he al kal i ne range.
Inadequate ri nsi ng of bl eached fabri c. Sodi um s i l i c at e i s di f f i c ul t t o
compl etel y ri nse from fabri c because the pH decrease wi th ri nsi ng l eads to
decreas ed s ol ubi l i t y of t he s i l i cat e. Pot assi um si l i cat e i s more sol ubl e
t han sodi um si l i cat e and t hus more f ree ri nsi ng. There are report s of t he
use of pot assi um ort hosi l i cat e t o repl ace sodi um si l i cat e and pot assi um
hydroxi de to repl ace sodi um hydroxi de i n bl eachi ng [11].
Oxycel l ul ose i s produced by the oxi dati on of chemi cal groups i n
cot t on f i bers . I n addi t i on t o reduci ng t he dyeabi l i t y of t he f i ber, t hi s
al so causes a reduct i on i n f i ber st rengt h. A vari et y of product s can
result from the oxidation, and some of the damage may not show up until
af t er subsequent al kal i ne t reat ment s such as merceri zat i on. Det ect i on of
oxycel l ul ose i s compl i cat ed by t he f act t hat t here are several di f f erent
types of oxi di zed products and any gi ven test may onl y be speci fi c to one
type of damage. A good di scussi on of t he vari ous t ypes of oxycel l ul ose and
det ai l s of t he t est met hods i s present ed by Garner [ 12] . The al kal i ne
si l ver ni t rat e ( Harri son' s Reagent ) t est i s probabl y most usef ul f or
det ect i ng l ocal i zed oxi dat i ve damage.
AATCC Test Method 82-1984, "Fl ui di t y of Di spersi ons of Cel l ul ose f rom
Bl eached Cotton Cl oth, " [2, p. 116] shoul d al so be conducted to assess the
degree of f i ber degradat i on duri ng bl eachi ng. The CUEN f l ui di t y of
bl eached cotton shoul d be between 0. 9 and 3. 3, and fl ui di ty val ues above
5. 5 i ndi cat e severe f i ber damage. Hi gh f l ui di t y val ues can resul t f rom
the pH bei ng too hi gh, unstabi l i zed peroxi de, metal contami nants i n
sol ut i on or f i bers, or ext reme condi t i ons of t i me t emperat ure or peroxi de
concentrati on. The test shoul d al so be conducted on a sampl e after boi l i ng
in 2.0% sodium hydroxide for 2 hours. A l arge i ncreas e i n f l ui di t y af t er
t he al kal i ne t reat ment i s an i ndi cat i on of oxycel l ul ose damage.
Other tests that shoul d be conducted on the bl eached fabri c i ncl ude:
(1) AATCC Test Method 79-1986, "Absorbency of Bleached Woven Cloth" [2, p.
114]. The f abri c shoul d wet i mmedi at el y wi t h t he specul ar ref l ect ance of
the water drop di sappeari ng i n at most 5 seconds and preferabl y 3 seconds.
(2) AATCC Test Method 97-1982, "Extractable Content of Greige and/or
Prepared Text i l es" [ 2, p. 152] . Tot al ext ract abl es shoul d be l ess t han
17
1.0% with the enzyme, water, and sol vent ext ract abl es each bei ng l ess t hat
0.2%. AATCC Test Method 78-1985, "Ash Content of Bleached Cellulosic
Te xt i l e s " [ 2, p. 113] . The ash content shoul d be l ess than 2. 0%.
\
There are several al t ernat e procedures f or bl eachi ng cot t on wi t h
hydrogen peroxide. These procedures have been devel oped because of the
probl ems caused by si l i cate deposi ti on on fabri c and machi nery, and they
do not i ncorporat e sodi um si l i cat e i n t he bl each bat h. "Si l i cat e- Free"
bl each f ormul at i ons [ l 3] use organi c sequest eri ng agent s t o prevent t he
decomposi t i on of hydrogen peroxi de caused by met al i ons. Di et hyl ene-
tri ami nepentaaceti c aci d (DTPA) i s the most commonl y used sequestrant.
Sodi um hydroxi de provi des t he al kal i ni t y necessary f or peroxi de act i vat i on,
and magnesi um sul fate i s requi red to prevent peroxi de decomposi ti on caused
by i ncreasi ng pH duri ng bl eachi ng. A surfactant i s al so commonl y added to
t he bl each sol ut i on as a di spersant . Other compounds incorporated in
propri et ary st abi l i zers i ncl ude oxal at es and phosphat es. The resul t s
obt ai ned wi t h "si l i cat e- f ree" bl eachi ng have been sat i sf act ory, but t he
cost of t he organi c sequest rant s, compared t o t hat of sodi um si l i cat e, has
l i mi t e d i t s us e .
These non-si l i cate peroxi de bl eachi ng systems are wi del y used on
kni ts i n modern "jet" bl each ranges. Problems commonly encountered in
t hes e operat i ons appear at f i rs t t o be unrel at ed, but es s ent i al l y al l
resul t f rom poor bat h st abi l i t y. These j et bl eachi ng ranges t ypi cal l y
have ei ght to twel ve compartments through whi ch the fabri c i s transported.
Usual l y some of these compartments are used for scouri ng/ bl eachi ng whi l e
others are used for washi ng and, i n produci ng market whi tes, for appl yi ng
t i n t s . When the bath foams, fabri cs bal l on excessi vel y, uneven dwel l ti mes
resul t , and t hi s may l ead t o i nconsi st ent bl eachi ng or shade i f appl yi ng
t i n t . Thi s uneven transport and bal l ooni ng frequentl y resul t from peroxi de
decomposition which produces oxygen. Addi ti on of defoamer can cause
yel l owi ng, s pot t i ng and preci pi t at es i n t he machi ne. The bes t s ol ut i on t o
this problem is to use products which produce minimum foam, use the minimum
amounts of peroxi de requi red to produce the desi red degree of whi teness,
i nsure maxi mum st abi l i t y of t he peroxi de bat h by usi ng a good st abi l i zer,
and removing as much iron, copper, and other metals (which may cause
decompos i t i on) f rom t he wat er pri or t o us e i n bl eachi ng. I t i s al s o
i mport ant t o have accurat e cont rol of al l chemi cal f eeds t o t he bl each
range, es peci al l y t he t i nt . A ti nt whi ch has sl ow, even exhausti on and
good l evel i ng properti es at extremel y l ow add-on l evel s must be chosen.
Aci d dyes are f requent l y used successf ul l y.
An al kal i -free system for bl eachi ng wi th hydrogen peroxi de has been
developed by BASF, and products are marketed by other companies. The
syst em does not requi re al kal i f or peroxi de act i vat i on but i nst ead a
speci al act i vat or i s i ncorporat ed i n a propri et ary compound. The compound
i s t he onl y one added t o t he peroxi de bl each sol ut i on, and bl eachi ng i s
normal l y carri ed out at a pH of 7. 5 for 60-90 mi nutes at 200-212F.
Acceptabl e resul ts have been obtai ned i n bl eachi ng 100% cotton and
pol yest er/ cot t on bl ends wi t h t hi s and ot her al kal i - f ree syst ems.
Merceri zati on
Merceri zati on i s the treatment of cotton under tensi on wi th a strong
sodi um hydroxi de sol uti on. Thi s process i mproves many properti es of
cotton fi bers and may actual l y reduce or el i mi nate some dyei ng probl ems.
Some of the properti es of cotton fi bers that are i mproved by thi s process
i ncl ude abs orpt i vi t y, dyeabi l i t y, t ens i l e s t rengt h, l us t er, and di mens i onal
s t a b i l i t y . The process produces cotton with more uniform properties which
i s parti cul arl y hel pful i n reduci ng some of the dyei ng probl ems caused by
immature cotton. Merceri zati on can be done at any stage duri ng prepara-
t i on- - f rom bef ore desi zi ng t o af t er bl eachi ng. Fewer probl ems are encoun-
tered, however, when merceri zi ng bl eached fabri c.
Merceri zati on i s general l y accompl i shed by paddi ng fabri c through a
st rong sodi um hydroxi de sol ut i on, al l owi ng t i me f or t he al kal i t o penet rat e
and swel l t he cot t on f i bers, f rami ng t o provi de t he t ensi on requi red f or
l uster devel opment, and thorough ri nsi ng to remove the al kal i . The sodi um
hydroxide concentration should be maintained between 25 and 30% (48-54
Tw). Lower concentrati ons wi l l resul t i n a l ower degree of merceri zati on
and l es s l us t er. Hi gher concent rat i ons have no addi t i onal ef f ect . A good
wetti ng agent or penetrant shoul d al so be added to the bath. It shoul d be
stabl e and effecti ve at the hi gh al kal i ne concentrati ons used (AATCC Test
Method 43-1985) [2, p. 98]. Onl y t hose desi gned speci f i cal l y f or merceri -
zati on shoul d be used. The temperature of the bath can affect the degree
of merceri zat i on. Swel l i ng of cotton and thus merceri zati on decreases wi th
i ncreasi ng temperature. The temperature should be maintained between 70
and lOO
o
F. Lower temperatures do not affect the process i f the sodi um
hydroxi de concent rat i on i s i n t he proper range. At l ower concent rat i ons
degree of merceri zat i on wi l l i ncrease as t emperat ure decreases. Lower
degrees of merceri zati on are obtai ned as temperature i ncreases above l OO
o
F.
Wet pi ck- up i n paddi ng can af f ect merceri zat i on i n several ways. Less
swel l i ng wi l l occur at l ow wet pi ck- up l eadi ng t o i ncompl et e merceri zat i on.
The caus t i c s ol ut i on al s o pl as t i ci zes t he f abri c s o t hat i t i s eas i l y
st ret ched. At l ow wet pi ck- ups l ess pl ast i ci zat i on occurs and t he f abri c
may tear duri ng stretchi ng on the frame. Wet pi ck-up shoul d be about 100%.
Af t er paddi ng at l east 30 seconds shoul d be al l owed f or t he caust i c t o
swel l t he cot t on f i bers bef ore t ensi on i s appl i ed on t he f rame. Short er
t i mes wi l l resul t i n i ncompl et e merceri zat i on.
As cot t on f i bers are s wol l en by t he al kal i , t he f abri c s hri nks . To
obtai n l uster and shri nkage control the fabri c must be stretched on a
frame. I t s houl d be s t ret ched i n t he f i l l i ng di rect i on t o i t s grei ge
wi dt h or sl i ght l y more. No st ret chi ng i n t he warp di rect i on i s requi red
unl ess ext reme l ust er i s desi red. If warp st ret chi ng i s requi red, t he
frame speed should not exceed the padder speed by more than 5 percent.
Removal of causti c from the fabri c i s very cruci al for the devel opment
of l ust er and shri nkage cont rol . The caust i c sol ut i on concent rat i on i n
t he f abri c ( not t he ri nse sol ut i on) shoul d be reduced t o l ess t han 5% wi t h
t he f abri c s t i l l on t he f rame. If not , l ow l ust er and shri nkage of t he
f abri c wi l l occur. If t he f abri c shri nks as i t comes of f t he f rame, t he
19
caust i c concent rat i on i n t he f abri c has not been reduced suf f i ci ent l y.
Af t er t he f abri c comes of f t he f rame t he remai ni ng caust i c shoul d be
thoroughl y ri nsed out. I t i s di f f i cul t t o remove t he res i dual amount s of
caust i c f rom t he f abri c by ri nsi ng al one,
so resi dual amount s are usual l y
neut ral i zed wi t h a di l ut e aci d s ol ut i on. Care shoul d be taken i n usi ng
aceti c aci d for neutral i zati on as some of the sodi um acetate formed may
remai n i n the fabri c and al ter the pH of the subsequent process.
The merceri zed fabri c can be anal yzed for degree of merceri zati on,
AATCC Test Method 89-1985, "Merceri zat i on i n Cot t on" [ 2, p. 127] . The
Bari um Number obtai ned from thi s test shoul d be at l east 130 and preferabl e
150. Low numbers-resul t from i ncompl ete swel l i ng of cotton fi bers whi ch
can be caused by f act ors previ ousl y di scussed. The t est shoul d be con-
duct ed at di f f erent poi nt s al ong t he l engt h of t he f abri c. Decreas i ng
Bari um Numbers al ong the l ength i ndi cates that the bath concentrati on i s
decreasi ng or t hat t he bat h t emperat ure i s i ncreasi ng. Bot h of t hese
condi t i ons can resul t i n merceri zi ng wet f abri c. Not onl y can the bath
become di l uted, but the reacti on between causti c and water generates heat
which may increase the bath temperature. When mercerizing wet fabric, the
t i me al l owed f or swel l i ng of t he f i bers must al so be i ncreased.
The test for determining Barium Numbers is long and tedious. A quick
t est f or anal yzi ng f or t he degree of merceri zat i on i s t o dye sampl es of t he
merceri zed fabri c al ong wi th a sampl e known to be properl y merceri zed usi ng
a di rect dye such as C. I. Di rect Bl ue 80. Any di f f erences i n t he dept h of
t he dyei ngs are i ndi cat i ve of di f f erent - degrees of merceri zat i on. A red or
bl ue dye s houl d be us ed s i nce i t i s eas i er t o vi s ual l y obs erve di f f erences
i n dept hs of t hese col ors.
There i s no st andard t est f or anal ysi s of t he l ust er of merceri zed
f abri c. It must be j udged vi sual l y. Many f act ors can resul t i n t he f abri c
havi ng l ow l ust er. They i ncl ude l ow caust i c concent rat i on i n t he merceri -
zi ng bath, bath temperature too hi gh, l ow wet pi ck-up, i nadequate ti me for
s wel l i ng t he f i bers , i nadequate stretchi ng on the frame, or too must
caust i c i n t he f abri c as i t comes of f t he f rame.
Summary
It i s i mpossi bl e t o di scuss al l t he probl ems al ong wi t h possi bl e
causes t hat can occur i n t he preparat i on processes. The approach taken
here i s to prevent many probl ems before they occur and to detect probl ems
bef ore l arge quant i t i es of i nf eri or qual i t y goods are produced. Anal ys i s
of raw materi al s such as the fabri c, water, and chemi cal s for contami nants
or act i vi t y provi des essent i al i nf ormat i on on t he t ypes and amount s of
i mpuri ti es that must be removed and any changes i n process condi ti ons that
may be necessary, i mpuri t i es t hat may i nt erf ere wi t h t he process, and t he
actual concentrati on of acti ve chemi cal s whi ch may vary due to decomposi -
t i on or i mproper di l ut i on by t he manuf act urer. The t echni cal aspect s
presented for each process al ong wi th the systemati c approach to i n-process
anal ysi s provi des a basi s f or det ect i ng and pi npoi nt i ng t he cause of
probl ems duri ng t he proces s s o t hat l arge quant i t i es of i nf eri or qual i t y
20
goods are not produced and possibly dyed. Although most of the procedures
di scussed are f or cont i nuous preparat i on of cot t on and pol yest er/ cot t on
bl ends, the pri nci pl es and systemati c approach to anal ysi s can be appl i ed
to other fi bers and batch processes wi th some modi fi cati ons.
1.
2.
3.
4.
5.
6.
7.
8.
9.
References
Gruni g, P. , " Pretreatment of Cel l ul osi c Fi bre Fabri cs: More Than a
Necessi t y, " Colouraqe, July 29, 1982, pp 3-11.
Techni cal Manual of the Ameri can Associ ati on of Texti l e Chemi sts and
Col ori sts, Ameri can Associ ati on of Texti l e Chemi sts and Col ori sts,
Research Triangle Park, NC, 62 (1987).
Garner, W., Texti l e Laboratory Manual , Vol . 3, Deterqents, El sevi er
Publishing Co., New York, 1967.
Schumb, W. C. et al. , Hydroqen Peroxide, Reinhold Publishing Corp., New
York, 1955, pp. 553-559.
Interox, A Bleachers Handbook, Interox America, Houston, TX, 1980.
Schonf el dt , N. , Surface Active Ethylene Oxide Adducts, Pergamon Press,
N. Y. , 1969, pp. 695-697.
Li vengood, Charl es D. , Spot Tes t s f or I dent i f i cat i on of War p Si zes on
Fabri c, Text i l e Indust ri es, Sept . , 1983, pp. 114, 116.
"Industri al Enzymes Battl i ng to Remai n Speci al ti es, " Chemi cal &
Engi neeri ns News, Sept. 15, 1986, pp. 11-14.
FMC Corporation, Desi zi ng wi th Hydrogen Peroxi de, Techni cal Bul l eti n
No. 44, FMC Corporation, Philadelphia, PA.
10. Ki bbel , Wi l l i am H. , Preparati on and Bl eachi ng of Cel l ul osi cs and
Blends, FMC Corporation, Philadelphia, PA.
11. Dalmas, Edward A., Method of Bl eachi ng Texti l e Materi al s, U. S. Patent
4, 337, 060, 1982.
12. Garner, W. Texti l e Laboratory Manual , Vo1. 5, Fi bers, El sevi er Publ i sh-
i ng Co. N. Y. , 1967.
13. Kowal ski , Xavi er, "Sequest eri ng Agent s i n Si l i cat e- Free Peroxi de
Bl eachi ng, " Text i l e Chemi st s and Col ori st s, August , 1978, pp. 32- 36.