— More than a Complex? NAR Alat, of Sarex Overseas, India, a processors must consider eee srs ees Cao Cee an Cee ena Cea nae SO Oe cee Cm quality of ground water is not always as oe oer eres Se eee SO ee eo using a water softening plant, which can Pe ees Cee eens Se ee ed Cec can ae Coan) CS eee eae cree?Wet Processing Even through water is softened, unwanted metal salts ean creep in trom one oF more sources, as mentioned below: 4) Basle raw material - Mineral cont Cotton, which varies from region region, or higher iron content of raw water. ) Metal contamination during storage and transport of other ingreients such as Mild Steel drums used for dyes and chemicals, Basie chemical Ike caustic Iye being transported in Mild Steel tankers of MS drums. ©) Poor quality of piping used for water from the softening plant to the dye house. 4) Rust during spinning, weaving or hanating of the substrate ©) Iron contamination trom machine parts such as joints, bolts ete, which are made from norespeciied material Thus, even if soft water Is used for processing, some problems due to metal impurities can crop up unexpected, leaving to value loss or reprocessing and putting pressure on thin margins Let us review situations where metal Impurities can create problem. 41, In the scouring of cotton, particularly package yarn and tery towel, the presence of caleium and magnesium leads to insoluble salt deposition on the substrate, leading to harsh feel and/or resist marks, Also, scale formation on continuous bleaching ranges anc package dyeing machines could take place due to presence of calcium. 2, In the bleaching of cotton with peroxide, pinhole marks in fabric and nsiery, lower tensile stengt in the case of yarn, and oor spinnabilty of bleached cotton fre are the result of iron and copper impurities. Sometimes, pinhole marks may not be seen but DP values would be lower, though whiteness remains the same. Also, the presence of calcium can rapidly decompose hydrogen peroxie 3, In reactive dyeing, precipitation of ‘yestulf could take place due to the presence of ealelum, leading to dye spots ‘and poor colour yield, and affecting reproductilty 4, In washing off of reactive dyestuffs, poor Wash fastness and wet ub fastness result from the presence of calcium. 5, Inthe case vat and sulphur dyes also, the presence of caleium reduces Tastness aroperties. 6, Inthe case of disperse dyes, the presence ‘of ealeium may lead to agglomeration ‘due to the formation of calcium salt, with anionte dispersing agent present in commercial disperse dyes. 7. Certain arthraguinone disperse dyes, blues, reds pinks and red violets, form a complex with Cue, Fe, NI, Co® present in races. The blue dyes precipitate and ather dyes change tone to ‘a dull, bluish shade. 8. In dyeing wool with chrome dyes, premature precipitation before chroming ‘ould take place and lead to poor rubbing fastness 8, Ditect dyes, which are used in a fow markets, ean also lead to precipitation in the presence of Cr", N*, Cu, Co™ if the dyestutf has specific groups in its structure ‘Thus, unwanted metal salts cause a lat of problems in processing. Now, with the focus fon minimising costs and maximising efficiency, consistency and fastness are two Important parameters that every dyer would like to achieve first time. This reduces reprocessing costs, making him compatitve. The dyer has to use a suitable sequestering ‘agent in the process, wherever i is required. Selection ofthe right sequestering agent fs very Imaortant. Fest and foremost, the sequestering ‘agent should chelate offending metal ons Under the glven condition and should form a stable complex, which does not decompose cover a prolonged processing period ‘Selective chelation is also critical For ‘example, n peroxide bleaching of cotton, calelum and iron has to be complexed, but not magnesium, since magnesium ions act as a stabiliser for peroxide. Ifthe chelating agent chelates magnesium also, ten the allon of magresium chloride is advisable, to stabilise the bath, Another example is the desizng af cotton fabric bythe enzymatic padbatch ot padsteamn method. Many customers try to remove iron impurties during desizing, to avoid pinhole rmaras during subsequent scouring/bleaching. A sequestering agent added during desizing should preferentially chelate iron and not calcium, as calcium acts as a stablser for enzymes. In dyeing with metalised reactive or dict {yes containing metal ons, the sequestering ‘agent should not demetalse the dyes, i. remove metal ions from dye molecules, which will lad to shade change. Lotus review the chemistry of various types of sequestering agents and the concitions Under which these are most effective. ‘Sequestering agents work by a mechanism of complex formation, also termed chelation. he sequestering/chelating agent has grouns al approprate locations in the molecule to form fone or more chelate rings with the metal ion ‘The complex thus formed remains soluble as ell as stable under given conditions. These Reprinted from INTERNATIONAL DYER, JUNE 2004 Figure 1 EDTA calcium complex 9 9 i ll ¢ /\ oH nad O. ‘ovat Ne, 04-1 Ne cH, CH ONar \7 wy ll ll 3 0 Figure 3 Nitrilo triacetic acid sodium salt (NTA) 9 l Nag fe None fo—cHy—N y ‘Hey oat e \ aN ‘e I 0 Figure 4 Diethylene triaminepentaacetic acid sodium salt (DTPA) i i hi aN Nad Cay pie ote Nosh Nat: A 4, coi the phe che—¢—oe tly os a es ll ° Il e 0 Figure § 1 - Hydroxy ethylidene- 1,1 ~ diphosphonic acid (HEDP) PO, ch, —¢—on POH,Wet Processing chemicals usually contain nitrogen, such as amines and substivted amines, and oxygen in ‘the form of carboxyl, phosphate or hycrxy groups. (see Figure 1) The three main types of commercial sequestering agents are: (© Aminocarboxylle acid based products ‘© Phosphates & Phosphonates © Hycrony carboxyates © Povyacryiates © Sugar acrylates Aminolycarboxylates In aminopotearbowlates, Figures 2 t0 4) tis ‘assumed that one molecule of sequestering agent complexes with one ion of metal Depending upon the pH ofthe medium, Le, acidic, neutral or alkaline, the preferential sequestering order for each product could change. For exemple, NTA has shawn the following preferential sequence at cfferert pi. Jeu +2 Ca [NTA Neal een = Cu" > Fe» 2 > Gn > Me™ ‘ka rnc = "> 205 00" Me ‘Some ofthe characterises of some of these sequestering agents are summarised as below. * EDTA Good sequestering agent for caeium and magnesium at akaline pH but no sequestering action on Fe™ at alkaline pH Not stable with oxidising agents. Low ‘Solubility in acidic medium. © NTA~ Sequestring of Fe" only at aie pH but sequestering of Cu between pH 3 to 112. Low solubility in acidic medium. Not Stable with oxidising agents, * DIPA~ Good sequestering action on Fe" under alkaline pH but complexes with alkaline earth sats are less stable than EDIA, Slignty more resistant to oxidising agents. Low solubilty in ace medium. Phosphates & Phosphonates These sequestering agents are divided in two broad classes: «© Inorganic polyphosphates such as sodium hhexameta phosphate (SHMP), sodium polyahosphate, sadium tiolyphosphate, sodium trmeta phosphate, sodium pyrophosphates ‘© Phosphonated aminopolearborates such ‘as EDIMP, DETMP, ATMP, HEDP, OTP Inorganie phosphates work under specific conditions and work as sequestering agents by comerting troublesome metal ions into water soluble complexes by a process of ion exchange, Na, No,P0,) +2634 —3 Na, C9, P90.) +8" HME But such complexes are not stable under high temperature and break down to simple phosphates, which cannot retain metal ons in ‘complex form. For example, a complex of calcium, SHMP, which Is shown here, is transformed to insoluble calcium corthephosphate on prolonged boiling, Phosphates of aminopaljcarbonyic acids or phosphonates are derivates of phospnorous ‘acid (H,P0,) and are characterised by a CP boone, which has stronger hydroytic stabiliy than the PAP bond of polyphosohates, This ‘ype of sequestering agent has emerged as mor class of sequestering agent, since these possess more features than mere chelation These characteristics are ‘© Threshold effect, ie. inhibition of precipitation of Caco, CaSO, with Substoichiomevic quantities of inhibitor © Corrosion inhibition (© Resistance to hydrolysis, © Deftacculation, ie. stailly effect on colloidal suspensions ‘The structures of the important commercial products are shown in Figures 5 t 7. Compared {to popular amino polyearboxlic acle-based sequestering agers, these phosohonateased ‘sequestering agents nave a high chelation rato, Table 2, shown above, gues a comparison ofthe chelation value as expressed in mg of CaCO,/ ‘gm of 100% sequestering agent in acid form, ‘ard chelation rato as moles of CaCO, chelated per mole of sequestering agent at pH12. Apart from better chelation value or better elation ratio, these phosphonates also have ‘etter iron chelation than EDTA and NTA. Hydroxy carboxylic acids Organi compounds that nae several hore poups oten have the propery of preventing pretation Band talent neal colons ran afaline medum, Some lth wettnew pet Os exten ae: Cie Trae at, Gone eld and cate acd shown in gre 801 Theta ae is portant equestrng ert, compared to sminocafbonfe sls or phosphonates. Gluconic acid/sodium fuconate he been ound oe an eect Chetan ager for on nde! aka condi. Polyacrylates Polacrylates are effective dispersants, with rill chelation values and protective colloid properties. The chelation values of polyacrylates have no demetalising effect on imetalcontaining dyestuffs. They are completely nontoaming (see Furs 12) Figure 6 Aminotrimethylenephosphonic id (ATMP) cH, — POH, nZ cH, —Poy \ oy ro Figure 7 Diethylene triaminepentamethylene phosphonic acid (OTPMP) Post ose, oh Gi, POsH, N—CH,=cHN-Ch=CihyH H.0yP-cH,7 \ CH, —P0,H, Figure 8 Citric acid wo fatte. ld it \ 4H On ROH OH Figure 11 Oxalc acid & ° \ 4 / \, Wé tH Reprinted from INTERNATIONAL DYER, JUNE 2004Wet Processing Kind Attn, Mistri Madam Figure 12 Polyacrylate Wa Figure 13 Gluconate ap No/ k—t—on Hot — H—f—on oT) on0H Figure 14 Citrate ‘They are very suitable as dyebath conditioners, soaping agents and washing aids, Being non surface-active agents they are easily rinsable and thus reduce the quantity of water required for removing tel traces fram the substrates, untae all surfactants, The ‘ypical chelation values offered by polyacrylates do not come close to the chelation values offered by amino polycarboxylates or the phosphonates. This problem has been ‘overcome by development of Sugar Acrylate. Sugar Acrylates ‘Sugar Acrylates have sequestering values as high as amino polyearboryates or the phosphonates. They are biodegradable, etfective components in cellosic fabric pretreatment curing desizing, scouring, bleaching and mercerising, These products are characterised by good chelation values fom the acidic to the alkaline range and trom temper- atures of 45 to 1158. They also exhiit no demetalising effect on metalcontaining vestutfs and are non foaming. They are ideally Fecommended in pretreatment for desing, ‘scouring and bleaching and as dyebath coriitioners during the cellulosic dyeing. Factors to be taken into consideration while selecting a sequestering agent for the process 4. Stabity constant As chelation is @ reversible reaction, the equllum is pendent onthe process pH and the concen tration of the metal ions an chelating agen, whieh react together to form a chelate, The stably of te metal complex is expressed in terms of ts stably constant we represent éhelation of metal ion, M™witn sequestering agent, AP, as: MP + A MA then the stability constant is Mam KS= eTT AAhigh value of Ks indicates high sequestering effect. For example, in the case of aminopolyear borates, the stably constant for same metal iron increases inthe order NTA < EDTA < DTPA In the case of metal lons, the stability constant increases inthe order. From the above information i ean be deduced that the NTAIMg® complex has the least stability, whereas OTPA Fe” has the highest stably: Thus, ina process, if more than one ‘metal ion is present, the metal ion having the highest stably wil be chelated preferential I ‘elating agent's present in sufficient quantity, the metal witn te highest stably constant wil be chelated completely, followed by the next ‘metal ion, in he order given above. Even after chelation is complete inthis order, addtional metal impurty, with metal having a higher stably constant, is introduced, then tis metal Jon wil d'splace low-stabiliy-constant metal ons from the complex. For example, Fe displaces Ca from a Ca®— chelating agent complex Ofcourse, the chelating agent should be capable of chelating Fo under given conditions, 2, The pl of the process - the pH of the system wil influence the formation of the chelation complex. For example, NTA, EDTA ‘cannot chelate Fe under alkaline conditions, whereas DTPA ean. HEDP can chelate Fo up to pH 12, and so also sluconie acta 3, Demetalisation — This property is particularly Important for dyeing and printing with premetalised dyes ~ for example, some direct, reactive and premetalised metal complex des. INE, Cu®, CP", CoP o is resent in prometalised dyes, these could be preferential chelated abead of Ca® and Me, due to the higher stability constant of these metal ions. Therefore pretrials in the Foprinted from INTERNATIONAL DYER, JUNE 2004 lab are required to estabish the suitably of the chelating agent, and also to arrve atthe ‘optimum concertvation fr the given process, wien premetalised dyes are to be used. 4, Other features ~ stabiliy of chelate to prolonged process periods, dispersing properties, crystalgrowth inhibition, effect fon equipment, ete ~ are also to be considered when selecting a commercial sequestering agent, ‘Thus, detning the requirement ofa chelating ‘agent and screening the avaliable products in the lab can avoid many unpleasant surprises or accidents in processing, Understanding these fundamentals, we at ‘SarexSupertex have developed a number of formations for texte processing, which are deserved briefly here. 41, Saraquest 2UD - For chelaton of ron curing desizing, peroxide bleaching and acid demineraising, without affecting ary other parameters. 2, Saraquest AE ~ For chelation of ealelum and iron during peroxide bleaching, for improved stably and whiteness, to produce full whit, 3, Sarakol PS /1583 - For preferential chelation ‘of calcium in reactive dyeing and reactive ashing off, to improve consistency of eyeing as well as improve fasiness properties does. not have any demetaising effect on metal 4, Saraquest W —For dheing of reactives where ater harness is more than 200 pom. This product also does not have demetalising effect on metalcontainng dyes when used at the required concentration 5. SarastabilMRS - A bleach bath stabiliser and sequestrant, having the capacity to chelate alkaline earth metals Ca, Mg: and Fe and Cu under highly alkaline conditions.