scribed in AATCC 'lest Method 20-1971 (1), Positive identification of a panicu1ar dye present on a fiber is, in most cases, extremely difficult, if not impossible with our present choice of methods Or equipment. and all practical systems ofidentiflcation are based on. dye classes rather than. on specific members of the class,
A comprehensive ami sophisticated methodology for the identifica-

tion of individual dyes can be found in Venkataraman's text (2). One of nhe earliest of such systems was (hat of Green (3), which a1tlwugh now out of date, is still a useful reference. Gayton {4) pubIished an up-dated version in 1946 and a second ocI!ition In 1963. A very

good discussion of methods for ideiltificanionof dyes 011 the flberis given in \bl.um.e 4 of Gamet'S manual (5) ..Derrett-Smith and. Gray (6) have recently published an. excellent discussion of the identification of va~ dyes on cellulosic materials. This chapter offers a system of identification based on work by the New York Section of the AI~rCC (7) and was published as a preliminary ieport (8) and as a chapter in the Second Edition of Analytical Methodsfora Textile Laboratory, published under the aegis of AAJrCC committee RAn. The schemes of analysis presented here include tests for the identification of she fiber and are based on both <II systematic exclusion of dyes which might be present, and a focusing of attention on a timit.ed number of remaining possibilities. Whenever possible, the slilgges~edprocedures employ laboratory tests and techniques available in practiccSIly all textile laboratories. More elaborate methods of analysis which may possibly be useful in dye identiflcation are discussed in other chapters of this book. There is no doubt that these methods will find increasing use in the future. The identifICation of dyes in blends of fibers is not yet clearly established, bu~ the more (!lIperiencedi analyst will be able to adapt these pro-

cedures to such problems. Dyes On Cellulosic Fibers

Cellutose fibers are .rapidly ~ by even burning, soft, ash, 110 bead and an odor characteristic of burning paper. After the fiber has been identified as cellulosic. then a systematic separation of the dye is necessary to determine which of the following possible classes has been used: direct, acid, basic, dlrect-aftertreated with resins, sulfur, vat, oxidation blacks (anili.ne and cliphenyl) directaftertreated with metals. direct-aftertreated with formaldehyde. naphthols and insoluble azo, diaeotizedand developed. pigments, and fiber reactive. Identification of dye classes on either cotton 0.[ rayon follows the same procedure. Solution-dyed viscose is usually identified by microscopic examination of a fiber cross section.




Group I inctudes direct, add, basleand direct dyes aftertreated with. resins. These dyes are not set apartas a group by any single test, but are
classified by· their bleeding in dilute ammonia or acetic acid provided the extractions are carried out in the prescribed order . .DIREcr DYFS. A 100-300 mg portion of the dyed sample is placed in

a 35 ml test tube, :5 to 10 mlof water and 0.5 to 1 ml of concentrated ammonia are added and the mixture boiled in order to bleed off a sufflcient amount of dye for redyein.g II piece of white cOUOIt cloth,
When a sufficient amount of dye bas bled from (he sample, the

sample is removed, a piece of white cotton cloth weighing IIJ-30 mg is placed in the test tubeand 5 to 30mg of common salt added. After boiling gently for 40-80 sec and coolling to room temperaeure, the cotton is removed, rinsed and examined. Redyeing oncotton in an ammoniacal solution in the presence of salt to a. shade ami strength comparable to the shade andstrength of the
original sample is definite evidence of a direct. dye. ACID Drns. Acid dyes are used very little on cellulosic fibers except for identification or for the dyeing of add dyeable myon .. If the sample in the test for direct dyes bled but left nhe test cotton

white or only slightly stained, the colored extract is neutraJiz:ed with acetic acid, 1 ml of 100/0 acetic acid is addedl. and ~0-.30 mg of white wool is placed in the liquor; After boiling for approximately half a
minute, the woo] is rinsed and examined. Redyeing 0111 wool from anacid bath indicates the presence of acid dyes, provid'ed! the presence of a direet or basic; dye 15 110t shown. BASIC DYES. Basic dyes have been used very little Oil cellulosic fibers in recent years since the advent of fiber reactive colors. They may be used! occasionally to brighten sulfur shades or on low-cost bright shades

with minimum fastness requlremerus. For these Instances, the following tests are suggested. If the dyed sample does not bleed, or bleeds only slightly, in the test fOF direct dye, it should be tested for the presence of a basic dye. A 1000JOO mg sample is placed in a J·S ml test tube, 0.25 to 0.5 ml of glacial acetic acid is added. After warming over a Bunsen burner, 3 W 5
ml of water are added and the mixture is brought to a boil, The sample

is removed, 5 to 20 mg of cationic dyeable acryITc fiber or tannln-mordanted cotton is added and boiling continued for ,60-80 sec. RedyeiJ1lg on acrylic fiber or on tannin~mordanted conon is evidence
of the presence of basic dyes. Confirmatory Test.. If the above bath still coruains color after the redyeing has been made. it am be used for the confirmatory test; other-






wise a fresh gladal acetic acid. extraction must be made. 10 this extract is added! :5to 7 ml of 10Ofo caustic soda solution. The mixture is cooled and 3 to 5 ml of ether added. The mouth of the test tube is closed M.cI tl1e
tube is shaken well. to assure extraction of the basic dye base into tile

ether layer: The mixture is allowed.


added to bring the. top of the ether Part of the ether layer is decanted into a ]0 ml test rube, two to five drops of too/a acetic acid are added and the tube is shaken well, The base of any basic dye will leavethe ether and appeal in the original color in the acetic add. layer. Drazcr DYES AFIERiREATEO WITH RESIN. If the dyed sample failed to bleed or bled bllt slightly when tested for direct dy~ and the test foe the presence of basic dyes was negative. investigate the possibility

separate into layers, and water is layer to the mouth of the test tube.

of resin-aftertreated direct dyes. A tOO no 300 mgsample is placed! ill a 3,:5 test tube, 10-1.:5 of a ml ml
acid is added and boiled for 60 sec'. The the procedure is repeated, followed by a rinse. This treatment removes the resin. If the sample now bleedsfreely in ammonia: waterand responds fully to the test fOf direct dyes, then the original dyeing was a direct dye afterWille solution of hydrochloric

acid is discarded, a fresh portion added,and

treated with resins.

Group D
Grollp U includes dyes which change shade On reduction with alkaline sodium hydroswfite and which revert tc the original shade cnreoxidation by air: sulfur dyes, vat dyes, aniline and diphenyl blacks. All samples should be tested for Group ,Ibefore testing for Group 1[, Preliminary Test. A 50 to 100 :mg sample Is placed in a test tube, 3 to 6 ml of water and 1 to 2 ml of 10000o sodium hydroxide are added. and themixture raised to the boil. Then 10-30 mg of sodium hydrosWfite are added! and. boiling cOIltinued for 2 to 5 soc. M dyes in this group change shade mdicalJiy, with the exception of the Indanthrene blues which bleed profusely when the sodium hydrostilfite is added and bleed onlysli,ghLly Of not at aU during the caustic soda treatmenr, The color of the Ieuco compound! of these lndanthfoene dyes Is blue, differing only slightly in shade from the fillly oxidized dye. 'The sample is removed and placed on flher paper. All dyes belonging to this group will rooxidize in air to Ute original shade within 5 to 6rnin. Confirmatory "TestFor Indont'lrrene Blues. A lA·inch square of the cloth sample is placed on several layers of fIIlter paper, weaedwith one or two drops of concentrated nitric acid. and the color observed. If the sample turns yeUow or green, me sample is blotted with filt.er paper. If

Ole 'blot is yeUow in color, this blot is touched with a few drops of a re-



duction solution, consisting of equal pam by weight of stannous chlor-

ide, concentrated hydrochloric acid and waw; The blue color of the
original Indanthrene blue will be restored. SULFUR DYES. A 100 to .300 mg dyed! sample is placed in a .3.5mI test tube Md to it are added 2 to 3 m1 of water, 1 to 2 ml of mOlil, sodium carbonate solution and 200400 mg of sodium sulfide chips, The mixture is raised to the boil anti boiled 1 to 2. minutes. The sample is, removed, and to the test tube ate added 25-50 mg of white conon and 10-20 mg of common salt. After boiiling for I to 2 min, the cotton sample is removed and placed Gill filter paper and allowed to reoxldlze. Underthese renditions sulfur dyesrJ;!dyecotton in a shade wlijch differs from the original only in strength. A few, easily reducible vat dyes will color die white cotton, but in a shade markedly wfferent from that 'of the original dyeing, Confirmatory Tesr For Sulfur Dyes. A 100-1S0 mg portion of the origins] sample is boiled in 5 ml of 100]0sodium hydroxide,rinsed well, and placed in a IS ml tesr tube. Thit IS added 2 to 3 ml of the reduction solution described under the COnfU1!l8tory test for Indanthrene blue. A piece of filter paper is wrapped. over the mouth of the test tube. A small drop of an alkaline solution of lead acetate .is placed on the center of the filter paper, and the test t,tll)e is placed into a 2S0 mlbeaker containing boiling water. In 40-80 sec, the lead acetate spot onthe filter paper will turn dark brown or black iJ sulfur dyes are present. Alkaline lead acetate is prepared by adding 100]'0sodium. hydroxide toa IOOfo solution of lead acetate until the precipitate which is first fQrmed redissolves. Th prevent this solutioa from drying on [he filter paper du:rlng the test fer sulfur dyes, 20-2:5% of glycerine is added. Further eonflrmatian may be detennlneclby wetting out ~he sample with sodium hypochlorite {a 10% concentration of commercial household bleach). The color should be virtually destroyed in 5 min.




quinone derivatives generally change very little with 10010 hypochlorite. TI:liioindigo and carbasol derivatives generally lose most of their color in the hypochlorite test and are reduced to a yellow color: A 100-300 mg dyed sample is placed! in a 35 mltest tube: to which are added 2 to 3 nil. o( water and O.S to ) mI of ]0% caustic soda solution. After being brough'n to a boil, 11, 10-20 rug portion otsodlum hydrosulfite is added boiling continued for another O.S to O.tmin, The sample is removed and 25-50 mg ofwhite cotton cloth and 1()'20 fig of salt added. Boiling is continued for 4O-8l) sec, followed by cooling to room temperature. The cotton is removed and placed on fllter paper to oxidize. Redyeing ofcotron to a..shade differing only in strength from the




original dyeing indicates tne presence of vat colors. This conclusion

valid only if sulfur dyes were ruled out QY tile preceding test. OXIDATION BLACKS (ANILINE AND DIPHBNYL). Neither of these dyes will redye cotton from sodium sulfide-sodium carbonate treatment or from sodiwn hydmsui:fite-caustic soda treatment. Confirmatory 1lst For Oxidation Blacks. A 100-3000 mg portlon of the dyed sample is placed in a. small evaporating dish, 2 to 3 m1 of concentrated sulfuric acid poured over the sample and the dish rotated just long enough to extract the dye, The extract is poured into a 3S ml test tube containing 25·30 mI of water, filtered through S to 7 em filter paper and washed several! limes with water; The side ef the paper is spotted with a few drops .of 100)'0 causuc soda solution. A redviolet spot COIlfirms the test.



Group III includesthe following dyes, whiehare destroyed in alkaline sodium lJydrosulfite and do net redye white cotton from their bleeding in water, water-ammonia Dr acetic acid: direct dyes aftertreatedwith metals. direct dyes aftertreated with formaldehyde, naphthols and insoluble azo dyes, and diaz.otized and developed dyes. Preliminary Group 'lest. A 100-300 mg portion ofthe dyed sample is placed in !Ii 35 ml test tube with 3 to 5 mJ of water, 1.5 to 3, m1 of 100)'0 sodium hydroxide and 2().4(1 mg of sodium hydrosulfite, The mlxture is brought to a boil and boiled for 3 to S min. All dyes of this group are destroyed; some immediate!'y and some on prolonged boillng. The destruction of dye is manifested by a permanent change from the original shade to white, grey, yellow, and orange shades. This change 'takes place both 011 the sample of cloth and in the extract. Reoxidation of the sample does not restore me origijnal shade. DIREc:r DYES Af'TE&TREATEO' WITH METALS.. These metal complexed dyes are recognized by the' presence of a metal residue: in, their ash. Procedure I. A sample of approximately 0.5 g; is ashed in a porcelain crucible, and the ash melted with four to five times its amount .of a mixturie of equal parts of sodium carbonate and sodium nitrate. Specific coloration of the cooled melt indicates presence of one of the following metals: copper, famt blue-green; nickel, brown; cobalt, royal blue; manganese, blue-green; chromium, yellow. Procedure 2. A sample of approximately O.S g is ashed in a porcelain crucible. Th this is added 2.5-3,.0 mil of 30"10 acetic acid. Specific tests For the presence of copper; nickel; cobalt, manganese or chromium are run immediately as follows.

Copyrghlcd rnaieria



Copper. A 0.5 ml sample of theilcetic acid solution is blended. with an equal volume of 10OJo ammonium thiocyanate solutionand a few drops of pyridine. When copper is present, a yellow-green cepper-pyridinethiocyanate complex is formed which is soluble in chloroform. A second 0.5 ml sample of the acetic acid solution can be mixed with an appreciable excess of ammonia, after which !II few drops of a IDJe .aqueous solution of sodi.tmJ dielhyl-dlthJocarbamate are added. A brown
the acetic acid solution is made alkaline of a )'tIle aqueous solution of disodium red precipitate indicates nickel, Cobalt. 1h 0.s:m1 of a saturated aqueous anunonium thiocyanate solution is added 0.5 m1 of the acetic acid test solution. If cobalt is present, blue cobalt thiocyanate will be formed. Alternatively, 0.5 mJ of tile acetic, acid lest solution may be added to 0.5 mI of a saturated acetone solution of ammonium thiocyanate. A deep blue coloration denotes cobalt. ' Manganese. A 0.5 ml sample of the acetic acid is heated, cooled, and a drops o.f 10010 sodium periodate are added. A characteristic: perman-

precipitate indicates the presence Nickel. A O.S ml portion of with ammonia, and. a few drops dimethylglyoxirne are added, A

of copper.

ganate color fOml.ed on warming lndlcares the presence of manganese. Chromium. 1b a O.S mil sample of the acetic acid solution are ad dedi a few drops of lead acetate solution, A yellow precipitate (leadchrom-


ate) indicates chromium.
of formaldehyde

DlRECf .DYESAFrERTREATED Ww FORMALDEffi'DE.The presence in the sample is evidence of the presence of this class of dyes. Jest For Formaldehyde. A sample is healedi to boiUng in :l! 5010solu-

tion of sulfuric acid and allowed to cool; Uris extract is added, drop by dr'oll, to 0 ..1'0/0 carbazole dissolved. in concemratedsulfuric add. The tor-

mation of a blue precipitate· indicates the presence, of formaldehyde.
The dyes whose fastness to washing is only slightly improved by aftertreatment willh metals or formaldehyde respond no tile tests under Group I hut their bleeding in dilute ammonia would be insufficient for a good redyeing on white cotton. NAP}fFHOLS AND INSOLUBLE AzO DYES; Dm!tZOTIZlID AND DEVEl...OPED DYES, These' two classes of insoluble awl' dyes are WlaJjy different in their properties but related to each other in that the (mal dye wlrich appears on the material is never present as such in a dyebath but is formed in situ on cotton. In the preparation of diazotized and developed dyes, cotton is dyed With a suitable direct dye which is then dlazotlzedand treated in a developer bath. in this way. a new dye of increased. molecular weight is

the fiber. Due to the increased size of the molecule, the solu-






bil'lty of this new dye in. water is greatly reduced and the prodlllcn has inIn the preparation of naphthol dyes, phenolic compounds possessing an affinity for cotton are first apptied and then treated with a sotution of stabilized diazonium salts, whereupon a dye is formed. in situ. Neither of the two parts entering wto the formation of the dye possesses water-

creased fastness to washing.

soluhiti.zjng groups., and the dye· fOrnl.oo is water insoluble,

In this syst,ematizedscneme of identification. these two classes of dyes are placed at the very end of the procedure. when all other possible classes of dyes have been eliminated, and the problem is narrowed down to thequestion of differentiating between them.

of this class is bleOOing ID pyridine. A 2()..SO :mg dyed sample is placed in a 10 to 15 ml test tube, I to 2 ml of pyridine added and the sample boiled. AU naphthol dyelngs bleed. to some extent. Due to their water insolubility. naphthols reduce much more slowly in sodium hydroxide and b!ydrosulfite than any other class of dyes in Group HI. Confirmafory'lest. A 1O()'200'·mg dyed sample is placed in a. 10 to 15 ml test tube, and 2 m1 of 10010sodium hydroxide and! 5 ml of alcohol are, added. The mixture is boiled, s: ml of water and 4().50 Illg of sodium hydrosulfite are added, and the mixture again brought to B! boil. After property
the color is reduced. the mixture is cooled and filtered. 10 the filtrate are added 10-20 mg of whJte eottonand 21).30 mg of salt. This is boiled I to 2 mill. cooled andthe cotton removed. A yellow dyeing which fluoresces in ultraviolet light confirms that the original was dyed with a naphthol or printedwieh an insoluble am dye. DIAZm'IZED AND DEVELOPED DyES. These dyes are identified. by exclusion of all other classes of this group .. Dlazotized and developed


.A2o DYEs. The most characteristic

tint pyridine, and for reassurance, the test may be repeated on. the same sample with two to three fresh portions of pyridine. The tinting by some or these developed dyes decreases rapidly and in most cases terminates complete1'y~ The bleeding in the case of naphthol dyeings, continues at the same rate, since solubility is an inherent propel"ty of all naphthol

dyein:gs do not bleed in pyridline. and they are reduced readily in belling sodium hydroxide and sodium ilydro.sulfite, Some of these dyes might

dyeillgs. Occasionally. part of the dye will be poorly coupled and bleed in water-ammonia in the tests of Group 1. "This, bleeding, however, is only
slight and of a differentshade straight direct dyes,

white cotton is impossible or too poor

than the original dyeing, Rediyeing on to warrant placing in the class of






PIGMENTS. WlleIl prior tests for other dye classes OIl cellulose show negative results, the presence of pigments or fiber reactive dyes should! be suspected. Microscopic examination, solvent bleedingand chemical tests can yi~ld information about the presence and! the type of resin bonded pigment. In mass pigmented viscose ray,oo, pigment particles show uniform distribution throughollt the fiber under the mieroscepe, Resin-bonded pigments show surface coloration. The surface coloration is obvious ill deep shades but not readily r·ec(lgnized in light shades. Extraction of the sample with a boiling solvent such as dimethylformamide can be useful in distinguishing between some classes of dyes and as a preliminary test for pigments, Resin-bonded pigments may betong (0 due azcic., phthalocyanine or vat classes but may also be in-

organic substances. The: water-tn-oll type: of resia-bonded pigments, especially the phthalocyanine blue and phthalocyanine green pigments. do not bleed in dimethylfermamlde, whereas the oil-in-water formulation does bleed, Microscopic Examfnaliol1. Samples of fiber may have a starch or resin type firnsh which should be removed 110 that they do not interfere with the identification. An enzyme scour with 2o;~·,enzyme and! 0.25070 detergent at lOOP' for 30 min will remove normal starch finishes. Strip. ping of the resin may be carried out by treatment with 10/9 hydrochloric acid for 5 min at the boil, followed by a rinse. A microscopic test may then be carried out by gently removing a few fibers from. the sample and! antwisting, The fibers are mounted in a drop' of e,thyl salicylate and! covered with a coverslip. A granular appearance of the fiber surface is characteristic of resin bonded pigments. DirnethYiformamfde Extraction. The fiber is placed in 5 ml of a 1:[
solution of dimethylformamide and water and brought to a boil, removed from the heat and staining of the so.lvent observed. Another sampie of the fiber is placed ill 5 mlof JOO'lG dimethylformamldeandthe procedure repeated. The degree of solvent staining serves to distinguish between pigments and fiber reactive dyes. If tile sample dyed 'With fiber reactive dyes is not adequately washed, a slight bleeding will be shown in the water-dimethyltorrnamide solution. The solvent staining behaviors of various types of dyes are summarized in Thble I.

REAcrlVE DYES. Reactive dyes are characterized by a relatively stabte chemical combination with the cellulose fiber .. This linkage gives
the dyeing excellent insolubility in solvents and water. There is no specific unambiguoas te$~ ror reactive dyes. It is necessary to eliminate the possibilities of oilier dyes which are fast 1.0 water bleeding, e.g .. azoic, sulfur, and vat dyes, before seeking to establish the color as a reactive




Table I. Dimethylromlamide Stalnlng'Festror Dyes
[:1 DMF:Waler Stained by: lOO"loIJMF Stained by.:

All Direct

Diazo,~ed and Dc:\Ieloped

SOme Basic Some Mol!danlS
Not Stained by: Fil.>et ReaCllivt Leceo VlllS Naphihols Pigments Some Basi~


Leuen Vats

Some Biask Some Mordants
NOI SIal .. ed by: Fiber Reactive

Some Mordants

dye. It should be noted tnatpigmeots resemble reactive dyes in several of the identi[l.Cation tests and that solvent insolubility and behavior with reducing: and oxidizing agents are key t,:sts in Pfovingthe presence of reactive dyes. Reagents. Reduction: SWosodium hydroxide and 5070sodium l:iydrosUlfite in water,. Acetic acid, 50'/0 in water.. Oxidation; SOle hydrogen peroxide or Willa sodium perborate in

DMF (dimethylformamide).. 100"'0.
Hypochlorite-sodium hyPochlorine bleach containing .2'7~ a.... ailable chlorine. Procedure. The sample is placed ill slow boiling reduction reagent and the reaction and time of reaction observed. Azoic dir,ect and diazotized and. developed dyes decolorize rapidly ..Vat,. sulfur and aniline black dyes are rapid1y converted to the alkaline leuco form, Some red pig. meats are stripped by this reduction, but the reaction is slow and is easily distinguished from the more rapid cases cited above. Some fiber reactive dyes co.ntaining anthraquinone cbtornopho.res will be reduced by the reagent but will seldom be converted to the original shade by oxidation. Others containing an .1liW chromophore win be decolorizedby the reducing reagent and by hypochlorite. If me test sample is converted to the alkaline leuco form in the reduction reagent; tthe sample is removed and placed in the acetic acid solution. Vatt, sulfur. aniline black and chrome dyes will form an acid leuco compound differing i.n color from both the nriginalsample WId. ttl:teBllka-

line leuco compound ..
The acid. Ieuco sample may be re-redueed and then placed in the oxidizing reagent. The original shade of the sample should be restored .. The effect of the hypochlorite on the diyed sample is observed after

immersing a. fresh sample in ~he reagent for a few minutes, blotting between paper towels and drying. Reactive dyes have many kinds of structure, but for reference purposes they may be classified by the kind of group which attaches the dye to the fiber molecule such as the vinyl sulfone, acrylamide, halopyriml~ dine and halotriazine. Within any series, the dyes may contain different dye ehromophores, For example, bright blues can have phthaloeyanine or anthraquinoae structures, Azo structureswith and without metal complexes are common in this group. A detaileddiscussion of the chemistry of reactive dyes has been given by Venkatanunan (2). Although reactive dyes are attached to the cellulose by primary valencies, certain types e.. . Remazols (vinylsulfones) and Primazins g (aerylamides], will hydrolyze when boiled under alkaline conditions (5010 sodium hydroxide). The bleedi!lg into the solution may indicate direct dyes, but the hydwlyzed dye will not redye cotton as direct dyes will. Reduction of fiber reactive dyes can giveshade changes similar to those experienced with vat dyes. Phthalocyanine and. anthraquinone structures in the fiber reactive dyes are reducible to leuco compounds which will return to the original shade Of! oxidation, The procedure for identification of reactive dyes should first eliminate the possibility of van, sulfur; and azoic dyes. 'Iests already described should be used after removLng any resin from the sample by boiling in a dilute acid solution, Specific tests [or azOIC, vat, Bind sulfurs should be carried out. Azoic dyes are soluble in cold cltloroform and! give a colored solution when a sample is shaken with this solvent in a test tube. Bright and strongly colored samples of vat diyes suggestive of fiber reactive dyes will bleed In the reduction reagent. Simi!laily. a dull yellow or orange-colored sample with some color bleeding into the solution indicates a sulfur dye. In both cases, if the reduced sample is washed and exposed to tile air, it will reo turn to its original shade. Some reactive blues will give strongly colored reduction products. although the Original shade remrns much more slowly. These blues can be distinguished from vat dyes since they are deeolorlaed in cold weak sodium hypochlorite, whereas vat dyes are not. Reactive PhthalocY,QJtine And Anthraquinone Dyes. Phthalocyanine and anthraquinone compounds are reducible to leuco compounds, which in turn can be reconverted. to tbe initial compounds by reoxidation. The reduction-oxidation process should be obvious and reversible, that is, the action of the reducing agent must produce a clearly visible shade change and on oxidation the original shade must be restored. The' optimum conditions for thls procedure consist of reduction o.f the spedmen for 30 secat room temperature in a water solution containing .20 g/l, of sodium Ilydfosulfite and .2.5 gIl. of sodium hydroxide. followed




by .2 min rinsing in cold water, 2 min rinsing in hot and again 2 min in cold water. Generally. phthalocyanines their original shade on rinsing,

while anrnraquinones do [Jot. Oxidation at 9o.9SC for 2.5 linin will restore tile original shade of the anthraquinenes. Reactive A,zo Dyes. Dyeings of reactive azo dyes can be reduced! to primary amines and decomposed so that the reactive fragment remains linked to the fiber while tile amine fragment or fragments can be washed!


off. mten the primary aromatic amino group of the resulting fiber-

linked compound can. be diazotized and the diazonium compound combined with a suitable coupling component to give it new reactive dyeing. 1b carry out this method for demonstrating the presence of a reactive a1!O dye" the amine 'bound to the fiber must be diazotizable. A number of cleavage products may be obtained which react with nitrollsacid in ways other than the: formation of a diazonium compound. The success: of litis method is therefore contingent upon carrying our the diazotizalion and coupling under suitable conditions and therefore requlres some knowledge of azo dye synthesis. The presence of reactive dyes may be confirmed by their resistance to bleeding when they are boiled with solvents. A summary of ~his behavior is included in Thble l. Disect dye-s can be siripped withmixed solvents such as 571110 pyridlne43'Cl/o water and 500/0 dimethylfonnamide-50Ofo water. Azoic dyes will bleed. into pyridine and into dime[hylformamlde. Vat dyes, with some exccpnions, are partially stripped by JOOOJo pyridine Of dimethylformamide, With the 'e;>.;.ceptiOI] of a few Levafix dyes and certain turquoise blues, reactive dyeings which have been freed of unfixed dye show :pracdcally :no bleeding when they are treated at the boil for 5 minutes with solvents. More detailed procedures for idenrificadcn of reactive dyes can be ol!J:tamed from the literature (9-11).

Dyes On Animal Fibers
A burning test serves to identify woo] or silk. These fiOOrs are also

dlfferentlated from others by their solubilitY in boiling .5"lc sodium
hydroxide. The following dye classes are normally used in the dyeing of wool or silk: Basic, Direct, Acid. Soluble Metallized (acid dyeing), Chrome, Metallized (neutral dyeing), Vat, Leuco Ester and Naphthols. Bask. Dyes A 100-300 mg sample of dyeing is placed in a35 mi. test tube, boiled in 10 ml alcohol for a few minutes and removed. The alcohol solution is evaporated almost to dryness" .5 mI of water added and the mixtm>e





boiled to remove the alcohol.1b the residue is added. 0 ..25 to 0.5 mI or 100)'0 sodium hydroxide. After cooling tile solution, 5 ml of ether is added. and tbe tube shaken to extract the basic dye. The layers are allowed to separate. the ether layer decanted into a 10 ml test tube and a few drops of 10% acetic add ace added with shaking. The salt fonn of the basic dye which results should have the original color of the dyed sample. Additional proof of the presence of basic dyes may be obtained by placing a sample of mordanted cotton or catlonic dyeable acrylic fiber in the test tube with the alcohol extract, adding: the sodium hydroxide and transferring the dye to these new fibers. Direct Dyes A 100.300 mg sample of dyeing is placed in a 35 ml test tube, 5 ~ of water and 1 ml of concentrated ammonia are added and the sample is boiled in tills solution for 1-2 min. The dye sample is removed, and 30 mg of salt and 10-30 mgof white. cotton are added. Boiling is continued for 1 to 2 min. The cotton is removed and rinsed. If a direct dye is present the cotton will be dyed a deep shade. Some acid dyes may stain cotton, but never to a deep shade.
Acid Dyes,

The procedure to be used is essentially the same as !:hat for direct dyes (above), but instead of adding salt, the ammonia is neutralized with a 101170 sulfuric acid solution, and a few drops of add are added in excess. A .2040 mg piece of wool is added, and the mixture boiled for 1 to 2 min. Redyeing of the extracted dyeon wool from this acid bath is evidence of nhe presence of acid dyes. This test is significant only if the previous test on redycing of cotton and the following tes: for soluble metallized dyes have been carried our, Positive evidence of directcotton dyes and acid dyes indicates a union dyeing on a blend of wool and cotton.
Soluble M.etallized Dyes ("Acid The procedure D),eing' ')

to be used is identical with the method! given above for acid dyes. Soluble metallized! dyes are distingUished by the presence

of chromium in tthe ash. The procedure for the determination of metals is described in the sectieo dealing viith direct dyes on cellulosic fibers.

Cllrome Dyes Chrome dyes are formed ill situ


wool. by treating a. chromh.lm-




wool complex with a water soluble dye. The resulting chrome dye is not soluble in water, and 'the procedure recommended above for acid! dyes will flot extract Wliydye. However, the procedure may produce considerable bleeding into the dilute ammonia. No redyemg of wool can be aecompllshed from this extract because it contains by-products of the dyeing process which were not removed prior to fmishi~. Some' further evidence f(lr chrome dyes can be obtained from the ash test discussed below, Metallized Dyes (Nelltr:al Dyeing)

The dye-metal complexes are preformed and are exhausted. from nile:
dispersion onto wool. Due to the poor solubilitty of these organometallic

complexes in water, only small amounts of dye calli be extracted from a.
sample of II. clyemg. Redyeing, of wool by such an extract does ~ak:e place however, in distinction from, the results of this test with chrome dyeings, but the shade is always much lighter than the original shade" ASH 'l.'EST FOR METALLIZED DYes, Neutral metallized. dyes may contain either chromiwn,cobalt, or manganese. When either of lfIe last two metals is found in the ash of a sample, metallized! dyes are lmmedlatelysuspected because chrome color dyeings invariabty contain chromhun omy ..A tlyeing produced with III. neutral dyeing chromium metallized dye always contains less chrome' than chrome dyes. To carry out the test ash, 20 mg of dyed sample is p.laced in a. No. 000 porcelain crucible and 500 mg of sodium carbonate-sodium Ilitrate

mixture added, The mixtufC is fused, allowed to cool and examined. If
the color of the flux is yellowish, a chrome dye is indicated .• If the flux is white. then the sample probably contained a neutral dyeing chromium metallized elye. The validity of the test is dependent on the positive test for chrome when a larger sample (300-S{10 mg) of this dyeing is used.

Vat Dyes
A 200-300 mg sample is placed in a 35 ml test tube" 2,5 ml of 100]'0 sodium hydroxide added, and the mixture boiled until all of the wool is dissolved. lb the wool solution are added 25-50 mg of sodium hydrosulfite; 1()'M.5 rng of while cotton and 25·50 mg of salt. The test tube is heated to near boiling for .1·2min and coaled to room temperature ..The cotton is removed and placed on filter paper for 1-2, min, then in an oxidizing bath containing sodium nitrite and acetic acid, Development of acolor on the couon is 'evidence of vat dyes. If the original sample was dyed in a light shade, theredyeins on cotton will be too faint and it is necessary to repeat the dyeing of the same piece of couon with several 2Q0-301[)rug samples of the original. Vat dyeing made in the past-may contain traces of chromlem due to




The ·vat component can be rooyed, on cotton by the procedure given above. which will destroy chrome dyes, The vat component can be completely removed by repealed extractions with pyridine leaving ~he chrome color intact on the sample.

the industrial practice of reoxidation of vat dyeings with sodium dichromate, but the quantity usually found is not significant. Occasionally indigo, or solubilized vat blue, and chrome colors may be dyedon the same doth. In this case, the analyst will detect the two classes of dyes.

Leueo ESters
These are water soluble, stable esters of van dyes. When they axe used to dye wool fiber. they are saponified and oxidizedi, produclfig a true vat color which can be identti.fied with the above procedure for vat dyes. Naphthol Dyes

These are water insoluble a2!O dyes formed on the fiber

in situ.


presence on the sample is determined by the exclusion of all other classes of dye and by the fact that naphthol dyeings bleed freely in pyridine. In addition they are reduced by sodium nydroxide-sodium hydmsulfite tto a yellow, orange shade, mcapabie of reoxidation. The procedure for the identification of naphthol dyes is detailed in the section dealing with ce1Iulos.lc fibers.

Dyes On Man-Made Fibers
Fiber Identiflcatliiln The solvent scheme used for the identification of acetate, rriacetate, polyamide, acrylic or polyester fibers may also give hints as to the nature of the dye present on a particular fiber. The procedure suggested here is



the exclusion principle, and Table II summarizes the sequence

of solvents used (Ii).

Dyes On

Ace.tate Or Cellulose 1Iiacetllte:
acetate, In a mixture

of 800/0 acetone and 20OJ~ water, secondary acetate dissolves immediately; whereas We triaeetate becomes translucent and tender but retains its
fiber form.
The following dye classes are used in the dyeing of both. of these fibers: disperse, acid, basic, vat, developed, pigments (co-spun or resinbonded). Appreciable quantities of acetate fibers are marketed with co-span

Solubility in cold acetone !dentifies secondary



Table II. SolubWl)' of Man-Made FIba'

Fibers III Viutiolls SOlvenlll


Cellulose Acetate,

AooonefWater. SOfW. Cokl iB<:nzy1 AlcohoilSOC)
Mtlhy~tI1e Chloride, Cold AcelOlleiWtter, 80/20" Co,ld Benzyl Alcohol (SOC) Dnnethylformamlde, Boiling A~eIOiit, Cold _ M¢lhyten~ Chloride. Cold

Q;llulose Triacetate Polyamide

8S% Formic Acid. Boiling

1'1),10106 NyIOll66

DimelilylfonnarnidelFom1icCydohexlmone Add (8S%). 1~12S. Boiling 'Cyclollexanone
Cyclo!u:mnonc N·MethylpyIToHdone, Bolling Dirneiltylfonnamidc, Boiling Dimethylformamide/Formic Acid (8SlI1d., 75/25, Boiling

Nylon Auylic Polyester


A~elillle.Cold Methylene OIJoridc, MethyleneChloride


N-MelliylpyftoIidOile, Bolling Aeetene COli:! Dimethyiformamidc, Boiling

pigments. For nhe most part" the dyeing of acetate fibers is with disperse

The diazotized and developed dyes are usually bla.cks and occasionally navies. AIl overa1l indication of the ttype of dYe present may be ebtalned by the following color transfer test and by solvenaextraction, A 100--300 mg sample is placed in 25 ml of a soap solution. (S g/L) with an equal weight of undyed acetate fabric and warmed. at 90(: for 10 min. The color of the solution. the change to calor of the original and the degree of color eansterred to the undyed acetate ate noted. The soaping test gives a clear tndleation of fibers dyed with disperse dyes .. Disperse dyes will transfer to the undyed acetate togive appreciable color. No transfer is observed with pigmented fibers. Basic dyes will transfer from the acetate fibers to the soap solution but will not redye the acetate. Azoic combinations will give only a light yellow 011 the acetate derived from uncoupled intermediates. The absenceof staininS on the acetate fiber does not rule out acetate fibers which have been dyed with add dyes or vat dyes. These dyes will not redye the acetate ~o

any significant extent.

TIle .altactio.1] test with N-methylpyrrolidoJie followed by distribution of the extracted dye between the toluene and water layer serves to distinguish among the possibilities in water soluble dyes. A 100-300 mg sample is placed in a 35 ml test tube and 5 m1 of a


added. The test tube is immersed






ina water bath and the temperature of the bath is raised to boiling. After 2040 sec, the tube is removed and the dyeing discarded. To the solution 3-S m1 of toluene and 20 ml of water are added. The lube is shaken well and tbe color of the water layer and the toluene layer noted. DISPERSE DYES. If theextraction tesn yields a toluene layer which is strongly colored. the dye is most likely a disperse dye. Confirmation is
made by separation of the toluene layer in a separatory funnel, The toluene is evaporated and the residue dispersed in water with a surfactant; e.g., lignin sulfonate (Marasperse N). A redyeing on acetate fabric

test results in a water layer which is sttrongly colored and the same shade as the original dyeing and! a colorless toluene layer, tllen the dye may be an add dye. Confirmation is made by treating a new sample with to ml of 5U7Q sodium hydroxide at the boll for 2 min. The sample is removed and an equal quantity of undyed. wool is added. Dilute sulfuric acid is added to a pH of 4.5 to 5.0 and warmed to 9OC. An acid dye will calor the wool under these conditions. BASIC DYES. If bash: dyes are present, the water layer and the toluene layer in the extraction test may both be colored. If a basic dye is suspected, a new sample shouid be extracted by heating in 5610 formic acid solution at 9()12 for 10 min. If the extract redves cationic dYeable acrylic fiber, the presence of basic dyes is indicated. VAT DYES. The exaacdon test gives colorless water and toluene layers with vat dyes. However, the lack of color may also be due to developed acetate dyeiIl!g or 'co-spun pigments. A lOl[)..300 mg sample of a dyeing is placed in a 35 m1 test tube and 1 to 2 ml of 2OOJo sodium hydroxide solution added, After boiling the sample for 1 to 2 min; 4 to 8 ml of water and 15 to 35 mg of sodium hydrosulfhe are added, and! boiling continued for another 0.5 to I min. The sample is removed, and a 25-50 mg piece of white cotton and 15-30 IDg of salt are added. Boiling is continued for 4O-8IJI sec and then the mixture is a1Jowedto 0001 to room temperature. The cotton is removed and placed on filter paper to oxidize by air. Redyeing of cotton by the above procedure: to a shade differing from the original dyeing only in strength Indicates the presence of vat colors. DEVELOPED DYES. Developed dyes may be suspected if the N·methyll'yrrolidone extract is colorless or colored a different. shade than the original dyeing ~ usually a shade of brown - no matter what tile original shade was. The water and toluene layers are colored; in some cases coloration of the nolue:lte is .sttl)flget;, in other cases the water; The coloring is different in shade: from the origin a! dyeing. and it is usually light brown.

is evidence of disperse dyes. ACID DYES. If theenracdou




Further differentiationbetween azoic and vat dyes. may be made by reduction, A sample is warmed at roc with ]0 ltd of 5010 sodium hydroxide to which are added :5 ml of CeUosolve and 50 mg of sodium hydrosulfite. Vat dyes are reduced to leuco compounds, which are differ~ eIlt .in color from the original dyeing but return to the onginal color 0111 exposure to air. If no change in color is noted at roc. heating to the boll decolorizes azoic dyeings, P[OMENrS. The presence of pigm.ents is indicated by the exclusion of other lypes of dyes and through their Failure to redye any fibers. Pigments vary in their chemical nat tire, and. no specific tests can be given .. Blacks are carbon blacks and do not decotorize in sodium hydroxide and hydrosulflne. Th.e presence of metals in the ash is indicative of the use of
,co-spun plgmentts .• Confirmation is by microscopic examination the section on pigments. Dyes On Polyester Fiibers

previously described in

Polyester fibers Me distinguished by their insolubility in boiling 8:5070 formic acid. Boiling nitrobenzene' dissolves polyester fibers of both types, diSper.se- and cationle dyeable. Polyacrylenitrile fibers are insoluble in boiling nitrabenzene. Boiling N"melhylpyrrolid.one dissolves poly· ester and pelyacrylonitrile fibers .. Polyesner fibers are hydrolyzed completely by boiling for a rew minutes with 2N sodium hydroxide in methanol. A Clear soluuon is obtained when the reaction product is diluted! with water. On addition of dilute sulfuric acid, the resulting terephthalic acid separates out as a precipitate ... The following dye classes are used for polyester: disperse, developed, cationic, pigments (c~spun or resin bonded), val. II)ENTlflCAT10N OF DYES1UFF CLASSES. A 310 5 s portion of capeolaetamis melted in a 50 mI test tube over ill smail Bunsen flame and 100-.300 mg of tile dyed polyester is dissolved in the molten mass while beieg stirred with a glass rod. 10 this is added. sufficient (3 ml) ethanol to prevcl1[ thecaprolactam from solidifying. After cooling the material below 35C, it is dilutedwith IS m1 of ether and filtered. If the ethereal solution :is colored, it is extracted twice with 20-30 ml of water to remove the caprolactam, 2~3 g of sod.ium sulfate being added to prev,el1~the fo.r-

rnation of an emulsion.
The etllereallayeris transferred to a 3:5 ml test tube and 10 ml of water together with a few drops of a IOUJo solution of dispersing agent.. (e.g., Marasperse N) are added. The ether is evapor.a~ed. by boillil:g the solution on the water bath and 100 mg of white acetate fabric is added to ~e aqueous dye dispersion, which is then kept for 10 min in the water bath.



The formation of an. intense coloration of the acetate fabric in the same shade as the original polyester material indicates the presence of disperse dyes. The formation of a slight coloration indicates the presence of deveIoped! dyes or vat dyes, In the latter case, the acetate fabric is removed; and the hot dye dispersion treated with 3 ml o:f IN sodium hydroxide and a few milligrams of sodium hydrosulfite and shaken, If the color disappears or changes and nhe orlginal shade does not reappear on shaking with air, then developed! disperse dyes of the azo type have been used! to dye the polyes~er, Vat dyes are reoxidized to the origina!l shade by shaking willi. air. If the polyester material has been dope-dyed with pigments Or has been dyed with basic dyes, then the ethereal extract of the molten caprolaetam is practically colorless, and the precipitated polyesteT On the filter is strongly colored. Another sample of the dyed polyester material is boiled for I min with glacial acetic add, the solutien is evaporated on the water Of' steam bath and! the residue is dissolved ill 5 ml of water" A piece of cotton mordanted with tannin OF a piece of acrylic fabric is then added, and the liquid is boiled for 1 min, Basic dyes transfer to the fabric. Pigments, can be recognized by the fact that the glacial acetic add extract is colorless or that the residue on evaporation is insoluble in water. Cross-sections of dope-dyed fibers ,show a uniform pigment distribution when examined under the microscope.

Dyes On AclYUc Fibers
Acrylic fibers censlst primarily of polyacrylonitrile and may be classified by the minor component with whim the acrylonioile is copolymerized. The cationic dyeableand acid dyeable types represent the major types. Modacryllcs, Which contain proportionately more oopolymer, represent the minor type. AcryUc fibers, are identified by their insolubility in boiming 8:50/0 formic acid and by !'heir solubility in boiling N-methylpyrroUdone. Tiley can be differentiated from polyester fibers by their insolubility in nitrobel1!~ene Of o-crescl,

The following diye classes are used in the dyeing of acrylic fibers: disperse, meralllzed acid (neutral dyeing), basic, acid and chrome.


acrylic fiberscan be separated Into two major groupings 011 the basis of solubility, as shown in Thole HI. The procedure is as follows. A 100-.300 mg sample is placed in a 35 mI test tube and 2 ml 'Of 40% aqueous solution of N-me~hylpyrrolidone added. The test tube is placed ill a beaker of boiling water for 10-20 min or until it sufficient amount of dye has bled Into the reagent. All alternative solvent which will extract






eaticaic 0'1' acid dyes 15 a 57143 mixture of pyddin.e and water. The test tube is removed fr·om the water bath, the fiber sample' discarded, and the extract poured into a 15 ml test. tube containing m ml of toluene. After shaking, 1 ml of water is added, and the test tube shaken again. The test tube is allowed to stand until two layers. are well separated. The distribution of dyes. in the two layers is as given ill Thble


ll!bte ~D. D!5tri!lJt~Uo!l o( Dy~ Used for Ac!,),1k Ft~ T1!I11I_ Layer'

Wakruye.r All Basic Dy~ All Acid Dyes
All Chrome Dyes Some Ncuua1 Dyeing

All Disperse Dyes
So!!1C NC!ltrai Dy.:ing

Premetalflzed Dyes

PremetalliZed. Dye:!.


Disperse A.nd Neutral Metallized Dyes. The toluene layer contains only two classes of dyes - disperse dyes and neutral dyeillg metallized acid dyes which contain no or very few water solubilizing groups in their

The presence of chromium, cobalt, or manganese in the ash of the original dyeings differentiates these metallized dyes from the disperse dyes, which contains no heavy metals. For a confirmatory test, the toluene layer can be. separated by means of a small separatory funnd, washed with water and evaporated, The residue is dispersed with iii drop of lOO'fQ water solutioa of a dispersing agent, such as Blancol, The dispersion can be used to I'edye wool and acetate. Metalliud dyes will dye wool only; Disperse dyes will dye wool and acetate'. Acetate is usually dyed heavier. The aqueous layer contains basic, acid or metallized acid dyes. Simple tests can differentiate them.

Basic Dyes. A 2 ml portion of 10070 sodium hydroxide solution is
added to the toluene solution cibttalnoo in the previous test. The test tube is placed in a beaker of boiling; water for a few minutes, removed, cooled, shaken and tile two layers allowed to separate. A major portion of the toluene layer is decanted into a 10 ml test tube and 0.5 ml of ll}% aceUc acid is added. The tube is shaken and allowed to stand .. A basic dye will. color the lower add layer in the shade of the original dyeing. Acid Dyes. If the ash of the original dyeing contains no heavy metal and if basic dyes have been. excluded, an acid dye is indlicated ..

Metallized Add Dyes {Neutral Dyeing} And Chrome Dyes. The ash (If the original dyeing is 'examined for the presence of cobalt, manganese

or chrome. When cobalt or manganese are found, the dyeing was probably made with metallized neutral dyeing acid dyes. When chromium






present. a distinction between chrome colors and neutral dyeing metallized dyes is made by semiquantitatlve determlnation of the amount of chrome present ill ~he ash. The procedure .suggested iii, the section dealing with wool dyes may be used. Remarks. There are a few basic dyes which may cause a tnlsinterpretation of the results of the toluene extractlen, These dyes are of the Chrysoldlne and Bismark Brown types and are used mostly :for compoendlng black shades. They color the toluene layer and have an affmity for acetate fibers. Therefore, when the sample is dyed a black shade' and its main constituents are basic dyes, one should not look for an, acetate color as a component. of this black dye but ascribe the yellow coloring of



the presence of Chrysoidine or Bismark Brown.

Dyl'll On Nylon

Nylon fibers are differentiated from other fibers by solubilitycharacteristics as outlined :in Table 11. The following dye classes are used in the dyeing of nylon: disperse, direct, add, basic, neutral metallized, add metallized. chrome, Iogwoed, naphthol, vat, and reactive disperse dyes of the Procinyl type. In order to get a general indication of the uypes. of dye presenu on a nylon sample, the following preliminary tests should be carried out: a wash test, followed by redyeing all. multifiber Cloth" an ash test for determination of metals, and a SOlubility test for distribution in water Or toluene layer. Wasil Test. A .200-300 mg sample ofthe original dyeing is placed in a 35 rnl test tube, and 10-1.5 ml of a solution composed of O.. 0OJD neutral! 5 soap and O.20C'Jo sodium carbonate is added. The lest. tube is placed in a beaker of boiling water for 15~30 min, then removed from. the water; the nylon sample is discarded. Half of this wash test solution is decanted into another 35 ml test uube.'lb one tube Is added 1-2 ml of glacial acetic acid. Then 8.3/8 to 1/2 inch .strip of Multifiber Fabric No .. 5" is added to each tesU tube, both test solutions are boiled for 3~5 min. The dyeings are rinsed well, and. which fibers are dyed and stained on both Ute alkaHue redyeing and the acid redyeing is noted. Ash Test. The presence or metallized dyes is detesmined by the analydeal. procedure already described for direct dyes aftertreated with metals. Solubility Test, A 100.300 mg sample of the original dyeing is placed in a 35 ml test tube, 1.5ml of 57/43 pyridiae/water (hp 95C) added; and the tube placed in a beaker of boiling water and boiJed 15-30 min. Extractions with pyridine should be carried out in a hood .. All classes of
'Multifib<. Fabric NQ. ,So:arl,~ oblailKd horn Rnra.brics ~ .• UlO 8lo,U<lI'II "''''' .. Mio1dlola. N,J. £8846
arid ,ro~lai_i\l:'t!hefnUowi"ll: fibm: acetale. IIcri'\an lM6, Arnel, ,roi;o~. Crwan 61, Daoron',S4, D3crol'! 64. n:1]fm 61\, Orlon "~, ~il~..... .-e! A. "'sco,.. and "'00:1.

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