AATCC Test Method 94-2012 Finishes in Textiles: Identification Developed in 1959 by AATCC Com- mittee RRS, reactivated to RAGS 2012; revised 1961, 1962, 1965, 1987; reaf- firmed 1969, 1973, 1977, 1985, 2002, 2007, 2012; editorially revised 1974, 2010; editorially revised and reaffirmed 1992, 1997, 1. Purpose and Seope 1.1 This test method gives guidelines for qualitative identification of ‘various finish components present on textile fab- rics, yams ot fibers. 1.2 The identification scheme may in- volve any of all of the following ap- 121 solvent extractions followed by identification of extracts by infrared spectroscopy (IR), gas chroma- tography (GO), high performance liquid cchromatograpty (HPLC), thi leyerchro- amatograpiy (TLC), nuclear magnetic rex ‘nance spectoscopy (NMR) or other in- strumental or wetchencal methods, 1.2.2 Direct mensire of elemental or chemical species on fbi by Xeray Duo- estence spectnscopy, al ellectanee Geetmacopy Rrmnre lem shoeptin Spectroscopy, and other insramnental or ‘et-chenical analysis methods, 12.3 Hentifiation of specific fish- ‘ng components by ciemical spot tests om, the texte or extracts from exiles. 2. Uses and Limitations 2.1 This test method isa flexible set of ‘guidelines for identification of textile fin- ‘shes. Appropriate adjustments and modi- fications will be needed as finishing ‘chemicals change and as new analytical test methods are 22 Any chemical which is on the tex tile prior to finishing may be present on ‘the finished fabric and could be removed ‘andlor detected as finish. Warp sizes, [eg.. starches, acrylics, waxes, poly: ste poly(vinyl alcohol], dyes dye ie tives, binders, spin fm Suen pled baheoe and processing chemicals (e., surfactants, beach stabilizers, dye carriers, and oils) ‘ay be present by design or unintention- ally. A working knowledge of these ‘chemicals is needed to properly detect ‘and identify them. Where possible, sup- plier should be consulted for futher ‘information, 3. Terminology 3.1 chemical finish, n—chemical 160 TM94-2012 ‘material other than colorants and residual processing chemicals added to textiles to impart desired fmstional ot aesthetic properties to the textile product. ‘NOTE: Chemical finish will hereafter be referred to as finish. 4. Salety Precautions NOTE: These safety precautions are {or information purposes only. The pre cautions are ancillary tothe testing proce- dures and are not intended to be all inc- sive. Tis the user's responsibility to use safe and proper techniques in handling ‘materials in this test method, Manufac- twers MUST be consulted for spec etails such as matevial safety data sheets and other manufacturer's recommenda ons. All OSHA standards. and rules ‘must also be consulted and followed, 4.1 Good laboratory practices should be followed. Wear safety glasses in all laboratory areas. 42 Use chemical goggles or face shield, impervious gloves and an imper- ‘vious apron during dispensing and :ix- img of alkalis, acids and organte solvents, ‘Concentrated acids should be handled only in an adequately ventilated labora tory hood. CAUTION: Always add acid tovwater, 43 Special precautions must be ob- served when using perchloric acid, All swork mist be done in. an exhaust hood ‘made of non-combustible material, Fre- ‘quent wash down ofthe exhaust system is recommended as accumulated perchlor- ate combinations are often explosive. Ad- dition. of dehydrating agents, unless con- trolled, will lead to the ankydrous acid ‘which is unstable, Care must be taken in handling perchloric acid. Use eye and face protection, and flush any spill or splash to the skin or eyes with water immediately. 4.4 Hexane and methanol are flamma- ble liquids and shoald be stored in the laboratory only in small containers away from heat, open flames and sparks. These chemicals should mot be used near an ‘open flame. 4.5 Camy out reflux procedure in a ‘well ventilated hood with an electrical heater or a water bath as the heating sowce, Use chemical goggles ot face shield. impervious gloves and an im- pervious apron when handling organic solvents. 4.6 An eyewashy/safety shower, organic ‘vapor respirator aad a self-contained ‘breathing apparatus should be located nearby for emergency use 4.7 Care should be taken in handling hhot weighing bottles and crucibles. Se- ‘vere burns can sesult from skin contact. 4.8 Manufacturer's safety recommen dations should be followed when operat ‘ng laboratory testing equipment. 4.9 Exposure to ciemicals used in this procedure must be controlled at or below levels set by governmental authorities [ez., Occupational Safety and Health Aduinistration’s (OSHA) permissible ex- ‘posure limits (PEL) as found in 29 CFR 1910.1000; see web site: www.osha.gov for latest version]. In addition, the Ameri- ‘can Conference of Governmental Indus ‘ial Hygienists (ACGIH) Threshold Limit Values (TLVs) comprised of time weighted averages (TLV-TWA), short tem exposure limits (TLV-STEL) and ceiling limits (TL-C) are recommended asa general guide for air contaminant ex- posure which should be met (see 14.1), 5, Sample Preparation 5.1 Textile samples should be dried at 105+ 1°C 221 +£2°F) and desiccated to constant weight prior to weighing for ‘subsequent extractions, 6, Solvent Extraction Procedures 6.1 Extraction with different solventsis intended to remove as many finishing chemicals as possible in a sequential der. The. extraction scheme. presented hare (see Table 1) was chosen onthe basis of solvent polarity, solibility. volatility, ‘conor ad safety 62 Changes in chemical finishes, safety considerations or personal prefer ences may dictate the use of other sol ‘enls. tis the responsiblity of the user 0 determine which finish types may be re anoved by different solvents 63 Some finishes may not be soluble in eny solvent, An alismate method for insoluble finishes such as filly crons= Tinked polymers [eg some acrylics, polyurethanes, silicones and poly(siayl celates)] would be to dissolve all of the ‘Gbrous material with a suitable solvent, leaving the residue of finish for further analysis [see AATCC Test Method (TM) 20, Fiber Analysis: Qualitative, Table V) 644 Procedure. A weighed textile sam ple (1-10 g depending on the size of the fxtracto) is extracted in sequence by the Solvents in Table T, using Soxhlet reflux fo beaker extraciions depending on ‘quipmeat availability. Extraction times AATCC Technical Manual2016 CCopyrih © 2015 American Associaton of Textile Chemists and ColorstsGroup 102 5 OA NHybochere acid 102 Bird and Jackson Typical Finishing Chemicals Removed Oils, was, soteners,sanes ‘Smal amounts unixed pymers, postr es, ays, pajurathanes, poylvin acts) LUntred oeliose reactants organ sas, sutonated organics nied celuose reactants wee nee starches, peli acho Fed close reactant, ranchad starches, Ineganic sats NOTE: Sora paso fers maybe partial isohed bythe soles. Pro-chcks onthe ier ypas (se TW20) ‘shoud be mado aid eos ‘may range fiom 45 min to several hours ‘depending onthe boiling point, exchange sate and knowledge of the history of fin- ish removal for the textile sample in ‘question, The samples should be com- pletely dried before beginning the next Solvent in the sequence. After the extmae- tons are complete, each solvent is file ‘tered and evaporated or distilled leaving the residual finish extract. (The extract may be transferred to a weighing pan prior to complete dryness: drying can ten be completed in an oven at 105 £ 1°C. Calculate the percent extract as follows: Extact= “Weight of Residue ‘Weight of Original Fabric NOTE: It may be useful to neutralize ‘the acid extract with dropwise addition of | dilute sodium hydroxide to avoid fisther ‘degradation of the finish during evapora- ‘ion. The quantitative results wall reflect tie presence of sodium chloride in the dried residue, In addition, contamination ‘of the solution by sodium carbonate from, ‘the reaction of sodium hydroxide with at- ‘mospherie carbon dioxide may interfere ‘with interpretation of subsequent infrared spectra. ‘The percent extract, coupled with sub- ‘sequent identification, will be useful in Getnmuishing tue finsh componeats from residual uon-finishing chemicals ‘that may have been left on the fabric; ‘eg. natural waxes from softeners. ‘The extracted finish may be identified by one of the analytical techniques de- scribed below. 100%: 7. Infrared Spectroscopic Procedures 17.1 Infrared spectroscopy offers a very ‘convenient way to identity extracted fine ‘sh from textiles, The basis for infrared spectroscopy is the structural information ‘about a compound that cau be found from AATCC Technical Manval2016 its infrared spectrum. Inftared absorption ‘hands in the 4000 to 250 wavenumbers segion result fiom specific functional fr0ups in a molecule, These can be com- pared with spectra of finishes in pub- lished of persoaal libraries. Visual in- spection by a tained analyst will quickly ‘Menify the general type of finish. Come puterized search-anmatch capabilities ‘on many iniaved sytem willbe helpful For more complete information, includ- ing typical wavenumbers for comparison fof spectra of textile materials, deserp- tions of newer technques such as Fourier ‘wansfonm stared spectroscopy TLR), attenuated total reflectance spectovsopy (ATR) and primary references, see 142. For representative spectra of chemical finishes, see 14.3 72 Both grating instruments and Fourier transform interferometers are capable of producing high quality spectra for identification and reference purposes. ‘Other spectroscopic techniques such as laserRaman spectroscopy. NMR. spec- troscopy and. UV-visible. spectroscopy amy also be utilized, if available, to fir ther identify the exacts. Figs. 1-5 repre= sent infrared specta sun on an FTIR specuophotometer with MCT detector at 4 resolution of 4 wavenumbers, sianal faveraged over 30 scans With HAPP- ‘Gensel apodization sast on KRS-S exysx tal. Big. 6 represeats a proton NMR spectrum of dimethylbdihydroxyethylene- ‘wea (DMDHEU), cellulose reactant in deuterium oxide, Figs. 7 and § represent laser Raman specta of aqueous solutions of celilose reactants using an argon ion laser source, Figs, 9 and 10 represent HPLC runs of celulose reactants using Refractive Indes (RL) detector, § micros (C-18 reverse phase cohimmn, with 100% ‘water mobile phase pumping at 1.0 mL! tin Fig. 11 represcats an Xoray fhionss= feence specinim taken from a scanning electron microscope imae using aliquid nitrogen cooled detector with an enetsy sauge of 0-5 kiloelecon-vols. For other examples of infiared spectra, see 143 and 14.4, 17.3 Infrared Sample Preparation. 73.1 Techniques. Finish samples can be prepared for infrared analysis by one of the following methods: dissolve the extract in suitable solvent, for analysis as a liquid of as a cast film: grind the textile ‘sample to small particle size and mull in mineral oil; pelletize the extract or ground textile sample into a homoge- neous mixture with potassium bromide (KBr) (see 14.2). "7.4 Infrared Analysis, 7.4.1 Obtain a spectrum of the sample or extract prepared by one of the above techniques. The identity of the applied finish 1s confirmed by comparison ofthe sample spectrum with known inftared specira, For more accurate identification, the spectrum of the known compound should be obtained with the same appli cation and extraction history as the i= Jnuown finish. polyacrylates are’ partially soluble in uuichloroethylene or 1,1,1-richloroethane, ‘The extract is concentrated and trans ferred toa clean KBr disk. 7.4.3 Durable Press Finishing Agents. ‘Since most durable press finishing agents ean be extracted with either water or hy= ddrochloric acid, this provides an alternate ‘method for removing finichee for infinred spectroscopy. Approximately 0.2 g fab- 7c, cut into small squares, is refluxed for '$ min in 0.1 V HCL The solution is then decanted into a $0 mL round-bottom ‘ask with 350 mg spectral grade KBr and evaporated to dryness on a rotary evapo rtor while the flask is immersed in an {ce-salt bath to prevent further hydrolysis. Final drying over phosphorus ‘produces a residue that is mixed with ‘more KBr (jn 2 $0 mg:300 mg ratio) and pressed into a disk. A spectrum is ob- tained and compared to that of known ‘compounds, with spectra of hydrolyzates ‘of known compounds preferable for ac- ‘curate comparison. Another method of sample preparation {for identification of durable press finishes by infiared spectroscopy is to grind the fabric and pelletize it with spectral arade KBr. Differential infrared spectra relative to ground unfinished fabric are then ob- tained. KBr disks containing equivalent amounts of specimen in both beams of a double beam spectrophorometer compen- spectral subtraction techniques may also ‘be used to achieve differential spectra. 7.4.4 A quick alternative for acquiring infrared spectra of finishes was described in the 1972 Tntersectional Technical Pa- pet Competition presented by AATCC Rhode Island Section (See 14.5). The ‘TMo4-2012 151 CCopyrih © 2015 American Associaton of Textile Chemists and Colorsts‘method relies on the transfer of finish by solvent from a small rectangle of fabric placed on the surface of an ATR erystal. ‘The solvent is evaporated leaving a thin film of finish residue. The crystal placed in the ATR accessory holder and ‘the spectrum recorded. 18. Direct Spectroscopic Analysis of Fabric 8.1 With certain types of accessories ‘and spectroscopic techniques, itis pose sible to acquire direct spectra of both the fabric substrate and the finishing com- ‘ponents on it. These techniques may in ‘ude infiared reflectance with ATR’ and diffuse reflectance accessories, photo- acoustic spectroscopy (PAS), laser Raman spectra, electron spectroscopy for ‘chemical analysis (ESCA) and near infra red reflectance spectroscopy (NIR). In ‘many cases, computerized spectral sub- ‘action teciques are usefal in identify ing small amounts of finish on fabric. 9. Chromatographic Procedures 9.1 Chromatography is a very usefl rmetod for the separation and tentative identification of some of the finishes on textile fabrics After separation is accom plished, identification is made by ehio- aoerpie io koowh cea pounds either in pure form oF after being Euhjected othe same appication md ex ‘wacton history as the unknown. identifi ‘atin eee Compson sales at est ‘tro different Seis of chromato conditions Altematvely, the chrommto- ‘graphic peak of interest may be identified Spectroscopically on line or afer isola ‘Hon, For most analyses, Soxhlet extracted resides oftheir derivatives may be ana- lyzed by GC. HPLC or TLC. Applica asin tts Section ae ple techniques for use with basic GC. or HPLC. For information on more complex ‘and diverse instruments and methods see 142 Ste Cima. Ge Clan raphy involves the separation of a fhienreof Vole substances a i is car tied through a colozn of surfaces that ine ‘eract differentially with the vious com> ponents of the mixtre ‘92.1 Formaldehyde. Formaldehyde re- leased ffom fabrics may be detected by ‘GC. A fabric sample is enclosed in vial ‘witha defined headspace and conditioned ‘under precise temperature and hnmidity Samples of the headspace nas are injected for GC analysis. Ths system can also be weed to determine the amount of mathe nol released by hydrolysis of methylated \Nametiylol groups found in some dura- bile press resins, Since the FID signal fron formaldehyde is not very strona, a amthanizer may be placed between the ‘column and the flame for conversion of fonmaldehyde to methane. Alcobols axe 162 TM94-2012 also converted to corresponding, hydro- ‘carbons. Conditions for formaldehyde analysis are: ‘Column: 3 m Porepak T Injection time: 9 s Bath: 65°C Needle: 150°C (Oven: 120°C Injection port: 180°C Detector: 480°C A photoionization detector may also be ‘used for increased sensitivity. For further information on this type of analysis see 142 9.2.2 Softeners, Labricants, and Emmul- sifiers. Solvents such as hexane or Freon T13 are used to exttact softeners, lubri- ‘cants and emulsifier from fabrics. These three groups of profucts are commonly ‘made from fatty acids and fatty acid es- ‘eis of their derivatives, Some of these ‘compounds can be cluomatoaraphed di- secily and some must be made into deriv- atives to be better detected by GC. Other long chain fatty compounds are ‘more easily analyzed after derivatization. Monocarboxylic acids are esterified. usually with methanol, and these methyl esters are analyzed as follows: Column: 48 m x 0.25 mm DEGS open tubular ‘column, Column temperature: 180°C. Silylation, another method of derivati- zation of fatty acids and fatty alcohols, forms non-polar, volatile, thermally stax ble ethers. These ethers form easily. and the reactions, are rerformed in it Edi, Hv Amora, 1968 Fig. 1—Infrared spectrum of a fatty ester softener. 154 ‘TM94-2012 Fig. 2—Infrared spectrum of a silicone softener. AATCC Technical Manual2016 CCopyrih © 2015 American Associaton of Textile Chemists and Colorsts. an) \ i iy I \ I i Fig. 3—infrared spectrum of a DMDHEU cellulase reactant. Fig. 5 Infrared spectrum of a fuorochemical soll release agent. (1,3 dichloropropyl) phosphate flame retardant, Fig. 6—Proton NMR spectrum of ‘DMDHEU cellulose reactant. \ | | ie i i is ‘A yi! | Lr ul NM / a abr * WAVENUMBER om Fig. 7—Laser-Raman spectrum of ‘DMDHEU cellulase reactant AATCC Technical Manval2016 oOo 8 ue 1 WAVENUMBER cm Fi, Ase Raman spect of ety * ‘carbamate cellulose ™! TMo94-2012 155 CCopyrih © 2015 American Associaton of Textile Chemists and Colorstsew AN __| wu! toa A Fig. 9—High performance liquid chromatogram of Fig. 10—High performance liquid chromatogram of SN DMOHED celiise reacant. 9% aeolted DMDHED caliose ree. Be g<7 Detector Response Fig. 11—XRay fluorescence spectrum of a magnesium ‘hloride-aluminum chloride catalyst. 4 6 8 10 Minutes —> Fig. 2 Separaton of 2 4-dntophenly ating rivatives of aldehydes: (A) solvent pe (@)aiveeradahyde DNPH: (C) fomaldehyte he (0) aztadomde DNPH: eprotoalehye ON isobutyladehyde DNPH 166 TM94-2012 AATCC Technical Manual2016 CCopyrih © 2015 American Associaton of Textile Chemists and Colorsts