Ultrasonic dyeing of cationized cotton fabric with natural dye.Part 1: Cationization of cotton using Solx EM.M. Kamel*, M.M. El Zawahry, N.S.E. Ahmed, F. AbdelghaffarNational Research Centre, Textile Research Division, El-Behoos Street, Dokki, P.O. Box 12622 Cairo, Egyptarti cle i nfoArticle history:Received 25 March 2008Received in revised form 22 July 2008Accepted 7 August 2008Available online 15 August 2008Keywords:CationizationCottonUltrasoundSonochemistryCochineal dyeDyeingabstractThe dyeing of cationized cotton fabric with Solx E using colouring matter extracted from Cochineal dyehas been studied using both conventional and ultrasonic techniques. Factors affecting dye extraction suchas ultrasound power, particle size, extraction temperature and time were studied. The results indicatedthat the extraction by ultrasound at 300 W was more effective at lower temperature and time than con-ventional extraction. The effect of various factors of dye bath such as pH, salt concentration, ultrasoundpower, dyeing time and temperature were investigated. The colour strength values obtained were foundto be higher with ultrasound than with conventional techniques. The results of fastness properties of thedyed fabrics were fair to good. The scanning electron microscope (SEM) images of the morphological andX-ray analyzes were measured for cationized cotton fabrics dyed with both conventional and ultrasoundmethods, thus showing the sonicator efciency. 2008 Published by Elsevier B.V.1. IntroductionThedyeingofcottonfabricswithanionicdyessuchasdirectand reactive dyes requires the presence of large quantities of elec-trolyte to increase dye uptake, resulting in serious environmentalproblems. As a result of this process, large volumes of wastewater,containingsignicant amounts of dyes andchemicals, aredis-charged from a typical cotton dye house [1]. One method of avoid-ing this problem is to cationize the cotton bre by cationic agentsthatincreasethecolourstrengthof thedyeingprocessandim-proved wash fastness [2].Naturaldyesaregenerallyenvironmentallyfriendlyandhavemanyadvantagesoversyntheticdyes[3]. Inrecentyears, therehas been an interest in the application of these dyes due to theirbio-degradability and higher compatibility with the environment[47]. Cochineal dyewhichisisolatedfromthedriedbodiesofthefemalescaleinsectswasthemainreddyeusedinCentralAmerica before the Spanish conquest. During the 16th century, itwas imported into Europe and began to replace the domestic ker-mes as an artists pigment and for dyeing [8]. These insects are stillcollected in Peru and India to furnish the permanent brilliant car-mine for the food,drink and cosmetic industries and artistscol-ours [8,9]. Thecompoundresponsiblefor thepurplecolour ofthis dye is carminic acid [1012].Theuseofultrasoundenergyfordyeingtextilesasacleanerproduction is very well known in the literature [1315], Although,it has not been applied in the area of dyeing with natural dyes asmuch as it is being used for direct and reactive dyes. Ultrasoundcanenhanceawidevarietyof chemical andphysical processes,mainly due to the cavitation effect in liquid mediums (that is thegrowth and explosive collapse of microscopic bubbles, whichcauses a large increase in the pressure and temperature) that en-hances the rate of dyeing process.The aim of this work was to focus on the use of ultrasound (US)for enhancingthe dyeing efciencyandfastness properties ofcationized cotton fabrics with Solx E using Cochineal as a naturaldye. Althoughit was previously reported that the exhaustionmethod was the applicable method for cationization of cotton fab-ricswithSolxE[16], ourpresentstudywastherstworktoinvestigateusingthepaddrycurecationizedmethodforcottonfabrics. Different factors affecting dyeability and fastness proper-ties were thoroughly investigated. Comparative results of the dye-ingefciencyofcationizedcottonfabricsusingboththeUSandconventional (CH) dyeing methods are also presented. The micro-scopicimagesobtainedbySEMandX-raydiffractiontechniqueswere also investigated to provide visual evidence of the existenceof ultrasonic effects.2. Materials and methods2.1. DyesThe whole insect part of Cochineal was used and it was suppliedfromlocal marketing inEgypt as a powder form, whichwas1350-4177/$ - see front matter 2008 Published by Elsevier B.V.doi:10.1016/j.ultsonch.2008.08.001*Corresponding author. Tel.: +20 2 33371718; fax: +20 2 33370931.E-mail address: mona_kamel_nrc@yahoo.com (M.M. Kamel).Ultrasonics Sonochemistry 16 (2009) 243249ContentslistsavailableatScienceDirectUltrasonics Sonochemistryj our nal homepage: www. el sevi er . com/ l ocat e/ ul t sonchimported from India. The characteristics of this commercial mate-rialwereasfollows:thebotanicalnameoftheCochinealdyeisDactylopiuscoccus, theC.I. nameisNatural Red4, theclassisAnthraquinone, and kmax in water is 532 nm.2.2. FabricsIn this work scoured and bleached cotton fabric (142 g/m2) wassuppliedfromMiser SpinningandWeavingCompany, MahallaEl-Kobra., Egypt. Before being used, the fabric was treated with asolution containing 5 g/L non-ionic detergent (HostapalCV,Clariant), at 95 C for 4 h. Then the fabric was thoroughly washedwith water and air dried at room temperature.2.3. Cationic agentsSolx E was supplied by Ciba GeigyCo., Germany as an aque-ous solutionof approximately40%solidcontent. It is a poly-aminochlorohydrin quaternary ammonium polymer with epoxidefunctionality thatcanreactwithcelluloseviaetherformationinthe presence of alkalis [16].2.4. Ultrasound equipmentA CREST Ultrasonic, TRU-SWEEPTMultrasonic bench top cleanerbath, model575 Dwithacapacity5.75 L, wasused. Theexperi-mentalsetupusedwascomposedofanelectricalgeneratoratafrequencyof 38.5 kHzandpowerrangingfrom135 Waverage/500 W. Theoutput powerlevelsarefrom50upto500 W, andare supplied by three transducers at the bottom of the industrialgrade tank. Precise digital control of time (090 min), thermostat-ically controlled heater (ambient to 80 C), power level and degasfunctions. Theinternal dimensionsofthetankwere11.5 6 6depth and 292 152 152 mm.2.5. Conventional extractionConventional extraction was carried out in 100 mL water usingavaryingamount of thedyematerials(0.11.0 g) for differenttimes (15120 min) and at different temperature (50 80 C).2.6. Ultrasound extractionUltrasound extraction was carried out as above in 100 mL dis-tilledwater usingvaryingamounts of thedyematerials (0.11.0 g) at different temperatures(5080 C) usingdifferent sonicpower (100500 W) for different time intervals (15120 min).2.7. Cationization of cotton with the pad dry cure methodCotton fabrics were padded at 100% wet pick up through a solu-tionofNaOH(15 g/L)anddifferentconcentrationofSolxE(0150 g/L). Tominimizereactant hydrolysis, thealkali wasaddedto the padding bath just prior to application. The padded sampleswere then dried at 80 C for 3 min and cured at 115 C for 4 min.Then samples were rinsed several time with water and nally neu-tralized with a dilute acetic acid solution (12 g/L), the fabric wasthoroughlyrinsedwithwater, followedbysoapingwith3 g/Lofnon-ionicdetergentataboilfor30 min, thenrinsedwithwaterand air dried.2.8. Dyeing procedureCationized cotton fabric was dyed with natural colouring mat-ter extracted fromCochineal insects (0.5 g/100 mL water) for60 min using US at 80 C. The fabrics were CH dyed with a liquorratio 1:30 at different pH values (210), concentrations of glaubersalt (015 g/L), for different durations (15240 min) and tempera-tures(3080 C). Forcomparison, thesameconditionsofdyeingwere carried out using US at different sonic power (100500 W).Finally, the dyed samples were rinsed with cold water and washedin a bath containing 3 g/L non-ionic detergent (Hostapal CV, Clari-ant) at 90 C for 30 min using a liquor ratio 1:30. The fabrics werethen rinsed and air dried. The optimum condition was elevated fordyed cationized cotton fabrics.2.9. Measurements and analysis2.9.1. Determination of nitrogen percentageNitrogen was determined by the Cole and Parks modication ofthe semi-micro Kjeldahl method [17].2.9.2. Fourier transform infrared spectroscopic analysisFouriertransforminfrared(FTIR)spectrawererecordedonaNexus 670 FTIR Spectrometer, Nicolet Company, USA using potas-sium bromide disks. A total of 32 scans for each sample were takenwith a resolution of 4 cm1, with a range of 4000400 cm1.2.9.3. Colour measurements of the dyed fabricsThecolourstrengthof thedyedsampleswasevaluatedbyalight reectance technique using the PerkinElmer, UVVis Spec-trophotometer(Model, Lambda3B). Therelativecolourstrength(K/S values) was assessed using the KubelkaMunk equation [18]K=S 1 R22R2.9.4. Scanning electron microscopeTheuntreatedandultrasonictreateddyedcottonfabricwereexamined using a SEM Model Philips XL 30 with an EDX Unit at-tached, withacceleratingvoltageof30 kVandmagnicationbe-tween10and400.000. All thesampleswerecoatedwithgoldbefore SEM testing.2.9.5. X-ray diffractionAn X-ray diffraction analysis was performed at room tempera-tureforthecationizedcottonfabricdyedwithbothCHandUSmethod, on an X-ray diffractometer model Philips XPert MPP witha type PW 3050/10 goniometer. The diffractometer controlled andoperated by a PC computer with the programs P Rot and used aMo Ka source with wavelength 0.70930 , operating with Motuberadiationat 50 kVand40 mA. Thescanparametersrangefrom2 < 2h < 50 with scanning step of 0.03 in the reection geometry.2.9.6. Particle size measurementThe mean diameters of the partially soluble Cochineal dye weremeasured by particle size analyzer (Fritsch Analystte 22, Laser ana-lyzer). All the samples were measured in the Research and Devel-opment Institute, Technical services Department.Table 1Effect of different concentrations of Solx EConcentration. of Solx E (g/L) Nitrogen content (%) K/SCH US0 0.00 0.0998 0.32525 0.169 5.37 5.7250 0.337 6.18 6.6275 0.680 6.39 6.84100 0.712 6.50 6.90125 0.740 6.61 6.98150 0.760 6.61 7.02244 M.M. Kamel et al. / Ultrasonics Sonochemistry 16 (2009) 2432492.9.7. Fastness propertiesThe dyed samples were tested according to ISO standard meth-ods. The specic tests were ISO 105-X12 (1987), colour fastness torubbing; ISO 105-C02 (1989), colour fastness to washing and ISO105-E04 (1989), colour fastness to perspiration.3. Results and discussion3.1. Effect of different concentrations of Solx EThe results in Table 1 reveal that as the concentration of Solx Eincreasedfrom0to150 g/L, thenitrogenpercent (N%) of thecationizedcottonfabric was alsoincreasedfrom0%to0.760%andduetothis increasethecolour strengthalsoincreased. Itwas observed that the maximum dye uptake with pronounced in-crease in K/S values was obtained at 75 g/L and above this the N%levelsoff. Theresultsalsoshowthatthecolourstrengthvaluesof US dyeing methods are generally higher than those of CH dyeingmethods. This enhancement effect of US power may be due to cav-itation effect [14]; this point will be discussed in detail later.3.2. FTIR analysisFTIR spectra were obtained for the untreated (A) and treated (B)cotton fabric with cationizing agent Solx E (nitrogen content of 0%and0.68%, respectively), asshowninFig. 1. Inthetreatedfabriccertain absorption bands can be observed in the 1116 cm1range(CN stretching vibration) as well as an intensive distinct band at1059 cm1which arecharacteristicofprimary-COH stretchingdeformation, which are not present in the untreated fabric in spec-trum (A). The spectrum of the cationized cotton fabrics with SolxE is markedly different from the uncationized fabric.In addition, the broad absorption band within 3352 and1032.71 cm1for the unmodied cotton fabric revealed the pres-enceof numeroushydroxyl groups. However, the(primary-OH)band of the cationized cotton become narrow with a higher inten-sity within 3346 and 1033 cm1with increasing nitrogen contentof the cationized fabric.These distinct narrow, high intensity bands (OH/N+R3) conrmpresenceof thequaternaryammoniumsalts. Inaddition, atwosplitting distinct bands can be observed in the spectrum (B) within 2922 and 2853 cm1, 1430 and 1373 cm1corresponding to ali-phaticCHstretching, bendingdeformationsandrockingvibra-tions of the methylene groups (CH2).3.3. Factors affecting dye extraction3.3.1. Effect of ultrasound powerThe effect of US on the extractability of Cochineal dye was con-ducted at different power levels (100500 W). As shown in Table 2,theresults indicatethat as theUSpower increasedfrom0to300 W, theaverageparticlesizeof theCochineal dyedecreasedand due to that the concentration of the extracted colouring matterwould also increase in the dye bath and the colour strength wasalsoincreased. However, at ahigher power level (400500 W),the average particle size increased slightly and due to that the con-centration of the extracted colouring matter decreased and the col-our strength of the dyed sample was also decreased. This may beattributedtoapowerlevel (400500 W)thatwastoohighandwould cause an increase in the bubble numbers in the dye solutionFig. 1. FTIR spectra of (A) untreated cotton fabric and (B) treated cotton fabric.Table 2Effect of ultrasound dye extraction power level on the colour strengthPower level (W) Particle size (lm)aStandard deviationaK/SCH US 1.5025 0.31 4.42 5.37100 1.2375 0.35 6.18 6.73200 1.190 0.37 6.50 7.23300 1.1475 0.33 6.73 7.50400 1.2103 0.31 6.61 7.10500 1.229 0.32 6.39 6.81aThe average particle size of two determinations and standard deviations.M.M. Kamel et al. / Ultrasonics Sonochemistry 16 (2009) 243249 245duringthecavitationphenomenonwhichmightreducetheef-ciencyof the ultrasoundenergytransmittedintothe medium[19,20]. Theseresultsemphasizetheenhancement effect of US,which increases the rate of dye extraction from Cochineal insectsbyvirtueof its dispersion, degassinganddiffusioncapabilities(accelerating the rate of dye desorption from the insect body). Onthe other hand, it can be observed from Table 2 that US in compar-ison with CH extractability will enhance the dyeability as the col-our strength values associated with pronounced increase using USthan CH dyeing method and this point will be discussed in detaillater.Consequently, a power level of300 Wwaschosen as anopti-mumpowerlevelforthedyeextractionmethod. Somedyesex-tractedviaUSaremoresusceptiblethanotherstotheeffectofUSwithdifferentpowerlevels. Thisobservationmeansthat, foreach dye there is an optimum US power level [21].3.3.2. Effect of extraction temperaturePrevious studies have shown that the CH extraction of naturaldyesintoanaqueoussolutionistemperature dependantandin-creasesasthetemperatureapproachedtheboilingpointof thesolution. To fully investigate the effect of the US efciency of thedye extraction, the temperature of the extraction mixture was re-duced below its boiling point.As shown in Fig. 2, it is clear that the concentration of colouringmatter increased when the extraction temperature was increasedup to 80 C while using US extraction method. This also producedapronouncedincreaseinthecolourstrengthoftheUSthantheCH dyeing method. The results emphasize the enhancement effectof power US on reducing the dye extracted temperature of Cochi-neal dye.3.3.3. Effect of dye amountThe extraction of Cochineal dye at different dye amounts (0.11.0 g/100 mL) performed using US (300 W) at 80 C for 60 min.Fig. 3 shows that as the dye amount increased, more dye extractalso increased up to 0.5 g/100 mL water which was associated witha higher colour strength values increment. The K/S value then lev-elsoffabovethisconcentrationwhenusingeithertheUSorCHdyeing method, and shows much higher values at all points in USextracted and dyeing methods as expected.3.3.4. Effect of extraction timeThe effect of the extraction time using US extraction of Cochi-nealdyewascarriedoutfordifferent times(15120 min). Fig. 4shows that the K/S value increases with increased extraction timefor both the US and CH dyed methods, with a pronounced increasein the US case than the CH case.The results in Fig. 4 clearly indicate that the K/S values of thedyed cationized cotton fabric using US increased rapidly in the rst60 min. It is worth mentioning that, as the time of dye extractionincreased; more dye was extracted, which leads to higher K/S val-ues of dyed cationized cotton fabric. After 90120 min the K/S val-ues began to decrease, which may be due to degradation of the dyemolecule. On the other hand, the K/S values of dyed cationized cot-ton using the CH method increased continuously as the extractiontime increased (15120 min). When the time of extraction reaches120 min, the K/S values of cationized cotton are still lower than theUS dyeing method at 60 min. These results illustrate the benet ofusing US waves in dye extraction due to dispersion, degassing anddiffusion(acceleratingtherateofdyeextractionfromtheinsectbody).3.4. Factors affecting dyeing properties3.4.1. Effect of dye bath pHFig. 5 shows the effect of the pH values of the dye bath on boththeCHandUSdyeingprocessforcationizedcottonfabrics. Itisobviousthat, asthepHvaluesofthedyebathincreasedfrom2to 4, the colour strength values also increased in both cases, witha slightly improvement in the dyeability in case of the US dyeingprocess. As the pH increased >4, the K/S values of cationized cottondecreased markedly. The effect of the dye bath pH can be attrib-uted to the correlation between the dye structure and cationizedcotton bres. Since the Cochineal dye used acts as an acid dye, itwould interact ionically with the protonated terminal aminogroupsofthecationizedcottonbresunderacidicmedium(pH4) via electrostatic dye attraction. In addition, additional interac-tionstakeplacetogetherwithionicforces. Thisionicattraction5.65.866.26.46.66.877.27.47.650 60 70 80Temperature (C)K/SCHUSFig. 2. Effect of dyeextractiontemperatureonthecolour strength(extractionconditions:concentrationof dye0.5 g/100 mL, 300 W, for60 min, dyeingcondi-tions: L.R. 1: 30, pH 4, 500 W, at 80 C for 60 min).3456780.1 0.2 0.3 0.5 0.7Dye amount ( w/v %)K/SCHUS1Fig. 3. Effect of dye extraction amount on the colour strength (extractionconditions: 300 W, at 80 C for 60 min, dyeing conditions: L.R. 1: 30, pH 4, 500 W,at 80 C for 60 min).K/S55.45.86.26.677.47.815 30 45 60 90 120Extraction time (min)CHUSFig. 4. Effect of dye extraction time on the colour strength (extraction conditions:concentration of dye 0.5 g/100 mL, 300 W, at 80 C, dyeing conditions: L.R. 1: 30, pH4, 500 W, at 80 C for 60 min).246 M.M. Kamel et al. / Ultrasonics Sonochemistry 16 (2009) 243249wouldincreasethedyeabilityofthebre, asisclearlyshowninFig. 5. However, atapHabove4, theionicinteractionbetweenthe dye and cationized cotton fabric decreased due to the decreas-ing number of protonated terminal amino groups of the cationizedcotton fabrics, thus lowering its dyeability [14].3.4.2. Effect of ultrasound powerTheeffectofultrasonicpoweronthedyeabilityofcationizedcotton fabrics withCochineal dye was conducted at differentpower levels (100500 W). As shown in Fig. 6, the colour strengthof dyed fabrics seemed to be directly increased proportionalwiththepower suppliedtill 300 W, thenalevelingoff occurs.Increasing the US power above 300 W does not have an additionaleffect on the dyeability of the cationized cotton fabrics.The improvement of the US dyeing process up to 300 W may bedue to the acoustic cavitation phenomenon, which would lead to[13,22]:dispersion(breakingupof micellesandhighmolecularweight aggregates into uniformdispersions in the dye bath),degassing (expulsion of dissolved or entrapped gas or air moleculesfrom bre into liquid and removal by cavitation, thus facilitatingdye-bre contact), and diffusion (accelerating the rate of dye diffu-sion inside the bre by piercing the insulating layer covering thebre and accelerating the interaction or chemical reaction betweenthe dye and cationized bre). Above 300 W an increase in the bub-ble numbers in the dye bath during the cavitation phenomenon oc-curs which may reduce the efciency of the US energy transmittedinto the medium [19,20].3.4.3. Effect of salt additionFig. 7 shows theeffect ofthe added saltconcentrationon thecolour strengthof thedyedfabrics usingboththeCHandUSmethods. It is clearly indicated that, in the absence of salt, the col-our strength in case of the US dyeing method was higher than theCH dyeing method. Moreover, as the salt concentration increasedfrom (015 g/L) the colour strength also decreased in both dyeingmethods, which is good for the environment.3.4.4. Effect of dyeing temperatureTheeffectof temperatureonthedyeabilityof thecationizedcottonfabricsdyedwithCochinealdyewasconductedunder USand CH conditions at different temperatures (3080 C). As shownin Fig. 8, it isclear that thecolour strength (K/S)values increasewithincreaseinthedyeingtemperatureinboththeUSandCHmethodswithamorepronouncedincreaseintheUScasethanthe CH method.Generally, in case of the US dyeing method, the K/S values in-crease as the temperature increased from 30 to 80 C. This resultmaybeduetothebreswellingeffectsthat enhancethedyediffusion. Also, theUSpowerprovidesotheradditional factorofde-aggregation of the dye molecules. This leads to a faster motionand stirring effect in the US dyeing method, thus leading to a fur-ther enhancementof dyediffusion and better dyeability as com-pared to the CH dyeing method.3.4.5. Effect of dyeing timeThe effect of dyeing time was studied under US and CH condi-tionsfordifferentdyeingtime(15240 min)torevealtheeffectof power ultrasonic on the dyeability of the cationized cotton fab-rics dyedwithCochineal dye. As showninFig. 9, the colourstrengthobtainedwasincreasedasthetimeincreasedforbothUS and CH methods, with a much higher colour strength value atall points in the US case. In both dyeing methods a plateau is at-tained after 60 min and then no change in K/S values was observedbeyond 90 min.K/S3456782 8pHvalueCHUS3 4 5 6 10Fig. 5. Effect of dye bath pH on the colour strength of dyed cationized cotton fabrics(extractionconditions: concentrationof dye 0.5 g/100 mL, 300 W, at 80 Cfor60 min, dyeing conditions: L.R. 1: 30, 500 W, at 80 C for 60 min).6.26.46.66.877.27.47.60 100 200 300 400 500Power level (W)K/SFig. 6. Effect of US power onthe colour strengthof cationizedcottonfabric(extractionconditions: concentrationof dye 0.5 g/100 mL, 300 W, at 80 Cfor60 min, dyeing conditions: L.R. 1: 30, pH 4, at 80 C for 60 min).456780 2.5 5 7.5 10 15Salt conc. (g/L)K/SCHUSFig. 7. Effect of salt additiononthecolour strengthof dyedcationizedcottonfabrics (extraction conditions: concentration of dye 0.5 g/100 mL, 300 W, at 80 Cfor 60 min, dyeing conditions: L.R. 1: 30, pH 4, 300 W, at 80 C for 60 min).34567830 40 50 60 70 80Temperature (C)K/SCHUSFig. 8. Effect of dyeingtemperatureonthecolour strengthof dyedcationizedcotton fabrics (extraction conditions: concentration of dye 0.5 g/100 mL, 300 W, at80 C for 60 min, dyeing conditions: L.R. 1: 30, pH 4, 300 W, no salt, for 60 min).M.M. Kamel et al. / Ultrasonics Sonochemistry 16 (2009) 243249 2473.4.6. Morphological studyTheSEM technique was usedto investigate the change in thesurface morphology of the dyed cationized cotton fabric with boththe CH and US dyeing methods. The results obtained are shown inFig. 10. It is obvious that the bres dyed with the CH method (a) aresmooth and distinct. In contrast, the bres dyed with US method(b)arenolongersmoothandbecomerough. Theseresultsmaybe due to the creation of voids in the bre structure, lead to a phys-ical looseningof themicrostructureof thedyedbrewithanincreasingmorepossibilityforthepenetrationofthedyemole-cules into the bres. On the other hand, the US dyeing method isassociatedwithcavitationeffects, whichwouldleadto[11,21]:dispersion, degassinganddiffusion(acceleratingtherateof dyediffusion inside the bre by piercing the insulating layer coveringthe bre and accelerating the chemical reaction between dye andbre).3.4.7. X-ray analysesTheX-raydiffractionpatternsforthecationizedcottonfabricwithSolxEdyedwithboththeCHandUSmethodareshownin Fig. 11. The CH dyed method (1) showed one major sharp peakat 2h 10.50 with a higher intensity that represent the crystallin-itytogetherwithothersmall broadpeaksat 2h 15.60 andaFig. 10. SEM photographs of cationized cotton fabrics (a) dyed with CH method and (b) dyed with US method.Fig. 11. X-ray diffraction patterns of cationized cotton fabric dyeing with (1) CH dyeing method and (2) US dyeing method.Table 3Effect of CH and US dyeing method on crystallinity, crystallite size, 2h angle and d-spacing of cationized cotton fabricDyeingmethodCrystallinity(%)2h () d-Spacing()Crystallite size()CH 51.35 6.83, 7.59, 10.50,15.603.87467 38.44US 44.00 6.69, 7.58, 10.43,15.393.90248 20.7655.566.577.5815 30 45 60 90 120 180 240Dyeing time (min)K/SCHUSFig. 9. Effect of dyeing time on the colour strength of dyed cationized cotton fabrics(extractionconditions: concentrationof dye 0.5 g/100 mL, 300 W, at 80 Cfor60 min, dyeing conditions: L.R. 1: 30, pH 4, 300 W, no salt, at 80 C).248 M.M. Kamel et al. / Ultrasonics Sonochemistry 16 (2009) 243249broad peak at 2h 6.83, 7.60 with a lower intensity. The US dyedmethod (2) is characterized by four peaks, one broad peak with lessintensive percent at 2h 6.69, 7.58 which is mainly amorphous,and a high intensive sharp peak at 2h 10.43 as well as anothersmall peak at 2h 15.39. The crystallinity percentage was calcu-latedbyevaluationoftheareaofthesharpandbroadpeaksinFig. 11 and estimated according to the following equation [23]:Cx% ICICIa100where Cx% is the crystallinity percentage and Ic and Ia are the inten-sities of the X-ray diffraction pattern of the crystalline and amor-phouscomponents, respectively. ItisclearfromTable3thattheUS dyeing method decreased the crystallinity as well as the crystal-lite size than the CH dyeing method, which indicates that the amor-phous region increases. An increase in the d-spacing values of theUS dyeing method as compared to CH dyeing method occurred intheindicatedregion. Itcanbeconcludedthatthedyeuptakein-creased via dyeing with the US method [24].4. Fastness propertiesThe fastness tests involving washing, rubbing, perspiration(acidalkali)andlightofdyedcationizedcottonfabricusingtheUS and CH methods are shown in Table 4. The results indicate fairto good fastness properties of the dyed samples using both the USand CH methods. Generally in the case of washing and perspirationfastness properties did not alter where a decrease in rubbing fast-ness was observed in both CH and US methods.5. ConclusionsUltrasound appears to be an effective technique for the extrac-tionof Cochineal dye andgave maximumextractionvalue at300 W which was associated with decreasing the average particlesize. BetterK/Svalueswereobservedfordyedcationizedcottonfabrics using ultrasound compared to the results obtained via theconventional method. The results of X-ray diffraction studies andSEMimagesprovidedvisual evidencethat theultrasoundtech-nique is useful in enhancing the dyeability as measured by K/S val-ues, than the conventional dyeing method. Comparing the fastnessproperties for the ultrasound and conventional method, the resultsindicate fair to good fastness properties of the dyed samples usingboth techniques.AppendixUltrasound USConventional CHFourier transform infrared FTIRNitrogen content percent N%References[1] P.J. Hauser, A.H. Tabba, Color. Technol. 117 (5) (2001) 282.[2] D.M. Lewis, S. Lei, Text. Chem. Color. 21 (1989) 23.[3] H.T. Deo, R. Paul, Int. Dyer. 188 (2003) 49.[4] H.T. Deo, R. Paul, Indian J. Fibre Text. Res. 25 (2000) 152.[5] R. Paul, C. Solans, P. Erra, ColloidsSurf. A: Physicochem. Eng. Aspects253(2005) 175181.[6] M.D. Teli, P. Roshan, P.D. Pardeshi, Colourage 12 (2000) 4348.[7] M.M. El-Zawahry, M.M. Kamal, J. Text. Assoc. 62 (3) (2001) 101106.[8] M.S. Maier, S.D. Parera, A.M. Seldes, Int. J. Mass Spectrom. 232 (2004) 225229.[9] M.V. Caamares, J.V. Garcia-Ramos, C. Domingo, S. Sanchez-Cortes, Vib.Spectrosc. 40 (2006) 161167.[10] C. Gurnham (Ed.), Industrial Waste Control, Academic Press, New York, 1965.[11] H. Schweppe, H. Roosen-Runge, in: R.L. Feller (Ed.), Artists Pigments: AHandbook of Their History and Characteristics, vol. 1, Oxford University Press,Washington, 1986, p. 255.[12] N. Willmott, J. Guthrie, G. Nelson, J Soc. Dyers Colour 114 (1998) 3841.[13] R. El-Shishtawy, M.M. Kamel, H.L. Hanna, N.S.E. Ahmed, Polym. Int. 52(3)(2003) 381388.[14] M.M. Kamel, R. El-Shishtawy, B. Youssef, H.M. Mashaly, DyesPigments73(2007) 279284.[15] M.M. Kamel, H.M. Mashaly, Man-Made Text. India (August) (2007) 280287.[16] R.M. El-Shishtawy, S.H. Nassar, Color. Technol. 118 (2002) 115.[17] A.I. Vogel, Elementary Practical Inorganic Analysis, second ed., Longman,London, 1975. p. 625.[18] D.B. Judd, G. Wysezchi, ColourinBusiness, ScienceandIndustry, thirded.,1975.[19] A.V. Filgueiras, J.L. Capelo, I. Lavilla, C. Bendicho, Talanta53(2000) 433441.[20] S. Vajnhandl, A.M. Le Marechal, Dyes Pigments 65 (2005) 89101.[21] M.B. Atul, J.C. Michael, N.M. Gary, AATCC International Conference andExhibition, September 1518, 1996, pp. 309322.[22] G.V. Datar, P. Banks-Lee, P.L. Grady, Appl. Acoust. 48 (1) (1996) 3345.[23] A. Guio, L. Aldo, JSDC 106 (1) (1990) 18.[24] J. Good, J. Zhan, D. Klutz, G. Mock, H.W. Beckham, ATCC InternationalConference and Exhibition, Atlanta, GA, 811 October, 1995.Table 4Fastness properties of dyed cationized cotton fabrics using CH and US dyeing methodsDyeing methods Washing Perspiration Rubbing fastness LightAcid AlkaliAlt. C W Alt. C W Alt. C W Dry WetCH 4 4 4 4 34 34 45 3 4 34 12 2US 34 45 45 34 4 34 4 3 34 34 23 2Alt. = alteration (change in colour), C = staining on cotton, W = staining on wool.M.M. Kamel et al. / Ultrasonics Sonochemistry 16 (2009) 243249 249