j. Cosmet. Sci.,49, 141-153 (May/June1998) The crackingof humanhair cuticlesby cyclical thermal stresses MANUEL GAMEZ-GARCIA, CrodaNorth AmericanTechnical Center,180 NorthfieldAvenue,Edison,NJ 08832. Accepted for publication May 15, 1998. Synopsis Cyclesof wetting and blow-dryingwere appliedto hair fibersand resultedin the formationof multiple crackson the hair cuticles.The peculiarityof thesecrackswasthat they alwaysappearedalignedparallelto the longitudinalaxisof the hair fiber. The cracksappearedto be initiated at the end of the cuticlesclose to the cortexand propagated invariablytowardsthe outercuticleedges.The maximumgrowthlengthof eachcrackwasseento be limited to the sizeof onecuticle.Crackformationdid not only occurat the outer edgesof the cuticlesbut alsotookplacein the secondand third overlaidhiddencuticlesections. The results showthat thesecracksform when the externalportionsof the cuticlesundergodrasticreductionin their hydrationwater.Under theseconditionsthe outercuticleportionsbecomerigid andbrittle andcrackby the action of circumferentialtensionstresses arising from the swelling pressureof both the cuticle layers underneathand the cortexitself. Hair cuticleanalysisfrom a panelof 100 individualsshowedthat these cracksarepresentin the hair of peoplewho commonlyblow-drytheir hair and appearto a muchlesserextent in the hair of subjectswho do not practicethis type of groomingprocess.The combingof hair fibers presentingthis type of crackingwasseento resultin the breakageof largeportionsof cuticle.The effectof some cosmetic actives on the formation of these cracks is also discussed. INTRODUCTION Hair cuticlesrepresentthe hair structurecomponentsmost exposedto variousgrooming and environmentalstresses during the life of a hair fiber. The outer cuticlesat the hair surfacearefrequentlysubjectedto harshstresses suchasabrasion,UV light, bleaching, andblow-drying(1-4). It is well knownthat oncethecuticlesareoneor two centimeters awayfrom the hair root,patternsof breakageand abrasionstart to appearat the cuticle edges(5). By the time the hair is about 14 or 20 cm long, if not enoughcareis taken, the cuticlesmight be totally absentat the tips, giving rise to the earlierformationof split ends(6). It is mostlybecause of thesereasons that the effectsof combingabrasion on hair cuticleshave been thoroughlystudied in the past. There are, however,other groomingpractices,suchas hair blow-drying,whoseeffectson the cuticledegradation processare still poorly understood. As it is well known,hair blow-dryingis nowadays a commonpracticeby manypeople. When keratinfibersareheated,not only wateradsorbed to hair by capilarityis rapidly evaporated but thereis alsoa rapid lossin the freeandboundwater of the hair (7,8). The rapid lossof hydrationwatermay causemorphologicalchangeswithin the cortexdue to 141 142 JOURNAL OF COSMETIC SCIENCE destabilization of the keratin crystallineregions(9). The consequences of this type of processin hair cuticlesafter cyclicalthermalstresses havenot yet beenanalyzed.This paperrepresents part of a studywhoseaim is to reproducepatternsof cuticledamage found in a panelof 100 individuals(10). This articlereportsthe productionof small longitudinalcracksby cyclicalthermalstresses. The cracksweremainlyfoundin the hair cuticlesof subjectswho frequentlyblow-dry their hair. EXPERIMENTAL METHODOLOGY The panelof 100 individualsparticipatingin this studywasmainlycomposed of women with Caucasianbrown hair never treated chemically.A total of ten fibers per each individualwasanalyzed.The differentpatternsof cuticledamagefoundin theseindividuals such as cuticle decementation, abrasion, craters, and crackswere classifiedand quantified. Cyclesof mechanicaltension,torsion,bending, and thermal stresses were then appliedto singlehair fibersin orderto reproducesuchpatterns(10). Only the cyclicalthermalstresses wereseento reproduce the typesof cracksmentionedabove,and therefore,onlythe experimental conditions relatedto thistypeof stress will bedescribed here. The other typesof damageand experimentalconditionsare describedelsewhere (10-12). Eachthermalcycleconsisted of immersingsinglehair fibersfor a periodof ten seconds into de-ionizedwaterfollowedby ten seconds of blow-drying.The temperatures used during blow-drying and measuredat the level of the wet hair surfacevaried between30ø and 120øC. The number of applied wetting/blow-dryingcyclesvaried betweenfive and 100 asrequired.A total of ten fibersper eachsetof thermalcycleswas analyzedfor shortlongitudinalcuticlecracks.The numberof thesecrackspermillimeter of hair was then counted. From this data, meansand standarddeviationswere calculated. Prior to the thermalcyclesthe fiberswerethoroughlywashedwith SLSandrinsedwith tap water. The hair usedin the single-fiberexperiments wasfrom a subjectwhosehair waswashed only with a 10% SLSaqueoussolutionfor a period of oneyear. Sectionsof hair fibers threeincheslong andcut closeto the rootwereusedin the experiments.The hair fibers were subsequently cut into two snippets1.5 incheslong each;onesnippetwasusedas a control while the other one was subjectedto thermal cycling. All selectedhair fibers presentedan averagediameter of 82 + ll l•m. Caucasianvirgin brown hair from InternationalHair Importersin the form of tresseswas alsousedto studyeffectsof combingabrasionon wet/blow-drycycledhair. Aqueoussolutionsof glycerin,propylene glycol, polyquaterniumll, cetrimoniumchloride,steralkoniumchloride,and hydrolyzedwheatproteinpolysiloxanecopolymer(13) at a 2% w/w were alsousedaswetting solutionsduring thermal cycling. These solutionswere preparedin order to test the effectof somecosmeticactiveson cuticlecracking.After thermalcycling,the fiberswere preparedfor SEM analysis. RESULTS SHORT AND DISCUSSION LONGITUDINAL CUTICLE CRACKS FOUND IN A HAIR ANALYSIS FROM A PANEL OF 100 INDIVIDUALS SEM analysisof hair fiberspertainingto subjects in the panelshowedthat mostof them presenteddifferentnumbersof shortlongitudinalcracksin their cuticles.The popula- CRACKING OF HUMAN HAIR CUTICLES 143 tion of theseindividualscould, however,be divided into two main groups,namelyone with a high numberof cuticlecracksand the other with a very low number.The first group,representing about40% of the panel,showedan averageof 184 + 15.5 cracksper mm of hair (cpmh), while the other 60% showedan averageof about 7 + 1.3 cpmh. Figures la and lb showtypical imagesof thesecracksas found in the panel analysis. Incidentally,the highernumberof cuticlecrackscorresponds to the hair of peoplewho manifestedto blow-dry their hair on a daily basis.It waspreciselythis observationthat suggested the possibilityof reproducingthe cracksin the laboratoryby cyclesof wetting and blow-drying.In Figure l it canbe seenthat the particularityof thesecracksis their positionon the cuticles,i.e., they alwaysappearalignedparallel to the longitudinal axis of the hair fiber, and their length is no longerthan a singlecuticlesize.The crackswere foundto occurmorefrequentlyat the discontinuities formedby the cuticleedges.They seemed to be initiated near the middle section of the cuticle at that end close to the cortex.Their directionof propagationalsoseemedto be towardsthe outer edgesof the cuticles.Figure lb shows,for instance,a long crackwhosewidth is largerat the cuticle endcloseto the cortexandverysharpat its tip towardsthe outeredgeof the cuticle;this crackhasnot yet beenable to propagateall the way throughoutthe outercuticleedge. CRACK REPRODUCTION IN THE LABORATORY After observingthat the short longitudinalcrackswere consistentlyfound in a large portion of people from the panel, a way to reproducethem in the laboratorywas researched. First, single hair fibers were subjectedsystematicallyto cyclicaltension, torsion, and bending stresses,and it was found that none of theseconditionscould reproducethe cracks.The cuticlepatternsof damageresultingfrom thesestresses have beenreportedelsewhere(10-12). The next stepwasto take fibersthree incheslong and ' la ='" x2.4k x4.0k lb Figure 1. Typical cuticlecracksfound in hair from individualswho blow-dry their hair. la, x2.4k; lb, x4.0k. 144 JOURNAL OF COSMETIC SCIENCE I . ! litk x -- 13k v 2?3 -- 7. 2b I .3tlkx 8kv 3•'9 Figure 2. Cuticlecracksreproduced in the laboratoryasfollows:2a and2b after20 thermalcycles;2c after 60 thermalcycles. CRACKING OF HUMAN HAIR CUTICLES 145 2o Figure 2. Continued. cut them in half. One half was usedas a control,and the other half was subjectedto cyclesof blow-dryingandwetting at differenttemperatures andfor differentintervalsof time. The numberof cracksalreadypresentin the controlwere countedand compared with thoseappearingin the thermallycycledfibers.A total of ten fibersper eachtrial wereanalyzed.The averagenumberof cracksper millimeterfoundin the controlsamples was 6 + 2.1. After severaltrials it wasfoundthat shortthermalcyclesof ten seconds of blow-drying at 75øC combinedwith ten secondsof wetting at 25øC were able to reproduceand increasedramaticallythe numberof shortlongitudinalcuticlecracks.In Figures2a, 2b, and 2c areshowntypicalimagesof hair fiberssubjectedto 20 and 60 of thesecycles.A total of 21 crackscanbe countedin the 76 x 52 micrometersectionof hair represented in Figure 2b. In Figure 2c it canbe seenthat the total numberof visible cracksreaches a valueof 26; the surfacehair dimensions capturedby thismicrographareapproximately 67 x 42 microns.The numberof cracksshownin Figures2b and 2c correspond to an averageof 472 and 562 cracksper millimeter of hair, respectively. Suchhigh concentrationsof cuticle cracksare rarelyfound in people'shair and can only be producedin the laboratory.Figures3a, 3b, and 3c showhighermagnifications of thesecracks,while Figure4 showsthe averagenumberof cuticlecracksfoundin hair samplesasa function of thermal cyclesin relationto the control.In this last figure it can be seenthat the numberof cracksper unit areaon the hair surfaceincreases up to a limit and then levels off with the numberof thermal cycles. A closeexaminationof Figures1, 2, and 3 revealsthat, in all cases,the appliedthermal cyclesresultedin the productionof crackssimilarto thosealreadyobservedin the panel 146 JOURNAL OF COSMETIC SCIENCE x2 4k " 3a x2.4k 3b 3c. Figure 3. Magnifiedviewsof cracksshownin Figure2 asfollows:3a after20 thermalcycles;3b and 3c after60 thermalcycles. Eachcycleconsisted of tenseconds of blow-drying at 75øCfollowedby tenseconds of wetting at 25øC. 700 Number of shortlongitudinalcuticlecracksper mm of hair (a) Average number of • . -- , 600 - cracksinha, 500 I I L ' - 4OO 3O0 200 - / ' (b) Averagenumber /•' '100 -f 0 5 . ofcra•sincontrols • (SD=2.1)'• 10 15 20 25 30 35 40 45 50 55 60 Numberof appliedthermalcycles Figure 4. Variationsin the averagenumberof cuticlecracksfound in the laboratoryas follows:(a) in thermallycycledfibersasthe numberof thermalcyclesincreases, and(b) in theircorresponding halfsnippet usedasa control(non-exposedto thermal cycles).Eachpoint representsaverageof cracksfound in ten hair samples.Each cycleconsistedof ten secondsof blow-dryingat 75øC followedby ten secondsof water immersionat 25øC. Error barsrepresentone standarddeviationabout the mean. analysis.This observation clearlyshowsthat the cuticlecracksfound in hair subjects fromthepanelarisemainlyasa consequence of subjecting hairto thermalstresses during blow-drying.An analysisof the cracksshownin Figures1, 2, and 3 indicatesthat their CRACKING OF HUMAN HAIR CUTICLES 147 formationis mainly limited to the outerpart of the cuticles.This observationsuggests that the stresses involvedin crackformationare more intenseat thosecuticleportions near the outer hair surface.Since blow-drying and wetting involves swelling and deswellingof the hair fiber, the followingexperimentwascarriedout in orderto test whetherthe phenomenonof swellingper seplays a role in crackformation.Several solventswith limited swellingcapacitywere usedin the thermal cyclingexperiments insteadof water. The solventswere ethanol,iso-propanol,and methanol;thesesolvents havealreadybeenreportedin the literatureaspoorkeratin swellingsolvents(14-16). The resultsshowedthat thermalcyclingexperimentswith thesesolventsdo not lead to crackproductionat all, indicatingthat cuticleswellingis a necessary phenomenon for cracks to occur. Increasingboth the water-swellingand blow-dryingtimes to periodslongerthan ten seconds did not haveanyeffecton the numberof producedcracks.Also,it wasobserved that non-swollenhair fibers, which were thermally cycledwith water immersiontime periodsasshortasfive seconds, underwentcuticlecracking.In suchshorttime periods of water immersion,only the cuticularsystemand a smallportionof the cortexcan be expectedto swell. Theseobservations indicatethat cuticlecrackingis not due to a thermal shockarisingfrom rapid changesin cuticle temperature.It seemsrather that cuticle crackingoccursbecausethoseouter cuticlessectionslack elasticityto comply with the dimensionalchangeseitherof the swellingcuticlelayersunderneathor of the swellingcortex. In the caseof blow-drying, the lack of elasticityin the outer cuticle sectionswill originatefrom rapid cuticledehydrationat high temperatures.Thus, it would appear that when hair is wet or dried at room temperature,all cuticleportionsand the cortex contractin a synchronous manner.However,if during a water evaporationprocessonly the outer cuticle sectionscontractmore rapidly than thosecuticle layersunderneathor than the cortexitself, crackingwill occur.Crackingduring blow-dryingtakesplace, thus, as a consequence of circumferentialextensionstresses set up on dry portionsof cuticleby the swollenpressure of boththe cuticlelayersunderneath andthe cortexitself. It shouldbe mentionedherethat circumferentialor "hoop"stresses are knownto occur in cyclindrical pipessubjected to internalpositivehigh pressures (17). Cracksat lower hair-swellingpressures may alsooccurif the cuticleslosetheir naturalelasticitydue to weathering.This might explainwhy cuticlevertical cracksare found at lower hairsurfaceconcentrations in peoplewho do not blow-dry their hair. The repetitiveactionof cuticle"rigidization"and water swellingset up on the outer cuticlesectionsby the absorptionand desorptionof water during thermal cyclingdid not lead immediately to crack formation. For instance,it was found that beforethe cracksbecamefully developed,they appearedfirst as sharpwhite lines on the cuticle surfaces (seeFigure 5a);then, uponfurtherthermalcycling,the white linesturned into full cracks.The appearance of thesewhite linesindicatesthat beforethe cuticlescrack, the mechanicalenergyaccumulatedby the circumferentialtensionstresses or "hoop stresses," is first dissipatedby the formationof localizedshearyield regions.This form of mechanicalenergy dissipationis a very commonphenomenonthat takes place in polymericmaterialsbeforethey fracture(18). Increasingthe watertemperatureduringthermalcyclingto about50øCresultedin more diffuse and wider shearyield regionsthat did not turn into crackseven after the 148 JOURNAL OF COSMETIC SCIENCE .... x2.4k 5a x2.4k 5b Figure 5. Cuticleswith shearyield regionsformedbeforecrackingtakesplace(5a) and with shearyield regionsproducedduring thermal cyclingwith water at 50øC (5b). applicationof a high numberof thermalcycles(seeFigure 5b). Belowthis temperature, shearyield regionsandcrackswerealwaysproduced.Thus, increasingthe water-swelling temperatureduring thermal cycling softensthe cuticle proteins,preventingthe shear yield regionsfrom becomingfull cracks.It shouldbe mentionedhere that thosecuticles crackedthermally were seento be easilybrokenduring hair combing. For instance, Figure 6 showsa hair fiber from a tressthat has been subjectedto thermal cycles followedby combing.This micrographshowsthat the removalof cuticlesby abrasion occursmainly at the crackedsites. EFFECTS OF BLOW-DRYING AND WATER TEMPERATURE The temperatureat which air from the blow-dryerreachesthe hair surfaceseemedto be crucialin the incubationand propagationof thermal cracks.In the trial experimentsit was observedthat the averagenumberof cracksproducedfor a particularnumber of cycleswas maximum when the hair surfacetemperaturewas maintainedfor about ten seconds between75ø and 95øC. In Figure7 is shownthe averagenumberof cracksasa function of air temperatureat the wet hair surface.In this figure it can be seenthat temperatureslower than 50øC do not increasethe averagenumber of cracksalready present in unexposedhair, while temperatureshigher than 95øC lead rather to hair surfaceand bulk distortion.It is quite plausible,thus, that temperatureslower than 65øCdo not producethe criticalrateof waterevaporation neededfor the top part of the cuticlesto contractand becomerigid, while temperatureshigher than 85øC might softenthe cuticleproteins,releasing,thereby,the mechanicalstresses by viscousflow. The temperaturerate usedduring thermal cyclingwas found also to be an important parameter.For instance,if the hair surfacetemperaturewasincreasedat a very slowrate, CRACKING 2.kx OF HUMAN HAIR CUTICLES 149 {}81 Figure 6. Typical combingabrasionpatternof hair with crackedcuticles. i.e., 10øCper minute up to 75øC, crackformationwasalmostnil. In contrast,if hair samplesat 25øC were suddenlyexposedto a temperatureof 75øC, they immediately showedan increasein the numberof new thermal cracks.Thus, high temperaturerates causecracksbecause theyproducea rapidcontractionof the top part of the cuticleswhile maintainingin a swollenstateboth the cuticlelayersunderneathand the cortexitself. Conversely,low temperatureratesdo not causecrackingbecausecuticlesand cortex contractin a more synchronous manner. It is worth mentioning here that crackssimilar to thoseproducedthermally were also formedin fibers swollenwith mixturesof strongswelling solventsand strongdehydrating solutions.As is well known, formic acid is a strongswellingsolventbecauseit is able to break hydrogenbondsand salt bridgesnot accessible to water and to cause higher levelsof swelling in keratin fibers(19,20). In contrast,solutionsof saturated NaCI areknownto dehydratethe fibers(21). Experimentswith mixturesof formicacid and saturatedsolutionsof NaCI (50/50%), or mixtures of formic acid and glycerin (20/80%), were seento producesimilar crackson the cuticles(seeFigure 8). The cuticle crackswere observedto appearafter ten hoursof fiber immersionin thesesolutions. Also, it wasobservedthat if a thin film of gold is depositedonto a cleanhair fiber and then allowed to swell in water, that part of the cuticle coveredwith gold showsalso vertical crackssomewhatsimilar to thoseproducedthermally (seeFigure 9). The explanationto thesephenomenais straightforward,i.e., in both cases,with the swelling experimentand with the gold film, only a portionof the cuticleis restrainedto expand during the swellingprocessof both the cuticlelayersunderneathand the cortex,and crackingoccursby the alreadyadvancedmechanism. 150 600 JOURNAL OF COSMETIC SCIENCE Averagenumberof shortlongitudinal cuticlecracksper mm of hair 5OO 4OO 300 2OO lOO 20 30 40 50 60 70 80 90 lOO 11o 12o Air temperature (C) Figure 7. Plot of averagenumberof cuticlecracksreproduced in the laboratory vs blow-dryingtemperature. The numberof applied thermalcycleswas kept constantat 20 cycles,and the air temperaturewas measuredat the level of the hair surface.Error barsrepresentone standarddeviationabout the mean. Figure 8. Cuticlecracksproducedafterimmersinga hair fiberin a 50/50% solutionof saturated NaCI and formic acid for ten hours. CRACKING OF HUMAN HAIR CUTICLES ! 5! • x2.4k 9b Figure 9. Fiber with a thin gold film depositedon its surfacebeforewaterimmersion(9a) and after water immersion (9b). EFFECT OF SOME COSMETIC ACTIVES When 2% w/w aqueoussolutionsof glycerinand propyleneglycol were usedduring thermal cycling insteadof water, the hair cuticlesdid not show any increasein the averagenumberof crackscharacteristic of virgin hair fibers.This observationsuggests that during thermal cyclingtheseactivesretard water evaporationand alsoare able to plasticizethe cuticles, thereby preventing crack formation. Glycerin and propylene glycolcould,however,beeasilyremovedfrom the hair fiberby simplewaterrinsing,and under theseconditionsthe cuticlescrackedagain. The useof 2% aqueoussolutionsof variousquarternaries insteadof waterduring thermalcyclingdid not indicateanycuticle crackpreventionat all. The quaternariesanalyzedwere as follows:polyquaternium11, cetrimonium chloride, and steralkonium chloride. The depositionof four alternatinglayersof a positivepolymer(polyethylenimine) and a negativepolymer(polyacrylate)on the hair surfacewasnot capableof preventingcrack formation.For instance,in Figure 10 it canbe seenthat cracksstill formed,both on the hair cuticlesand alsoon the depositedpolymerlayers.Other substances that did not preventcrackformationwhen depositedonto the hair surfacewere oils suchas triglycerides,silicon oils, mineral oil, and petrolatum.In contrast,an aqueoussolutionof hydrolyzedwheat proteinpolysiloxane copolymerat 2%, usedinsteadof water during thermalcycling,preventedcuticlecracking.The crackpreventioneffectwasseento take placeevenafter the hair waswater rinsed.This proteincopolymer,which crosslinksupon heat application, is believed to retard water evaporationand also to give a strong cohesiveness to the cuticles,therebypreventingthermalcrackformation. CONCLUSIONS Hair blow-dryingproducescuticlecracksthat canbe reproducedin the laboratoryby the applicationof alternatingcyclesof hair wetting and blow-drying.The crackswereseen to result as a consequence of circumferentialtension stressesimposedon the dried portionof the cuticlesat the top by the swollencortex.The temperaturerangeat which 152 JOURNAL OF COSMETIC SCIENCE I . ::-:kx ;kv Figure 10. Cracksformedon cuticlesof hair treatedwith four alternatinglayersof polyethylenimineand polyacrylate. thesecracksseemto take place is between75ø and 95øC. It was alsoshownthat the combingof hair with crackedcuticlesresultsin the removalof big portionsof cuticle. The preventionof crackformationby the useof somecosmeticactiveswasshownto be possible. ACKNOWLEDGMENTS The author wishes to thank Ann Harder for her valuable technical assistance and Herb Eldesteinfor his helpful discussions. REFERENCES (1) R. 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