ReviewReview ofof TextileTextile ChemistryChemistry andand ManufacturingManufacturing

DavidDavid HinksHinks

TextileTextile Engineering,Engineering, ChemistryChemistry andand ScienceScience NorthNorth CarolinaCarolina StateState UniversityUniversity

[email protected]@ncsu.edu Overview

• BackgroundBackground – IntroductionIntroduction toto thethe CollegeCollege ofof TextilesTextiles atat NCSUNCSU • InnovationInnovation inin textitextilele manufacturingmanufacturing – TechnicalTechnical trendstrends • Now and in near future – NonwovenNonwoven technologytechnology – BicomponentBicomponent fibersfibers

2 NCSU College of Textiles

• LargestLargest TextileTextile InstitutiInstitutionon inin WesternWestern WorldWorld – 5050 facultyfaculty – 800800 undergraduatesundergraduates – 150150 graduategraduate studentsstudents • ModelModel ManufacturingManufacturing FacilFacilitiesities – SpinningSpinning toto ChemicalChemical FinishingFinishing • TheThe NonwovensNonwovens InstituteInstitute • TextileTextile ProtectionProtection andand ComfortComfort CenterCenter

3 NCSU College of Textiles • MoleculesMolecules toto MarketsMarkets – ChemistryChemistry – EngineeringEngineering andand TechnologyTechnology ofof FibersFibers – MarketingMarketing andand MerchandizingMerchandizing – FashionFashion andand BrandBrand ManagementManagement • MaintainMaintain excellentexcellent relatirelationshipsonships withwith – allall majormajor dyestuffdyestuff andand chemicalchemical supplierssuppliers – allall majormajor fiberfiber producersproducers – allall majormajor USUS retailersretailers • Walmar, Target, Nike, Gap, JC Penneys, Victoria Secret • Many maintain sample library of almost all production batches 4 NCSU College of Textiles Research Areas • ChemistryChemistry – Dye chemistry and molecular modeling – Design of functional chemical finishes – Polymer synthesis – Polymer extrusion (fibers) – Analytical chemistry • EngineeringEngineering – Spinning – Fabric construction • knitting, 2D and 3D weaving, nonwovens

5 Forensics at NCSU

• FacultyFaculty expertise:expertise: – AnthropologyAnthropology – ArcheologyArcheology – ChemistryChemistry – FibersFibers andand TextilesTextiles – EntomologyEntomology – CriminologyCriminology • NCNC ForensicForensic ScienceScience ProgramProgram -- 20042004

6 NCSU Professional Forensic Short-Courses

• DistanceDistance EducationEducation • TextileTextile fundamentalsfundamentals • ForensicForensic TextilesTextiles – AugustAugust • DiscoveryDiscovery andand Recovery.Recovery. DeathDeath inin NaturalNatural EnvironmentsEnvironments – MayMay • AdvancedAdvanced DiscoveryDiscovery andand RecoveryRecovery – AugustAugust 7 8 On-going fiber/dye research

• DegradationDegradation ofof natural/syntheticnatural/synthetic fibersfibers inin soilssoils foundfound inin SouthSouth EastEast • SearchableSearchable databasedatabase developmentdevelopment – DyeDye characterizationcharacterization

9 Degradation of fibers. Soil burial Acid Alkaline pH 4.4-6.5 pH 7.5 Rayon 1 2 Silk 15 7 Time for Cotton (treated) 10 7 significant Wool 15 5 strength loss Nylon >48 >48 (months) Acrylic >48 >48 Acetate >48 >48 Plastic >48 >48

10 P.L. Turner, Biodeterioration of Materials, Vol. 2, 1972 Polymers: Building blocks of all fibers/plastics

• Polymers are very long chain of connected atoms poly = many mer = unit (latin) • Examples: – DNA – Protein – Starch – All plastics – All fibres (almost) – All textiles

11 A fiber is….

• A class of materials that are long filaments, composed of oriented or semi-oriented polymers • Fibers may be very long (continuous filament) – hundreds of feet in length OrOr • Relatively short (staple) (about(about 11 inchinch long)long)

12 Natural Fibers

• About 200 natural fibers – Vegetable • Cotton (21 million tons, $20 billion market) • Linen • Hemp • Jute, Flax, Soy…. – Animal • Wool (1.3 million tons), cashmere (goat), angora (rabbit), camel, dog, cat, etc • Silk (from silk worm, spider…) – MineralMineral • Asbestos

13 Synthetic Fibers

• Dozens of different types of synthetic fibers • Polyester regular, basic dyeable • Poly(propylene) • Poly(amide) nylon 6.6, nylon 6, kevlar, nomex • Poly(acrylonitrile) acrylic • Poly(urethane) Elastomeric (Spandex)

• Chemically modified natural fibers – Viscose, • Lyocell (environmentally benign spinning process) – Cellulose diacetate / triacetate – Cellulose nitrate, others

14 Textiles are…. • any material made mainly from fibers – Yarn – Woven fabric – Knitted fabric – Carpet – Nonwoven – Composite material with fibers (e.g. Formica, carbon fiber reinforced plastic

15 Technology trends What’s happening now

• PolyesterPolyester nownow higherhigher volumevolume thanthan cottoncotton – AverageAverage USUS teenagerteenager stillstill ownsowns 1919 denimdenim garments,garments, though!though! • FarFar moremore stretchstretch garmentsgarments – SpandexSpandex • Jeans, T-shirts, • PerformancePerformance sportssports wearwear (wicking(wicking sweatsweat awayaway fromfrom body)body) – IncreasingIncreasing useuse ofof microfibersmicrofibers – BicomponentBicomponent fibersfibers

16 New Fiber: Poly(Lactic acid)

• Environmentally benign process • Large projected market growth • Manufactured from corn starch D- and L-Lactic acid • Biodegradeable • Made by Cargill-Dow

17 Technology trends The near future…

• DyeDye ChemistryChemistry • MatureMature industryindustry – FewFew newnew highhigh volumevolume dyesdyes – UnlikelyUnlikely toto changechange muchmuch • Replacement of toxic dyes • NewNew FunctionalFunctional DyesDyes – PorphyrinsPorphyrins asas selfself cleaningcleaning textilestextiles • Light activated • Antimicrobial (filters, masks) • Bioterrorism (chemical and biological agents)

18 Technology trends The near future….

• SurfaceSurface (finishing)(finishing) chemistrychemistry – PlasmaPlasma treatmenttreatment • formsforms carboxyliccarboxylic acidsacids onon surfacesurface ofof nonpolnonpolarar fibersfibers • fluorocarbonsfluorocarbons • otherother functionalfunctional groupsgroups – NewNew flameflame retardantretardant chemistrychemistry • AllAll householdhousehold textiltextileses maymay requirerequire flameflame retardantretardant finishfinish

19 Technology trends The near future….

• SecuritySecurity taggingtagging ofof garmentsgarments byby retailersretailers maymay leadlead toto easilyeasily traceabletraceable garmentsgarments • NewNew polymerpolymer systemssystems – FibersFibers thatthat swellswell whenwhen wetwet (reversible)(reversible) • WaterWater proofproof – No surface chemistry applied • HighlyHighly breathablebreathable drydry

20 What can we analyze?

21 Textile, Fiber and Chemical Analysis. Visual and Instrumental Assessment • MacroscopicMacroscopic • Color • Texture • Weave/knit properties • Micro-analyticalMicro-analytical – MicroscopyMicroscopy – Transmission/ReflectanceTransmission/Reflectance measurementmeasurement • ChemicalChemical analysisanalysis – IR,IR, NMR,NMR, MS,MS, GC,GC, HighHigh PerformancePerformance LiquidLiquid Chromatography,Chromatography, AtomicAtomic Absorption,Absorption, ICP,ICP, UV/vis,UV/vis, DSC,DSC, elemental,elemental, x-rayx-ray crystallography.crystallography. 22 Cotton – Weave (or Knit) Analysis • YarnYarn propertiesproperties – Twist, type of spinning • FabricFabric densitydensity • WeaveWeave oror knitknit typetype

23 Absorption and scattering with a colored surface

incident reflection scattering

absorption

pigment particles

transmission24 Microfibers • VeryVery smallsmall fiberfiber micro diameterdiameter • OftenOften polyesterpolyester oror nylonnylon • ShapeShape isis oftenoften indicativeindicative ofof manufacturersmanufacturers processprocess

25 standard Synthetic fiber cross- sections

• MayMay bebe circular,circular, Y-shaped,Y-shaped, X-shaped,X-shaped, oror otherother

Trilobal Circular Hollow

26 Chemical analysis of fibers • Example: Cotton – Physical and chemical properties of cotton depend on where it was grown (Texas, California, Egypt…..) – Chemical properties vary from season to season • Cotton fields irrigated in the field due to drought in Texas have much higher levels of metals (Iron, Magnesium…) than ‘non drought’ cotton – Common traceable chemical treatments Chemicals applied to textiles

• PotentiallyPotentially traceabletraceable levelslevels ofof aa numbernumber ofof chemicalschemicals maymay bebe presentpresent onon fibersfibers – DuringDuring manufacturemanufacture – DuringDuring consumerconsumer useuse

28 Potentially traceable chemical finishes applied to textiles • DuringDuring ManufactureManufacture – SoftenersSofteners (flexible(flexible polymericpolymeric materials)materials) • Silicones, Quaternary ammonium surfactants – FlameFlame retardantsretardants • all childrens’ nightware • Likely to be required in all upholstery/drapes, etc. – WaterWater repellentrepellent materialsmaterials • Silicone, fluorocarbon

29 Traceable chemical finishes applied to textiles

• DuringDuring ManufactureManufacture (cont.)(cont.) – StainStain repellentrepellent finishesfinishes (‘Teflon®’-based(‘Teflon®’-based polymers)polymers) • Fluorocarbon-alkoxylated block copolymers – CreaseCrease resistantresistant finishesfinishes • Dimethyloldihydroxyurea (DMDHEU), others – AntimicrobialAntimicrobial finishesfinishes • Ag based, quaternary ammonium – FluorescentFluorescent brighteningbrightening agentsagents • Stilbenes, others – UVUV blockingblocking finishesfinishes (new)(new) 30 Traceable chemical finishes applied to textiles

• ConsumerConsumer useuse – LaundryLaundry detergentdetergent formulationsformulations • SurfactantsSurfactants • FluorescentFluorescent brighteningbrightening agentsagents • SoftenersSofteners – AntistaticAntistatic agentsagents (Bounce®)(Bounce®)

31 Nonwovens

• NonwovensNonwovens areare EngineeredEngineered FabricsFabrics • NonwovensNonwovens areare manufacturedmanufactured byby hihigh-speed,gh-speed, low-costlow-cost processesprocesses –– LargeLarge Volume,Volume, LowerLower CostCost thanthan traditionaltraditional processesprocesses • NonwovensNonwovens areare inin manymany applicatiapplicationsons already,already, butbut mostmost areare hiddenhidden andand youyou dodo notnot seesee themthem

32 Courtesy: prof. Behnam Pourdeyhimi, The Nonwovens Institute Nonwovens Markets and Applications A $50 Billion Market!

• DisposablesDisposables (55-65%) • DurablesDurables (35-45%) • Baby Diapers • Filtration • Adult Incontinence • Protective Garments • Feminine Hygiene • Interlinings • Medical • Home Furnishing • Geotextiles • Wipes Geotextiles • Agricultural • Automotive • Carpet Backing

33 Courtesy: prof. Behnam Pourdeyhimi, The Nonwovens Institute 34 Courtesy: prof. Behnam Pourdeyhimi, The Nonwovens Institute Basic methods of manufacture of nonwovens

• From Fibers • From Polymers – WebWeb FormingForming – Extrusion & Web Forming • Spunbond • Dry-lay (Carding) Spunbond • Meltblown • Air-lay – Bonding • Wet-lay Bonding • Mechanical – BondingBonding – Hydroentangling • Mechanical • Thermal – Needling – Calendering – Hydroentangling – Thru-air • Thermal – Calendering – Thru-air • Chemical • Adhesive 35 Courtesy: prof. Behnam Pourdeyhimi, The Nonwovens Institute Web Formation

The dry-laid process Web is produced from staple fibers Production takes place in a carding machine fitted with rotating rollers.

The wet-laid process The fibers are separated by water and laid on a circulating screen belt on which the water is drained off.

36 Courtesy: prof. Behnam Pourdeyhimi, The Nonwovens Institute Web Formation

The spunbonding process This is a continuous production process, from raw material (polymer granulate) to web. The web requires bonding.

The meltblowing process Air This is a continuous production Manifold process, from raw material Polymer pellets Nonwoven (granulate) to web. The web Extruder Requires no bonding.

Gear Winder Pump Die Collector

37 Courtesy: prof. Behnam Pourdeyhimi, The Nonwovens Institute Web Bonding

Adhesive bonding Needling Here the fibers are Here the fibers are bonded by means of bonded using needles an adhesive. with barbs.

Thermal bonding Hydroentangling This is homogenous This is mechanical bonding of the fibers bonding by means of between hot, rotating ultrafine, powerful jets cylinders. of water.

38 Courtesy: prof. Behnam Pourdeyhimi, The Nonwovens Institute Nonwoven manufacture is high speed • SpunMeltSpunMelt – >> 300-1000300-1000 metersmeters perper minuteminute –– 55 toto 66 metersmeters widewide

• HighHigh SpeedSpeed CardsCards – >> 300-400300-400 metersmeters perper minuteminute –– 55 toto 66 metersmeters widewide

39 Courtesy: prof. Behnam Pourdeyhimi, The Nonwovens Institute Bicomponent fibers

40 Courtesy: prof. Behnam Pourdeyhimi, The Nonwovens Institute 41 Courtesy: prof. Behnam Pourdeyhimi, The Nonwovens Institute Bicomponent Variants

42 Courtesy: prof. Behnam Pourdeyhimi, The Nonwovens Institute Melt Blown, Sheath/Core 50/50 PE/PP

43 Courtesy: prof. Behnam Pourdeyhimi, The Nonwovens Institute Cross-section of S/C PP Meltblown

44 Courtesy: prof. Behnam Pourdeyhimi, The Nonwovens Institute Side by Side Trilobal Cross Section

45 Courtesy: prof. Behnam Pourdeyhimi, The Nonwovens Institute 46 Courtesy: prof. Behnam Pourdeyhimi, The Nonwovens Institute Sixteen Segment Pie

47 Courtesy: prof. Behnam Pourdeyhimi, The Nonwovens Institute 16 Segment Split, Pie

48 Courtesy: prof. Behnam Pourdeyhimi, The Nonwovens Institute Concentric Ring

49 Courtesy: prof. Behnam Pourdeyhimi, The Nonwovens Institute 37 Islands-in-the-Sea

50 Courtesy: prof. Behnam Pourdeyhimi, The Nonwovens Institute 25 Islands-in-the-sea Spunbond

51 Courtesy: prof. Behnam Pourdeyhimi, The Nonwovens Institute 52 Courtesy: prof. Behnam Pourdeyhimi, The Nonwovens Institute 600 Islands-in-the-Sea

53 Courtesy: prof. Behnam Pourdeyhimi, The Nonwovens Institute Tri – Segmented Pie

54 Courtesy: prof. Behnam Pourdeyhimi, The Nonwovens Institute Estimated Worldwide Bicomponent Fiber Production Capacity (Tons/Year)

Filament (150,000) 23%

Spunbond (300,000) 46%

Staple (200,000) 3% of total Worldwide31% Melt Spun Fiber capacity

Approximately 75% of all bicomponent fibers go to a nonwoven end use

Most bicomponent capacity is55 extruder fed. Courtesy: prof. Behnam Pourdeyhimi, The Nonwovens Institute Medical applications • In medical applications, nonwovens offer maximized levels of safety and hygiene. They are used in adhesive plasters, wound pads and compresses, orthopedic waddings and stoma products. • The nonwovens used here must, for example, be particularly absorbent and air-permeable, must not stick to the wound, and also have to ensure a skin-friendly micro- climate. 56 Courtesy: prof. Behnam Pourdeyhimi, The Nonwovens Institute 57 Courtesy: prof. Behnam Pourdeyhimi, The Nonwovens Institute 58 Courtesy: prof. Behnam Pourdeyhimi, The Nonwovens Institute 59 Courtesy: prof. Behnam Pourdeyhimi, The Nonwovens Institute

60 Courtesy: prof. Behnam Pourdeyhimi, The Nonwovens Institute Thinsulate™ Insulation

61 Courtesy: prof. Behnam Pourdeyhimi, The Nonwovens Institute InsulationInsulation ProductsProducts

Thinsulate™

62 Courtesy: prof. Behnam Pourdeyhimi, The Nonwovens Institute Sorbents

63 Courtesy: prof. Behnam Pourdeyhimi, The Nonwovens Institute 64 Courtesy: prof. Behnam Pourdeyhimi, The Nonwovens Institute Furniture/TextileFurniture/Textile ApplicationsApplications • In furniture/textile applications, nonwovens satisfy even the most disparate functional requirements for producing upholstered furniture, bedware and quilted products, and protective clothing. • Nonwovens here excel in terms of their textile look, their air-permeable breathability, and high abrasion resistance values. 65 Courtesy: prof. Behnam Pourdeyhimi, The Nonwovens Institute TuftedTufted CarpetsCarpets

• InIn Carpets,Carpets, nonwovensnonwovens constituteconstitute thethe invisibleinvisible supportingsupporting insideinside layerlayer ofof tuftedtufted carpetscarpets andand carpetcarpet tiles.tiles. • InIn automotiveautomotive carpets,carpets, nonwovensnonwovens areare usedused asas firstfirst andand secondsecond backingsbackings mainlymainly forfor makingmaking moldedmolded automobileautomobile carpets.carpets.

66 Source: Freudenberg Nonwovens Courtesy: prof. Behnam Pourdeyhimi, The Nonwovens Institute InIn Shoes…Shoes…

• AA broadbroad spectrumspectrum ofof applicationsapplications including:including: – liners,liners, – counterliners,counterliners, – interlinersinterliners andand – reinforcingreinforcing materialsmaterials • MembranesMembranes andand insolesinsoles ensureensure aa healthyhealthy footfoot climateclimate andand aa highhigh degreedegree ofof footfoot comfort.comfort. 67 Source: Freudenberg Nonwovens Courtesy: prof. Behnam Pourdeyhimi, The Nonwovens Institute FiltrationFiltration MediaMedia TechnologyTechnology

Meltblown Split Film

68 Source: 3M Courtesy: prof. Behnam Pourdeyhimi, The Nonwovens Institute 69 Courtesy: prof. Behnam Pourdeyhimi, The Nonwovens Institute AutomotiveAutomotive InteriorsInteriors

• FacingsFacings andand structuralstructural reinforcementreinforcement materialsmaterials areare usedused inin aa varietyvariety ofof differentdifferent applicationsapplications including:including: – headliners,headliners, – trunkliners,trunkliners, – doordoor trim,trim, – packagepackage trays,trays, – sunsun visorsvisors andand

– seats.seats. 70 Source: Freudenberg Nonwovens Courtesy: prof. Behnam Pourdeyhimi, The Nonwovens Institute LowLow DensityDensity AbrasivesAbrasives

Mineral Coated Fiber

71 Source: 3M Courtesy: prof. Behnam Pourdeyhimi, The Nonwovens Institute Thank you

72

Cotton

Mineral oil, not consistent in color change in crossed polarizer

10x 10x polarizer 40x 40x polarizer

74 Cotton – higher magnification

• UseUse ScanningScanning ElectronElectron MicroscopyMicroscopy (SEM)(SEM) • ShapeShape isis – Flat,Flat, ribbon-likeribbon-like – TwistedTwisted – uniqueunique

75 Cotton – Cross-section

• ScanningScanning ElectronElectron MicroscopyMicroscopy (SEM)(SEM)

76 Wool Cross-section

• WoolWool hashas uniqueunique complexcomplex cellcell structurestructure • ScalesScales onon outerouter surfacesurface

77 Infra-red analysis

• BestBest approachapproach forfor fiberfiber identiidentificationfication isis toto useuse bothboth microscopymicroscopy andand IRIR analanalysisysis ofof fiberfiber surfacesurface (and(and otherother preferablypreferably non-invasivenon-invasive methods)methods) • NoNo nationalnational standardstandard iinn placeplace forfor fiberfiber I.D.I.D. • SBI-RaleighSBI-Raleigh useuse bothboth PLMPLM andand IRIR – UsuallyUsually concludeconclude whetherwhether twotwo fibersfibers areare a) different, or b) data for each fiber are consistent

78 IR analysis of cotton • Infra-redInfra-red lightlight hashas energyenergy toto stretch,stretch, bendbend andand vibratevibrate bondsbonds inin materimaterialsals • EnergyEnergy absorbedabsorbed isis measuredmeasured andand producesproduces aa ‘finger‘finger print’print’ ofof aa fifiberber – CanCan identifyidentify singlesingle fiberfiber – MixtureMixture ofof fibersfibers – UseUse IRIR databasedatabase (at(at NCSU)NCSU)

79 IR spectrum of:

Cellulose Acetate

vs.

Cotton

80 Sample #14B: Human hair

81