What is the nano? Nano is from Greek word Nanos-meaning "dwarf. It is a prefixmeaning 10-9.

In the matric system, A nanometre is a billionth of ametre, or 1/80,000 of the diameter of a human hair 10 times the diameter of a hydrogen atom. 1 metre vs. 1 nanometre = Diameter of Earth(12760km) vs. Diameter of M&M(1.2cm) 1 ELECTROSPINNINGDEVELOPMENT 1.1 Early Electrospinning (1600-1995) In the late 1500s William Gilbert set out to describe thebehaviour of magnetic and electrostatic phenomena. Hiswork [a.1] is an early example of what would becomethe modern scientic method. He received funding fromQueen Elizabeth I, whereupon he moved to London,caught bubonic plague, and passed away. He had,however, already distinguished between the

magneticforces arising from a lodestone (natural magnet) andthe electrostatic forces arising from rubbed amber.One of his more obscure observations was that whena suitably charged piece of amber was brought near adroplet of water it would form a cone shape and smalldroplets would be ejected from the tip of the cone - therst recorded observation of electrospraying.T h e f i r s t d e s c r i p t i o n o f a p r o c e s s r e c o g n i s a b l e a s electrospinning was in 1902 when J. F. Cooley led aUnited States patent entitled Apparatus for electricallydispersing bres [a.2]. In his patent (US 692631)he describes a method of using high voltage powersupplies to generate yarn. Even at this early stage itwas recognised that to form bres rather than dropletsthe (i) uid must be sufciently viscous, (ii) solventvolatile enough to evaporate to allow regeneration of the solid polymer, and (iii) electric eld strength withina certain range.T h e

n e x t s i g n i f i c a n t a c a d e m i c d e v e l o p m e n t w a s achieved by John Zeleny, who published work onthe behaviour of uid droplets at the end of metal capillaries in 1914 [a.3]. His work began the effortst o m a t h e m a t i c a l l y m o d e l t h e b e h a v i o u r o f f l u i d s under electrostatic forces. Between 1964 and 1969,Sir Geoffrey Ingram Taylor produced the theoreticalunderpinning of electrospinning [a.4-a.6]. Taylors workon electrostatics was performed during his retirementafter a broad career including modelling of turbulentmixing of air at the Arctic, signicant contributionsto the elds of uid mechanics and solid mechanicsvia work on the Manhattan Project and developmentof supersonic aircraft. Taylors work contributed toelectrospinning by mathematically modelling the shapeof the cone formed by the uid droplet under the effectof an electric eld; this characteristic droplet shape isnow known as the Taylor cone. He further worked withJ.R. Melcher to develop the leaky dielectric model forconducting uids [a.7].In parallel to the academic work of Zeleny and Taylorcame a sequence of patents (Table 1), starting with thedesign by Cooley who separated the charging devicefrom the spinning head [a.2]. In the same year, Mortonp a t e n t e d a s i m p l e r l o w - t h r o u g h p u t m a c h i n e [ a . 8 ] . Melt spinning and air-blast assist were proposed byNorton [a.9] then a sequence of constant pressure feedhighthroughput machines by Anton Formhals wasled between 1934 and 1944 [a.10-a.16] to producec o n t i n u o u s f i n e f i b r e s f o r u s e o n s t a n d a r d t e x t i l e machinery. Gladding also proposedtheuseoftheprocessto produce staple (discontinuous bres) [a.17].

Electrospinning5 1.2 Recent History (1995-present) E l e c t r o s p i n n i n g w a s r e - d i s c o v e r e d i n 1 9 9 5 i n t h e form of a potential source of nano-structured materialb y Doshi and Reneker who, whilst

i n v e s t i g a t i n g electrospraying, observed that bres could easily beformed with diameters on the nanometre scale [a.18].Huang and co-workers noted that between 1995 and2000 fewer than 10 journal papers were publishedannually, but from 2000 onwards the number of papersper year grew, reaching over 50 by 2002 and reectingthe growing interest in electrospinning by, at least, theacademic community [a.19].S i n c e 1 9 9 5 t h e r e h a v e b e e n f u r t h e r t h e o r e t i c a l developments of the driving mechanisms o f t h e e l e c t r o s p i n n i n g p r o c e s s . R e z n i k a n d c o - w o r k e r s describe extensive work on the shape of the Taylorcone and the subsequent ejection of a uid jet [a.20].The work by Hohman and co-workers investigatesthe relative growth rates of the numerous proposedinstabilities in an electrically forced jet once in ight[a.21]. Also important has been the work by Yarinand co-workers that endeavours to describe the mostimportant instability to the electrospinning process, thebending (whipping) instability [a.22].Using the keyword electrospinning for a search in ascientic database (Compendex and Inspec) returnsabout 3,200 papers (Search performed 25/11/08, range1884-2008). The term

electrospinning was rst coinedin 1995 by Doshi and Reneker. Figure 1 demonstratesthe recent strong growth in this area by plotting thenumber of scientic papers on the subject publishedper year. The gure also shows which countries aremost active in electrospinning research. Use of the samekeyword for a search of a patent database returns about1,460 documents at the time of writing (2006 beingthe last year for which complete gures are available).Performing the same search limited to the years 2004-2008 returns about 1,000 documents. These numbersshow how the commercial environment surroundingthe electrospinning process is currently something of apatent storm. Given that there are only a small handfulof companies that produce electrospinning

apparatusor electrospun products, there is a need for focusedelectrospinning research on specic applications.

Electrospinning6 2 BACKGROUND THEORY 2.1 Polymer Solutions 2.1.1 Intermolecular and Solute/Solvent Interactions in Polymers A polymer molecule can be thought of as having astructure analogous to a coiled ball of string. Thisconformation (the 3D structure of a molecule) is due tothe tetrahedral nature of the carbon atoms that form thebackbone of most polymers. A collection of these ballswhere the coils are entangled represents the amorphous(random molecular orientation) state of a polymer asopposed to the crystalline state in which the moleculesare more ordered. In a solvent a polymer will open upits coil or separate from the crystal surface, allowingsolvent molecules to surround the chain. The extentto which this occurs depends on the solvent-polymerinteraction. If there is poor interaction the polymer willnot dissolve and is simply dispersed. If the interaction isstrong then the coil will be very open due to a signicantnumber of solvent molecules surrounding the chain. If the solvent-polymer interaction is equal to that of theintramolecular interaction (interaction between differentparts of the same molecule) then the resulting solutionis known as an ideal solution. A polymer melt can alsobe thought of as an ideal solution since the solventis simply other polymer molecules of the same type.For a polymer solution to electrospin there must be asufcient degree of intramolecular interaction to copewith the tensile forces associated with the process of bre drawing. 2.1.2 Viscoelasticity

In order to talk about a bulk material property such asviscoelasticity, one rst needs to dene the quantitiesof normal stress, shear stress and strain. Stress in onedimension is the force exerted (F) divided by the area(A) (see Equation 1). Normal stress (often shortened tosimply stress) is force applied perpendicular to the faceof the material, whereas a shear stress involves a forceparallel to the face of the material. Strain is the changein length per unit length (see Equation 2 where l is thechange in length and l is the total length). Viscoelasticitydescribes the behaviour of a material that is both viscousand elastic under stress, so it has properties of boththe solid and the liquid phase. A viscous material willundergo viscous ow to relieve the application of shearstress as described by Newtons law (see Equation 3).This behaviour can be modelled with a dashpot whichis a loosely tting piston in a cylinder containing auid of viscosity (see Figure 2). A perfectly elasticmaterial obeys Hookes law (see Equation 4 where E isthe elastic modulus) and hence behaves like a perfectspring. As such this behaviour could be modelled by a

perfect spring which acts as an energy storage element,gaining energy with extension and releasing it when thematerial returns to its original shape.Figure 2 Diagram of a dashpot with auid of viscosity .The combination of a viscous and an elastic behaviour,as shown by polymers and polymer solutions, becomesmore complicated. The stress strain behaviour showselements that obey Hookes law, but unlike an elasticresponse the viscous response acts to dissipate energyas heat, resulting in hysteresis and creep. Hysteresis isdue to the viscous response causing the loss

of energy,meaning that the material cannot return to its originalshape. Creep is the tendency of a material to slowlydeform under continuous stress below the yield strengthin order to relieve the applied stress.One of the rst models of viscoelastic behaviour wast h e M a x w e l l m o d e l . T h e M a x w e l l m o d e l a s s u m e s that the contribution to the stain from the elastic andviscous behaviour is additive (i.e., ).As such, mathematically it represents a spring elementin series with a dashpot element. Another early modelwas the Voigt-Kelvin model. This model proposes thatthe applied stress is now shared between the elasticand viscous response, mathematically represented by aspring element in parallel with a dashpot element (seeEquation 5, where ). Typically in modernmodelling situations the Standard Linear Model isused, which consists of a spring element in series withthe Voigt-Kelvin model and a further dashpot in series.This better represents the important features in thetypical behaviour of a polymer. For a fuller treatmentof viscoelasticity see Cowie [a.23].Equation 1 Equation 2 Equation 3Equation 4Equation 5 2.1.3 Surface Tension A molecule in a solution is surrounded on all sidesby other molecules that will normally interact with it.When the solution exists in an equilibrium state the pullfrom each of the surrounding molecules is matched bythe pull from another molecule on the opposite side.However, consider that the molecule is on the surfaceof a boundary between two uids. On this surface therewill be an imbalance in the forces because the forcebetween the molecules of the two uids will be differentfrom the force when the molecule is surrounded byits native uid. This results in a force that pulls theliquid in such a way as to minimise the surface area tovolume ratio. In the case of the airliquid interface, airhas little interaction with the liquid so the force is nearits maximum. The

physical meaning of surface tensionis summarised in the approximate denition shownin Equation 8 (Approximate denition is taken fromWolfram Researchs website 'World of Physics' accessedon 16 March 2008 at http://scienceworld.wolfram.com/ physics/SurfaceTension.html )A uid under the forces of surface tension will adopt aspherical shape, as this is the minimum surface area fora given volume. Figure 3 shows the forces experiencedby uid molecules. As there is a force acting on the outersurface it is possible to calculate the amount of workrequired to change the shape of the uid. Equation 6gives the energy (work) that must be either expendedor will be generated when the surface changes its area(where is the surface tension, E is the work energyand A is the change in area). It is also possible tocalculate the pressure due to the force from surfacetension from Equation 7 (where P is the internal dropletpressure and r is the radius of the droplet). In a freedroplet this pressure is the same from all sides but forthe hemispherical droplet used in electrospinning thispressure would need to be matched by the uid pressurethat supplies the droplet. It can be said that for any uidthat has reached its equilibrium state there will need tobe some other force acting in order for the uid to adoptany shape other than that of the least surface area.

Electrospinning8 Figure 3 Diagram of the forces experienced by molecules in a liquid. Equation 6 Equation 7 Equation 8

2.1.4 Conductivity The conductivity of a solution is determined by thep o t e n t i a l f o r b u l k m o t i o n o f i o n s i n t h e s o l u t i o n . When a potential difference is applied across a volumeof solution, a current will ow that is proportionalto the type of ions in solution and their

respectiveconcentrations. Conductivity due to a particular iontype in aqueous solutions can be seen in tables of molar conductivity ( ). For very dilute solutions thecontribution to the conductivity of a solution can becalculated from the Debye-Huckel-Onsager equation(Equation 9), where is the molar conductivity, is the molar conductivity at innite dilution, c is theion concentration and A and B are typically takento be 60.20 and 0.229, respectively, (see [a.24] fora full exposition). At higher concentrations a strongelectrolyte typically has a constant molar conductivitywhereas a weak electrolyte will commonly vary overall concentrations. The conductivity of a given cellis related to the molar conductivity by Equation 10,where is conductivity with units of mS/cm, c is ionconcentration with units of mol/l and hence the molarconductivity, has units of Scm 2 /mol.Equation 9Equation 10

2.2 External Forces 2.2.1 Electrodynamic Force A single electron (having a negative charge) travellingin a vacuum in the presence of an electric eld willexperience a force given by Equation 11 (where F is theforce exerted, q is the charge and E is the electric eld).As it is a force, this is a vector equation and hence theelectron will

travel in the direction of the electric eld.A proton (having a positive charge) would experience asimilar force but in the opposite direction of the electron;all charge produces its own electric eld. Like lines of magnetic ux (lines perpendicular to the equipotential

Electrospinning9 Figure 4 Electric ux lines from a source and a sink.surfaces), lines of electric ux cannot cross. A negativecharge acts as a sink for eld lines and a positive chargeacts as a source. All eld lines must either travel from asource to a sink or to the edge of innity, which can beeither a source or sink. For further discussion of electricforces refer to a physics textbook [a.25]. Equation 11 2.2.2 Surface Charge If two charges of the same sign are next to each otherthere will be a force repelling them from one another.As like charges will both act as either a source or a sinkfor lines of electric ux (see Figure 4), this force isthe result of the eld warping to a higher energy statebecause the lines of electric ux cannot cross. The forceof this repulsion is given by Coulombs law (Equation12 where F is the force, q 1 and q 2 are charge, d is thedistance between the charges and 0 is the permittivityof free space). Therefore, if a number of equally spacedcharges of the same sign were deposited on the surfaceof a balloon then the surface would be stretched untilthe elastic force of the rubber was balanced with therepulsion force from the charge.The case of the droplet present at the moment theelectric eld is applied to initiate electrospinning issimilar to the balloon example given previously. In thissituation, surface tension is acting like the elastic forceof the rubber, trying to contract the total volume to theminimum possible. As shown in Section 2.1.3 of thisChapter, the

force from surface tension can be seen asa pressure pointing inwards whereas the force from theself-repulsion of the charge built up on the surface will bea pressure pointing outwards. This pressure is given by asimilar relationship (Equation 13 where V is the appliedvoltage and r is the droplet radius) to Equation 7 fromSection 2.1.3 [a.26]. Both equations can be combinedto give Equation 14, a relationship for the total pressureinside the droplet. It should be noted that this does notinclude the attraction due to the electric eld present,but only the force due to surface charge repulsion, andbecomes invalid once the droplet changes shape, becauseit is based on a spherical capacitor approximation. Equation 12 Equation 13 Equation 14 2.2.3 Fluid Pressure Pressure can be generated in a uid in a number of ways.Hydrostatic pressure resulting from the weight of uidabove a chosen point is given by Equation 15. This isalso known as the head pressure. Pressure can also besupplied by pressurising the supply tank for the uidtypically with an inert gas. In this case as a liquid istypically incompressible, the pressure from the gas willbe directly translated to the other boundaries of the uid.Another common procedure in electrospinning is the useof a syringe pump to provide a controlled volume owrate. Here, as long as the uid pressure does not exceedthe power of the

syringe pump, the pressure will berelated to the other forces and geometry in the system. Equation 15

Electrospinning10 3 ELECTROSPINNINGPROCESSES AND APPARATUS 3.1 Simple Process Description 3.1.1 Axis Conventions In order to discuss the electrospinning process in aconcise and transparent way it is important to note thecommon axis conventions used in models. Typicallya cylindrical co-

o r d i n a t e s y s t e m i s u s e d [ a . 2 7 ] . This system describes a point in 3-D space given adistance along a Z axis followed by an angle to rotatearound the Z axis then a distance to travel perpendicularto the direction of the Z axis (Figure 5). The direction of the Z axis is chosen to be such that the maximum levelof symmetry is obtained around that axis. If the axis ischosen such that it passes through the centre of the rstelectrode, then through the centre of the polymer dropletand lastly through the centre of the second electrode,it often obtains the maximum symmetry possible. Thisaxis can then be referred to as the primary axis.Figure 5 Cylindrical axis convention. 3.1.2 Basic Physics of Electrospinning Electrospinning can be viewed as a special case of electrospraying. The latter is a method of atomisinguids that nds applications in mass spectrometry,industrial applications

(e.g., coating of automotiveparts with complex shapes) and consumer products(e.g., deposition of ink by inkjet printers).As with electrospraying, the feedstock for electrospinningis connected to a high voltage power supply to raise theelectrostatic potential of the uid. Polymer solutions ormelts with a minimum degree of molecular interactioncan be used as the feedstock. Increasing the electrostaticpotential increases the surface charge of the liquid.Normally the shape of a volume of uid is dictated byits surface tension. However, when the uid is chargedthe surface charge acts in the opposite manner to surfacetension, resulting in the uid changing shape, formingthe structure known as the Taylor cone [a.4].If the surface of a conductor forms a sharp point, theelectric stresses will concentrate on that point. In aTaylor cone, there is a sharp point at the tip of thecone, so this concentration of electric stresses leads tothe ejection of a uid jet due to the increased electricalattraction at the tip. This uid jet carries a charge, so itwill be drawn in the direction of the local electrostaticeld. After a certain amount of ight time this jet willbecome vulnerable to a number of instabilities. Carefulcontrol of these instabilities ensures successful breformation. For example, the axisymmetric Plateau-Rayleigh*instability, which causes atomisation in theelectrospraying process, must be avoided to ensuref i b r e f o r m a t i o n . I n c l u d e d i n t h e e l e c t r o s p i n n i n g process is the off-axis bending instability that is largelyresponsible for the narrow bre diameter obtainedduring electrospinning [a.28].The off-axis bending instability occurs due to smallp e r t u r b a t i o n s i n the straight line trajectory of thefibre, which generate a force

p e r p e n d i c u l a r t o t h e primary axis due to the self-repulsion of the charged jet when perfect symmetry is lost (see Figure 6). Thisforce is very small and is initially countered by theviscoelastic nature of the polymer solution. The viscouscomponent will resist the motion generated by thisforce and the elastic component will work to restorethe perturbed bre to

its original position. However, atsome point the perturbation forces become larger thanthe resistance, at which point the bending instabilitybegins to grow, causing additional stretching of the jet. This will continue throughout the rest of the jetsight assuming the localised electrostatic repulsions t a y s larger than the mechanical resistance of

t h e jet/bre to stretching [a.22].The high surface area of these narrow uid jets allowsrapid solvent loss, leading to the conversion of the uid jet into a solid bre within the short ight time. It has * Plateau-Rayleigh instability is the result of surface tension reinforcing small perturbations in a uid columns surface eventually leading to thebreaking up of the uid column and the formation of droplets. For a full mathematical treatment see Lecture 7.5 of the MIT course 1.63J/2.21JAdvanced Fluid Dynamics of the Environment accessed on the 12 March 2008 from http://web.mit.edu/1.63/www/lecnote.html

Electrospinning11

Figure 6 Physical diagram of perturbations causing the bending instability (modied from [a.29]).Here A, B and C represent three discrete equally charged sections of the jet where B has beenperturbed from the symmetrical axis. * Centimetre-Gram-Second as opposed to MKS or Meter-Kilogram-Second been observed that polymer molecules within thesebres can have a high degree of orientation (409). Thishas been explained both by the alignment of polymermolecules due to the electrostatic eld and by the highdraw ratio of the bre while in ight. 3.2 Process Models I n t h e p a s t d e c a d e , s i g n i f i c a n t p r o c e s s m o d e l developments h a v e b e e n m a d e s i n c e t h e w o r k o f Zeleny [a.3] and Taylor [a.4]. Many of the proposedmodels have had some validation against experimentaldata and have been used to help explain experimentalobservations. This suggests that a good understandingin the models, though unable to fully predict results, cansignicantly reduce research and development time fornew bre applications. Thompson and co-workers claimin the proposedmodel is the only existing model of electrospinning,a c c o u n t i n g f o r t h e l a r g e n o n l i n e a r p e r t u r b a t i o n s , viscoelasticity, evaporation and solidication [a.22,a.30]. This would make it the most complete modelproposed at this time. The following sections expandthe discussion outlined in Section 3.1.2. 3.2.1 Jet Initiation J e t i n i t i a t i o n i s o n e o f t h e d i r e c t c o n s e q u e n c e s o f exposing a uid drop in contact with a conductor to astrong electric eld. As a result, much of the work on jet initiation has been reference to Yarin and co-workers that

done in tandem with theoreticaltreatments of electrospraying. Many authors [a.3, a.4,a.31] have focused on the concept of a critical voltage:the voltage at which discharge of mass begins (eitherof a smooth uid jet or an aerosol stream).Taylor [a.4-a.6] undertook a theoretical examination of jetsbeing initiated from a polymeric uid on the end of metalcapillaries. Taylor described cone formation with a semi-vertical angle of 49.3 (see Figure 7), apparently true forany conducting uid. The validity of this cone geometryhas been questioned by Yarin and co-workers [a.32] andReznikandco-workers[a.20],whondittobe 33.Taylor found a relationship between his initial conditionsand the formation of his cone (Equation 16). Here H isthe distance between electrodes, L is the length of thecapillarytube(syringeneedle),Ristheradiusofthetubeand is the uids surface tension (all expressed in CGS* Figure 7 Taylor cone formed by a 98% glycerine and2% of 10% NaCl solution with an exposure timeof 1 ms [a.6].

Electrospinning12 Figure 8 Critical electric Bond number versus static contact angle [a.20].units as per the original paper). Although Taylors modelof electrospinning might only hold true for speciccases[a.20],hissimpleequationnegatestheneedforextensivemodelling anditcanstillbeusedtopredictthecriticalvoltage required to begin jet initiation.Later work by Reznik and co-workers on the evolutionof droplets on an innite plane over time showed thatthe static contact angle formed by the uid dropletswas critical in predicting jet initiation. Reznik andco-workers introduce the concept of the electric Bondnumber (see Equation 17 where E is the applied eld, is the surface tension and a 0 is the equivalent-volumed r o p radius or characteristic length) allowing

t h e description of the relative importance of electric andcapillary stresses [a.20]. For a range of contact angles,the critical values for the electric Bond number werecalculated (Figure 8) and hence, the critical voltageneeded to form the Taylor cone can be calculated for agiven polymer solution.Evolution of the droplet shape can be either subcriticalor supercritical. If the electric Bond number is low thena subcritical evolution occurs. Here the droplet adoptsa partial cone shape, but the hydrodynamic forcesstill dominate and the droplet will not evolve into a jet. If the electric Bond number is above the criticallevel then a supercritical evolution towards the

typicalTaylor cone will occur because the mechanical stressesfrom the electric eld dominate the droplet evolution.Concentration of electric stress at the tip of the cone[a.32] will cause the continued formation of a typicalelectrospinning jet. Equation 16 Equation 17 3.2.2 Jet Thinning Once the jet has left the Taylor cone it will begin to thindue to the forces acting on it and the requirements of conservation of mass, until it hits the collector electrode.The thinning of the jet has two different stages. Theinitial stage is a period of thinning as a straight jet andthe later stage is a period of thinning due to the bendinginstability (see Section 3.2.4).T h e i n i t i a l t h i n n i n g b e h a v i o u r o f t h e j e t c a n b e described simply with the Bernoulli principle [a.33].In electrospinning, losses due to viscous ow mustb e i n c o r p o r a t e d i n t o t h e B e r n o u l l i f o r m u l a a n d electrodynamic forces will replace gravity as the drivingforce. This treatment, such as that by Spivak and co-w o r k e r s , r e s u l t s i n o n e - d i m e n s i o n a l a x i s y m m e t r i c differential equation (Equation 18, where R~and z~aredimensionless lengths, N W is the Weber number, N E isthe Euler number and N R is the Reynolds number) thatusually can be solved directly [a.34].As the jet continues to thin, its surface area increases andhence the potential for solvent loss increases. At somepoint all the solvent is lost and the jet is no longer uid,becoming a material with a modulus of elasticity ratherthan a viscosity, and at this point the mode of thinning