Apparatus for preparing electrospun nanofibres: a comparative review

J.-H. He*1,3, Y. Liu2 and L. Xu1,3

A brief introduction to the development of electrospinning is given, and various apparatus to fabricate nanofibres or nanoporous materials are systematically reviewed with emphasis on the vibration electrospinning and melt electrospinning for enlarging electrospinability, siro-electrospinning for mimicking the spinning procedure of a spider, magneto-electrospinning for controlling the instability arising in the electrospinning process and bubble electrospinning for mass production of nanofibres. Electrospinning for producing nanoporous materials and the nano-effect for improving the properties of nanofibres are also introduced.
Published by Maney Publishing (c) IOM Communications Ltd
Keywords: Nanofibres, Vibration electrospinning, Siro-electrospinning, Magneto-electrospinning, Bubble electrospinning

This paper is part of a special issue on Electrospun nanofibres and electrospun nanoporous materials

Introduction
Seventy-ve years after the discovery of the principle of electrospinning by Formhals in 1934,1 we are only just beginning to understand the depth and complexity of how nanobres behave unusually well in many aspects, for example, remarkable strength, high surface energy and surface reactivity, as well as excellent thermal and electric conductivity, and to consider their roles in the scientic and economical revival, especially of the developing world.2 Although there are many methods of fabricating nanobres, electrospinning is perhaps the simplest, the cheapest and the most straightforward way to produce nanobres by forcing a polymer melt or solution through a spinnerette with an electric eld. Owing to its ultrahigh specic surface, electrospun nanobres and electrospun nanoporous microspheres have caught much attention as the most promising material in nanotechnology, and served as a highly versatile platform for a broad rang of applications in widely different areas such as photonic structures, microuid channels (nanouidics), catalysis, sensors, medicine, pharmacy, drug deliver, invisibility device (e.g. stealth plane, stealth clothes), radioprotection and tissue engineering, etc. Electrospinning technology also raises new hope for spinal cord repair and prevention of virus infection.3 Electrospinning becomes a hot topic in both academic and industrial communities. According to Web of Science, publications on electrospinning are rocketing (see Fig. 1). Recently, a number of excellent reviews and comments dealing with specic aspects of electrospinning,4 nanobres5 and their applications,6,7 properties,8 assemblies

and mathematical models916 of electrospinning have already been published. However, a systematic and contemporary review of the development on electrospinning apparatus is still lacking. Recently many new apparatus have appeared to prepare for various nanobres, such as vibration electrospinning, melt electrospinning, siro-electrospinning, magneto-electrospinning and bubble electrospinning. A comparative review on apparatus is therefore much needed.

Brief history of electrospinning technology

The basic principle of electrospinning goes back to as early as 1882 when Rayleigh17 published an article on the thin liquid jets in electric elds and their stability. The article might be the rst literature on the electrohydrodynamics. In 1902, Cooley18 and Morton19 issued their patents about apparatus, which is now called electrospraying, for electrically dispersing uids. Though their inventions were not called electrostatic spinning or electrospinning, the fundamental principle is the same as that of electrospinning patented by Formhals1 in 1934. The essential difference between electrospraying and electrospinning is that the former used a low molecular weight solution, while the latter used a polymer solution (see Fig. 2). Formhals was considered as the originator of electrospinning,1 because he presented systematically the process for the production of articial bres from polymer solutions under the application of a high electrical eld in his 1934 patent. The schematic drawing of Formhals apparatus was shown in Fig. 3. He called the process as the electrical spinning of bres. From the mid-1940s to the early 1990s, Formhals invention did not catch much attention. In 1971 Baumgarten20 obtained experimentally the acrylic microbres via electrostatic spinning. The term electrospinning was rst used in Baumgartens article.20 The research on electrospinning took a big leap during the 1990s with the development of nanoscience and

Modern Textile Institute, Donghua University, 1882 Yanan Xilu Road, Shanghai 200051, China School of Textiles, Tianjin Polytechnic University, 63 Chenglin Road, Tianjin 300160, China 3 National Engineering Laboratory of Modern Silk, Soochow University, Suzhou, 215021, China
2

*Corresponding author, email jhhe@dhu.edu.cn

2010 Institute of Materials, Minerals and Mining. Published by Maney on behalf of the Institute Received 1 October 2008; accepted 2 December 2009 DOI 10.1179/026708310X12798718274430

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1 Rise of publications on electrospinning indexed in Web of Science

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technology. Up to now, electrospun nanobres have become one of the fast moving elds of science and technology that have undergone a variable revolution over the last two decades, leading to the major advances in the understanding and application at nano- and microlevels.

electrospinning apparatus, which can be divided into four regions including solution storage and feeding system, spinneret, spinning area and collector system. The syringe and the syringe pump make up of the solution storage and feeding system. A metal needle, y1 mm in diameter, is usually used as the spinneret. A charged pendent drop of polymer solution at the tip of the spinneret is elongated to a conical shape, which is known as the Taylor cone. A grounded collector was placed beneath the electrospinning spinneret. A DC high voltage generator,15 though few experiments were conducted successfully using an AC generator, is employed and usually connected with the spinneret and produces an electric eld in spinning area between the spinneret and the collector. Once the electric eld exceeds the critical value needed to overcome the surface tension, a uid jet ejects from the apex of the cone. The traditional electrospinning is subject to instability in the electrospinning process, low electrospinability, low properties compared with nature bres and low productivity; therefore, to overcome the shortcomings, new apparatus have appeared.

Vibration electrospinning
The traditional electrospinning has to overcome the surface tension of the polymer solution, while the surface tension depends strongly upon the viscosity of the polymer, which might be too high to be electrospun into nano- or microbres. The threshold voltage scales with the surface tension in the form

Classical electrospinning apparatus

Generally, the simplest electrospinning apparatus consists of a syringe with a metal needle, a syringe pump, a DC high voltage generator and a metal plate collector.2128 Figure 4 shows a schematic diagram of this traditional

2 Schematic of two processes: electrospinning and electrospraying

3 Schematic drawing of apparatus for production of articial bres by Formhals

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4 Schematic diagram of traditional electrospinning apparatus

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Ethreshold !c1=2 where Ethreshold is the critical voltage needed for the ejection of the jet from the Taylor cone and c is the surface tension of the solution, which is the intrinsic property of the solution and strongly depends upon the solution viscosity. A facile strategy for preparing electrospun nanobres by vibration technology is, therefore, suggested by Wan et al.26 Vibration is applied to the polymer solutions or melts, leading to a dramatic reduction in viscosity, as a result, a moderate voltage is needed to produce ne nanobres that are commonly observed during conventional electrospinning procedure at an elevated voltage. The novel strategy produces ner nanobres than those obtained without vibration and expands the range of this technique by making bres from macromolecules, which cannot be electrospun by traditional ways.

For acrylic solution, Baumgarten20 found that the scaling exponent is y1/2.

Effect of vibration on viscosity

Vibration technology3335 has been introduced into polymer processing for many years. Initially, it was only applied in researches for polymer melt viscosity measurement. Subsequently, the principle of melt vibration was introduced into practical applications including injection moulding, extrusion and compression moulding/thermoforming for the reduction of viscosity to lowering processing temperature and pressure to eliminate melt defects and weld lines, and for the enhancement of mechanical properties by modifying the amorphous and semicrystalline texture and orientational state. Ibar36 observed the effect of low frequency vibration during processing for polymethyl methacrylate (PMMA) (Fig. 5). The result showed that increasing frequency makes the solution viscosity decreased. The lower the frequency, the greater the differences of viscosity at various temperatures. At low frequencies, the solution viscosity decreased quickly, while at frequencies ranging from 100 to 500 rad s21, the increase in frequency was not obvious. However,

Effect of viscosity on diameter of electrospun fibre26,2931

Even under very high voltage, not every solution can be electrospun, and the jet might break up into droplets as a result of the surface tension in the case of small molecules with low viscosity liquids of small molecules (known as electrospraying). For high viscosity liquids of macromolecules the jet does not break up, but travels as a jet to the grounded target (known as electrospinning). For very high viscous solutions or melts, the process can be used in electro-extrusion in plastic industry.32 The experimental data and theoretical analysis29 show that the solution viscosity has great effects on the diameter of electrospun bres, initiating droplet shape and the jet instability. The increase in solution viscosity has been associated with the production of larger diameter bres, and it was shown that the bre diameter depends allometrically on the solution viscosity in the form29 d!ga (1)

where d is the average diameter of the electrospun bre, g is the viscosity and a is the scaling exponent. The exponent value might differ between different polymers.

5 Solution viscosity g frequency v (Ref. 36)

of

PMMA

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frequencies .200 rad s21 would decrease the viscosity gradient due to temperature. Ibar explained the effect of vibration frequency and amplitude on melt viscosity in terms of shear thinning criteria. When a vibrating force is applied to a concentrated and entangled polymer solution or melt, the weak van der Waals force connecting with macromolecules becomes weaker, and the entanglement is relaxed, so that the viscous force between the macromolecules decreases dramatically, resulting in the reduction in viscosity. According to the experimental observation, the following allometric scaling can be obtained g!v{b (2)

(i) dramatic reduction in viscosity, so that the jet length can be controlled by frequency (ii) finer fibres can be produced compared with traditional electrospinning apparatus under the same conditions; or the patented apparatus can even spin such fibres whereas the traditional apparatus cannot; or can spin fibres with the same diameter at much lower voltage (iii) the patented electrospinning process, as that in polymer extrusion, can enhance the mechanical properties of electrospun fibres by modifying the amorphous and semicrystalline texture and orientational state.

Thermo-electrospinning apparatus
It is well known that most melting polymers can be electrospun into nanobres; however, research efforts on melt electrospinning are relatively scarce,37 largely because a melt electrospinning apparatus is complex and expensive for the heater and the cooler are a must in this apparatus. While it is not as prevalent as polymer solution electrospinning, melt electrospinning eliminates the need for organic solvents, and has the potential to increase throughput due to no loss in mass by solvent evaporation.37 Melt blowing process is a process, which produces microbres directly from polymer resin. Melt blowing is used commercially as a one step process for converting polymer resin directly into a non-woven mat of bres. In the process a very high velocity gas impacts a molten polymer stream, as illustrated in Fig. 8. As a result, the polymer stream is attenuated rapidly by the high velocity hot air, and the resultant bres are collected upon a screen as a non-woven mat. The bre diameter can be reduced from 700 to 1 mm in 50 ms, and this dramatic change in diameter signicantly weakens its mechanical strength and affects other bre characteristics such as pore size, air permeability, loft, drape, feel, etc.

where b is a scaling exponent that varies with the characteristics of polymers. For PMMA solution at 239uC, g!v22/5 can be obtained from the experiment by Ibar.36

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Application of vibration technology to polymer electrospinning

When an additional vibrating force is applied to conducting polymer solutions or melts, a dramatic reduction in viscosity occurs. The voltage is applied to polarise dielectrics, where the charges are not completely free to move, but the positive and negative charges that compose the body may be displaced in relation to one another when a vibrating force is applied (see Fig. 6). Owing to its lower viscosity, a relatively lower voltage is needed to eject jet from the spinnerette. From equations (1) and (2), the following power law can be obtained29 d!v{d (3)

where d is the scaling exponent that varies among different polymers. The scheme of the vibration electrospinning set-up was shown in Fig. 7. The needle tip was connected to a DC high voltage generator via an alligator clip. An ultrasonic generator was used to provide vibration in vibration electrospinning set-up. The main advantages of vibration electrospinning are:

Controlling stability by temperature

In order to control the solvent evaporation, a furnace is added as illustrated in Fig. 9. In the furnace the temperature eld can be adjusted, and the temperature

a without electric eld; b with electric eld plus vibrating force which leads to high molecular orientation due to electronic force, and high mechanical properties 6 Effect of electronic eld on entangled macromolecule

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7 Schematic of vibration technology in polymer electrospinning. This apparatus was patented (China Patent 200420020596?3). To use this principle to prepare electrospun bres, transfer agreement must be made29

9 Schematic of electrospinning process with controllable temperature eld

near the orice is lower than that of the melts and higher than that near collector. Owing to the gradient of temperature, cold air ows up along the furnace wall, and comes down along the bre, and the low velocity gas further impacts the polymer jet, as illustrated in Fig. 9. Convection currents occurred in the upper half of the furnace and were enhanced by the injection of comparatively cool feedstock down the axis. It is believed that the gas moved upward beside the furnace walls and downward in the centre of the tube. As a result, the polymer jet is further attenuated and the jet length can be increased, so that the instability can be controlled. It would be more effective if a set-up can be devised by taking into account the controllable temperature (Fig. 9). High temperature can also dramatically reduce the viscosity, and the electrospinning of polymer melts can offer an advantage over solution electrospinning.38 Figure 10 illustrates an apparatus of melt electrospinning system. The effects of various melt electrospinning parameters on the morphology and bre diameter of polypropylene of different tacticities were studied.39

Recently, He et al.40 suggested some novel melt electrospinning apparatus such as vibrationmelt electrospinning and aero-melt electrospinning, as shown in Figs. 1113. Hot air is applied in aero-electrospinning (see Fig. 13). Hot air further attenuates the laments, making the electrospun bres ever smaller. Melts are extruded by static electronic force through small orice into convergent streams of hot air that rapidly attenuate the charged jet into small diameter bres. The air streams can also control the instability in the electrospinning process, and transport bres to a collector where they bond at brebre contact points to produce a cohesive non-woven web. Additionally, McCann et al.41 developed a melt coaxial electrospinning, similar to coelectrospinning in solution electrospinning, for the encapsulation of solid materials and fabrication of phase change nanobres. Ogata et al.42 presented a new melt electrospinning system equipped with a laser melting device. They employed the laser beams from three directions to irradiate the end of rod-like sample. The bres obtained were collected onto a grounded rotating disc.

8 Schematic of thermo-electrospinning

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10 Schematic illustration of set-up for melt electrospinning

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13 Aero-electrospinning40

If a magnetic eld is applied in the electrospinning process, as illustrated in Fig. 15, an Ampere force is generated due to the current in the polymer jet F ~LI B
11 Melt electrospinning does not require solvent: temperature of melts can be controlled by electronic heater40
I II

(4)

12 Vibrationmelt electrospinning40

Magneto-electrospinning
As it is well known that during the electrospinning process, the charged jet is of intrinsic instability that leads to the uneven construction of nanobres and waste of most energy which, otherwise, can be used to further stretch the jet into even smaller bres (Fig. 14). The instability also leads to low molecular orientation, as a result, low mechanical properties arise. Our group suggests a completely novel approach to control the instability in electrospinning, and the technology is termed as megnetio-electrospinning.40,43 It can be concluded that the magnetic approach is the most effective and economical way to control instability and improve the mechanical properties as well.

where I is the current, oating inside the conductor, B is the value of magnetic eld induction and L is the conductor length. The resultant force of electric force and the viscous force of the jet ow enlarges the whipping circle. If a magnetic eld is applied in the electrospinning, the problem can be completely overcome. The current in the jet, under the magnetic eld, produces a centripetal force, i.e. the direction of the Ampere force is always towards the initial equilibrium point (see Fig. 15), leading to the shrinking of the radius of whipping circle. As a result, the stability condition is enormously improved. The magnetic force is perpendicular to the velocity, so it contributes no work to the moving jet; the shrunken circle means less energy waste in the instability process, and the saved energy is used to increase the kinetic energy of the moving jet. According to the conservation of mass pr2ru5Q, thus r2<1/u, the radius becomes much smaller than that without magnetic eld. Macromolecule chains of polymer jet are subject to the coupled forces of electronic force and magnetic force and arranged again (see Fig. 16). The produced magnetic force can ameliorate the inner structure of macromolecules, resulting in a remarkable amelioration of the strength of nanobre.

Siro-electrospinning
Two strand spun or Sirol yarns44,45 have now been widely used in the worsted industry. The strands are texturised to improve the bulk of the resultant yarns, which have been demonstrated to possess more desirable properties. For example, the weaveability of the fabric formed by the Sirol yarns is signicantly improved over its counterpart yarns. Dragline silk is made of many nanobres, similar to siro-spinning. To mimic the spider

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14 Instability in electrospinning: most energy was wasted due to instability

16 Macromolecules under coupled forces of electronic force and magnetic force

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spinning (see Fig. 17), siro-electrospinning is created (see Fig. 18). Li et al. patented a conjugate electrospinning apparatus,4648 as illustrated in Fig. 19. Two or more bres are combined together by weak static electronic force. An apparatus is devised where a twist is added (see Fig. 18), causing the bres to have a tendency to twist and crimp. Fabrics so produced can improve its mechanical characteristics, furthermore, its strength, toughness, softness and feel can be improved dramatically. The present technology can also be taken in conjunction with other ones. For example, the vibration technology can be added. Using this technique, it is now possible to spin conductive polymer bres under ambient conditions by depositing nanometre metal particle in the polymer solutions or melts. If some titanium dioxide is added in the solutions or melts, the electrospun bres are self-clearing.

Spider spinning
After 400 million years of evolution, nature endows spiders with genius of spinning exible, lightweight bres which have the strongest strength in the world, at least ve times stronger by weight than steel, and have remarkable toughness and elasticity.49,50 Even in the modern times, it is difcult to synthesise a material having advantages of strength and toughness except carbon nanotube bres, which is spun from solution in very hot temperature or pressure,51 while the spider silks are produced at room temperature and from aqueous solutions. Spider silk is the only natural material that combines the properties unmatched by any known synthetic high performance bres. Spider silks are protein based biopolymer laments or threads secreted by specialised epithelial cells as concentrated soluble precursors of highly repetitive primary sequences.52 Many experiments have been conducted, and much research has focused on gene

a application of magnetic eld to electrospinning; b Ampere force in electronic jet induced by magnetic eld 15 Effect of magnetic eld on electrospinning43

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This gives 1 T~ r(Pi {Po ) (7) 4 Hendricks et al.56 calculated the minimum spraying potential of a suspended, hemispherical, conducting drop in air as Ethreshold ~30020pcr1=2 Buchko et al.
2 Ethreshold ~
57

(8)

modied equation (8) in the form (9) (10)

4H 2 2L 3 : ( ln { )0 117pcR R 2 L2

Ethreshold !c1=2

17 Sirol technology to improve mechanical properties of mother bres

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18 Siro-electrospinning40

sequencing of spider, and a biomimicry technology has been developed;5355 however, theoretical analysis is not yet dealt with it, and our understanding of the mechanism of spider spinning is rare and primitive. If the mystery in its mechanism can be solved, then the mechanism can be applied to synthetic high performance bres such as electrospun bres with combination of great strength and stretch. The devised method must be much economical, so this could be the beginning of a new materials revolution.

where Ethreshold is the critical voltage needed for the ejection of the jet from the Taylor cone, H is the separation distance between the needle and the collector, L is the length of the needle (or capillary), R is the radius of the needle and c is the surface tension of the solution. From Fig. 20, it can be clearly observed that dragline silk is made of many nanobres with a diameter of y20 nm. Therefore, it can be assumed that a bubble can be produced at the apex of each tube with a diameter of y20 nm. According to equation (7), the surface tension of such bubbles is extremely small, thus it can be easily overcome either by the body weight of spider or tension created by the rear legs. Most natural spider silk is only 2?54 mm in diameter, and the weight of most spiders varies from 90 to 1500 mg. Consider a dragline silk with a diameter of 361026 m which consists of many nanoscale brils with a diameter of y20 nm (see Fig. 20). Therefore, the number of nanobres in the assembly can be estimated, which reads 3|10{6 2 ) &2|104 (11) 20|10{9 It means that there are tens of thousands of nanobres in the assembly! Similar to the HallPetch relationship, the nanobre strength depends upon the bre diameter in nanoscale (from few nanometres to tens of nanometres) n~( kt (12) d 1=2 where kt is the tting parameters (material constants), t0 is the strength of the bulk material and d is the bre diameter, as shown in Fig. 21. Comparing the strength of a single bre tSF with the diameter of 361026 m with the strength of a dragline assembly tDA consisting of 26104 nanobres with the diameter of 2061029 m, the following can be estimated tDA {t0 ~2:4|106 (13) tSF {t0 t~t0 z Extraordinarily high strength of a dragline assembly is predicted compared with a single bre with the same section area and same material. The nding shows that it is a challenge to develop technologies capable of preparing for nanobres within 50 nm. It means that there are tens of thousands of nanotubes in spinneret of spider! A weight of G51024 kg of a spider is assumed. In the spinning process, the spider can

Mystery in spider spinning process

It is still an enigma how a spider produces a silk which human needs ten thousands voltage to do. One possible answer is that a spider applies sufciently the nanoeffect of bubble dynamics. The pressure difference between the inside and outside of a bubble depends upon the surface tension and the radius of the bubble. For a bubble with two surfaces providing tension, the net upward force on the top hemisphere of the bubble is just the pressure difference times the area of the equatorial circle Fupward ~pr2 (Pi {Po ) (5)

The surface tension force downward around circle is twice the surface tension times the circumference, since two surfaces contribute to the force Fdownward ~2pr(2T) (6)

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19 Schematic set-up used for conjugate electrospinning experiments4648

from which the pressure difference between the inside and outside of a bubble can be determined, which reads 4G 4|10{4 ~ N m{2 (15) 1 DP Pi {P0~ ~ ~ nr (2|104 )(20|10{9 ) Extremely small force is needed in the spider spinning!

Bubble electrospinning
From the hint of the mechanism of the spider spinning, a new approach is designed to overcome the bottleneck in present electrospinning technology, which is to minimise the surface tension of the electrospun solutions mimicking the spider spinning. Compressed gas is widely used in textile industry,59 and this technology will be used to reduce the surface tension. Our system6062 consists of a vertical solution reservoir with a gas tube feeding from the bottom, in which a metal electrode is xed along the centreline of the tube, and a grounded collector over the reservoir (see Fig. 22). It has been found that many small bubbles with different sizes were produced on the solution surface. The mechanism of the new electrospinning process is deceptively simple: in the absence of an electric eld, the aerated solution forms various bubbles on the surface. When an electric eld is present, it induces charges into the bubble surface, and these quickly relax to the bubble surface. The coupling of surface charge and the external electric eld creates a tangential stress, resulting in the deformation of the small bubble into a protuberance induced upward directed reentrant jet. Once the electric eld exceeds the critical value needed to overcome the surface tension, a uid jet ejects from the apex of the conical bubble (see Fig. 23). The threshold voltage needed to overcome the surface tension depends upon the size of the bubble and inlet air pressure. Although the maximal or minimal size of a bubble might depend upon the solution viscosity, the surface tension of bubbles is independent of properties of the spun solutions, such as viscosity, which is the main obstruction in traditional electrospinning. Temperature can be used to adjust the bubble sizes in practical application of the new electrospinning process. The key advantages of this electrospinning process used here, compared with the traditional electrospinning process, are that it can produce smaller nanobres without requirement of nozzles, which are the main shortcoming of the traditional electrospinning technology; furthermore, in our method, with a relatively low voltage, millions of protruded bubbles can be easily produced which can be electrospun into nanobres simultaneously, and electrospinnability does not strongly

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20 Spider spinning process reproduced with the permission of Dennis Kunkel Microscopy, Inc. The diameter of a single nanobre is y20 nm, its spinneret on the posterior portion of the abdomen of spider consists of millions of nanoscale tubes and a bubble can be produced at apex of each nanotube. The surface tension of each bubble is extremely small such that it can be spun into nanobres with an awfully small force, either by the body weight of spider or tension created by the rear legs

21 E modulus of nanobres: redrawn according to experimental data by Gu et al.;58 dots are experimental data

use its weight to overcome the surface tension of all bubbles produced at apex of nanotubes, which requires T~G (14)

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24 Minimum diameter of nanobres was 50 nm (Ref. 63)

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22 Experimental set-up of aerated solution electrospinning. This principle to prepare for nanoproducts was patented (China Patent 200710036447?4). To use this principle to prepare for nanoporous products, transfer agreement must be made63

of the jet is minimal, and macromoleculars of the polymers are compacted together tighter and tighter as illustrated in Fig. 25. There must exist a critical minimal radius rcr for all electrospun jet r(rcr for continuous ultrane bres, and the critical maximal velocity is ucr ~Q=prr2 . However, the velocity can exceed this cr critical value ucr if a higher voltage is applied. When the radius of the jet reaches the critical value r5rcr, and the jet speed exceeds its critical value u.ucr, in order to keep conservation of mass equation, the jet dilates by decreasing its density, leading to porosity of the electrospun bres (see Figs. 26 and 27), which is called electrospinning dilation. Nanoporous microspheres are especially useful for invisibility device (e.g. stealth plane)64,13 and drug deliver.65,66

New electrospinning apparatus for mass production of nanofibres

In recent development and application of electrospun nanobres, one key bottleneck is the lack of capacity to the mass production of nanobres. It is limited for a traditional electrospinning apparatus to increase the ability of nanobre throughout because there are many seemingly insurmountable difculties. One is the small diameter (about 0?12 mm) of the spinneret and the low owrate (from 0?1 to dozens of mm h21) of the solution. If the diameter is enlarged, the suspended droplet may

23 Ejected jets captured by digital camera63

depend upon the solution viscosity, overcoming completely the main shortcoming of the traditional electrospinning. The average diameter of nanobres can be easily controllable, and the minimum diameter in our experiment reached as small as 50 nm (see Fig. 24). This new technology is of critical importance for the new generation of electrospinning, especially for the specialists in design, manufacturing and using nanobres.

Electrospinning dilation and electrospun nanoporous microspheres

During the electrospinning process, the charged jet is accelerated by a constant external electric eld, and the spinning velocity probably reaches maximum and perhaps exceeds the velocity of sound in air in a very short time before the spinning becomes instable. According to the conservation of mass equation pr2 ru~Q (16)

where r is the radius of the jet, u is the velocity, Q is the owrate and r is the density. The radius of the jet decreases with increasing velocity of the incompressible jet. When the velocity reaches its maximum, the radius

25 Macromolecular chains are compacted during electrospinning

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26 Electrospinning dilation phenomenon of poly (butylenes succinate) (PBS) electrospun bres64

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limited the bre output. Dosunmu et al.69 suggested a new multiple porous tube apparatus in which the polymer solution was electried and pushed by air pressure through the walls of a large diameter cylindrical porous tube (see Fig. 28a). Multiple jets formed on the porous surface and electrospun into nanobres in their process. However, the existing problem of this process might be also the non-uniform bre mat (see Fig. 5 in Ref. 69). In order to eliminate the problems of increasing the nanobres of mass production of traditional electrospinning apparatus, some researchers demonstrated various novel electrospinning apparatus in recent years. Yet these apparatus, different as they seem, have one thing in common. The Taylor cone was formed on the free surface of the solution and the jets were ejected upward. Yarin and Zussman70 proposed an upward needleless electrospinning which consisted of a two layer system with the lower layer being a ferromagnetic suspension and the upper layer a polymer solution (see Fig. 28b). In the process, many vertical spikes of magnetic suspension perturbed the interlayer interface as the Taylor cones. Though the production rate is higher than that of traditional electrospinning process, there are some aws such as not easy operation of two layers liquids. So far only one electrospinning process, Nanospider spinning technology, is claimed to be a commercial success in the mass production of nanobres all over the world. The principle of Nanospider is to use a cylinder to form the bres. The cylinder is partially immersed in

27 Electrospun nanoporous microspheres, where kind of traditional Chinese drugs called Yunnan Baiyo was used as additive65

not be formed as a stable Taylor cone at the orice because of the gravity and other factors, and so is the increasing owrate. Unlike the traditional dry spinning process or wet spinning process in which the jet is extruded from the spinneret with high speed, the traditional electrospinning process depends on the electrostatic force, which just provides a stable and slow liquid ow to form a stable Taylor cone at the tip of the spinneret, rather than the extrusion pressure. The spinning speed is much less than that of the dry spinning or wet spinning. The other shortcomings are easily jammed, difcult clean, etc. As a result, the possible technique of the use of traditional electrospinning apparatus to produce nanobres of mass production is to t the multiple spinnerets together with a line or matrix pattern. Many researchers adopted this technique to produce nanobres from the early period of the invention of this technology to now. It is prevailing until Theron et al.67 found both experimentally and in the simulations, that the jets were pushed away from their neighbours by the Coulombic forces applied by the latter. A non-uniform non-woven mat would be obtained as an immediate consequence of this phenomenon. Fang et al.68 once reported that they solved the problem of the mutual Coulombic interactions by the incorporation of secondary electrodes to isolate the electric eld distribution of the primary electrode spinnerets. But the problem of the small diameter of the spinneret and the low owrate still

a Dosunmus apparatus; b upward needleless electrospinning 28 New electrospinning apparatus for produing mass production of nanobres

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the polymer solution, and, as it rotates, the polymer solution is carried to the top part of the cylinder where Taylor cones are created. The Taylor streams are formed next to each other, throughout the entire length of the cylinder, resulting in the high production capacity of this apparatus.71 The above novel approaches are exciting for the researchers and the engineers. When we cheer and applaud for these much progress of electrospinning; however, a new problem caused by the opened liquid surface has risen up. In every electrospinning process, the volatilisation of the solvent from the ying jet is a must. In the above new upward electrospinning apparatus, the free liquid surface can be used to create many Taylor cones and increase the throughput of nanobres, at the same time, can be facilitated to the escape of the volatilising solvent. With the process proceeding, the viscosity of the polymer solution will increase, which will introduce some new problems such as increasing the difculty of spinning and changing the properties of the solution.

Universities Science and Technology Development Fund Project No.20080322.

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Conclusions
It is clear that an understanding of the electrospinning and its nanobres was greatly advanced by the nanoscience and technology in the 1990s and by the subsequent development of the many effective applications available in many elds today. Remarkable advances in electrospinning technology have been possible due to developments in modern technology. Various novel and useful electrospinning techniques are reviewed in this work according to their different modications. Some modied apparatus were used to produce different nanobre mats with special structures for some special applications, and some for mass production of nanobres. Most of the advances achieved to date have been made in the collector system of the traditional electrospinning apparatus, but other parts such as solution storage and feeding system, spinneret, and spinning area, have been studied as well. More recently, emphasis has been placed on creating new apparatus to mass production of nanobres. New techniques have been designed and improved, and more electrospinning apparatus have been developed to better produce nanobres. Collectively, the studies about electrospinning and nanobres carried out so far have furnished a useful database for the electrohydrodynamics and some other elds. Although this eld is in its infancy, it is becoming increasingly clear that there are multiple forms of new techniques. Identifying the similarities and differences in various apparatus will enhance our understanding of this technology. The next decades are expected to not only enrich the existing knowledge, but also signicantly advance the technology into the commercial domain.

Acknowledgements
The present work is supported financially by National Natural Science Foundation of China under Grant Nos. 10802021 and 10972053, National Natural Science Foundation of Shanghai under Grant No. 08ZR1400300, Shanghai Rising-Star Program under Grant No.09QA1400100, Key Project of Chinese Ministry of Education No.210006, National Science Foundation of Tianjin No.10JCYBJC02200, Tianjin

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