5

Liquid Crystal-Functionalized Nano- &
Microfibers Produced by Electrospinning II

5.1 Introduction: Why Electrospinning with LCs?
5.2 What is Electrospinning?
5.3 Low Molar Mass LCs inside Electrospun
Fibers
5.4 Application Potential of LC-Containing
Electrospun Fibers

By Prof. Chia-Rong Lee
Liquid crystal Photonics lab.

5.3 Low Molar Mass LCs inside
Electrospun Fibers
ƒ Not only somewhat more complex but also much more
versatile (多功能) due to the immense catalog of available
materials, is the spinning of LMW LCs.
* The trick (竅門) is to spin the non-polymeric, and thus “unspinnable” LCs as a core fluid contained inside a polymer
sheath solution.
* Two approaches that have been explored for achieving
this situation is

X Mix polymer and LC in a common solvent and then rely on phase
separation during the spinning process for obtaining the coresheath structure
Y Use coaxial electrospinning to establish the core-sheath geometry

* The resulting core-sheath fibers constitute an entirely new
configuration for studying — and applying — LMW LCs,
opening possibilities very different from standard device
configurations.
* The LC gives the fibers new functionality and responsiveness
and the encapsulation ( 封裝 ) of the LC in the narrow
cylindrical fiber core allows easy investigation of 1D
confinement effects.
* The fibers also have large application potential. While we
are still at the very beginning of the research on
development of LC-functionalized electrospun fibers and nonwovens one can envisage applying them in fields ranging
from full spatial resolution temperature sensing, via dynamic
camouflage (偽裝) clothing, to wearable electronics and displays.

5.3.1 Non-coaxial Electrospinning of LC Core
Composite Fibers
ƒ Buyuktanir et al. devised an approach to LC
electrospinning that is very attractive through its
simplicity and the fact that a standard electrospinning setup can be used.
* The commonly studied NLC 5CB was dissolved together
with polylactide (PLA (聚乳酸), Mw=186,000 g/mol) in a
chloroform-acetone solvent mixture (3:1 volume ratio), in
proportions giving a PLA concentration of 7.3 wt%. This
polymer concentration was kept fixed while the
proportion of 5CB to PLA was varied in the range of
7~86%, spinnable solutions being those with 5CB
concentrations below 70%. During the spinning process
the 5CB phase separates from the polymer, forming the
LC core of the fibers.

* The phase separation between 5CB and PLA is however
not complete but the fiber sheath actually becomes a
mixture of PLA and 5CB.
* The authors found that phase separation started at 5CB to
PLA ratios > 28 wt%, meaning that the excess 5CB then
started forming a polymer-free LC core within the mixed
composition sheath. Above this LC fraction the clearing
transition enthalpy ( 焓 ) peak could be detected in
differential scanning calorimetry (DSC) measurements
and the fibers appeared clearly birefringent for more than
40% 5CB, with the director generally aligned along the fibers as
detected by polarizing microscopy.

* Generally. the degree of control is quite limited. . the coaxial approach to LC electrospinning requires the basic set-up to be extended with a tailored (定做的) temperature regulation system.2 Coaxial Electrospinning of Fibers with Solvent-free LC Core Fluid: Practical Requirements ƒ While (儘管) the previous approach is practically straightforward to realize.3.5. as only a single solvent-rich isotropic liquid phase is being spun. allowing the user to choose the phase adopted by the LC material at the onset of spinning.

* Moreover. higher-ordered LC phases such as smectics or cholesterics are often too viscous.* While nematics can be relatively easy to electrospin. a large difference in elongational viscosity between inner and outer fluids complicates the spinning process such that a continuous filling of the fibers may be impossible. It is thus highly desirable to have the possibility to heat the material into the isotropic phase if we wish to prepare fibers with a core that eventually is in a high-ordered LC state. the shear viscosity η2 in fact being even lower than the shear viscosity of the material heated to its isotropic phase. It may be difficult to achieve continuous and smooth flow to the spinneret of a highly viscous fluid. .

preventing true control of the spinning parameters and making repeatability challenging. since the substance to be heated is spatially distributed over the full length of tubing. * The simplest solution is to heat the whole system up to the spinneret with a heat gun. and it also heats many components that would better stay at Troom. the access ( 使 用 ) for a heating system being very difficult in certain places. such as the syringe pump in case this device is used. This method is readily accessible but obviously lacks precision.ƒ It is not trivial (不重要) to realize a precise and versatile temperature control for electrospinning. .

ƒ For some LC substances the inner fluid can in fact sometimes be in a cholesteric or even smectic phase during spinning. 7. 8CB (Fig. 7. 7. . close enough to the 2nd-order N-SmA transition that the material still flows reasonably easily. * Likewise. the short-pitch cholesterics formed by doping the commercial NLC RO-TN-403/015 S with the chiral dopant CB15 (Figs.7b-d) had sufficiently low viscosity to be spun at Troom.7a) could be spun at Troom where the LC is in a SmA phase. This mixture (mixture 1) is much less viscous than the three-component cholesteryl ester mixture 2 (Fig. * For instance.7e) although both have about the same very short pitch of the director helix at Troom.

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ƒ While the fiber is very stable with a well-defined morphology. the fact that the sheath consists mainly of TiO2 makes characterization of the LC core more challenging. and the optical properties of the LC are inaccessible ( 難 見 到 ) behind this strongly scattering and birefringent sheath.3 Sheath Morphology of Coaxially Spun LC Core Fibers ƒ The first few experiments on coaxial LC core-polymer sheath electrospinning were carried out with an outer spinning solution containing polymer and Ti(OiPr)4 sol-gel precursor (前驅物).3. . h The verification of the director alignment & the investigation of the phase sequence therefore had to be done with polarized Raman spectroscopy.5. The result is a polymer-TiO2 composite sheath that is particularly stable and a LC core.

14 mL/h (a) and 0. 7.5% PVP in ethanol solution as outer fluid appearing quite uniform in optical microscopy and the LC optical properties being easily detectable. 10 cm spinneret-collector distance. This generally worked very well. Depending on the degree of LC filling. the outer diameter ranged between one and a few microns. FIGURE 7. This was pumped at a flow rate of 1. . fibers produced using a 12. Both samples were spun at Troom with 25~35% relative humidity.5% PVP in ethanol solution as the outer fluid. with a 12.8 SEM images of pure PVP sheath fibers with CLC core (mixture 1.8 mL/h while the inner fluid was pumped at flow rates of 0.ƒ In later work the fibers were spun with a pure PVP sheath that is largely nonbirefringent.36 mL/h (b). ƒ The outer morphology of these fibers was investigated by SEM (Fig. 7.7d). Fig. and 10 kV spinning voltage. The fibers were generally cylindrical although some examples of essentially flat ribbons were also found.8).

. The result was complete separation into oil droplets and solid fibers of pure PVP. because earlier attempts by Li and Xia to spin mineral oil coaxially inside a PVP ethanol solution failed due to structural breakdown of the coaxial jet.ƒ The fact that coaxial spinning with LC core and pure PVP sheath can produce stable fibers is actually somewhat surprising.

ƒ It is obviously of great interest to know also the internal structure of the fiber. something which turned out to be very difficult to avoid for pure PVP sheath fibers. the similar electron density of the sheath polymer and the LC would lead to too weak contrast for distinguishing the two regimes in TEM. the inner diameter being the most important parameter to establish. at best after having dissolved the core fluid with a suitable solvent that does not affect the sheath. In addition. * This is however not trivial to realize experimentally since the fibers are generally too thick for transmission electron microscopy (TEM) imaging. . * One approach that has been successful in the characterization of similar systems is to carry out SEM on the fractured (斷裂) end surface of fibers that have been broken in two sections. This however requires that the fiber sheath does not collapse during the fracture.

leaving only the polymer sheath to form the image. Upon hitting the substrate the fiber had collapsed from the normal cylindrical geometry into a horizontal cylinder segment morphology. The channel holding the LC can easily be seen in the regions where the FIB has cut away the sheath. ƒ When exposed to the vacuum of the FIB chamber the low molar mass LC molecules of the core evaporate. dissected using FIB milling and imaged by the FIB. FIGURE 7. LC .10 A richly filled fiber with pure PVP sheath and CLC core. either along or across them. and then image the dissected (切開) fiber using SEM or FIB.ƒ The approach that eventually brought success in imaging the internal structure was to use Focused Ion Beam (FIB) milling (聚焦離子束銑) to cut sections through the fibers.

this alignment produces a defect-free director field within the cylindrical fiber. hence an alignment along the fiber is to be expected considering the spinning conditions. .5. the minimum viscosity is along the director.3. * Moreover. In case of a nematic.4 How Does the LC Alignment inside the Fiber? ƒ The cylindrical symmetry of the fiber might intuitively suggest a director alignment along the fiber for a nematic phase.

ƒ In case of clear and isotropic polymer sheaths the alignment of the director within the fibers is easily investigated with POM. In this case. This allows the director orientation and the effective degree of orientational order to be assessed (估計) also in such fibers. such that this straightforward technique (POM) cannot be used for the purpose. * The strength of the LC peaks depends on the alignment of the director with respect to the polarization of the excitation laser. going to zero for perpendicular alignment and being maximal for parallel. Some fiber sheaths are however too scattering. or birefringent in themselves. <EX> The fibers with composite sheaths containing a large amount of TiO2 are both strongly scattering and birefringent. polarized Raman spectroscopy turned out to be highly useful since the LC has a very characteristic response spectrum that can easily be distinguished from that of the sheath. .

beaded fibre Fibres consisting of LC core and TiO2–PVP sheath. The fibres were spun with a sheath solution feed rate of 0.2 (a. b) or 0.4 mLh-1 and a LC feed rate of 0. 2008.Coaxial electrospinning of microfibres with LC in the core.3 (c) mLh-1. Chem. aligned sample) and by differential interference optical microscopy (c). non-woven. Commun. . 5420–5422. b. which were observed by SEM (a.

* In the bottom section. respectively. (aromatic ring stretching mode. reference spectra of a bulk sample of the LC at Troom (black curve) and of a non-filled TiO2-PVP composite fibre (grey curve) are shown. 1610 cm-1) (slightly weaker cyano group stretching mode 2230 cm-1) . at three different temperatures surrounding the clearing point of the bulk LC (top section).* Raman spectra of an electrospun TiO2-PVP fibre containing the LC in the core. The solid-line and dotted-line spectra were obtained with polarization along and perpendicular to the fibre.

g.* The 85 oC spectra are very interesting: despite the fact that they were obtained above the Tc of the bulk LC. e. of the aromatic ring stretching Raman mode. a weak anisotropy being detected even at 100 oC.and antiferroelectric). the ratio remains above 1 (which correspond to an isotropic state) throughout the temperature range investigated. as a function of temperature. Ratio of the intensities for polarization parallel and perpendicular to the fibre. the polarization sensitivity of the response is almost as strong as at Troom. * By incorporating more complex phases. the technique should allow new functionality to be added to the fibres. * The method provides an easy way to study confinement effects on LCs by incorporating selected mesomorphic materials and systematically varying fibre diameter and/or core-sheath ratio. * The director was aligned along the fibre and the range of the nematic phase was substantially extended via a confinement-induced up-shift of the Tc by ~20 oC. cholesteric. . columnar or smectic phases (which can be ferro. * While the anisotropy decreases monotonously as expected. respectively. revealing that the mixture inside the fibre is still nematic.

perpendicular to the fiber axis. . allowing the type of LC alignment in the fiber to be elucidated from the X-ray scattering diffractograms. <EX> This is particularly useful for smectic LC cores.ƒ In case the fibers have been spun with uniform fiber orientation they can also be placed in an X-ray scattering set-up. A convenient approach is to roll up an aligned and relatively dense fiber mat into a scroll. since we can then study the director alignment and the layer formation independently. which can then be inserted into an X-ray capillary for the experiment.

(b) isotropic state at 45 oC. Chem. 5.3762/bjoc.5. .Coaxial electrospinning LC-containing poly(vinylpyrrolidone) microfibres (X-Ray investigations on fibres) Beilstein J. Org. 2009. doi:10.58 POM photographs of 8CBcontaining composite fibres (a) SmA phase at Troom.

These scattering patterns from the composite fibres should be compared to those from unfilled PVP fibres and bulk 8CB. This is mainly due to the facts that in the b) case the X-ray beam is directed along rather than across the fibres in a large part of the sample. . Before After rolling incident X-ray beam incident X-ray beam a). * For this purpose two samples of uniformly aligned fibres with maximum LC content were spun between bars of Al foil and were then rolled up in 2 perpendicular directions. thereby not producing any significant scattering response. * The orientation being more clearly distinguishable in the a) pattern than in b) pattern.* To gain information about the LC orientation (and the layers of the SmA phase) inside the fibres. 2D X-ray diffraction patterns were recorded. b): 2D X-ray diffraction pattern of oriented fibres at two perpendicular roll-up directions schematically sketched in c) and d).

The corresponding layer spacing dA = 3. Schematic sketch of the arrangement of LC molecules and the smectic layers in an electrospun fibre.08 nm can be very well compared to the value of 3. . respectively (b to d). In the middle and wide angle regions of the diffractogram two diffuse rings can be seen. caused by the polymer sheath.* The layer reflections of the SmA phase can be seen on the equator in the small angle region.14 nm measured for bulk 8CB and to literature values. nematic and isotropic phase. 2D X-ray diffraction pattern of oriented 8CB-containing PVP composite fibre X-ray diffraction patterns of PVP fibres without LC (a) and of surface-aligned samples of bulk 8CB in the SmA.

particularly sensitive phases such as the chiral smectic-C intermediate phases. .5 Phase Sequence and Phase Transitions of LCs inside Electrospun Fibers ƒ It is well known that the phase sequence of LCs can be strongly affected by confinement.3. ƒ Moreover. ƒ In the first few experiments on coaxial electrospinning with a NLC mixture inside a composite PVP–TiO2 sheath a dramatic increase of the clearing temperature by about 20oC compared to the bulk LC was found. the first-order character of the N-I transition also seemed to have disappeared as a result of the strong confinement.7.

ƒ However. .ƒ In a series of elegant AFM investigations on LCs in the vicinity of solid substrates.戰 勝. ƒ In the electrospun fibers. the team around Igor Musevic in Ljubljana demonstrated how LC order prevails (勝過.優勝) very near the surface even at temperatures well above the Tc. the molecules in the vicinity of the surface now constitute a much greater fraction of the whole LC volume than in usual samples. where the LC core is fully surrounded by a solid sheath with an inner diameter typically a few hundreds of nanometers the same phenomenon should occur. ƒ We may thus explain the observation of increased Tc and the loss of first-order transition character as a result of a surface-induced stabilization of the LC phase that gets less effective on going from the sheath to the core.

the ratio of nematic to isotropic phase continuously getting smaller until finally.ƒ As we continue heating the fiber from the bulk clearing temperature the mixture gradually turns isotropic from the center. even the surface layer has lost its orientational order. . ƒ In this way the phase transition appears continuous to the outside world and LC order is detectable at much higher temperatures than for bulk samples. some 20oC above the bulk Tclearing.

Chem. Org.5. (b) isotropic state at 45 oC.Coaxial electrospinning of LC-containing poly(vinylpyrrolidone) microfibres (influences of feeding rate and applied volatge) Beilstein J. 5.3762/bjoc. doi:10. 2009.58 POM photographs of 8CB-containing composite fibres (a) SmA phase at room temperature. .

Upper row: sample seen without polarisers. lower row: same sample position seen between crossed polarisers. Outer fibre diameters as a function of LC flow rate as determined from 50 measurements by optical microscopy on each sample. .Varying the feeding rate of the LC Microscopy photographs of characteristic samples when varying the flow rate of the liquid crystal Vin while retaining the flow rate of the polymer solution constant.

. most likely because the encapsulation was not as strong in these pure PVP sheaths as in case of the TiO2–PVP composite fibers. until they could no longer be resolved in the thinnest fibers. N Iso.Varying the feeding rate of the LC * The effect of confinement on the LC phase sequence can be clearly seen. and the two transitions approached each other upon increasing confinement. * The increase in clearing point was here less pronounced than in the previous study. SmA DSC thermograms on heating of 8CB as bulk and as inclusion compound in PVP fibres produced with different flow rates of the LC (Vin). * The phase transition peaks became weaker and more smeared out than for a bulk sample.

leading to the strong super-cooling/heating effects. * When first passing a certain phase transition temperature the mesogens at the inner surface of the polymer sheath are strongly anchored in an arrangement corresponding to the starting LC phase. N Iso. SmA DSC thermograms on heating of 8CB as bulk and as inclusion compound in PVP fibres produced with different flow rates of the LC (Vin).* The strong effect on the smecticnematic transition temperature was explained as a result of an encapsulation-induced kinetic stabilization (super-heating/cooling) of whatever molecular arrangement that is in place. . * This surface-stabilized cylindrical layer of molecules will counteract (對 抗) reorganization into a less or more ordered phase.

Influence of applied voltage The liquid crystal core shows a transformation from bubbly to smooth and to bubbly again with increasing electric field strength. . Influence of the applied voltage and the flow rate of the polymer solution on the mean fibre diameter. the threshold voltage being dependent on the ratio of outer to inner flow rate.

gets thicker and the sheath thinner (since the same volume of sheath solution must now surround the larger-diameter LC core).5. ƒ In the experiments the LC flow rate and that of the sheath solution was varied. and thus the fiber. .3. ƒ The continuity of LC filling depended strongly on the flow rate. At low flow rates the fibers were not only thinner but the LC was also distributed in elongated drops along the fiber rather than forming a continuous thin core. With increasing LC flow rate the fiber core.6 Optical Properties and Phase Behavior of Cholesteric & Blue Phases inside Electrospun Fibers ƒ Enz and Lagerwall prepared a series of PVP sheath fibers containing the short-pitch CLC mixture 1. reflecting a bluegreen color when observed straight on.

Chem. phases and structures changing in response to small changes in the environment. . other ranges being accessible via further modifications of the spinning parameters. 2010. They demonstrated that the thinnest fibres display quantised colours. whereas the thicker fibres allow a quasi-continuous change in colour if the CLC pitch changes. Lagerwall. Because of the strong response function of LCs. Enz and J. giving the fibres iridescent colours due to selective reflection within a narrow band of the visible wavelength spectrum.E. 6866 They applied coaxial electrospinning to produce core-sheath polymer composite fibres with encapsulated short-pitch CLC. Mater. 20. Electrospun microfibres with temperature sensitive iridescence from encapsulated cholesteric liquid crystal. in particular in sensing applications. the resulting non-woven fibre mats have potential for smart textiles. By modifying the feed rate of the LC during spinning they can tune the fibre diameter from the sub-μm range to about 7 μm. J. determined primarily by the core diameter.

albeit much lower than that of the LC). .* Since they wish their fibres to exhibit the optical properties of the N* core it is important that the polymer sheath is transparent. x As a compromise they kept the sheath thin by using a rather dilute polymer solution (12. a goal that is more challenging. * The final criterion would require refractive index matching to the core. * They meet the first two requirements quite well (optical isotropy and weak scattering) by using poly(vinyl pyrrolidone) — PVP — as sheath material. essentially solidifying in an amorphous state (the electrospinning process actually results in a weak birefringence of the PVP sheath.5 wt. optically isotropic and induces a minimum of scattering.% PVP in ethanol) for their spinning experiments.

* At first sight it might seem surprising that they succeed in obtaining a stable coaxial jet and well-formed core-sheath fibres using this sheath solution. . Together with strong differences in elongational viscosity between core and sheath fluids this may lead to beading and eventually to complete phase separation. h These normally unwanted scenarios can be understood as a result of the Rayleigh instability promoting a separation of a jet of a Newtonian fluid into droplets in order to minimise the interfacial tension. because previous experiments with isotropic LMW core fluids spun inside pure PVP solutions resulted either in structural break-up and deposition of droplets of the core liquid next to solid fibres of pure PVP or in strongly irregular fibres where the core fluid was concentrated inside beads along the fibres rather than in a continuous cylindrical core.

however. . the core fluid is LC at Troom and it is thus in fact weakly non-Newtonian. the N* phase is replaced by a so-called blue phase (BP*) at 28.5 oC. * Their cholesteric LC in bulk reflects selectively in the band 440 to 480 nm. succeeded by the isotropic liquid phase at 30. giving it a distinctly blue colour when viewed in reflection. We propose that this property supports the coaxial jet structure sufficiently to allow the stability of the core sheath structure throughout the electrospinning process. On heating.* In their case.2 oC (the clearing point). allowing the extraction of comparatively long filaments from a drop of the liquid without structural break-up.

viewed in reflection (a). This results in fibres with increasing outer diameter.Results and Discussion * They vary the flow rate of the LC from 0. corresponding to a fibre thickness ~5 μm.7 ml h-1.13 to 0.80 mlh-1 while keeping all other spinning parameters constant. the polymer sheath solution being pumped at a flow rate of 1. (1) For low LC flow rates the macroscopic appearance of the fibres is dominated by scattering of the polymer sheath. . the selective reflection being easily discernible by the naked eye. (2) For LC flow rates greater than about 0.[圖(a)(b)] Fibre mat with the colour of the selective reflection of the LC being visible even macroscopically by the naked eye. rendering the spun mat white when viewed without magnification.8 ml h-1 (standard setting). transmission (b). the fibre mat macroscopically takes on the optical properties of the encapsulated cholesteric.

the difference being greater the lower the LC flow rate and the corresponding fibre thickness. * A careful look at the photo reveals.* If the mat is heated above the Tc in the fibre core. The reason is that the encapsulation of the LC in the fibres may affect the temperature range of LC phases considerably. where this turns into an ordinary isotropic liquid and thus loses its peculiar optical properties. x As in these cases. the Tc is higher than in the bulk mixture. the mat accordingly turns white [圖(c)]. however. viewed in reflection (a). that some blue areas remain. transmission (b) and reflection after heating the LC to the isotropic phase (c). This electrospun mat thus has a threshold-type temperature sensing capability. as we also found previously for nematic and smectic LCs in coaxially electrospun fibres. . Fibre mat with the colour of the selective reflection of the LC being visible even macroscopically by the naked eye.

leading to this effect. hence we may conclude that the remaining blue regimes have a fibre thickness that is slightly lower than the average for the mat. Within a mat there is a certain polydispersity in terms of fibre diameter. . any such contamination would decrease (not increase) Tc. this is highly unlikely as the polar sheath solution is immiscible with the nonpolar LC.* From literature it is known that for coaxial electrospinning a decrease of inner flow rate corresponds especially to a decrease of core diameter. Moreover. the encapsulation of the LC consequently becoming stronger. Fibre mat with the colour of the selective reflection of the LC being visible even macroscopically by the naked eye. the encapsulated LC there consequently having a somewhat higher clearing point. viewed in reflection (a). * For the thinnest fibres the shift in Tc leads to an extension of the N* temperature range of ~ 15 K compared to the bulk sample. * While one might argue that contamination (污 染) from the solvent or polymer used for the sheath solution could also influence the LC phase sequence. transmission (b) and reflection after heating the LC to the isotropic phase (c).

The drops exhibit selective transmission that in some cases is very weak. d). c) and weak transmission (b. revealing close to no orientation dependence in reflection as well as in transmission. The flow rates used to produce these fibres were 1. Polarising microscopy photos of the punctuated texture found in reflection and transmission in the thinnest fibres showing selective reflection in all colours (a. For photos c and d the sample has been rotated compared to a and b.8 ml h-1 for the polymer solution and 0.13 ml h-1 for the LC. At low LC feed rates. sometimes in one and the same fibre. thus thin fibres. . three main configurations can be distinguished: 1. the core is not continuous but the LC seems to separate into elongated drops inside the fibres. The LC in these drops selectively reflects in various colours ranging from red to blue. resulting in a punctuated texture.Results and Discussion On the whole.

Pictures c–f show another area of the same sample with greenish selective reflection (c. a semicontinuous to continuous LC core is the result.63 ml h-1 inner flow rates. strongly coloured red and yellow sections being most pronounced in the former due to the effect of overlaid birefringence in transmission. . In transmission (d. The first row shows the same sample position in reflection (a) as well as transmission (b). At medium to large feed rates. e). overlaid with weak birefringence. These fibres were spun with 1. Polarising microscopy photos of the semicontinuous texture found in fibres with medium to large diameter.1 ml h-1 outer and 0. the most common in the thickest fibres. This shows selective reflection/transmission at all colours of the spectrum. yellow to blue being most common. f) the colour is again weaker due to overlaid birefringence.2. yielding thicker fibres.

Example of one of the quite rare fibre samples exhibiting strong birefringence but no selective reflection/transmission.3. . The sample has been rotated between a– b and c–d to demonstrate the orientation dependence of the texture Polarising microscopy photos of the punctuated texture found in reflection and transmission. A few fibres are quite strongly birefringent without any selective reflection/transmission. with the optic axis along the fibre axis.

Results and Discussion It is helpful to briefly consider what director configurations expected for an N* phase encapsulated inside a very thin cylindrical fibre. The helix could be unwound. . [圖(a)] Schematic illustration of three possible director configurations for an N* phase encapsulated inside a cylindrical fibre. In principle one may distinguish three distinctly different cases: (a). The latter is certainly not our case but strong surface anchoring with n along the fibre (planar anchoring) is expected from our previous studies of achiral LCs in fibres of similar composition. (a) Planar director anchoring at the core-sheath interface and unwound helix. a scenario one might expect for strong surface anchoring and extremely thin fibres and/or long pitch.

k . The same director alignment at the interface to the polymer sheath is compatible with a helical structure with k perpendicular to the fibre if the inner fibre diameter is on the order of the natural N* pitch length or greater. corresponding to the most commonly occurring texture. Schematic illustration of three possible director configurations for an N* phase encapsulated inside a cylindrical fibre. [圖(c)] Although the optical appearance of a fibre with director configuration as in 圖(c) should be dominated by selective reflection/transmission. This explains why also the selectively reflecting fibres typically exhibit weak birefringence.(c). the fibre will also be birefringent since k rotates radially around the fibre. This configuration would produce selective reflection/transmission. being entirely in the sample plane at the longitudinal cross section at mid-fibre height. (c) planar anchoring at the core-sheath interface and helix perpendicular to the fibre.

A third possibility is that the helix (helical axis) develops along the fibre. [圖(b)] Schematic illustration of three possible director configurations for an N* phase encapsulated inside a cylindrical fibre.(b). the optical result will be strong birefringence and no selective reflection/transmission. (b) no or weak director anchoring and helix along the fibre . Since we are then looking perpendicular to a short-pitch helical modulation of the director.

albeit with the quantisation then being in half-pitch steps for the CLC used in our work. as the pitch must adjust to the actual fibre diameter. this is not allowed in the fibre because the cylindrical symmetry requires the director at the centre of the fibre also to be directed along the fibre. inner radius ~ multiple of P/2). * Because we have a certain variation of fibre diameter we must then also have a variation in selective reflection/transmission colour.* As can be seen in the cross section drawing in 圖(c) the planar anchoring boundary condition requires the inner diameter to be a multiple of the full pitch P (that is. where the same boundary condition imposes a quantisation into halfpitch units. * Note that in contrast to standard flat samples. * The same phenomenon is easily seen in a classical Cano wedge cell geometry. .

defect 10 μm . changing the selectively reflected colour which reaches the longest wavelengths in the thin regime of the sample.* A so-called ‘Cano preparation’ of the CLC used in this work. To fulfil these boundary conditions the helix is quantised into half-pitch units regardless of distance between the substrates. The helix must then be compressed or expanded at any location where the distance is not equal to an integer number of natural half pitches. Between regions of compression and expansion a defect appears where the number of half-pitch units in the helix changes by one.

The red color of the fiber shown in the left example is possible only for a fiber with inner diameter of about 480 nm.FIGURE 7. average refractive index 1. leading to a reflection color that depends on the inner fiber diameter d (black curve).5.13 The confinement of the CLC inside thin cylindrical fibers forces the director helix to expand or compress from its natural pitch. but more likely is a somewhat greater inner fiber diameter of about 640 nm. green. The curve is calculated for a natural pitch p0=300 nm. and red have been indicated with horizontal lines in the respective color. . As a guide for the eye the wavelengths of blue. and a director field as in Fig. 7.14. The blue-green color shown on the right could occur for even thinner fibers. The scale bar is 50 μm.

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4 Application Potential of LC-Containing Electrospun Fibers ƒ The addition of the responsiveness and functionality of liquid crystals to the nano-to-microscale fibers produced by electrospinning produces a new material that clearly has strong potential for application. employing the fibers in non-woven smart textiles.5. convenient for academic studies but generally problematic in a device context.dk .itu. www. ƒ While much work so far has been done with hygroscopic ( 吸 濕 的 ) polymers such as PVP.

core77.com www.gizmag.com .Smart Fabrics: Context is developing wearable sensors that could detect www.

Luminous. heat-sensitive fiber researchers plan to weave into bandages www.com .gizmag.europaregina. vibrating or energy-generating smart textiles are a market worth billions The color-changing.eu www.

. ƒ Since we see the color also in fibers containing the CLC. ƒ The strongly colored selective reflection from short-pitch CLCs renders these phases most attractive and the temperature dependence of the pitch makes it straightforward to apply CLCs as temperature sensors. wearable displays might be realized in this way. giving it a surface that continuously reveals the temperature at every part. with full spatial resolution. for instance by using carbon nanotubecontaining fibers. ƒ One could for instance spin a web of CLC-containing fibers over an apparatus of arbitrary shape. autonomous (not needing any power supply) fiber matintegrated sensors could easily be produced by electrospinning.ƒ If a convenient way of applying electric fields to the fibers can be found.

pipes or tubes can be coated with the fibers to monitor the temperature of liquids or gases flowing through a complex system in a cheap and efficient way. with the right type of polymer sheath the CLC phase could be incorporated into synthetic textiles that could find use in clothing. useful for monitoring the performance of a cooling water system. Judging from the lack of information on the actuation properties of the fibers produced so far there are still problems to be addressed. ƒ Electrospun fibers from LC elastomers have obvious application potential in actuators. Such textiles could obviously provide a temperature read-out. ƒ Finally.ƒ Alternatively. the textile could even function as a chemical sensor. . but if the fibers in addition are spun with a porous (有孔洞可透氣) sheath and if the CLC mixture has an adequate composition. but the concept is certainly very attractive and should be further explored. useful for people working in hazardous (有危險的) environments.

ferroelectric and discotic liquid crystals. ƒ The future looks bright for LC electrospinning and we can expect to see some very exciting developments in this field in the coming years. .g. e.. opening for various new application possibilities.ƒ Many LC types have not yet been integrated into electrospun fibers. for instance in energy conversion. They would allow the production of new functional fibers for instance with spontaneous electric polarization or photoconductivity.

Supercooling. superheating (sometimes referred to as boiling retardation.補充資料 ƒ 牛頓流體(Newtonian fluid):流體流動行為符合牛頓黏度定律 者稱之。大部份流體如水、酒精、空氣等屬於此類。 非牛頓流體(non-Newtonian fluid):流體流動行為不符合牛頓黏 度定律者,如牙膏、強力膠、水泥漿、玉米粉泥漿等。 ƒ Super-heating/cooling: In physics. also known as undercooling. or boiling delay) is the phenomenon in which a liquid is heated to a temperature higher than its boiling point. . is the process of lowering the temperature of a liquid or a gas below its freezing point without it becoming a solid. without boiling.