NMR studies of modified nasicon-like, lithium conducting solid electrolytes*1

²⁷Al, ³¹P and ⁷Li NMR measurements have been performed on lithium conducting ceramics based on the LiTi₂(PO₄)₃ structure with Al, V and Nb metal ions substituted for either Ti or P within the framework NASICON structure. The ²⁷Al magic angle spinning NMR measurements have revealed that, although Al is intended to substitute for octahedral Ti sites, additional substitution into tetrahedral environments (presumably phosphorous sites) occurs with increasing amount of Al addition. This tetrahedral substitution appears to occur more readily in the presence of vanadium, in Li_1+xAl_xTi_2−x(PO₄)_2.9(VO₄)_0.1, whereas similar niobium additions (in place of vanadium) appear to stifle tetrahedral substitution. ⁷Li static NMR spectra reveal quadrupolar structure with C_q approximately 42 kHz, largely independent of substitution. Measurement of the ⁷Li central transition linewidth at room temperature reveals a relatively mobile lithium species (300–900 Hz) with linewidth tending to decrease with Al substitution and increase with increasing V or Nb. This new structural information is discussed in the context of ionic conduction in these ceramics.

Solid state NMR characterization of lithium conducting ceramics

⁷Li solid state NMR has been used to characterize lithium aluminium titanium phosphate and lithium lanthanum titanate ceramics. Both materials have high ionic mobilities at room temperature and this is reflected in their static ⁷Li powder patterns. In the case of the phosphate based ceramic, a narrow Lorentzian peak is observed above 300 K, which narrows further with increasing temperature. The accompanying quadrupolar structure, with C_Q (quadrupolar coupling constant) ~ 40 kHz, suggests that the lithium ions are hopping rapidly between equivalent, high electric field gradient sites. The ²⁷Al and ³¹P magic angle spinning (MAS) spectra reveal an asymmetric phosphorus peak and two distinct aluminium resonances. The room temperature powder pattern of Li_0.33La_0.57TiO₃ shows a dipolar broadened peak which narrows quite suddenly at 310 K revealing quadrupolar satellites with C_Q ~ 900 Hz. A second lithium site is also observed in this material, as indicated by a further, weaker quadrupolar structure (C_Q ~ 40 kHz).

Quantifying rubber degradation using NMR

Ageing can lead to the degradation of the tensile properties of natural rubber. The ageing process causes changes in the polymer segmental motion as well as the chemical structure, both of which can be monitored using nuclear magnetic resonance (NMR) spectroscopy. This work demonstrates that NMR can quantify rubber degradation due to ageing, and also that relatively simple NMR equipment can be used. This simpler equipment can be made portable and so could give a simple and fast indication of the condition of rubber in service. The 1H NMR transverse relaxation time, T2, and the 13C NMR spectrum using cross polarization and magic angle spinning (CP MAS) for samples taken at various levels of a degraded natural rubber liner were compared. These experiments showed that, as the level of degradation increased, the 1H NMR transverse relaxation time decreased. The 13C spectra showed considerable peak broadening, indicative of decreased mobility with increased level of degradation as well as the presence of degradation products. Further investigations using lower powered NMR equipment to measure the 1H NMR transverse relaxation times of two different series of natural rubbers were also performed. This work has shown that this simpler method is also sensitive to structural and mechanical property changes in the rubber. This method of monitoring rubber degradation could lead to the non-destructive use of NMR to determine the condition of a part in service.

Towards elucidating microscopic structural changes in Li-ion conductors Li1+yTi2–yAly[PO4 ]3 and Li1+yTi2–yAly[PO4 ]3–x [MO4 ]x(M=V and Nb) : X-ray and27Al and31P NMR studies

A combination of X-ray powder diffraction (XRD) and nuclear magnetic resonance (NMR) studies has demonstrated that attempted substitutions of Al, V and Nb into the framework of LiTi₂(PO₄)₃ yield several impurity phases in addition to direct substitutions of Al into Ti and V, Nb into P sites. Direct substitutions were confirmed by changes in the unit cell dimensions as indicated by the peak shifts observed in the X-ray diffractographs and by analyses of the ²⁷Al and ³¹P magic angle spinning (MAS) spectra. A major impurity phase was identified as AlPO₄ (found in at least two polymorphs) and the amount present increases with increasing Al additions. The formation of AlPO₄ appeared to be enhanced by further V but suppressed by Nb substitution. These results suggest that the presence of AlPO₄ , together with the non-stoichiometric modified LTP, may be the cause for the observed densification of this material upon sintering and the increased ionic conductivity.

Gyration

European Renaissance and Romantic landscape appeared in vistas. The conditions of the industrial revolution and, according to Patrick Maynard and Jonathon Crary, the film camera especially, led to a Modernist re-vision vividly recorded in Xavier Herbert’s contrary Modernist vision, prompted by seeing the Australian bush, its ‘... stunted trees, the mulga and the wilga and the gimlet gum, doing a kind of dance, spinning past, seeming to swing away from the train to the horizon and race ahead, to come back...the same set of trees in endless gyration’.

A new way to nanostructure hydrogels : electrospun thermo-responsive islands-in-the-sea nanofibres

Islands-in-the-sea nanofibres are a very interesting system: one polymer (islands) is distributed in fibrillar domains within a second polymer (sea). This fibre geometry is often used in microfiber technologies to obtain very fine fibers, by removing the “sea” polymer. This geometry also allows to combine two polymers with very different properties. In this work this geometry is introduced applied to electrospun hydrogel nanofibers, in a novel fashion, and as a way to improve and stabilize the hydrogel nanofibers. Thermo-responsive islands-in-the-sea nanofibers are here produced by electrospinning solutions of a hydrogel-forming thermo-responsive polymer (crosslinked poly(N-isopropylacrylamide), PNIPAM) and a reinforcing polymer (polyetherketone cardo, PEK-c). The two polymers are thermodynamically incompatible in solution and phase separation takes place, which allows the instant formation of islands-in-the-sea nanofibers upon electrospinning. PNIPAM was then crosslinked post-spinning using an oligomeric silsesquioxane. The formed nanocomposite nanofibers showed intrinsic nanostructure, where the fibril-like PNIPAM domains are intimately adjacent to the strong PEK-c domains. Upon contacting with water, the hydrogel domains became instantly highly swollen, while the PEK-c domains did not. As a result, very wrinkly, swollen fibers were obtained, with increased capillary action, as demonstrated through confocal microscopy. The composite nanofibers in water showed excellent swelling ratios and very fast responses to temperature variations (of the order of 1 second) with morphological and optical effects: variations in fiber-diameter were accompanied by optical transitions: transparent-opaque. The produced hydrogel nanofibers also presented improved mechanical properties (even with small amounts of PEK-c), when compared to their crosslinked-PNIPAM-only nanofibers. It will be also shown how these materials can be used as optical actuators and smart hydrogel platforms with tuneable contact angle and morphology. In brief, this work aims to demonstrate a new platform technology which can be applied to several hydrogel systems, to achieve hydrogel-based composites with new and improved properties, while retaining (and improving) the main properties of the hydrogel. Here this was demonstrated by showing that the composite materials showed thermo-responsiveness, and enhanced transition kinetics.

Electrospinning of continuous nanofiber bundles and twisted nanofiber yarns

Spinning is a prehistoric technology in which endless filaments, shorter fibers or twisted fibers are put together to produce yarns that serve as key element to assemble multifarious structural designs for diverse functions. Electrospinning has been regarded as the most effective and versatile technology to produce nanofibers with controlled fiber morphology, dimension and functional components from various polymeric materials (Dersch et al., 2007, Frenot and Chronakis, 2003, Schreuder-Gibson et al., 2002). However, most electrospun fibers are produced in the form of randomly-oriented nonwoven fiber mats (Doshi and Reneker, 1995, Madhavamoorthi, 2005). The relatively low mechanical strength and difficulty in tailoring the fibrous structure have restricted their applications. With the rapid development in nanoscience and nanotechnology, yarns composed of nanofibers may uncover new opportunities for development of well-defined three dimensional nano fibrous architectures. This chapter focuses on recent research and advancement in electrospinning of nanofiber bundles and nanofiber yarns. The preparation, morphology, mechanical properties and potential applications of these fibrous materials are discussed in details.

Role of microstructure in the low cycle fatigue of multi-phase steels

The low cycle fatigue (LCF) behaviour of several commercially-produced multiphase steels was studied; including dual-phase (DP) and transformation induced plasticity (TRIP). In addition, a novel TRIP980 hybrid microstructure was examined that consisted of coarse ferrite grains along with low temperature bainite regions interspersed with retained austenite. Fully reversed strain controlled fatigue tests were conducted on the different steels to determine the cyclic stress response and strain to failure. The effects of the cyclic deformation on the microstructures were analysed using electron backscattered diffraction (EBSD) and X-ray diffraction (XRD). Results showed that the initial cyclic hardening behaviour and low cyclic softening ratio observed in the TRIP steels was not necessarily due to austenite to martensite transformation. Differences between the austenite transformation behaviour of the conventional and novel hybrid TRIP microstructures was related to the different surrounding phases and the size of the retained austenite.

Toughening of a carbon-fibre composite using electrospun poly(Hydroxyether of Bisphenol A) nanofibrous membranes through inverse phase separation and inter-domain etherification

The interlaminar toughening of a carbon fibre reinforced composite by interleaving a thin layer (~20 microns) of poly(hydroxyether of bisphenol A) (phenoxy) nanofibres was explored in this work. Nanofibres, free of defect and averaging several hundred nanometres, were produced by electrospinning directly onto a pre-impregnated carbon fibre material (Toray G83C) at various concentrations between 0.5 wt % and 2 wt %. During curing at 150 °C, phenoxy diffuses through the epoxy resin to form a semi interpenetrating network with an inverse phase type of morphology where the epoxy became the co-continuous phase with a nodular morphology. This type of morphology improved the fracture toughness in mode I (opening failure) and mode II (in-plane shear failure) by up to 150% and 30%, respectively. Interlaminar shear stress test results showed that the interleaving did not negatively affect the effective in-plane strength of the composites. Furthermore, there was some evidence from DMTA and FT-IR analysis to suggest that inter-domain etherification between the residual epoxide groups with the pendant hydroxyl groups of the phenoxy occurred, also leading to an increase in glass transition temperature (~7.5 °C).

Production, properties and processing of American bison (Bison bison) wool grown in southern Australia

American bison grow a thick coat of fibres which assists them to withstand severe climatic conditions. Bison fibre was traditionally used in textiles by native North Americans. This study aimed to quantify the production, fibre attributes and dehairing processing of bison fibre produced from bison grazed in north-eastern Victoria. Three age/sex classes were sampled (n = 16) at seven body positions in spring. The fibre growing area was measured. Fibre was tested for diameter distribution, clean washing yield, proportion of fine fibres <36µm and fine fibre length, and processed by cashmere dehairing. Bison were 12 years of age, liveweights 160450 kg and had mean fibre growing area of 1.4 m². They produced an average 1184 g (range 5301640 g) of fine fibre with mean fibre diameter 18.5µm, clean washing yield 76.5%, wax content 9.8%, suint content 14.5%, clean fine fibre yield 56.4%, fine fibre length 37 mm and fibre curvature was 93/mm. Mid-side fibre had a crimp frequency of 6.5/cm and mean resistance to compression of 6.6 kPa. Fibre had a tenacity of 8.7 cN/tex and an extension of 39.3%. Restricted maximum likelihood mixed model analysis showed age/sex class and sampling site significantly affected all fibre attributes. Finer and longer fibre was produced in anterior sites and in younger bison. Fibre curvature declined 5.3°/mm for each 1-µm increase in mean fibre diameter. Dehaired fibre had a mean fibre diameter of 17.8 µm and mid-length of 28 mm, suitable for woollen spinning. The production by bison of coats containing significant amounts of fibre indicates that careful harvesting of fibre could form an important source of income in bison enterprises.

Needleless electrospinning of uniform nanofibers using spiral coil spinnerets

Polyvinyl alcohol nanofibers were prepared by a needleless electrospinning technique using a rotating spiral wire coil as spinneret. The influences of coil dimension (e.g., coil length, coil diameter, spiral distance, and wire diameter) and operating parameters (e.g., applied voltage and spinning distance) on electrospinning process, nanofiber diameter, and fiber productivity were examined. It was found that the coil dimension had a considerable influence on the nanofiber production rate, but minor effect on the fiber diameter. The fiber production rate increased with the increased coil length or coil diameter, or the reduced spiral distance or wire diameter. Higher applied voltage or shorter collecting distance also improved the fiber production rate but had little influence on the fiber diameter. Compared with the conventional needle electrospinning, the coil electrospinning produced finer fibers with a narrower diameter distribution. A finite element method was used to analyze the electric field on the coil surface and in electrospinning zone. It was revealed that the high electric field intensity was concentrated on the coil surface, and the intensity was highly dependent on the coil dimension, which can be used to explain the electrospinning performances of coils. In addition, PAN nanofibers were prepared using the same needleless electrospinning technique to verify the improvement in productivity.

Crosslinking neat ultrathin films and nanofibres of pH-responsive poly(acrylic acid) by UV radiation

Electrospun polyelectrolyte hydrogel nanofibres are being developed for many applications including artificial muscles, scaffolds for tissue engineering, wound dressings and controlled drug release. For electrospun polyelectrolytes, a post-spinning crosslinking process is necessary for producing a hydrogel. Typically, radiation or thermal crosslinking routines are employed that require multifunctional crosslinking molecules and crosslink reaction initiators (free radical producers). Here, ultraviolet subtype-C (UVC) radiation was employed to crosslink neat poly(acrylic acid) (PAA) nanofibres and films to different crosslink densities. Specific crosslink initiators or crosslinking molecules are not necessary in this fast and simple process providing an advantage for biological applications. Scanning probe microscopy was used for the first time to measure the dry and wet dimensions of hydrogel nanofibres. The diameters of the swollen fibres decrease monotonically with increasing UVC radiation time. The fibres could be reversibly swollen/contracted by treatment with solutions of varying pH, demonstrating their potential as artificial muscles. The surprising success of UVC radiation exposure to achieve chemical crosslinks without a specific initiator molecule exploits the ultrathin dimensions of the PAA samples and will not work with relatively thick samples.

Improved incorporation of fibres for more abrasion resistant yarns

Rubbing of the fibrous strand after drafting, but before twist insertion improves the incorporation of surface fibres. The method delivers the benefits of a small spinning triangle like compact spinning and improved fibre trapping like siro and solo spinning. The yarns produced are less hairy and more resistant to degradation in downstream processing. This can improve the weavability of the yarns, reduce the sizing costs and increase service life of the fabrics by making them more resistant to wear and pilling.