Electrospinning and characterisation of ceria doped yttria fibres

Abstract

Homogeneous inorganic-organic composite fibres were produced using electrospinning technique from alcoholic solutions containing polyvinyl butyral and precursors of yttrium and cerium ions. Upon heat treatment, ceria and yttria doped ceria fibres retaining the original morphological features observed in the as spun composition were obtained. X-ray diffraction was used to identify the crystalline phases of the final products. Scanning electron microscopy, thermogravimetric analysis, differential thermal analysis and Brunauer-Emmett-Teller analysis were used to study the ceramic phase formation and the evolution of morphological features of the fibres. Thus, several micrometres long, uniform ceria and yttria doped ceria fibres of high phase purity were produced. The CeO₂ and the CeO₂ with Y₂O₃ fibres presented average diameter that ranged from 19 to 25?μm, and the distribution of specific surface ranged from 33 to 43?m²?g^?1.     

Migration of divalent ions in nylon 6 films

The migration of ions through a nylon-6 film is studied by MRI. For this study the paramagnetic ions Mn²⁺ and Cu²⁺ are used as they act as a contrast agent and are detectable by MRI.     

Isothermal crystallization and melting behaviors of nylon 11/nylon 66 alloys by in situ polymerization

Nylon 11/nylon 66 alloys were prepared by in situ polymerization. Analysis of the isothermal crystallization behaviors of nylon 11/nylon 66 alloys was carried out using differential scanning calorimetry (DSC) and X-ray diffraction (XRD). The crystallization kinetics of the primary stage under isothermal conditions could be described by the Avrami equation. The crystal morphology observed by means of polarized optical microscope (POM). In the DSC scan after isothermal crystallization process, the multiple melting behaviors were found and each melting endotherm has a different origin. The real-time XRD measurements confirmed that no crystalline transition existed during the isothermal crystallization process. The multiple endotherms were experimentally evidenced due to melting of the recrystallizated materials or the lamellae produced under different crystallization processes. The equilibrium melting point of samples for isothermal crystallization was also evaluated.     

Crystallization behavior of nylon 6 nanocomposites

The crystallization behavior of nylon 6 nanocomposites formed by melt processing was investigated. Nanocomposites were produced by extruding mixtures of organically modified montmorillonite and molten nylon 6 using a twin screw extruder. Isothermal and non-isothermal crystallization studies involving differential scanning calorimetry (DSC) were conducted on samples to understand how organoclay concentration and degree of clay platelet exfoliation influence the kinetics of polyamide crystallization. Very low levels of clay result in dramatic increases in crystallization kinetics relative to extruded pure polyamide. However, increasing the concentration of clay beyond these levels retards the rate of crystallization. For the pure nylon 6, the rate of crystallization decreases with increasing the molecular weight as expected; however, the largest enhancement in crystallization rate was observed for nanocomposites based on high molecular weight polyamides; this is believed to stem from a higher degree of platelet exfoliation in these nanocomposites. Wide angle X-ray diffraction (WAXD) and DSC were further used to characterize the polymer crystalline morphology of injection molded nanocomposites. The outer or skin layer of molded specimens was found to contain only γ-crystals; whereas, the central or core region contains both the α and γ-forms. The presence of clay enhanced the γ-structure in the skin; however, the clay has little effect on crystal structure in the core. Interestingly, higher levels of crystallinity were observed in the skin than in the core for the nanocomposites, while the opposite was true for the pure polyamides. In general, increasing the polymer matrix molecular weight resulted in a lower degree of crystallinity in molded samples as might be expected.     

Polyaniline fibres as electrodes.: Electrochemical characterisation in acid solutions

Polyaniline fibre microelectrodes prepared from a doped solution of polyaniline protonated with 2-acrylamido-2-methyl-1-propanesulphonic acid in dichloracetic acid were characterized electrochemically for the first time. Low scan rate cyclic voltammetry was used for characterisation in different acid electrolyte solutions, hydrochloric, nitric, perchloric, sulphuric and phosphoric, at low pH values with varying positive potential limits. Electrochemical impedance spectroscopy was also utilised. The electrochemical behaviour of polyaniline (PANI) fibres was found to be similar to that of PANI films obtained by electropolymerisation on metallic electrode substrates. The conduction potential window was found to be from +0.20 to +0.60 V versus SCE, with small variations in the different acid solutions as well as with pH. The standard electrochemical redox couple hexacyanoferrate(III), was found to behave quasi-reversibly in the conduction potential region and rate constants were evaluated.     

Preparation and characterization of nylon 11/organoclay nanocomposites

Nylon 11/organoclay nanocomposites have been successfully prepared by melt-compounding. X-ray diffraction and transmission electron microscopy indicate the formation of the exfoliated nanocomposites at low clay concentrations (less than 4 wt%) and a mixture of exfoliated and intercalated nanocomposites at higher clay contents. Thermogravimetric and dynamic mechanical analyses as well as tensile tests show that the degree of dispersion of nanoclay within polymer matrix plays a vital role in property improvement. The thermal stability and mechanical properties of the exfoliated nylon 11/clay nanocomposites (containing lower clay concentrations) are superior to those of the intercalated ones (with higher clay contents), due to the finer dispersion of organoclay among the matrix.     

Crystallization kinetics and morphology of nylon 1212

The isothermal and non-isothermal crystallization processes of nylon 1212 were investigated by polarized optical microscopy. The crystal growth rates of nylon 1212 measured in isothermal conditions at temperatures ranged from 182 to 132 °C are well comparable with those measured by non-isothermal procedures (cooling rates ranged from 0.5 to 11 °C/min). The kinetic data were examined with the Hoffman-Lauritzen nucleation theory on the basis of the obtained values of the thermodynamic parameters of nylon 1212. The classical regime I→II and regime II→ III transitions occur at the temperatures of 179 and 159 °C, respectively. The crystal growth parameters were calculated with (100) plane assumed to be the growth plane. The regime I →II→ III transition is accompanied by a morphological transition from elliptical-shaped structure to banded spherulite and then non-banded spherulite. The development of morphology during isothermal and non-isothermal processes shows a good agreement.     

Effect of sodium montmorillonite source on nylon 6/clay nanocomposites

The effect of sodium montmorillonite source on the morphology and properties of nylon 6 nanocomposites was examined using equivalent experimental conditions. Sodium montmorillonite samples acquired from two well-known mines, Yamagata, Japan, and Wyoming, USA, were ion exchanged with the same alkyl ammonium chloride compound. The resulting organoclays were extruded with a high molecular weight grade of nylon 6 under the same processing conditions. Quantitative analysis of TEM photomicrographs of the two nanocomposites reveal a slightly larger average particle length and a slightly higher degree of platelet exfoliation for the Yamagata based nanocomposite than the Wyoming version, thus, translating into a higher particle aspect ratio. The stress-strain behavior of the nanocomposites appears to reflect the nanocomposite morphology, in that higher stiffness and strengths are attainable with the increased particle aspect ratio. Moreover, the trends in stiffness behavior between the two types of nanocomposites may be explained by conventional composite theory.     

The influence of ions on water transport in nylon 6 films

Nylon 6 films are directly exposed to saline solutions containing mono-valent ions and the water uptake is measured with magnetic resonance imaging (MRI). Both the amount of water uptake and the rate of water uptake are studied. First, the films are exposed to solutions with different concentrations of NaCl. Later, solutions of salts such as LiCl, KCl and KNO₃ are used. It is shown that all salts act similar. They reduce the amount of water ingressing the nylon film and also slow down the rate of uptake. It seems that water uptake can be predicted by knowing the activity of the salt solution on top of the nylon film. Element analysis shows that ions migrate into the nylon film. Although ions do enter the film, their amount is not large enough to influence the diffusivity and chemical potential of water in the nylon film.     

Aggregation structure and molecular motion of (glass-fiber/matrix nylon 66) interface in short glass-fiber reinforced nylon 66 composites

Aggregation structure and thermal molecular motion of an adhered polymer layer on a glass-fiber (GF) surface after a removal of nylon 66 from a short glass-fiber reinforced nylon 66 were studied on the basis of photoacoustic spectroscopy-infrared spectroscopy (PAS-IR), pyrolysis-gas chromatography (Py-GC), X-ray photoelectron spectroscopy (XPS) and scanning viscoelasticity microscopy (SVM). PAS-IR, Py-GC and XPS measurements of the GF surface showed the presence of strongly adhered nylon 66 layer on the surface of aminosilane-treated GF. The glass transition temperature, T_g, of the adhered nylon 66 layer on the glass-fiber surface was directly evaluated on the basis of SVM measurement. In the case of the GF treated with an aminosilane coupling agent and a sizing agent, the magnitude of T_g at the (GF/nylon 66) interfacial layer was higher than that of the matrix nylon 66 due to the effective restriction of thermal molecular motion of nylon 66 at the (GF/nylon 66) interfacial layer. It is reasonable to consider that the sizing agent affects the strong interfacial interaction between a glass-fiber surface and matrix nylon 66 with covalent bond formation accompanying the network structure formation.     

Fabrication of MWNTs/nylon conductive composite nanofibers by electrospinning

MWNT/nylon 6, 6 composite nanofibers were fabricated using an electrospinning method, and the electrical properties were examined as a function of the filler concentration. Initially, the pristine, purified MWNTs were treated with a 3:1 mixture of concentrated H₂SO₄/HNO₃ to introduce carboxyl groups onto the MWNT surface. The carboxylated MWNTs were then treated with thionyl chloride and an ethylenediamine solution for amide functionalization. FT-IR spectroscopy was used to examine the functionalization of the MWNTs. Nylon 6, 6 is readily soluble in formic acid. Therefore, the amide functionalized MWNTs were dispersed in formic acid. The solution remained stable and uniform for more than 40 h. –NH₂ termination of the MWNTs improved the dispersion stability of the MWNTs in formic acid. The MWNTs-suspended in a solution of nylon 6, 6 in formic acid was electrospun to obtain the nanofibers. The electrical properties of the nanofibers were examined as a function of the filler concentration. The results showed that the I–V properties of the nanofiber sheet improved with increasing filler concentration.     

Multi-walled carbon nanotubes reinforced nylon 6 composites

Multiwalled carbon nanotubes (MWNT) were functionalized with amine groups using a ‘grafting to’ technique. The oxidized MWNT (MWNT-COOH) were converted to the acyl chloride functionalized MWNT (MWNT-COCl) by treating them with thionyl chloride (SOCl₂), and then MWNT-COCl was reacted with hexamethylenediamine to prepare MWNT-NH₂. The formation of MWNT-NH₂ was confirmed through the FTIR observation. MWNT-NH₂/nylon 6 composites with different MWNT loadings were prepared by the simple melt compounding approach. A fine dispersion of MWNTs throughout nylon 6 matrix was observed by SEM and TEM. The fractured surface of the composites showed not only a uniform dispersion of MWNTs but also a strong interfacial adhesion with the matrix, as evidenced by the presence of many broken but strongly embedded MWNTs in the matrix in the absence of debonding of MWNTs from the matrix. Incorporation of MWNTs improved the mechanical properties significantly. Higher thermal stability was obtained for the composites with better dispersed MWNTs.     

A polarised μ-FTIR study on a model system for nylon 6 6: implications for the nylon Brill structure

Polarised transmission FTIR microscopy studies (μ-FTIR) have been performed on a monodisperse 3-amide oligomer. The oligomer is a model compound for nylon 6 6; it has essentially the same room temperature crystal structure, and it undergoes the same high temperature transition, the Brill transition, prior to melting. However, the oligoamide forms extended chain, rather than chain-folded, crystals, and so crystals are produced that are essentially 100% crystalline, and of μm–mm size. Consequently, this material is ideally suited for polarised μ-FTIR single crystal studies. The thermal polarised FTIR behaviour of this material provides definitive proof that the Brill transition does not involve major rearrangement of hydrogen bonds, since the strong parallel polarisation of both the NH stretch and amide I bands are retained right up to melting. Quantitative infrared dichroism measurements indicate that a maximum of 5° rotation of the N–H bonds about the extended chain axis occurs prior to melting. These results strongly suggests that the equivalent Brill transition in nylon 6 6 also proceeds without significant hydrogen bond rearrangement. In addition we have investigated the behaviour of designated ‘Brill’, ‘crystalline’, ‘amorphous’ and ‘fold’ bands that are present in our spectra.     

Effect of organoclay structure on nylon 6 nanocomposite morphology and properties

A carefully selected series of organic amine salts were ion exchanged with sodium montmorillonite to form organoclays varying in amine structure or exchange level relative to the clay. Each organoclay was melt-mixed with a high molecular grade of nylon 6 (HMW) using a twin screw extruder; some organoclays were also mixed with a low molecular grade of nylon 6 (LMW). Wide angle X-ray scattering, transmission electron microscopy, and stress-strain behavior were used to evaluate the effect of amine structure on nanocomposite morphology and physical properties. Three surfactant structural issues were found to significantly affect nanocomposite morphology and properties in the case of the HMW nylon 6: decreasing the number of long alkyl tails from two to one tallows, use of methyl rather than hydroxy-ethyl groups, and use of an equivalent amount of surfactant with the montmorillonite, as opposed to adding excess, lead to greater extents of silicate platelet exfoliation, increased moduli, higher yield strengths, and lower elongation at break. LMW nanocomposites exhibited similar surfactant structure-nanocomposite behavior. Overall, nanocomposites based on HMW nylon 6 exhibited higher extents of platelet exfoliation and better mechanical properties than nanocomposites formed from the LMW polyamide, regardless of the organoclay used. This trend is attributed to the higher melt viscosity and consequently the higher shear stresses generated during melt processing.     

Transport properties of electrically conducting nylon 6/foliated graphite nanocomposites

In this work, we analyze the conductivity data of the nylon 6/FG nanocomposites using the normalized percolation equations and the general effective equation. From the interpretations of the derived results, we demonstrate that the microstructure of the nanocomposites can be readily deduced. Taking several factors into account, it turns out that the tunneling mechanism should be responsible for the observed non-universality of the critical exponents. Experimental evidences show that the existence of the tunneling conduction should be attributed to the particular structure of the prepared materials.     

Modelling of liquid crystalline compound fibres

A model for slender, liquid crystalline, bicomponent fibres at low Reynolds and Biot numbers based on the slenderness ratio as the perturbation parameter, is presented. The model results in one-dimensional equations for the fibre's radii, axial velocity component and temperature, to which we have added two transport equations for the molecular orientation and crystallization and the effects of these variables on the elongational viscosity. The crystallization kinetics is based on Avrami–Kolmogorov theory and is affected by the molecular orientation, while the latter is based on Doi's slender body theory for liquid crystalline polymers. It is shown that the model depends on a large number of dimensionless parameters, and shows that the axial strain rate and the degree of molecular orientation increase as the activation energy of the dynamic viscosity of the core, the heat transfer losses, the thermal conductivity ratio and the pre-exponential factors ratio are increased, whereas they decrease as the thermal capacity of the core is increased. It is also shown that the degree of molecular orientation increases and reaches a value equal to one, whereas no complete crystallization is achieved. It is also shown that the crystallization first increases sharply and then at a smaller pace. It is also shown that the axial stresses on liquid crystalline bicomponent fibres are much higher than those on amorphous ones.     

Melting behaviors, isothermal and non-isothermal crystallization kinetics of nylon 1212

Isothermal crystallization, subsequent melting behavior and non-isothermal crystallization of nylon 1212 samples have been investigated in the temperature range of 160-171 °C using a differential scanning calorimeter (DSC). Subsequent DSC scans of isothermally crystallized samples exhibited three melting endotherms. The commonly used Avrami equation and that modified by Jeziorny were used, respectively, to fit the primary stage of isothermal and non-isothermal crystallizations of nylon 1212. The Avrami exponent n was evaluated, and was found to be in the range of 1.56-2.03 for isothermal crystallization, and of 2.38-3.05 for non-isothermal crystallization. The activation energies (ΔE) were determined to be 284.5 KJ/mol and 102.63 KJ/mol, respectively, for the isothermal and non-isothermal crystallization processes by the Arrhenius' and the Kissinger's methods.     

Structural studies of electrospun nylon 6 fibers from solution and melt

Nylon 6 (N6) fibers have been fabricated via two different electrospinning schemes, from solution of N6 and formic acid at room temperature as well as from N6 melt at elevated temperature. The crystal structures of electrospun N6 fibers from solution and melt, and the annealing effect on the structures were studied by using various techniques. Combined analysis of the differential scanning calorimetry (DSC) at various heating rates, temperature-dependent X-ray diffraction (XRD), and Fourier-transform infrared (FTIR) spectroscopy indicates that N6 fibers from melt predominantly exhibit the meta-stable γ-crystalline forms and low molecular orientation, while solution electrospun fibers from slowly evaporating solvent show both α- and γ-form crystals and higher degree of molecular orientation. At high annealing temperature, the meta-stable γ-crystals in melt electrospun fibers easily transform into thermodynamically stable α-form crystals, while crystals in solution electrospun fibers exhibit higher thermal stability. Nonisothermal modeling and in-situ measurements of jet temperature indicate that rapid quenching due to enhanced heat transfer by electrohydrodynamically driven air flow near the jet is responsible for the less stable γ-crystals and lower degree of molecular orientation in melt electrospun fibers.     

尼龙酸二丁酯的合成及其性能

以尼龙酸和丁醇为原料,浓硫酸为催化剂,环己烷为带水剂,合成出了3种尼龙酸二丁酯.以正丁醇和异丁醇为原料时反应速率最快,仲丁醇为原料时反应速率最慢.考察了反应的醇酸物质的量比对酯化反应的影响,n（醇）∶n（酸）=1.1∶1是最适宜的反应条件.测试了3种产品的性能,其中尼龙酸二正丁酯性能最佳,适合作为润滑油添加剂和耐寒型增塑剂.