Stacking faults and microstructural parameters in non-mulberry silk fibres

We have analysed the broadening of X-ray reflections observed in nonmulberry silk fibres in terms of stacking faults and microstructural parameters using a single-order method and have, with these parameters, developed, for the first time, a procedure to compute the whole pattern of these silk fibres. The essential deviations in the values of microstructural parameters obtained from line profile and whole pattern fitting procedures are discussed in this paper.     

Spider silk as a model biomaterial

Spider silk combines strength and extensibility, and a wide range of mechanical properties can be achieved with only minute (if any) changes in chemical structure. It appears that the full range of thermo-mechanical properties of such silk fibres can be predicted by examining the energy imparted during stretching with the theoretical framework provided by Mean Field Theory for Polymers. This approach attempts to integrate strain and tensile stress with a range of relevant energetic and mechanical parameters such as the loss tangent and potential energy of atomic inter-chain bonding as well as the tensile and bulk elastic moduli. The model reveals that the underlying design principle of silks seems to share an inherent and surprising simplicity at the macromolecular level. We conclude that our modelling approach allows in-depth analysis of natural silks as well as a comparison with synthetic fibres.     

Origin of the variability of the mechanical properties of silk fibres: 3. Order and macromolecule orientation in Bombyx mori bave,hand‐stretched strings and Nephila madagascarensis spider fibres

The comparison of the low wavenumber of polarized Raman spectra (50–300 cm^–1) from Bombyx mori (fresh cocoons fibres, hand‐stretched ‘Crins de Florence’ strings from the gland content, dried gland, regenerated silk films) and Nephila madagascarensis silks reveals the high polarisation of fibre modes and the absence of polarisation for dried gland and regenerated silk films. This is consistent with X‐ray diffraction measurements. The orientation of the fibroin/spidroin chains is due to the stretching during production, as for advanced synthetic fibres. The bandwidth of the ‘ordered chains’ signature is almost the same for the different fibres. However, the degree of polarisation seems to be higher in the case of spider fibre. The huge bandwidth of low wavenumber components of regenerated films indicates high disorder. Measurements along the fibre point out conformation changes with a periodicity (~20 mm) related to the silkworm head motion during the fabrication of the cocoon. Copyright © 2012 John Wiley & Sons, Ltd.     

Affinity of protein fibres towards sulfation

Wool, Bombyx mori and Antheraea pernyi (Tussah) silk fibres were treated with chlorosulfonic acid in pyridine and investigated by FT‐IR and FT‐Raman spectroscopies as well as mechanical measurements. The reactivity towards sulfation was found to decrease along the series: wool > Bombyx mori silk fibroin > Tussah silk fibroin, in agreement with weight gain which decreased along the same series. Accordingly, Tussah silk maintained its intrinsic tensile properties essentially unchanged upon the treatment, while for Bombyx mori silk fibroin, the tensile performance decreased sharply especially at longer reaction times. Sulfated wool was characterized by an increased fibre extensibility. New IR and Raman bands attributable to various vibrations of sulfated groups were detected in sulfated wool and to a lower extent in Bombyx mori silk fibroin fibres; all the fibres underwent conformational rearrangements upon sulfation, independent of the sulfation yield. Wool fibres treated with chlorosulfonic acid in pyridine bound considerable amounts of sulfate mainly through the hydroxyl groups of serine, threonine and tyrosine. Also, tryptophan and basic amino acids were found to participate to the reaction. B. mori silk fibroin fibres appeared to bind a minor amount of sulfate groups mainly trough the hydroxyl groups of Ser. Weight gain, spectroscopic and mechanical data are discussed in relation to the difference in fibre morphology, structure and crystallinity, as well as to the amount and accessibility of potentially reactive amino acids. Copyright © 2012 John Wiley & Sons, Ltd.     

Comparative Raman spectroscopic analysis of orientation in fibers and regenerated films of Bombyx mori silk fibroin

This study is focused on the Raman spectroscopic analysis of degummed silk fibroin (SF) fibers and regenerated Bombyx mori silk fibroin films: a correlation was found between some spectral features related to the methylene deformation modes and the molecular orientation of the samples. Polarized Raman spectra on SF fibers were used to obtain the orientation distribution function of carbonyl groups along the protein backbone. The variation of the intensity ratio of 1400/1450 cm⁻¹ for the peaks attributed to the wagging and bending deformation modes of CH₂ groups with respect to the angular orientation of the fiber was measured and quantitatively correlated with the orientation distribution function of the carbonyl groups. Unpolarized Raman spectra were measured for regenerated silk fibroin films and lyophilized solutions. The variation of the intensity ratio of 1415/1455 cm⁻¹, which is related to the deformation modes of CH₂ groups in SF regenerated materials, was qualitatively related to the microstructural orientation of the samples observed by scanning electron microscopy (SEM), and to the presence of Silk I phase as suggested by the analysis of samples obtained in different casting conditions and also by the measurements on mechanically deformed films. The results obtained showed the utility of the spectroscopic intensity ratio of 1400/1450 cm⁻¹ for the rapid assessment of molecular orientation in silk fibers, which could be useful for quality and process control of regenerated silk‐based textiles. Moreover, the qualitative dependence of the intensity ratio of 1415/1455 cm⁻¹ was found to be sensitive to both the microstructural orientation and Silk I content of regenerated silk fibroin films, suggesting a possible correlation of this Raman marker of the Silk I phase with the degree of molecular order brought about by this polymorph. Copyright © 2006 John Wiley & Sons, Ltd.     

Predicting the mechanical properties of spider silk as a model nanostructured polymer

Spider silk is attractive because it is strong and tough. Moreover, an enormous range of mechanical properties can be achieved with only small changes in chemical structure. Our research shows that the full range of thermo-mechanical properties of silk fibres can be predicted from mean field theory for polymers in terms of chemical composition and the degree of order in the polymer structure. Thus, we can demonstrate an inherent simplicity at a macromolecular level in the design principles of natural materials. This surprising observation allows in depth comparison of natural with man-made materials.     

Size exclusion chromatography for analyses of fibroin in silk: optimization of sampling and separation conditions

A direct goal of this paper was to improve the methods of sample preparation and separation for analyses of fibroin polypeptide with the use of size exclusion chromatography (SEC). The motivation for the study arises from our interest in natural polymers included in historic textile and paper artifacts, and is a logical response to the urgent need for developing rationale-based methods for materials conservation. The first step is to develop a reliable analytical tool which would give insight into fibroin structure and its changes caused by both natural and artificial ageing. To investigate the influence of preparation conditions, two sets of artificially aged samples were prepared (with and without NaCl in sample solution) and measured by the means of SEC with multi angle laser light scattering detector. It was shown that dialysis of fibroin dissolved in LiBr solution allows removal of the salt which destroys stacks chromatographic columns and prevents reproducible analyses. Salt rich (NaCl) water solutions of fibroin improved the quality of chromatograms.     

Environmentally friendly surface modification of silk fiber: Chitosan grafting and dyeing

In this paper, the surface modification of silk fiber using anhydrides to graft the polysaccharide chitosan and dyeing ability of the grafted silk were studied. Silk fiber was degummed and acylated with two anhydrides, succinic anhydride (SA) and phthalic anhydride (PA), in different solvents (dimethyl sulfoxide (DMSO) and N,N-dimethyl formamide (DMF)). The effects of anhydrides, solvents, anhydride concentration, liquor ratio (L:R) and reaction time on acylation of silk were studied. The polysaccharide chitosan was grafted to the acylated silk fiber and dyed by acid dye (Acid Black NB.B). The effects of pH, chitosan concentration, and reaction time on chitosan grafting of acylated silk were investigated. The physical properties show sensible changes regardless of weight gain. Scanning electron microscopy (SEM) analysis showed the presence of foreign materials firmly attached to the surface of silk. FTIR spectroscopy provided evidence that chitosan was grafted onto the acylated silk through the formation of new covalent bonds. The dyeing of the chitosan grafted-acylated silk fiber indicated the higher dye ability in comparison to the acylated and degummed silk samples. The mechanism of chitosan grafting over degummed silk through anhydride linkage was proposed. The findings of this research support the potential production of new environmentally friendly textile fibers. It is worthwhile to mention that the grafted samples have antibacterial potential due to the antibacterial property of chitosan molecules.     

Ultrasonic characterization of ceramic fibres at ambient and elevated temperatures

A non-destructive laser-generated ultrasonic inspection system has been developed to evaluate the elastic properties of ceramic fibres. The approach uses a pulsed Nd:YAG laser to excite ultrasonic signals in fibres. The signal is detected by a piezoelectric acoustic emission transducer to obtain the appropriate frequency response suitable for an elastically one-dimensional sample. By using a differential time-of-flight system, a very accurate measure of the velocity can be obtained in the fibre, with a total scatter of less than 0.5%. This approach has been used to investigate the Young's modulus of polycrystalline carbon and boron fibres as a function of stress. Both types of fibres were found to have a Young's modulus increase as greater applied loads were imposed. The carbon and boron fibres, along with silicon carbide fibres, were evaluated at elevated temperatures up to 700 °C. The carbon fibres were found to have an immediate decrease in the Young's modulus as the temperature was increased, due to oxidation of the carbon. The Young's modulus of the boron fibres decreased only at temperatures higher than 200 °C, probably the result of a microstructural transformation or relaxation. The silicon carbide fibres were found to have no significant change in the elastic properties up to 700 °C. The ultrasonic technique was also applied to polycrystalline alumina fibres and fibre tows between ambient temperature and 1200 °C in a specially designed furnace. Using this technique, it was possible to distinguish the changes in the elasticity of the alumina fibres as they were processed into -alumina. The change in the Young's modulus was readily apparent during phase transformations to -alumina. In addition, the ultrasonic velocity can be used to infer information concerning any coatings that were applied to the alumina fibres. This can be used to aid in the quantification of the coating thickness and uniformity. The application of the ultrasonic inspection system has demonstrated the ability to determine rapidly and non-destructively the elastic properties in ceramic fibres. The information gained from the measurements can be used as a quality assurance technique, or can be modified to be a real-time process control/process monitoring system.     

Origin of the variability of the mechanical properties of silk fibres: 2 The nanomechanics of single silkworm and spider fibres

The variability in mechanical stress–strain behaviour of various silks obtained from Bombyx mori silkworm and Nephila madagascarensis spider fibres has been studied by high resolution Raman analysis using the Raman shift induced by application of a controlled strain on the νN–H mode as a probe. Silk fibres exhibiting typical 1, 2, 3 and 4 Types have been selected from their characteristic tensile stress–strain behaviour. A perfect relationship between the nanomechanic (at the scale of the chemical bond) and macroscopic (silk single fibre) behaviour is observed as in the case of other polyamide fibres (natural keratin and synthetic PA66). Copyright © 2012 John Wiley & Sons, Ltd.     

Effect of microwave radiation on surface charge, surface sites and ionic state of iron, and the activity of crocidolite asbestos fibres

Surface charge, surface sites, and the content of ferrous ions of crocidolite asbestos fibres are some of the properties which are considered to play a role in determining their activity in biological systems. Any treatment which changes these properties may therefore change their activity and subsequently increase or decrease their toxicity in biological surroundings. Surfaces of crocidolite fibres are shown to be negatively charged. In the present study, microwave radiation at 300^°C was able to increase the number of positive charges within the bulk of the crocidolite fibres. In the presence of atmospheric oxygen, this increase could simultaneously reduce the hydroxyl groups on the surface of the fibres. The increase in positive charge was monitored by: (i) Mössbauer spectroscopy, where a change in the oxidation state of iron from ferrous to ferric was observed, (ii) visual microscopic observations of the irradiated fibres where there was an increase in their aggregation, and (iii) the difficulty to suspend these radiated fibres in solution. A decrease in the number of the surface hydroxyl groups on the other hand, was monitored by infrared spectroscopy. The reduction in the activity of the radiated crocidolite fibres was investigated by studying their ability to peroxidize lipids. Results have shown that changes in their surface charge, surface site and a reduction of the content of ferrous ions produce a concomitant decrease in their ability to initiate lipid peroxidation.     

Preparation and mechanical properties of layers made of recombinant spider silk proteins and silk from silk worm

Layers of recombinant spider silks and native silks from silk worms were prepared by spin-coating and casting of various solutions. FT-IR spectra were recorded to investigate the influence of the different mechanical stress occurring during the preparation of the silk layers. The solubility of the recombinant spider silk proteins SO1-ELP, C16, AQ24NR3, and of the silk fibroin from Bombyx mori were investigated in hexafluorisopropanol, ionic liquids and concentrated salt solutions. The morphology and thickness of the layers were determined by Atomic Force Microscopy (AFM) or with a profilometer. The mechanical behaviour was investigated by acoustic impedance analysis by using a quartz crystal microbalance (QCMB) as well as by microindentation. The density of silk layers (d<300 nm) was determined based on AFM and QCMB measurements. At silk layers thicker than 300 nm significant changes of the half-band-half width can be correlated with increasing energy dissipation. Microhardness measurements demonstrate that recombinant spider silk and sericine-free Bombyx mori silk layers achieve higher elastic penetration modules E_EP and Martens hardness values H_M than those of polyethylenterephthalate (PET) and polyetherimide (PEI) foils.     

Ultrasound regulated flexible protein materials: Fabrication,structure and physical-biological properties

Ultrasound can be used in the biomaterial field due to its high efficiency, easy operation, no chemical treatment, repeatability and high level of control. In this work, we demonstrated that ultrasound is able to quickly regulate protein structure at the solution assembly stage to obtain the designed properties of protein-based materials. Silk fibroin proteins dissolved in a formic acid-CaCl₂ solution system were treated in an ultrasound with varying times and powers. By altering these variables, the silks physical properties and structures can be fine-tuned and the results were investigated with Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA), gas permeability and water contact angle measurements. Ultrasonic treatment aids the interactions between the calcium ions and silk molecular chains which leads to increased amounts of intermolecular β-sheets and α-helix. This unique structural change caused the silk film to be highly insoluble in water while also inducing a hydrophilic swelling property. The ultrasound-regulated silk materials also showed higher thermal stability, better biocompatibility and breathability, and favorable mechanical strength and flexibility. It was also possible to tune the enzymatic degradation rate and biological response (cell growth and proliferation) of protein materials by changing ultrasound parameters. This study provides a unique physical and non-contact material processing method for the wide applications of protein-based biomaterials.     

Tensor theory of electromagnetic radiometry

A theory of electromagnetic radiometry is built on the premise that the electromagnetic generalised radiance has a tensor structure, represented by the electric, magnetic and mixed generalised radiance tensors as fundamental quantities. They allow overcoming the limitations due to the scalar generalised radiances, proposed for characterizing stationary random electromagnetic sources. Furthermore, they provide a unified framework for completely describing the energy flux and the states of spatial coherence and polarization of random electromagnetic fields. So, the fundamental quantities of both the scalar generalised radiometry and the classical radiometry or photometry are deduced as particular cases of the tensor theory. A new procedure of analysis of (second-order) correlations, subject to the accomplishment of conservation laws, is also introduced. It reveals that (1) the primary sources of the measurable radiometric quantities associated to the random electromagnetic fields in any states of spatial coherence and polarization are the individual radiators of the radiant source (the correlations of the electric and magnetic field vectors only modulate the contributions given by those radiators) and (2) there are two physical mechanisms for the transport of measurable radiometric quantities by the electromagnetic field, i.e. the propagation of the contributions from individual radiators and their redistribution over each wavefront on propagation. The term redistribution refers to the transfer of portions of the measurable quantity over the wavefronts on propagation, without change its total value over each wavefront. In this context, a physical meaning is given to the negative values of the generalised radiance, which gives new insight about the Poynting’s theory of energy transport.     

老化丝织品的红外光谱分析研究

古代丝织品老化程度的检测有助于了解丝织品的保存状况及保护方法的选择与改进,通过红外光谱分析对丝织品老化原因及程度进行了研究。样品为经光老化、热老化和水解老化的白色丝织品和出土于湖北、内蒙古、青海的古代丝织品。对这些样品进行了显微红外分析,结果表明,红外光谱分析虽然只是提供半定量分析,但是对于发生了水解老化的丝织品来说,由于羧基含量的增加,红外分析能很容易提供定性及较好的半定量的分析结果,因此对于出土古代丝织品保存状况及老化机理的研究来说很有实用价值。     

Helium effects on the microstructural evolution of reactor irradiated ferritic and austenitic steels

Abstract

Microstructural evolution in neutron irradiated austenitic stainless steels and Cr-Mo ferritic steels is reviewed. Important highlights are: (1) there is a strong correlation between precipitation and void evolution in austenitic steels; (2) helium affects precipitate evolution in austenitic steels, but observations indicate no effect on precipitation in ferritic steels; (3) helium has a pronounced effect on the cavity evolution of the two steel types. Helium effects are explained in terms of the interrelationship between microstructural evolution and point-defect annihilation processes. In stainless steel, three relative regimes of microstructural behavior for different helium generation rate-displacement rate ratios are recognized: (1) “low” He/dpa ratio, where helium effects on the radiation-induced microstructural evolution are negligible or develop slowly, (2) “medium” He/dpa ratio, where helium effects strongly enhance the microstructural changes, and (3) “high” He/dpa ratio, where helium effects are limited to the early development of a high density of fine bubbles which interfere with other radiation-induced microstructural changes, but allow enhanced thermal microstructural evolution to take place instead. The extensive data on austenitic steels fall within these regimes. Ferritic steels are known to be highly resistant to void swelling without helium. It is suggested that enhanced cavity formation due to helium in ferritic steels makes higher swelling a potential concern for fusion reactor applications.     

Critical dynamics of superconductors in the charged regime

We investigate the finite temperature critical dynamics of three-dimensional superconductors in the charged regime, described by a transverse gauge field coupling to the superconducting order parameter. Assuming relaxational dynamics for both the order parameter and the gauge fields, within a dynamical renormalization group scheme, we find a new dynamic universality class characterized by a finite fixed point ratio between the transport coefficients associated with the order parameter and gauge fields, respectively. We find signatures of this universality class in various measurable physical quantities, and in the existence of a universal amplitude ratio formed by a combination of physical quantities.     

The use of stable isotopes to evaluate water mixing and water use by flood plain trees along the Garonne valley

Before the confluence of the Tarn, the Garonne valley was the driest area in the entire south-west of France, due to the relatively low rainfall and low summer discharge of the Garonne River and its tributaries. The natural abundance of the stable isotope of oxygen (18O) and ionic charge of surface and ground water were used to estimate the water source for the Garonne River and phreatic subsurface water. We also measured these constituents in the sap of trees at several flood plain sites to better understand the source of water used by these trees. 18O signatures and conductivity in the Garonne River indicated that the predominance of water was from high altitude surface runoff from the Pyrenees Mountains. Tributary inputs had little effect on isotopic identity, but had a small effect on the conductivity. The isotopic signature and ionic conductivity of river water (delta18O: -9.1 per thousand to -9.0 per thousand, conductivity: 217-410 microS/cm) was distinctly different from groundwater (delta18O: -7.1 per thousand to -6.6 per thousand, conductivity: 600-900 microS/cm). Isotopic signatures from the sap of trees on the flood plain showed that the water source was shallow subsurface water (<30 cm), whereas trees further from the river relied on deeper ground water (>1 m). Trees at both locations maintained sap with ionic charges much greater (2.3-3.7x) than that of source water. The combined use of 18O signatures and ionic conductivity appears to be a potent tool to determine water sources on geographic scales, and source and use patterns by trees at the local forest scale. These analyses also show promise for better understanding of the effects of anthropogenic land-use and water-use changes on flood plain forest dynamics.     

Atomic force microscopy characterization of the surface wettability of natural fibres

Natural fibres represent a readily available source of ecologically friendly and inexpensive reinforcement in composites with degradable thermoplastics, however chemical treatments of fibres are required to prepare feasible composites. It is desirable to characterize the surface wettability of fibres after chemical treatment as the polarity of cellulose-based fibres influences compatibility with a polymer matrix. Assessment of the surface wettability of natural fibres using conventional methods presents a challenge as the surfaces are morphologically and chemically heterogeneous, rough, and can be strongly wicking. In this work it is shown that under atmospheric conditions the adhesion force between an atomic force microscopy (AFM) tip and the fibre surface can estimate the water contact angle and surface wettability of the fibre. AFM adhesion force measurements are suitable for the more difficult surfaces of natural fibres and in addition allow for correlations between microstructural features and surface wettability characteristics.