The crystal modulus of silk (Bombyx mori)

It is shown that experimentally determined values of the crystal modulus of Bombyx mori silk agree reasonably well with the computationally determined values, if account is taken of the stress relaxation, which occurs during the experimental measurements. The experimental are 16-22 GPa depending on the sample and the computational are 13 or 16 GPa depending on the method of analysis.     

The preparation of high performance silk fiber/fibroin composite

An all-silk composite, in which uniaxially-aligned and continuous-typed Bombyx mori silk fibers were embedded in a matrix of silk protein (fibroin), was successfully prepared via a solution casting process. The structure, morphology, mechanical and thermal properties of such silk fiber/fibroin composites were investigated with X-ray diffraction, scanning electron microscopy, tensile and compression tests, dynamic mechanical analysis and thermogravimetric analysis. The results demonstrated that the interface adhesion between silk fiber and the fibroin matrix was enhanced by controlling the fiber dissolution through 6 mol L⁻¹ LiBr aqueous solution. Compare to those of the pure fibroin counterparts, the overall mechanical properties as well as the thermal stability of such silk fiber/fibroin composites were significantly improved. For example, the composite with 25 wt% fibers showed a breaking stress of 151 MPa and a breaking elongation of 27.1% in the direction parallel to the fiber array, and a compression modulus of 1.1 GPa in the perpendicular direction. The pure fibroin matrix (film), on the other hand, typically had a breaking stress of 60 MPa, a breaking elongation of 2.1% and a compression modulus of 0.5 GPa, respectively. This work suggests that such a controllable technique may help in the preparation of animal silk based materials with promising properties for various applications.     

X-ray diffraction and computational studies of the modulus of silk (Bombyx mori)

X-ray diffraction with the assumption of uniform stress has been used for determining the crystal modulus of polymers. Values of the modulus of silk obtained previously using such an approach were found to be an order of magnitude lower than, those obtained by computational modeling. The differences are outside the limits of experimental and computational errors. This study re-examined the values in an improved manner. For the X-ray technique, moduli of different samples along the length of cocoon fibers were measured. The values obtained are 20-28 GPa depending on the crystallinity index and degree of orientation of the samples. For the computational calculation, the longitudinal acoustic mode (LAM) frequency of silk systems having three different c-axis dimensions were calculated. An acoustic dispersion curve was generated from the frequency values. The slope of the curve at the origin gave a crystal modulus of 13 GPa. A 3D-fluctuation analysis yielded an average modulus of approximately 16 GPa. These low values result from the out-of-plane torsioning of molecules in the β-pleated structure of the silk crystals. The experimental and computational results are in reasonable agreement with one another as well as with data reported in the literature for other pleated molecules.     

Flow analysis of aqueous solution of silk fibroin in the spinneret of Bombyx mori silkworm by combination of viscosity measurement and finite element method calculation

Bombyx mori silk fibers possess outstanding mechanical properties in spite of being spun at room temperature and from the aqueous solution. Therefore, the mechanism of the structural transition has been studied with great attention, but still not be well understood. In this study the flow simulation of the silk fibroin aqueous solution using finite element method was performed on the basis of both the relationship between the viscosity and shear rate of the silk fibroin solution prepared from the silk gland, and the detailed structure of the spinneret including silk press part of the silkworm obtained from the optical micrographs. The viscosity of the silk fibroin solution decreased with power-law till the shear rate, about 1.5 s⁻¹ with increasing shear rate. Then the viscosity increased reversely which is speculated due to the fiber formation as a result of aggregation of the molecules. In the flow simulation analysis, the initiation site of the fiber formation was calculated by regulating the extrusion pressure. The fiber formation occurs in 550 μm from the spigot at 1 MPa and in 600 μm from the spigot at 50 MPa. The extrusion pressure in the range from 1 MPa to 50 MPa induces the fiber formation in the stiff plates (550-600 μm from the spigot), that is, the silk press part in the spinneret.     

Mechanical properties of single‐brin silkworm silk

Mechanical tests were performed on single brins of Bombyx mori silkworm silk, to obtain values of elastic modulus (E), yield strength, tensile breaking strength, and shear modulus (G). Specimen cross‐sectional areas, needed to convert tensile loads into stresses, were derived from diameter measurements performed by scanning electron microscopy. Results are compared with existing literature values for partially degummed silkworm baves. The tensile modulus (16 ± 1 GPa) and yield strength (230 ± 10 MPa) of B. mori brin are significantly higher than the literature values reported for bave. The difference is attributed principally to the presence of sericin in bave, contributing to sample cross‐section but adding little to the fiber's ability to resist tensile deformation. The two brins in bave are found to contribute equally and independently to the tensile load‐bearing ability of the material. Measurements performed with a torsional pendulum can be combined with tensile load‐extension data to obtain a value of E/ that is not sensitive to sample cross‐sectional dimensions or, therefore, to the presence of sericin. The value of E measured for brin can be used together with this result to obtain G = 3.0 ± 0.8 GPa and E/G = 5.3 ± 0.3 for brin. The latter value indicates a mechanical, and therefore microstructural, anisotropy comparable to that of nylon. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 1270–1277, 2000     

Structure of the spinning apparatus of a wild silkworm Samia cynthia ricini and molecular dynamics calculation on the structural change of the silk fibroin

Silkworms have been developed over thousands years to optimize folding and crystallization of fibroin under highly controlled conditions which have resulted in their efficient fiber formation. In this paper, we reconstructed the three-dimensional architecture of the spinneret of a wild silkworm Samia cynthia ricini from approximately 1000 optical micrographs of the semi-thin cross sections. The chitin plates and muscles were observed in the silk press part together with large change in the diameter of the spinneret lumen at the press part by large shear stress. This is similar to the case of the spinneret of Bombyx mori silkworm, indicating that the structural change in the silk fibroin of S.c. ricini silkworm occurs exclusively at the silk press part due to large shear stresses. Molecular dynamics (MD) calculations were then performed to study the structural change that occurs in the crystalline region of S.c. ricini silk fibroin under shear stress. Namely, using the peptide AGGAGG(A)₁₂GGAGAG as a model of the crystalline part of the silk fibroin under different shear stresses in the presence of water molecules and followed by molecular mechanics (MM) calculation after removal of water molecules. The simulation indicates that the Ala residues in the model peptides adopt a predominantly β-sheet structure under shear stresses of above 1.0 GPa.     

The Preparation and Characterization of Silk/Gelatin Biocomposites

There is a growing interest in the use of composite materials. Silk fiber/gelatin biocomposites were fabricated using compression molding. The fiber content in the composite varied from 10–30 wt%. Composite containing 30 wt% silk showed the best mechanical properties. Tensile strength, tensile modulus, bending strength, bending modulus and impact strength, hardness of the 30% silk content composites were found 54 MPa, 0.95 GPa, 75 MPa and 0.43 GPa and 5.4 kJ/m², 95.5 Shore A, respectively. Water uptake properties at room temperature, accelerated weathering aging, irradiation, thermomechanical analysis, and degradation in soil were carried out in this experiment.     

Regeneration of Bombyx mori silk by electrospinning—part 1: processing parameters and geometric properties

We studied the effect of electrospinning parameters on the morphology and fiber diameter of regenerated silk from Bombyx mori. Effects of electric field and tip-to-collection plate distances of various silk concentrations in formic acid on fiber uniformity, morphology and diameter were measured. Statistical analysis showed that the silk concentration was the most important parameter in producing uniform cylindrical fibers less than 100 nm in diameter.     

Rigid thermosetting liquid molding resins from renewable resources. II. Copolymers of soybean oil monoglyceride maleates with neopentyl glycol and bisphenol A maleates

Soybean oil monoglycerides (SOMG), obtained by the glycerolysis of soybean oil, were reacted with maleic anhydride to produce SOMG maleate half esters. The copolymers of the SOMG maleates with styrene produced rigid thermosetting polymers. The dynamic mechanical analysis (DMA) of this polymer showed a glass‐transition temperature (T_g) around 133°C and a storage modulus (E′) value around 0.94 GPa at 35°C. The tensile tests performed on this polymer showed a tensile strength of 29.36 MPa and a tensile modulus of 0.84 GPa. Mixtures of SOMG with neopentyl glycol (NPG) and SOMG with bisphenol A (BPA) were also maleinized under the same reaction conditions and the resulting maleates were then copolymerized with styrene. The resulting polymers were analyzed for their mechanical properties. The T_g of the copolymers of the SOMG/NPG maleates with styrene was 145°C and the E′ value at 35°C was 2 GPa. The tensile strength of this polymer as calculated from the stress–strain data was 15.65 MPa and the tensile modulus was 1.49 GPa. The T_g of the copolymers of SOMG/BPA maleates, on the other hand, was found to be around 131°C and the E′ value was 1.34 GPa at 35°C. The changes observed in the mechanical properties of the resulting polymers with the introduction of NPG maleates and BPA maleates to the SOMG maleates can be explained by the structural changes on the polymer backbone. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 972–980, 2002     

Copolymerization of dichlorodiphenylsulfone with bis(chlorophthalimide) catalyzed by NiBr2/PPh3/Zn

A new high-performance material, poly(sulfone-imide) was prepared by Ni(0)-catalyzed coupling of aromatic dichlorides containing imide structure and 4,4'-dichlorodiphenylsulfone. The copolymers were produced with high yield and moderate to high inherent viscosities of 0.52-1.13 dL/g. Wide-angle X-ray diffractograms revealed that the polymers were amorphous. Most of the polymers exhibited good solubility and could be readily dissolved in various solvents such as N-methyl-2-pyrrolidinone(NMP) and N,N-dimethylacetamide (DMAc). These polysulfone-imides had glass-transition temperatures between 317 and 345 °C and 10% weight loss temperatures in the range of 450-476 °C in nitrogen atmosphere. The tough polymer films, obtained by casting from cresol solution, had a tensile strength range of 21-158 MPa and a tensile modulus range of 2.1-3.3 GPa.     

Silkworm Gut Fibres from Silk Glands of Samia cynthia ricini—Potential Use as a Scaffold in Tissue Engineering

High-performance fibroin fibres are ideal candidates for the manufacture of scaffolds with applications in tissue engineering due to the excellent mechanical properties and optimal biocompatibility of this protein. In this work, the manufacture of high-strength fibres made from the silk glands of Samia cynthia ricini is explored. The glands were subjected to soaking in aqueous dissolutions of acetic acid and stretched to manufacture the fibres. The materials produced were widely characterized, in terms of morphology, mechanical properties, crystallinity and content of secondary structures, comparing them with those produced by the standard procedure published for Bombyx mori. In addition, mechanical properties and biocompatibility of a braided scaffold produced from these fibres was evaluated. The results obtained show that the fibres from B. mori present a higher degree of crystallinity than those from S. c. ricini, which is reflected in higher values of elastic modulus and lower values of strain at break. Moreover, a decrease in the elongation values of the fibres from S. c. ricini was observed as the concentration of acetic acid was increased during the manufacture. On the other hand, the study of the braided scaffolds showed higher values of tensile strength and strain at break in the case of S. c. ricini materials and similar values of elastic modulus, compared to those of B. mori, displaying both scaffolds optimal biocompatibility using a fibroblast cell line.     

Regeneration of Bombyx mori silk by electrospinning. Part 3: characterization of electrospun nonwoven mat

Regenerated Bombyx mori silk fibroin in formic acid was electrospun and the morphological, chemical and mechanical properties of these nanofibers were examined by field emission environmental scanning electron microscopy (FESEM), Raman spectroscopy (RS), Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD) and tensile testing. FESEM indicated that the average fiber diameter was less than 100 nm and circular in cross section. This paper maps the silk fibroin molecular conformations of each step of the sample preparation and the electrospinning process. The secondary structural compositions (random and β-sheet) of the fibroin were determined by FTIR and RS. The crystallinity index of the electrospun fiber, calculated as the intensity ratio of 1624 (β-sheet) and 1663 (random) cm⁻¹ FTIR bands was higher than that of the pristine fiber. Raman spectra of the amide I (1665 cm⁻¹, random) to amide III (1228 cm⁻¹, β-sheet) ratio of the electrospun fiber was less than that of the pristine fiber indicative of higher β-sheet content. The fiber crystallinity, determined by XRD, showed a lower value for the electrospun fiber. The electrospun fiber shows small but significant increases in the β-sheet content in comparison with the pristine fiber. Dissolution of fibroin in formic acid enhances β-sheet crystallization and may facilitate β-sheet formation in electrospun fiber. The electrospun random silk mat had a Young's modulus, ultimate tensile strength and strain of 515 MPa, 7.25 MPa and 3.2%, respectively.     

Synthesis and properties of soluble poly[bis(benzimidazobenzisoquinolinones)] based on novel aromatic tetraamine monomers

Four aromatic tetraamine monomers possessing flexible ether linkages were successfully synthesized by nucleophilic aromatic substitution of hydroquinone, 4,4′-dihydroxybiphenyl, 2,2′-bis(4-hydroxyphenyl)propane, and 2,7-dihydroxynaphthalene with 5-chloro-2-nitroaniline, followed by reduction, respectively. With these monomers, a new class of soluble poly[bis(benzimidazobenzisoquinolinones)] was prepared by a one-step, high-temperature solution polycondensation. The resulting polymers were completely soluble in phenolic solvents and had high inherent viscosities ranging from 1.2 to 1.5 g dL⁻¹. These polymers had glass transition temperatures in the range of 427-449 °C. Thermogravimetric analysis showed that all polymers were thermally stable, with 5% weight loss recorded above 510 °C in nitrogen. The tough polymer films, obtained by casting from solution, had tensile strength, elongation at break, and tensile modulus values in the range of 79.5-114.5 MPa, 10.3-23.0%, and 1.1-1.7 GPa, respectively. It is demonstrated that these semiladder polymer membranes displayed high CO₂ permeability coefficients (P₂CO=31.6−96.5barrer) and permeability selectivity of CO₂ to CH₄(P₂CO/P₄CH=30.6−43.4).     

Synthesis,spinning, and properties of very high molecular weight poly(acrylonitrile-co-methyl acrylate) for high performance precursors for carbon fiber

In this paper, synthesis of very high molecular weight (VHMW) polyacrylonitrile-co-methyl acrylate (PAN-co-MA) polymers with weight average molecular weights of at least 1.7 million g/mole were repeatedly achieved on a laboratory scale using emulsion polymerization. The development of a hybrid dry-jet gel solution spinning technique for the VHMW PAN-co-MA enabled continuous spinning of 100 filament count tows, 100s of meters in length. Single filaments were analyzed and tested for tensile performance. Experimentally, the hybrid spinning method coupled with VHMW polymers produced precursor fibers with excellent tensile properties, averaging 954 MPa in strength and 15.9 GPa in elastic modulus (N = 296), with small filament diameters (5 μm). Results indicate a strong correlation between decreasing filament diameter, facilitated by high molecular weight polymer, and exponentially increasing tensile properties, using a hybrid dry-jet gel spinning process.     

Preparation of non-woven nanofibers of Bombyx mori silk, Samia cynthia ricini silk and recombinant hybrid silk with electrospinning method

Electrospinning is a good method to obtain nanoscale fibers from polymer solutions. In this paper, we successfully prepared non-woven nanofibers of Bombyx mori and Samia cynthia ricini silk fibroins, and of the recombinant hybrid fiber involving the crystalline domain of B. mori silk and non-crystalline domain of S. c. ricini silk from hexafluoroacetone (HFA) solution using electrospinning method. ¹³C cross polarization/magic angle spinning NMR spectroscopy was used to monitor the structural change of silk fibroins together with the detection of the residual HFA during the process of the fiber formation. Scanning electronic microscope was used to determine the diameters and their distributions of the fibers.     

Development of silk-like materials based on Bombyx mori and Nephila clavipes dragline silk fibroins

In order to develop new silk-like materials in the form of fiber and non-woven nano-fiber, this study synthesized a new silk-like protein by selecting the sequence from the crystalline region of Bombyx mori silk fibroin, (GAGSGA)₆, to imitate the processing condition of the silk fibroin with the combination of the sequence YGGLGSQGAGRG, the hydrophilic motif of spider dragline silk which was considered as the origin of supercontraction of spider dragline silk (Yang Z, et al. J Am Chem Soc 2000;122: 9019-25). The CD pattern of the silk-like protein in hexafluoroacetone (HFA) indicates that it takes helical structure. The solid-state structures of the silk-like protein before and after methanol treatment were determined to be random coil and Silk II structure (mainly β-sheet structure), respectively, using ¹³C CP/MAS NMR. The ¹³C CP/MAS NMR spectra of the protein after methanol treatment in hydrated state showed that the random coil peaks from Ala Cβ and Ser Cβ carbons become sharper compared with the corresponding peaks in the dry state. The 2D-WISE spectra in the hydrated state also showed increase of the narrow components for these carbons. Thus, water molecules are relatively easy to access at the random coil regions of the protein. The fiber formation of the silk-like protein was possible with wet-spinning or electrospinning methods using HFA as dope solvent and methanol as coagulation solvent.     

Silk‐inspired polyurethane containing glyalaglyala tetrapeptide. III. morphological,thermal, and mechanical features of electrosprayed and electrospun deposition

Morphological, thermal, and mechanical features of electrosprayed and electrospun deposition of the silk‐inspired polyurethane (PU) containing GlycineAlanineGlycineAlanine (GlyAlaGlyAla, the featured peptide sequence of silkworm silk fibroin) tetrapeptide, which was synthesized by the traditional liquid‐phase peptide synthesis method and the classical two‐step polymerization method using Boc‐protected amino acids and diisocyanates as starting materials, were characterized. The results show that the synthesized silk‐inspired PU dissolved in tetrahydrofuran (THF) can be easily electrosprayed or electrospun into the film form, although its molecular weight ranging from 13,000 to 15,000 is quite low. Elastomeric fibrous membranes with surface morphologies of “droplets,” “bead‐on‐string,” and “nonwoven fibers” have been obtained by electrospraying and electrospinning the silk‐inspired PU/THF solution of varying concentrations. The thermograms confirm high thermostability of the silk‐inspired PU between 350 and 400°C due to the polar peptide linkages. The tanδ peak of dynamic mechanical analysis curve corresponding to its glass transition temperatures is detected at ?34.3°C. Its elongation at break is about 140–150%, and the breaking tensile strength ranges from 22 to 27 MPa, which is consistent with the data of other PUs containing l ‐alanine residue. Information provided by this study can be used to better understand the correlation between the natural and man‐made silk polymers. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40245.     

Synthesis and characterization of new soluble cardo poly(amide-imide)s derived from 2,2-bis[4-(4-trimellitimidophenoxy)phenyl]norbornane

A series of new soluble poly(amide-imide)s were prepared from the diimide-dicarboxylic acid, 2,2-bis[4-(4-trimellitimidophenoxy)phenyl]norbornane, and various diamines by the direct polycondensation in N-methyl-2-pyrrolidinone containing CaCl_2, using triphenyl phosphite and pyridine as condensing agents. All the polymers were obtained in quantitative yields with inherent viscosities of 1.01-1.42 dL g⁻¹. Gel permeation chromatography (GPC) of the polymers showed number-average and weight-average molecular weight up to 67,300 and 118,000, respectively. The poly(amide-imide)s were amorphous and were readily soluble in various solvents such as N-methyl-2-pyrrolidinone (NMP), N,N-dimethylacetamide (DMAc), N,N-dimethylformamide (DMF), dimethylsulfoxide (DMSO), pyridine, cyclohexanone and tetrahydrofuran. Tough and flexible films were obtained by casting their DMAc solution. The films had tensile strength of 89-110 MPa and a tensile modulus range of 1.8-2.2 GPa. The glass transition temperatures of the polymers were determined by DSC method and they were in the range of 265-295 °C. The polymers were fairly stable up to a temperature around or above 450 °C, and lose 10% weight in the range of 472-504 °C and 490-520 °C in nitrogen and air, respectively.     

Post-spinning modification of electrospun nanofiber nanocomposite from Bombyx mori silk and carbon nanotubes

Electrospinning is an effective procedure for fabricating submicron to nanoscale fibers from synthetic polymer as well as natural proteins. We successfully electrospun regenerated silk protein from cocoons of Bombyx mori to produce random as well as aligned fibers with diameter less than 100 nm. The fibers were characterized using field emission environmental scanning electron microscope (ESEM), Fourier transform infrared spectroscopy (FT-IR), Raman spectroscopy and wide angle X-ray diffraction (WAXD) studies. Post-spinning treatment with methanol and/or stretching and co-electrospinning with single walled carbon nanotubes (CNT) were carried out to alter the strength, toughness, crystallinity and conductivity of silk nanofibers. Addition of just 1% CNT along with post-spinning treatments resulted in 7-fold increase in the strength and 35-fold increase in the modulus of silk nanofibers. Raman spectroscopy confirmed that CNTs were incorporated in the silk fibers. FT-IR spectroscopy and WAXD studies proved that silk-CNT nanofibers had more crystallinity compared to silk nanofibers without CNT. Four-probe method demonstrated that silk-CNT nanofibers had 4 times higher electrical conductivity compared to silk nanofibers without CNT.