Stress relaxation and inverse stress relaxation in silk fibers

Stress‐relaxation experiments on four varieties of Indian silk fiber show that stress relaxation is significantly greater in non‐Mulberry silks than in the Mulberry silk and that the differences among non‐Mulberry silk fibers are relatively small. All the fibers studied also exhibit inverse stress relaxation. It has been shown that the Maxwell–Wiechert model, with two Maxwell elements in parallel, can be used to analyze and explain both the stress‐relaxation and inverse stress‐relaxation behaviors. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1147–1154, 2001     

Studies of mechanical and moisture regain properties of methyl methacrylate grafted silk fibers

The mechanical properties such as the tenacity, breaking extension, initial modulus, elastic and work recovery, and stress relaxation behavior of methyl methacrylate (MMA) grafted silk fibers prepared under different conditions were measured and explained in terms of the relative dominance of the stress concentration, reduction in the interchain cohesion, and fiber matrix stiffening at different grafting percentages. The moisture regain characteristics of fibers grafted in the presence of different solvents were also studied and compared. The grafting of MMA on silk was found to improve the recovery properties significantly without affecting the stress relaxation behavior. The moisture regain studies indicate that moisture regain is reduced with increasing length of the grafted poly(MMA) chains. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 969–974, 2002; DOI 10.1002/app.10202     

Studies on Indian silk. III. Effect of structure on dyeing behavior

This third in a series of articles deals with the analysis of the dyeing behavior of two mulberry and three nonmulberry varieties of silk. The results of the dyeing tests carried out were discussed in relation to the physical and chemical structure of the silk fibers. Noticeable differences in the dye uptake were observed among the different varieties of silk. Mulberry varieties showed higher dye uptake compared to that of all three nonmulberry varieties. Among the nonmulberry varieties, tasar shows higher dye uptake followed by eri and muga. Interestingly, dye uptake reduces significantly within a variety from the outer to the inner layers. The reduction within a variety was found to correlate well with the morphological parameters. Determination of morphology of fibers confirmed significant differences in structural parameters such as crystallinity, orientation, density, and birefringence, for example, between and within varieties. An increase in all these parameters was observed as one moves from the outer to the inner layers within a variety. The differences in the dye uptake of different varieties of silk correlated well with the physical as well as chemical structure of silk fibers. Dye uptake differences between the varieties were found to correlate with the end amino groups. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1116–1123, 2004     

Softness evaluation of keratin fibers based on single‐fiber bending test

The evaluation of single‐fiber softness by bending is an ingenious and vital approach for the basic investigation of both the fiber bending properties and the textile softness. The bending behavior and bending modulus of wool, alpaca and silk fibers have been measured by an axial‐buckling method developed by the authors, which uses the fiber compression bending analyzer (FICBA). The bending properties of single fibers were quantified by calculating the equivalent bending modulus and the flexural rigidity by measuring the protruding length and diameter of fiber needles and the critical force, P_cr, obtained from the peak point of the force‐displacement curve. The measured data showed that the equivalent bending modulus of the alpaca fiber is higher than that of wool fiber, and even the rigidity is 10 times as high as wool, but its friction coefficient is lower than that of wool, which means that the soft handle of alpaca fabrics is mainly due to the smooth surface and low friction coefficient of alpaca fibers in contrast to that of wool fiber. For the silk fiber, despite high equivalent bending modulus, the smoother handle of silk should be mainly due to the thin fiber diameter in contrast to that of keratin fibers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 701–707, 2006     

Effect of heat treatment on the structure and properties of Lyocell fibers

Lyocell fibers were heat‐treated under different conditions. The tensile strength and initial modulus of the heat‐treated Lyocell fibers increased sharply, whereas the elongation at break decreased. Moreover, applying tension to the fibers during the heat treatment further improved the tensile strength and initial modulus. In addition, the crystallinity of the heat‐treated fibers increased slightly, and there was no obvious change with an increase in the tension; the general orientation of the heat‐treated fibers increased, the crystalline orientation little changed, and the amorphous orientation improved. Also, the improved mechanical properties of the Lyocell fibers via the heat treatment could not be preserved for long. The reason may be that the crystalline structure of the Lyocell fibers was not destroyed and no new crystallites were formed during the heat‐treatment process. Therefore, the heat‐treated Lyocell fibers reverted to their original state with time because there was no crosslinking point to fix the orientation, although the cellulose molecules of the amorphous region of the Lyocell fibers were more oriented by the heat treatment with tension. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1738–1743, 2006     

Fine‐structure and physical properties of polyethylene fibers in high‐speed spinning. I. Effect of melt‐flow rate in the high‐density polyethylene

High‐density polyethylene (HDPE) fibers, obtained from a melt‐flow rate (g/10 min) of 11 and 28, was produced by a high‐speed melt‐spinning method in the range of take‐up velocity from 1 to 8 km/min and from 1 to 6 km/min, respectively. The change of fiber structure and physical properties with increasing take‐up velocity was investigated through birefringence, wide‐angle X‐ray diffraction (WAXD), differential scanning calorimetry (DSC), a Rheovibron, and a Fafegraph‐M. With an increase in take‐up velocity, the birefringence showed a sigmoidal increase, which has distinct changes in the range of 1–5 km/min. Throughout the whole take‐up velocities, the birefringence of HDPE(11) was higher than that of HDPE(28). With increasing take‐up velocity, the crystalline orientation was transformed from a‐axis orientation to c‐axis orientation. These crystalline relaxations are confirmed by the tan δ peak of high‐speed spun HDPE fibers. The intensity of the crystalline relaxation peak decreases with increasing take‐up velocity in both HDPE(11) and HDPE(28). As above, the crystalline relaxation peaks shift to lower temperature with increasing take‐up velocity. With increasing take‐up velocity, the ultimate strain decreases while both specific stress and the initial modulus increase. The mechanical behavior may be closely related to, as investigated by birefringence, orientation of the amorphous region, etc., the take‐up velocity. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1182–1195, 2000     

Effect of fiber size on structural and tensile properties of electrospun polyvinylidene fluoride fibers

We use electrospinning to obtain polyvinylidene fluoride (PVDF) fibers and demonstrate simultaneous improvements in β‐crystal microstructure and in tensile properties of fibers with reduction of their diameter. PVDF fibers with average diameters ranging from 70 to 400 nm are obtained by controlling the concentration of the polymer in the electrospinning solution. The amount of β‐crystals present is found to be greater for finer diameter fibers, yielding a maximum β‐phase fraction of 0.86 in the 70‐nm fibers. Moreover, the deformation behavior of the fibers reveals that the tensile modulus and strength improve with reductions in fiber size. Sharp increases in tensile properties are demonstrated when the size of the fibers is reduced below 175 nm. We attribute the enhanced concentration of β‐crystals and the tensile behavior of finer diameter fibers to the extensional forces experienced by the material during electrospinning. POLYM. ENG. SCI., 55:1812–1817, 2015. © 2014 Society of Plastics Engineers     

Physical properties of 2-hydroxyethyl methacrylate-grafted silk fibers

This paper deals with the physical properties of silk fibers grafted with 2-hydroxyethyl methacrylate (HEMA). Both tensile strength and elongation measured in the dry and wet states gradually decreased with increasing weight gain. The initial modulus of the grafted silk fibers in the dry state sharply increased in the weight gain range of 0–16%, then decreased to a lower value than the reference untreated sample. The refractive indices parallel and perpendicular to the fiber axis decreased, though the former showed a steeper slope. Accordingly, birefringence and isotropic refractive index also decreased, suggesting a lower degree of crystallinity and molecular orientation of grafted silk fibers. DSC, TMA, and TGA curves of the HEMA-grafted silk fibers indicated an increased higher thermal stability of silk fibers due to the HEMA grafting. The dynamic mechanical measurements showed that the thermally induced molecular movement of both amorphous and crystalline domains of silk fibers was enhanced by HEMA grafting. X-ray diffraction curves, however, implied that the crystalline structure of the silk fibroin remained unchanged regardless of HEMA polymerization. The introduction of HEMA polymer in silk fibers was evidenced by the infrared spectra, exhibiting the absorption bands characteristic of either the grafted HEMA polymer and the fibroin molecules with ordered β structure. © 1993 John Wiley & Sons, Inc.     

Effect of winding speed on the structure and properties of as‐spun poly(trimethylene 2,6‐naphthalenedicarboxylate) fibers as compared to poly(ethylene terephthalate) fibers

We present a comparative study of melt spinning of poly(trimethylene 2,6‐naphthalenedicarboxylate) (PTN) and poly(ethylene terephthalate) (PET) fibers with respect to the effect of winding speed (2000–6000 m/min): Structural changes were followed by X‐ray analysis, calorimetry, and measurements of density, boiling water shrinkage, and birefringence. As‐spun PTN fibers exhibited a low degree of crystallinity at relatively low speeds (< 2000 m/min). An increase in winding speed up to 6000 m/min only resulted in a minor enhancement of crystallinity and orientation. The small change of structural parameters accounted for the fact that tenacity and modulus did not rise significantly with increasing winding speed, contrary to the PET fibers. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2489–2497, 2002     

Effect of degumming on the tensile properties of silkworm (Bombyx mori) silk fiber

Forcibly reeled silkworm (Bombyx mori) silk was used to study how exposure to a degumming treatment (boiling in distilled water for 30 min) affects tensile properties. Because forcibly reeled and naturally spun fibers exhibit comparable mechanical behavior, the results can be generalized to material obtained conventionally from cocoons. The effects of degumming include: a decrease in the initial elastic modulus, a decrease in the stress at the proportional limit (yield strength), a change in the qualitative shape of force‐displacement curves, and significant qualitative and quantitative variability in force‐displacement data from samples subjected to nominally identical degumming histories. Immersion in water at room temperature or heating in air at 100°C for 30 min are both qualitatively equivalent to a 30‐min degumming treatment in boiling water, in terms of the effect on silk tensile properties. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1431–1437, 2002; DOI 10.1002/app.10366     

Influence of the cross‐sectional shape on the structure and properties of polyester fibers

The effects of the fiber cross‐sectional shape on the structure and properties of polyester fibers were investigated. Fully drawn yarn (FDY) polyester fibers (167 dtex and 48 filaments) were produced under the same spinning conditions used in a spinning plant. The only difference between the fibers was their cross‐sectional shapes. Four different cross‐sectional shapes were chosen for the experimental work: round, hollow‐round, trilobal, and hollow‐trilobal. The crystallinity and values of the maximum stress, maximum strain, modulus, yield stress, shrinkage in boiling water, and unevenness of the fibers were determined. The difference in the cross‐sectional shapes influenced the modulus, maximum strain, yield stress, and shrinkage in boiling water. No effects on the crystallinity and maximum stress were observed. The results suggested that the hollow fibers had higher amorphous orientation than the full fibers. The hollow‐round fiber had the highest unevenness value. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2615–2621, 2007     

Preparation and characterization of nylon 6/organoclay nanocomposite filament fibers

A series of nylon 6 (NY6)/organoclay nanocomposites were prepared via in situ polymerization of ε‐caprolactam in the presence of 1,2‐aminododecanoic acid‐intercalated montmorillonite (ADA‐MMT) organoclay (1–5 wt%) using 6‐aminocaproic acid as polymerization catalyst. The extent of organoclay dispersion in NY6 matrix was analyzed using WAXD and SEM measurements. DSC studies revealed marginal shift in melting and melt‐crystallization peaks toward lower temperature with increasing clay content. Melt viscosity studies for NY6/ADA‐MMT exhibited higher shear‐thinning behavior than neat NY6 probably due to the slip between NY6 matrix and exfoliated organoclay platelets during shear flow. The prepared nanocomposites were melt‐spun and studied for their property improvements against varying clay content, draw ratios, and annealing conditions. Birefringence and sonic velocity values increased initially at lower draw ratios (≤2.5) due to increased orientation of molecular chains along the drawing direction but saturated at higher draw ratio (3.0) for all the samples. At the same draw ratio; compared to neat NY6, NY6/organoclay fibers showed increased chain orientation along the drawing direction which can be attributed to the “tethering effect” of organoclay on NY6 matrix. The initial modulus and stress at break were sensitive to factors such as draw ratio, clay content, and annealing conditions. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Mechanical and thermal properties of waste silk fiber‐reinforced poly(butylene succinate) biocomposites

This article reports the mechanical and thermal properties of poly(butylene succinate) (PBS) biocomposites reinforced with industrially available waste silk fibers, fabricated with varying fiber contents and lengths. The result indicates that use of waste silk fibers may be a potential as reinforcement for effectively improving the static and dynamic mechanical properties of a biodegradable polymer matrix resin, depending on the waste silk fiber content and length in the present biocomposite system. The “as‐separated” waste silk/PBS biocomposites showed the maximum tensile and flexural properties at a fiber loading of 40 wt %, and the “chopped” waste silk/PBS biocomposites showed the optimal strength and modulus with waste silk fibers of 12.7 mm length. The chopped waste silk fibers play a more contributing role in improving the mechanical properties of waste silk/PBS biocomposites than the as‐separated waste silk fibers at a fixed fiber loading. Above the glass transition temperature, the storage modulus of waste silk/PBS biocomposites was significantly greater than that of PBS resin, especially in the higher temperature region. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4972–4980, 2006     

Dynamic viscoelasticity of hybrid kevlar and glass fiber reinforced LLDPE in the molten state

Kevlar and glass fibers were used to reinforce linear low density polyethylene (LLDPE), and composite sheets of 0.8, 1.5 and 2.5 mm thicknesses were obtained by using a compression molding technique. Dynamic viscoelastic properties of non‐hybrid and hybrid composites of various compositions at 200°C are evaluated. Storage modulus (G′) and loss modulus (G″) increase with angular frequency (ω) and reinforcement. Replacement of glass fiber by Kevlar at constant loading of fibers in LLDPE increases the value of G′, G″ and η′. The fractured surface of composite shows the gradient orientation of fibers particularly in 2.5 mm thick sheet. Top and bottom layers show relatively two‐dimensional orientation as compared to the middle layer, which shows random orientation. The orientation of fibers decreases G′ and η′ of Kevlar fiber and hybrid fiber hybrid fiber reinforced LLDPE composites. The effect of change in distance between parallel plate of rheometer (change in strain amplitude) on dynamic rheological properties is studied and reported here.     

Structure and properties of cellulose fibers from ionic liquids

1‐Butyl‐3‐methylimidazolium chloride ([BMIM]Cl) was used as a solvent for cellulose, the rheological behavior of the cellulose/[BMIM]Cl solution was studied, and the fibers were spun with a dry‐jet–wet‐spinning process. In addition, the structure and properties of the prepared cellulose fibers were investigated and compared with those of lyocell fibers. The results showed that the cellulose/[BMIM]Cl solution was a typical shear‐thinning fluid, and the temperature had little influence on the apparent viscosity of the solution when the shear rate was higher than 100 s^?1. In addition, the prepared fibers had a cellulose II crystal structure just like that of lyocell fibers, and the orientation and crystallinity of the fibers increased with the draw ratio increasing, so the mechanical properties of the fibers improved. Fibers with a tenacity of 4.28cN/dtex and a modulus of 56.8 cN/dtex were prepared. Moreover, the fibers had a smooth surface as well as a round and compact structure, and the dyeing and antifibrillation properties of the fibers were similar to those of lyocell fibers; however, the color of these dyed fibers was brighter than that of lyocell fibers. Therefore, these fibers could be a new kind of environmentally friendly cellulose fiber following lyocell fibers. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effect of short chain‐branching distribution on crystallinity and modulus of metallocene‐based ethylene–butene copolymers

In this article, the short chain‐branching distribution (SCBD) of some metallocene‐based ethylene–butene copolymers was evaluated by DSC, and some conventional ethylene copolymers were also studied for the purpose of comparison. It is found that metallocene‐based ethylene copolymers have a relative narrower SCBD. These copolymers were crystallized under different modes, and the crystallinity and initial modulus of them were examined. The metallocene‐based ethylene copolymers contain less interfacial regions, and the melting temperatures of them decrease more rapidly with the decrease of density than those of conventional ethylene copolymers. Moreover, the metallocene‐based and conventional ethylene copolymers of similar density have close initial modulus when they are quenched or annealed at 100°C, but conventional ethylene copolymers show higher initial modulus when stepwise crystallized from 120°C. These differences in crystallinity and initial modulus were explained based on their differences in short‐chain branching distributions. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1709–1715, 2000     

Effect of the chain‐transfer‐agent content on the emulsion polymerization process and adhesive properties of poly(n‐butyl acrylate‐co‐acrylic acid) latexes

The effect of water on regenerated silkworm silk fibers has been studied and compared with that of water on natural silkworm silk fibers. Regenerated fibers are spun from an N‐methylmorpholine‐N‐oxide (NMMO) fibroin solution through a wet‐spinning process, leading to fibers with two distinct tensile behaviors, labeled as brittle and ductile, respectively. Regenerated fibers show a significant contraction when immersed in water. Contraction increases further after drying. In contrast, natural silkworm silk fibers show a negligible contraction when submerged in water. Regenerated fibers tested in water are considerably more compliant than samples tested in air, though their stiffness and tensile strength are significantly reduced. It has been shown that the tensile properties of brittle regenerated fibers can be modified by a wet‐stretching process, which consists of deforming the fiber while immersed in water. Regenerated wet‐stretched fibers always show a ductile behavior independent from their initial tensile behavior. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

High modulus polypropylene fibers. II. Influence of fiber preparation upon structure and morphology

The influence of drawing on the limiting draw ratio upon formation of the morphological structure of fibers spun from binary polypropylene (PP) blends was studied. Fibers were spun from a fiber‐grade CR‐polymer and from the blends of a fiber‐grade CR‐polymer with a molding‐grade polymer in the composition range of 10–50 wt % added. As‐spun fibers were immediately moderately and additionally highly drawn at the temperature of 145°C. The structure and morphology of these fibers were investigated by small‐angle X‐ray scattering, wide‐angle X‐ray scattering, differential scanning calorimetry, scanning electron microscopy, density, birefringence, and sound velocity measurements. It was shown that continuously moderately drawn fibers are suitable precursors for the production of high tenacity PP fibers of very high modulus, because of so called oriented “smectic” structure present in these fibers. With drawing at elevated temperature, the initial metastable structure of low crystallinity was disrupted and a c‐axis orientation of monoclinic crystalline modification was developed. Hot drawing increased the size of crystallites and crystallinity degree, the orientation of crystalline domains, and average orientation of the macromolecular chains and resulted in extensive fibrillation and void formation. It was found that the blend composition has some influence on the structure of discontinuously highly drawn fibers. With increasing the content of the molding‐grade polymer in the blend, the size of crystalline and amorphous domains, density and crystallinity, as well as amorphous orientation decreased. Relationship has been established between the mechanical properties, crystallinity, and orientation of PP fibers. It was confirmed that by blending the fiber‐grade CR‐polymer by a small percentage of the molding‐grade polymer, maximization of elastic modulus is achieved, mainly because of higher orientation of amorphous domains. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1067–1082, 2006     

An investigation into transition metal ion binding properties of silk fibers and particles using radioisotopes

Silk is a structural protein fiber that is stable over a wide pH range making it attractive for use in medical and environmental applications. Variation in amino acid composition has the potential for selective binding for ions under varying conditions. Here we report on the metal ion separation potential of Mulberry and Eri silk fibers and powders over a range of pH. Highly sensitive radiotracer probes, ⁶⁴Cu²⁺, ¹⁰⁹Cd²⁺, and ⁵⁷Co²⁺ were used to study the absorption of their respective stable metal ions Cu²⁺, Cd²⁺, and Co²⁺ into and from the silk sorbents. The total amount of each metal ion absorbed and time taken to reach equilibrium occurred in the following order: Cu²⁺ > Cd²⁺ > Co²⁺. In all cases the silk powders absorbed metal ions faster than their respective silk fibers. Intensive degumming of the fibers and powders significantly reduced the time to absorb respective metal ions and the time to reach equilibrium was reduced from hours to 5–15 min at pH 8. Once bound, 45–100% of the metal ions were released from the sorbents after exposure to pH 3 buffer for 30 min. The transition metal ion loading capacity for the silk sorbents was considerably higher than that found for commercial ion exchange resins (AG MP‐50 and AG 50W‐X2) under similar conditions. Interestingly, total Cu²⁺ bound was found to be higher than theoretically predicted values based on known specific Cu²⁺ binding sites (AHGGYSGY), suggesting that additional (new) sites for transition metal ion binding sites are present in silk fibers. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Transport and mechanical properties of iPP–sPP fibers

The drawing behavior of a blend of syndiotactic and isotactic polypropylene (iPP–sPP 50:50 w/w) was investigated at different temperatures and compared to that of pure polymers. The film of pure sPP showed that the presence of iPP allowed the blend to reach a much higher draw ratio. Fibers were obtained by drawing the blend at 110°C. The axial elastic modulus of the fibers was measured as a function of draw ratio up the highest λ = 10. The sorption and diffusion of dichloromethane vapors in the undrawn and drawn samples were studied in order to provide information about the structural organization of the amorphous phase. The elastic modulus of the fibers displayed a more‐than‐linear increase with the draw ratio, suggesting a good interconnection of the amorphous phases. The orientation of the chains with increasing λ determined a decrease of entropy and fractional free volume (FFV) and a tighter packing of the chains along the drawing direction, explaining the strong increase of the elastic modulus. The transport properties, which confirmed the mechanical properties, showed a stiffening of the amorphous phase after λ = 6, evidenced by a dual‐type sorption isotherm for the fibers and a sharp drop in the zero‐concentration diffusion coefficient. As a consequence, the permeability of the fibers was much lower than that of the unoriented sample. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 539–545, 2001