Influence of metal ions on structure and properties of acrylic fibers

The acrylic fibers containing 10.8 wt % of acrylic acid as a comonomer were treated with 5% aqueous solution of sulphates of alkali metals (sodium and potassium) and transition metals (cobalt and nickel) at 90°C for 5 min. The effect of this treatment on the chemical structure, thermal behavior and mechanical properties of this fiber was investigated through FTIR, X-ray, DSC, and TGA techniques. The changes in the chemical structure of the fibers have been noticed as a change in the intensity of characteristic infrared absorption bands. Broadening of the absorption band at 1700 cm⁻¹ due to COO⁻ stretch is also noticed in the case of fibers treated with salts of alkali metals, probably because of formation of a COO⁻M⁺ structure. WAXD studies of the fibers treated with metal salts showed the decrease in the crystallinity of the treated fibers. DSC curves of metalated fibers showed the onset of exothermic cyclization at a higher temperature. The initial modulus of the samples increased after this treatment. The fibers treated with sulphates of alkali metals showed an approximately twofold increase in elongation at break compared to the untreated ones. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:1647–1659, 1998     

从丝素水溶液中再生的丝纤维的结构与性能

通过使用表面皿直接拉伸、毛细管重力纺丝和人工拉伸3种不同的成丝方法,从高浓度再生丝素水溶液中制得了丝纤维。用偏光显微镜观察了丝纤维的取向,用拉曼光谱仪和Instron拉力仪表征了丝纤维的结构和力学性能。结果发现,经毛细管剪切流动后再拉伸有利于再生丝性能的提高,所得的丝有较好的取向和较多的β折叠结构,力学性能也相对较好。剪切在丝纤维的成形过程中起重要的作用。     

Effects of superfine silk protein powders on mechanical properties of wet‐spun polyurethane fibers

Mechanical measurements were employed to investigate the effects of three types of superfine silk protein powder on tensile strength, elongation, and elasticity of wet‐spun Pellethane^® 2363‐80AE polyurethane (PU) fiber. These superfine silk protein powders included undegummed silk (with both native silk fibroin and sericin, water insoluble), native silk fibroin (with native silk fibroin only, water insoluble), and regenerated silk fibroin (with regenerated silk fibroin only, water soluble) in powder form. Experimental data derived from the mechanical measurements illustrated that the miscibility between the PU and regenerated silk fibroin were superior to that between PU and the other two silk proteins. This may be attributed to the similar chemical structure and microphase separation of PU and regenerated silk fibroin with lower molecular weight than native silk fibroin. This preliminary work may provide some information for biomimetic processing of silk‐inspired PU biofibers, which combine elasticity of synthetic PU with biofunction of natural silk fibroin for special biomedical applications. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Metal ion binding properties of novel wool powders

Wool fibres have shown potential for the removal and recovery of toxic chemical and metal ions; however, their slow kinetics of binding has limited their widespread application. In this study three wool powders have been prepared from chopped wool fibre using various milling operations. Brunauer, Emmett, Teller analysis (BET) showed negligible change in surface area and Positron annihilation lifetime spectroscopy indicated no change in nanoporosity of the powders on processing. Binding of the transition metal ions, Co²⁺, Cu²⁺, and Cd²⁺ was investigated over the pH range 3–9 at ambient temperature (23°C) using their respective radioisotopes (i.e. ⁵⁷Co, ⁶⁴Cu, or ¹⁰⁹Cd). The optimum pH for binding of Cu²⁺ and Cd²⁺ was in the range 6–8, while Co²⁺ absorption peak was sharp at pH 8. The rate of uptake of Cu²⁺ for each of the wool powder was dramatically faster (～ 42 fold) than that of the wool fibre. In comparison with commercial cation exchange resins, the wool powders showed significantly higher (two to nine fold) metal ion loading capacity. Selective binding of the metal ions could be enhanced by varying pH and/or incubation times. The use of radioisotopes to monitor the metal ion binding allowed the development of a highly sensitive and rapid high‐throughput analysis method for assessing wool powder binding properties. The ability to produce large quantities of wool powders and their ease of handling indicate that they have potential for application in separation and recovery of metal ions from industrial effluents and environmental waterways. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Structure and properties of tussah silk fibers graft-copolymerized with methacrylamide and 2-hydroxyethyl methacrylate

Tussah silk fibers were graft-copolymerized with methacrylamide (MAA) and 2-hydroxyethyl methacrylate (HEMA) in aqueous media, using a chemical redox system as an initiator. High weight gain values were obtained with both grafting agents (up to 175%). The extent of homopolymerization was negligible for the MAA grafting system over the entire range of monomer–silk ratios examined, while polymer deposition on the fiber surface occurred when the HEMA–silk ratio exceeded 0.5% (w/w). The moisture content of poly(MAA)-grafted silk fibers was enhanced by grafting. Breaking load, elongation at break, and energy decreased at low weight gain (0–20%) and then remained rather constant. The DSC curves of poly(MAA)-grafted silk showed a new endotherm at about 280°C, due to the melting of poly(MAA) chains. The loss modulus peak of poly(HEMA)-grafted silk fibers broadened and shifted to a lower temperature, showing a tendency to split into two peaks at high weight gain. On the other hand, grafting with poly(MAA) induced a noticeable upward shift of the loss peak. The TMA curves showed that grafting with poly(MAA) resulted in a higher extent of fiber contraction from room temperature to about 250°C. Moreover, the intensity of the final contraction step at about 350°C decreased with increasing weight gain and shifted to a lower temperature. The Raman spectra of grafted fibers were characterized by overlapping of the characteristic lines of both silk fibroin and polymer, the latter showing an intensity proportional to the amount of weight gain. Among the conformationally sensitive vibrational modes of tussah silk fibroin, the amide III range was significantly modified by grafting with both poly(MAA) and poly(HEMA). © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:1393–1403, 1998     

Metal ion permeation properties of silk fibroin/chitosan blend membranes

Silk fibroin/chitosan (SF/CS) blend membranes were prepared and characterized by infrared spectroscopy (FTIR), thermogravimetric analysis (TGA) and scanning electron microscopy. It was found that SF and CS were compatible in the blend membranes and that the membranes were dense without microscopic phase separation. Swelling experiments showed that the swelling ratio of the blend membranes increased with CS content and reached the highest value when CS content was 70 wt%. Experiments indicated that the permeability coefficient of K⁺ through the blend membrane was 2–4 times higher than that of pure CS membrane, and 10 times higher than that of pure SF membrane. The permeation rate of K⁺ increased linearly with CS content in the blend membrane for the lower concentration feeding solution. For different metal ions, the permeability through SF/CS blend membranes was in the sequence K⁺ > Ca²⁺ > Cd²⁺ > Pb²⁺ > Cu²⁺ > Ni²⁺. Copyright © 2006 Society of Chemical Industry     

Optothermal properties of fibers. IX. Study changes of optical parameters by multiple-beam technique due to thermal annealing for natural silk fibers

Multiple-beam Fizeau fringes were used for studying the effect of the annealing process on the refractive indices and birefringence of natural silk fibers (best yellow Italian silk, Ford & Co. Ltd). Silk fibers were annealed at a constant time of 2 h with different annealing temperatures ranging from 60 to 160 ± 1°C. A scanning electron microscope was used for measuring the cross-sectional shape and a longitudinal view of the natural silk fibers. The Becke-line method was used for measuring the skin refractive indices and the birefringence of the natural silk fibers. The thermal coefficient of the refractive index, Cauchy dispersion constants, dispersive power, dielectric constant at infinity, polarizability per unit volume, isotropic polarizability, and isotropic refractive index were determined interferometrically. Microinterferograms and curves are given for illustration. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 1495–1504, 1998     

Studies on sorption isotherm models of ion exchange modified acrylic fibers

The sorption behavior, favorability, shape and thermodynamic parameters of Cu(II), Ni(II), Pb(II), and Fe(III) ions sorption onto the ion exchage acrylic fiber were studied by applying Langmuir, Freundlich, Dubinin‐Radushkevich and Redlich–Peterson models. Analytical studies from sorption isotherms proved that sorption process follows mono layer adsorption mechanism. Gibbs free energy was spontaneous for all interactions. The adsorption processes all exhibited endothermic enthalpy values and were accompanied by increasing in entropy. The activation energies for the sorption of metal ions on aminated acrylic fiber were at the same order of magnitude as the activation energy of ion exchange. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Metal ion binding properties of poly(N-vinylimidazole) hydrogels

The ability of poly(N-vinylimidazole) hydrogels to bind Cu(II), Co(II), Ni(II), Zn(II), Cd(II), Pb(II), Hg(II), Na(I) and Ca(II) cations, as well as uranyl, vanadium, rhenium, and molybdenum complexes, was studied by a batch equilibrium procedure using atomic absorption spectroscopy and UV-Vis spectrophotometry. The optimum pH for ion adsorption was determined in any case. The influence of the crosslinking degree of the hydrogel on the sorption kinetics and the sorption capacity at equilibrium were also studied. Sorption from the binary mixture Cu(II) + U(VI) was also analyzed at the optimum pH. Elution of the ions adsorbed from single and binary solutions was achieved in all cases. A selective desorption of loaded hydrogels with two types of ions was attained. The general conclusion is that poly(N-vinylimidazole) hydrogels are excellent materials for retention of all the ions studied here [except for Pb(II), Na(I), and Ca(II)]. The elution, which can be selective, allows regeneration of the hydrogel. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:1109–1118, 1998     

Preparation and metal ion adsorption properties of the resin containing sulfonic acid groups

In this study, we explored a new ion exchange material synthesized by radical polymerization of styrene and 2‐acrylamido‐2‐methyl‐1‐propane sulfonic acid by using 2,2′‐azo‐isobutyronitrile (1 mol %) and divinylbenzene (0.5 mol %) as initiator and crosslinking reagents, respectively. The resin was obtained from a large excess (90%) of styrene in the feed. The yield was 72.3%. The resin was completely insoluble in water and characterized by elemental analysis, FTIR spectroscopy, scanning electron microscopy, and thermal analysis. The metal ion retention capability was investigated for Ag(I), Hg(II), Cd(II), Zn(II), Pb(II), and Cr(III). The effect of pH, time, and resin/metal ion mol ratio on the metal ion retention was studied. Selectivity of the resins from a mixture of metal ions and the maximum retention capacity at optimum pH were also determined. The recovery of the resin by using 1 and 4 M HClO₄ and HNO₃ demonstrated that it is possible to recover the resin above 80%. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1230–1235, 2003     

Absorption of metal cations by modified B. mori silk and preparation of fabrics with antimicrobial activity

Silk fabrics were modified by treatment with tannic acid (TA) solution or by acylation with ethylenediaminetetraacetic (EDTA) dianhydride. Kinetics of modification with TA and acylation with EDTA–dianhydride was investigated. The physico‐mechanical properties of silk fabrics acylated with EDTA–dianhydride remained unchanged regardless of chemical modification. The absorption of metal cations (Ag⁺, Cu²⁺) by untreated and modified silk fabrics was studied as a function of the kind of modifying agent, weight gain, and pH of the metal solution. The absorption of Cu²⁺ at alkaline pH was not significantly influenced by chemical modification of the silk substrate. The absorption of Ag⁺ by acylated silk remained at a level as low as untreated silk, while was enhanced by TA. The higher the content of TA, the higher the absorption of Ag⁺. With respect to the pH of the metal solution, the acylation with EDTA–dianhydride enabled silk to absorb and bind metal cations even in the acidic and neutral pH range, where tannic acid had no effect. Medium to high levels of metal desorption were exhibited by untreated and modified silk fabrics towards the metal cations, with the only exception of the silk–tannic acid–Ag complex, which displayed an extraordinary stability. All metal‐containing silks exhibited significant antibacterial activity. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 297–303, 2001     

Novel water‐soluble acryloylmorpholine copolymers: Synthesis,characterization, and metal ion binding properties

Poly(4‐acryloylmorpholine), poly(4‐acryloylmorpholine‐co‐2‐acrylamido‐2‐methyl‐1‐propane sulfonic acid), and poly(2‐acrylamido‐2‐methyl‐1‐propane sulfonic acid) were synthesized by radical polymerization. The water‐soluble polymers obtained, containing tertiary amino, amide, and sulfonic acid groups, were investigated, in view of their metal binding properties, as polychelatogens by using the liquid‐phase polymer‐based retention technique, under different experimental conditions. The metal ions investigated were Ag(I), Cu(II), Co(II), Ni(II), Cd(II), Pb(II), Zn(II), Cr(III), and Al(III). © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 180–185, 2006     

Tensile stress–strain and recovery behavior of Indian silk fibers and their structural dependence

The tensile stress–strain and recovery behavior of all the four commercial varieties of Indian silk fibers, namely Mulberry, Tasar, Eri, and Muga, have been studied along with their structures. Compared to the non‐Mulberry silk fibers, Mulberry silk fiber is much finer and has crystallites of smaller size, higher molecular orientation, and a more compact overall packing of molecules. These structural differences have been shown to result in (1) the presence of a distinct yield and a yield plateau in non‐Mulberry silk and their absence in Mulberry silk, and (2) relatively higher initial modulus and tenacity along with lower elongation‐to‐break and toughness and superior elstic recovery behavior of mulberry silk compared to non‐Mulberry silk. It is also observed that fine silk fibers have a relatively more ordered and compact structure with higher orientation compared to their coarse counterparts, and this gives rise to higher initial modulus and higher strength in the finer fibers. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2418–2429, 2000     

Adsorption behavior of copper(II) ion from aqueous solution on methacrylic acid‐grafted poly(ethylene terephthalate) fibers

The adsorption behavior of methacrylic acid‐grafted poly(ethylene terephthalate) fibers was studied toward the copper(II) ion in aqueous solutions by a batch equilibriation technique. The influence of treatment time, temperature, pH of the solution, metal ion concentration, and graft yield were considered. One hour of adsorption time was found sufficient to reach adsorption equilibrium for the copper(II) ion. It was found that the adsorption isotherm of Cu(II) fits Langmuir‐type isotherms. The adsorption process is not affected by the temperature when treated with low ion concentration, but is remarkably decreased at a high ion concentration. The heat of adsorption value was calculated as 0.71 kcal/mol. It was found that the reactive fibers are stable and regenerable by acid without losing their activity. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 766–772, 2000     

Characterization of microvoids in mulberry and tussah silk fibers using stannic acid treatment

To investigate the volume, size, and number of microvoids in mulberry and tussah silk fibers, stannic acid gel was used as a contrasting medium to the small-angle X-ray scattering (SAXS). The influence of the stannic acid treatment on the structure of silk fibers was first investigated by using the wide-angle X-ray diffraction prior to characterization of the microvoids. The changes in crystallite size and degree of orientation with increasing stannic acid gel fraction in fibers are investigated, and it was found that the stannic acid treatment does not cause serious changes in crystallite size and degree of orientation. The changes in crystallinity indices were observed when the volume fractions of stannic acid gel in the fibers exceeded about 10%. Thus, it was confirmed that the structure of silk fibers was retained in the region of the stannic acid gel fraction less than 10%. SAXS measurements revealed that the number and the fraction of the microvoids are larger, while the sizes of the microvoids are smaller, for the mulberry silk fibers compared with the tussah silk fibers. The fraction macrovoids, however, is considered to be larger for the tussah silk fibers. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 363–367, 1999     

Synthesis of 1,4,8,11‐tetraazacyclotetradecane monomer by addition of acryloyl chloride and its polymer for specific transition metal binding

1,4,8,11‐Tetraazacyclotetradecane (cyclam) was reacted with acryloyl chloride in a 1 : 2 molar ratio in dichloromethane in the presence of pyridine at 0°C. The modified cyclam was polymerized by adding an azobisisobutyronitrile initiator and irradiated with a UV lamp under reflux for 6 h. Precipitated cyclam containing polymer in the bulk structure was removed from the suspension by filtration. After washing and drying the final polymeric materials were used for transition metal ion adsorption and desorption studies. A Fourier transform IR spectrophotometer and thermogravimetric analyzer were used to characterize the polymeric structure. The affinity of the polymeric material for transition metal ions was used to test the adsorption–desorption of selected ions [Cu(II), Ni(II), Co(II), Cd(II), Pb(II)] from aqueous media containing different amounts of these metal ions (5–800 ppm) at different pH values (2.0–8.0). It was found that the adsorption rates were high and the adsorption equilibrium was reached in about 30 min. The uptake of the transition metal ions onto the polymer from solutions containing a single metal ion was 3.17 mmol/g for Cu(II), 0.98 mmol/g for Cd(II), 0.79 mmol/g for Co(II), 0.78 mmol/g for Ni(II), and 0.32 mmol/g for Pb(II). This polymer showed high affinity for Cu(II) compared to the other metal ions in the single ion solution and in the mixture of transition metal ions. The affinity order of the transition metal ions was Cu(II) ? Ni(II) > Cd(II) > Co(II) > Pb(II) for competitive adsorption. More than 95% of the adsorbed transition metal ions were desorbed in 2 h in a desorption medium containing 1.0M HNO₃. Poly(cyclam) was found to be suitable for repeated use of more than five cycles without a noticeable loss of adsorption capacity. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1406–1414, 2002     

混合金属离子定量萃取分离时酸度范围的探讨

提出了混合金属离子定量萃取分离时酸度范围的简便计算方法,并应用于双硫腙-CC l4溶液定量萃取分离Hg2+和Zn2+体系,所得计算结果与实验值一致。     

Compatibilization of acrylic polymer–silk fibroin blend fibers: 2. Morphology and mechanical properties of the compatilized blend fibers

Three synthesized acrylonitrile-graft-silk fibroin copolymers (AN-g-SF), denoted as COP-65, COP-87, and COP-106, were used as potential compatilizers for acrylic polymer–silk fibroin blend fibers. Due to their different molecular weights and architecture, the compatibilizing efficiency is in the order of COP-106 > COP-65 > COP-87. To maintain the “sheath-core” structure of the blend fiber, COP-65 was chosen as the compatilizer. It was found that the addition of a small amount of COP-65 (up to 2 wt %) results in finer and more even distribution of the SF fibrils. On the contrary, excess COP-65 will cause flocculation and coalescence of the SF phase. Similarly, mechanical properties are enhanced with an optimum amount of the compatilizers. However, when excess COP-65 is added, the mechanical properties of the blend fibers are even worse than that of the uncompatilized samples. The mechanism of these findings is also discussed. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2255–2264, 1999     

First-principles investigation of elastic and electronic properties of double transition metal carbide MXenes

We use first-principles-based density functional theory (DFT) calculations to investigate the structural, elastic, and electronic properties of various pristine and oxygen (O)-functionalized double transition metal (DTM) MXenes with general formulas of M₂′M′′C₂ and M₂′M′′C₂O₂, where M′ = Mo, Cr and M′′ = Ti, V, Nb, Ta. The dynamic stability of the DTM MXenes are assessed and elastic stiffness constants (C_ij) are used to investigate the mechanical stability and properties of the compositions. The calculated elastic properties of the pristine Mo-based MXenes are found to be superior compared to Cr-based compounds. Furthermore, the O-functionalized MXenes exhibit improved in-plane elastic constants, Young's moduli, and shear moduli compared to their pristine counterpart. We observe that the hybridization of the energy states results in stronger covalent interactions as such increased elastic properties for the M₂′M′′C₂O₂ MXenes. Ashby plot clearly demonstrates superior materials properties of O-functionalized Mo-based DTM MXenes compared to other commonly known two-dimensional materials. All the MXenes exhibit metallic character evident from the density of states (DOS) calculations. Additionally, the work functions are studied and the calculated values are higher in the case of O-functionalized MXenes. Overall, this work will be a guide for future investigations on the mechanical properties of DTM MXenes for their targeted applications in structural nanocomposites.     

Preparation of metal‐containing protein fibers and their antimicrobial properties

Bombyx mori silk, Antheraea pernyi silk, and wool fibers were chemically modified by treatment with tannic acid (TA) or by acylation with ethylenediaminetetraacetic (EDTA) dianhydride. Kinetics of TA loading or acylation with EDTA‐dianhydride varied from fiber to fiber. B. mori silk and wool displayed the highest weight gains with TA and EDTA‐dianhydride, respectively. The uptake of different metal ions (Ag⁺, Cu²⁺, Co²⁺) by protein fibers, either untreated or chemically modified, was studied as a function of weight gain and pH of the aqueous metal solution. Below pH 7, absorption of metal ions by untreated and TA‐treated fibers was negligible. Acylation with EDTA‐dianhydride enabled protein fibers to absorb and bind significant amounts of metal ions in the acidic and neutral pH range. The levels of metal desorption at acidic pH depended on the fiber‐metal combination. Untreated protein fibers usually displayed the lowest stability of the metal complex. Metal complexes with protein fibers exhibited prominent antimicrobial activity against the plant pathogen Cornebacterium. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 638–644, 2003