Diffusion behavior of reducing agents into keratin fibers using microspectrophotometry

To investigate the penetration of thioglycolic acid (TG), thiolactic acid (TL), and L ‐cysteine (CYS), into keratin fibers, cross‐sectional samples of virgin white human hair treated with TG, TL, and CYS were prepared. A new method for analyzing the diffusion behavior of reducing agents into human hair was developed. The diffusion pattern of reducing agents into human hair, which cannot be determined by optical microscopy, can be determined by the method developed. The method involves treating virgin hair fibers with TG, TL, and CYS. After the treatment, the cross‐sectioned hair samples were dyed with methylene blue and the cross‐sectional intensity scans were measured at a wavelength of 664 nm (λ_max of methylene blue) with a microspectrophotometer. The three different diffusion patterns from the three reducing agents were obtained. The penetration of TG and TL into virgin human hair clearly increased by increasing the treatment time and pH. On the other hand, the penetration of CYS was less than TG and TL (CYS could not penetrate into the cortex region of the virgin human hair). Also, the diffusion pattern of TG showed Fickian type characteristics. The apparent diffusion coefficient of TG into human hair at pH 9.0 determined from the TG concentration profile was found to be 10^?9 cm²/s. On the other hand, the apparent diffusion coefficient of TG into human hair at pH 7.0 was 10^?10 cm²/s, and thus, the apparent diffusion coefficient of TG depended on the pH of the TG solution. From these experiments, we have concluded that the diffusion patterns of the three reducing agents in this study depended on the electrostatic interaction between the human hair and the reducing agents. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1131–1138, 2004     

The kinetics and mechanism of cure of an amino-glycidyl epoxy resin by a co-anhydride as studied by FT-Raman spectroscopy

The thermal curing behavior of tetraglycidyl-4,4′-diaminodiphenylmethane (TGDDM) and a co-anhydride mixture consisting of maleic anhydride (MA) and hexahydrophthalic anhydride (HHPA) was studied from 55 to 100 °C by real-time FT-Raman spectroscopy. The quantitative changes in concentrations of anhydride, epoxy, and new-formed ester were measured and empirical reaction rate curves were constructed reflecting the kinetics of the curing process. After an induction period a simple kinetic scheme that is first order in both epoxy and anhydride monomer consumption described the reaction profile until the reaction was influenced by chemo-rheological changes due to vitrification transition.FT-Raman analysis revealed that curing propagation mainly occurs by polyesterification between epoxide and anhydride. Possible side reactions including the homopolymerization of MA are considered. The main side reaction is decarboxylation of MA that may produces some autocatalysis, but this is a minor contribution to the kinetics of cure. No conclusive evidence has been found for homopolymerization of MA or initiation of the curing reaction by the reaction product of TGDDM and MA, compared to the polyesterification.     

Diffusion behavior of poly(ethylene imine) into keratin fibers using microspectrophotometry

In order to investigate the diffusion behavior of poly(ethylene imine) (PEI) into keratin fibers, cross‐sectional samples of bleached white human hair treated with PEI were prepared. We were successful in developing a method for analyzing the diffusion behavior of PEI into human hair, which to our knowledge is a first. The diffusion pattern of PEI into human hair, which cannot be determined by optical microscopy, can be determined by our method. After the treatment, the cross‐sectioned hair samples were dyed with Orange II and the cross‐sectional intensity scans were measured at a wavelength of 487 nm (λ_max of Orange II) with a microspectrophotometer. In our method, the diffusion pattern of PEI at pH 11.1 showed Fickian type characteristics. This suggests that the diffusion coefficient of PEI is essentially independent of the PEI concentration. By calculating the diffusion coefficient from the PEI concentration profile, the diffusion coefficient of PEI [number‐average molecular weight (M_n) = 300 and 600] into the bleached human hair was found to be on the order of 10^?10 cm²/s. In addition, the diffusion coefficient of PEI (M_n = 600) with urea added increased twofold in comparison with that of PEI without urea added. This experiment demonstrated that urea acts as a penetration accelerator for PEI. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 65–71, 2005     

New method of dyeing keratin fibers using poly(ethylene imine) and its coloring mechanism

To improve the colorability of keratin fibers at lower temperatures, we developed a novel coloring method using poly(ethylene imine) (PEI) as a counterion reagent (human hair was treated beforehand with a PEI solution and then was colored with an acid dye). As a result of this new method, the coloring and color fastness to shampooing clearly improved with respect to the usual method. Next, to study the coloring mechanism with PEI, we investigated the penetration of PEI and Orange II into bleached human hair by optical microscopy. The results showed that the penetration of PEI and Orange II into bleached human hair increased with an increasing PEI treatment time and with a decreasing PEI molecular weight. With these experiments, we demonstrated that PEI, which penetrated the cortex region, exerted counterionization on Orange II, thereby increasing the penetration of Orange II into bleached human hair. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3806–3810, 2003     

Estimating crystallinity in high density polyethylene fibers using online Raman spectroscopy

Online Raman spectra, obtained at different points along the spin line during pilot‐scale nonisothermal melt spinning of high density polyethylene (HDPE) fibers, are presented for the first time. The fraction of the crystalline phase corresponding to each spectrum was determined from the normalized integrated intensity of the 1418 cm^?1 Raman band. It is well established that this band represents the orthorhombic crystalline phase in polyethylene. The estimates of percent crystallinity obtained from decomposition of the Raman spectrum were compared with the percent crystallinity from differential scanning calorimetry (DSC) measurements. It is concluded that online Raman spectroscopy can be successfully used to monitor the development of crystallinity in HDPE fibers as a function of distance from the spinneret. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 545–549, 2003     

Raman spectroscopic analysis of L‐phenylalanine and hydrolyzed eggwhite protein penetration into keratin fibers

To investigate the penetration of amino acids and hydrolyzed protein derived from eggwhites (HEWP) into keratin fibers, the structure of cross‐sectional samples at various depths of virgin white human hair treated with L ‐phenylalanine (Phe) and bleached black human hair treated with HEWP was directly analyzed without isolating the cuticle and cortex using Raman spectroscopy. The hydrophobic amino acids clearly penetrated into the virgin white human hair, while hydrophilic amino acids did not penetrate at all. The Phe hydrophobic amino acid content at various depths of the virgin white hair increased by performing the Phe treatment (at 50°C for 16 h), indicating that Phe deeply penetrated into the virgin human hair. Also, the disulfide (? SS? ) and random coil contents at various depths of the bleached human hair increased by performing the HEWP treatment, indicating that HEWP also deeply penetrated into the bleached human hair. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Study of the structure transformation of wool fibers with Raman spectroscopy

Raman spectroscopy and tensile tests were used to investigate the structure transformation of stretched wool fibers with stretching ratios up to 110%. The typical bands analyzed in this article included the amide I region, the amide III region, the C? C skeletal vibration region, and the S? S and C? S bond vibration region. To investigate the variations of the crystallinity and orientation of the wool fibers, the density and birefringence of the fibers were also measured. The results showed that the secondary structure of the wool fibers was transformed from an α‐helical structure to a β‐pleated‐sheet structure during the early stage of stretching. When the fiber was stretched more than 80%, the mechanism of stretching mainly relied on the slippage of the peptides. Meanwhile, the pretreatment of the wool fibers with sodium bisulfite and the setting processing resulted in the reduction of the concentration of the S? S bonds. The results for the density and birefringence showed that the degree of crystallinity of the wool fibers decreased, whereas the degree of orientation increased during the stretching. The tensile behavior of the stretched wool also supported the α→β microstructure transformation. The diameter results showed that the extent of slenderization was about 25.3% when the stretching ratio was 80%. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1–7, 2007     

Chemical modification of keratin fibers using 2‐iminothiorane hydrochloride

For the purpose of improving the properties of keratin fibers by chemical modification, we attempted to introduce new disulfide (–SS–) groups into hair using 2‐iminothiorane hydrochloride (2‐IT). After the evaluation of the setting ability of human hair, the waving permanence (66%) of our proposed permanent hair‐setting process clearly improved compared with that of a conventional permanent hair‐setting process (48%). Next, it became clear that new –SS– groups were created in the human hair samples as a result of introducing and then oxidizing new –SH groups. This –SS– content in the hair samples was estimated by employing FT‐Raman spectroscopy. By examining the Raman bands of the treated and untreated hair, it was seen that each band of treated hair did not change, except for the increase of the –SS– groups. This suggests that hair damage does not occur as a result of the investigated treatment. From these experiments, the chemical modification of keratin fibers using 2‐IT was clearly effective for a permanent hair‐setting process. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3646–3651, 2003     

Effect of processing conditions on crystallization behavior and mechanical properties of poly(lactic acid) staple fibers

Within this study, the applicability of Raman spectroscopy to characterize the crystallinity of PLA staple fibers was evaluated. The influence of the fiber alignment on the possibility to detect crystallinity by using Raman spectroscopy was studied. PLA staple fibers were produced by melt spinning by varying both draw temperature and draw ratio. Systematic interrelationships between the processing parameters of PLA staple fibers and the degrees of crystallinity and the cold crystallization enthalpies were established. Raman spectroscopy showed that the carbonyl stretching band of Raman spectra measured in fiber axis and parallelly polarized was not sensitive to detect crystallinity. However, for perpendicularly polarized measurements, a higher sensitivity was observed. With increasing degree of crystallinity, a reduction of the band width of the normalized carbonyl stretching band was found. The morphology affected the mechanical properties significantly. Increased draw ratio resulted in increased tensile strength and decreased elongation at break. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42432.     

Positron annihilation spectroscopy of polyacrylonitrile-based carbon fibers embedded with multi-wall carbon nanotubes

Polyacrylonitrile (PAN)-based carbon fibers, embedded with multi-wall carbon nanotubes (MWCNT) in different concentrations, have been prepared by an electrospinning technique and investigated using scanning electron microscopy, Raman, and positron annihilation spectroscopy. An analysis of the positron lifetime and Doppler broadened spectral line shape has been made. Positron lifetime spectra for all the samples give best fit for three distinct lifetime components. Raman data has been used to estimate the sp² mole fraction in the fiber. It is found that the gradual changes incorporated in the fiber due to the addition of MWCNTs are reflected as well defined changes in the positron lifetime and the S parameter of the Doppler broadened spectral line. Annihilation parameters are discussed from the point of view of formation of distinct positron trapping sites in the form of vacancy type defects at the interfaces of MWCNTs and the PAN matrix, and their variations in concentration due to different amount of MWCNTs added.     

Surface composition of carbon fibers subjected to oxidation in nitric acid followed by oxygen plasma

Type II, PAN-based carbon fibers (unsized and commercially treated) have been exposed to nitric acid and oxygen plasma individually and also to combined nitric acid/oxygen plasma treatments and the surface compositions have been determined using angle-resolved X-ray photoelectron spectroscopy (ARXPS) and ion scattering spectroscopy (ISS). Most of the oxygen on the as-received carbon fibers resides within the outermost 10-15 Å of the surface. Fiber exposure to nitric acid at 115°C for 20-90 min enhances the oxygen surface concentration to a point of saturation and the oxygen depth distribution is increased and becomes more uniform within the maximum XPS sampling depth (~60-100 Å). In addition, the fiber surface area is believed to be increased. After treating fibers to various degrees in nitric acid, subsequent exposure to oxygen plasma yields an additional increase in the surface oxygen content, particularly in the outermost fiber layers (10-15 Å). Under the conditions of the investigation, the maximum amount of surface oxidation occurs after sequential fiber exposure to nitric acid at 25°C for 30 s and oxygen plasma. As the extent of initial nitric acid treatment is increased, the synergism with subsequent plasma oxidation decreases, and the oxygen concentration becomes more uniform within the outer layers of the oxidized fibers. Overall, the data are consistent with a proposed oxidation mechanism in which oxygen plasma acts to enhance the surface density of oxygen on roughened and pitted nitric acid-oxidized fiber surfaces. As the duration of nitric acid exposure is increased, it is hypothesized that subsequent exposure to oxygen plasma smoothes the fiber surfaces but the surface density of oxygen remains essentially constant.     

Electrospinning of gelatin fibers using solutions with low acetic acid concentration: Effect of solvent composition on both diameter of electrospun fibers and cytotoxicity

Gelatin fibers were prepared by electrospinning of gelatin/acetic acid/water ternary mixtures with the aim of studying the feasibility of fabricating gelatin nanofiber mats at room temperature using an alternative benign solvent by significantly reducing the acetic acid concentration. The results showed that gelatin nanofibers can be optimally electrospun with low acetic acid concentration (25%, v/v) combined with gelatin concentrations higher than 300 mg/mL. Both gelatin solutions and electrospun gelatin mats (prepared with different acetic acid aqueous solutions) were analyzed by Fourier transform infrared spectroscopy and differential scanning calorimetry techniques to determine the chemical and structural changes of the polymer. The electrospun gelatin mats fabricated from solutions with low acetic acid content showed some advantages as the maintenance of the decomposition temperature of the pure gelatin (～ 230°C) and the reduction of the acid content on electrospun mats, which allowed to reach a cell viability upper than 90% (analyzed by cell viability test using human dermal fibroblast and embryonic kidney cells). This study has also analyzed the influence of gelatin and acetic acid concentration both on the solution viscosity and the electrospun fiber diameter, obtaining a clear relationship between these parameters. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42115.     

Comparison of different methods for lignin determination as a basis for calibration of near-infrared reflectance spectroscopy and implications of lignoproteins

Three commonly employed methods for lignin determination, i.e., the thioglycolic acid (TGA), the acetylbromide (AB), and the acid detergent fiber (ADF) method, were compared using leaves and xylem tissue from five species (Nicotiana tabacum, Populus x canescens, Fagus sylvatica. Quercus robur, and Picea abies). In each case, cell walls were isolated before lignin determination. Each of the three methods estimated a different lignin concentration in a given tissue, except for spruce wood. The lignin concentration determined with the AB method was strongly dependent on whether or not the cell walls were subjected to alkaline hydrolysis to remove covalently bound aromatic nonligneous components before lignin determination. Lignin concentrations determined in hydrolyzed cell walls of different tissues and species by the AB method showed a good correlation with those obtained by the TGA method and, thus, were convertible. In contrast, gravimetrically estimated ADF lignins did not or only moderately correlate with lignins measured with methods based on the UV absorbance of the solubilized lignin degradation products. Leaves of a given species generally contained higher ADF-lignin concentrations than the corresponding stem tissue. Both ADF and TGA lignin data of beech were used to calibrate near-infrared reflectance spectra (NIRS) for lignin prediction. Both NIRS calibration procedures gave good statistical fits with correlation coefficients close to 1, indicating that TGA and ADF lignin concentrations of beech can be estimated by NIRS with high accuracy. However, the two calibrations were based on different empirical terms, showing that TGA and ADF lignins did not share the same physical basis for calibration. C/N analysis revealed the presence of 3.1 and 1.4% nitrogen in ADF lignins of beech leaves and wood, respectively. The major fraction of this nitrogen was recovered in amino acids, which corresponded to 14% and 3% protein in ADF lignins of leaves and wood, respectively. These results show that ADF lignins contain significant concentrations of lignin-bound proteins, which renders this method unsuitable to determine genuine lignin.     

Influence of urea on the coloring ability of a low‐temperature coloring method of keratin fibers using polyethyleneimine

For the purpose of improving the coloring ability of keratin fibers at a lower temperature, we investigated the influence of urea on the coloring ability of a low‐temperature coloring method using polyethyleneimine (PEI) as a counter ion reagent (the human hair was previously treated with a PEI solution, and then was colored with acid dye). The coloring and color fastness to shampooing of the hair pretreated with a PEI solution containing urea clearly improved compared with those pretreated with a PEI solution not containing urea. Also, we prepared cross‐sectional samples of the treated hair and investigated the penetration of PEI and Orange II into human hair by optical microscopy. The results showed that the penetration of PEI and Orange II into human hair pretreated with a PEI solution that contained urea clearly increased compared with those pretreated with a PEI solution that did not contain urea. From these experiments, we concluded that urea acts as a penetration accelerator for PEI; and PEI, which penetrates deeper into human hair by adding urea, exerts counter ionization on Orange II, thus increasing the penetration of Orange II into human hair and thereby improving the coloring ability. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3827–3834, 2004     

Reduction of aging tendency in p‐aramide fibers using ultrasound

The impact of ultrasound pretreatment of p‐aramide fibers is investigated to reduce negative effects of fiber aging induced by artificial white light (Suntest), as well as by sunlight and weathering. The investigations indicate that such a pretreatment has a beneficial influence in reducing the aging tendency of the fibers. The ultrasound pretreatment reduces strength losses due to aging in a natural environment by up to 40%, and as much as 60% in artificial environment. A positive impact of the duration of ultrasound treatments is also established in assessing the resistance of p‐aramide fibers to aging. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2340–2345, 2000     

Structure of heat-treated Nylon 6 and 6.6 fibers. I. The shrinkage mechanism

Nylon 6 and 6.6 fibers were submitted to thermal annealing in a wide range of temperatures (below and above their glass transition temperatures) under inert atmosphere and slack condition, allowing free shrinkage. The structural changes due to the heat settings were analyzed by several techniques (differential scanning calorimetry analysis, wide- and small-angle X-ray scattering, and birefringence). The results revealed different recrystallization responses of the fibers to the applied thermal annealings and consequently different shrinkage mechanisms. In the recrystallization of the Nylon 6 fibers were involved a generation of nuclei crystallites in the interfibrillar regions, as well as growth and perfection of these new crystallites and preexisting ones. But, recrystallization of the Nylon 6.6 fiber was accompanied only by growth and perfection of the preexisting crystals. The existence of the nuclei crystallites at temperatures of heat treatments above 120°C was the major commanding factor for the Nylon 6 fiber to undergo less shrinkage than the Nylon 6.6 fiber. These very tiny crystallites worked as crosslinking points that would impose restrictions in the mobility of the chains segments, inhibiting subsequent disorientation of the amorphous regions and consequently intense shrinkage, thus resulting in recrystallization in a preferred direction of the fiber axis. The Nylon 6.6 fiber experienced an instantaneous shrinkage at the annealing temperature around 70°C. That was the temperature necessary to release its hydrogen bonds and the starting temperature for presenting its major structural changes, including global disorientation of the amorphous and crystalline regions. Thus, its recrystallization occurred with no preferred orientation. Also, it was suggested that the occurrence of so different shrinkage mechanisms reside in the different crystalline morphology that these fibers originally possessed before the heat treatments. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 441–452, 1998     

Diffuse reflectance Fourier transform infrared spectroscopy of oleic acid adsorption on silicic acid

Diffuse reflectance Fourier transform infrared spectroscopy was used to observe adsorption complexes of oleic acid and isopropanol (IPA) on silicic acid in hexane. The spectra provide definite evidence of the molecular nature of the surface interaction. In addition, the effect on oleic acid adsorption of modifying the solvent with IPA, which competes for adsorption sites and modifies the solvent polarity, was studied. Oleic acid adsorption was reduced in the presence of an equimolar IPA concentration in hexane, relative to that from hexane alone. This could be explained by a combination of competitive adsorption of IPA and IPA interacting with oleic acid in solution. IPA, in solution, and silica are probably competing for the lipid. This is additional evidence that suggests that lipid adsorption onto silicic acid is influenced by competitive adsorption. The adsorption of oleic acid and IPA, from a mixture of the two in hexane, was controlled by (i) the equilibrium between surface-bound species and molecules in solution and (ii) the polar interaction between oleic acid and IPA in solution. Thus, washing pre-bound oleic acid with hexane removed only a small amount of oleic acid, while washing with a solution of IPA in hexane removed most of the pre-bound oleic acid.     

芳香族聚噁二唑纤维的酸老化行为及降解机理研究

研究了芳香族聚-1,3,4-噁二唑(POD)纤维浸泡于不同酸溶液中的力学性能和表面形貌的变化,表征了酸老化前后POD纤维的聚集态结构与分子结构,探讨了POD纤维的酸老化机理.结果表明:POD纤维力学性能在体积分数30％的硫酸溶液中下降最快,在硝酸溶液中老化最严重;POD纤维老化后线密度变大,温度越高,力学性能下降越快;...     

Coimmobilization of malic enzyme and alanine dehydrogenase on organic–inorganic hybrid gel fibers and the production of L‐alanine from malic acid using the fibers with coenzyme regeneration

Malic enzyme (EC 1.1.1.39) and alanine dehydrogenase (EC 1.4.1.1) were entrap‐immobilized on hybrid gel fibers of cellulose acetate (CA) and zirconium (Zr) alkoxide by air‐gap wet spinning. The production of L ‐alanine from malic acid with coenzyme regeneration was examined with the enzymes immobilized on the fibers. The productivity of L ‐alanine of the immobilized enzymes decreased to approximately one‐fifth of that of free enzymes, but the CA–Zr‐fiber‐immobilized enzymes retained a high level of productivity after repeated use. Reduced form of nicotinamide adenine dinucleotide (NADH) recycling also occurred effectively for the enzymes immobilized on the fiber. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010