• Journal of Conservation Science
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• v.36 no.1
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• pp.1-14
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• 2020

This study investigates the crystallinity distribution of ancient silk. Owing to the inherent multi-hierarchical structure of silk protein and the complicated structural changes that occur due to various burial environments, it is challenging but worthwhile to study ancient silk ageing behavior, which is based on the fact that ageing begins with a single fiber and then spreads to a whole fabric. Crystallinity was one of the most effective indicators found to reveal the ageing status of silk. Therefore, a synchrotron radiation-based X-ray diffraction(SR-XRD) method was employed to study the crystallinity distribution of single fibers of ancient silk unearthed from seven archaeological sites in China from historical periods including the warring states, Han dynasty, Song dynasty, and Ming dynasty. In comparison, the conventional X-ray diffraction method, which uses large amounts of samples, was also performed to determine the integral crystallinity of ancient silk. Thermal stability experiments by thermogravimetry(TG) as well as morphology observations by scanning electron microscopy(SEM) and optical microscopy(OM) all confirmed the deterioration of ancient silk. Moreover, the ageing mechanism of ancient silk was proposed with the assistance of an artificial ageing study. The results confirmed the effectiveness of SR-XRD as an ageing indicator, revealing the crystallinity distribution. This research could provide motivation to determine the deterioration status of ancient silk, and would also aid in explaining the fragility of ancient silk due to ageing.

• Journal of Sericultural and Entomological Science
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• v.35 no.1
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• pp.52-59
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• 1993

Raw silk degumming, by which the sericin and other marterials are eliminated from fibroin, is very essential process to produce silk fabrics. Alkali chemicals and enzymes have been used for the silk-degumming process. In this paper, the effect of heat treatment was investigated on silk fibers degummed by two different methods, soap and enzymatic degumming method. The difference between these two degumming methods was analyzed on the basis of results of mechanical testing, thermal analysis and intrated spectroscopy. The tenacity and the elongation of silk fiber are decreased by the heat-treatment in wet state. This tendency is observed in both cases of two degumming methods. The peak temperature in DSC analysis, which is attributed to thermal decomposition of silk fiber, was shifted to higher value with the heat-treatment temperature for the soap degummed silk fiber, however, it was not for the enzymatic degummed one. The IR crystallinity of soap digummed silk fiber is increased with the heat-treatment temperature, while that of enzymatic degummed fiber is not.

• International Journal of Industrial Entomology and Biomaterials
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• v.26 no.1
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• pp.54-60
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• 2013

The partial degumming of silk has recently attracted researchers' attention because of its ability to produce silk textiles with new tactile properties, intermediate between the softness of fully degummed silk and the hardness of raw silk. However, it is difficult to obtain partially degummed silk in a homogenously degummed state due to the heterogeneous character of sericin removal. It is also difficult to examine the homogeneity of degumming. In the present study, Fourier transform infrared (FTIR) spectroscopy with attenuated total reflection (ATR) geometry was used to evaluate the effect of processing conditions on the degumming of silk yarns. The crystallinity index, calculated from FTIR spectra, showed an increase with the degumming ratio. Therefore, the homogeneity of degumming could be evaluated by the variation of crystallinity index for 30 different spots in silk yarns. The homogeneity of degumming was influenced by the total degumming time, the content of surfactant, and the liquor rate. No effect was observed upon changing the number of degumming cycles at the same total degumming time.

• International Journal of Industrial Entomology and Biomaterials
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• v.28 no.1
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• pp.19-24
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• 2014

Silk has always been one of the most favored textile materials. Fully degummed silk fiber (i.e., silk fibers without sericin) shows better luster than raw silk fiber (with sericin); it is also softer. On the other hand, raw silk fiber feels cooler because of the presence of sericin, making it useful as a textile for the summer season. Recently, partially degummed silk has attracted researchers' attention because it provides better luster, feel, and dyeing properties. However, the partial degumming of silk is very difficult because it results in inhomogeneously degummed fiber. In the present study, silk yarns were degummed with surfactant aqueous solutions and the effects of each surfactant on the degumming ratio, crystallinity, and homogeneity of the degummed silk yarn were examined. The degumming ratio and crystallinity index of silk yarn varied depending on the type of surfactant. On the whole, anionic surfactants resulted in higher degumming ratios and better homogeneity than nonionic surfactants.

• International Journal of Industrial Entomology and Biomaterials
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• v.43 no.1
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• pp.22-28
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• 2021

Natural nonwoven silk fabric has attracted researchers' attention owing to its unique properties as a biomaterial. It is fabricated by reeling, wetting, and hot pressing natural silk filament from silkworm cocoons. In this study, silkworm cocoons were immersed in water at different temperatures for various durations to examine the effects of wet treatment on their crystallinity and morphology. As the treatment temperature and time increased, the cocoon's silk filament separation became more evident, and fibroin strands were observed in it. The crystallinity indexes of the silkworm cocoons increased until a treatment time of 2 h and remained constant thereafter. The increase in the crystallinity index using wet treatment was enhanced by increasing the treatment temperature. Although the weight loss of the silkworm cocoon was insignificant until 40℃, it was appreciable above this temperature, and the degree of weight loss constantly increased with increases in the treatment temperature and time.

• Textile Coloration and Finishing
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• v.6 no.2
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• pp.24-29
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• 1994

In order to investigate the crystallization in silk fibroin induced by acid treatment and its photo-yellowing reduction effect. silk fibroin were immersed in PH 3.5~4.0 sulfuric acid and 0.01N hydro-chloric acid at 2$0^{\circ}C$, and the changes of crystallinity were measured by infrared spectroscopy, X-ray diffraction. Yellowness index caused by UV irradiation were also observed. The results are as follows : 1. ${\beta}$-form transition occurs when the silk fibroin are immersed at 2$0^{\circ}C$ in pH 3.5~4.0 sulfuric acid and 0.01N hydro-chloric acid. Formation of new hydrogenbond in molecules on the amorphous region induced ${\beta}$-form structure, and increased crystallinity. 2. Crystallization owing to $\beta$-form transition reduced the initial yellowness index by ultraviolet irradiation.

• Journal of Sericultural and Entomological Science
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• v.37 no.2
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• pp.142-153
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• 1995

This study is undertaken to investigate proper condition and dissolution method of silk fibroin to use it functional material as powder or membrane. Silk fibroin was dissolved with calcium chloride ethanol aqueous solution and hydrochloric acid. When silk fibron was dissolved with calcium chloride ehanol aqueous solution, main chain of silk fibroin was degradaded and molecular conformation was changed. Silk fibroin powder was made from silk fibroin solution. It showed lower thermal decomposition temperature and crystallinity than those of native silk fibroin. And Its molecular conformation was random coil structure. By acid gydrolysis, main chain of silk fibroin was attacked randomly. Silk fibroin powder from hydrolysate showed high crystallinity and thermal decomposition temprature. $\beta$-form molecular conformation was found by IR and X-ray diffraction. Silk fibroin powder form dissolved part with hydrochloric acid showed low thormal decomposition temperature but high crystallinity. During acid hydrolysis, transition of molecular structure of silk fibroin occurred, and it changed to $\alpha$-helix. Silk fibroin film was achieved by casting silk fibroin solution by ehanol solution or saturated vapor treatment, and its molecular conformation changed to $\beta$structure.

• Journal of Sericultural and Entomological Science
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• v.39 no.2
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• pp.186-196
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• 1997

The IR crystallinity index of Calcium nitrate treated silk fiber decreased proportionally to the concentration of calcium nitrate. A partial change of conformation was observed in the concentration of over 46.4-47.6% changing from $\beta$-sheet or to random coil in the crystalline region. This is in coincidence with the result of crystallinity index, which was started to be reduced in the concentration range of 46.4-47.6%. A same trend was observed for the X-ray order factor, birefringence, degree of orientation and surface structure. These structural parameters were remarkably changed on the treatment of silk fibers with concentration of 46.4-17, 6% calcium nitrate. Therefore, it seems that there exists a critical concentration of calcium nitrate in affection the structure and morphology of silk fibers. According to the examination of surface morphology, the fine stripe was observed in the direction of fiber axis at 46.4% concentration. However, the treated concentration was exceeded by 47.6%, the cracks were appeared severely on the fiber surface in the transverse direction as well as fiber axis direction. This result might be related to the tensile properties, specially a tenacity of silk fibers. As a result of quantitative analysis of a dilute acid hydrolysis, three different regions, which are known as a amorphous, semi-crystalline and crystalline region, could be obtained. The hydrolysis rate curves were different with various concentrations of treatment and the relative contents of each region could be calculated.

• International Journal of Industrial Entomology and Biomaterials
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• v.44 no.1
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• pp.12-20
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• 2022

In this research, the silk web was hot-pressed for various times, the effect of press time on the structure and mechanical properties of silk non-woven fabric was also investigated. The yellowing appeared in the silk non-woven fabric and became more apparent as press time was increased. The crystallinity of silk was decreased by the hot press treatment and it did not change significantly with an increase of hot press time. The porosity of silk non-woven fabric was constantly decreased until 120 s and it did not change much after that. The thickness of silk non-woven fabric was significantly decreased by a press time of 10 s and slightly decreased with a further increase of hot press time. The hot press treatment increased the maximum stress and elongation of silk non-woven fabrics. The press time had a significant impact on the mechanical properties of silk non-woven fabric, with 90 s being the optimum condition for the best work of rupture of silk non-woven fabric.

• International Journal of Industrial Entomology and Biomaterials
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• v.26 no.2
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• pp.113-118
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• 2013

In this study, silk sericin films were prepared using different extraction methods, and the molecular conformation of sericin was examined using Fourier-transform infrared spectroscopy with attenuated total reflection geometry. Additionally, the effect of the film side (air-facing side or plate-facing side) on the molecular conformation of the sericin films was investigated. Interestingly, the molecular conformation of the sericin film depended on the film side. The molecular conformation of air-facing side of the sericin film was significantly influenced by extraction solution and time. The ${\beta}$-sheet crystallization and the crystallinity index of the sericin film markedly increased with an increase in the extraction time in hot water. The order of the crystallinity indices for the sericin films obtained with different extraction solutions was as follows: citric acid solution > urea solution >> hot water. In contrast, no remarkable differences were observed in the molecular conformation of the plate-facing side of the sericin film after extraction in hot water for different time periods. Urea and citric acid solution extractions showed remarkably higher crystallinity indices for sericin than those obtained after hot water extraction. However, no significant differences were observed in the crystallinity index of sericin between urea and citric acid solution extraction in plate-facing side of the film.