Ultrasonic dyeing of cellulose nanofibers

Textile dyeing assisted by ultrasonic energy has attained a greater interest in recent years. We report ultrasonic dyeing of nanofibers for the very first time. We chose cellulose nanofibers and dyed with two reactive dyes, CI reactive black 5 and CI reactive red 195. The cellulose nanofibers were prepared by electrospinning of cellulose acetate (CA) followed by deacetylation. The FTIR results confirmed complete conversion of CA into cellulose nanofibers. Dyeing parameters optimized were dyeing temperature, dyeing time and dye concentrations for each class of the dye used. Results revealed that the ultrasonic dyeing produced higher color yield (K/S values) than the conventional dyeing. The color fastness test results depicted good dye fixation. SEM analysis evidenced that ultrasonic energy during dyeing do not affect surface morphology of nanofibers. The results conclude successful dyeing of cellulose nanofibers using ultrasonic energy with better color yield and color fastness results than conventional dyeing.     

Fourier‐transform surface‐enhanced Raman spectroscopy (FT‐SERS) applied to the identification of natural dyes in textile fibers: an extractionless approach to the analysis

In the present study, an application of a silver colloid substrate in order to obtain Fourier‐transform surface‐enhanced Raman (FT‐SER) spectra of natural historical dyes is presented. In detail, we collected a spectral database from solutions of pure dyes and then we carried out extractionless both hydrolysis and non‐hydrolysis FT‐SERS analyses on wool fibers previously dyed in our laboratory and on ancient textiles. The term ‘extractionless’ refers to a method of SERS analysis applied directly on the fiber, thus avoiding the extraction of dyes from textile samples. The combination of a low‐energy source of radiation, as in the FT‐Raman technique, with SER spectroscopy can bring the important advantage of reducing the fluorescence typical of ancient samples and organic dyes. In some historical textile samples, for which SER spectra by use of visible excitation could not be obtained, the FT‐SER spectrum of an iron‐gall dye was recorded without hydrolysis, while, with an HF hydrolysis pre‐treatment on ancient fibers, madder, lac dye and brazilwood were clearly recognized. Copyright © 2014 John Wiley & Sons, Ltd.     

Physicochemical characterization of thermally aged Egyptian linen dyed with organic natural dyestuffs

A number of organic natural dyestuffs used in dyeing in ancient times, i.e. indigo, madder, turmeric, henna, cochineal, saffron and safflower, have been used to colour Egyptian fabrics based on linen. Their physicochemical properties have been evaluated on thermally aged linen samples. The aged dyed linen samples were thoroughly examined by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), X-ray diffraction (XRD) and tensile strength and elongation measurements. It was found that, in the molecular level, dyes interact mainly with the cellulose compounds of the aged linen while in the macroscopic level tensile and elongation parameters are altered. Tensile strength is positively related to the dye treatment while elongation depends specifically on the type of the dye used. Results converge that the dyed textiles did indeed play a role as protecting agents affecting strength and reducing thermal deterioration.     

Cold Pad-Batch dyeing method for cotton fabric dyeing with reactive dyes using ultrasonic energy

Reactive dyes are vastly used in dyeing and printing of cotton fibre. These dyes have a distinctive reactive nature due to active groups which form covalent bonds with -OH groups of cotton through substitution and/or addition mechanism. Among many methods used for dyeing cotton with reactive dyes, the Cold Pad Batch (CPB) method is relatively more environment friendly due to high dye fixation and non requirement of thermal energy. The dyed fabric production rate is low due to requirement of at least twelve hours batching time for dye fixation. The proposed CPB method for dyeing cotton involves ultrasonic energy resulting into a one third decrease in batching time. The dyeing of cotton fibre was carried out with CI reactive red 195 and CI reactive black 5 by conventional and ultrasonic (US) method. The study showed that the use of ultrasonic energy not only shortens the batching time but the alkalis concentrations can considerably be reduced. In this case, the colour strength (K/S) and dye fixation (%F) also enhances without any adverse effect on colour fastness of the dyed fabric. The appearance of dyed fibre surface using scanning electron microscope (SEM) showed relative straightening of fibre convolutions and significant swelling of the fibre upon ultrasonic application. The total colour difference values ΔE (CMC) for the proposed method, were found within close proximity to the conventionally dyed sample.     

中国人头发纤维在UVA紫外光老化中的光谱学研究

生活中,日光中的紫外辐射是导致头发光老化/光损伤的重要环境因素。长时间光照可使染发和天然发出现包括颜色褪变在内的退行性变化。以中老年人的自然灰发为样本来源,通过分离和人工漂染处理,获得了包括自然发色、漂白和染黑的六种头发类型,经过UVA(320～400 nm)紫外光老化,采用漫反射光谱、三维荧光光谱和衰减全反射傅里叶变换红外光谱对头发纤维的老化特征进行无损分析,结合头发中光产生过氧化氢的定量分析,探讨了不同发色和漂染处理对头发耐光性的影响。结果表明,UVA辐照可通过Ⅱ型电子转移机制诱导头发中的光敏基团产生过氧化氢,导致纤维表面蛋白和色素分子的光氧化降解。自然发色与漂染发在光老化中的颜色变化不同： 灰发和白发主要发生光黄化,人工染发和漂白发分别发生光褪色和光漂白。高湿度环境能加速头发的光降解。化学漂染处理会使头发中的光致过氧化氢水平升高,使纤维处于较高的氧化压力从而影响头发的光稳定性;而头发中的黑色素分子,包括天然黑色素和染发剂的人工黑色素,可能具有自由基产生与清除双重性。研究结果为建立中国人头发光损伤的光谱学评价方法和进一步研发针对国人发质的染护发产品提供了重要的实验基准数据。     

Ultrasound-assisted dyeing of cellulose acetate

The possibility of reducing the use of auxiliaries in conventional cellulose acetate dyeing with Disperse Red 50 using ultrasound technique was studied as an alternative to the standard procedure. Dyeing of cellulose acetate yarn was carried out by using either mechanical agitation alone, with and without auxiliaries, or coupling mechanical and ultrasound agitation in the bath where the temperature range was maintained between 60 and 80 °C.The best results of dyeing kinetics were obtained with ultrasound coupled with mechanical agitation without auxiliaries (90% of bath exhaustion value at 80 °C). Hence the corresponding half dyeing times, absorption rate constants according to Cegarra–Puente modified equation and ultrasound efficiency were calculated confirming the synergic effect of sonication on the dyeing kinetics. Moreover the apparent activation energies were also evaluated and the positive effect of ultrasound added to mechanical agitation was evidenced by the lower value (48 kJ/mol) in comparison with 112 and 169 kJ/mol for mechanical stirring alone with auxiliaries and without, respectively.Finally, the fastness tests gave good values for samples dyed with ultrasound technique even without auxiliaries. Moreover color measurements on dyed yarns showed that the color yield obtained by ultrasound-assisted dyeing at 80 °C of cellulose acetate without using additional chemicals into the dye bath reached the same value yielded by mechanical agitation, but with remarkably shorter time.     

二维相关红外光谱法鉴别不同染发剂染色头发

采用红外光谱法(FTIR)并结合二维相关光谱分析技术,对不同染发剂染过的头发进行了鉴别研究,普通头发和染过的头发在一维谱图上差别不显著,而在二维谱图上具有显著性的差别。在1000—2000cm-1区域同步相关红外谱图上,普通头发与高档染发剂染色的头发在1500cm-1附近有3个强的自动峰,2个弱的自动峰。低档染发剂染色的头发在1500cm-1附近有3个弱的自动峰,在2000cm-1附近有3个弱的自动峰。在2800—4000cm-1区域同步相关红外谱图上,普通头发与高档染发剂染色的头发在3300cm-1附近有1个强的自动峰,1个弱的自动峰。低档染发剂染色的头发在3400cm-1附近有1个弱的自动峰。在异步谱图上普通头发与高档染发剂染色的头发也相似,同时区别于低档染发剂染色的头发。     

Ecofriendly laccase–hydrogen peroxide/ultrasound-assisted bleaching of linen fabrics and its influence on dyeing efficiency

This study evaluates the bleaching efficiency of enzymatically scoured linen fabrics using a combined laccase–hydrogen peroxide bleaching process with and without ultrasonic energy, with the goal of obtaining fabrics with high whiteness levels, well preserved tensile strength and higher dye uptake. The effect of the laccase enzyme and the combined laccase–hydrogen peroxide bleaching process with and without ultrasound has been investigated with regard to whiteness value, tensile strength, dyeing efficiency and dyeing kinetics using both reactive and cationic dyes. The bleached linen fabrics were characterized using X-ray diffraction and by measuring tensile strength and lightness. The dyeing efficiency and kinetics were characterized by measuring dye uptake and colour fastness. The results indicated that ultrasound was an effective technique in the combined laccase–hydrogen peroxide bleaching process of linen fabrics. The whiteness values expressed as lightness of linen fabrics is enhanced by using ultrasonic energy. The measured colour strength values were found to be slightly better for combined laccase–hydrogen peroxide/ultrasound-assisted bleached fabrics than for combined laccase–hydrogen peroxide for both reactive and cationic dyes. The fastness properties of the fabrics dyed with reactive dye were better than those obtained when using cationic dye. The time/dye uptake isotherms were also enhanced when using combined laccase–hydrogen peroxide/ultrasound-assisted bleached fabric, which confirms the efficiency of ultrasound in the combined oxidative bleaching process. The dyeing rate constant, half-time of dyeing and dyeing efficiency have been calculated and discussed.     

Broadband tunability of dye lasers

A double compartment dye cell to hold two or more dyes has been found to increase the frequency range of dye lasers. Results are compared with those obtained by mixing the same two dyes in a single cell. The dye cells are transversely pumped by a nitrogen laser. Broadband tunability results from dyes having similar absorption ranges but different Stokes shifts.     

Surface‐enhanced Raman spectroscopy of various madder species on wool fibers: the role of pseudopurpurin in the interpretation of the spectra

Madder has been used as a textile dye and pigment in works of art since antiquity. Madder dyes from different botanical species are characterized by different series of anthraquinone derivatives. The occurrence of one or more of these compounds in various relative amounts may provide a useful indication of the plant species used to obtain the dye. In this work, surface‐enhanced Raman spectroscopy (SERS) was applied to the analysis of textile fibers dyed with madder from two different botanical species, Oldenlandia umbellata L. and Rubia tinctorum L. The resulting SERS spectra were interpreted in light of the actual composition of the madder dyes as determined by high‐performance liquid chromatography. Interestingly, the SERS spectra were found to exhibit very distinctive spectral features depending on the different anthraquinone derivatives present in the dyes. In particular, the SERS spectrum of O. umbellata L. was found to match the spectrum of alizarin, while the SERS spectrum of R. tinctorum L. was surprisingly dominated by signals due to the less studied anthraquinone compound pseudopurpurin. With this study, we demonstrate that SERS spectra may offer valuable information regarding the major coloring constituents present in different madder species. Moreover, our work shows that not only can SERS be used successfully to differentiate among closely related anthraquinone derivatives, but also that this technique is particularly suitable for the detection of pseudopurpurin, leading to the identification of this compound in a number of works of art. Copyright © 2015 John Wiley & Sons, Ltd.     

清末传世纺织品的材质鉴别和所用染料的微量分析

从早期纺织品保护的视角出发,通过对这一行业国内外大量文献资料梳理分析,对比了织物的常规系统分析方法,结合现代的科学技术方法,对早期纺织品的面料种类、所用染料种类以及染色工艺进行测定分析。面对目前服饰博物馆清末传世朱红女袄保藏面临的严峻考验,运用傅里叶变换红外光谱仪鉴定该纺织品的材质,以萃取法提取纺织品上的染料,用反射分光色度仪对提取前后的纺织品进行表面颜色分析,并用高压液相色谱和质谱对色素进行结构分析,尝试确定分析早期纺织品上染料的结构成分和上染方式。将现代分析技术（液质联用）和理念（色度学）融入传统研究中,使用客观科学技术获取更多有效数据和信息,佐证以主观目鉴方法得出的结论,弥补这一研究领域的空白,使对于传统服饰的研究更具深度。与传统的纺织品鉴别方法横向比较,现代的科学技术方法获得的相关信息更加详尽可靠。有利于根据不同染料特性和不同纤维种类特性提出具有针对性的保藏措施,对博物馆馆藏纺织品的保护和保存具有重要的意义。采用傅里叶变换红外仪对样品的面料进行简单分析,通过不同的特殊特征峰确定了样品为蚕丝面料。该研究建立了一种普遍适用的染料提取方法,采用丙酮、乙腈、吡啶：水（1∶1）、N,N-二甲基甲酰胺、0.1%乙二胺四乙酸水溶液/N,N-二甲基甲酰胺（1∶1）、甲醇六种不同的溶剂提取样品上的染料,采用反射分光光度仪对样品表面剥色前后的颜色进行色度测量分析。结果表明,吡啶的水溶液对染料具有最佳的提取效果;发现提取染料时加入少量乙二胺四乙酸,会提高剥色效率,即染色方式可能是媒染法,因为乙二胺四乙酸可以破坏染料和媒染金属离子间的络合作用。从染料提取前后织物的颜色变化可以推断样品的颜色可能是由染料拼色得到,利用液质联用技术（LC-MS）对提取的染料进行检测,根据染料上染方式和分子量推测分析,纺织品上染料可能含有小檗碱。经过标准小檗碱染料进行验证,进一步证明了染色纺织品上其中一种染料为小檗碱。     

Investigation of natural dyes and ancient textiles from korea using TOF-SIMS

The identification of the colorants used on ancient textiles provides a historical pathway to the understanding of the processes associated with one of the oldest of chemical technologies, namely textile dyeing. In this paper, time-of-flight secondary ion mass spectrometry (TOF-SIMS) was used to detect dyes on textiles avoiding the time-consuming and destructive extraction procedures necessary for the spectrophotometric and chromatographic methods previously used. The plant dyes investigated belong to a variety of chemical groups, which include curcumin, crocin, carthamin, purpurin, alizarin, brazilin, shikonin, and indigo. Reference textile samples were prepared with dye extracts of plants and were characterized by TOF-SIMS. TOF-SIMS spectra for the dyed textiles showed element ions from metallic mordants, specific fragment ions, and molecular ions from organic dyes. Remnant dyes on excavated textiles have also been identified using TOF-SIMS. The ancient textile sample showed the presence of indigo clearly, although the fiber itself had degraded badly. From the results, it was concluded that most of plant dyes can be identified with TOF-SIMS and it is a very promising technique for the archaeology field.     

Dopant-enhanced ablation of nitrocellulose by a nitrogen laser

The photoetching behavior of pure nitrocellulose and of nitrocellulose dyed with stilbene-420, coumarin-120 and rhodamine 6G by 337 nm nitrogen laser pulses has been studied. Ablation with a low power nitrogen laser is hereby reported for the first time. A two step photochemical mechanism is proposed to account for the ablation of the pure material. With the addition of dyes strongly absorbing at 337 nm the photoetching rate of nitrocellulose can be increased significantly. This increase is proportional to the molar extinction coefficient of the dye at 337 nm and its concentration in the polymer. The photoetching mechanism and the energy transfer processes from the dye to the polymer are discussed in detail.     

Studies on the use of power ultrasound in leather dyeing

Uses of power ultrasound for acceleration/performing the chemical as well as physical processes are gaining importance. In conventional leather processing, the diffusion of chemicals through the pores of the skin/hide is achieved by the mechanical agitation caused by the paddle or drumming action. In this work, the use of power ultrasound in the dyeing of leather has been studied with the aim to improve the exhaustion of dye for a given processing time, to reduce the dyeing time and to improve the quality of dyed leather. The effect of power ultrasound in the dyeing of full chrome cow crust leather in a stationary condition is compared with dyeing in the absence of ultrasound as a control experiment both in a stationary as well as conventional drumming condition. An ultrasonic cleaner (150 W and 33 kHz) was used for the experiments. Actual power dissipated into the system was calculated from the calorimetric measurement. Experiments were carried out with variation in type of dye, amount of dye offer, temperature and time. The results show that there is a significant improvement in the percentage exhaustion of dye due to the presence of ultrasound, when compared to dyeing in absence of ultrasound. Experiments on equilibrium dye uptake carried out with or without ultrasound suggest that ultrasound help to improve the kinetics of leather dyeing. The results indicate that leathers dyed in presence of ultrasound have higher colour values, better dye penetration and fastness properties compared to control leathers. The physical testing results show that strength properties of the dyed leathers are not affected due to the application of ultrasound under the given process conditions. Apparent diffusion coefficient during the initial stage of dyeing process, both in presence and in absence of ultrasound was calculated. The values show that ultrasound helps in improving the apparent diffusion coefficient more for the difficult dyeing conditions such as in the case of metal-complex dyes having bigger aggregate size compared to less difficult dyeing conditions.     

Ultrasonic-assisted dyeing of Nylon-6 nanofibers

We first time report ultrasonic dyeing of the Nylon 6 nanofibers with two disperse dyes CI Disperse blue 56 and CI Disperse Red 167:1 by utilising ultrasonic energy during dyeing process. The Nylon 6 nanofibers were fabricated via electrospinning and dyed via batchwise method with and without sonication. Results revealed that ultrasonic dyeing produce higher color yield (K/S values) and substantially reduces dyeing time from 60 min for conventional dyeing to 30 min can be attributed to breakage of dye aggregate, transient cavitation near nanofiber surface and mass transfer within/between nanofibers. Color fastness results exhibited good to very good dye fixation. SEM images exhibit insignificant effect of sonication on morphology of the nanofibers. Our research results demonstrate ultrasonic dyeing as a better dyeing technique for Nylon 6 nanofibers with higher color yield and substantially reduced dyeing time.     

Effects of ultrasonic energy on dyeing of polyamide (microfibre)/Lycra blends

Although ultrasonic energy is widely used cleaning and degreasing of parts and assemblies in automotive and other industries, the use of ultrasonic energy in an industrial scale for textile washing is very new. This is due to the complexity of controlling the combination of chemical and mechanical effects, whereas with degreasing of machine parts only the mechanical effects is applied. The use of ultrasonic energy in dyeing PA/Lycra fabrics with reactive dyes has been studied spectrophotometrically in this work. PA/Lycra (85/15) blends have been dyed using conventional and ultrasonic dyeing techniques with three reactive dyes containing different chromophore and reactive groups. The dyeing carried out conventionally and by the use of ultrasonic techniques. The results were compared in terms of percentage exhaustion; total dye transferred to the washing bath after dyeing and the fastness properties.     

Linear and cross-linked polymeric solid-state dye lasers based on 8-substituted alkyl analogues of pyrromethene 567

The lasing properties of analogues of the commercial laser dye pyrromethene 567 (PM567) incorporated (dissolved or copolymerized) into polymeric matrices have been studied using both linear and cross-linked methyl methacrylate-based copolymers with different degrees of functionalization. All synthesized dyes have the chromophore core of PM567 but with an ω-acyloxypolymethylene chain at position 8. In general, the new materials exhibited laser emission with higher efficiencies and much higher photostabilities than those containing the commercial dye PM567 under the same experimental conditions. Lasing efficiencies of up to 40% were obtained under transversal pumping at 534 nm. The highest photostabilities, with the laser output remaining stable or dropping by less than 15% after 100 000 pump pulses at the same position of the sample, were reached in cross-linked materials with dyes covalently linked to the polymeric chains. When the polymeric samples were incorporated into a grazing-incidence grating oscillator, narrow-line-width operation with tuning ranges of up to 40 nm was obtained. These results show that efficient and photostable solid-state dye lasers competitive with their liquid counterparts can be developed by adequate chemical modifications in the dye molecules, as well as by the selection of appropriate polymeric formulations.     

Ultrasonic dyeing of cationized cotton fabric with natural dye. Part 1: cationization of cotton using Solfix E

The dyeing of cationized cotton fabric with Solfix E using colouring matter extracted from Cochineal dye has been studied using both conventional and ultrasonic techniques. Factors affecting dye extraction such as ultrasound power, particle size, extraction temperature and time were studied. The results indicated that the extraction by ultrasound at 300 W was more effective at lower temperature and time than conventional extraction. The effect of various factors of dye bath such as pH, salt concentration, ultrasound power, dyeing time and temperature were investigated. The colour strength values obtained were found to be higher with ultrasound than with conventional techniques. The results of fastness properties of the dyed fabrics were fair to good. The scanning electron microscope (SEM) images of the morphological and X-ray analyzes were measured for cationized cotton fabrics dyed with both conventional and ultrasound methods, thus showing the sonicator efficiency.     

“爱迪生”珍珠及染色处理有核珍珠的谱学特征

颗粒大、圆度高并具有浓郁颜色的淡水有核养殖珍珠（商贸名称为“爱迪生”珍珠）为珍珠市场提供了更高的品质与价值,然而受利益的驱使,染色的有核养殖珍珠也逐渐流入市场,扰乱了消费者的健康消费,在一定程度上阻碍了“爱迪生”珍珠产业的良性发展。本文利用红外光谱仪、紫外-可见分光光度计和光致发光光谱仪对养殖和染色“爱迪生”珍珠进行了系统的谱学研究,并将其与海水珍珠、染色海水珍珠进行了比较。结果表明：（1）染色与养殖“爱迪生”珍珠在红外光谱上均显示1 445,882和725 cm-1处的文石振动峰,其中染色“爱迪生”珍珠在3 800 cm-1处均出现宽缓的弱吸收峰;（2）染色“爱迪生”珍珠的紫外可见光光谱中280 nm处的吸收峰明显弱于养殖“爱迪生”珍珠,染色后的“爱迪生”珍珠整体反射率降低,可能与染剂使珍珠中的蛋白质分子受损有关。染黄色“爱迪生”珍珠缺失养殖橙黄色“爱迪生”珍珠在360～380 nm处的吸收峰,而与染色海水金珠430 nm处的强吸收峰相似。染黑色“爱迪生”珍珠在425 nm处有吸收峰,染色海水黑珍珠在480和645 nm处有吸收峰,养殖海水黑珍珠在702 nm处有吸收峰,三者图谱的差异可能为各自的染料不同所致;（3）养殖“爱迪生”珍珠在光致发光光谱中450～550 nm范围内可见一组吸收峰,染色“爱迪生”珍珠的发光中心向红区偏移且在650 nm附近出现强度不等的与染色剂相关的吸收峰,染色海水金珠也在600 nm处有和染色剂有关的吸收峰。     

Identification of single archaeological textile fibres from the cave of letters using synchrotron radiation microbeam diffraction and microfluorescence

Single 2000-year-old archaeological fibres from textile fragments excavated in the Cave of Letters in the Dead Sea region were investigated by a combined approach using microscopy (optical and SEM), X-ray microbeam diffraction and X-ray microbeam fluorescence. In comparison with modern reference samples, most of the fibres were identified as wool, some as plant bast fibres (flax). The molecular and supermolecular structure of both keratin (wool) and cellulose (flax) were found completely intact. In many fibres, mineral crystals were intimately connected with the fibres. The fluorescence analysis of the dyed wool textiles suggests the possible use of metal-containing mordants for the fixation of organic dyes. PACS 61.10.Nz; 78.70.En; 81.05.Lg