The roles of polymer relaxation phenomena,aqueous dye solubility and the physical properties of water in the mechanism of adsorption of a disperse dye on poly(ethylene terephthalate) fibres: Part 4 further aspects related to polymer relaxation phenomena

To further investigate the contribution of polymer relaxation times to the mechanism of disperse dye adsorption on poly(ethylene terephthalate) fibres, the temperature-dependent uptake of Teratop Yellow HL-G 150% on both cotton and polyamide 66 fabrics at temperatures between 30 and 130°C was compared with that on poly(ethylene terephthalate) fabric. Although uptake of the commercial grade dye on polyester fabric is governed by the thermally regulated, broad glass transition of the water-saturated poly(ethylene terephthalate) substrate, as this was not observed for either cotton or nylon 66 fabrics, the respective cellulose or polyamide 66 polymer glass transition does not present a major thermal impediment to dye uptake over the wide range of dyeing temperatures used. This is because the onset and end-set temperatures of the glass transition of the water-plasticised poly(ethylene terephthalate) material reside within the range of dyeing temperatures employed, whereas those of the water-plasticised cotton and polyamide materials occur below the lowest dyeing temperature examined (30°C). The thermal dependency of disperse dye solubility also likely makes a meaningful contribution to the temperature-dependent dye uptake observed for each type of fibre.     

合成纤维及其混纺纤维用染料的研究 Ⅰ.用于锦纶染色的含β-羟乙基砜硫酸酯基活性分散染料

本文综合了应用于锦纶染色的弱酸性染料酸性浴上色的高竭染率,活性染料与纤维的共价键结合,分散染料在纤维上迁移、匀染、盖染性好等优点,提出一类含β-羟乙基砜硫酸酯基的活性分散染料。用分子较小的分散染料结构,以含β-羟乙基砜硫酸酯为活性基;在弱酸性浴中染色,再在弱碱性浴中与聚酰胺纤维反应成共价键结合。 合成了一系列偶氮型和蒽醌型染料。进行了合成工艺、对锦纶的染色性能以及染色锦纶的牢度等试验。并讨论了染料与聚酰胺纤维的结合 这类染料可用于锦纶66和锦纶6丝纺、弹力锦纶丝和针织品,还可用于桑丝、柞丝及其与人造丝的提花织物。这类染料在锦纶上色泽鲜艳,竭染率较高,益染性优良,耐晒、耐湿处理等牢度较好,适于各种锦纶织物的染色。这类活性分散染料,具有酸性染料、活性染料和分散染料染锦纶的主要特点。     

The roles of polymer relaxation phenomena,aqueous dye solubility and the physical properties of water in the mechanism of adsorption of a disperse dye on poly(ethylene terephthalate) fibres: Part 3 physical properties of water and water-derived fibre properties

In the absence of published information regarding the temperature dependency of water-derived poly(ethylene terephthalate) fibre properties, the findings reported for the thermally regulated interactions between water and 100% amorphous poly(ethylene terephthalate) materials were interpreted from the perspective of the amorphous domains that reside within semi-crystalline polyester textile fibres. This analysis suggests that the pronounced temperature dependent uptake of a commercial grade disperse dye on poly(ethylene terephthalate) fabric achieved during an aqueous dyeing process at temperatures between 30 and 130°C is the likely result of the combination of three separate, but inherently inter-related, thermally activated phenomena, namely, polymer structural relaxation, in which polymer glass transition assumes a dominant role, dissolution of disperse dye in the aqueous dyebath, as well as various water–fibre interactions, in the guise of water sorption, water molecule diffusivity, water-induced swelling and water-induced plasticisation. Although thermally regulated macromolecular relaxation processes adopt the principal role in dye uptake, temperature dependent dye solubility and water-derived fibre properties nevertheless likely provide crucially important supportive roles.     

Temperature dependence of diffusion of a disperse dye in the multiple layers of nylon fabric

The apparent diffusion coefficients of a disperse dye in the multiple layers of nylon fabric at 45-75°C are determined as the dyeing model of the textile assembly. The modified pore model is introduced to explain the diffusion behavior in the multiple fabric. The Arrhenius plot of the diffusion coefficient of dye in the spaces or pores of nylon fabric gave a straight line and the activation energy of diffusion was about 9.4 kcal/mol. The temperature dependence of the dye diffusivity in polymer matrix was quantitatively described by a WLF-type relation, where a_T is a shift factor of diffusion and T_s is the reference temperature.     

Effect of reactive dyeing on the UV protection affected by knitted fabric made from different types of cotton fibre

In this study, 100% cotton knitted fabrics made from combed cotton and combed pima cotton were dyed with reactive dye, with different dye concentrations. Colour properties such as CIE L*a*b* values as well as dyeing uniformity of the dyed fabrics were measured. The relationships between colour properties and the ultraviolet protection afforded by cotton knitted fabrics were investigated. Experimental results revealed that dye concentration is the most important factor. In addition, only L* values have a direct mathematical relationship with the ultraviolet protection factor; a* and b* values and dyeing uniformity were not found to have a significant correlation with ultraviolet protection factor values. Meanwhile, knitted fabric made from combed cotton fibre has better ultraviolet protection performance than fabric made from combed pima cotton fibre.     

Modified polyurethane with improvement of acid dye dyeability

This article concerns the modification of polyurethane using polyamide 6,6 prepolymer to improve the dyeability properties of the polyurethane copolymer with acid dye. First, the carboxyl‐terminated polyamide 6,6 prepolymer was synthesized from adipic acid and 1,6‐diaminohexane. The isocyanate‐terminated polyurethane prepolymer was also synthesized from polytetramethylene glycol and 4,4′‐diphenylmethane diisocyanate in N,N‐dimethylformamide. The polyurethane prepolymer was then extended with a mixture of 1,4‐butanediol and the polyamide 6,6 prepolymer (molar ratios of 1,4‐butanediol to prepolymer being 100%, 75%, 50%, and 25%, respectively). Finally, the poly(urethane–amide) copolymers were dyed with acid dyes. The chemical, physical, and the dyeing properties of the poly(urethane–amide) coploymers are discussed. From the experimental results, it is found that the inherent viscosity of poly(urethane–amide) coploymers is increased with the increasing amount of polyamide content. The structure is proven by infrared spectra, which exhibits the absorption peaks of urethane and amide groups as we expected. From the differential scanning calorimetry measurements, it is found that the poly(urethane–amide) coploymers have two‐phase structures and good phase separation. There are four transition temperatures (T_gs, T_gh, T_ms, and T_mh), but only those copolymers in PTMG 2,000 series possess T_ms. Moreover, the T_gs is found to change with the length of soft segment, and the T_gh is increased with the increasing amount of polyamide content. Also, the dyed copolymers exhibit higher T_gh than those without dyeing of dye molecule, but the T_gs is not obviously changed. For mechanical properties, it is indicated that both the modulus and the strength of the coploymers are higher than those of unmodified polyurethane, but they are lowered after being dyed with dye molecule due to further separation of intermolecular distance of the dyed polyurethanes. For dye uptake in dyeing properties, it is found to increase with increasing amount of polyamide content. For dye fastness, the dyed copolymers exhibit higher grade of water fastness than that of unmodified polyurethane. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1397–1404, 2003     

Studies of the fibre structure and dyeing properties of Calotropis gigantea,kapok and cotton fibres

Calotropis gigantea, kapok and cotton fibres are all natural cellulose fibres, but the first of these is rarely used in textile fabrics. In this study, the structure and chemical composition of these three kinds of fibre were studied, and the dyeing properties of fabrics made from each of them were compared. The purpose of this was to provide a theory basis for the application of C. gigantea fibre in the textile industry. The surface morphology and cross‐section of C. gigantea fibre in comparison with kapok and cotton were studied by scanning electron microscopy. Their fibrous structures were analysed by Fourier Transform‐infrared spectroscopy and X‐ray diffraction. The mechanical properties and water absorption capabilities were also measured and compared. Both C. gigantea fibre and kapok fibre exhibit a high degree of hollowness (80–90%), and no natural twist exists; there is a certain amount of lignin and hemicellulose in C. gigantea fibres; the crystallinity of C. gigantea fibres is 42.54%, and its crystallinity orientation index is 85.40%. C. gigantea fibre has the lowest tenacity but has the highest water content of the three kinds of fibre. The results of dyeing tests show that C. gigantea fabric has the lowest dye uptake and dye fixation.     

Influence of the nigrosine dye on the thermal behavior of polyamide 66

To reveal the effect of the nigrosine dye, that the addition of the dye lowers the crystallization point (T_c) of molten polyamide resins with substantially no shift in the melting point (T_m), thus suppressing the crystallization enhancement of the crystalline nucleation agents, the characteristics of polyamide 66 (PA‐66) containing nigrosine dye EX (N‐EX) were investigated. Differential scanning calorimetry (DSC) analysis showed that the addition of N‐EX reduced the crystallization rate and T_c of molten PA‐66 with substantially no shift in T_m, and the crystallization enthalpy per unit of weight of PA‐66 was substantially constant. T_c of molten PA‐66 was lowered with an increase in the amount of N‐EX and reached its maximum at 13 wt % N‐EX. Dynamic mechanical analysis showed that the glass‐transition temperature and the secondary glass‐transition temperature increased with an increasing amount of the dye. On the other hand, the DSC and X‐ray diffraction results indicated that no dye molecule was present in the crystal structure of PA‐66. This effect of the nigrosine dye on PA‐66 is in contrast to those of crystalline nucleation agents, plasticizers, and antiplasticizers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3270–3274, 2006     

Coloration of Apocynum venetum/cotton blends with an acid dye through combined pretreatment using cationic nanoparticles

Cationic copolymer nanoparticles were used to modify Apocynum venetum/cotton blended fabrics. The modified blends were then dyed using CI Acid Red 14. In order to enhance the colour performance, the effects of combined pretreatment using nanoparticles and sodium hydroxide (NaOH) or carboxymethylcellulose (CMC) or plasma were investigated. The results show that combined pretreatment with NaOH and nanoparticles improved the dyeing effect. The optimum concentrations of NaOH and nanoparticles were 100 and 2 g l⁻¹ respectively. In addition, using CMC to pretreat the fabrics could also improve the acid dyeing performance. However, the combination of plasma pretreatment and cationic nanoparticle modification produced the best colour performance for acid-dyed A. venetum/cotton blends. The dye exhaustion rate is highest (up to 95%) with plasma pretreatment. Scanning electron microscopy revealed that combined treatment with plasma and nanoparticles resulted in a far greater number of nanoparticles being deposited on the fibre surface. X-ray photoelectron spectroscopy indicated that the pretreatments with different procedures significantly changed the chemical components of the fibre surfaces. The aromatic rings of acid dye molecules covered the fibre surfaces after plasma and nanoparticle pretreatment and acid dyeing.     

Supercritical carbon dioxide (SC-CO2) dyeing of cellulose acetate: An opportunity for a “greener” circular textile economy

This article compares the dyeing of cellulose diacetate (cellulose-based) and polyester fabrics using supercritical carbon dioxide (SC-CO₂) and aqueous media. The benefits of dyeing in SC-CO₂ were clearly demonstrated in laboratory-based and pilot-scale studies in terms of increased colour strength, uniformity, fastness and the absence of auxiliaries such as dispersing agents or surfactants. In addition, the “super-levelling” nature of the SC-CO₂ medium was demonstrated in the reprocessing of polyester “waste textile” and the re-use of the “locked-in waste” colourant. The SC-CO₂ processing medium can be utilised to accurately colour “multiple life” polyester and cellulose acetate uniformly and to creatively tie-dye polyester and cellulose acetate fabrics. Through SC-CO₂ fluid technology, we can envisage a viable waterless circular manufacturing and recycling/remanufacturing framework for the predominantly polyester global fibre market coupled to the sustainably sourced, biodegradable cellulose diacetate as a replacement for cotton. The key technical and commercial advantages being the use of a single solvent dye class for both polyester and the cellulose diacetate, saving on energy costs, integrated simpler processing, reduced water usage and associated efficient recycling. Further, repositioning the cellulosic fibre industry towards using sustainable forests is attractive in terms of improved land, water and environmental management.     

A significant approach to dye cotton in supercritical carbon dioxide with fluorotriazine reactive dyes

A series of fluorotriazine reactive dyes have been synthesized and applied to dye cotton in supercritical carbon dioxide (scCO₂) with good dyeing results. The pieces of cotton to be dyed were previously presoaked in a protic solvent and cosolvents were applied during dyeing. The colour strength of the dyeings was evaluated by K/S measurements. The K/S values achieved on cotton dyed were up to 35.8 ± 4.2. Even after the cotton was subjected to a Shoxlet extraction at 358 K for 1 h, a maximum K/S value of 20.2 ± 1.8 was measured. The percentage of dye molecules chemically fixed to the cotton was on average 85%. The excellent reactivity of fluorotriazines allowed a reduction of 3 h on the dyeing time. It is noticeable that a dye concentration of 10% on weight of the fibre (owf) can be applied to dye cotton with fluorotriazines, since no damage of the cotton fibres occurred, as observed for the chlorotriazines at this high dye concentration.Dyes with fluorotriazine as reactive group were found to be the most preferable dyes for dyeing cotton in scCO₂, as they were able to exceed the limitation of the reaction with the cotton.     

Photophysical processes in poly(hexamethylene adipamide)–acid dye complexes: Energetics of nylon 66 phototendering

The mechanism of dye-sensitized photo-oxidative degradation of nylon 66 was investigated. A known phototendering dye, C.I. Acid Blue 40 (1-amino-4-(p-aminoacetanilide)-2-anthraquinone sodium sulfonate), was used for this study. Excitation and emission spectra of the dyed and undyed nylons indicated that a ground-state complex between the dye and the polyamide was formed upon dyeing. The energy level of the complex's electronic states favor triplet–triplet energy transfer from the nylon to the complex. Quenching studies show that the energy transfer occurs efficiently with a rate constant of 45.8 l. mole^?1 sec^?1. An additional energy transfer occurs between the excited free dye and the complex by either a singlet–triplet or a triplet–triplet mechanism. Kinetic analysis of the nylon-complex energy transfer suggests that the triplet energy of nylon migrates 24 to 33 Å along the amide chromophores in an exciton fashion until an energy trapping complex is reached. Energy is then transferred by an exchange mechanism. Photo-oxidative studies verify that the dye–nylon complex sensitizes the polyamide photo-oxidative degradation at its own expense without dye photobleaching.     

Dyeing of nylon 66 with a disperse-reactive dye using supercritical carbon dioxide as the transport medium

Nylon 66 fabric was dyed with a disperse-reactive yellow dyestuff which was synthesised in our laboratory, using a supercritical carbon dioxide dyeing process. The structure of the disperse-reactive yellow dyestuff and its covalent bond with nylon 66 fibres were confirmed by FTIR, NMR, EA and MS analysis. The nylon fabric was also dyed with CI Disperse Yellow 3 and the dyeing results compared. Colour yield values were measured for both dyed fabrics, with those of the disperse-reactive dye showing much better values than CI Disperse Yellow 3. Wash fastness of the fabric dyed with the disperse-reactive yellow dye was tested by the ISO 2 method and showed excellent results. Light fastness was tested by the ISO 105 B05 method and the results were satisfactory. The results obtained indicate fabric immersed in supercritical carbon dioxide does not undergo any fibre damage.     

An Experimental Study of the Dyeability of Barry Nylon Fibre with Acid Dyes

When nylon fibre is dyed with acid dyes, the rate of diffusion into the fibre depends on the draw to normal ratio than for one more highly drawn. The ratio of the diffusion coefficients for two such substrates is independent of both the dye used and the amount of dye fixed on the fibre. The differences which appear in the dyeing of barry nylon textiles relate to the time parameter Dt/r² (D is the diffusion coefficient in cm² /s, t, the dyeing time in s, and r, the substrate radius in cm). The greater this parameter, the better is the coverage of barriness arising from variations in the draw ratio. Since the diffusion coefficient for a given substrate is specific to the dye, acid dyes differ in their suitability for dyeing barry nylon textile fabrics.     

Synthesis and application to cellulose of reactive dye precursor of anti‐bacterial N‐halamine

To achieve textile dyeing and functional finishing in one process, a bleach‐resistant reactive dye precursor to anti‐bacterial N‐halamine was synthesised by reacting a type of dichlorotriazine reactive dye with 4‐amino‐2,2,6,6‐tetramethylpiperidine. The synthesised compound, which can be transformed to an N‐halamine molecule by exposure to dilute bleach solution, was used to dye cotton fabrics. After exposure to a dilute sodium hypochlorite solution, dyed cotton fabrics showed excellent anti‐bacterial properties against Staphylococcus aureus and Escherichia coli O157:H7, facilitating a ca. 6‐log reduction in bacteria within a short period of contact. Compared with the dichlorotriazine reactive dye, the reactive dye precursor demonstrated comparable dyeing properties including exhaustion and fixation values. No differences in rub fastness, wash fastness or bleach fastness were detected between fabrics dyed with, respectively, dichlorotriazine reactive dye and the reactive dye precursor to N‐halamine.     

Vapor phase dyeing of synthetic fibers with disperse dyes

Dyeing of synthetic fibers by the heat transfer process of disperse dye vapors is performed by contacting white receptor polyester or polyamide fabric with other dyed polyester fabrics (donor) under the influence of heat. The dye vapours flowing away will diffuse across the very slight air gap enclosed between the inner donor and receptor surfaces under the applied pressure. It is found that the dye uptake by the receptor fabric is dependent on the original dye content of the donor fabric, transfer temperature and dwell time. The released dye from the donor fabric under the influence of heating is found to be dependent on the original dye content of the donor fabric as well as the transfer temperature. The efficiency of the dye transfer is also attributed to the original shading of the donor fabric. Evaluation of the imparted colors on the receptor fabric (polyester, polyamide) obtained by heat contact with the same donor fabric showed visually the same colour level up to the 13th run. Thermodynamic interpretation of the standard affinity (Δu⁰) and heat of dyeing (ΔH⁰) as well as the partition coefficient of the dye show that the dyeing process has an exothermic character. The rate controlling step in this dyeing process is found to be dependent on the diffusion of the dye vapors into the fiber phase.     

Criteria for the affinity of dyes for fibres

An equation was obtained for evaluating the thermodynamic affinity of a disperse dye for a fibre. Quantities Δh _D and K _D , which are functions of the composition of the dye bath, temperature, and state of the fibre material, can characterize the change in the affinity of the dye for the fibre when the dyeing conditions are varied.     

The dyeing of nylon with a microencapsulated disperse dye

Melamine resin microcapsules containing CI Disperse Blue 56 were prepared by in situ polymerisation. The microcapsules were characterised by their thermal properties and morphology, such as particle size and particle size distribution. The dyeing behaviour of the microcapsules on nylon 6.6 was evaluated. The microencapsulated dye exhibited good build-up, levelness and fastness properties. It has been demonstrated that microencapsulated disperse dye can be used to replace commercial disperse dyes in dyeing polyamide fabric without dyeing additives, and the resulting effluent can be easily recycled after filtration.     

Effect of microencapsulation on dyeing behaviors of disperse dyes without auxiliary solubilization

Microencapsulated disperse dye can be used to dye hydrophobic fabric in the absence of auxiliaries and without reduction clearing. However, little available information for dyeing practice is provided with respect to the effect of microencapsulation on the dyeing behaviors of disperse dyes. In this research, disperse dyes were microencapsulated under different conditions. The dyeing behaviors and dyeing kinetic parameters of microencapsulated disperse dye on PET fiber, e.g., dyeing curves, build up properties, equilibrium adsorption capacity C_∞, dyeing rate constant K, half dyeing time t_1/2, and diffusion coefficient D were investigated without auxiliary solubilization and compared with those of commercial disperse dyes with auxiliary solubilization. The results show that the dyeing behaviors of disperse dye are influenced greatly by microencapsulation. The diffusion of disperse dyes from microcapsule onto fibers can be adjusted by the reactivity of shell materials and mass ratios of core to shell. The disparity of diffusibility between two disperse dyes can be reduced by microencapsulation. In addition, the microencapsulation improves the utilization of disperse dyes due to no auxiliary solubilization. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Alkaline dyeing of polyester and polyester/cotton blend fabrics using sodium edetate

An alkaline dyeing of polyester with an alkali‐stable disperse dye, Dianix® Scarlet AD‐RG, was developed using sodium edetate as an alkaline buffering agent. The results obtained indicate the suitability of using sodium edetate for alkaline dyeing of polyester when compared with the control alkaline dyeing using Dianix AD system. Selected mono and bifunctional reactive dyes were used in combination with the alkali‐stable disperse dye for dyeing of polyester/cotton blend. Different dyeing methods for cotton and polyester/cotton blend fabrics using sodium edetate were evaluated in comparison with their respective control alkaline dyeing methods. The results of using sodium edetate in one‐bath two‐stage and two‐bath dyeing of polyester/cotton blend were comparable with that of the control dyeing method. Particularly, no change in the leveling and fastness properties was evaluated for all samples irrespective of the dyeing method. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008