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 5 analysis of polymer relaxation phenomena for different polymers

The temperature dependent uptake of a commercial disperse dye on cotton and polyamide 66 fabrics at dyeing temperatures between 30°C and 130°C adhered to the Williams–Landel–Ferry equation, insofar as, very good correspondence was observed between plots of experimentally determined colour strength data points (log1/f_k) and the respective structural relaxation times of the cellulose and nylon 66 polymers (loga_T data points), as a function of the parameter (T − T_g). Adsorption of the dye on both types of fibre therefore concurs with the fundamental precept of the free volume model of dye diffusion. Comparison of the adherence of the uptake of the commercial dye on cotton and polyamide 66 fabrics with that secured on polyester fabric revealed that despite the major chemical and physical differences between the three types of fibre, the same dyeing mechanism likely applies to each fibre type. The marked temperature dependent uptake of the commercial grade disperse dye each of the three types of substrate is the consequence of two, different, but inherently interconnected, thermally activated phenomena, namely the relaxation times of the molecular rearrangements occurring within the respective cellulose, nylon 66 or poly(ethylene terephthalate) macromolecule, in which polymer glass transition assumes the principal role, and the aqueous solubility of the commercial grade disperse dye.     

Disperse dyeing of polyester fibers: Kinetic and equilibrium study

The effect of temperature on the dyeing rate constant k, diffusion coefficient D, and time of half‐dyeing t_1/2 was evaluated for the dyeing of polyester fibers with two disperse dyes, an azo and an anthraquinone dye. Activation energies of diffusion E were calculated. The polyester dyeing equilibrium was also studied and the partition coefficient K and standard affinity Δμ° at various temperatures were determined for the anthraquinone dye. Standard enthalpy ΔH° and standard entropy ΔS° of dyeing were also obtained. The same equilibrium parameters were not obtained for the azo dye because of its dyeing behavior. A similar kinetic and equilibrium study was made for the pure azo and anthraquinone compounds free from the dispersing agents present in the commercial dyes and the results are discussed. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 123–128, 2002     

Disperse dyeing of polyester fibers: Kinetic and equilibrium study

The effect of temperature on the dyeing rate constant k, diffusion coefficient D, time of half‐dyeing t_1/2 was evaluated for the dyeing of polyester fibers with two disperse dyes, an azo and an anthraquinone dye. Activation energies of diffusion E were calculated. The polyester dyeing equilibrium was also studied and the partition coefficient K and standard affinity Δμ° at various temperatures were determined for the anthraquinone dye. Standard enthalpy ΔH° and standard entropy ΔS° of dyeing were also obtained. The same equilibrium parameters were not obtained for the azo dye because of its dyeing behavior. A similar kinetic and equilibrium study was made for the pure azo and anthraquinone compounds free from the dispersing agents present in the commercial dyes and the results are discussed. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2785–2790, 2002; DOI 10.1002/app.10254     

Effect of N,N‐diethyl‐m‐toluamide on the structure and dyeing properties of meta‐aramid and para‐aramid fibre

N,N‐Diethyl‐m‐toluamide has been widely used in the mosquito‐repellent finishing of textiles over the past few decades, but the use of N,N‐diethyl‐m‐toluamide as a dye carrier for aramid dyeing with disperse dye has been seldom reported. Meanwhile, the application of aramid fibre in clothing is limited because it is difficult to dye. In this work, the effect of N,N‐diethyl‐m‐toluamide on the dyeing properties of aramid fibre was examined by measuring the percentage disperse dye exhaustion under different conditions. In order to understand the mechanism by which N,N‐diethyl‐m‐toluamide promotes the exhaustion of disperse dye on aramid fibre, the ultraviolet‐visible spectrum of the dye and N,N‐diethyl‐m‐toluamide solution, the glass transition temperature, the crystalline structure, and the degree of orientation of aramid fibre treated with N,N‐diethyl‐m‐toluamide were measured by ultraviolet‐visible spectrophotometry, differential scanning calorimetry, X‐ray diffraction analysis, and velocity‐oriented tests respectively. The results indicated that N,N‐diethyl‐m‐toluamide not only could reduce the glass transition temperature and degree of orientation of aramid fibre but could also improve the solubility of disperse dye in aqueous solution, and therefore could enhance the percentage disperse dye uptake on aramid fibre, whereas treatment with N,N‐diethyl‐m‐toluamide showed little effect on the crystalline structure of aramid fibre. The results implied that N,N‐diethyl‐m‐toluamide was beneficial to the diffusion of disperse dye molecules into the amorphous region of aramid fibre under the dyeing conditions, but seldom affected the mechanical properties of aramid fibre.     

Reaction and diffusion of reactive disperse dye in nylon 6

The diffusion of a reactive disperse dye with a vinylsulfonyl group accompanied by simultaneous reaction with the amino end groups in nylon 6 was examined by the method of cylindrical film roll at 70°C and pH 2.2–8.0. The experimental diffusion profiles of the active and fixed species of the dye in nylon 6 were confirmed to be described by the diffusion equation accompanied by the chemical reaction with substrate taking the limited amount of the end groups into account, where the active species of dye were assumed to react only with the free base of amino end groups. The completion of the reaction with the amino end groups was observed in the first layer from the surface at pH 6.0–8.0. The value of diffusion coefficient was constant (8.0 × 10^?10 cm²/s) at all the pH's. The product of the second-order rate constant, k₂, of reaction of the dye and the dissociation constant, K_a, of the amino end groups was constant (k₂K_a = 4.0 × 10^?9 s^?1) at pH 2.2–8.0. The k₂ values of the reaction with various substrates for vinylsulfonyl and monochlorotriazinyl-reactive dyes were compared and the practical dyeing conditions were discussed.     

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.     

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     

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.     

Dyeing mechanism and model of nylon 6 fiber dyeing in low‐temperature hydrogen peroxide–glyoxal redox system

This article reports the results of a study of nylon 6 fiber dyed in a low‐temperature hydrogen peroxide–glyoxal redox system. It was expected that the dyed fiber would have better dye fastness and higher economic value than would conventional fiber. In addition, this article presents the proposed mechanism for and model of a free‐radical dyeing system as well as a derived theoretical equation. From the experimental results, it was found that formation of covalent bonds by the coupling of the dye and the fiber radical in free‐radical dyeing was only 25%–40%, whereas with the conventional type of ionic dyeing, it was almost 60%–75%. Because the initiation efficiency of free‐radical formation is affected by many factors, such as the pH of the dye bath and the concentrations of the oxidant and reductant, the aims of this study were to investigate the formation of free radicals and the effects on dye uptake of the concentrations of dye, oxidant, and reductant and of the fiber amine end group. In addition, the dyeing properties of dyed fiber were investigated, and the dyeing order and rate constant of the rate equation were evaluated from the experimental data. From the experimental results, the following conclusions were drawn. (1) The hydrogen peroxide–glyoxal redox system produced many free radicals in the dye bath as temperature reached 70°C. (2) The amine end group in the nylon fiber was the main site of ionic and covalent bonding between nylon 6 fiber and dye. (3) The proposed model of free‐radical dyeing showed, from the fit of the experimental data into the equation and the evaluation of the equation parameters, that the order fit the theoretical value well, with the rate constant dependent on the dyeing conditions; at pH = 3, it could match the equation's best (rate equation of the proposed model: d[D]_R/dt = k_A[GO]¹[H₂O]^m[D]^1/2[F]^1/2). (4) The optimum dyeing conditions in the hydrogen peroxide–glyoxal redox system were: [H₂O₂] = 0.15–0.20M, [glyoxal] = 0.07–0.10M, pH = 3, dyeing temperature = 70°C, and dyeing time = 45–50 min. (5) The redox dyeing system had better dye fastness than did the conventional system. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4197–4207, 2006     

Dyeing as-spun polypropylene fibres with disperse dyes using periodic technology

The major possibility of dyeing PP fibres medium hues with disperse dyes using periodic technology was demonstrated. It was found that dyeing as-spun PP fibres ensures diffusion of the dye inside the fibre material. Use of Neonol AF 9/6 nonionogenic wetting agent during dyeing increases the amount of dye sorbed by PP fibre material. Translated from Khimicheskie Volokna, No. 1, pp. 24-26, January-February, 2008.     

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 Acrilan with Basic Dyes in the Presence of Benzyl Alcohol*

The dyeing of Acrilan with C.I. Basic Green 4 from water containing benzyl alcohol and benzyl alcohol containing water has been examined. Benzyl alcohol in water acts as a plasticizing agent for the fibre. The plasticizing action of small quantities of water in benzyl alcohol has also been detected and in both systems the rate of diffusion of dye into the fibre is related to the plasticizing action. The equilibrium absorption is a function of the difference between the dyeing temperature (T) and the glass transition temperature (T_g) of the fibre. The differences in the behaviour of the dye in the aqueous and benzyl alcohol dyebaths are related to the degree of dissociation of the dye and the mechanical properties of the fibres.     

The mechanism of carrier dyeing

The accelerated rate of diffusion of disperse dyes into synthetic fibers caused by various dyebath additives (“carriers”) has been correlated with their plasticizing action. The rate of change in length of Acrilan filaments with temperature under dyebath conditions enabled the effects of the carrier on the T_g of the filaments to be measured, and the results for different concentrations of carrier at one temperature could be superimposed on a common curve by employing suitable shift factors. The shift factors, as well as the variations of the diffusion coefficients of dyes with temperature and carrier concentration, both matched a WLF relationship, confirming that the dyeing process is controlled by the segmental mobility of the polymer. Indirect experimental evidence suggests that the same relation will describe the effect of carriers on the dyeing of poly(ethylene terephthalate) substrates with disperse dyes.     

The mathematical expression of rate constants in empirical rate of dyeing equations in disperse dyeing

The relationship between the rate constants in empirical rate of dyeing equations and the diffusion coefficient of dye in the fibre have been clarified by means of a statistical curve fitting method, where the rate of dyeing curves calculated from the theoretical equations (those of Wilson and Newman) have been compared with those from the empirical equations in the range M_t/M∞ from zero to about 0.8. The comparisons revealed that many of the empirical equations are suitable for describing the dyeing rate when there is a delay of dye sorption in the early stages, and one of them is useful for determining the dyeing rate when there is rapid dye sorption at the initial stages. The fact that these empirical equations fit well to practical dyeing can be explained in terms of the sorption delay caused by the stagnant solution layer surrounding the fibres.     

The carrier dyeing of synthetic fibers

The mode of action of carriers in augmenting the rate of dyeing of disperse dyes with acrylic and polyester fibers is discussed in terms of the plasticizing action of the carrier. It is shown that the effectiveness of a carrier is determined by its ability to reduce the glass transition temperature of the fiber and not by the fiber swelling. The rate of dyeing as measured by the diffusion coefficient of the dye is shown to be uniquely related to the difference between the dyeing temperature and the glass transition temperature (T – T_g). In the light of these results, some aspects of carrier action in dyeing from perchlorethylene are discussed. Treatment of polyester fibers with carrier also increases crystallinity. Changes in diffusion for a series of copolyesters have been correlated with the long spacing obtained from small angle X-ray scattering (SAXS).     

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.     

Confocal Raman study of poly(ethylene terephthalate) fibres dyed in supercritical carbon dioxide: dye diffusion and polymer morphology

Confocal Raman microscopy (CRM) has been used to extract dye diffusion data from poly(ethylene terephthalate) (PET) fibres dyed with Disperse Yellow 23 under supercritical CO₂ conditions. Spectral information as a function of depth was measured in a non-destructive manner using dry and oil objectives in confocal Raman mode. Mapping along the radius of the fibre cross-section was performed and compared to the data from the confocal measurements. A significant dye concentration gradient has been observed along the line normal to the fibre surface which the data from the oil confocal measurements accurately describes to a depth of 45 μm. The effect of the supercritical CO₂ dyeing process on the fibre morphology has also been evaluated using CRM.     

Carrier‐free dyeing of radiation‐grafted polyester fabrics with disperse dyes

Carrier‐free dyeing of radiation‐grafted polyester fabrics with disperse red dye was studied in the temperature range 283–363 K. 1‐vinyl 2‐pyrrolidone (NVP), acrylic acid (AA) or their mixture was used to graft poly(ethylene terephthalate) (PET) fabric. The effects of pH of the dye solution, graft yield (GY), dyeing time (t), dye concentration (C), and dyeing temperature (T) on the colour difference (CD) of PET fabric were studied. The best dyeing condition was achieved at pH 5.5. CD increases linearly with the increase in GY, with slopes depending on the type of grafted copolymer. CD increased rapidly as the dyeing time increased; this was followed by a relatively slow dyeing rate within a few minutes. The initial dyeing rate (R) was found to increase with an increase in C and T. The dyeing rates for all grafted samples followed 0.35‐order kinetics and are temperature‐independent. Average activation energy 9.26 kJ mol^?1 is calculated for the dyeing process and is independent of the fabric treatment. Pre‐exponential rate constants 1976, 1839, and 1579 (CD/GY) s^?1 were calculated for dyeing PET samples grafted with AA/NVP mixture, NVP and AA, respectively, while 1074 CD s^?1 was evaluated for carrier dyeing of ungrafted fabric. Analysis of the kinetic parameters and the dyeing mechanism revealed that dyeing PET fabric was diffusion‐controlled. Grafting PET fabric improved significantly the dyeing affinity of the DR dye over ungrafted samples dyed in solutions containing a carrier. Copyright © 2005 Society of Chemical Industry     

Carrier dyeing of polyphenylene sulphide fabric with disperse dye

Polyphenylene sulphide is considered to be a high‐performance thermoplastic material and has been used in many areas over the past few decades. But the application of polyphenylene sulphide fabric used for protective clothing is limited because of difficulties in its dyeing and printing. In this work, carrier dyeing of polyphenylene sulphide fabric with disperse dye is discussed, and the effect of the structure of the carrier, dyeing temperature, dyeing time, usage of carrier and usage of dye on colour strength of the dyed sample and the percentage of dye exhaustion were investigated. In addition, the glass transition temperature, crystalline structure and orientation degree of treated polyphenylene sulphide fibre with benzyl benzoate were measured by differential scanning calorimetry, X‐ray diffraction analysis and velocity‐oriented tester, respectively. The results indicated that benzyl benzoate could increase the percentages of dye exhaustion and colour strength values, while at the same time reduce the glass transition temperature and orientation degree of the treated polyphenylene sulphide fibre. Thus, it would be beneficial to the diffusion of the dye molecules into the amorphous region of the fibre. Furthermore, the decrease of tensile strength and limiting oxygen index of the dyed polyphenylene sulphide sample was very little, and the colour fastness and levelness of the dyed polyphenylene sulphide samples were also satisfactory.