Perylene-Based Fluorescent Sizing Agent for Precise Evaluation of Permeability and Coating Property of Sizing Paste

Abstract

Warp sizing is considered as the most important process of weaving preparation in the textile field. The quality of sized warp yarns is directly determined by the permeation and coating of sizing paste into/on warp yarns. However, many significant flaws of the current method of permeability and coating property of sizing paste, such as low accuracy and narrow variety adaptability for sizing agents and warp yarns, have emerged in the evaluation process. In order to eliminate the inherent flaws in the current method, the investigation chose chitosan (CS) as a representative of common sizing agents, introduced various amounts of perylene units onto molecular chains of the CS, and prepared a new functional sizing agent—fluorescent CS with different labeling degrees of perylene. Furthermore, PVA-perylene was synthesized to evaluate the permeability and coating property of PVA sizing paste. Then, three indexes to indicate the permeability and coating property of sizing paste, i.e. permeation percentage, coating percentage and integrity percentage of sizing film, were evaluated using the CS-perylene and PVA-perylene derivatives prepared. Due to the fluorescence emitted by the perylene units, the three indexes can be determined accurately and conveniently depending on only fluorescent microscope and common image processing software. The investigation efficiently solves the difficult problem of evaluating permeation and coating property of the pastes of both bio-based and petroleum-based sizing agents with appropriate degrees of labeling and has a significant guiding function on accurate determination of the quality of sized yarns.

Graphic abstract

Introduction

Warp sizing is a major process of weaving preparation and determines the weaving efficiency directly [1,2,3]. Sizing agent is a basic material in the process, acts as a polymer adhesive and its consumption ranks only second to fibre material in textile industry [4]. The sizing paste adsorbed by warp yarns is generally divided into two parts during the sizing process. One part coats the surface of the yarn to form sizing film and the other part penetrates the interior of the yarn. The quality of sized yarns can be guaranteed only when proper coating and permeating actions exist simultaneously [5, 6]. Therefore, the coating property and permeability of the sizing paste become the focus of sizing process design. However, there is no appropriate general method to accurately characterize and evaluate the properties.

At present, the permeability and coating property of sizing paste are determined according to an industry standard (FZ/T 94041-1995, a criterion regulated by Textile Association of China). The sized yarn is firstly cut into cross sections and then immersed into color-developing agent to be colored. The surface morphology of the colored yarn section is observed and taken photos by ordinary optical microscope. Based on the photos, the permeability and coating property are estimated using three indexes, i.e. permeation percentage, coating percentage and integrity percentage of sizing film. As shown in Fig. 1, the cross section of a sized yarn consists of three parts from the outside to the inside, namely, sizing film, the parts permeated and not permeated by sizing agent.

Fig. 1
figure1

Cross section of sized yarn (S1, S and S2 denote cross sectional areas of sized yarn, raw yarn, and non-permeated part of sized yarn, respectively; αi denotes the angle formed by each part of sizing film surrounding the raw yarn)

There are many problems with the above determination method. At first, only two kinds of color-developing agents, i.e. I2-KI and I2-H3BO3, can be currently used to dye warp yarns sized by two main sizing agents, i.e. starch and polyvinyl alcohol (PVA), respectively [7, 8]. As for other common sizing agents, such as polyacrylamide [9], vegetable/animal gum [10, 11] and chitosan [12], their color-developing agents have not been studied yet. A long time will be consumed if the researchers want to find corresponding color-developing agents for every sizing agent. Secondly, owing to the limited resolution, ordinary optical microscope can only provide blurred cross section photo of sized yarn as shown in Fig. 2. The boundary between the sizing film part and the part permeated by sizing agent is too difficult to be distinguished because both the parts show nearly the same color after contacting with the color-developing agent. Large errors are scarcely avoidable in the calculations of the permeation percentage, coating percentage, and integrity percentage of sizing film due to the unclear boundary between the two parts. Furthermore, as to colored spun yarns, especially the black, blue and purple ones, it is impossible for the observer to distinguish the three parts of the cross section using color-developing agent due to the interference of the original color of warp yarns.

Fig. 2
figure2

The photos of cross sections of the yarns sized by starch (a) and PVA (b) color-developed by I2-KI and I2-H3BO3, respectively

The above problems of the traditional method have seriously interfered with the evaluation of the quality of sized yarns so it is urgent to develop a new determination method to avoid the problems. The present study has synthesized and utilized a functional polymer material, which is named fluorescent sizing agent, based on good photoluminescence effect for the evaluation of permeability and coating property of sizing paste. Every part of cross section of the warp yarn sized by fluorescent sizing agent can be distinguished directly by fluorescent microscope. Under bright field of fluorescent microscope, the boundary of the sizing film part and the part permeated by sizing agent of the yarn can be clearly observed because the former possesses much higher visible light transmittance than the latter [13, 14]. Under UV-light or blue excitation light field of fluorescent microscope, only the part not permeated by the fluorescent sizing agent cannot emit any fluorescence. As a result, the sizing film part and the part not permeated by sizing agent can be identified under bright and UV-light or blue excitation light fields, respectively. Hence, the permeability and coating property of the sizing paste can be conveniently evaluated without any color-developing agent, limited by neither the sizing agents nor the warp yarns.

Perylene derivatives own many outstanding properties, such as stable molecular structure, high pigmentation degree, wide color gamut, chemical inertness, good dyeing properties and high thermal stability [15]. Moreover, perylene derivative has quite a low price. For example, perylene tetracarboxylic acid (PTCA) is only about 2 dollars/kg. Chitosan (CS) is a kind of natural polysaccharide with wide sources, simple manufacturing process and good biodegradability [12]. As a result, CS is widely used as a bio-based sizing agent. From economic perspective and easy availability, the study introduced various amounts of perylene units onto molecular chains of native CS and prepared the fluorescent CS sizing agents with different degrees of labeling (DL) of perylene. After the comparisons of the fluorescence intensity and photostability of the CS-perylene and the ease of observation of the sized yarn cross section, the CS-perylene sizing agent with appropriate DL of perylene was selected. In addition, the perylene units were labeled onto the molecular chain of a commonly used petroleum-based sizing agent—PVA. The permeability and coating property of PVA sizing paste could be also evaluated accurately with the help of the fluorescence emitted by the perylene units labeled. To the best of our knowledge, there is no report on the application of fluorescent CS or PVA as sizing agent. It is practical, convenient, and economical to utilize the fluorescent sizing agent containing perylene to determine the permeability and coating property of sizing paste accurately in textile industry.

Experimental Section

Materials

CS (Mw: 260,000, degree of deacetylation: 90%) was purchased from Qufu Shengjiade Biotechnology Co., Ltd. (China). PVA (degree of polymerization: 1700, degree of alcoholysis: 99%) was provided by Shanghai Petrochemical Industry Co., Ltd. (China). PTCA, dibutyltin dilaurate (DBTDL), dicyclohexylcarbodiimide (DCC), 4-dimethylaminopyridine (DMAP), LiCl, and dimethylacetamide (DMAc) were purchased from Sigma-Aldrich and Alfa Aesar (USA). Cotton warp yarns (27.6 tex) were kindly supplied by Weifang Yubang Textile Co., Ltd. (China). All chemicals were of analytical grade and used as received without further purification.

Preparation of CS-Perylene Derivatives

The general procedure of synthesizing CS-perylene is illustrated with an example of the feed molar ratio of PTCA to constitutional unit of CS = 1/970 (Ratio ranges from 1/485 to 1/3880).

At first, anhydrous LiCl (9.7770 g) was dissolved into 120 mL of DMAc under vigorous stirring at 60 °C to form a LiCl/DMAc compound solvent (weight percentage of LiCl: 8%). Then, 0.5286 g of CS (molar number of constitutional units: 0.0032 mol), 0.0244 g of DMAP (catalyst) and 0.2476 g of DCC (dehydrator) were added into 120 mL of the LiCl/DMAc compound solvent to obtain Solution A. In addition, 0.0214 g of PTCA was dissolved in 100 mL of DMAc to obtain Solution B. Then, 6.6 mL of the PTCA/DMAc solution (Solution B) was transferred into the Solution A. The mixture was refluxed at 100 °C for 1.5 h and then cooled to ambient temperature. The solution was precipitated with ethanol, centrifuged at a ratio of 10,000 r/min and washed with ethanol thoroughly. The CS-perylene precipitate was dissolved in dilute acetic acid (0.1 mol/L) and the unreacted reagents were removed via dialysis in distilled water for 24 h. The CS-perylene was freeze dried, pulverized and stored in desiccator. The synthetic route of CS-perylene is shown in Fig. 3. CS-perylene samples were numbered according to the feed molar ratio of the constitutional unit of CS to PTCA.

Fig. 3
figure3

Synthetic route of CS-perylene

Preparation of PVA-Perylene Derivatives

At first, 4.3560 g of PVA (molar number of constitutional units: 0.0981 mol), 0.2928 g of DMAP (catalyst) and 2.9712 g of DCC (dehydrator) were added into 120 mL of DMAc to obtain Solution A. In addition, 0.3424 g of PTCA was dissolved in 100 mL of DMAc to obtain Solution B. Then, 20 mL of the PTCA/DMAc solution (Solution B) was transferred into the Solution A. The mixture was refluxed at 100 °C for 1.5 h and then cooled to ambient temperature. The solution was precipitated with ethanol, centrifuged at a ratio of 10,000 r/min and washed with ethanol thoroughly. The PVA-perylene precipitate was dissolved in distilled water and the unreacted reagents were removed via dialysis in distilled water for 24 h. The PVA-perylene was freeze dried, pulverized and stored in desiccator. The synthetic route of PVA-perylene is shown in Fig. 4.

Fig. 4
figure4

Synthetic route of PVA-perylene

Characterization Methods

1H-NMR spectroscopy analysis was conducted to verify the labeling of perylene using an AVAMCE III 400 MHz Digital NMR spectrometer (Bruker Co. Ltd. Switzerland) and the CS-perylene and PVA-perylene were dissolved in D2O/trifluoroacetic acid-d blended solvent and DMSO-d, respectively. Fourier transform infrared spectrometer (FTIR) was also used to verify the labeling of the perylene and the measurement was taken on Nicolet Nexus spectrophotometer through the diffuse reflectance technique with a spectral resolution of 2 cm–1 for 64 scans. PL intensity of the CS-perylene solution was measured with Hitachi F-7000 fluorescence spectrophotometer. The CS-perylene samples were dissolved in dilute acetic acid (0.1 mol/L) to form solutions (1 g/L). Degree of labeling (DL) and Efficiency of labeling (EL) of the CS-perylene and PVA-perylene were tested with Shimadzu UV-2450 UV–visible spectrophotometer, and the CS-perylene and PVA-perylene samples were dissolved in dilute acetic acid (0.1 mol/L) and distilled water, respectively, to form solutions. The DL denotes the molar ratio of the perylene labeled onto the CS/PVA to constitutional unit of the CS/PVA while the EL denotes the molar ratio of the perylene labeled onto the CS/PVA to the perylene fed totally.

Sizing Experiment

The CS-perylene and PVA-perylene were dissolved in 2% of dilute acetic acid and distilled water, respectively, to form a 10% (w/w) solution. The solution was heated and maintained at 95 °C under magnetic stirring for 1 h. The sizing experiment for pure cotton warp yarns was carried out using a GA392 laboratory single-yarn sizing machine purchased from Jiangyin Tongyuan Textile Machinery Co. Ltd. Sizing style of the machine was single-dip-single-nip. The warp yarns were wound in the machine and the cooked sizing paste was poured into size box, where it was adjusted to 95 °C. Sizing tension was 1.0 N and the running speed of sizing machine was 30 m/min. Hot air and cylinder allied drying style was employed in drying chamber, where it was adjusted to 110 °C. The sized yarns were dried in the chamber for 3 min and finally conditioned at 65% relative humidity and 20 °C for at least 48 h before performance tests.

Evaluation of Permeability and Coating Properties through the Method of Current Industry Standard (FZ/T 94041-1995)

The sized yarn was cut into thin cross sections (thickness ≤ 20 μm) by Hardy fiber microtome at first. The yarn section was saturated into color-developing agent to get color. Then, the surface morphology of the color-developed yarn section was observed and taken photos by ordinary optical microscope. Finally, the permeability and coating property were evaluated using three basic indexes, i.e. permeation percentage (P), coating percentage (C) and integrity percentage of sizing film (I), which were calculated in accordance with Fig. 1 and Eqs. 13.

$$ {\text{P}} = {\text{ S}}_{{\text{p}}} /{\text{S }} = \, \left( {{\text{S}} - {\text{S}}_{2} } \right)/{\text{S}} \times 100\% $$
(1)

where S, Sp and S2 denote cross sectional areas of unsized yarn, permeated part and non-permeated part of sized yarn, respectively.

$$ {\text{C}} = {\text{ S}}_{{\text{f}}} /{\text{S }} = \, \left( {{\text{S}}_{1} - {\text{S}}} \right)/{\text{S}} \times 100\% $$
(2)

where S, Sf and S1 denote cross sectional areas of unsized yarn, sizing film on the surface of the yarn and the whole sized yarn, respectively.

$$ I = \, \Sigma \alpha_{i} /360^\circ \times 100\% $$
(3)

where αi denotes the angle formed by each part of sizing film surrounding the yarn.

Evaluation of Permeability and Coating Property of CS-Perylene and PVA-Perylene Sizing Pastes

The sized yarn was cut into thin cross sections (thickness ≤ 20 μm) by Hardy fiber microtome at first. The cross sections of the sized yarn were taken photos under bright field and blue excitation light by fluorescent microscope (Leica DM300 Microsystems), respectively. As shown in Fig. 1, the areas of S, S1 and S2 were delimited under bright field and blue excitation light, respectively and were measured through Photoshop. The permeation percentage, coating percentage and integrity percentage of sizing film were also calculated in accordance with the three equations described above. For every sample, ten replications were taken and the mean values were obtained.

Measurement of Application Properties of the Sized Yarns

Tensile strength and elongation of the yarns were determined on a model YG023A electric strength tester purchased from Laizhou Electronic Instrument Factory. The initial chuck-distance and drawing speed were 500 mm and 500 mm/min respectively. For every sample, twenty replications were taken and their mean values were obtained.

The yarns were abraded reciprocatively on an LFY109B electric yarn abrader purchased from Textile Science Research Institute of Shandong. The resistance to reciprocating friction of the sized yarns was evaluated in the reciprocal motion times of the yarns until breaking. The tension exerted on the yarns was 9.8 cN. The values reported were mean value of twenty tests for each case. The abrasive material used was W5(06) abrasive paper manufactured by Shanghai Emery Wheel Company.

Dense and long hairiness on surface of warp yarns frequently causes unclear shed and high breakage rate. The hairiness (≥ 3 mm) has adverse impact on weaving and is regarded generally as “harmful hairiness”. The amount of yarn hairiness, of which length was in the range of 3–9 mm, was evaluated by YG171B-2 hairiness tester purchased from Nantong Sansi Electronic Instrument Factory. The values reported were mean value of ten tests for each case. Each test requires a 10-m-long yarn with a drawing speed of 30 m/min.

Statistical Analysis

The data of permeation percentage, coating percentage and integrity percentage of sizing film were analyzed using SAS software (SAS Institute, Inc., Cary, NC). The confidence interval was set at 95% and a p value smaller than 0.05 was considered to be a statistically significant difference. In Figs. 13, 14 and 15, data points with the same small letter were not statistically significantly different from each other.

Results and Discussion

1H-NMR Characterization

1H-NMR spectra of unlabeled CS and CS-perylene are shown in Fig. 5. Chemical shift at about 4.8 ppm corresponds to proton peak of the solvent (D2O). Besides chemical shift of unlabeled CS (Fig. 5a), such as the ones in the range of 2.9–4.1 ppm corresponding to methine and methylene in the backbone of CS [16], new chemical shift in the range of 7.0–8.0 ppm were found in the spectra of the CS-perylene derivatives and able to be considered as the proton of aromatic rings of perylene [17]. Due to low DL of the CS-perylene, the proton peaks of perylene were quite low or even not able to be found when the feed molar ratio of PTCA to constitutional unit of CS was lower than 1/970.

Fig. 5
figure5

1H-NMR spectra of unlabeled CS (a) and CS-perylene conjugates with DL values of 0.0667 mol% (b), 0.0918 mol% (c) and 0.1145 mol% (d)

1H-NMR spectra of unlabeled PVA and PVA-perylene are shown in Fig. 6. Chemical shifts at about 2.5 and 3.3 ppm correspond to proton peaks of the solvent (DMSO-d) and residual water, respectively. In addition to chemical shift of unlabeled PVA, such as the ones in the range of 3.5–4.5 and 0.9–1.5 ppm corresponding to the protons of hydroxyl and alkyl chain [18], new but low chemical shift peaks in the range of 7.0–8.0 ppm were found in the spectra of the PVA-perylene like CS-perylene derivatives. The new chemical shift peaks confirmed the successful labeling of perylene units.

Fig. 6
figure6

1H-NMR spectra of unlabeled PVA (a) and PVA-perylene with a DL value of 0.0515 mol% (b)

FTIR Characterization

FTIR spectra of unlabeled CS and CS-perylene are shown in Fig. 7. It could be observed that two peaks appeared at 1660 cm−1 and 1550 cm−1 due to characteristic absorption bands of the amide I and amide II bands, respectively [12]. FTIR spectrum of CS-perylene showed a new characteristic peak of asymmetric C-O stretch assigned to –COOH at 1250 cm−1 [18] in addition to the absorption bands of unlabeled CS. The peak at 1250 cm−1 confirmed the labeling of perylene onto the CS.

Fig. 7
figure7

FTIR spectra of unlabeled CS (a) and CS-perylene conjugates with DL values of 0.0667 mol% (b), 0.0918 mol% (c) and 0.1145 mol% (d)

FTIR spectra of unlabeled PVA and PVA-perylene are described in Fig. 8. It could be observed that a wide absorption peak appeared in the range of 3250–3350 cm−1 due to the stretching vibration of the hydroxyl [18]. Similar to CS-perylene, a new characteristic peak of asymmetric C-O stretch assigned to –COOH at 1265 cm−1 appeared in the FTIR spectrum of PVA-perylene in addition to the absorption bands of unlabeled PVA and was also regarded as the proof of the labeling of perylene units.

Fig. 8
figure8

FTIR spectra of unlabeled PVA and PVA-perylene with a DL value of 0.0515 mol%

Characterization of UV–Visible Spectrophotometer

Due to low DL of the CS-perylene and PVA-perylene derivatives, UV–visible spectrophotometer had to be used to evaluate the DL and EL of the derivatives. The original data, such as relationship between the concentration of PTCA solution and its absorbance, feed and actual weight ratios of PTCA to CS/PVA, were displayed in Fig. S1, Tables S1 and S2 in supporting information. As shown in Table 1, the DL increased with the increase in the feed molar ratios of PTCA to constitutional unit of CS while the EL gradually decreased.

Table 1 DL and EL of CS-perylene derivatives with various feed molar ratios of PTCA to constitutional unit of CS

The esterification and amidation reactive sites of the CS with PTCA are hydroxyl and amino, respectively. It should be noted that the number of the hydroxyl and amino groups in CS are limited. With the increase in the amount of PTCA fed, the reactive sites of CS were taken up gradually and thus it turned more difficult for PTCA to react with CS. As a result, the EL decreased stepwise with the increase in the feed concentration of PTCA.

Fluorescence Property of CS-Perylene

The images of CS and CS-perylene solutions under visible and UV lights and fluorescence intensities of CS-perylene with various DL values are displayed in Figs. 9 and 10, respectively. As observed from the figures, fluorescence intensity initially increased with the increase in the DL of the CS-perylene, reached the maximum when the DL was 0.0667 mol% (i.e. CS-perylene 970), and then started to decrease.

Fig. 9
figure9

Images of the solutions of unlabeled CS and CS perylene derivatives (the six solutions are unlabeled CS, CS-perylene 3880, 1940, 970, 647, and 485 from left to right) under visible light (a) and UV light (b)

Fig. 10
figure10

PL spectra of the solutions of CS-perylene derivatives

PTCA is a kind of aggregation caused quenching (ACQ) luminogen used widely as fluorescence material and is able to endow CS with good fluorescence property after appropriate amount of the luminogens are labelled onto the macromolecule. In this case, the fluorescence intensity of the CS-perylene directly relates to its DL value. Consequently, the initial increase in the amount of the perylene labelled onto CS helped to enhance the fluorescence intensity. However, fluorescence quantum yield decreased when the DL exceeded 0.0667 mol% due to the occurrence of ACQ phenomenon. Therefore, 0.0667 mol% could be considered as a critical DL from which the perylene began to aggregate. The concentration of the CS-perylene solution for the PL intensity test was 1 g/L. In the case of the critical DL (i.e. 0.0667 mol%), a perylene molecule took up about a cubic space 411,184 nm3 (edge length: 74.35 nm). The major reason for the aggregation of the conjugated ACQ luminogens is the π-π stacking interaction between perylene and the distance of π-π stacking interaction is in the range of 0.34–0.40 nm [19, 20]. Obviously, the average distance between perylene at the critical DL of CS-perylene is far longer than 0.40 nm. As a result, we could speculate that ACQ had occurred in the CS-perylene solution before the perylene fell in the range of the π-π stacking interaction. The cause for the occurrence of the ACQ phenomenon was the intense thermal motion the perylene experienced owing to the lack of spatial constraint. Consequently, the perylene might still collide with each other or fall into the range of π-π stacking to result in ACQ phenomenon even in a large space.

Permeability and Coating Property of CS-Perylene Sizing Paste

The images of the cross sections of the cotton warp yarns sized by CS-perylene and PVA-perylene conjugates under fluorescent microscope are shown in Figs. 11 and 12, respectively. As is illuminated above, the sizing film part and the part not permeated by sizing agent of the yarn section can be identified under bright field and blue excitation light field, respectively. The areas of the three parts of the cross section, i.e. sizing film, the parts permeated and not permeated by the sizing agent, were directly acquired by common image processing software, e.g. Photoshop in this study. Thereafter, three indexes [i.e. permeation percentage (P), coating percentage (C) and integrity percentage of sizing film (I)] used to indicate permeability and coating property of the sizing agent were calculated in accordance with Eqs. 13. The three indexes of the CS-perylene with various DL values are displayed in Fig. 13. As shown in the figure, the values of P and C both initially increased with the increase in the DL of the CS-perylene, reached the maximum when the DL was 0.0667 mol% (i.e. CS-perylene 970), and then started to decrease. As for the I, the DL exhibited no significant influences and all the values were around 89.6%. Compared with Fig. 2b, the photo of cross section of the yarns sized by PVA-perylene is quite clear due to the adequate fluorescence emitted by the perylene units. It is more accurate for the researchers to calculate the three indexes (i.e. P, C and I) of PVA sizing paste than using I2-H3BO3 color-developing agent to dye the sized yarns.

Fig. 11
figure11

Images of cross sections of the yarns sized by CS-perylene 3880 (a, b), CS-perylene 1940 (c and d), CS-perylene 970 (e, f), CS-perylene 647 (g, h) and CS-perylene 485 (i, j) under bright field and blue excitation light field by fluorescent microscope

Fig. 12
figure12

Image of cross section of the yarn sized by PVA-perylene under bright field (a) and blue excitation light field (b) by fluorescent microscope (P, C and I of the PVA-perylene: 38.3%, 69.0% and 95.8%, respectively)

Fig. 13
figure13

Permeation percentage (P), coating percentage (C) and integrity percentage of sizing film (I) of CS-perylene sizing pastes

In this study, the same cotton warp yarns were sized by the fluorescent CS with the same sizing machine and processing parameters. Therefore, the three indexes of all the fluorescent CS sizing pastes should be similar in theory. However, the permeation percentage and coating percentage of the sizing pastes of the CS-perylene both changed in a parabolic fashion. On one hand, when the DL was lower than the critical value (i.e. 0.0667 mol%), there were not enough perylene luminogens in the molecular chains of the fluorescent CS and the fluorescence it emitted was not intensive enough. Consequently, the areas of the sizing film and the part permeated by CS-perylene sizing paste observed under excitation light field by fluorescent microscope were both smaller than their actual areas. P and C were calculated according to Eqs. 1 and 2, respectively. It can be deduced from the two equations that, the smaller the areas of the permeated part and the sizing film, the lower the P and C. On the other hand, when the DL was higher than the critical value, the P and C started to decrease instead due to the occurrence of ACQ phenomenon of the perylene. As a result, P and C were both lower than their actual values. Obviously, only the CS-perylene conjugate with appropriate DL (0.0667 mol%) is suitable to serve as a functional sizing agent to evaluate the permeability and coating property. As to I, it did not have a close relationship to the areas of the sizing film and the part permeated by CS-perylene sizing paste observed under excitation light field so the values of the CS-perylene with various DL were quite similar.

3.4 Comparison of Application Properties of Warp Yarns Sized by Unlabeled CS and CS-Perylene

Comparison tests on major application properties (e.g. tensile strength and elongation, resistance to abrasion, and hairiness adhering property) of warp yarns sized by unlabeled CS and the CS-perylene with appropriate DL (i.e. 0.0667 mol%) were carried out to verify whether the labeling of perylene had remarkable effects on the properties. If the labeling changes the application properties remarkably, it will be meaningless to evaluate the permeability and coating property of a sizing agent using its fluorescence-modified product labeled by perylene.

The mechanical properties and the number of the hariness with different lengths of unsized yarns and the yarns sized by the CS and PVA samples are shown in Figs. 14 and 15, Tables S3 and S4, respectively. The original data of Fig. 14 are displayed in Table S5. As shown in the two figures and tables, the yarns sized by the CS-perylene/PVA-perylene had similar application properties to those sized by unlabeled CS/PVA. Nearly all the major application properties of sized yarns greatly depend on permeability and coating property of the sizing paste. Thus, similar application properties indicated that the unlabeled and labeled sizing pastes possessed similar permeability and coating property to the cotton yarns. In this case, the permeability and coating property of the CS-perylene/PVA-perylene can be regarded as true reflections of the properties of unlabeled CS.

Fig. 14
figure14

Mechanical properties of unsized yarn and the yarns sized by unlabeled CS and CS-perylene 970

Fig. 15
figure15

The number of the hairiness with different lengths of unsized yarn and the yarns sized by unlabeled CS and CS-perylene 970

Conclusions

In summary, a new kind of functional sizing agent based on fluorescence effect through the introduction of perylene has been developed for the accurate evaluation of permeability and coating property of sizing paste. CS was taken as an example of common sizing agents in this study and its fluorescent products (CS-perylene) with appropriate DL were utilized to evaluate the permeability and coating property successfully and conveniently. After the evaluation of fluorescence and sizing application properties of the CS-perylene with various DL, the one with DL of 0.0667 mol% exhibited adequately intensive fluorescence able to be observed and similar application properties to unlabeled CS. Therefore, three important indexes (i.e. permeation percentage, coating percentage and integrity percentage of sizing film) of the CS-perylene paste can be regarded as the true reflections of the unlabeled CS paste. In addition, a PVA-perylene derivative with DL of 0.0515 mol% was synthesized and the permeability and coating property of PVA sizing paste were evaluated more accurately and conveniently than using I2-H3BO3 color-developing agent to dye sized yarns. It is expected that the perylene can be also labeled onto the molecular chains of other common sizing agents, both bio-based and petroleum-based ones, to prepare corresponding fluorescent products in an appropriate chemical way. The fluorescent sizing agents containing perylene have great potential to replace the traditional method to be adopted by textile industry in the accurate evaluation of permeability and coating property of sizing paste.

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Acknowledgements

This work was financially supported by Science Fund for Distinguished Young Scholars of Zhejiang Province (No. LR20E030004), National Natural Science Foundation of China (No. 51873187), National Basic Research Program of China (No. 2017YFE0117700 and 2018YFC1004803), Postdoctoral Science Foundation of China (No. 2018M632467), Project of Key Laboratory of Clean Dyeing and Finishing Technology of Zhejiang Province (No. QJRZ1902), and Fundamental Research Funds for the Central Universities (No. K20200127).

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Correspondence to Zhengke Wang.

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Jin, E., Wang, Z., Hu, Q. et al. Perylene-Based Fluorescent Sizing Agent for Precise Evaluation of Permeability and Coating Property of Sizing Paste. Adv. Fiber Mater. (2020). https://doi.org/10.1007/s42765-020-00050-y

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Keywords

  • Fluorescent sizing agent
  • Perylene
  • Chitosan
  • PVA
  • Permeability
  • Coating property