Journal of Textile Research ›› 2025, Vol. 46 ›› Issue (08): 53-61.doi: 10.13475/j.fzxb.20241104401

• Fiber Materials • Previous Articles     Next Articles

Study on crystallization kinetics of titanium polyester for industrial yarns

JIANG Tingguo1,2, KUANG Jun3, SI Hu4, ZHANG Yumei1,2, CHEN Ye1,2(), WANG Huaping1,2   

  1. 1. College of Materials Science and Engineering, Donghua University, Shanghai 201620, China
    2. State Key Laboratory of Advanced Fiber Materials, Donghua University, Shanghai 201620, China
    3. Sinopec (Shanghai) Petrochemical Research Institute Co., Ltd. Shanghai 201208, China
    4. Sinopec Yizheng Chemical Fiber Co., Ltd., Yizheng, Jiangsu 211900, China
  • Received:2024-11-19 Revised:2025-04-07 Online:2025-08-15 Published:2025-08-15
  • Contact: CHEN Ye E-mail:chenye@dhu.edu.cn

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Abstract:

Objective In this paper, two crystallization kinetics were used to analyze the crystallization behavior of titanium and antimony series high viscosity polyesters, and the effects of different catalytic systems on the crystallinity of high viscosity polyester chips were discussed. The differences and improvement measures of titanium polyester industrial yarn in production and other aspects compared with antimony polyester industrial yarn were deduced, and the application of titanium polyester industrial yarn in related fields was finally expanded.

Method The thermal stability of polyester chips for industrial yarns was characterized by thermogravimetry and differential scanning, and the crystallization performance of the chips was tested by combining XRD with differential scanning. In addition, the isothermal crystallization and non-isothermal crystallization tests were carried out by differential scanning calorimeter, and the Avrami equation was used to analyze and fit them.ResultsThrough the thermal stability test, it was found that polyester chips catalyzed by titanium and antimony for industrial yarns had only one weight loss step, and the initial decomposition temperatures of the two were very close. The crystallization performance test was characterized by the combination of differential scanning and XRD. Both differential scanning and XRD showed that the crystallinity of the titanium system was higher than that of the antimony system. In addition, in terms of differential scanning, the cooling crystallization peak of the titanium system is narrower and sharper than that of the antimony system, which preliminarily proves that the crystallization rate of the titanium system is faster. In the XRD test, there were four crystal planes (0,-1,1), (0,1,0), (-1,1,0), (1,0,0), which proves that there is no significant difference between the crystal plane structure and the conventional polyester. From the perspective of slicing, the production of industrial yarns was only related to its own intrinsic viscosity. In the isothermal crystallization test, as the temperature continues to increase, the crystallization peak continued to shift to the right and the peak shape gradually became wider. The molecular chain movement appeared more intense, the crystal nucleus was not conducive to formation, and the crystallization time became longer. Through the analysis and fitting of Avrami equation, it was found that ln(-ln(1-Xt)) (Xt means relative crystallinity) has a good linear relationship with lnt. With the continuous increase of temperature, the n value showed a decreasing trend. It is speculated that with the increase of crystallization temperature and the increase of melting time, the structure of microcrystalline nucleus is greatly destroyed, the growth point of crystallization is greatly reduced, and the molecular chain is difficult to achieve large-scale diffusion and adjustment.. In the non-isothermal crystallization test, the peak value was constantly shifted to the left and the peak shape is gradually widened with the increase of the cooling rate, due to the fact that the polyester molecular chain is too late to crystallize. Through the analysis and fitting of the Avrami equation, it is found that the semi-crystallization time of the titanium system was shorter, leading to the upward movement of the curing point in the spinning and cooling process, the increase of the stress gradient and the velocity gradient, which may cause uneven spinning and drawing. Therefore, in the follow-up, the first roller speed would be appropriately reduced to alleviate this problem.

Conclusion Both differential scanning and XRD tests show that the crystallinity of the titanium system is higher than that of the antimony system. Isothermal crystallization and non-isothermal crystallization were used to characterize the crystallization kinetics. It can be found that the crystallization rate of the titanium system is faster, and the crystallization performance is better. The activation energy of non-isothermal crystallization of titanium system is lower, and non-isothermal crystallization activation energy is usually related to the activation energy required for nucleation stability and the activation energy required for segment diffusion into the crystal plane, so the previous relevant conclusions can be verified. Finally, due to the shorter half crystallization time of the titanium system, there may be some problems in the spinning process, so the subsequent drafting process will be adjusted by appropriately reducing the drafting speed of the first roller.

Key words: polyester chips for industrial yarn, crystallization kinetics, spherulites, non-isothermal crystallization activation energy, titanium system polyester, antimony system polyester

CLC Number: 

  • TQ323.41

Fig.1

TG(a) and DTG(b) curves of polyester chips for industrial yarn"

Fig.2

DSC curves of polyester chips for industrial yarn. (a) Heating curves; (b) Cooling curves"

Fig.3

X-ray diffraction curves of polyester chips for different industrial yarns"

Fig.4

Isothermal crystallization DSC curves of polyester chips for industrial yarn at different crystallization temperatures"

Fig.5

Relationship between relative crystallinity and time of polyester chips for industrial yarn at different crystallization temperatures"

Fig.6

Relationship between ln(-ln(1-Xt))and lnt at different crystallization temperatures of polyester chips for industrial yarn"

Tab.1

Isothermal crystallization kinetic parameters of polyester chips for industrial yarn"

样品 Tc/℃ n t1/2/min lnZt R2
180 2.590 1.565 -1.495 52 0.989 16
Sb 185 2.348 2.106 -2.051 59 0.986 83
190 2.262 2.195 -2.079 29 0.988 10
195 2.080 3.053 -2.647 14 0.984 63
196 2.279 0.429 1.481 00 0.991 40
Ti 199 2.064 0.626 0.343 96 0.984 36
202 1.867 0.888 -0.450 81 0.971 05
205 1.920 1.475 -1.389 77 0.963 83

Fig.7

Non-isothermal crystallization DSC curves of polyester chips for industrial yarn at different cooling rates"

Fig.8

Relationship between relative crystallinity and temperature of polyester chips for different industrial yarns"

Fig.9

Relationship between relative crystallinity and time of polyester chips for different industrial yarns"

Fig.10

Relationship between ln (-ln(1-Xt)) and lnt of polyester chips for different industrial yarns"

Tab.2

Non-isothermal crystallization kinetic parameters of polyester chips for different industrial yarns"

样品 β/(℃·min-1) n t1/2/min Zt R2
5 2.675 4.13 0.018 0.983 83
Sb 10 2.604 3.44 0.032 0.979 11
15 2.597 2.87 0.052 0.975 12
20 2.837 2.10 0.099 0.991 77
5 2.302 5.87 0.004 0.948 82
Ti 10 2.343 3.00 0.024 0.950 83
15 2.663 1.81 0.113 0.950 34
20 3.154 1.50 0.230 0.968 88

Fig.11

ln (Φ/ T p 2)-1/Tp relation curve of polyester chips for industrial yarn"

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