Journal of Textile Research ›› 2025, Vol. 46 ›› Issue (07): 28-36.doi: 10.13475/j.fzxb.20240805401

• Fiber Materials • Previous Articles     Next Articles

Influences of sodium tetraborate/tannic acid cross-linking on structure and properties of calcium alginate fibers

ZHU Lei1, LI Xiaojun2, CHENG Chunzu1,2(), XU Jigang1,2, DU Xinyu2   

  1. 1 College of Materials Science and Engineering, Donghua University, Shanghai 201620, China
    2 National Key Laboratory of Bio-based Fiber Materials, China Textile Academy, Beijing 100025, China
  • Received:2024-08-28 Revised:2025-01-06 Online:2025-07-15 Published:2025-08-14
  • Contact: CHENG Chunzu E-mail:chunzuc@163.com

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Abstract:

Objective Calcium alginate fiber has poor mechanical properties and saline stability, which seriously limits its application in textile and garment fields. Most of the studies achieved the performance enhancement of calcium alginate fibers by chemical treatment of sodium alginate spinning stock solution and coagulation bath, and fewer studies related to direct cross-linking treatment of calcium alginate fibers. This paper introduces an effort to overcome the performance defects of calcium alginate fibers by impregnating them with cross-linking agents.

Method Calcium alginate (CA) fibers with different cross-linking types were prepared by impregnation method, and the structure and properties of the fibers were characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and optical microscopy (POM) moisture absorption and retention test, salt resistance and washing resistance test, and mechanical properties test.

Results Sodium tetraborate (STB) is bonded to calcium alginate (CA) macromolecules through B—O covalent bonds, effectively improving the saline and washing stability of CA fibers. Tannic acid (TA) was employed to regulate the calcium ion cross-linking between CA macromolecules through its chelating action with calcium ions in CA, indirectly enhancing the coordinated action of CA macromolecules through the strong hydrogen bond between phenolic hydroxyl groups and CA. These two actions, while improving the stability of CA fibers, also more effectively improved the mechanical properties of CA fibers. By combining STB and TA to cross-link CA successfully, a synergistic cross-linking network of ″borate covalent bond-tannic acid chelation-hydrogen bond″ was formed. On the one hand, it dispersed STB and promoted the cross-linking effect of STB on CA more effectively. On the other hand, it positioned TA and promoted the enhancement of strong hydrogen bond coordination between CA macromolecules more effectively, achieving a significant improvement in the tensile strength and elongation at break of CA fibers. As a result, the breaking strength of calcium alginate fibers was increased by 27.18% and the elongation at break by 7.48%, thereby achieving a significant improvement in the saline and washing stability and mechanical properties of CA fibers.

Conclusion Both TA and STB inhibit the calcium-sodium ion exchange of the fibers in metal ion-containing solution. TA improves the crystallinity of CA fibers, enhances the intermolecular hydrogen bonding, and increases the strength of CA fibers, while STB improves the elongation at break and the washing stability of CA fibers. Through the combination of TA and STB crosslinking CA, a synergistic crosslinking network of “borate covalent bonding-tannic acid-hydrogen bonding” was successfully constructed, which increased the breaking strength of calcium alginate fibers by 27.18% and the elongation at break by 7.48%, and the morphology and size of the fibers did not change much after being treated with saline and washing solution, and the saline resistance and washing resistance were significantly improved.

Key words: bio-based fiber, calcium alginate fiber, sodium tetraborate, tannic acid, cross-linking network, salt and washing resistance, mechanical property

CLC Number: 

  • TQ341.5

Fig.1

Preparation process of STB/TA/CA fiber"

Fig.2

Infrared spectra of crosslinkers (a) and fibers (b)"

Fig.3

Cross-linking mechanism of fibers"

Fig.4

XRD patterns of fibers"

Fig.5

SEM images of surfaces (a) and cross sections (b) of CA, TA/CA, STB/CA, STB/TA/CA fibers"

Fig.6

TGA (a) and DTG (b) curves of CA, TA/CA, STB/CA and STB/TA/CA fibers"

Tab.1

Mass loss rates of CA,STB/CA,TA/CA and STB/TA/CA fibers at different temperatures"

纤维种类 m75/% m190/% Tm/℃ m350/% m600/%
CA 5.83 16.62 258 50.85 63.67
STB/CA 6.11 16.97 268 49.25 63.77
TA/CA 5.81 15.59 259 49.93 62.23
STB/TA/CA 5.56 16.12 262 49.50 62.36

Fig.7

Moisture absorption rates and moisture retention rates of CA,STB/CA, TA/CA and STB/TA/CA fibers in closed container"

Fig.8

Solubilities (a) and diameter swelling rates (b) of CA, STB/CA, TA/CA, STB/TA/CA fibers after immersion"

Fig.9

SEM images of fibers after immersing in saline (a) and washing solution (b)"

Fig.10

Breaking strength (a) and elongation at break (b) of CA, STB/CA, TA/CA, STB/TA/CA fibers"

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